JP2008069355A - Water-based ink, water-based ink set, and method for producing dispersion - Google Patents

Abstract

A water-based ink that produces high-color development with little bleeding on plain paper, and can produce a water-based ink having fixing properties in addition to sufficient color development on special paper, and has superior ejection stability in water-based inkjet recording. A water-based ink comprising a dispersion that enables the production of a water-based ink.
A microcapsule including a colorant contained in a polymer and dispersible in water is used, and the amount of an aromatic ring in the polymer is 20% by weight or more and 70% by weight or less of the polymer. , Aqueous ink.
[Selection figure] None

Description

The present invention relates to a water-based ink that can obtain high print quality on plain paper, recycled paper or coated paper, and glossy media, and is excellent in storage stability.
The present invention also relates to an aqueous ink set excellent in color reproducibility and print quality on a printing medium such as glossy media usually used for plain paper or aqueous inkjet printing.
The present invention also relates to a dispersion comprising two steps: a dispersion production process in which a colorant is included in a polymer so that the dispersion can be dispersed in water; and a dispersion process in which the dispersion is dispersed in an aqueous medium. A method for producing an aromatic ring in the polymer, wherein the amount of the aromatic ring is 20% by weight or more and 70% by weight or less of the polymer, a dispersion produced by the method, and an aqueous solution using the dispersion It relates to ink.

  In recent years, the characteristics required for water-based inks for water-based ink jet printers include good fastness such as water resistance and light resistance of printed images, and irregular water-based ink flow regardless of the type of printing medium. In addition, there are no problems such as spreading larger than adhering water-based ink droplets (hereinafter referred to as “smudge”), and high print image density and color reproducibility regardless of the type of print medium.

  Among these purposes, in order to secure fastness of printed images, it has been studied to use pigments having excellent fastness instead of dyes. Unlike dyes, pigments are not soluble in water, so it is necessary to disperse pigments in water in the form of fine particles, but it is very difficult to keep this dispersed state stable. For this purpose, various techniques for stably dispersing the pigment in water have been proposed. As a means therefor, a method using a dispersible surfactant as disclosed in JP-A-1-301760, or Japanese Patent Publication No. 5-64724. As disclosed in the publication, a method using a dispersion polymer having a hydrophobic part and a hydrophilic part has been proposed. Further, as a method of coating the surface of the colorant with a polymer, as a water-based ink for a water-based inkjet printer, JP-A-62-95366 discloses a method using microcapsules encapsulating a dye-based water ink, and JP-A-1-170672. No. 5-39447 discloses a method of using a microencapsulated dye obtained by dissolving or dispersing a dye in a water-insoluble solvent and emulsifying the dye in water with a dispersible surfactant. And a method of using a microcapsule containing an inclusion in which a sublimable disperse dye is dissolved or dispersed in at least one kind of polyester as a recording liquid, Japanese Patent Application Laid-Open No. 6-313141 discloses a method of using colored emulsion polymerization particles and an aqueous material. In Japanese Patent Application Laid-Open No. 10-140065, a method using a phase inversion emulsification reaction or an acid precipitation method is proposed.

  In addition, for the realization of a printed image with good color reproducibility, JP-A-5-155006 and JP-A-10-52925 disclose a yellow aqueous ink in which a specific pigment is dispersed in a water-soluble resin, A method for forming an image by combining a magenta water-based ink, a cyan water-based ink, and a black water-based ink. JP-A-2001-354886 discloses a yellow water-based ink, a magenta water-based ink, and a cyan water-based ink in which a pigment is dispersed in a water-soluble resin. A method of forming an image by combining black aqueous ink, green aqueous ink, and red aqueous ink has been proposed.

  However, conventional dispersions are unstable, and when a substance having a hydrophilic part and a hydrophobic part such as a surfactant or glycol ether is present, adsorption / desorption tends to occur, and the storage stability of the aqueous ink is poor. There is. Ordinary water-based inks need a substance having a hydrophilic part and a hydrophobic part, such as a surfactant and glycol ether, in order to reduce bleeding on paper. Water-based inks that do not use these substances have insufficient permeability to paper, and there is a problem that the type of paper is limited in order to perform uniform printing, which tends to cause a reduction in the printed image.

Furthermore, additives (acetylene glycol, acetylene alcohol, silicon surfactant, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether or 1,2-alkylene as used in the present invention for conventional dispersions. If glycol or a mixture thereof is used, long-term storage stability cannot be obtained, and the water-based ink is poorly re-dissolvable, so that the water-based ink is dried and easily clogged with a nozzle of a water-based inkjet head or a pen tip of a writing instrument. Had problems.
In addition, the pigment dispersed with such a dispersant has a residual dispersant remaining in the water-based ink system, and the dispersant does not sufficiently contribute to the dispersion and becomes detached from the pigment, resulting in a high viscosity. There was a problem. When the viscosity is high, the amount of coloring material such as pigment is limited, and sufficient image quality cannot be obtained particularly on plain paper.

  Therefore, the present invention solves such problems, and the object of the present invention is to produce a water-based ink that has high bleeding and low color on plain paper, and has fixing properties in addition to sufficient color on special paper. In the case of water-based inkjet recording, an object of the present invention is to provide a water-based ink containing a dispersion that enables the preparation of a water-based ink having excellent ejection stability.

  The water-based ink of the present invention is a water-based ink containing a dispersion in which a colorant is included in a polymer (hereinafter also referred to as “dispersion polymer”) and is dispersible in water, and the amount of aromatic rings in the polymer Is not less than 20% by weight of the polymer (hereinafter sometimes simply referred to as%) and not more than 70%.

  It is possible to provide a water-based ink that has high bleeding and little bleeding on plain paper, has sufficient fixability and has excellent discharge stability on special paper.

  According to the present invention, a water-based ink is excellent in stability of a dispersion, has a high coloration with little blurring on plain paper, and can produce a water-based ink having fixing properties in addition to sufficient color development on a special paper. This is based on the result of intensive studies in view of the fact that characteristics such as excellent discharge stability of water-based ink from the water-based inkjet head are required.

Preferred embodiment (a) of the present invention
The water-based ink of the present invention includes a dispersion in which a colorant is included in a polymer so as to be dispersible in water, and the amount of aromatic rings in the polymer is 20% to 70% of the polymer. . When the amount of the aromatic ring is 20% or more of the polymer, the polymer can be favorably adsorbed to the colorant on the hydrophobic surface. Further, the adsorbed polymer becomes stable even when an additive suitably used in the present invention is added. On the other hand, when the amount of the aromatic ring exceeds 70%, dispersion becomes difficult and, on the contrary, stability cannot be obtained. More preferably, it is 25% or more and 50% or less.

Hereinafter, the water-based ink of the present invention will be described.
First, the dispersion that is a feature of the water-based ink of the present invention will be described. As described above, the dispersion comprising the water-based ink of the present invention is one in which a colorant is included in a polymer so that it can be dispersed in water.

Pigments Examples of inorganic pigments or organic pigments that can be used as colorants are given below.
Examples of the inorganic pigment for black include carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, or channel black.
Examples of organic pigments that can be used include phthalocyanine pigments, quinacridone pigments, condensed azo pigments, isoindolinone pigments, quinophthalone pigments, anthraquinone pigments, benzimidazolone pigments, and perylene pigments.

  Specifically, for example, organic pigments for yellow include C.I. I. Pigment Yellow 1 (Hansa Yellow G), 2, 3 (Hansa Yellow 10G), 4, 5 (Hansa Yellow 5G), 6, 7, 10, 11, 12 (Disazo Yellow AAA), 13, 14, 16, 17, 24 (flavantron yellow), 55 (disazo yellow AAPT), 61, 61: 1, 65, 73, 74 (fast yellow 5GX), 75, 81, 83 (disazo yellow HR), 93 (condensed azo yellow 3G), 94 (condensed azo yellow 6G), 95 (condensed azo yellow GR), 97 (fast yellow FGL), 98, 99 (anthraquinone), 100, 108 (anthrapyrimidine yellow), 109 (isoindolinone yellow 2GLT), 110 ( Isoindolinone Yellow 3RLT), 113, 117, 120 (Benzimidazolone) Yellow H2G), 123 (anthraquinone yellow), 124, 128 (condensed azo yellow 8G), 129, 133, 138 (quinophthalone yellow), 139 (isoindolinone yellow), 147, 151 (benzimidazolone yellow H4G), 153 (Nickel nitroso yellow), 154 (benzimidazolone yellow H3G), 155, 156 (benzimidazolone yellow HLR), 167, 168, 172, 173 (isoindolinone yellow 6GL), 180 (benzimidazolone yellow), etc. Can be mentioned.

  Examples of organic pigments for magenta water-based ink include C.I. I. Pigment Red 1 (Para Red), 2, 3 (Toluidine Red), 4, 5 (lTR Red), 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21 , 22, 23, 30, 31, 32, 37, 38 (pyrazolone red B), 40, 41, 42, 88 (thioindigo Bordeaux), 112 (naphthol red FGR), 114 (brilliant carmine BS), 122 (dimethyl) Quinacridone), 123 (perylene vermilion), 144, 146, 149 (perylene car red), 150, 166, 168 (antanthrone orange), 170 (naphthol red F3RK), 171 (benzimidazolone maroon HFM), 175 ( Benzimidazolone Red HFT), 176 (Benzimidazolone Carmine) F3C), 177, 178 (perylene red), 179 (perylene maroon), 185 (benzimidazolone carmine HF4C), 187, 188, 189 (perylene red), 190 (perylene red), 194 (perinone red), 202 (quinacridone) Magenta), 209 (dichloroquinacridone red), 214 (condensed azo red), 216, 219, 220 (condensed azo), 224 (perylene red), 242 (condensed azo scarlet), 245 (naphthol red), or C.I. I. Pigment violet 19 (quinacridone), 23 (dioxazine violet), 31, 32, 33, 36, 38, 43, 50, and the like.

Furthermore, as organic pigments for cyan, C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6 (all are phthalocyanine blue), 16 (
(Metal-free phthalocyanine blue), 17: 1, 18 (alkali blue toner), 19, 21, 22, 25, 56, 60 (slen blue), 64 (dichloroindantron blue), 65 (violanthrone), 66 (indigo) Etc.
Moreover, as the organic pigment for black, a black organic pigment such as aniline black (CI Pigment Black 1) can be used.

Furthermore, as an organic pigment used in a color aqueous ink other than yellow, cyan, or magenta aqueous ink,
C. I. Pigment Orange 1, 2, 5, 7, 13, 14, 15, 16 (Vulcan Orange), 24, 31 (Condensed Azo Orange 4R), 34, 36 (Benzimidazolone Orange HL), 38, 40 (Pyrantron Orange) ), 42 (isoindolinone orange RLT), 43, 51, 60 (benzimidazolone-based insoluble monoazo pigment), 62 (benzimidazolone-based insoluble monoazo pigment), 63;
C. I. Pigment Green 7 (phthalocyanine green), 10 (green gold), 36 (salt brominated phthalocyanine green), 37, 47 (violanthrone green); I. Pigment brown 1, 2, 3, 5, 23 (condensed azo brown 5R), 25 (benzimidazolone brown HFR), 26 (perylene Bordeaux), 32 (benzimidazolone brown HFL), and the like.

In the water-based ink used in the present invention, the above pigments can be used alone or in combination of two or more.
The pigment to be used is preferably pulverized in advance before being encapsulated with a polymer to form a microcapsule (meaning a dispersion). The pulverization treatment of the pigment can be carried out by wet pulverization or dry pulverization using a pulverization medium such as zirconia beads, glass beads, and inorganic salts. it can.
When the pigment is atomized by a pulverization treatment, it is conceivable that not a few components of the pulverization media (beads) are mixed in the pigment. Specifically, if glass beads are used for the grinding media, Si may be mixed in the pigment, and Zr may be mixed in the case of zirconia beads. Furthermore, mixing from the members of the crushing device is also conceivable. When a crushing device composed of a stainless steel member is used, mixing of Fe, Cr, Ni, etc. is conceivable. Therefore, after the pulverization treatment, it is desirable to remove contamination components generated from the pulverization media and the pulverizer by washing the pigment, ultrafiltration, and the like.

There is also a method (salt milling method) that uses a water-soluble inorganic salt (NaCl, BaCl ₂ , KCl, Na ₂ SO _4, etc.) as the grinding media, and in this case, theoretically washing with ion-exchanged water etc. The crushed media components mixed in can be removed. However, since it is also a method of mixing a pigment with a large surface area and the inorganic salt as described above, care must be taken because there may be a large amount of inorganic salt remaining as the dispersion medium if washing after grinding is insufficient. It is.
As a dispersion method, known dispersion methods such as ultrasonic dispersion, bead mill, sand mill, roll mill, jet mill and the like can be used.

When used in water-based inkjet among water-based inks, the addition amount of these pigments is preferably 0.5 to 30%, more preferably 1.0 to 12%. If the addition amount is less than this, the print density cannot be secured, and if the addition amount is more than this, the viscosity of the water-based ink is increased and the structural property is generated in the viscosity characteristics, and the discharge stability of the water-based ink from the water-based inkjet head is deteriorated. Become a trend.
The pigment particle size is preferably 5 μm or less, more preferably a pigment composed of particles of 0.3 μm or less, and still more preferably a pigment composed of particles of 0.01 to 0.15 μm.

Dispersion polymer The dispersion polymer used in the water-based ink of the present invention includes the pigment and makes it dispersible in water, and the amount of the aromatic ring in the dispersion polymer is 20% or more and 70% or less of the dispersion polymer. . The hydrophobic group of the substance forming the dispersion polymer is preferably at least one selected from an alkyl group, a cycloalkyl group or an aromatic ring, but the amount of the aromatic ring is preferably within the above range. In the alkyl group and cycloalkyl group, an alkyl group having 4 or more carbon atoms is preferable. When an aromatic ring is included in the dispersion polymer, an aryl group (specifically, a phenyl group, a naphthyl group, an anthryl group, etc.) and / or their derivatives, other aromatic rings, heterocycles and / or their derivatives Can be included in the form. The substance forming the dispersion polymer preferably has a hydrophilic functional group, and the hydrophilic functional group includes at least a carboxyl group, a sulfonic acid group, a hydroxyl group, an amino group, an amide group, and a base thereof. It is preferable that As specific examples of the substance forming these dispersion polymers, there can be used monomers and oligomers having an acryloyl group, methacryloyl group, vinyl group or allyl group having a double bond.

  In addition, the polymer including the pigment is at least one selected from the group consisting of polyacrylate ester, styrene-acrylic acid copolymer, polystyrene, polyester, polyamide, polyimide, silicon-containing polymer, and sulfur-containing polymer. It is preferable to use as a component. Acetylene glycol surfactant, acetylene alcohol surfactant, silicon surfactant, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol used in the present invention In addition, since one or more kinds of substances cause an adsorption / desorption reaction with the dispersant used for normal dispersant dispersion, the detached dispersant is likely to float in the water-based ink, resulting in a phenomenon in which printing is disturbed. . However, it is preferable to carry out suitable dispersion using the above-mentioned polymer because the polymer stably contains a colorant and thus hardly absorbs and desorbs.

  Furthermore, it is preferable that the colorant including the above-described pigment as a polymer includes at least a dispersant having a polymerizable group and a copolymerizable monomer and including the pigment. Here, the dispersant having a polymerizable group has at least a hydrophobic group, a hydrophilic group and a polymerizable group, and the polymerizable group is an acryloyl group, a methacryloyl group, an allyl group or a vinyl group, and is a copolymerizable group. Are acryloyl group, methacryloyl group, allyl group or vinyl group. As water-based inks for water-based inkjet recording, it is preferable that the particle diameters are relatively uniform from the viewpoint of clogging and ejection stability. Therefore, a colorant containing a pigment in a polymer is produced by emulsion polymerization or phase inversion emulsification. It is preferred that Further, an acetylene glycol-based surfactant and an acetylene alcohol-based surfactant that the benzene ring in the polymer is within the scope of the present invention, and becomes a firm polymer by suitable dispersion with a suitable dispersant, and may be used in the present invention. Dispersion stability can also be obtained by adding one or more substances selected from silicone surfactants, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol. It is preferable because stability is obtained for a long time.

  The colorant including the above pigment as a polymer was dispersed in the pigment with a dispersant having a polymerizable group, and then emulsion polymerized in water using a monomer copolymerizable with the dispersant and a polymerization initiator. Phase inversion emulsification in water is preferred so that the polymer or pigment is covered.

Specific examples of the monomer of the dispersion polymer used in the aqueous ink of the present invention include, for example, styrene, (α, 2, 3 or 4) -alkylstyrene, ( α, 2, 3 or 4) -alkoxystyrene, 3,4-dimethylstyrene, α-phenylstyrene, divinylbenzene, vinylnaphthalene, styrene macromer,
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, di (meth) acrylate of an ethylene oxide adduct of bisphenol A or F, and the like can be used. Other monomers include tetrahydrofurfuryl acrylate, butyl methacrylate, dimethylamino (meth) acrylate, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl acrylamide, N, N-dimethylaminoethyl acrylate, acryloylmorpholine, N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, ethylhexyl (meth) acrylate, other alkyl (meth) acrylates, methoxydiethylene glycol (Meth) acrylate, ethoxy group, propoxy group, butoxy group of diethylene glycol or polyethylene glycol ( Acrylate), cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, hydroxyalkyl (meth) acrylate, other fluorine-containing, chlorine-containing, silicon-containing (meth) acrylate, (meth) acrylamide, maleic acid amide, (meth) acrylic An acid or the like can be used. In addition to the above monofunctional monomer, when a crosslinked structure is introduced into the dispersion polymer (mono, di, tri, tetra, poly) ethylene glycol di (meth) acrylate, 1,4-butanediol, 1, (Meth) acrylates such as 5-pentanediol, 1,6-hexanediol, 1,8-octanediol and 1,10-decanediol, trimethylolpropane tri (meth) acrylate, glycerin (di, tri) (meth) A compound having an acrylic group or a methacryl group such as acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or the like can be used.

The polymer containing an aromatic ring was selected from the group consisting of a styrene-acrylic acid copolymer, polystyrene, polyimide, and the other polymer consisting of polyacrylate, polyester, polyamide, silicon-containing dispersion polymer, and sulfur-containing dispersion polymer. It can also be created while adding these dispersion polymers so as to have one or more kinds as a main component.
Polymerization initiators include potassium persulfate and ammonium persulfate, hydrogen persulfate, azobisisobutyronitrile, benzoyl peroxide, dibutyl peroxide, peracetic acid, cumene hydroperoxide, t-butylhydroxyperoxide, paramenthane Common initiators used for radical polymerization such as hydroxy peroxide can be used.

The dispersion polymer used in the water-based ink of the present invention can be prepared by emulsion polymerization, and in that case, a chain transfer agent can also be used. For example, in addition to t-dodecyl mercaptan, n-dodecyl mercaptan, n-octyl mercaptan, xanthogens such as dimethylxanthogen disulfide, diisobutylxanthogen disulfide, or dipentene, indene, 1,4-cyclohexadiene, dihydrofuran, xanthene It is done.
By using the dispersion having the pigment and the dispersion polymer as constituents as described above, it is possible to obtain a water-based ink suitable for water-based inkjet printing having excellent storage stability. Furthermore, in the water-based ink of the present invention, by containing a water-soluble organic solvent such as described later, an image having a good fixability and color reproducibility with less bleeding regardless of the type of printing medium such as plain paper or glossy media. Can be formed. Moreover, the above-mentioned dispersion can be suitably used for water-based ink for writing instruments.

In addition, it is preferable that the colorant including the above-described pigment as a polymer includes the pigment as a copolymer of at least a dispersant having a polymerizable group and a copolymerizable monomer. Here, the dispersant having a polymerizable group has at least a hydrophobic group, a hydrophilic group and a polymerizable group, and the polymerizable group is an acryloyl group, a methacryloyl group, an allyl group or a vinyl group, and is a copolymerizable group. Are also acryloyl, methacryloyl, allyl or vinyl.
As water-based inks for water-based inkjet recording, it is preferable that the particle diameters are relatively uniform from the viewpoint of clogging and ejection stability. Therefore, a colorant containing a pigment in a polymer is produced by emulsion polymerization or phase inversion emulsification. It is preferred that Further, the benzene ring in the polymer is within the scope of the present invention, and it is preferable because the polymer becomes a firm polymer by suitable dispersion with a suitable dispersant, dispersion stability is obtained, and stability is obtained for a long time.
A dispersion containing the above-described pigment as a polymer was dispersed in the pigment with a dispersant having a polymerizable group, and then emulsion-polymerized in water using a monomer copolymerizable with the dispersant and a polymerization initiator. It is preferable.

Water-based ink The water-based ink of the present invention is characterized by containing at least a penetrating agent, a humectant, water, and the dispersion described above.
Further, the water-based ink used in the present invention may be added with a penetrant for the purpose of enhancing the permeability to a recording medium such as paper, which is a recording medium of the water-based ink. Moisturizers, dissolution aids, penetration control agents (penetration agents), viscosity modifiers, pH adjusters, antioxidants, antifungal agents, corrosion inhibitors, metals that affect dispersion Various additives such as chelate for capturing ions may be added.

(Penetration agent)
Addition of penetrants improves the drying of printed matter, and even if continuous printing is performed, the previous printed portion is not transferred to the back side of the next medium. To do. Further, when used as a water-based ink for a water-based ink jet printer, those having less foaming and properties that are difficult to dry in the nozzles of a water-based ink jet head are particularly suitable.
Such penetrants are preferably one or more selected from acetylene glycol surfactants, acetylene alcohol surfactants, silicon surfactants, glycol ethers, and alkylene glycols. . By using these penetrants, bleeding on plain paper can be reduced, and the line width on glossy media can be adjusted to an appropriate level.

Specific product names of acetylene glycol surfactants or acetylene alcohol surfactants that can be suitably used as penetrants include, for example, Surfinol TG, Surfinol 104, Surfinol 420, Surfinol 440, Surfinol 465. , Surfinol 485, Surfinol 61, Surfinol 82 (all manufactured by Air Products Co., Ltd.), Orphine E1010, Orphin E1004, Orphine STG (All manufactured by Nissin Chemical Industry Co., Ltd.), or Acetylenol E00, Acetylenol E40, acetylenol E100 (all of which are manufactured by Kawaken Fine Chemical Co., Ltd.) and the like.
Examples of glycol ethers that can be suitably used as penetrants include diethylene glycol mono (C 4-8 alkyl) ether, triethylene glycol mono (C 4-8 alkyl) ether, propylene glycol mono (C 3 carbons). -6 alkyl) ether, dipropylene glycol mono (C3-6 alkyl) ether, and the like. Specific examples include diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monobutyl ether, and dipropylene. And glycol monobutyl ether.

Examples of the alkylene glycol that can be used as the penetrant include 1,2- (alkyl having 4 to 10 carbon atoms) diol, 1,3- (alkyl having 4 to 10 carbon atoms) diol, and 1,5- (4 to 10 carbon atoms). Alkyl) diol, 1,6- (alkyl having 4 to 10 carbon atoms) diol, and the like. Specific examples include 1,2-pentanediol, 1,2-hexanediol, 1,3-butanediol. 1,5-pentanediol, 1,6-hexanediol and the like.
Addition of these glycol ethers and / or alkylene glycols improves the dryness of printing, and the previous printed portion is not transferred to the back side of the next medium even if printing is continued. In particular, high-speed printing is possible in aqueous ink jet recording. Further, the glycol ethers and / or alkylene glycols have an effect as a penetrating agent and also have characteristics as a dissolution aid for other hardly soluble water-based ink additives. For example, when a compound having low solubility in water alone is used among the above-mentioned acetylene glycols, the solubility of acetylene glycols can be increased and the addition amount thereof can be increased by adding glycol ethers in combination.

Furthermore, since glycol ethers and / or alkylene glycols have a bactericidal and antibacterial action, they can contain about 3 to 5% in aqueous ink to suppress the generation of microorganisms and fungi. It also has the effect.
In the water-based ink of the present invention, the acetylene glycol surfactant, acetylene alcohol surfactant, glycol ethers, and alkylene glycols described above can be used alone or in combination as penetrants. The amount is preferably from 0.01 to 30% by weight, more preferably from 0.1 to 10% by weight. If the added amount is less than 0.01%, the effect of improving the printing quality is lowered, and if it exceeds 30% by weight, the periphery of the nozzles of the water-based ink discharge head is wetted unevenly, and stable discharge becomes difficult.
It is preferable to contain 0.1% or more and 5% or less of one or more selected from the above-mentioned acetylene glycol surfactants, acetylene alcohol surfactants and silicon surfactants. If it exceeds 5%, the effect of the print quality will reach its peak, and even if it is added, the viscosity will increase and it will be difficult to use, water-based ink will easily adhere to the tip of the head, and the print will be confused. If it is less than 0.1%, the effect of improving the print quality becomes low. A more preferable addition amount is 0.15 to 2%.

  And at least one selected from the above-mentioned acetylene glycol surfactants, acetylene alcohol surfactants and silicon surfactants, and di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and It is preferable to simultaneously add one or more selected from 1,2-alkylene glycol. Acetylene glycol and / or acetylene alcohol surfactant and at least one selected from di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol are preferably used simultaneously. Print quality is improved.

  One or more selected from the above-mentioned acetylene glycol surfactants, acetylene alcohol surfactants and silicon surfactants is 0 to 0.5%, and di (tri) ethylene glycol monobutyl ether, ( It is preferable that at least one selected from di) propylene glycol monobutyl ether and 1,2-alkylene glycol is 1% or more. One or more selected from acetylene glycol surfactants, acetylene alcohol surfactants and silicon surfactants have the effect of improving permeability in small amounts. Accordingly, the print quality is 0.5% or less, and at least one selected from di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol is 1% or more. Is further improved.

In addition, as the penetrant for the water-based ink of the present invention, the aforementioned alcohols, nonionic surfactants, silicon surfactants, water-soluble organic solvents, and other surfactants can be similarly used.
For example, BYK is a specific example of a silicon surfactant that can be suitably used as a penetrant.
-307, BYK-331, BYK-333, BYK-347, BYK-348 (all of which are manufactured by Big Chemie Co., Ltd.).
In the water-based ink used in the present invention, these penetrants can be used alone or in combination of two or more.
In particular, the above-mentioned alkylene glycol monoalkyl ether is preferably an alkylene glycol having 10 or less repeating units and an alkyl ether having 3 to 10 carbon atoms. Among them, di (tri) ethylene glycol monobutyl ether and / or (di) propylene glycol monobutyl ether are preferable, and the aforementioned 1,2-alkylene glycol is 1,2-hexanediol, and / or 1,2-pentanediol is preferred.

Further, the amount of addition of one or more substances selected from the aforementioned di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether, and 1,2-alkylene glycol is 0.5% to 30%. It is preferable that More preferably, it is 1% or more and 15% or less.
And at least one selected from the aforementioned acetylene glycol surfactants and acetylene alcohol surfactants, and di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether, and 1,2-alkylene glycol It is preferable in terms of printing quality that one or more selected from the above are added simultaneously.

  One or more selected from the above-mentioned acetylene glycol surfactants and acetylene alcohol surfactants are 0.01 to 1.0%, and are di (tri) ethylene glycol monobutyl ether, (di) propylene glycol mono One or more selected from butyl ether and 1,2-alkylene glycol is preferably 1% or more. One or more selected from acetylene alcohol surfactants and acetylene alcohol surfactants have the effect of improving permeability in a small amount. Therefore, even if the addition amount is 1.0% or less, at least one selected from di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol is added at 1% or more. As a result, the print quality is further improved.

The aforementioned 1,2-alkylene glycol is a 1,2-alkylene glycol having 4 to 10 carbon atoms, and the addition amount is preferably 10% or less. However, it is not limited to this for writing instruments. More preferably, it is 1% or more and 8% or less.
Further, di (tri) ethylene glycol monobutyl ether means diethylene glycol monobutyl ether and / or triethylene glycol monobutyl ether, but addition of 20% or less is preferable as a necessary level of permeability for improving print quality. More preferably, it is 0.5 to 10%.
In the aqueous ink used in the present invention, as an aid for the penetrant, the penetrability of the aqueous ink is controlled, and the nozzle clogging resistance, the moisture retention of the aqueous ink, or the solubility of the penetrant is improved. 1 type of the above-mentioned or other surfactants, and high-boiling low-volatile polyhydric alcohols, or hydrophilic high-boiling low-volatile solvents such as monoetherified products, dietherified products, or esterified products thereof. Or in combination of two or more.

  The 1,2-alkylene glycol described above is a 1,2-alkylene glycol having 4 to 10 carbon atoms, and the addition amount is preferably 10% or less. If it exceeds 10%, it becomes difficult to use as an aqueous ink jet due to an increase in viscosity, and even if it is added more than that, there is no effect of improving the printing quality. However, it is not limited to this for writing instruments.

The 1,2-alkylene glycol described above is preferably 1,2-pentanediol or 1,2-hexanediol. 1,2-pentanediol is preferably 3 to 10% or less. If it is less than 3%, the effect of improving the permeability is low, and therefore, bleeding is often generated. When the number of carbon atoms exceeds 10, the viscosity becomes high and it is difficult to use the water-soluble water-based ink as in the present invention. 1,2-hexanediol is preferably 0.5 to 10%. If it is less than 0.5%, the effect of improving the permeability is low, and if the carbon number exceeds 10, the water-solubility is low. When the addition amount of the acetylene glycol and / or acetylene alcohol surfactant is 0.5% or more, the ratio of 1,2-alkylene glycol is between 1: 0 and 1:50 in terms of print quality. From the above, when 1,2-alkylene glycol exceeds 50 times the amount of acetylene glycol and / or acetylene alcohol surfactant, the effect of improving the printing quality is peaked, and even if added more, the effect is low, and the viscosity is increased. Cause the negative effects.

And it is preferable to contain the above-mentioned (di) propylene glycol monobutyl ether 10% or less. If it exceeds 10%, the effect of improving the printing quality will reach its peak, and conversely, the adverse effect of increasing the viscosity and the low water solubility make it necessary to add a dissolution aid. More preferably, it is 0.5 to 5%.
The ratio of the aforementioned acetylene glycol and / or acetylene alcohol surfactant to (di) propylene glycol monobutyl ether is preferably 1: 0 to 1:10. (Di) When propylene glycol monobutyl ether exceeds 10 times the amount of acetylene glycol and / or acetylene alcohol surfactant, the effect of improving the print quality is peaked, and even if added more, the effect is low, and adversely the viscosity increases. Produce.

  It is preferable to contain 20% or less of the aforementioned di (tri) ethylene glycol monobutyl ether. If it exceeds 20%, it becomes difficult to use due to an increase in viscosity. More preferably, it is 1% or more and 15% or less. Di (tri) ethylene glycol monobutyl ether refers to diethylene glycol monobutyl ether (DEGmBE) and / or triethylene glycol monobutyl ether (TEGmBE). As a necessary level of permeability for improving print quality, addition of 20% or less preferable. If it exceeds 20%, the effect of improving the printing quality will reach its peak, and the adverse effect of increasing the viscosity will occur. More preferably, it is 0.5 to 10%.

  It is preferable that the addition amount of the above-mentioned acetylene glycol and / or acetylene alcohol surfactant is 0.5% or more, and the ratio with di (tri) ethylene glycol monobutyl ether is 1: 0 to 1:50. From the viewpoint of printing quality, it is preferable to add up to 50 times the amount of acetylene glycol and / or acetylene alcohol surfactant. Di (tri) ethylene glycol monobutyl ether is useful for improving the solubility of acetylene glycol surfactants and improving print quality. However, if the amount of addition exceeds 50 times, the effect will reach its peak, so for water-based inkjet As it becomes difficult to use.

(Humectant)
Water-soluble glycols for suppressing drying on the nozzle surface of a water-based inkjet or the nib include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol having a molecular weight of 2000 or less, 1 , 3-propylene glycol, isopropylene glycol, isobutylene glycol, thiodiglycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, glycerin, mesoerythritol, Pentaerythritol, trimethylolethane, trimethylolpropane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, cyclohexanethiol, etc. A.

In the present invention, many kinds of saccharides can be used in order to prevent the water-based ink from being dried and clogged in front of the nozzle. There are monosaccharides and polysaccharides, and in addition to glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucosose, maltose, cellobiose, sucrose, trehalose, maltotriose, etc., alginic acid and its salts, cyclo Dextrins and celluloses can be used. The addition amount is preferably 0.05% or more and 30% or less. Monosaccharides and polysaccharides that are common saccharides and more preferable addition amounts of glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitol, maltose, cellobiose, sucrose, trehalose, maltotriose, etc. Is 3 to 20%. Alginic acid and its salts, cyclodextrins, and celluloses need to be added in such an amount that the viscosity is not too high when used as an aqueous ink.

  In addition, it is compatible with water, improves the solubility of glycol ethers and water-based ink components that are poorly soluble in water contained in water-based ink, and further improves the permeability to a recording medium such as paper, or C1-C4 alkyl alcohols such as ethanol, methanol, butanol, propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether can be used to prevent clogging of the nozzle and nib , Ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol No-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono- t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropy Glycol ethers such as diglycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, formamide, acetamide, dimethyl sulfoxide, sorbit, There are sorbitan, acetin, diacetin, triacetin, sulfolane, and the like, which can be appropriately selected and used.

(Other additives)
The water-based ink for water-based inkjet recording in the present invention is a moisturizer, a dissolution aid, a penetration control agent, a viscosity adjuster, a pH adjuster, for the purpose of ensuring its standing stability, achieving stable discharge from the aqueous ink discharge head, Various additives such as antioxidants, antifungal agents, corrosion inhibitors, chelates for capturing metal ions that affect dispersion may be added. Hereinafter, they will be exemplified.
It is preferable to add water-soluble glycols to suppress drying on the nozzle surface of an aqueous inkjet or the pen tip of a writing instrument. Examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, Propylene glycol, polyethylene glycol having a molecular weight of 2000 or less, 1,3-propylene glycol, isopropylene glycol, isobutylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexane Examples include diol, glycerin, mesoerythritol, and pentaerythritol.

In the present invention, many kinds of saccharides can be used in order to prevent the water-based ink from drying and clogging at the front surface of the nozzle. There are monosaccharides and polysaccharides, and in addition to glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucosose, maltose, cellobiose, sucrose, trehalose, maltotriose, etc., alginic acid and its salts, cyclo Dextrins and celluloses can be used. The addition amount is preferably 0.05% or more and 30% or less. If it is less than 0.05%, the effect of recovering the clogging phenomenon in which the water-based ink dries and clogs at the tip of the head is small, and if it exceeds 30%, the viscosity of the water-based ink increases and appropriate printing cannot be performed. Monosaccharides and polysaccharides that are common saccharides and more preferable addition amounts of glucose, mannose, fructose, ribose, xylose, arabinose, lactose, galactose, aldonic acid, glucitol, maltose, cellobiose, sucrose, trehalose, maltotriose, etc. Is 3 to 20%. Alginic acid and its salts, cyclodextrins, and celluloses need to be added in such an amount that the viscosity is not too high when used as an aqueous ink.

  In addition, it is compatible with water, improves the solubility of glycol ethers and water-based ink components that are poorly soluble in water contained in water-based ink, and further improves the permeability to a recording medium such as paper, or C1-C4 alkyl alcohols such as ethanol, methanol, butanol, propanol, isopropanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether can be used to prevent clogging of the nozzle and nib , Ethylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, ethylene glycol No-iso-propyl ether, diethylene glycol mono-iso-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol mono-n-butyl ether, ethylene glycol mono-t-butyl ether, diethylene glycol mono- t-butyl ether, 1-methyl-1-methoxybutanol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-t-butyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-iso-propyl ether, Dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropy Glycol ethers such as diglycol mono-n-propyl ether, dipropylene glycol mono-iso-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol mono-n-butyl ether, formamide, acetamide, dimethyl sulfoxide, sorbit, There are sorbitan, acetin, diacetin, triacetin, sulfolane, and the like, which can be appropriately selected and used.

In addition, other surfactants can be added to the water-based ink according to the present invention in order to control the permeability to a medium such as paper or special paper. The surfactant to be added is preferably a surfactant having good compatibility with the aqueous ink system of the present invention, and among the surfactants, those having high permeability and stability are preferable. Examples thereof include amphoteric surfactants and nonionic surfactants. Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Ethers such as ethylene alkyl ether and polyoxyalkylene alkyl ether (polyoxypropylene polyoxyethylene alkyl ether), polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan mono Stearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, Ester such as polyoxyethylene stearate, and the like other fluorine alkyl esters, fluorine-containing surfactants such as perfluoroalkyl carboxylates.

  Moreover, amines such as diethanolamine, triethanolamine, propanolamine and morpholine as pH adjusters, solubilizers or antioxidants and their modified products, inorganic salts such as potassium hydroxide, sodium hydroxide and lithium hydroxide, Ammonium hydroxide, quaternary ammonium hydroxide (tetramethylammonium, etc.), potassium carbonate (hydrogen), carbonate (hydrogen) sodium, carbonates such as lithium carbonate (hydrogen), other phosphates, or N-methyl-2- Examples thereof include ureas such as pyrrolidone, urea, thiourea and tetramethylurea, allophanates such as allophanate and methylallohanate, biurets such as biuret, dimethylbiuret and tetramethylbiuret, and L-ascorbic acid and salts thereof. Commercially available antioxidants, ultraviolet absorbers and the like can also be used. Examples include Ciba-Geigy Tinuvin 328, 900, 1130, 384, 292, 123, 144, 622, 770, 292, Irgacor 252, 153, Irganox 1010, 1076, 1035, MD1024, or lanthanide oxides.

Furthermore, examples of the viscosity modifier include rosins, alginic acids, polyvinyl alcohol, hydroxypropylcellulose, carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, polyacrylate, polyvinylpyrrolidone, gum arabic starch and the like.
From the viewpoint of durability of the head member and stability of the water-based ink, the pH adjuster is preferably in an amount such that the pH value of the water-based ink is about 7-10.
In addition, the pigment dispersion of the present invention and the aqueous ink containing the same may contain other additives such as a fungicide, a preservative, or a rust preventive as benzoic acid, dichlorophene, hexachlorophene. Sorbic acid, p-hydroxybenzoic acid ester, ethylenediaminetetraacetic acid (EDTA), sodium dehydroacetate, 1,2-benzothiazoline-3-one, 3,4-isothiazoline-3-one, or 4,4-dimethyloxazolidine Oxazolidine compounds such as alkyl isothiazolone, chloroalkyl isothiazolone, benzisothiazolone, bromonitroalcohol and / or chloroxylenol. Furthermore, urea, thiourea, and / or ethylene urea may be included for the purpose of preventing nozzle drying.

Water-based ink physical properties Various properties of the water-based ink used in the present invention can be appropriately controlled. However, according to a preferred embodiment, the viscosity of the water-based ink is preferably 10 mPa · sec or less, more preferably 5 mPa · sec or less ( 20 ° C.). Water-based ink in this viscosity range is stably ejected from the water-based ink ejection head. The surface tension of the water-based ink can be appropriately controlled, but is preferably 25 to 50 mN / m (20 ° C.), more preferably 30 to 40 mN / m (20 ° C.).

Aging treatment of water-based ink When the above-mentioned surfactant or water-soluble organic solvent is added to the water-based ink of the present invention, it may take time until the respective physical property values after the addition are stabilized. In such a case, the ink may be subjected to an aging process such as heating as necessary.
The heating temperature when such aging treatment is performed is preferably in the range of room temperature (25 ° C.) to 100 ° C., more preferably 40 ° C. to 80 ° C. The time for performing the aging treatment is preferably in the range of about several minutes to several days, and more preferably in the range of several hours to 24 hours. However, since the aging treatment conditions vary depending on the type of pigment or resin used, the aging treatment conditions are not particularly limited as long as necessary effects are obtained.
For example, the physical properties of the ink can be stabilized by performing an aging treatment at a heating temperature of 70 ° C. and a treatment time of about 12 to 24 hours.

Other Preferred Embodiments of the Present Invention The water-based ink of the present invention can be made into various preferred embodiments as described below based on the configuration described in the above-described embodiment (a).

Other preferred embodiments (b)
The water-based ink of the present invention is characterized in that the weight ratio of the pigment and its dispersion polymer is in the range of 10:90 to 90:10. Within this range, the dispersion and water-based ink using the dispersion are excellent in dispersion stability, and when this dispersion is used in water-based inks for water-based inkjet printers, not only plain paper but also glossy media (for example, glossy paper) The printed image on the special paper such as is excellent in fixing property, coloring property and glossiness.

  The weight ratio of the pigment to the dispersion polymer is 40:60 to 90:10 when a black pigment is used as the pigment, 50:50 to 90:10 when a yellow pigment is used, and a red pigment. Is in the range of 50:50 to 90:10, in the case of blue pigments, 30:70 to 70:30. If each pigment is within the above range, the dispersion and aqueous ink using the dispersion are excellent in dispersion stability, and in water-based inkjet recording, color development, fixing property and glossiness are not only on plain paper but also on glossy media. An excellent clear printed image can be obtained. Here, if the amount of the dispersed polymer is small relative to the pigment even within the above range, when this dispersion is used in the water-based ink for water-based inkjet recording, the dispersion in the water-based ink can be added even if a relatively large amount of the dispersion is added. The solid content concentration of the ink can be reduced, so clogging due to drying of the water-based ink at the nozzle tip is less likely to occur, and it is easy to prepare water-based ink with excellent color development on plain paper, but glossiness and fixing on glossy media It may be difficult to obtain the characteristics. On the other hand, if the amount of the dispersed polymer relative to the pigment is large, the solid content concentration in the water-based ink increases when a relatively large amount of the dispersion is added to the water-based ink for the purpose of enhancing the color developability on plain paper. Although clogging due to drying of the water-based ink at the tip tends to occur, glossiness and fixability on glossy media are easily obtained. Therefore, when the balance of both is considered, when using a black pigment as the pigment, 50:50 to 70:30, when using a yellow pigment, 60:40 to 80:20, and when using a red pigment, 60:40. In the case of -90: 10 and a blue pigment, the range of 40: 60-70: 30 is more preferable. As described above, the reason why the range of the weight ratio of the suitable pigment and the dispersed polymer is different depending on each pigment is not clear in detail, but the surface state of the particles of each pigment is different. This is presumed to be due to the influence of the dispersed polymer adsorption state and the surface state of the dispersion. However, this estimation is not limited in the present invention.

Other preferred embodiments (c)
The water-based ink of the present invention is a dispersion in which a colorant is included in a polymer so that it can be dispersed in water, and the amount of the aromatic ring in the polymer is 20% by weight of the polymer (hereinafter, what is simply referred to as% is weight). %) And 70% or less, further comprising addition of polymer fine particles, and the absolute value of the zeta potential in the mixed state of the microcapsules and the polymer fine particles is 30 millivolts or more. .
The absolute value of the zeta potential of the microcapsule and the polymer fine particle is independently 30 millivolts or more, and the difference between the zeta potential value of the microcapsule and the zeta potential value of the polymer fine particle Is preferably ± 10 millivolts or less. By setting the zeta potential within the above range, it is possible to stably exist in the water-based ink. The aforementioned zeta potential difference is preferably ± 5 millivolts or less. Moreover, it is preferable that the polarity of the ion of the polymer fine particle is the same as that of the microcapsule. Furthermore, the pH difference at the isoelectric point is preferably ± 2 or less.

  Further, the zeta potential of the water-based ink in the present invention is 20 ° C. and pH 8 to pH 9 when measured as a diluted solution diluted with ion-exchanged water so that the dispersion concentration is 0.001 to 0.01% by weight. The absolute value of the zeta potential of the dispersion is preferably 40 mV or more. More preferably, it is 45 mV or more, and an even more preferable absolute value of the zeta potential is 50 mV or more. In the case of a dispersion having an absolute value of zeta potential of 20 mV or less, the storage stability of the water-based ink is lowered.

Other preferred embodiments (d)
In the aqueous ink of the present invention, the amount of each ion of Si, Ca, Mg, Fe, Cr, Ni, and Zr contained in the liquid component of the aqueous ink is 50 ppm or less, and the liquid property of the aqueous ink The total amount of polyvalent metal ions contained in the component is 200 ppm or less.
In the present embodiment (c), the “liquid component” of the water-based ink is divided into a solid part such as pigment particles in the water-based ink and a liquid part that disperses and holds the solid part. Means the liquid part. Therefore, the “liquid component” includes impurities mixed in the vehicle (liquid portion of the aqueous ink itself) when preparing the aqueous ink. In addition, for example, the aqueous ink is centrifuged to separate the supernatant component and the precipitation component, and the supernatant component is measured by any known method to obtain Si, Ca contained in the “liquid component”. , Mg, Fe, Cr, Ni, Zr, and other polyvalent metal ions can be measured. A polyvalent metal ion refers to a divalent or higher valent metal ion.

Other preferred embodiments (e)
The water-based ink of the present invention contains a dispersion in which a pigment is included in a polymer so as to be dispersible in water. The amount of polyvalent anions contained in the liquid component of the water-based ink is 1000 ppm or less.

The water-based ink used in the present invention is characterized in that it contains at least the above-mentioned dispersion, and the content thereof is preferably 0.5 to 30% by weight, more preferably 1.0 to 12% by weight as the pigment weight concentration. %, Most preferably 2 to 10% by weight. If the pigment content of the water-based ink is less than 0.5% by weight, the print density may be insufficient. If it exceeds 30% by weight, the amount of the moisturizing component added to the water-based ink may be increased from the viewpoint of the water-based ink viscosity. This may limit the nozzle clogging of the water-based inkjet head, or the viscosity of the water-based ink may increase and stable ejection may not be obtained.
In addition, the water-based ink used in the present invention may be subjected to a purification treatment such as reverse osmosis membrane, ultrafiltration, electrodialysis, and water washing with Nutsche, if necessary, in the water-based ink or dispersion in the production process. Can do. In particular, when a large amount of polyvalent anions are present in the liquid component of the water-based ink, in order to prevent the adverse effects (decrease in storage stability, ejection stability, print quality, etc.) It is preferable to carry out such a purification treatment.

Specific examples of such polyvalent anions include sulfate ions, phosphate ions, and low molecular weight polycarboxylate ions.
The mixing route may be originally included in the raw materials of pigments and dispersed polymers, and in particular, surface-modified pigments (pigments whose surfaces have been modified by oxidation treatment, etc.) are used as pigments used in the production of dispersions. In that case, the surface modifier may remain. Moreover, the case where it mixes from a manufacturing apparatus in water-based ink manufacturing processes, such as a dispersion | distribution process, is considered.
By controlling the amount of polyvalent anions in the liquid component to a certain level or less by the purification treatment as described above, physical property value fluctuations during storage of aqueous ink (decrease in storage stability) are prevented, and from the aqueous inkjet head It is possible to maintain the ejection characteristics and to secure the print density of the printed matter which is much higher than that of the conventional water-based ink. The amount of the polyvalent anion in the aqueous ink liquid component is preferably 1000 ppm or less, more preferably 800 ppm or less, and still more preferably 600 ppm or less.

Recently, the characteristics required for water-based inks for water-based inkjet printers are increasing, and while maintaining high storage stability and ejection stability, there is no need to bleed or bleed the printed matter and the print density must be sufficiently high. It is said that.
Conventionally used dispersion resins with high hydrophilicity have been difficult to ensure storage stability and ejection stability, and have no bleeding or bleeding, so that it is difficult to obtain a high printing density.
In other words, in conventional pigment-based inks using highly hydrophilic dispersion resins, the dispersion resin dissolves in a water-based ink solvent mainly composed of water, which is a factor that impairs storage stability and ejection stability. It was. Further, since the constituent component of the paper as the recording medium is hydrophilic cellulose, the recording paper does not stay on the hydrophilic cellulose surface due to the influence of the dispersion resin adsorbed on the pigment surface or the dissolved resin in the solvent. It was difficult to ensure a high print density because it entered the inside.

The pigment dispersion of the water-based ink of the present invention can be suitably adsorbed to a pigment having a hydrophobic surface when the amount of the aromatic ring in the dispersion polymer is 20% or more of the polymer. It becomes difficult to detach from the pigment inside. Further, the water-based ink of the present invention using such a dispersion as a colorant tends to stay on the surface of the recording paper as compared with a water-based ink using a dispersion resin having high hydrophilicity that has been conventionally used. Has a characteristic of having a very high print density.
The reason why a high print density can be obtained is not clearly understood, but the dispersion of the colorant quickly aggregates on the paper as soon as the water-based ink is ejected from the recording head and landed on the recording medium. It is estimated that it is to remain.
However, even with such excellent water-based inks, if a large amount of ionic substances are present, the physical properties of the water-based ink may change during long-term storage, and if the ink is left unprinted for a long time and then reprinted, ejection failure There has occurred.

In the process of developing the water-based ink according to the present invention, when the amount of polyvalent anions in the liquid component of the water-based ink exceeds a certain amount, the physical property value of the water-based ink varies during storage (storage stability It was confirmed that a decrease in discharge characteristics from the water-based inkjet recording head, a decrease in print density, and the like occurred.
The water-based ink of the present invention has excellent characteristics as described above. However, when a large amount of charged ions such as polyvalent anions are present in the water-based ink, the above-described characteristics are affected. It is thought that this may cause a decrease in.
The present inventors have succeeded in preventing the above-described deterioration in characteristics by determining the upper limit of the amount of polyvalent anions in the water-based ink.
That is, when the amount of the polyvalent anion present in the liquid component of the water-based ink exceeds 1000 ppm, ejection failure or the like is likely to occur. If it is 800 ppm or less, both ejection characteristics and storage stability can be secured, and 600 ppm or less. Then, the present inventors have found that the ejection characteristics and the storage stability are very good, and have reached the present invention.

Other preferred embodiments (f)
The aqueous ink of the present invention is characterized in that the total amount of monovalent cations contained in the liquid component of the aqueous ink is 5000 ppm or less.
That is, when such a monovalent cation present in the liquid component of the water-based ink exceeds 5000 ppm, ejection failure or the like is likely to occur.
The reason why the properties of the water-based ink are deteriorated by such a monovalent cation is not clearly understood, but it is considered that it reacts with the dispersion resin covering the pigment surface to cause aggregation or the like.

However, since sodium hydroxide or ammonia is used to neutralize the hydrophilic functional group of the dispersion resin, a certain amount of such a monovalent cation is inevitably contained in the water-based ink (several ppm to several tens of ppm). ) Will exist. Purification by reverse osmosis membrane, ultrafiltration, electrodialysis, etc. is effective for reducing monovalent cations, but according to our evaluation, the amount of monovalent cations present in the liquid component of aqueous ink Is not particularly problematic as long as it is 2500 ppm or less.
Further, in the evaluation by the present inventors, when an alkali metal hydroxide is used for neutralizing the hydrophilic functional group of the dispersion resin, the printing density on the plain paper in the printing evaluation tends to be improved. Therefore, it is more preferable that a slight amount of such alkali metal ions is present in the liquid component of the water-based ink from the viewpoint of securing the print density.

The monovalent cation is an alkali metal ion, and the alkali metal ion is any one of a sodium ion, a lithium ion, and a potassium ion.
Furthermore, the monovalent cation is an ammonium ion.
In the present specification, the “liquid component” of the water-based ink refers to a liquid portion when divided into a solid portion such as a dispersion in the water-based ink and a liquid portion that disperses and holds the solid portion. Means. Accordingly, the “liquid component” includes impurities mixed into the vehicle (liquid portion of the aqueous ink itself) when preparing the pigment dispersion or the aqueous ink. In addition, for example, the alkali metal ion contained in the “liquid component” is obtained by centrifuging the aqueous ink to separate the supernatant component and the precipitation component, and measuring the supernatant component by any known method. Monovalent cations such as can be measured. The cation refers to a positively charged ion (cation).
Specifically, the monovalent cation refers to lithium ions (Li ⁺ ), sodium ions (Na ⁺ ), potassium ions (K ⁺ ), ammonium ions (NH ₄ ⁺ ), and the like, which are alkali metal ions.

Other preferred embodiments (g)
The aqueous ink of the present invention is characterized in that the total amount of monovalent anions contained in the liquid component of the aqueous ink is 3000 ppm or less.
That is, if such monovalent anion present in the liquid component of the water-based ink exceeds 3000 ppm, ejection failure or the like tends to occur. If it is 1500 ppm or less, both ejection characteristics and storage stability are improved.
Examples of such monovalent anions present in water-based inks include halogen ions, nitrate ions, and low molecular carboxylate ions. Such monovalent anions are considered to be mixed in water-based inks as carbon black containing salts, organic pigments having halogen groups as auxiliary color groups, decomposition by-products when synthesizing dispersion resins, and the like. Purification by reverse osmosis membrane, ultrafiltration, electrodialysis and the like is effective for reducing such monovalent anions.
The monovalent anion is a halogen ion, and the halogen ion is any one of a chlorine ion (Cl ⁻ ), a bromine ion (Br ⁻ ), and an iodine ion (I ⁻ ). And

In the present specification, the “liquid component” of the water-based ink refers to a liquid portion when divided into a solid portion such as a dispersion in the water-based ink and a liquid portion that disperses and holds the solid portion. Means. Accordingly, the “liquid component” includes impurities mixed into the vehicle (liquid portion of the aqueous ink itself) when preparing the pigment dispersion or the aqueous ink. Further, for example, the aqueous ink is centrifuged to separate into a supernatant component and a precipitation component, and the supernatant component is measured by any known method to determine halogen ions contained in the “liquid component”. The monovalent anion can be measured. An anion refers to an ion having a negative charge.

Other preferred embodiments (h)
The water-based ink of the present invention contains a dispersion in which a pigment is included in a polymer so as to be dispersible in water, and the amount of the aromatic ring in the polymer is 20% by weight (hereinafter simply referred to as%). The amount of free polymer contained in the liquid component of the water-based ink is 3% or less.
In a preferred embodiment of the present invention, the amount of free polymer contained in the liquid component of the water-based ink is 2% or less.
In the present specification, the “liquid component” of the water-based ink refers to a liquid portion when divided into a solid portion such as a dispersion in the water-based ink and a liquid portion that disperses and holds the solid portion. Means. Accordingly, the “liquid component” includes impurities mixed into the vehicle (liquid portion of the aqueous ink itself) when preparing the pigment dispersion or the aqueous ink.

In the present specification, the “free polymer” in the water-based ink means a polymer that does not include the pigment surface in the water-based ink (not adsorbed on the pigment surface). Therefore, for example, the aqueous ink is centrifuged to separate the supernatant component and the precipitation component, and the supernatant component is TOC (total organic carbon meter) or gravimetric method (method of evaporating and drying and measuring the amount of polymer) The structure of the “free polymer” and the amount thereof can be measured by measuring by any known method.
As estimated by the inventors, when a polymer component that is incompletely polymerized is mixed as an impurity in the production process of the dispersion polymer of the water-based ink, such an incomplete polymer component has a weak adsorption power to the pigment surface. Therefore, it is presumed that it is dissolved as a free polymer in the liquid component of the aqueous ink due to the influence of a surfactant or a hydrophilic organic solvent added as a penetrating agent in the aqueous ink. As a result, it is considered that the above-described deterioration in water-based ink characteristics has occurred.

  In the production of the dispersed polymer, the inventors have optimized the production process and previously performed washing such as ultrafiltration to reduce the amount of these free polymers in the liquid component of the aqueous ink to a certain amount or less. The present invention succeeded in solving the problems such as fluctuations in physical property values (decrease in storage stability), deterioration in ejection characteristics from the aqueous inkjet head, and decrease in print density of printed matter as described above. The water-based ink of the present invention is a result obtained from the above findings.

Other preferred embodiments (i)
The water-based ink set of the present invention includes a dispersion, a humectant, which includes a pigment in a dispersion polymer so that the pigment can be dispersed in water, and the amount of aromatic rings in the dispersion polymer is 20% or more and 70% or less of the dispersion polymer. The aqueous ink comprising at least a penetrant and water is characterized by comprising at least a black aqueous ink, a yellow aqueous ink, a magenta aqueous ink, and a cyan aqueous ink.

According to a preferred aspect of the aqueous ink set of the present invention, the black aqueous ink is C.I. I. Pigment black 1, C.I. I. At least one selected from CI Pigment Black 7, wherein the yellow aqueous ink is C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 128, C.I. I. Pigment Yellow 180, and the magenta water-based ink comprises C.I. I. Pigment red 122, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. Pigment Violet 19 and at least one selected from the group consisting of C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. It includes at least one selected from CI Pigment Blue 16.

According to a preferred aspect of the aqueous ink set of the present invention, the aqueous ink set further comprises a red aqueous ink and / or a blue aqueous ink and / or a green aqueous ink.
According to a preferred aspect of the aqueous ink set of the present invention, the red aqueous ink is C.I. I. Pigment red 178, C.I. I. It comprises at least one selected from CI Pigment Red 190.
According to a preferred aspect of the aqueous ink set of the present invention, the blue aqueous ink is C.I. I. Pigment Violet 23 is included.
According to a preferred aspect of the aqueous ink set of the present invention, the green aqueous ink is C.I. I. Pigment green 7, C.I. I. It comprises at least one selected from Pigment Green 36.

  The aqueous ink set of the present invention comprises at least one selected from the above-mentioned pigments, and includes a black aqueous ink, a yellow aqueous ink, a magenta aqueous ink, and a cyan aqueous ink containing at least a penetrant, a humectant, and water, which will be described later. By forming an image in combination, it is possible to obtain a print image with less blur and good fixability and color reproducibility regardless of the type of print medium. Especially in the secondary colors (red, blue, green), in order to obtain a printed image having no blur and excellent color reproducibility, the aqueous ink set is further combined with red aqueous ink, blue aqueous ink, and green aqueous ink as appropriate. An image can also be formed. Specific examples of pigments suitable for red aqueous ink, blue aqueous ink, and green aqueous ink include C.I. I. CI Pigment Red 178 and 190 are C.I. I. Pigment Violet 23 may be C.I. I. Pigment Green 7, 36.

The amount of the pigment described above is preferably in the range of 0.5 to 30%, more preferably 1.0 to 12% with respect to the total amount of the aqueous ink. If the added amount is less than 0.5%, the printing density cannot be secured, and if the added amount is more than 30%, the viscosity of the water-based ink is increased and the viscosity characteristics are structurally stable. It tends to be worse.
The pigment particle size is preferably 5 μm or less from the viewpoint of dispersion stability, more preferably 0.3 μm or less, and still more preferably in the range of 0.01 to 0.15 μm.

Other preferred embodiments (j)
The aqueous ink set of the present invention includes a dispersion in which a pigment is included in a dispersion polymer so that the pigment can be dispersed in water, and the amount of aromatic rings in the dispersion polymer is in the range of 20% to 70% by weight of the dispersion polymer; A water-based ink set comprising a water-based ink comprising at least a humectant, a penetrant, and water, wherein the water-based ink set is a combination of a dark water ink and a light water ink, and the dark water ink is at least a dark black aqueous solution. Ink, dark yellow water-based ink, dark magenta water-based ink, and dark cyan water-based ink, wherein the light water-based ink is at least a light magenta water-based ink and a light cyan water-based ink.
The aqueous ink set of the present invention is characterized in that the aqueous ink set further comprises a light black aqueous ink as the light aqueous ink.
The water-based ink set of the present invention is characterized in that the water-based ink set further includes a light yellow water-based ink as a light water-based ink.

  In the aqueous ink set of the present invention, the dark black aqueous ink and the light black aqueous ink are C.I. I. Pigment black 1, C.I. I. The dark yellow aqueous ink and the light yellow aqueous ink comprise at least one pigment selected from CI Pigment Black 7. I. Pigment yellow 74, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 128, C.I. I. The dark magenta water-based ink and the light magenta water-based ink include at least one pigment selected from CI Pigment Yellow 180; I. Pigment red 122, C.I. I. Pigment red 202, C.I. I. Pigment red 209, C.I. I. Pigment Violet 19 at least one pigment selected from the above, and the deep cyan aqueous ink and the light cyan aqueous ink are C.I. I. Pigment blue 15, C.I. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 2, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. It comprises at least one pigment selected from CI Pigment Blue 16.

Furthermore, in the aqueous ink set of the present invention, the penetrant is selected from acetylene glycol surfactants, acetylene alcohol surfactants, silicon surfactants, alkylene glycol monoalkyl ethers, and 1,2-alkylene glycols. It is characterized by more than seeds.
The water-based ink set of the present invention includes at least one selected from the above-mentioned pigments, and a dark black water-based ink, a dark yellow water-based ink, a dark magenta water-based ink, a light magenta ink containing at least a penetrant, a humectant, and water described later. By combining magenta water-based ink, dark cyan water-based ink, light cyan water-based ink, and if necessary, light black water-based ink and light yellow water-based ink to form an image, plain paper and paper for water-based inkjet printers (especially glossy ink) Regardless of the type of printing medium such as (media), it is possible to obtain a printed image with little blurring and excellent fixability, color reproducibility, and graininess.

The amount of the pigment described above is preferably in the range of 0.5 to 30% by weight with respect to the total amount of water-based ink. More preferably, it is in the range of 0.5 to 5% by weight for light aqueous ink and 1 to 12% by weight for concentrated aqueous ink. The pigment concentration ratio between the dark water ink and the light water ink of the same color is preferably in the range of dark water ink: light water ink = 10: 1 to 4: 1 by weight ratio from the viewpoint of graininess. When the pigment concentration is less than 0.5% by weight, the printing density is too low to achieve the desired purpose with respect to color reproducibility and graininess. Structural viscosity occurs in the characteristics, and the discharge stability of the water-based ink from the water-based inkjet head tends to deteriorate.
The pigment particle size is preferably 5 μm or less from the viewpoint of dispersion stability, more preferably 0.3 μm or less (300 nm or less), and still more preferably 0.01 to 0.15 μm (10 to 150 nm).

Other preferred embodiments (k)
The method for producing a pigment dispersion contained in the aqueous ink of the present invention includes a production process of a dispersion in which a colorant is included in a polymer so that the dispersion can be dispersed in water, and a dispersion process in which the dispersion is dispersed in an aqueous medium. The method for producing a dispersion comprising the two steps described above is characterized in that the amount of the aromatic ring in the polymer is 20% by weight or more and 70% by weight or less of the polymer.
The dispersion step is a step of performing a dispersion treatment in a mixed liquid state of at least the dispersion, water, and a dispersion accelerator.

The pigment-encapsulating resin dispersion according to the present invention can use a dispersion accelerator in its production process, and the dispersion efficiency can be improved by adding it in the dispersion process of the dispersion in an aqueous medium.
Since the dispersion used in the pigment dispersion of the present invention is a microcapsule that includes a pigment in a polymer and is dispersible in water, the dispersion composed of the microcapsule is converted into an aqueous medium (ion-exchanged water or It is not dispersed in distilled water, etc., but when added during dispersion, it has the effect of making the dispersion easy to adjust to the dispersion medium (easy to wet), and increases the contact resistance between the dispersed particles in the dispersion medium. This has the effect of increasing the dispersion efficiency. As a result, the shear conditions of the apparatus in the dispersion treatment process can be relaxed (the shear force applied to the dispersion liquid by the apparatus can be reduced), the time required for the dispersion treatment can be shortened, and polyvalent metal ions in the dispersion liquid can be reduced. Contaminant components can be reduced.

What can be used as a dispersion accelerator can be used without particular limitation as long as it has an effect of increasing the dispersion efficiency, and particularly preferred are acetylene glycols, acetylene alcohols, glycols. Examples thereof include ethers and alkylene glycols. In addition, lower alcohols and nonionic surfactants can be used, and other alcohols, water-soluble organic solvents, anionic, cationic and amphoteric surfactants, saccharides, etc. can be used. The same ones as listed as the water-soluble organic solvents such as the penetrant and the moisturizing agent already described in the embodiment (a) can be used.
The addition amount of the dispersion accelerator may be appropriately determined in consideration of the liquidity of the water-based ink that is the final product. An example is described below.

The amount of acetylene glycols and acetylene alcohols added in the dispersion step is preferably in the range of 1/50 to 2 times the weight of the pigment. In particular, if the addition amount is less than 1/50, a sufficient dispersion effect cannot be obtained, and if it is added in a large amount (for example, several times or more of the pigment), the surface tension is lowered, so that the aqueous ink wets and spreads in the vicinity of the aqueous inkjet head. It becomes difficult to ensure the discharge characteristics.
When it is desired to minimize the amount of the dispersion accelerator mixed in the water-based ink or to suppress the permeability of the water-based ink, it is preferable to use acetylene alcohols having a small molecular weight as the dispersion accelerator. For example, when the above-mentioned Surfynol 61 is used as a dispersion accelerator, it can be volatilized by heating the dispersion after the dispersion step to minimize the remaining amount.

Further, the amount of the dispersion accelerator added is not particularly limited as long as at least the effect of improving the dispersion efficiency can be obtained by addition, and the dispersion state of the dispersion and the actual use of the dispersion are not adversely affected. A preferable addition amount is 0.05 wt% to 50 wt% with respect to the pigment dispersion in the dispersion step, and a more preferable addition amount is 0.1 to 30 wt%. When the addition amount is less than 0.05% by weight, the effect as a wetting agent may not be sufficiently obtained, and when it exceeds 50% by weight, dispersion of pigment particles may become unstable.
These dispersion accelerators are used when a dispersion in which the above pigment is coated and coated with a polymer is dispersed in an aqueous medium. The pigment-encapsulating resin dispersion obtained in the dispersion production process, or a slurry thereof, Add a wet cake, etc. to a water-based medium (especially ion-exchanged water or distilled water) so as to have a concentration of about 5 to 40% by weight together with a dispersion accelerator, neutralizer, etc. A dispersion can be obtained by applying an appropriate shearing force using an apparatus and dispersing the dispersion in an aqueous medium.

These “dispersion production process” and “dispersion process” can also be carried out continuously. In particular, when producing a dispersion in which a pigment is coated and coated with a resin in an aqueous medium, the dispersion is produced. Since the dispersion medium of the process and the dispersion process can be made the same aqueous system, it is easy to assemble continuous processes. However, the removal of residual unreacted products, reaction by-products and the like in the production process is easier to obtain a pigment dispersion that is finally more excellent in dispersion stability if carried out before the dispersion process.
On the other hand, if the solvent in the dispersion production process is a non-aqueous solvent, residual unreacted materials and the like may be easily separated and removed from the target dispersion.
The zeta potential of the pigment dispersion in the present invention is 20 ° C. and pH 8 to 8 when measured as a diluted solution obtained by diluting the pigment dispersion with ion-exchanged water so that the pigment concentration is 0.001 to 0.01% by weight. The absolute value of the zeta potential of the pigment particles at pH 9 is preferably 40 mV or more. More preferably, it is 45 mV or more, and an even more preferable absolute value of the zeta potential is 50 mV or more. In the case of a pigment dispersion in which the absolute value of the zeta potential of the pigment particles is 20 mV or less, the storage stability of the pigment dispersion decreases as in the case where the amount of the dispersibility-imparting group introduced is insufficient.

  Next, the dispersion liquid in the invention and the water-based ink containing it will be described. The water-based ink of the present invention is characterized in that it contains at least a pigment dispersion produced by the pigment production method of the present invention, and the content thereof is preferably 0.5 to 30% by weight as a pigment concentration. Preferably it is 1.0-12 weight%, Most preferably, it is 2-10 weight%. If the pigment content of the water-based ink is less than 0.5% by weight, the print density may be insufficient. If it exceeds 30% by weight, the amount of the moisturizing component added to the water-based ink may be increased from the viewpoint of the water-based ink viscosity. This may limit the nozzle clogging of the water-based inkjet head, or the viscosity of the water-based ink may increase and stable ejection may not be obtained.

  When a dispersion accelerator such as the above-mentioned surfactant or water-soluble organic solvent is added to the pigment dispersion contained in the water-based ink of the present invention, it may take time until each physical property value after stabilization is stabilized. In such a case, the pigment dispersion may be subjected to an aging treatment such as heating as necessary.

The heating temperature when such aging treatment is performed is preferably in the range of room temperature (25 ° C.) to 100 ° C., more preferably 40 ° C. to 80 ° C. The time for performing the aging treatment is preferably in the range of about several minutes to several days, and more preferably in the range of several hours to 24 hours. However, since the aging treatment conditions vary depending on the type of pigment or resin used, the aging treatment conditions are not particularly limited as long as necessary effects are obtained.
For example, the physical properties of the pigment dispersion can be stabilized by performing an aging treatment at a heating temperature of 70 ° C. and a treatment time of about 12 to 24 hours.

  Further, after preparing a water-based ink using the pigment dispersion subjected to the aging treatment, the ink can be aged by the same method as the aging treatment of the water-based ink described above.

In the course of developing the pigment dispersion according to the present invention, the present inventors have obtained the following knowledge. However, the present invention is not limited by the following reasoning.
As described above, it has recently become difficult to ensure stable ejection characteristics particularly in pigmented water-based inks due to higher image quality and higher speed of water-based inkjet printers.
In addition to these days, for printing on water-based inkjet printers with a small nozzle diameter and high head drive frequency for higher image quality and higher speed, flying deflection of water-based ink dots occurs, and printing is not performed for a long time. When printing was attempted again after being left, the nozzles were clogged due to pigment aggregation and the like, resulting in ejection failure. In the process of developing a pigment-encapsulating resin dispersion, the present inventors suppress the above-described ejection failure, pigment aggregation, etc. by suppressing the content of polyvalent metal ions in the dispersion and aqueous ink to a certain amount or less. Successfully solved the problem.

Although there is no clear cause for the discharge failure, especially storage stability, due to contamination such as polyvalent metal ions mixed in the water-based ink, the presence of such polyvalent metal ions in the water-based ink This is thought to be due to the occurrence of agglomeration and the like by reacting with the resin covering the surface. Such aggregation is likely to occur when divalent or higher metal ions are present, and in our experiments, monovalent alkali metal ions such as Na, K, and Li are present in water-based ink to some extent. Even so (several tens to several hundred ppm), the stability and ejection stability of the water-based ink were not greatly impaired.
Further, the addition of a chelating agent such as EDTA (ethylenediaminetetraacetic acid) to the water-based ink can slightly reduce the influence of the above polyvalent metal ions, but it has not led to a fundamental solution.

For example, if the polyvalent metal ions are mixed into the pigment dispersion and aqueous ink as described above, the pigment inside the dispersion may be mixed from the reaction tank during the synthesis of pigment molecules, or a specific synthesis. It is conceivable that the pigment is incorporated into the pigment by the reaction (for example, Mg in the Grignard reaction), and these are mixed in the aqueous ink solvent component at the time of dispersion. In particular, Mg or the like mixed into the dispersion liquid and aqueous ink from the inside of such pigment particles is difficult to prevent even if the dispersion medium and the dispersion tank are devised at the time of dispersion, and as a result, water-based ink discharge and This will adversely affect the long-term storage stability of the water-based ink.
Moreover, Si by glass beads, Zr by zirconia beads, Fe, Ni, Cr, etc. by the inner wall of a stainless steel dispersion tank are mixed in the aqueous ink solvent component by dispersion media used at the time of dispersion. Furthermore, in the case of an apparatus that has been used for a long period of time, residues from previous use may be mixed as contamination.

  The present inventors succeeded in significantly shortening the dispersion processing time (about 1/10) by adding an appropriate wetting agent at the time of pigment dispersion, and the polyvalent metal ions are aqueous during dispersion as described above. Succeeded in preventing ink contamination. As a result, in order to achieve higher image quality and higher speed, both stable printing characteristics and storage stability without changes in physical properties are ensured in water-based inkjet printers that have a nozzle diameter and a head driven at a high frequency. The pigment aqueous ink for water-based inkjet printers was successfully manufactured.

Other preferred embodiments (l)
The water-based ink of the present invention is a water-based ink containing a dispersion in which a pigment is included in a polymer so as to be dispersible in water, and the amount of aromatic rings in the polymer is 20% by weight (hereinafter simply referred to as%). Is 70% or less), and the amount of polyvalent cation contained in the dispersion is 1000 ppm or less.
In the process of preparing the water-based ink according to the present invention, by changing the amount of polyvalent cation contained in the dispersion to the above range, the property value fluctuation (reduction in storage stability) during water-based ink storage and the water-based inkjet head It is possible to prevent the occurrence of problems such as the deterioration of the discharge characteristics.
That is, when such polyvalent cations present in the aqueous ink dispersion exceed 1000 ppm, ejection failure or the like tends to occur. When the concentration is 800 ppm or less, both ejection characteristics and storage stability are improved.

Other preferred embodiments (m)
The water-based ink of the present invention is a water-based ink containing a dispersion in which a pigment is included in a polymer so as to be dispersible in water, and the amount of aromatic rings in the polymer is 20% by weight (hereinafter simply referred to as%). Is 70% or less), and the amount of polyvalent anions contained in the dispersion is 800 ppm or less.
In the process of preparing the water-based ink according to the present invention, by changing the amount of polyvalent anions contained in the dispersion within the above range, the property value fluctuation (storage stability decrease) during water-based ink storage and the water-based inkjet head It is possible to prevent the occurrence of problems such as the deterioration of the discharge characteristics.
That is, when the amount of such a polyvalent anion present in the aqueous ink dispersion exceeds 800 ppm, discharge failure or the like is likely to occur. If it is 600 ppm or less, both discharge characteristics and storage stability can be secured. If it is 400 ppm or less, both ejection characteristics and storage stability are improved.

Other preferred embodiments (n)
The water-based ink of the present invention is a water-based ink containing a dispersion in which a pigment is included in a polymer so that it can be dispersed in water, and the amount of aromatic rings in the polymer is 20% by weight (hereinafter simply referred to as%). Is 70% or less), and the amount of monovalent cation contained in the dispersion is 3500 ppm or less.
In the process of preparing the water-based ink according to the present invention, by changing the amount of monovalent cation contained in the dispersion to the above range, the property value fluctuation (reduction in storage stability) during water-based ink storage and the water-based inkjet head It is possible to prevent the occurrence of problems such as deterioration of the discharge characteristics from
That is, it has been found that such monovalent cations present in the dispersion of the water-based ink are liable to cause ejection failure when it exceeds 3500 ppm, and if it is 2500 ppm or less, both ejection characteristics and storage stability are improved. . The present invention is based on such findings.

Other preferred embodiments (p)
The water-based ink of the present invention is a water-based ink containing a dispersion in which a pigment is included in a polymer so as to be dispersible in water, and the amount of aromatic rings in the polymer is 20% by weight (hereinafter simply referred to as%). Is 70% or less), and the amount of monovalent anions contained in the dispersion is 5000 ppm or less.
In the process of preparing the water-based ink according to the present invention, by changing the amount of monovalent anions contained in the dispersion in the above range, the property value fluctuation (storage stability decrease) during water-based ink storage and the water-based inkjet head It is possible to prevent the occurrence of problems such as the deterioration of the discharge characteristics.
That is, when such monovalent anions present in the aqueous ink dispersion exceeds 5000 ppm, ejection failure and the like are likely to occur, and when it is 3500 ppm or less, it has been found that both ejection characteristics and storage stability are improved. . The present invention is based on such findings.

  In addition, from the other preferable embodiment (l) to the other preferable embodiment (p) described above, the pigment dispersion in the method for producing the dispersion of the aqueous ink of the present invention and the pigment dispersion included in the aqueous ink of the present invention. It is description about the dispersion | distribution which contains.

Next, the present invention will be described in detail with specific examples, but the present invention is not limited to such specific examples.
The following Example A corresponds to the above-described preferred embodiment (a), and Example B corresponds to the preferred embodiment (b).

[Example A]
Next, a specific embodiment (a) in the present invention will be described.
The case where an organic or inorganic pigment is used as an example of the colorant shown in the present invention will be described. In Examples and Comparative Examples, the pigment A1 was a carbon black pigment, the pigment A2 was a phthalocyanine pigment, the pigment A3 was a dimethylquinacridone pigment, and the pigment A4 was a diketopyrrolopyrrole pigment. However, it is not limited to these, and many organic and inorganic pigments can be used. Each average particle diameter is shown in <> in nm (nanometer) units.
In the present invention, the pigment can also be obtained by dispersing the pigment with a reactive dispersant and then performing emulsion polymerization in water in the presence of a catalyst.

(Production of dispersions A1 to A4)
First, as the dispersion A1, Raven C (produced by Columbian Carbon Co., Ltd.), which is carbon black that is an inorganic pigment, was used. 25 parts of Raven C (manufactured by Columbian Carbon Co., Ltd.) in a reaction vessel equipped with an ultrasonic generator, a stirrer, a dripping device, a water-cooled reflux condenser, and a temperature controller Then, 5 parts of Adeka Soap SE-10N manufactured by Asahi Denka Co., Ltd., which is a polymerizable surfactant, was added to 180 parts of ion-exchanged water, and ultrasonic treatment was performed for 4 hours.
Next, a methyl ethyl ketone solution of 5 parts of styrene, 1.6 parts of α-methylstyrene and 0.5 part of azobisisobutyronitrile is further added, and a polymerization reaction is carried out at 60 ° C. for 8 hours. The resulting solution was subjected to centrifugal filtration to take out the pigment contained in the polymer, and further filtered through a 0.4 μm membrane filter to remove coarse particles. The pigment solution included with the polymer was re-dispersed by loosening with a homogenizer.

Then, a methyl ethyl ketone solution of the aforementioned pigment is added to the reaction vessel, and further 27 parts of ion exchange water and 0.05 part of sodium lauryl sulfate are added, and 100 parts of ion exchange water and 0.5 part of potassium persulfate as a polymerization initiator are added. The nitrogen atmosphere was maintained at 70 ° C. Next, a mixed solution containing 25 parts of styrene, 1 part of tetrahydrofurfuryl methacrylate, 15 parts of butyl methacrylate, 5 parts of triethylene glycol methacrylate and 0.02 part of t-dodecyl mercaptan was dropped and reacted, and then a rotary evaporator was used. Methyl ethyl ketone and a part of water were distilled off, neutralized with sodium hydroxide and adjusted to pH 8.5, and then filtered through a 0.3 μm filter to obtain dispersion A1.
A part of this dispersion was taken out, acidified by adding 0.1 mol / l HCl, and only the dispersion polymer was taken out by Soxhlet extraction using acetone, and C ¹³ -NMR and DMSO-DM ₆ were used. The amount of the aromatic ring based on the total weight of the dispersed polymer as measured by H ¹ -NMR (AMX400 manufactured by Bruker (Germany)) was 40%.

  Dispersions A2 to A4 were obtained in the same manner as above. As the dispersion A2, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant), which is an organic pigment, was used. As the dispersion A3, Pigment Red 122 (dimethylquinacridone pigment: Clariant), which is an organic pigment, was used. As the dispersion A4, Pigment Yellow 180 (diketopyrrolopyrrole: manufactured by Clariant), which is an organic pigment, was used.

(Production of dispersions A5 to A8)
First, Monarch 880 (manufactured by Cabot), which is carbon black, was used as dispersion A5. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 20 parts of styrene, 5 parts of α-methylstyrene, 15 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t-dodecyl Add 0.3 part of mercaptan and heat to 70 ° C., separately prepared 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile. Was placed in a dropping funnel and the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.

40 parts of the above dispersion polymer solution, 30 parts of Monarch 880 (manufactured by Cabot), carbon black, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed and stirred with a homogenizer for 30 minutes. Thereafter, 300 parts of ion-exchanged water was added and further stirred for 1 hour. Then, the whole amount of methyl ethyl ketone and a part of water were distilled off using a rotary evaporator, neutralized with 0.1 mol / L sodium hydroxide, adjusted to pH 9, and filtered through a 0.3 μm membrane filter. Thus, a dispersion A5 having a solid content (dispersion polymer and carbon black) of 20% was obtained.
A part of this dispersion was taken out, acidified by adding 0.1 mol / l HCl, and only the dispersion polymer was taken out by Soxhlet extraction using acetone, and C ¹³ -NMR and DM13 using DMSO-d ₆ The amount of the aromatic ring based on the total weight of the dispersed polymer as measured by H ¹ -NMR (AMX400 manufactured by Bruker (Germany)) was 36%.

  Dispersions A6 to A8 were obtained in the same manner as above. As the dispersion A6, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used. As the dispersion A7, Pigment Red 122 (dimethylquinacridone pigment: manufactured by Clariant) was used. As the dispersion A8, Pigment Yellow 180 (diketopyrrolopyrrole: manufactured by Clariant) was used.

(Preparation example of water-based ink)
Specific examples of the composition of the water-based ink suitable for the water-based ink for water-based inkjet recording according to the present invention are shown below. The added amount of the dispersion is shown as the amount (solid content concentration: the total amount of the pigment and the dispersed polymer surrounding it) converted by weight. <> Indicates the particle size of the pigment in nm units. The remaining amount of water in this example is 0.05% for Proxel XL-2 to prevent corrosion of the aqueous ink, and 0.02% for benzotriazole to prevent corrosion of the aqueous inkjet head member. In order to reduce the influence of metal ions in the water-based ink system, 0.04% of EDTA · 2Na salt was added to ion-exchanged water.

Example A-1 Addition amount (%)
Dispersion A1 <105> 9.5
TEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Olfine E1010 ... 1.0
Glycerin ... 9.0
1,5-pentanediol ... 5.0
Triethanolamine ... 0.8
Water ........................ Remaining amount

TEGmBE: Triethylene glycol monobutyl ether orphine E1010 (acetylene glycol surfactant: manufactured by Nissin Chemical Industry Co., Ltd.)

Example A-2 Addition amount (%)
Dispersion A2 <85> ... 4.5
DEGmBE ... 10.0
Dipropylene glycol ... 5.0
Surfinol 465 ... 1.2
Triethanolamine ... 0.9
Water ........................ Remaining amount

DEGmBE: Diethylene glycol monobutyl ether surfinol 465 (acetylene glycol surfactant: manufactured by Air Products (USA))

Example A-3 Addition amount (%)
Dispersion A3 <90> ... 8.5
1.2-Hexaneyl ... 4.0
Olphine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
Diethylene glycol 7.0
Thiodiglycol ... 1.5
1,6-hexanediol ... 5.0
Triethanolamine 1.0
Potassium hydroxide ... 0.1
Water ........................ Remaining amount

Olphine STG (acetylene glycol surfactant: manufactured by Nissin Chemical Industry Co., Ltd.)

Example A-4 Amount added (%)
Dispersion A4 <80> ... 10.0
TEGmBE ... 3.0
1,2-pentanediol ... 5.0
Surfinol 61 ... 0.5
Tetraethylene glycol ... 9.0
1,5-pentanediol ... 2.0
Dimethyl-2-imidazolidinone ... 2.0
Sodium benzoate 0.1
Triethanolamine 0.7
Water ........................ Remaining amount

Surfynol 61 (acetylene alcohol-based surfactant: manufactured by Air Products (USA))

Example A-5 Addition (%)
Dispersion A5 ... 8.0
DPGmBE ... 2.0
DEGmBE ... 7.0
Glycerin ... 14.0
Triethanolamine ... 0.9
Water ........................ Remaining amount

DPGmBE: Dipropylene glycol monobutyl ether

Example A-6 Addition amount (%)
Agent Dispersion A6 ... 10.0
Olfine E1010 ... 1.0
TEGmBE ... 6.0
Glycerin ... 15.0
Thiodiglycol ... 2.0
1,5-pentanediol ... 1.0
Triethanolamine ... 0.9
Water ........................ Remaining amount

Example A-7 Addition amount (%)
Dispersion A7 ... 12.0
Surfinol 61 ... 0.5
DEGmBE ... 8.0
Glycerin ... 15.0
Trimethylolpropane ... 1.0
Trimethylolethane ... 1.0
Surfinol 465 ... 1.0
Triethanolamine ... 0.5
KOH ......... 0.05
Water ........................ Remaining amount

Example A-8 Addition amount (%)
Dispersion A8 ... 10.5
Olphine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.0
PGmBE ... 2.0
DEGmBE ... 10.0
Glycerin 7.0
Diethylene glycol ... 5.0
Tetrapropylene glycol ... 5.0
Triethanolamine ... 0.9
KOH ... 0.1
Water ........................ Remaining amount

PGmBE: Propylene glycol monobutyl ether

  The composition of the water-based ink used in the comparative example is shown below.

Comparative Example A-1 Addition amount (%)
Pigment A1 <105> ... 7.0
Glycerin ... 10.0
Dispersant ... 3.0
Nonionic surfactant ... 1.0
Ion exchange water

Nonionic surfactant: Neugen EA160 (Daiichi Kogyo Seiyaku Co., Ltd.)
The dispersant was prepared by performing dispersion treatment for 2 hours with a bead mill mini-zeta (manufactured by Ajisawa Co., Ltd.) using Solsperse 27000 (manufactured by Avisia).

Comparative Example A-2 Addition amount (%)
Acid Blue 9 ... 6.5
DEGmME ... 7.0
Diethylene glycol ... 10.0
2-pyrrolidone ... 5.0
Ion exchange water

DEGmME: Diethylene glycol monomethyl ether

Comparative Example A-3 Addition amount (%)
Direct black 154 ... 2.5
Diethylene glycol ... 10.0
Nonionic surfactant ... 1.0
Ion exchange water

Nonionic surfactant: Epan 450 (Daiichi Kogyo Seiyaku Co., Ltd.)

  Table 1 shows an evaluation result of bleeding when characters are printed as an evaluation result of printing. In Table 1, A is very good, B is good, C is bad, and D is very bad.

As is clear from the results in Table 1, it can be seen that the aqueous ink used in the comparative example has poor print quality, and that the print quality is good when the aqueous ink used in the present invention is used.
In addition, these printing evaluation was performed by using the water-based inkjet printer PM-900C by Seiko Epson Corporation. The papers used for these evaluations are ordinary papers commercially available in Europe, America and Japan, such as Conqueror paper, Favorit paper, Modo Copy paper, Rapid Copy paper, EPSON EPP paper, Xerox 4024 paper, Xerox 10 paper, Neenha. Bond paper, Rcopyy 6200 paper, Yamayuri paper, Xerox R paper.
As described above, in the present invention, it is possible to provide a high-quality and practical water-based ink suitable for water-based inkjet recording in which bleeding of a printed image on a recording medium such as paper is reduced.

In addition, the water-based inks of Examples A-1 to 8 were put in glass sample bottles and sealed, and then left at 60 ° C./week for 1 week, respectively. ) Was investigated.
As a result, none of the water-based inks produced foreign matter and hardly changed the physical property values, and had good storage stability.
On the other hand, when the experiment was conducted in the same manner by changing the dispersion to the pigment of Comparative Example A-1 with the composition of Example A-1, there was little change in the surface tension, but foreign matter was generated and the filterability was reduced. A thickening phenomenon occurred and ejection stability could not be obtained.

Further, in the composition of Example A-1, other additives (acetylene glycol surfactants, acetylene alcohol surfactants, silicon surfactants, di (triethylene glycol) surfactants) that may be used in the present invention instead of DEGmBE and E1010. This is a water-based ink prepared by using a) a water-based ink prepared by using (a) a substance composed of one or more selected from ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether, and 1,2-alkylene glycol). Additives that may be used in the invention (acetylene glycol surfactants, acetylene alcohol surfactants, silicon surfactants, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene Is it at least one selected from glycols? (Examples A-9 to 18 in Table 2) were similarly left at 60 ° C./1 week, and the generated foreign matter, physical properties (viscosity, surface tension) of the aqueous ink after being left Table 2 shows the results of examining the discharge stability. Foreign matter generation amount is 60
The amount of foreign matter after standing at 0 ° C./initial amount of foreign matter, the viscosity is the viscosity after standing at 60 ° C./initial viscosity, the surface tension is the value of the surface tension after leaving at 60 ° C./initial surface tension, and the ejection stability is Seiko Epson Using the water-based inkjet printer PM-900C manufactured by Co., Ltd., printing 100 pages on A4 Xerox P paper continuously, A with no printing disturbance, etc. B, printing with less than 10 printing irregularities, B, 10 or more C indicates that there is a printing disorder in less than 100 places, and D indicates that there is a printing disorder in 100 or more places.

As can be seen from the results in Tables 1 and 2, the water-based ink using the dispersion according to the present invention has good print quality, and is excellent in discharge stability and storage stability. I understand that Moreover, about Example A-2-8, when the test was done similarly changing the additive, the substantially same result was obtained.
In addition, Table 3 shows the results of determining the relationship between the amount of aromatic ring and storage stability by carrying out polymerization in which the amount of aromatic ring of the dispersion polymer used in Example A-1 and Example A-5 was changed. Storage stability was determined by placing the water-based inks of Examples A-1 to 8 in glass sample bottles and sealing them, and then leaving them at 60 ° C. and 70 ° C./1 week, respectively. (Viscosity) was examined. The amount of foreign matter generated is the amount of foreign matter after standing at 60 ° C. and 70 ° C./initial amount of foreign matter, and the viscosity is the viscosity after standing at 60 ° C. and 70 ° C./initial viscosity.

  As can be seen from the results in Table 3, the amount of the aromatic ring in the dispersion polymer of the present invention is 20% or more and 70% or less, preferably 25% or more and 50% or less.

As described above, the additives (acetylene glycol surfactants, acetylene alcohol surfactants, silicon surfactants, di (tri-ethylene) surfactants, and the like that may be used in the present invention when dispersed with a general dispersant as in the prior art. It is difficult to use (a) a substance comprising one or more selected from (di) propylene glycol monobutyl ether and (di) propylene glycol monobutyl ether and 1,2-alkylene glycol), so that sufficient print quality cannot be obtained. It is a macrocapsule that includes the colorant of the invention as a polymer and is dispersible in water. The amount of the aromatic ring in the polymer is 20% by weight or more and 70% or less of the polymer, so that sufficient color developability is obtained. However, it becomes a water-based ink suitable for water-based inkjet recording that can provide storage stability and ejection stability. Furthermore, since a pigment is suitably used as the colorant, the water resistance has an effect that the printed matter is superior to the case where a normal dye is used (for example, Comparative Examples A-2 and 3). In addition, the function of the polymer that coats the colorant can be freely changed by the polymerization monomer and other reactants, so it can have various functions (light resistance, gas resistance, colorability, glossiness, fixability, etc.). It also has the effect of being able to. When conventional dispersants are used as in the past, the dispersants are basically weakly adsorbed by the colorant and have a weak adsorption force, causing partial desorption. Since the viscosity is increased by the agent, the amount of the colorant added is limited, and it is difficult to obtain sufficient color development.
The present invention should not be considered to be limited to these examples, and various modifications can be made without departing from the gist of the present invention.

[Example B]
Next, examples of another preferred embodiment (b) according to the present invention will be described.
As an example of the colorant shown in the present invention, the following examples and comparative examples describe cases where some organic or inorganic pigments are used. However, the present invention is not limited thereto, and many organic and inorganic pigments may be used. it can. Each average particle diameter is shown in <> in nm (nanometer) units.
In the present invention, it can also be obtained by dispersing a colorant with a reactive dispersant and then performing emulsion polymerization in water in the presence of a catalyst.

(Production of Black Dispersion B1)
First, as the black dispersion B1, Raven C (manufactured by Columbian Carbon Co., Ltd.), which is an inorganic pigment carbon black, was used as a colorant. A reaction vessel equipped with an ultrasonic generator, a stirrer, a dripping device, a water-cooled reflux condenser, and a temperature controller, 58 parts of Raven C (manufactured by Colombian Carbon Co., Ltd.) Then, 5 parts of Adeka Soap SE-10N manufactured by Asahi Denka Co., Ltd., which is a polymerizable surfactant, was added to 180 parts of ion-exchanged water, and ultrasonic treatment was performed for 4 hours.

Next, a methyl ethyl ketone solution of 5 parts of styrene, 1.6 parts of α-methylstyrene and 0.5 part of azobisisobutyronitrile was further added, and a polymerization reaction was carried out at 60 ° C. for 8 hours. The obtained solution was subjected to centrifugal filtration to take out the pigment included in the dispersed polymer, and further filtered through a 0.4 μm membrane filter to remove coarse particles. The pigment solution included in the dispersion polymer was loosened with a homogenizer and redispersed.
Then, a methyl ethyl ketone solution of the aforementioned pigment is added to the reaction vessel, and further 27 parts of ion exchange water and 0.05 part of sodium lauryl sulfate are added, and 100 parts of ion exchange water and 0.5 part of potassium persulfate as a polymerization initiator are added. The nitrogen atmosphere was maintained at 70 ° C. Next, a mixed solution containing 25 parts of styrene, 1 part of tetrahydrofurfuryl methacrylate, 15 parts of butyl methacrylate, 5 parts of triethylene glycol methacrylate and 0.02 part of t-dodecyl mercaptan was dropped and reacted, and then a rotary evaporator was used. Methyl ethyl ketone and a part of water were distilled off, neutralized with sodium hydroxide and adjusted to pH 8.5, and then filtered through a 0.3 μm filter to obtain a black dispersion B1.

A part of this dispersion was taken out, acidified by adding 0.1 mol / L HCl, and only the dispersion polymer was taken out by Soxhlet extraction using acetone, and ¹³ C-NMR and DMSO-DM ₆ were used. The amount of the aromatic ring relative to the total weight of the dispersed polymer as measured by ¹ H-NMR (AMX400 manufactured by Bruker (Germany)) was 40%.

(Production of cyan dispersion B1)
Cyan Dispersion B1 was produced with the same composition and method as Black Dispersion B1, except that 58 parts of Pigment Blue 15: 3 (copper phthalocyanine pigment, Clariant), an organic pigment, was used as the colorant. did.

(Production of magenta dispersion B1)
The magenta dispersion B1 was produced by the same composition and method as the production of the black dispersion B1, except that 58 parts of Pigment Red 81 (manufactured by Clariant), which is an organic pigment, was used as a colorant.

(Production of yellow dispersion B1)
The yellow dispersion B1 was produced by the same composition and method as the production of the black dispersion B1, except that 58 parts of Pigment Yellow 180 (diketopyrrolopyrrole pigment, Clariant), an organic pigment, was used as a colorant. did.

(Production of Black Dispersion B2)
As the black dispersion B2, Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant. A reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 20 parts of styrene, 5 parts of α-methylstyrene, 15 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t-dodecyl Add 0.3 part of mercaptan and heat to 70 ° C., separately prepared 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile. Was placed in a dropping funnel and the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 50%.

40 parts of the above dispersion polymer solution, 30 parts of Monarch 880 (manufactured by Cabot), carbon black, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed and stirred with a homogenizer for 30 minutes. Thereafter, 300 parts of ion-exchanged water was added and further stirred for 1 hour. Then, the whole amount of methyl ethyl ketone and a part of water were distilled off using a rotary evaporator, neutralized with 0.1 mol / L sodium hydroxide to adjust to pH 9, and filtered through a 0.3 μm membrane filter. Thus, a black dispersion B2 having a solid content (dispersion polymer and carbon black) of 20% was obtained.
A part of this dispersion was taken out, acidified by adding 0.1 mol / L HCl, and only the dispersion polymer was taken out by Soxhlet extraction using acetone, and ¹³ C-NMR and DMSO-DM ₆ were used. The amount of the aromatic ring relative to the total weight of the dispersed polymer as measured by ¹ H-NMR (AMX400 manufactured by Bruker (Germany)) was 36%.

(Production of Black Dispersion B3)
Black dispersion B3 was produced by the same composition and method as the production of black dispersion B2, except that 2.2 parts of Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant.
(Production of Black Dispersion B4)
The black dispersion B4 was produced by the same composition and method as the production of the black dispersion B2, except that 5 parts of Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant.
(Production of Black Dispersion B5)
Black dispersion B5 was produced by the same composition and method as the production of black dispersion B2, except that 8.6 parts of Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant.

(Production of Black Dispersion B6)
Black dispersion B6 was produced by the same composition and method as the production of black dispersion B2, except that 13.3 parts of Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant.
(Production of Black Dispersion B7)
Black dispersion B7 was produced by the same composition and method as the production of black dispersion B2, except that 20 parts of Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant.
(Production of Black Dispersion B8)
Black dispersion B8 was produced by the same composition and method as the production of black dispersion B2, except that 46.7 parts of Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant.

(Production of Black Dispersion B9)
Black dispersion B9 was produced by the same composition and method as the production of black dispersion B2, except that 80 parts of Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant.
(Production of Black Dispersion B10)
Black dispersion B10 was produced by the same composition and method as the production of black dispersion B2, except that 180 parts of Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant.

(Production of cyan dispersion B2)
The cyan dispersion B2 was produced by the same composition and method as the production of the black dispersion B2, except that 30 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment, manufactured by Clariant) was used as a colorant.
(Production of cyan dispersion B3)
Cyan Dispersion 3 was produced by the same composition and method as the production of Black Dispersion B2, except that 2.2 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment, Clariant) was used as the colorant.
(Production of cyan dispersion B4)
The cyan dispersion B4 was produced by the same composition and method as the production of the black dispersion B2, except that 5 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment, manufactured by Clariant) was used as a colorant.

(Production of cyan dispersion B5)
Cyan Dispersion B5 was produced by the same composition and method as that of Black Dispersion B2, except that 8.6 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment, manufactured by Clariant) was used as a colorant.
(Production of cyan dispersion B6)
Cyan Dispersion B6 was produced by the same composition and method as that of Black Dispersion B2, except that 13.3 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment, Clariant) was used as a colorant.

(Production of cyan dispersion B7)
The cyan dispersion B7 was produced by the same composition and method as the production of the black dispersion B2, except that 20 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment, manufactured by Clariant) was used as a colorant.
(Production of cyan dispersion B8)
The cyan dispersion B8 was produced by the same composition and method as the production of the black dispersion B2, except that 46.7 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment, manufactured by Clariant) was used as a colorant.
(Production of cyan dispersion B9)
Cyan Dispersion B9 was produced by the same composition and method as that of Black Dispersion B2, except that 80 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment, manufactured by Clariant) was used as a colorant.
(Production of cyan dispersion B10)
The cyan dispersion B10 was produced by the same composition and method as the production of the black dispersion B2, except that 180 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment, manufactured by Clariant) was used as a colorant.

(Production of magenta dispersion B2)
The magenta dispersion B2 was produced by the same composition and method as the production of the black dispersion B2, except that 30 parts of Pigment Red 122 (dimethylquinacridone pigment, Clariant) was used as a colorant.
(Production of magenta dispersion B3)
The magenta dispersion B3 was produced by the same composition and method as the production of the black dispersion B2, except that 2.2 parts of Pigment Red 122 (dimethylquinacridone pigment, manufactured by Clariant) was used as a colorant.
(Production of magenta dispersion B4)
The magenta dispersion B4 was produced by the same composition and method as the production of the black dispersion B2, except that 5 parts of Pigment Red 122 (dimethylquinacridone pigment, Clariant) was used as a colorant.

(Production of magenta dispersion B5)
Magenta dispersion B5 was produced by the same composition and method as the production of black dispersion B2, except that 8.6 parts of Pigment Red 122 (dimethylquinacridone pigment, Clariant) was used as a colorant.
(Production of magenta dispersion B6)
The magenta dispersion 6 was produced by the same composition and method as the production of the black dispersion B2, except that 13.3 parts of Pigment Red 122 (dimethylquinacridone pigment, Clariant) was used as a colorant.
(Production of magenta dispersion B7)
The magenta dispersion B7 was produced by the same composition and method as the production of the black dispersion B2, except that 20 parts of Pigment Red 122 (dimethylquinacridone pigment, manufactured by Clariant) was used as a colorant.

(Production of magenta dispersion B8)
Magenta dispersion B8 was produced by the same composition and method as in the production of black dispersion B2, except that 46.7 parts of Pigment Red 122 (dimethylquinacridone pigment, Clariant) was used as a colorant.
(Production of magenta dispersion B9)
The magenta dispersion B9 was produced by the same composition and method as the production of the black dispersion B2, except that 80 parts of Pigment Red 122 (dimethylquinacridone pigment, manufactured by Clariant) was used as a colorant.
(Production of magenta dispersion B10)
The magenta dispersion B10 was produced by the same composition and method as the production of the black dispersion B2, except that 180 parts of Pigment Red 122 (dimethylquinacridone pigment, manufactured by Clariant) was used as a colorant.

(Production of yellow dispersion B2)
The yellow dispersion B2 was produced by the same composition and method as the production of the black dispersion B2, except that 30 parts of Pigment Yellow 74 (Clariant) was used as a colorant.
(Production of yellow dispersion B3)
The yellow dispersion B3 was produced by the same composition and method as the production of the black dispersion B2, except that 2.2 parts of Pigment Yellow 74 (Clariant) was used as a colorant.
(Production of yellow dispersion B4)
The yellow dispersion B4 was produced by the same composition and method as the production of the black dispersion B2, except that 5 parts of Pigment Yellow 74 (manufactured by Clariant) was used as a colorant.

(Production of yellow dispersion B5)
The yellow dispersion B5 was produced by the same composition and method as the production of the black dispersion B2, except that 8.6 parts of Pigment Yellow 74 (Clariant) was used as a colorant.
(Production of yellow dispersion B6)
Yellow Dispersion B6 was produced by the same composition and method as in the production of Black Dispersion B2, except that 13.3 parts of Pigment Yellow 74 (Clariant) was used as the colorant. (Production of yellow dispersion B7)
Yellow dispersion B7 was produced by the same composition and method as the production of black dispersion B2, except that 20 parts of Pigment Yellow 74 (manufactured by Clariant) was used as a colorant.

(Production of yellow dispersion B8)
The yellow dispersion B8 was produced by the same composition and method as the production of the black dispersion B2, except that 46.7 parts of Pigment Yellow 74 (Clariant) was used as a colorant. (Production of yellow dispersion B9)
Yellow Dispersion B9 was produced by the same composition and method as in the production of Black Dispersion B2, except that 80 parts of Pigment Yellow 74 (manufactured by Clariant) was used as the colorant.
(Production of Yellow Dispersion B10)
The yellow dispersion B10 was produced by the same composition and method as the production of the black dispersion B2, except that 180 parts of Pigment Yellow 74 (Clariant) was used as a colorant. (Production of yellow dispersion B11)
Yellow dispersion B11 was produced by the same composition and method as the production of black dispersion B2, except that 46.7 parts of Pigment Yellow 110 (Isoindolinone Pigment, Clariant) was used as a colorant.

(Preparation example of water-based ink)
Specific examples of the composition of the water-based ink suitable for the water-based ink for water-based inkjet recording according to the present invention are shown below. The amount of dispersion added indicates the amount of solid content in the dispersion (total amount of pigment and the dispersion polymer surrounding it). <> Indicates the particle size of the pigment in nm units. In the present embodiment, the remaining amount of water indicates 0.05% Proxel XL-2 for preventing corrosion of aqueous ink, 0.02% for benzotriazole for preventing corrosion of aqueous inkjet head members, In order to reduce the influence of metal ions in the aqueous ink system, 0.04% EDTA · 2Na salt was added to ion-exchanged water.

(Example B-1)
Additive amount (%)
Black dispersion B1 <105> ... 9.5
TEGmBE ... 5.0
Olfine E1010 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.0
Glycerin ... 9.0
1,5-pentanediol ... 5.0
Triethanolamine ... 0.8
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

  In the above composition, TEGmBE represents triethylene glycol monobutyl ether, and Orphine E1010 represents an acetylene glycol surfactant (trade name, manufactured by Nissin Chemical Industry Co., Ltd.).

(Example B-2)
Additive amount (%)
Cyan dispersion B1 <85> ... 4.5
DEGmBE ... 10.0
Dipropylene glycol ... 5.0
Surfinol 465 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.2
Triethanolamine ... 0.9
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether, and Surfynol 465 represents an acetylene glycol surfactant (trade name, manufactured by Air Products (USA)).

(Example B-3)
Additive amount (%)
Magenta dispersion B1 <90> ... 8.5
1,2-hexanediol ... 4.0
Olphine STG ... 0.5
Diethylene glycol ... 7.0
Thiodiglycol ... 1.5
1,6-hexanediol ... 5.0
Triethanolamine ... 1.0
Potassium hydroxide ... 0.1
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

  In the above composition, orphine STG represents an acetylene glycol surfactant (trade name, manufactured by Nissin Chemical Industry Co., Ltd.).

(Example B-4)
Additive amount (%)
Yellow dispersion B1 <80> ... 10.0
TEGmBE ... 3.0
1,2-pentanediol ... 5.0
Surfynol 61 ... 0.5
Tetraethylene glycol ... 9.0
1,5-pentanediol ... 2.0
Dimethyl-2-imidazolidinone ... 2.0
Sodium benzoate ... 0.1
Triethanolamine 0.7
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

  In the above composition, Surfynol 61 represents an acetylene alcohol surfactant (trade name, manufactured by Air Products (USA)).

(Example B-5)
Additive amount (%)
Black dispersion B2 <110> ... 8.0
DPGmBE ... 2.0
DEGmBE ... 7.0
Glycerin ... 14.0
Triethanolamine ... 0.9
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

  In the above composition, DPGmBE represents dipropylene glycol monobutyl ether.

(Example B-6)
An aqueous ink of Example B-6 was prepared with the same composition as Example B-5, except that the black dispersion B3 was used as the dispersion.
(Example B-7)
An aqueous ink of Example B-7 was prepared with the same composition as in Example B-5, except that the black dispersion B4 was used as the dispersion.
(Example B-8)
A water-based ink of Example B-8 was prepared with the same composition as Example B-5 except that the black dispersion B5 was used as the dispersion.
(Example B-9)
A water-based ink of Example B-9 was prepared with the same composition as Example B-5 except that the black dispersion B6 was used as the dispersion.

(Example B-10)
An aqueous ink of Example B-10 was prepared with the same composition as Example B-5, except that the black dispersion B7 was used as the dispersion.
(Example B-11)
A water-based ink of Example B-11 was prepared with the same composition as Example B-5, except that the black dispersion B8 was used as the dispersion.
(Example B-12)
A water-based ink of Example B-12 was prepared with the same composition as Example B-5, except that the black dispersion B9 was used as the dispersion.
(Example B-13)
A water-based ink of Example B-13 was prepared with the same composition as Example B-5 except that the black dispersion B10 was used as the dispersion.

(Example B-14)
Additive amount (%)
Cyan dispersion B2 <90> ... 10.0
Olfine E1010 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.0
TEGmBE ... 6.0
Glycerin 15.0
Thiodiglycol ... 2.0
1,5-pentanediol ... 1.0
Triethanolamine ... 0.9
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

(Example B-15)
A water-based ink of Example B-15 was prepared with the same composition as Example B-14, except that cyan dispersion B3 was used as the dispersion.
(Example B-16)
A water-based ink of Example B-16 was prepared with the same composition as Example B-14, except that cyan dispersion B4 was used as the dispersion.
(Example B-17)
A water-based ink of Example B-17 was prepared with the same composition as Example B-14, except that cyan dispersion B5 was used as the dispersion.
(Example B-18)
A water-based ink of Example B-18 was prepared with the same composition as Example B-14, except that cyan dispersion B6 was used as the dispersion.
(Example B-19)
An aqueous ink of Example B-19 was prepared with the same composition as Example B-14, except that Cyan Dispersion B7 was used as the dispersion.
(Example B-20)
A water-based ink of Example B-20 was prepared with the same composition as Example B-14, except that cyan dispersion B8 was used as the dispersion.
(Example B-21)
A water-based ink of Example B-21 was prepared with the same composition as Example B-14, except that cyan dispersion B9 was used as the dispersion.
(Example B-22)
A water-based ink of Example B-22 was prepared with the same composition as Example B-14, except that cyan dispersion B10 was used as the dispersion.

(Example B-23)
Additive amount (%)
Magenta dispersion B2 <105> ... 12.0
Surfynol 61 ... 0.5
DEGmBE ... 8.0
Glycerin 15.0
Trimethylolpropane ... 1.0
Trimethylolethane ... 1.0
Surfinol 465 ... 1.0
Triethanolamine ... 0.5
Potassium hydroxide ... 0.05
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

(Example B-24)
A water-based ink of Example B-24 was prepared with the same composition as Example B-23 except that magenta dispersion B3 was used as the dispersion.
(Example B-25)
A water-based ink of Example B-25 was prepared with the same composition as Example B-23 except that magenta dispersion B4 was used as the dispersion.
(Example B-26)
An aqueous ink of Example B-26 was prepared with the same composition as Example B-23, except that magenta dispersion B5 was used as the dispersion.
(Example B-27)
A water-based ink of Example B-27 was prepared with the same composition as Example B-23, except that magenta dispersion B6 was used as the dispersion.
(Example B-28)
An aqueous ink of Example B-28 was prepared with the same composition as that of Example B-23, except that magenta dispersion B7 was used as the dispersion.
(Example B-29)
An aqueous ink of Example B-29 was prepared with the same composition as Example B-23, except that magenta dispersion B8 was used as the dispersion.
(Example B-30)
A water-based ink of Example B-30 was prepared with the same composition as Example B-23 except that magenta dispersion B9 was used as the dispersion.
(Example B-31)
An aqueous ink of Example B-31 was prepared with the same composition as Example B-23, except that magenta dispersion B10 was used as the dispersion.

(Example B-32)
Additive amount (%)
Yellow dispersion B2 <85> ... 10.5
Olphine STG ... 1.0
PGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 2.0
DEGmBE ... 10.0
Glycerin ... 7.0
Diethylene glycol ... 5.0
Tetrapropylene glycol ... 5.0
Triethanolamine ... 0.9
Potassium hydroxide ... 0.1
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

  In the above composition, PGmBE represents propylene glycol monobutyl ether.

(Example B-33)
An aqueous ink of Example B-33 was prepared with the same composition as Example B-32 except that Yellow Dispersion B3 was used as the dispersion.
(Example B-34)
A water-based ink of Example B-34 was prepared with the same composition as Example B-32 except that Yellow Dispersion B4 was used as the dispersion.
(Example B-35)
A water-based ink of Example B-35 was prepared with the same composition as Example B-32 except that Yellow Dispersion B5 was used as the dispersion.
(Example B-36)
A water-based ink of Example B-36 was prepared with the same composition as Example B-32 except that Yellow Dispersion B6 was used as the dispersion.
(Example B-37)
A water-based ink of Example B-37 was prepared with the same composition as Example B-32 except that Yellow Dispersion B7 was used as the dispersion.
(Example B-38)
A water-based ink of Example B-38 was prepared with the same composition as Example B-32 except that Yellow Dispersion B8 was used as the dispersion.
(Example B-39)
A water-based ink of Example B-39 was prepared with the same composition as Example B-32 except that Yellow Dispersion B9 was used as the dispersion.
(Example B-40)
A water-based ink of Example B-40 was prepared with the same composition as Example B-32 except that Yellow Dispersion B10 was used as the dispersion.
(Example B-41)
A water-based ink of Example B-41 was prepared with the same composition as Example B-32 except that Yellow Dispersion B11 was used as the dispersion.

(Example B-42)
Additive amount (%)
Yellow dispersion B8 <85> ... 9.5
Yellow dispersion B11 <105> ... 0.5
Surfinol 465 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
Olphine STG ... 0.3
TEGmBE ... 1.0
Glycerin ... 13.0
1,2-hexanediol ... 2.0
Trimethylolpropane …… 6.0
Triethylene glycol ... 5.0
2-Pyrrolidone ... 2.0
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

  In the above composition, TEGmBE represents triethylene glycol monobutyl ether.

(Example B-43)
Additive amount (%)
Yellow dispersion B8 <85> ... 4.29
Magenta dispersion B9 <105> ... 3.75
Surfinol 465 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
Olphine STG ... 0.3
TEGmBE ... 1.0
Glycerin ... 13.0
1,2-hexanediol ... 3.0
Trimethylolpropane …… 8.0
Triethylene glycol ... 5.0
2-Pyrrolidone ... 2.0
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

  In the above composition, TEGmBE represents triethylene glycol monobutyl ether.

(Example B-44)
Additive amount (%)
Yellow dispersion B8 <85> ... 4.29
Cyan dispersion B7 <90>... 6.0
Surfinol 465 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
Olphine STG ... 0.3
TEGmBE ... 1.0
Glycerin ... 16.0
1,2-hexanediol ... 2.0
Trimethylolpropane ... 3.0
Triethylene glycol ... 5.0
2-Pyrrolidone ... 2.0
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

  In the above composition, TEGmBE represents triethylene glycol monobutyl ether.

(Example B-45)
Additive amount (%)
Magenta dispersion B9 <105> ... 3.75
Cyan dispersion B7 <90>... 6.0
Surfinol 465 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
Olphine STG ... 0.3
TEGmBE ... 1.0
Glycerin 15.0
1,2-hexanediol ... 2.0
Trimethylolpropane ... 3.0
Triethylene glycol ... 5.0
2-Pyrrolidone ... 2.0
Water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Remaining amount

  In the above composition, TEGmBE represents triethylene glycol monobutyl ether.

(Comparative Example B-1)
In Comparative Example B-1, a water-based ink for water-based inkjet recording was prepared using the carbon black pigment used in the black dispersion B1 as a colorant and a polymer dispersant and a surfactant as the dispersant. Its composition is shown below.

Additive amount (%)
Carbon black pigment <105> ... 7.0
Glycerin ... 10.0
Polymer dispersant ... 3.0
Nonionic surfactant ... 1.0
Ion exchange water

  In the above composition, Raven C (trade name, manufactured by Columbian Carbon Co., Ltd.) is used as the carbon black pigment, Neugen EA160 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) is used as the non-ionic surfactant, and polymer. The dispersant is Solsperse 27000 (trade name, manufactured by Avicia). The composition was subjected to a dispersion treatment for 2 hours with a bead mill mini-zeta (manufactured by Ajisawa Co., Ltd.) to prepare a water-based inkjet ink according to Comparative Example B-1. In this comparative example, Proxel XL-2, EDTA2Na salt and benzotriazole were not added.

(Comparative Example B-2)
In Comparative Example B-2, a water-based ink for aqueous inkjet recording was prepared using the carbon black pigment used in the black dispersion B1 as the colorant and the surfactant as the dispersant. Its composition is shown below.

Additive amount (%)
Carbon black pigment <105> ... 8.0
Anionic surfactant ... 1.5
DEGmME ... 7.0
Diethylene glycol ... 10.0
2-Pyrrolidone ... 5.0
Ion exchange water

  In the above composition, the carbon black pigment is Raven C (trade name, manufactured by Columbian Carbon Co., Ltd.), the anionic surfactant is Hytenol N07 (trade name, manufactured by Daiichi Pharmaceutical Co., Ltd.), and DEGmME is Diethylene glycol monomethyl ether is shown. In this comparative example, Proxel XL-2, EDTA.2Na salt, and benzotriazole were not added.

(Comparative Example B-3)
In Comparative Example B-3, a black dispersion B11 was produced using the carbon black pigment used in the black dispersion B2 as a colorant and the dispersion polymer used in the black dispersion B2 as a dispersant, and comparison was made using this. The water-based ink of Example B-3 was prepared. However, the black dispersion B11 used in this comparative example was produced by the following method.
40 parts of the 50% concentration dispersion polymer solution used in the production of the black dispersion B2, and 0.4 parts of Monarch 880 (trade name, manufactured by Cabot, Pigment Black 7) as a carbon black pigment, 0.1 mol / L. 100 parts of an aqueous sodium hydroxide solution and 30 parts of methyl ethyl ketone were mixed and stirred with a homogenizer for 30 minutes. Thereafter, 300 parts of ion-exchanged water was added and further stirred for 1 hour. Then, the whole amount of methyl ethyl ketone and a part of water were distilled off using a rotary evaporator, neutralized with 0.1 mol / L sodium hydroxide to adjust to pH 9, and filtered through a 0.3 μm membrane filter. Thus, a black dispersion B11 according to Comparative Example B-3 having a solid content (dispersion polymer and carbon black) of 20% was obtained.
The composition of the aqueous ink of Comparative Example B-3 is shown below. In addition,% of the following black dispersion B11 shows solid content (what combined the pigment and the dispersion polymer).

Additive amount (%)
Black dispersion B11 <80> ... 15.0
Diethylene glycol ... 10.0
Glycerin ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Nonionic surfactant ... 1.0
Ion exchange water

  In the above composition, the nonionic surfactant represents Epan 450 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). In this comparative example, Proxel XL-2, EDTA.2Na salt, and benzotriazole were not added.

(Comparative Example B-4)
In Comparative Example B-4, a black dispersion B12 was produced using the carbon black pigment used in the black dispersion B2 as a colorant and the dispersion polymer used in the black dispersion B2 as a dispersant. The water-based ink of Example B-4 was prepared. However, the black dispersion B12 used in this comparative example was produced by the method shown below.
40 parts of the 50% concentration dispersion polymer solution used in the production of the black dispersion B2, 300 parts of Monarch 880 (trade name, manufactured by Cabot Corporation, Pigment Black 7) as a carbon black pigment, 0.1 mol / L of hydroxylated water 100 parts of an aqueous sodium solution and 30 parts of methyl ethyl ketone were mixed and stirred with a homogenizer for 30 minutes. Thereafter, 300 parts of ion-exchanged water was added and further stirred for 1 hour. Then, the whole amount of methyl ethyl ketone and a part of water were distilled off using a rotary evaporator, neutralized with 0.1 mol / L sodium hydroxide to adjust to pH 9, and filtered through a 0.3 μm membrane filter. Thus, a black dispersion B12 according to Comparative Example B-4 having a solid content (dispersion polymer and carbon black) of 20% was obtained.
The composition of the aqueous ink for aqueous inkjet recording of Comparative Example B-4 is shown below. In addition,% of the following black dispersion B12 shows solid content (what combined the pigment and the dispersion polymer).

Additive amount (%)
Black dispersion B12 <180>... 8.0
Diethylene glycol ... 10.0
Glycerin ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Nonionic surfactant ... 1.0
Ion-exchanged water: the remaining amount In the above composition, the nonionic surfactant represents Epan 450 (trade name, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.). In this comparative example, Proxel XL-2, EDTA.2Na salt, and benzotriazole were not added.

(Evaluation of dispersion and water-based ink)
<Print quality on plain paper>
The water-based ink created in the above examples and comparative examples is mounted on the water-based inkjet printer PM-900C (trade name, manufactured by Seiko Epson Corporation), and characters are printed on plain paper to evaluate the print density and the print quality due to bleeding. did. The plain papers used in this evaluation are commercially available papers such as Conqueror paper, Favorit paper, Modo Copy paper, Rapid Copy paper, EPSON EPP paper, Xerox 4024 paper, Xerox 10 paper, Neenha. Bond paper, Rcopyy 6200 paper, Yamayuri paper, Xerox R paper. Evaluation was made visually. The evaluation criteria are shown below. The evaluation results are shown in Table 4.

Evaluation A: Characters are dark and clear, or bleeding is not known.
B: A thin character looks slightly thin or a slight blur is recognized (practical level).
C: Thin characters look thin and faint, or bleeding such as thickening and bending of characters is observed.
D: Some characters have low density and cannot be read, or some characters have bad bleeding and cannot be read.

As is clear from the results in Table 4, the aqueous inks of Comparative Examples B-1 to B-4 had low character density or significant bleeding, but the aqueous inks of Examples B-1 to 40 had high character density and bleeding. There were few. Among these, Examples B-1, 2, 5, 10, 11, 12, 13, 14, 18, 19, 20, 21, 22, 23, 29, 30, 31, 32, 38, 39, 40, With the water-based inks 41, 42, 43, 44, and 45, a clear image with high character density and no blur was obtained regardless of the paper type.
As described above, according to the present invention, it is possible to provide a water-based ink suitable for water-based inkjet recording with high quality and high practicality, which is darker and clearer than plain paper and has less bleeding.

<Glossiness on glossy media>
The water-based ink created in the above examples and comparative examples is mounted on the water-based inkjet printer PM-900C (trade name, manufactured by Seiko Epson Corporation), and the duty is changed in increments of 10% from 10% to 100% on the glossy media. A solid pattern was printed, and the gloss of the printed material was evaluated. The glossy media used in this evaluation are commercially available glossy media in Europe, the United States, and Japan. (1) Photo print paper 2, (2) MC photo paper (Both (1) and (2) are trade names, Seiko (Epson Co., Ltd.), (3) Ink Jet Paper Photo Glossy Paper Super Photo Grade, (4) Ink Jet Paper Photo Paper High Grade (Both (3) and (4) are trade names, manufactured by Fuji Photo Film Co., Ltd.), ( 5) Ink Jet Photographic Quality Paper Photo Weight (trade name, manufactured by Kodak Company), (6) Photo like QP QP20A4GH (trade name, manufactured by Konica Corporation). Evaluation was made visually. The evaluation criteria are shown below. The evaluation results are shown in Table 5. In Table 5, the numbers are shown for the paper types.

Evaluation A: Glossiness is recognized in all solid patterns.
B: Although the printed part of 100% duty is slightly lacking in gloss, it is a level at which there is no practical problem.
C: The printed part of 50% duty or more lacks gloss.
D: All the solid patterns lack gloss.

As is clear from the results in Table 5, the aqueous inks of Comparative Examples B-1, 2, and 4 lacked gloss. In Comparative Example B-3, the glossiness was relatively maintained, but even with a 100% duty solid pattern, the density was low and practicality was lacking. On the other hand, the water-based inks of Examples B-1 to 40 maintained glossiness. Among them, Examples B-1, 2, 3, 4, 5, 9, 10, 11, 14, 17, 18, 19, 23, 28, 29, 30, 32, 37, 38, 39, 4
Images printed with 1, 42, 43, 44, and 45 water-based inks were dark and clear and excellent in gloss.
As described above, the present invention provides a water-based ink suitable for water-based inkjet recording that is excellent in gloss, high-quality and practical in glossy media such as glossy paper that is usually used in water-based inkjet. be able to.

<Fixability of printed matter>
The water-based ink created in the above examples and comparative examples is mounted on a water-based inkjet printer PM-900C (trade name, manufactured by Seiko Epson Corporation), and characters are printed on plain paper and glossy media used in the above evaluation. Then, the fixability of the printed matter was evaluated. The evaluation was performed by visually observing the misalignment / blurred state of characters after rubbing with a finger, using a printed matter dried at 20 to 25 ° C./40 to 60% RH for one hour after printing. The evaluation criteria are shown below. The evaluation results are shown in Table 6. In Table 6, for glossy media paper types, the glossy media numbers shown in <Glossiness on Glossy Media> are shown.

Evaluation A: Misalignment and blurring are not recognized.
B: A slight deviation is recognized, but there is no practical problem.
C: Misalignment or fading is observed.
D: Displacement and faintness are severe, and characters are difficult to read.

As is apparent from the results of Tables 6 and 7, the aqueous inks of Comparative Examples B-1, 2, and 4 lacked fixing ability particularly on glossy media. Comparative Example B-3 had relatively good fixability, but had a low character density and lacked practicality. On the other hand, the water-based inks of Examples B-1 to 40 had good fixability for both plain paper and glossy media. Among them, Examples B-1, 2, 4, 5, 9, 10, 11, 14, 17, 18, 19, 23, 28, 29, 30, 32, 37
, 38, 39, 41, 42, 43, 44 and 45, the images printed with water-based inks were excellent in fixability even on glossy media.
As described above, in the present invention, not only plain paper but also glossy media such as glossy paper usually used for water-based inkjet, it is excellent in fixing property, suitable for water-based inkjet recording with high quality and high practicality. A water-based ink can be provided.

<Storability of water-based ink 1>
The water-based inks of the above examples and comparative examples were put in glass sample bottles and sealed tightly, then left at 60 ° C. for 1 week, and the amount of foreign matter generated and physical properties (viscosity and surface tension) before and after being left. Examined. The evaluation criteria are shown below. The evaluation results are shown in Table 8.

Evaluation A: The ratio of the amount of foreign matter / physical properties after standing at 60 ° C. to that before standing is in the range of 0.99 to 1.01.
B: The ratio is in the range of 0.95 to 0.99, or 1.01 to 1.05 (practical level).
C: The ratio is in the range of 0.90 to 0.95, or 1.05 to 1.10.
D: Ratio is less than 0.90 or greater than 1.10.

As is clear from the results in Table 8, the aqueous inks of Comparative Examples B-1 to B-4 were inferior in storage stability. On the other hand, the water-based inks of Examples B-1 to 40 had good storage stability for both foreign matters and physical properties. Among them, Examples B-1, 2, 4, 5, 9, 10, 11, 12, 13, 14, 17, 18, 19, 20, 23, 28, 29, 30, 31, 32, 37, 38 , 39, 40, 41, 42, 43, 44, and 45 were excellent because there was almost no difference in the amount of foreign matter generated and property values before and after being left at 60 ° C.
On the other hand, when a similar experiment was conducted by changing the dispersion to the pigment of Comparative Example B-1 with the composition of Example B-1, there was little change in the surface tension (B on the above evaluation criteria), but there was a large amount of foreign matter. (D on the above evaluation criteria) and the filterability was lowered, and the water-based ink was thickened (D on the above evaluation criteria), and stable storage stability was not obtained.

  As described above, in the present invention, it is possible to provide a water-based ink suitable for water-based inkjet recording having excellent storage stability and high quality and high practicality. In addition, when the print quality, glossiness, and fixability of the printed matter described above are observed, the weight ratio of the colorant and the dispersion polymer exhibiting excellent characteristics in any evaluation should be within the range more preferable in the present invention. I understand. Furthermore, even when two types of dispersions are mixed as the water-based ink (the water-based inks of Examples B-41 to 45), the water-based ink is excellent in storability and suitable for water-based inkjet recording with high quality and high practicality. Ink can be provided.

  Further, in the composition of Example B-1, other additives (acetylene glycol surfactants, acetylene alcohol surfactants, silicon surfactants, di surfactants) that may be used in the present invention instead of DEGmBE and Olphine E1010 A water-based ink prepared using (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and a substance composed of one or more selected from 1,2-alkylene glycol) and the water-based material shown in Comparative Example B-1 Additives that may be used in the present invention for the ink (acetylene glycol surfactants, acetylene alcohol surfactants, silicon surfactants, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1, Selected from 2-alkylene glycol In the case of adding a substance comprising more than seeds (water-based ink compositions 1 to 10 in Table 8), it was left to stand at 60 ° C./week for the same time, and the amount of foreign matter generated and physical properties (viscosity, surface after standing) (Tension) was examined. The evaluation criteria were the same as in the above <Water-based ink storage stability 1>. The evaluation results are shown in Table 9.

  Furthermore, the discharge stability of the water-based ink was evaluated. The evaluation method is to visually observe printing irregularities when 100 pages are continuously printed on A4 Xerox P paper by mounting each of the above water-based inks on a water-based inkjet printer PM-900C (trade name, manufactured by Seiko Epson Corporation). Performed. The evaluation criteria are shown below. The evaluation results are shown in Table 8.

Evaluation A: Printing disorder does not occur at all.
B: Printing disorder was observed, but the number was less than 10 (practical level).
C: There is printing disorder in the range of 10 or more and less than 100.
D: Disturbance of printing occurred at 100 locations or more.

  As can be seen from the evaluation results described above, the water-based ink using the dispersion according to the present invention exhibits good print quality regardless of plain paper or glossy media, and is excellent in discharge stability and storage stability. It can be seen that the water-based ink is suitable for recording. Moreover, about Example B-2-8, when the test was done similarly changing the additive, the substantially same result was obtained.

<Stability 2 of water-based ink>
In the dispersion polymer used for the production of the black dispersion B1, the ratio of styrene and α-methylstyrene, which are monomers containing aromatic rings, and other monomers, tetrahydrofurfuryl methacrylate, butyl methacrylate, and triethylene glycol methacrylate, are changed. Thus, polymerization was performed to change the amount of the aromatic ring in the dispersion polymer. And black dispersion B13-B21 was manufactured using this dispersion polymer, and the water-based ink was created with the composition and method similar to Example B-1. In the black dispersions B13 to B21, the weight ratio of Raven C (trade name, manufactured by Columbian Co., Ltd.), which is carbon black, as a colorant and the dispersion polymer was set to be the same as that of the black dispersion B1. The compositions of the black dispersions B13 to B21 are shown below. Moreover, the result of measuring the amount of aromatic rings in the dispersion polymer by the same method as that for the black dispersion B1 is shown next to the dispersion name.

(Black dispersion B13; amount of aromatic ring in dispersion polymer: 0%)
Raven C: 58 parts Adekari Soap SE-10N (trade name, polymerizable surfactant, manufactured by Asahi Denka Co., Ltd.): 5 parts Styrene: 0 parts α-methylstyrene: 0 parts Azobisisobutyronitrile: 0. 5 parts Sodium lauryl sulfate: 0.05 parts Potassium persulfate: 0.5 parts Styrene: 0 parts Tetrahydrofurfuryl methacrylate: 2.5 parts Butyl methacrylate: 37.5 parts Triethylene glycol methacrylate: 12.5 parts t-dodecyl Mercaptan: 0.02 part

(Black dispersion B14; amount of aromatic ring in dispersion polymer: 10%)
Raven C: 58 parts Adekari Soap SE-10N (trade name, polymerizable surfactant, manufactured by Asahi Denka Co., Ltd.): 5 parts Styrene: 1.3 parts α-methylstyrene: 0.45 parts Azobisisobutyro Nitrile: 0.5 part Sodium lauryl sulfate: 0.05 part Potassium persulfate: 0.5 part Styrene: 6.3 parts Tetrahydrofurfuryl methacrylate: 2.1 parts Butyl methacrylate: 31.9 parts Triethylene glycol methacrylate: 10 .6 parts t-dodecyl mercaptan: 0.02 parts

(Black dispersion B15; amount of aromatic ring in dispersion polymer: 20%)
Raven C: 58 parts Adekari Soap SE-10N (trade name, polymerizable surfactant, manufactured by Asahi Denka Co., Ltd.): 5 parts Styrene: 2.6 parts α-methylstyrene: 0.9 parts Azobisisobutyro Nitrile: 0.5 part Sodium lauryl sulfate: 0.05 part Potassium persulfate: 0.5 part Styrene: 12.6 parts Tetrahydrofurfuryl methacrylate: 1.74 parts Butyl methacrylate: 26.1 parts Triethylene glycol methacrylate: 8 .7 parts t-dodecyl mercaptan: 0.02 parts

(Black dispersion B16; amount of aromatic ring in dispersion polymer: 25%)
Raven C: 58 parts Adekari Soap SE-10N (trade name, polymerizable surfactant, manufactured by Asahi Denka Co., Ltd.): 5 parts Styrene: 3.25 parts α-methylstyrene: 1.125 parts Azobisisobutyro Nitrile: 0.5 part Sodium lauryl sulfate: 0.05 part Potassium persulfate: 0.5 part Styrene: 15.75 parts Tetrahydrofurfuryl methacrylate: 1.55 parts Butyl methacrylate: 23.25 parts Triethylene glycol methacrylate: 7 .75 parts t-dodecyl mercaptan: 0.02 parts

(Black dispersion B17; amount of aromatic ring in dispersion polymer: 30%)
Raven C: 58 parts Adekari Soap SE-10N (trade name, polymerizable surfactant, manufactured by Asahi Denka Co., Ltd.): 5 parts Styrene: 3.9 parts α-methylstyrene: 1.35 parts Azobisisobutyro Nitrile: 0.5 part Sodium lauryl sulfate: 0.05 part Potassium persulfate: 0.5 part Styrene: 18.9 parts Tetrahydrofurfuryl methacrylate: 1.35 parts Butyl methacrylate: 20.25 parts Triethylene glycol methacrylate: 6 .75 parts t-dodecyl mercaptan: 0.02 parts

(Black dispersion B18; amount of aromatic ring in dispersion polymer: 50%)
Raven C: 58 parts Adekari Soap SE-10N (trade name, polymerizable surfactant, manufactured by Asahi Denka Co., Ltd.): 5 parts Styrene: 6.5 parts α-methylstyrene: 2.25 parts Azobisisobutyro Nitrile: 0.5 part Sodium lauryl sulfate: 0.05 part Potassium persulfate: 0.5 part Styrene: 31.5 parts Tetrahydrofurfuryl methacrylate: 0.59 parts Butyl methacrylate: 8.82 parts Triethylene glycol methacrylate: 2 .94 parts t-dodecyl mercaptan: 0.02 parts

(Black dispersion B19; amount of aromatic ring in dispersion polymer: 60%)
Raven C: 58 parts Adekari Soap SE-10N (trade name, polymerizable surfactant, manufactured by Asahi Denka Co., Ltd.): 5 parts Styrene: 7.55 parts α-methylstyrene: 2.65 parts Azobisisobutyro Nitrile: 0.5 part Sodium lauryl sulfate: 0.05 part Potassium persulfate: 0.5 part Styrene: 36.55 parts Tetrahydrofurfuryl methacrylate: 0.25 parts Butyl methacrylate: 4.2 parts Triethylene glycol methacrylate: 1 .35 parts t-dodecyl mercaptan: 0.02 parts

(Black dispersion B20; amount of aromatic ring in dispersion polymer: 70%)
Raven C: 58 parts Adekari Soap SE-10N (trade name, polymerizable surfactant, manufactured by Asahi Denka Co., Ltd.): 5 parts Styrene: 7.8 parts α-methylstyrene: 3.15 parts Azobisisobutyro Nitrile: 0.5 parts Sodium lauryl sulfate: 0.05 parts Potassium persulfate: 0.5 parts Styrene: 44.1 parts Tetrahydrofurfuryl methacrylate: 0 parts Butyl methacrylate: 0 parts Triethylene glycol methacrylate: 0 parts t-dodecyl Mercaptan: 0.02 part

(Black dispersion B21; amount of aromatic ring in dispersion polymer: 72%)
Raven C: 58 parts Adekari Soap SE-10N (trade name, polymerizable surfactant, manufactured by Asahi Denka Co., Ltd.): 1 part Styrene: 10 parts α-methylstyrene: 0 parts Azobisisobutyronitrile: 0. 5 parts Sodium lauryl sulfate: 0.05 parts Potassium persulfate: 0.5 parts Styrene: 46 parts Tetrahydrofurfuryl methacrylate: 0 parts Butyl methacrylate: 0 parts Triethylene glycol methacrylate: 0 parts t-dodecyl mercaptan: 0.02 parts

  The storage stability of the water-based ink using the dispersion prepared by the methods and materials described above was evaluated. In the evaluation method, the water-based ink was put in a glass sample bottle and sealed, and then allowed to stand at 60 ° C. and 70 ° C./1 week, respectively, and the generated foreign matter and physical property value (viscosity) of the water-based ink before and after being left were examined. The evaluation criteria were the same as in the above <Water-based ink storage stability 1>. The evaluation results are shown in Table 10.

  From the results in Table 10, it can be seen that the storage stability can be secured when the amount of the aromatic ring in the dispersion polymer of the present invention is 20% or more and 70% or less. Further, it can be seen that a content of 25% or more and 50% or less is a preferable form because there is no foreign matter generation and no viscosity change.

As described above, additives (acetylene glycol surfactants, acetylene alcohols) that may be used in the present invention when dispersed with a conventional dispersant (for example, a water-soluble polymer dispersant, a surfactant) as in the past. It is difficult to use a surfactant, a silicon-based surfactant, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and one or more selected from 1,2-alkylene glycol), Therefore, sufficient print quality cannot be obtained. However, in the dispersion in which the pigment according to the present invention is included in the dispersion polymer so as to be dispersible in water and the amount of the aromatic ring in the dispersion polymer is 20% or more and 70% or less of the dispersion polymer, the pigment and the dispersion When the weight ratio with respect to the polymer is in the range of 10:90 to 90:10, storage stability and ejection stability can be obtained while having sufficient color developability even in the aqueous ink containing the additive. Further, the weight ratio between the colorant and the dispersion polymer, which is preferable in the present invention, is 40:60 to 90:10 in the case of a black pigment, 50:50 to 90:10 in the case of a yellow pigment, and a red pigment. In the case of blue pigments, the range is 20:80 to 70:30 in the case of blue pigments, so that not only plain paper but also glossy paper or the like normally used in water-based inkjet printers. Also for glossy media, it is possible to provide a water-based ink suitable for water-based inkjet recording, which provides a clear image with high density and excellent glossiness and fixability. In addition, since a pigment is preferably used as the colorant, it has an effect that a printed matter having excellent water resistance and light resistance can be obtained as compared with the case of using a dye that has been conventionally used as a colorant for water-based inks for water-based inkjet printers. . In addition, the function of the dispersion polymer that coats the colorant can be freely changed by the polymerization monomer and other reactants, so there are many more functions (light resistance, gas resistance, colorability, glossiness, fixability, etc.) There is also an effect that can be provided. Conventionally, when a dispersant (for example, a water-soluble polymer dispersant or a surfactant) that has been used to disperse a colorant in an aqueous system is used, the adsorptive power of the dispersant to the colorant is basically weak. Because of this, partial desorption occurs. As a result, the viscosity of the water-based ink is increased by the desorbed material and the dispersant that has not been adsorbed, so that the amount of colorant added is limited and it is difficult to obtain sufficient color development. In particular, when an additive that can be used in the present invention is used, desorption is significant.
The present invention should not be considered to be limited to these examples, and various modifications can be made without departing from the gist of the present invention.

[Example C]
Next, examples of other preferable embodiment c according to the present invention will be described.
The case where an organic or inorganic pigment is used as an example of the colorant shown in the present invention will be described. In Examples and Comparative Examples, the pigment C1 was a carbon black pigment, the pigment C2 was a phthalocyanine pigment, the pigment C3 was a dimethylquinacridone pigment, and the pigment C4 was a diketopyrrolopyrrole pigment. However, it is not limited to these, and many organic and inorganic pigments can be used. Each average particle diameter is shown in <> in nm (nanometer) units.
In the present invention, it can also be obtained by dispersing a colorant with a reactive dispersant and then performing emulsion polymerization in water in the presence of a catalyst.

(Production of dispersions C1 to C4)
First, Raven C (manufactured by Columbian Carbon Co., Ltd.), which is carbon black that is an inorganic pigment, was used as the dispersion C1. 25 parts of Raven C (manufactured by Columbian Carbon Co., Ltd.) in a reaction vessel equipped with an ultrasonic generator, a stirrer, a dripping device, a water-cooled reflux condenser, and a temperature controller Then, 5 parts of Adeka Soap SE-10N manufactured by Asahi Denka Co., Ltd., which is a polymerizable surfactant, was added to 180 parts of ion-exchanged water, and ultrasonic treatment was performed for 4 hours.
Next, a methyl ethyl ketone solution of 5 parts of styrene, 1.6 parts of α-methylstyrene and 0.5 part of azobisisobutyronitrile was further added, and a polymerization reaction was carried out at 60 ° C. for 8 hours. The resulting solution was subjected to centrifugal filtration to take out the pigment contained in the polymer, and further filtered through a 0.4 μm membrane filter to remove coarse particles. The pigment solution included with the polymer was re-dispersed by loosening with a homogenizer.

  Then, a methyl ethyl ketone solution of the aforementioned pigment is added to the reaction vessel, and further 27 parts of ion exchange water and 0.05 part of sodium lauryl sulfate are added, and 100 parts of ion exchange water and 0.5 part of potassium persulfate as a polymerization initiator are added. The nitrogen atmosphere was maintained at 70 ° C. Next, a mixed solution containing 25 parts of styrene, 1 part of tetrahydrofurfuryl methacrylate, 15 parts of butyl methacrylate, 5 parts of triethylene glycol methacrylate and 0.02 part of t-dodecyl mercaptan was dropped and reacted, and then a rotary evaporator was used. Methyl ethyl ketone and a part of water were distilled off, neutralized with sodium hydroxide to adjust to pH 8.5, and then filtered through a 0.3 μm filter to obtain dispersion C1.

A part of this dispersion was taken out, acidified by adding 0.1 mol / l HCl, and only the dispersion polymer was taken out by Soxhlet extraction using acetone, and C ¹³ -NMR and DMSO-DM ₆ were used. The amount of the aromatic ring based on the total weight of the dispersed polymer as measured by H ¹ -NMR (AMX400 manufactured by Bruker (Germany)) was 40%.
Dispersions C2 to C4 are obtained in the same manner as described above. As the dispersion C2, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant), which is an organic pigment, was used. For dispersion C3, Pigment Red 122 (dimethylquinacridone pigment: Clariant), which is an organic pigment, was used. As the dispersion C4, Pigment Yellow 180 (diketopyrrolopyrrole: manufactured by Clariant), which is an organic pigment, was used.

(Production of dispersions C5 to C8)
First, Monarch 880 (manufactured by Cabot), which is carbon black, is used as dispersion C5. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 20 parts of styrene, 5 parts of α-methylstyrene, 15 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t-dodecyl Add 0.3 part of mercaptan and heat to 70 ° C., separately prepared 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile. Is placed in a dropping funnel and the dispersion polymer is polymerized while being dropped into the reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.

40 parts of the above dispersion polymer solution, 30 parts of Monarch 880 (manufactured by Cabot), carbon black, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed and stirred with a homogenizer for 30 minutes. Thereafter, 300 parts of ion-exchanged water was added and further stirred for 1 hour. Then, the whole amount of methyl ethyl ketone and a part of water were distilled off using a rotary evaporator, neutralized with 0.1 mol / L sodium hydroxide, adjusted to pH 9, and filtered through a 0.3 μm membrane filter. Thus, a dispersion C5 having a solid content (dispersion polymer and carbon black) of 20% was obtained.
A part of this dispersion was taken out, acidified by adding 0.1 mol / l HCl, and only the dispersion polymer was taken out by Soxhlet extraction using acetone, and C ¹³ -NMR and DM13 using DMSO-d ₆ The amount of the aromatic ring based on the total weight of the dispersed polymer as measured by H ¹ -NMR (AMX400 manufactured by Bruker (Germany)) was 36%.

  Dispersions C6 to C8 were obtained in the same manner as above. As the dispersion C6, Pigment Blue 15: 3 (copper phthalocyanine pigment: manufactured by Clariant) was used. As the dispersion C7, Pigment Red 122 (dimethylquinacridone pigment: manufactured by Clariant) was used. Dispersion C8 was Pigment Yellow 180 (diketopyrrolopyrrole: manufactured by Clariant).

(Manufacture of polymer fine particles)
The reaction vessel is equipped with a dripping device, thermometer, water-cooled reflux condenser, and stirrer, and 100 parts of ion-exchanged water is added and 0.2 part of polymerization initiator potassium persulfate is added at 70 ° C. while stirring. I kept it. Monomer solution containing 0.05 part of sodium lauryl sulfate, 4 parts of glycidoxy acrylate, 5 parts of styrene, 6 parts of tetrahydrofurfuryl acrylate, 5 parts of butyl methacrylate and 0.02 of t-dodecyl mercaptan in 7 parts of ion-exchanged water Was dropped to 70 ° C. and reacted to prepare a primary substance. To the primary substance, 2 parts of 10% ammonium persulfate solution was added and stirred. Further, 30 parts of ion-exchanged water, 0.2 part of potassium lauryl sulfate, 30 parts of styrene, 25 parts of butyl methacrylate, 6 parts of butyl acrylate A reaction solution consisting of 2 parts of acrylic acid, 1 part of 1,6-hexanediol dimethacrylate and 0.5 part of t-dodecyl mercaptan was added at 70 ° C. with stirring, followed by polymerization with sodium hydroxide. Emulsion A was prepared by preparing a 30% aqueous solution of polymer fine particles that had been adjusted to pH 8 to 8.5 and filtered through a 0.3 μm filter.

(Preparation example of water-based ink)
Specific examples of the composition of the water-based ink suitable for the water-based ink for water-based inkjet recording according to the present invention are shown below. The added amount of the dispersion is shown as the amount (solid content concentration: the total amount of the pigment and the dispersed polymer surrounding it) converted by weight. <> Indicates the particle size of the pigment in nm units. The remaining amount of water in this example is 0.05% for Proxel XL-2 to prevent corrosion of the aqueous ink, and 0.02% for benzotriazole to prevent corrosion of the aqueous inkjet head member. In order to reduce the influence of metal ions in the water-based ink system, 0.04% of EDTA · 2Na salt was added to ion-exchanged water.

(Example C-1) Addition amount (%)
Dispersion C1 <105> ... 9.5
Emulsion A ... 15.0
TEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Olfine E1010 ... 1.0
Glycerin ... 9.0
1,5-pentanediol ... 5.0
Triethanolamine ... 0.8
Water ........................ Remaining amount

TEGmBE: Triethylene glycol monobutyl ether orphine E1010 (acetylene glycol surfactant: manufactured by Nissin Chemical Industry Co., Ltd.)

(Example C-2) Addition amount (%)
Dispersion C2 <85> ... 4.5
Emulsion A ... 10.0
DEGmBE ... 10.0
Dipropylene glycol ... 5.0
Surfinol 465 ... 1.2
Triethanolamine ... 0.9
Water ........................ Remaining amount

DEGmBE: Diethylene glycol monobutyl ether surfinol 465 (acetylene glycol surfactant: manufactured by Air Products (USA))

(Example C-3) Addition amount (%)
Dispersion C3 <90> ... 8.5
Emulsion A ... 10.0
1.2-Hexaneyl ... 4.0
Olphine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
Diethylene glycol 7.0
Thiodiglycol ... 1.5
1,6-hexanediol ... 5.0
Triethanolamine 1.0
Potassium hydroxide ... 0.1
Water ........................ Remaining amount

Olphine STG (acetylene glycol surfactant: manufactured by Nissin Chemical Industry Co., Ltd.)

(Example C-4) Addition amount (%)
Dispersion C4 <80> ... 10.0
Emulsion A ... 10.0
TEGmBE ... 3.0
1,2-pentanediol ... 5.0
Surfinol 61 ... 0.5
Tetraethylene glycol ... 9.0
1,5-pentanediol ... 2.0
Dimethyl-2-imidazolidinone ... 2.0
Sodium benzoate 0.1
Triethanolamine 0.7
Water ........................ Remaining amount

Surfynol 61 (acetylene alcohol-based surfactant: manufactured by Air Products (USA))

(Example C-5) Addition amount (%)
Dispersion C5 ... 8.0
Emulsion A ... 15.0
DPGmBE ... 2.0
DEGmBE ... 7.0
Glycerin ... 14.0
Triethanolamine ... 0.9
Water ........................ Remaining amount

DPGmBE: Dipropylene glycol monobutyl ether

(Example C-6) Addition amount (%)
Dispersion C6 ... 10.0
Emulsion A ... 10.0
Olfine E1010 ... 1.0
TEGmBE ... 6.0
Glycerin ... 15.0
Thiodiglycol ... 2.0
1,5-pentanediol ... 1.0
Triethanolamine ... 0.9
Water ........................ Remaining amount

(Example C-7) Addition amount (%)
Dispersion C7 ... 12.0
Emulsion A ... 10.0
Surfinol 61 ... 0.5
DEGmBE ... 8.0
Glycerin ... 15.0
Trimethylolpropane ... 1.0
Trimethylolethane ... 1.0
Surfinol 465 ... 1.0
Triethanolamine ... 0.5
KOH ......... 0.05
Water ........................ Remaining amount

(Example C-8) Addition amount (%)
Dispersion C8 ... 10.5
Emulsion A ... 10.0
Olphine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 1.0
PGmBE ... 2.0
DEGmBE ... 10.0
Glycerin 7.0
Diethylene glycol ... 5.0
Tetrapropylene glycol ... 5.0
Triethanolamine ... 0.9
KOH ... 0.1
Water ........................ Remaining amount

PGmBE: Propylene glycol monobutyl ether

  The composition of the water-based ink used in the comparative example is shown below.

(Comparative Example C-1) Addition amount (%)
Pigment C1 <105> ... 7.0
Glycerin ... 10.0
Dispersant ... 3.0
Nonionic surfactant ... 1.0
Ion exchange water

Nonionic surfactant: Neugen EA160 (Daiichi Kogyo Seiyaku Co., Ltd.)

  The dispersant was prepared by performing dispersion treatment for 2 hours with a bead mill mini-zeta (manufactured by Ajisawa Co., Ltd.) using Solsperse 27000 (manufactured by Avisia).

(Comparative Example C-2) Addition amount (%)
Acid Blue 9 ... 6.5
DEGmME ... 7.0
Diethylene glycol ... 10.0
2-pyrrolidone ... 5.0
Ion exchange water

DEGmME: Diethylene glycol monomethyl ether

(Comparative Example C-3) Addition amount (%)
Direct black 154 ... 2.5
Diethylene glycol ... 10.0
Nonionic surfactant ... 1.0
Ion exchange water

Nonionic surfactant: Epan 450 (Daiichi Kogyo Seiyaku Co., Ltd.)

  Table 11 shows the bleeding evaluation results when characters are printed as the printing evaluation results. In Table 11, A is very good, B is good, C is bad, and D is very bad.

As is clear from the results in Table 11, it can be seen that the aqueous ink used in the comparative example has poor print quality, and that the print quality is good when the aqueous ink of the present invention is used.
In addition, these printing evaluation was performed by using the water-based inkjet printer PM-900C by Seiko Epson Corporation. The papers used for these evaluations are ordinary papers commercially available in Europe, America and Japan, such as Conqueror paper, Favorit paper, Modo Copy paper, Rapid Copy paper, EPSON EPP paper, Xerox 4024 paper, Xerox 10 paper, Neenha. Bond paper, Rcopyy 6200 paper, Yamayuri paper, Xerox R paper.

As described above, in the present invention, it is possible to provide a high-quality and practical water-based ink suitable for water-based inkjet recording in which bleeding of a printed image on a recording medium such as paper is reduced.
In addition, the water-based inks of Examples C-1 to 8 were put in glass sample bottles and sealed, then left at 60 ° C./week for 1 week, and the foreign matter and physical properties (viscosity and surface tension) generated before and after the water-based ink were left. ) Was investigated.
As a result, none of the water-based inks produced foreign matter and hardly changed the physical property values, and had good storage stability.
On the other hand, when the experiment was carried out in the same manner by changing the dispersion to the pigment of Comparative Example C-1 with the composition of Example C-1, there was little change in surface tension, but foreign matter was generated and the filterability was reduced. A thickening phenomenon occurred and ejection stability could not be obtained.

In addition, in the composition of Example C-1, other additives (acetylene glycol surfactant, acetylene alcohol surfactant, silicon surfactant, di (tri-oxide) that may be used in the present invention instead of DEGmBE and E1010 This is a water-based ink prepared by using a) a water-based ink prepared using (a) a substance composed of at least one selected from ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol). Additives that may be used in the invention (acetylene glycol surfactants, acetylene alcohol surfactants, silicon surfactants, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene Is it at least one selected from glycols? (Examples C-9 to 18 in Table 12) were similarly added and left at 60 ° C./week, and the generated foreign matter, physical properties (viscosity, surface tension) of the aqueous ink after being left and Table 12 shows the results of examining the discharge stability. The amount of foreign matter generated is the amount of foreign matter after standing at 60 ° C./initial amount of foreign matter, the viscosity is the viscosity after standing at 60 ° C./initial viscosity, and the surface tension is the value of surface tension after standing at 60 ° C./initial surface tension. Stability was measured using an A4 version Xerox using a water-based inkjet printer PM-900C manufactured by Seiko Epson Corporation.
100 pages of continuous printing on P paper, A that does not cause printing disturbances at all, B that has printing disturbances in less than 10 places, B that has printing disturbances in 10 to 100 places, C that has printing disturbances in 100 places or more Let D be a certain thing.

As can be seen from the results in Tables 11 and 12, the water-based ink using the dispersion according to the present invention has good print quality and is excellent in ejection stability and storage stability and is suitable for water-based inkjet recording. It turns out that it becomes. Moreover, about Example C-2-8, when the test was done similarly changing the additive, the substantially same result was obtained.
In addition, Table 13 shows the results of determining the relationship between the amount of aromatic ring and storage stability by carrying out polymerization in which the amount of aromatic ring of the dispersion polymer used in Example C-1 and Example C-5 was changed. Storage stability was determined by placing the water-based inks of Examples C-1 to C-8 in glass sample bottles and sealing them, and then leaving them at 60 ° C. and 70 ° C./1 week, respectively. Viscosity) was examined. The amount of foreign matter generated is the amount of foreign matter after standing at 60 ° C. and 70 ° C./initial amount of foreign matter, and the viscosity is the viscosity after standing at 60 ° C. and 70 ° C./initial viscosity.

As can be seen from the results in Table 13, the amount of the aromatic ring in the dispersion polymer of the present invention is 20% or more and 70% or less, preferably 25% or more and 50% or less.
Table 14 shows the results of the evaluation of the fixing property, using the water-based inks of Examples C-1 to C-8 and those to which no emulsion was added as a comparative example. The evaluation of the fixing property is the degree of image peeling when plain paper (Xerox 4024 paper) and special paper (PM photographic paper) are used and the printed surface and the back surface are moved at a speed of 1 m / s with a load of 300 g. Depending on how you observe. The results immediately after printing, 5 minutes, 1 hour, 2 hours and 3 hours are shown. In Table 14, A indicates that there is no peeling, B indicates that there is slight peeling, C indicates that there is peeling and moves to the back surface, and D indicates that there is considerable peeling and moves to the back surface.

As can be seen from the results in Table 14, it can be seen that there is no peeling after 1 hour, especially in the special paper, and there is good fixability.
Table 15 shows the zeta potential of the microcapsules (dispersions) in Examples C-1 to 8, the zeta potential of the polymer fine particles, the zeta potential in the mixed state of the microcapsules and the polymer fine particles, and each aqueous ink at 60 ° C. As a comparative example, the generation state of foreign matters when left standing for a day is shown as a comparative example of a dispersion having a low zeta potential absolute value and a dispersion having a large difference in zeta potential from polymer fine particles. The evaluation of the foreign matter in Table 15 is shown as a value of the ratio between the initial foreign matter amount and the foreign matter amount when left at 60 ° C. for 7 days. In Table 15, the zeta potential was measured for pH dependency from pH 4 to 11 using a Zetasizer 3000HS manufactured by Malvern (UK). And the value of pH9 which particle | grains can exist stably is shown.

  As can be seen from the results in Table 15, the water-based ink according to the present invention has excellent storage stability, and it can be seen that foreign matters are likely to be generated when the absolute value of the zeta potential is low and the difference in zeta potential between the polymer fine particles is large. .

As described above, the additives (acetylene glycol surfactants, acetylene alcohol surfactants, silicon surfactants, di (tri-ethylene) surfactants, and the like that may be used in the present invention when dispersed with a general dispersant as in the prior art. It is difficult to use (a) a substance comprising one or more selected from (di) propylene glycol monobutyl ether and (di) propylene glycol monobutyl ether and 1,2-alkylene glycol), so that sufficient print quality cannot be obtained. It is a macrocapsule that includes the colorant of the invention as a polymer and is dispersible in water. The amount of the aromatic ring in the polymer is 20% by weight or more and 70% or less of the polymer, so that sufficient color developability is obtained. However, it becomes a water-based ink suitable for water-based inkjet recording that can provide storage stability and ejection stability. Further, since a pigment is preferably used as the colorant, the water resistance has an effect that the printed matter is superior to the case where a normal dye is used (for example, Comparative Examples C-2 and 3). In addition, the function of the polymer that coats the colorant can be freely changed by the polymerization monomer and other reactants, so it can have various functions (light resistance, gas resistance, colorability, glossiness, fixability, etc.). It also has the effect of being able to. When conventional dispersants are used as in the past, the dispersants are basically weakly adsorbed by the colorant and have a weak adsorption force, causing partial desorption. Since the viscosity is increased by the agent, the amount of the colorant added is limited, and it is difficult to obtain sufficient color development.
It should be noted that the present invention should not be considered as being limited to these Examples C-, and various modifications can be made without departing from the gist of the present invention.

[Example D]
Next, examples of another preferred embodiment d according to the present invention will be described.
In addition, the Example demonstrated below does not limit the scope of the present invention by these. Further, the physical properties (surface tension, average particle size) of the dispersion obtained in this example were measured by the following methods.
"Measurement of surface tension"
The surface tension at 20 ° C. of the pigment dispersions obtained in each Example or Comparative Example was measured with a surface tension meter (CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.).
"Measurement of average particle size"
The pigment dispersion obtained in each example or comparative example was diluted with ion-exchanged water so that the pigment concentration was 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement varies slightly depending on the pigment). The average particle size of the dispersed particles at 20 ° C. was measured with a particle size distribution meter (DLS-800 manufactured by Otsuka Electronics Co., Ltd.). The average particle diameter is shown in <> in nm (nanometer) in <>.

In this example, a pigment is included in a reactive dispersant, and emulsion polymerization is carried out in water in the presence of a catalyst to produce a dispersion. Subsequently, a neutralizing agent and a dispersion accelerator were added to the produced dispersion and dispersed in water to obtain each dispersion.
The method for producing the dispersion according to the present invention will be specifically described below.

-Production of dispersion (dispersion D1)
Raven C (manufactured by Columbian Carbon Co., Ltd.), which is a carbon black pigment, was used for the production of dispersion D1. In a reaction vessel equipped with an ultrasonic generator, a stirrer, a dropping device, a water-cooled reflux condenser, and a temperature controller, 25 parts of carbon black pigment (hereinafter, simply indicated as part indicates part by weight), a polymerizable surfactant 6 parts of Adeka Soap SE-10N manufactured by Asahi Denka Co., Ltd. was added to 180 parts of ion-exchanged water, and ultrasonic waves were applied for 4 hours.
Next, a methyl ethyl ketone solution of 5 parts of styrene, 1.7 parts of α-methylstyrene and 0.5 part of azobisisobutyronitrile was further added, and a polymerization reaction was carried out at 60 ° C. for 8 hours. The pigment contained in the polymer was removed by centrifugal filtration, and further filtered through a 5 μm membrane filter to remove coarse particles.

  Next, after the pigment solution contained in the polymer is loosened with a homogenizer, a methylethylketone solution of the pigment described above is further added to the reaction vessel, and 30 parts of ion-exchanged water and 0.05 part of sodium lauryl sulfate are added. 0.5 parts of potassium persulfate as a part and a polymerization initiator were added, and a nitrogen atmosphere was maintained at 70 ° C. Next, a mixed solution containing 25 parts of styrene, 1 part of tetrahydrofurfuryl methacrylate, 15 parts of butyl methacrylate, 5 parts of triethylene glycol methacrylate and 0.02 part of t-dodecyl mercaptan was dropped and reacted, and then a rotary evaporator was used. Dispersion D1 was obtained by distilling off part of methyl ethyl ketone and water and then filtering.

・ Production of dispersion (dispersion process)
(Dispersion D1)
15 parts of the dispersion D1, 0.5 part of sodium hydroxide as a neutralizing agent and 84.5 parts of ion-exchanged water were added, and a paint shaker (using zirconia beads; bead filling rate = 60%; media diameter = 1.7 mm) The dispersion was dispersed until the average particle size (secondary particle size) of the dispersion became 110 nm, to obtain a dispersion D1 (surface tension: 56 mN / m).
Measurement of the amount of aromatic ring The required amount of dispersion D1 was taken out, acidified by adding 0.1 mol / l concentration HCl, only the dispersed polymer was taken out by Soxhlet extraction method using acetone, and DMSO-d ₆ was used. The amount of the aromatic ring based on the total weight of the dispersed polymer as measured by C ¹³ -NMR and H ¹ -NMR (AMX400 manufactured by Bruker (Germany)) was 43%.

Measurement of polyvalent metal ion amount A necessary amount of the dispersion D1 was taken out and centrifuged with a centrifugal ultrafiltration device (C-15; Millipore). As the filter, type NMWL10000 was used, and the centrifugation conditions were 2500 G × 60 minutes. 10 mg of the obtained filtrate was treated by an oxygen flask method combustion method and then absorbed in a 0.2% nitric acid aqueous solution. Subsequently, the amount of ions of Si, Ca, Mg, Fe, Cr, Ni, and Zr was 28 ppm, 36 ppm, 40 ppm, respectively, when quantified by ion chromatography (column ionPac AS12A; Nippon Dionex Corporation DX-500). They were 55 ppm, 70 ppm, 62 ppm, and 25 ppm, and all were 100 ppm or less. The total amount of polyvalent metal ions was about 326 ppm, which was 500 ppm or less.

  Dispersions D2 to D7 were obtained in the same manner as the dispersion D1. Dispersion D2 uses a phthalocyanine green pigment (CI Pigment Green 7) as an organic pigment, and dispersion D3 uses a condensed azo yellow pigment (CI Pigment Yellow 128) as an organic pigment. D4 is an organic pigment, quinacridone violet pigment (CI Pigment Violet 19), Dispersion D5 is an organic pigment, Perinone Orange Pigment (CI Pigment Orange 43), and Dispersion D6 is an organic pigment. Benzimidazolone brown pigment (CI Pigment Brown 32), and perinone red pigment (CI Pigment Red 178), which is an organic pigment, was used as dispersion D7. Table 16 shows the pigments used in the production of the dispersions D1 to D7, and the dispersion method of the neutralizing agent, the type of dispersed beads, etc. The measurement result of quantity is shown.

Next, production of the dispersion D8 using a production method different from the dispersion D1 will be described.
-Manufacturing process of dispersion (dispersion D8)
For the production of Dispersion D8, Monarch 880 (manufactured by Cabot Corporation) which is a carbon black pigment was used. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 21 parts of styrene, 5 parts of α-methylstyrene, 16 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t-dodecyl Add 0.3 part of mercaptan and heat to 70 ° C., separately prepared 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile. Was placed in a dropping funnel and the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
40 parts of the above dispersed polymer solution, 30 parts of Monarch 880 (manufactured by Cabot), carbon black, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 35 parts of methyl ethyl ketone are mixed and stirred for 30 minutes with a homogenizer, followed by ion exchange Add 350 parts of water and stir for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, the dispersion D8 was obtained by filtering.

・ Production of dispersion (dispersion process)
(Dispersion D8)
15 parts of the dispersion D8, 1 part of acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.) as a dispersion accelerator, 1 part of sodium hydroxide as a neutralizing agent, and 83 parts of ion-exchanged water are added to a paint shaker (using glass beads; The dispersion D8 (surface tension: 31 mN / m) was dispersed until the average particle diameter (secondary particle diameter) of the dispersion reached 100 nm using a bead filling ratio = 60%; media diameter = 1.7 mm). Obtained.
-Measurement of the amount of aromatic rings A part of the dispersion D8 was taken out and the amount of aromatic rings was measured by the same method as in the case of the dispersion D1, and the amount of aromatic rings was 46% based on the total weight of the dispersion polymer.

・ Measurement of the amount of polyvalent metal ions The required amount of the dispersion D8 was taken out and the amount of metal ions was measured by the same method as in the case of the dispersion D1. Respectively were 38 ppm, 21 ppm, 22 pm, 9 ppm, 8 ppm, 12 ppm, and 5 ppm, and all were 100 ppm or less. The total amount of polyvalent metal ions was about 115 ppm, which was 200 ppm or less.

Dispersions D9 to D14 were obtained in the same manner as above. Dispersion D9 is a phthalocyanine blue pigment (CI Pigment Blue 15: 4), Dispersion D10 is an insoluble monoazo yellow pigment (CI Pigment Yellow 74), and Dispersion D11 is a condensed azo yellow pigment ( CI yellow 110), dispersion D12 uses anthraquinone yellow pigment (CI pigment yellow 147), and dispersion D13 uses benzimidazolone yellow pigment (CI pigment yellow 180), As the dispersion D14, quinacridone red pigment (CI Pigment Red 122) was used.
Table 18 shows the pigments used in the production of dispersions D8 to D14, and dispersion methods such as dispersion accelerators, neutralizers, and dispersed bead types. Table 19 shows the ratio of pigment to dispersed polymer, and the amount of aromatic rings. The measurement result of the amount of polyvalent metal ions is shown.

(Preparation example of water-based ink)
Specific examples of the composition of the water-based ink suitable for the water-based ink for water-based inkjet recording according to the present invention are shown below. The ion-exchanged water added as the remaining amount in this example includes Proxel XL-2 for preventing corrosion of aqueous ink and EDTA (ethylenediaminetetraacetic acid) for reducing the influence of metal ions in the aqueous ink system. ) Were added and stirred so that the concentrations in the water-based ink were 0.05% and 0.01%, respectively.

(Example D-1)
The aqueous ink composition of Example D-1 is shown below.

Amount added (%)
Dispersion D1 ... 40.0
Olfin E1010 ... 0.5
TEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
1,5-pentanediol ... 5.0
Glycerin ... 9.0
Triethanolamine ... 1.0
Ion exchange water ...

Olfine E1010 (acetylene glycols: manufactured by Nissin Chemical Industry Co., Ltd.)
TEGmBE: Triethylene glycol monobutyl ether

-Quantitative determination of metal ions A required amount of the aqueous ink prepared in Example D-1 was taken out and centrifuged by a centrifugal ultrafiltration device (C-15; Millipore). As the filter, type NMWL10000 was used, and the centrifugation conditions were 2500 G × 60 minutes. 10 mg of the obtained filtrate was treated by the oxygen flask method combustion method and then absorbed in a 0.2% nitric acid aqueous solution. Subsequently, when quantified by ion chromatography (column ionPac AS12A; Nippon Dionex Corporation DX-500), the amounts of ions of Si, Ca, Mg, Fe, Cr, Ni, and Zr were respectively 15 ppm, 19 ppm, 28 ppm, They were 20 ppm, 38 ppm, 31 ppm, and 12 ppm, and all were 50 ppm or less. The total amount of polyvalent metal ions was about 164 ppm, which was 200 ppm or less.

(Example D-2)
The aqueous ink composition of Example D-2 is shown below.

Amount added (%)
Dispersion D2 ... 30.0
Surfinol TG ... 0.3
DEGmBE ... 10.0
Dipropylene glycol ... 5.0
Trimethylolethane ... 4.0
Triethanolamine ... 0.9
Ion exchange water ...

Surfynol TG (acetylene glycols: manufactured by Air Products) DEGmBE: diethylene glycol monobutyl ether

-Quantification of metal ions A required amount of the water-based ink prepared in Example D-2 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were in order of 12 ppm, 10 ppm, 20 ppm, 35 ppm, 39 ppm, 29 ppm, and 10 ppm, respectively, and all were 50 ppm or less. The total amount of polyvalent metal ions was about 155 ppm, which was 200 ppm or less.

(Example D-3)
The aqueous ink composition of Example D-3 is shown below.

Amount added (%)
Dispersion D3 ... 50.0
Olphine STG ... 0.3
1,2-hexanediol ... 2.0
1,6-hexanediol ... 4.0
Triethylene glycol ... 10.0
Thiodiglycol ... 1.5
Triethanolamine ... 1.0
Potassium hydroxide ... 0.1
Ion exchange water ...

Olphine STG (acetylene glycols: manufactured by Nissin Chemical Industry Co., Ltd.)

-Quantification of metal ions A required amount of the water-based ink prepared in Example D-3 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were in order of 22 ppm, 25 ppm, 13 ppm, 32 ppm, 20 ppm, 26 ppm, and 15 ppm, respectively, and all were 50 ppm or less. The total amount of polyvalent metal ions was about 153 ppm, which was 200 ppm or less.

(Example D-4)
The water-based ink composition of Example D-4 is shown below.

Amount added (%)
Dispersion D4 ... 60.0
Surfinol 104 0.5
TEGmBE 3.0
1,2-pentanediol 5.0
1,5-pentanediol 2.0
Tetraethylene glycol 9.0
Dimethyl-2-imidazolidinone 2.0
Sodium benzoate 0.1
Triethanolamine 0.7
Ion exchange water

  Surfynol 104 (acetylene glycols: manufactured by Air Products)

-Quantification of metal ions A required amount of the water-based ink prepared in Example D-4 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were 26 ppm, 16 ppm, 43 ppm, 36 ppm, 37 ppm, 33 ppm, and 5 ppm in order, respectively, and all were 50 ppm or less. The total amount of polyvalent metal ions was about 196 ppm, which was 200 ppm or less.

(Example D-5)
The aqueous ink composition of Example D-5 is shown below.

Amount added (%)
Dispersion D5 ... 50.0
DPGmBE ... 2.0
DEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 7.0
Glycerin ... 5.0
Triethylene glycol ... 5.0
Trehalose ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Triethanolamine ... 0.9
Ion exchange water ...

DPGmBE: Dipropylene glycol monobutyl ether

-Quantification of metal ions A required amount of the water-based ink prepared in Example D-5 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were 41 ppm, 25 ppm, 22 ppm, 15 ppm, 14 ppm, 26 ppm, and 6 ppm, respectively, and were all 50 ppm or less. The total amount of polyvalent metal ions was about 149 ppm, which was 200 ppm or less.

(Example D-6)
The aqueous ink composition of Example D-6 is shown below.

Amount added (%)
Dispersion D6 ... 40.0
Acetylenol EO ... 0.5
TEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
1,2-pentanediol ... 1.0
Glycerin ... 13.0
Thiodiglycol 2.0
2-Pyrrolidone ... 2.0
Triethanolamine ... 0.9
Ion exchange water ...

Acetylenol EO (acetylene glycols: Kawaken Fine Chemical Co., Ltd.)

-Quantification of metal ions A required amount of the water-based ink prepared in Example D-6 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were 39 ppm, 34 ppm, 14 ppm, 18 ppm, 22 ppm, 15 ppm, and 8 ppm in order, respectively, and all were 50 ppm or less. The total amount of polyvalent metal ions was about 150 ppm, which was 200 ppm or less.

(Example D-7)
The aqueous ink composition of Example D-7 is shown below.

Amount added (%)
Dispersion D7 ... 30.0
Surfinol 465 ... 0.5
Surfinol 61 ... 0.5
TEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 6.0
Glycerin ... 15.0
Trimethylolpropane ... 1.0
Trimethylolethane ... 1.0
Triethanolamine ... 0.5
KOH ... 0.05
Ion exchange water ...

-Quantification of metal ions A required amount of the water-based ink prepared in Example D-7 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were in order of 20 ppm, 15 ppm, 27 ppm, 23 ppm, 21 ppm, 41 ppm, and 7 ppm, respectively, and all were 50 ppm or less. The total amount of polyvalent metal ions was about 154 ppm, which was 200 ppm or less.

(Example D-8)
The aqueous ink composition of Example D-8 is shown below.

Amount added (%)
Dispersion D8 ... 40.0
Surfinol 420 ... 0.5
PGmBE ... 2.0
DEGmBE ... 10.0
Tetrapropylene glycol ... 5.0
Glycerin ... 7.0
Diethylene glycol ... 5.0
Triethanolamine ... 0.9
KOH ... 0.1
Ion exchange water ...

Surfynol 420 (acetylene glycols: manufactured by Air Products Co., Ltd.)
PGmBE: Propylene glycol monobutyl ether

Quantitative determination of metal ions A required amount of the aqueous ink prepared in Example D-8 was taken out, and the amount of metal ions in the aqueous ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were in order of 15 ppm, 8 ppm, 10 ppm, 3 ppm, 5 ppm, 7 ppm, and 1 ppm, respectively, and all were 20 ppm or less. The total amount of polyvalent metal ions was about 49 ppm, which was 100 ppm or less.

(Example D-9)
The aqueous ink composition of Example D-9 is shown below.

Amount added (%)
Dispersion D9 ... 40.0
Surfinol 485 ... 1.5
DEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
1,5-pentanediol ... 5.0
Glycerin ... 9.0
1,4-cyclohexanedimethanol ・ 5.0
Triethanolamine ... 1.0
Ion exchange water ...

Surfynol 485 (acetylene glycols: manufactured by Air Products)

-Quantification of metal ions A required amount of the water-based ink prepared in Example D-9 was taken out, and the amount of metal ions in the water-based ink was measured in the same manner as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were in order of 13 ppm, 14 ppm, 11 ppm, 7 ppm, 5 ppm, 7 ppm, and 1 ppm, respectively, and all were 20 ppm or less. The total amount of polyvalent metal ions was about 58 ppm, which was 100 ppm or less.

(Example D-10)
The aqueous ink composition of Example D-10 is shown below.

Amount added (%)
Dispersion D10 ... 30.0
Surfinol TG ... 0.3
DEGmBE ... 10.0
Dipropylene glycol ... 5.0
Triethanolamine ... 0.9
Ion exchange water ...

Surfynol TG (acetylene glycols: manufactured by Air Products) DEGmBE: diethylene glycol monobutyl ether

-Quantification of metal ions A required amount of the water-based ink prepared in Example D-10 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were 11 ppm, 8 ppm, 19 ppm, 4 ppm, 5 ppm, 9 ppm, and 4 ppm, respectively, and were all 20 ppm or less. The total amount of polyvalent metal ions was about 60 ppm, which was 100 ppm or less.

(Example D-11)
The aqueous ink composition of Example D-11 is shown below.

Amount added (%)
Dispersion D11 ... 50.0
Olphine STG ... 0.3
1,2-hexanezil ... 4.0
1,6-hexanediol ... 4.0
Diethylene glycol: 7.0
Thiodiglycol ... 1.5
Triethanolamine ... 1.0
Ion exchange water ...

Olphine STG (acetylene glycols: manufactured by Nissin Chemical Industry Co., Ltd.)

-Quantification of metal ions A required amount of the aqueous ink prepared in Example D-11 was taken out, and the amount of metal ions in the aqueous ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were in the order of 8 ppm, 15 ppm, 16 ppm, 10 ppm, 11 ppm, 13 ppm, and 7 ppm, respectively, and all were 20 ppm or less. The total amount of polyvalent metal ions was about 80 ppm, which was 100 ppm or less.

(Example D-12)
The aqueous ink composition of Example D-12 is shown below.

Amount added (%)
Dispersion D12 ... 60.0
Surfinol 485 ... 1.5
TEGmBE ... 3.0
1,2-pentanediol ... 2.0
1,5-pentanediol ... 2.0
Tetraethylene glycol ... 9.0
Dimethyl-2-imidazolidinone ... 2.0
Sodium benzoate 0.1
Triethanolamine 0.7
Ion exchange water ...

  Surfynol 104 (acetylene glycols: manufactured by Air Products)

-Quantification of metal ions A required amount of the water-based ink prepared in Example D-12 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were 16 ppm, 5 ppm, 9 ppm, 5 ppm, 6 ppm, 5 ppm, and 0 ppm (below the present limit value), respectively, and all were 20 ppm or less. The total amount of polyvalent metal ions was about 46 ppm, which was 100 ppm or less.

(Example D-13)
The aqueous ink composition of Example D-13 is shown below.

Amount added (%)
Dispersion D13 ... 50.0
Surfinol 465 ... 0.5
Surfinol TG ... 0.1
TEGmBE ... 2.0
1,2-hexanediol ... 2.0
Glycerin ... 5.0
Triethylene glycol ... 5.0
Trimethylolpropane ... 5.0
Tripropanolamine ... 0.9
Ion exchange water ...

Quantitative determination of metal ions A necessary amount of the water-based ink prepared in Example D-13 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were in the order of 8 ppm, 6 ppm, 7 ppm, 9 ppm, 10 ppm, 12 ppm, and 4 ppm, respectively, and all were 20 ppm or less. The total amount of polyvalent metal ions was about 56 ppm, which was 100 ppm or less.

(Example D-14)
The aqueous ink composition of Example D-14 is shown below.

Amount added (%)
Dispersion D14 ... 40.0
Acetylenol EL ... 0.5
Acetylenol EO ... 0.1
TEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 6.0
1,2-pentanediol ... 1.0
Glycerin ... 15.0
Thiodiglycol 2.0
Triethanolamine ... 0.9
Ion exchange water ...

Acetylenol EL (acetylene glycols: Kawaken Fine Chemical Co., Ltd.)

-Quantification of metal ions A required amount of the water-based ink prepared in Example D-14 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were 5 ppm, 7 ppm, 20 ppm, 3 ppm, 2 ppm, 2 ppm, and 0 ppm (less than the detection limit value), respectively, and all were 20 ppm or less. The total amount of polyvalent metal ions was about 39 ppm, which was 100 ppm or less.

(Comparative Example D-1)
In Comparative Example D-1, as in Example D-1, Raven C (produced by Colombian Carbon Co.), which is a carbon black pigment, was dispersed using Solsperse 27000 (produced by Avicia) as a dispersant.
15 parts of Raven C, 4 parts of Solsperse 27000 (Avisia), 4 parts of diethanolamine, 0.5 part of 2-propanol, and 76.5 parts of ion-exchanged water for 2 hours using a bead mill minizeta (manufactured by Ajisawa Corporation) Dispersion treatment was performed to make dispersion liquid D15 used in Comparative Example D-1.
The aqueous ink composition of Comparative Example D-1 is shown below.

Amount added (%)
Dispersion D15 <120> ... 7.0
Glycerin ... 15.0
Dispersant ... 3.0
Nonionic surfactant ... 1.0
Ion exchange water ...

Nonionic surfactant: Neugen EA160 (Daiichi Kogyo Seiyaku Co., Ltd.)

Quantitative determination of metal ions A necessary amount of the water-based ink prepared in Comparative Example D-1 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were 68 ppm, 52 ppm, 72 ppm, 51 ppm, 54 ppm, 52 ppm, and 50 ppm, respectively, and each was 50 ppm or more. The total amount of polyvalent metal ions was about 399 ppm, greatly exceeding 200 ppm.

(Comparative Example D-2)
In Comparative Example D-2, the dispersion D1 was used in the same manner as in Example D-1. Further, in Comparative Example D-2, a water-based ink was prepared intentionally using water containing polyvalent metal ions.
The aqueous ink composition of Comparative Example D-2 is shown below.

Amount added (%)
Dispersion D1 ... 40.0
Ethylene glycol ... 5.0
Glycerin ... 10.0
Nonionic surfactant ... 1.0
Multivalent metal ion-containing water

Quantitative determination of metal ions A required amount of the water-based ink prepared in Comparative Example D-2 was taken out, and the amount of metal ions in the water-based ink was measured by the same method as in Example D-1. Si, Ca, Mg, Fe , Cr, Ni, and Zr were in order of 110 ppm, 105 ppm, 118 ppm, 103 ppm, 101 ppm, 108 ppm, and 103 ppm, respectively, greatly exceeding 50 ppm and 100 ppm or more. The total amount of polyvalent metal ions was about 748 ppm, greatly exceeding 200 ppm.
Table 20 shows the bleeding evaluation results when characters are printed as the printing evaluation results. In Table 20, A is very good, B is good, C is bad, and D is very bad.

As is apparent from the results in Table 20, the water-based ink used in the comparative example has poor print quality, and it can be seen that the print quality is good when the water-based ink of the present invention is used.
In addition, these printing evaluation was performed by using Seiko Epson Corporation water-based inkjet printer PM-900C. The papers used for these evaluations are commercially available papers such as Conqueror paper, Faborit paper, Modo Copy paper, Rapid Copy paper, EPSON EPP paper, Xero.
x 4024 paper, Xerox 10 paper, Neenha Bond paper, Rcopy 6200 paper, Yamayuri paper, XeroxR paper.

As described above, in the present invention, it is possible to provide a high-quality and practical water-based ink suitable for water-based inkjet recording in which bleeding of a printed image on a recording medium such as paper is reduced.
In addition, the water-based inks of Examples D-1 to 14 and Comparative Examples D-1 and D-2 were placed in a glass sample bottle and sealed, and then left at 60 ° C./1 week and −20 ° C./1 week, respectively. Table 21 shows the results of examining the generated foreign matter and physical properties (viscosity and surface tension) of the aqueous ink before and after.
The amount of foreign matter generated is the amount of foreign matter after standing / initial amount of foreign matter, the viscosity is the viscosity after standing / initial viscosity, the surface tension is the value of surface tension after standing / initial surface tension, and the discharge stability is Seiko Epson Corporation Using the company's water-based inkjet printer PM-900C, 200 pages are continuously printed on A4 version Xerox P paper. A is printed with no printing disorder, B is printed with less than 10 printing disturbances, 10 is printed with 10 or more printing positions. A sample having a printing disorder of less than one location was designated as C, and a sample having printing irregularities of 100 or more locations was designated as D.

As can be seen from the results of Tables 20 and 21, the aqueous ink using the dispersion according to the present invention has good print quality and is excellent in ejection stability and storage stability, and is suitable for aqueous inkjet recording. It turns out that it becomes. Further, since a pigment is preferably used as the colorant, the water resistance has an effect that the printed matter is superior to the case where a normal dye is used. In addition, the function of the polymer that coats the colorant can be freely changed by the polymerization monomer and other reactants, so it can have various functions (light resistance, gas resistance, colorability, glossiness, fixability, etc.). It also has the effect of being able to. When conventional dispersants are used as in the past, the dispersants are basically weakly adsorbed by the colorant and have a weak adsorption force, causing partial desorption. Since the viscosity is increased by the agent, the amount of the colorant added is limited, and it is difficult to obtain sufficient color development.

[Example E]
Next, examples of another preferred embodiment e according to the present invention will be described.
In addition, the Example described below does not limit the scope of the present invention.
(Measurement method of aromatic ring amount, pigment: polymer ratio, average particle diameter, polyvalent anion amount, and surface tension)
Each measured value (amount of aromatic ring, pigment: polymer ratio, average particle diameter, amount of polyvalent anion, surface tension) obtained in this example was measured by the following method.

"Measurement of the amount of aromatic rings"
A part of the dispersion polymer solution obtained in each example or comparative example was taken out, the solvent component was distilled off, and only the polymer component was taken out, dissolved in DMSO-d ₆ , ¹³ C-NMR and ¹ H-NMR ( The amount of aromatic rings in the polymer was measured using Bruker (Germany AMX400).
“Measurement of pigment: polymer ratio”
A part of the dispersion obtained in each Example or Comparative Example was taken out, 0.1 mol / l concentration HCl was added, and only the dispersion was acidified, and the dry weight was measured. Next, the pigment: polymer weight ratio was calculated by taking out only the dispersed polymer by Soxhlet extraction using acetone and measuring the dry weight.

"Measurement of average particle size"
Dilute with ion-exchanged water so that the dispersion concentration of the water-based ink obtained in each Example or Comparative Example is 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement varies slightly depending on the water-based ink). The average particle size of the dispersed particles at 20 ° C. was measured with a particle size distribution meter (DLS-800 manufactured by Otsuka Electronics Co., Ltd.).
"Measurement of polyvalent anion content"
A necessary amount of the water-based ink obtained in each Example or Comparative Example was taken out and centrifuged by a centrifugal ultrafiltration device (C-15; Millipore). As the filter, type NMWL10000 was used, and the centrifugation conditions were 2500 G × 60 minutes. The amount of polyvalent anion was measured for the obtained filtrate by an ion chromatography method (column ionPac AS12A; Nippon Dionex Corporation DX-500).

"Measurement of surface tension"
The surface tension at 20 ° C. of the water-based ink obtained in each example or comparative example was measured with a surface tension meter (CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.).

<Example E-1>
(1) Production of liquid dispersion: Dispersion E1
For the production of the dispersion E1 used in Example E-1, a carbon black pigment, color black FW18 (manufactured by Degussa), which is an inorganic pigment, was used.
First, after replacing the reactor equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel with nitrogen, 22 parts of styrene, 5 parts of α-methylstyrene, 15 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2.5 parts of acrylic acid , Added with 0.3 parts of t-dodecyl mercaptan and heated to 70 ° C., separately prepared 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and azobisisobuty The dispersion polymer was polymerized while dropping 3 parts of nitrile into the dropping funnel and dropping into the reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.

A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 59%.
40 parts of the above dispersion polymer solution, 30 parts of carbon black pigment Color Black FW18 (manufactured by Degussa), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 35 parts of methyl ethyl ketone are mixed and dispersed with a homogenizer for 30 minutes or more. Then, 350 parts of ion exchange water is added and dispersed for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, filtration and washing are repeated using a Buchner funnel. Next, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added to the filtered pigment-encapsulating resin dispersion while stirring to adjust the pH to 7.5, and then filtered with a filter having an average pore diameter of 0.5 μm. By filtering, a dispersion E1 containing 20% of the dispersion E1 (a dispersion in which a carbon black pigment was included by a polymer having an aromatic ring content of 59%) was obtained.
Table 22 shows the pigment used in dispersion E1, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Preparation of water-based ink In Example E-1, the dispersion E1 obtained in Example E-1 (1), Olphine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.) which is an acetylene glycol surfactant. Diethylene glycol monobutyl ether which is alkylene glycol monoalkyl ether and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion E1 was added so that the content of the dispersion E1 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element E1 measured by the method described in "Measurement of Average Particle Size" above.
In addition, ion exchange water added as “remaining amount” in the aqueous ink composition of Example E-1 below is used to prevent corrosion of water-based inks in order to prevent corrosion of Proxel XL-2 and aqueous inkjet head members. In order to reduce the influence of benzotriazole and metal ions in the aqueous ink system, the EDTA · 2Na salt should be 0.01%, 0.01%, and 0.02%, respectively, based on the total weight of the aqueous ink. What was added was used.

Dispersion E1 <120> ... 8.0%
Olphine E1010 ... 0.5%
Diethylene glycol monobutyl ether ... 3.0%
1,2-pentanediol ... 2.5%
Diethylene glycol ... 3.0%
Glycerin ... 11.5%
Trimethylolpropane ... 6.0%
Tripropanolamine ... 0.3%
Ion exchange water ...

(3) Measurement of amount of polyvalent anion The aqueous ink prepared in Example E-1 (2) was measured by the method described in "Measurement of amount of polyvalent anion". Was 640 ppm. Details of the measurement results are shown in Table 24.

(4) Printing Evaluation For the printed image evaluation, an aqueous inkjet printer PM-950C (manufactured by Seiko Epson Corporation) that discharges aqueous ink by an aqueous inkjet head using a piezoelectric element (piezo element) was used. The printing evaluation of the water-based ink adjusted in -1 (2) was performed.
As evaluation papers, (a) Conqueror paper, (b) Reymat paper, (c) Mode Copy paper, (d) Rapid Copy paper, (e) Xerox P paper , (F) Xerox 4024 paper, (g) Xerox 10 paper, (h) Neenha Bond paper, (i) Riccopy 6200 paper, and (j) Hammer mill Copy Plus paper.
In addition, evaluation was performed visually and was performed based on the following evaluation criteria.

A: No blur is seen in the characters at all points.
B: Slight bleeding is observed with characters of 5 points or less (practical level).
C: Characters of 5 points or less appear thick due to bleeding.
D: The bleeding is remarkable and characters of 5 points or less cannot be distinguished.

  Table 23 shows the results of the print evaluation.

(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example E-1 (4), 200 pages are continuously printed on A4 size Xerox P paper, and the disorder of printing is observed. The ejection stability was evaluated.
In addition, evaluation was performed visually and was performed based on the following evaluation criteria.

A: Printing disorder does not occur at all.
B: Printing disorder was observed, but the number was less than 10 (practical level).
C: There is printing disorder in the range of 10 or more and less than 100.
D: Disturbance of printing occurred at 100 locations or more.

  Table 24 shows the results of the discharge stability evaluation.

(6) Storage stability evaluation The water-based ink prepared in Example E-1 (2) was placed in a glass bottle and sealed, then left at 60 ° C./1 week and −20 ° C./1 week, respectively. The generated foreign matter and physical property value fluctuation (viscosity, surface tension) were evaluated.
The evaluation was performed based on the following evaluation criteria.

A: The ratio of the amount of foreign matter / physical properties after standing at 60 ° C. or −20 ° C. to that before standing is in the range of 0.99 to 1.01.
B: The ratio is in the range of 0.95 to 0.99, or 1.01 to 1.05 (practical level).
C: The ratio is in the range of 0.90 to 0.95, or 1.05 to 1.10.
D: Ratio is less than 0.90 or greater than 1.10.

  Table 24 shows the storage stability evaluation results.

<Example E-2>
(1) Production of dispersion: Dispersion E2
For the production of the dispersion E2 used in Example E-2, an insoluble monoazo yellow pigment (CI Pigment Yellow 74), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 12 parts of styrene, 9 parts of lauryl methacrylate, and 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 3 parts of methacrylic acid, 0.3 part of mercaptoethanol and heated to 70 ° C., separately prepared 25 parts of styrene, 30 parts of lauryl methacrylate, Methoxy polyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) 15 parts, isobutyl methacrylate macromer (AW-6S; manufactured by Toagosei Co., Ltd.) 15 parts, methacrylic acid 10 parts, methyl ethyl ketone 20 parts, mercaptoethanol 1 While over 4 hours to put 0 parts to a dropping funnel was added dropwise to the reaction vessel and the dispersed polymer is the polymerization reaction. Next, methyl ethyl ketone was added to the reaction vessel to prepare a 35% concentration dispersion polymer solution.

  A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 25%.

  40 parts of the above dispersion polymer solution, 30 parts of an insoluble monoazo yellow pigment (CI Pigment Yellow 74) as an organic pigment, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed, and 30 parts are mixed with a homogenizer. Disperse for at least minutes, add 380 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore diameter of 5 μm to obtain dispersion A2 (insoluble monoazo A dispersion E2 containing 20% of a dispersion in which a yellow pigment was included by a polymer having an aromatic ring content of 25% was obtained.

  Table 22 shows the pigment used in the dispersion E2, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example E-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

2) Preparation of water-based ink In Example E-2, the dispersion E2 obtained in Example E-2 (1), Surfynol 440 (produced by Air Products Co., Ltd.), which is an acetylene glycol surfactant, and Olfine are used. STG (manufactured by Nissin Chemical Industry Co., Ltd.), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion E2 was added so that the content of the dispersion E2 was 7.0%. The value in <> indicates the average particle size (unit: nm) of Dispersing Element E2 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example E-2 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example E-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion E2 <120> ... 7.0%
Surfynol 440 ... 0.2%
Olphine STG ... 0.2%
Triethylene glycol monobutyl ether ... 3.0%
1,2-pentanediol ... 2.0%
2-Pyrrolidone ... 3.0%
Glycerin ... 13.5%
Trimethylolethane ... 5.0%
Triethanolamine ... 0.1%
Ion exchange water ...

(3) Measurement of amount of polyvalent anion The aqueous ink prepared in Example E-2 (2) was measured by the method described in "Measurement of amount of polyvalent anion". The total amount was 451 ppm. Details of the measurement results are shown in Table 24.
(4) Printing evaluation Aqueous ink prepared in Example E-2 (2) using an aqueous inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example E-1 (4). Using the same evaluation paper as in Example E-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example E-1 (4). The results of printing evaluation are shown in Table 23.

(5) Evaluation of ejection stability Using the same printer and aqueous ink as in Example E-2 (4), the same evaluation method as in Example E-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 24.
(6) Storage Stability Evaluation For the water-based ink prepared in Example E-2 (2), the same evaluation method as in Example E-1 (6) was used, and the same as in Example E-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 24.

<Example E-3>
(1) Production of dispersion: Dispersion E3
For the production of the dispersion E3 used in Example E-3, quinacridone red pigment (CI Pigment Red 122), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 12 parts of styrene, 6 parts of styrene macromer (AS-6; manufactured by Toagosei Co., Ltd.), n-dodecyl methacrylate 3.5 Parts, N, N-dimethylaminoethyl methacrylate 12 parts, methoxypolyethylene glycol methacrylate (NK ester M40G; manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts, azobisisobutyronitrile 0.3 part, and heated to 70 ° C. 15 parts of styrene prepared separately, 8 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 7 parts of n-dodecyl methacrylate, 20 parts of N, N-dimethylaminoethyl methacrylate, methoxypolyethylene glycol methacrylate (NK ester M40G) ; Shin-Nakamura Chemical Co., Ltd.) 30 parts, methyl ether Ketone 50 parts of the dispersion polymer dropwise into the reaction vessel over 4 hours and placed in a dropping funnel and 1.5 parts of azobisisobutyronitrile was polymerized reaction. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 38%.

A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 40%.
40 parts of the above dispersion polymer solution, 25 parts of an organic pigment, quinacridone red pigment (CI Pigment Red 122), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 40 parts of methyl ethyl ketone are mixed, and 30 minutes with a homogenizer. Dispersion treatment is performed as described above, and 380 parts of ion exchange water is added and further dispersed for 1 hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm, whereby dispersion E3 (quinacridone red Dispersion E3 containing 20% of a dispersion in which the pigment was covered with a polymer having an aromatic ring content of 40% was obtained.

  Table 22 shows the pigment used in dispersion E3, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example E-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example E-3, the dispersion E3 obtained in Example E-3 (1) above, Olphine E1010 (made by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant. And Surfynol 104PG50 (produced by Air Products), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-hexanediol which is 1,2-alkylene glycol. A specific composition is shown below.
In preparing the water-based ink, the dispersion E3 was added so that the content of the dispersion E3 was 7.5%. The value in <> shows the average particle size (unit: nm) of Dispersing Element E3 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the water-based ink composition of Example E-3 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example E-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion E3 <140> ... 7.5%
Olphin E1010 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.1%
Surfinol 104PG50 ... 0.4%
Triethylene glycol monobutyl ether ... 1.0%
1,2-hexanediol ... 2.5%
Triethylene glycol: 2.0%
2-Pyrrolidone ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 4.0%
Glycerin ... 13.8%
Trimethylolpropane ... 6.0%
Ion exchange water ...

(3) Measurement of amount of polyvalent anion The aqueous ink prepared in Example E-3 (2) was measured by the method described in "Measurement of amount of polyvalent anion". The total amount was 557 ppm. Details of the measurement results are shown in Table 24.
(4) Printing Evaluation Regarding water-based ink prepared in Example E-3 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example E-1 (4). Using the same evaluation paper as in Example E-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example E-1 (4). The results of printing evaluation are shown in Table 23.

(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example E-3 (4), Example E
-1 (5), the ejection stability was evaluated according to the same evaluation criteria as in Example E-1 (5). The results of the discharge stability evaluation are shown in Table 24.
(6) Storage Stability Evaluation For the water-based ink prepared in Example E-3 (2), the same evaluation method as in Example E-1 (6) was used, as in Example E-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 24.

<Example E-4>
(1) Production of dispersion: Dispersion E4
For the production of the dispersion A4 used in Example E-4, a phthalocyanine blue pigment (CI Pigment Blue 15: 4), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 20 parts of styrene, 9 parts of lauryl methacrylate, and 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 10 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 n-dodecyl mercaptan And heated to 70 ° C., separately prepared 25 parts of styrene, 30 parts of lauryl methacrylate, 20 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), isobutyl methacrylate macromer (AW-6S; Toa) Synthetic strain 15 parts), 15 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 20 parts of methyl ethyl ketone, 1.5 parts of n-dodecyl mercaptan are placed in the dropping funnel and reacted for 4 hours. The dispersion polymer was subjected to a polymerization reaction while dropping into the container. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.

A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 46%.
40 parts of the above dispersion polymer solution, 40 parts of an organic pigment phthalocyanine blue pigment (CI Pigment Blue 15: 4), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed together. Disperse for 30 minutes or more, add 350 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion E4 (phthalocyanine blue Dispersion E4 containing 20% of a dispersion in which the pigment was covered with a polymer having an aromatic ring content of 46% was obtained.

  Table 22 shows the pigment used in dispersion E4, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example E-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example E-4, the dispersion E4 obtained in Example E-4 (1), acetylenol E100 (produced by Kawaken Fine Chemical Co., Ltd.), which is an acetylene glycol surfactant, Propylene glycol monobutyl ether which is alkylene glycol monoalkyl ether and 1,2-hexanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparation of the water-based ink, the dispersion E4 was added so that the content of the dispersion E4 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element E4 measured by the method described in "Measurement of Average Particle Size" above.
In the water-based ink composition of Example E-4 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example E-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion E4 <100> ... 8.0%
Acetylenol E100 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5%
Propylene glycol monobutyl ether ... 3.0%
1,2-hexanediol ... 1.0%
Triethylene glycol ... 3.0%
Glycerin ... 13.8%
Trimethylolpropane ... 5.2%
Tripropanolamine 0.2%
Ion exchange water ...

(3) Measurement of amount of polyvalent anion The aqueous ink prepared in Example E-4 (2) was measured by the method described in "Measurement of amount of polyvalent anion". The total amount was 563 ppm. Details of the measurement results are shown in Table 24.
(4) Printing evaluation Aqueous ink prepared in Example E-4 (2) using an aqueous inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example E-1 (4). Using the same evaluation paper as in Example E-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example E-1 (4). The results of printing evaluation are shown in Table 23.

(5) Evaluation of ejection stability Using the same printer and aqueous ink as in Example E-4 (4), the same evaluation method as in Example E-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 24.
(6) Storage Stability Evaluation For the water-based ink prepared in Example E-4 (2), the same evaluation method as in Example E-1 (6) was used, as in Example E-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 24.

<Example E-5>
(1) Production of dispersion: Dispersion E5
A perinone orange pigment (CI Pigment Orange 43) was used for the production of the dispersion E5 used in Example E-5. Otherwise, in the same manner as described in Example E-4 (1), 20% of dispersion E5 (dispersion containing a perinone orange pigment with a polymer having an aromatic ring content of 56%) is contained. Dispersion E5 was obtained.
Table 22 shows the pigment used in dispersion A5, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example E-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example E-5, the dispersion E5 obtained in Example E-5 (1), Surfynol 485 and Surfynol TG which are acetylene glycol surfactants (both are air) Products), dipropylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol. A specific composition is shown below.
In preparing the water-based ink, the dispersion E5 was added so that the content of the dispersion E5 was 10.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element E5 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the following Example E-5, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example E-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion E5 <150> ... 10.0%
Surfynol 485 ... 0.5%
Surfinol TG ... 0.2%
Dipropylene glycol monobutyl ether ... 2.0%
1,2-pentanediol ... 2.0%
N-methyl-2-pyrrolidone ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0%
Glycerin ... 11.2%
Trehalose ... 5.8%
Ion exchange water ...

(3) Measurement of amount of polyvalent anion The aqueous ink prepared in Example E-5 (2) was measured by the method described in "Measurement of amount of polyvalent anion". The total amount was 362 ppm. Details of the measurement results are shown in Table 24.
(4) Printing evaluation Aqueous ink prepared in Example E-5 (2) using an aqueous inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example E-1 (4). Using the same evaluation paper as in Example E-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example E-1 (4). The results of printing evaluation are shown in Table 23.

(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example E-5 (4), using the same evaluation method as in Example E-1 (5), the Example E- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 24.
(6) Storage Stability Evaluation For the water-based ink prepared in Example E-5 (2), the same evaluation method as in Example E-1 (6) was used, and the same as in Example E-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 24.

<Example E-6>
(1) Production of dispersion: Dispersion E6
A benzimidazolone brown pigment (CI Pigment Brown 32) was used for the production of the dispersion E6 used in Example E-6. Otherwise, in the same manner as described in Example E-4 (1), 20% of dispersion E6 (dispersion containing benzimidazolone brown pigment by a polymer having an aromatic ring content of 69%) is contained. A dispersion E6 was obtained.
Table 22 shows the pigment used in dispersion E6, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example E-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example E-6, the dispersion E6 obtained in Example E-6 (1), Surfynol 420 which is an acetylene glycol surfactant, and alkylene glycol monoalkyl ether are used. Some diethylene glycol monobutyl ether was used. A specific composition is shown below.
In preparing the water-based ink, the dispersion E6 was added so that the content of the dispersion E6 was 5.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element E6 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the following Example E-6, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example E-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion E6 <140> ... 5.0%
Surfynol 420 ... 0.1%
Diethylene glycol monobutyl ether ... 3.0%
1,6-hexanediol ... 2.0%
Tetraethylene glycol ... 5.5%
Glycerin ... 13.5%
Triethanolamine 0.5%
Ion exchange water ...

(3) Measurement of polyvalent anion amount The aqueous ink prepared in Example E-6 (2) was measured by the method described in "Measurement of polyvalent anion amount". The total amount was 695 ppm. Details of the measurement results are shown in Table 24.
(4) Printing evaluation Aqueous ink prepared in Example E-6 (2) using an aqueous inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example E-1 (4). Using the same evaluation paper as in Example E-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example E-1 (4). The results of printing evaluation are shown in Table 23.

(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example E-6 (4), using the same evaluation method as in Example E-1 (5), the Example E- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 24.
(6) Storage Stability Evaluation For the water-based ink prepared in Example E-6 (2), the same evaluation method as in Example E-1 (6) was used, as in Example E-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 24.

<Example E-7>
(1) Production of dispersion: Dispersion E7
In the production of the dispersion E7 used in Example E-7, quinacridone violet pigment (CI Pigment Bio Red 19) was used as an organic pigment. Otherwise, dispersion containing 20% dispersion E7 (dispersion containing quinacridone violet pigment with a polymer having an aromatic ring content of 21%) in the same manner as described in Example E-4 (1) above A liquid E7 was obtained.
Table 22 shows the pigment used in dispersion E7, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example E-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example E-7, the dispersion E7 obtained in Example E-7 (1), Surfynol 61 and Surfynol TG which are acetylene alcohol surfactants (both are air) Products), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2 alkylene glycol. A specific composition is shown below.
In preparing the water-based ink, the dispersion E7 was added so that the content of the dispersion E7 was 6.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element E7 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example E-7 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example E-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion E7 <120> ... 6.0%
Surfinol 61 ... 0.3%
Surfynol TG ... 0.1%
Triethylene glycol monobutyl ether ... 1.5%
1,2-pentanediol ... 2.0%
Diethylene glycol ... 2.0%
Thiodiglycol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 4.0%
Glycerin ... 12.6%
Trimethylolethane ... 7.0%
Ion exchange water ...

(3) Measurement of amount of polyvalent anion The aqueous ink prepared in Example E-7 (2) was measured by the method described in “Measurement of amount of polyvalent anion”. The total amount was 540 ppm. Details of the measurement results are shown in Table 24.
(4) Printing Evaluation About water-based ink prepared in Example E-7 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example E-1 (4). Using the same evaluation paper as in Example E-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example E-1 (4). The results of printing evaluation are shown in Table 23.

(5) Evaluation of ejection stability Using the same printer and aqueous ink as in Example E-7 (4), the same evaluation method as in Example E-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 24.
(6) Storage Stability Evaluation For the water-based ink prepared in Example E-7 (2), the same evaluation method as in Example E-1 (6) was used, and the same as in Example E-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 24.

<Example E-8>
(1) Production of dispersion: Dispersion E8
For the production of the dispersion E8 used in Example E-8, a phthalocyanine green pigment (CI Pigment Green 7) as an organic pigment was used. Otherwise, a dispersion containing 20% of dispersion E8 (dispersion containing a phthalocyanine green pigment with a polymer having an aromatic ring content of 30%) in the same manner as described in Example E-1 (1). A liquid E8 was obtained.
Table 22 shows the pigment used in dispersion E8, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example E-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example E-8, the dispersion E8 obtained in Example E-8 (1) above, Olfine E1010 (made by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant. And Surfynol 104 (produced by Air Products Co., Ltd.), dipropylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion E8 was added so that the content of the dispersion E8 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element E8 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the following Example E-8, ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example E-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion E8 <110> ... 8.0%
Olfine E1010 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.3%
Surfinol 104 ... 0.1%
Dipropylene glycol monobutyl ether ... 1.0%
1,2-Pentanediol ... 3.0%
Triethylene glycol: 2.0%
Thiodiglycol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 4.0%
Glycerin ... 13.8%
Trimethylolpropane ... 6.0%
Triethanolamine ... 0.1%
Ion exchange water ...

(3) Measurement of amount of polyvalent anion The aqueous ink prepared in Example E-8 (2) was measured by the method described in "Measurement of amount of polyvalent anion". The total amount was 798 ppm. The measurement results are shown in Table 24.
(4) Printing evaluation Aqueous ink prepared in Example E-8 (2) using an aqueous inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example E-1 (4). Using the same evaluation paper as in Example E-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example E-1 (4). The results of printing evaluation are shown in Table 23.

(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example E-8 (4), the same evaluation method as in Example E-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 24.
(6) Storage Stability Evaluation For the water-based ink prepared in Example E-8 (2), the same evaluation method as in Example E-1 (6) was used, and the same as in Example E-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 24.

<Comparative Example E-1>
(1) Production of dispersion: Dispersion E9
In this comparative example E-1, similarly to the example E-1 (1), the carbon black pigment color black FW18 (manufactured by Degussa Co., Ltd.), which is an inorganic pigment, was used, and the dispersion used in this comparative example E-1 was used. Liquid E9 was produced.
However, in this comparative example E-1, the filtration and washing by the Buchner funnel carried out in Example E-1 (1) were not carried out.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was purged with nitrogen, and then 25 parts of styrene, 5 parts of α-methylstyrene, 15 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t -0.5 part of dodecyl mercaptan was added and heated to 60 ° C in this comparative example. Separately, 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile were placed in a dropping funnel, and this comparison was made while dropping into the reaction vessel. In the example, the dispersion polymer was polymerized in 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.

A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 40%.
40 parts of the above dispersion polymer solution, 30 parts of carbon black pigment Color Black FW18 (manufactured by Degussa), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 35 parts of methyl ethyl ketone are mixed and dispersed with a homogenizer for 30 minutes or more. Then, 350 parts of ion exchange water is added and dispersed for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, in this comparative example, filtration and washing with a Buchner funnel were not carried out. Is appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore diameter of 5 μm to obtain Dispersion E9 (a dispersion in which a carbon black pigment is contained by a polymer having an aromatic ring content of 40%) ) 20% was obtained.
Table 22 shows the pigment used in dispersion E9, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Adjustment of water-based ink In this comparative example E-1, the water-based ink was adjusted using the dispersion liquid E9 obtained by the said comparative example E-1 (1). A specific composition is shown below.
In preparing the water-based ink, the dispersion E9 was added so that the content of the dispersion E9 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element E9 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the present Comparative Example E-1 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example E-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion E9 <140> ... 8.0%
Nonionic surfactant ... 1.0%
Ethylene glycol ... 5.0%
Glycerin ... 15.0%
Ion exchange water ...

  In the above composition, Epan 450 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of polyvalent anion amount The aqueous ink prepared in Comparative Example E-1 (2) was measured by the method described in "Measurement of polyvalent anion amount". The total amount was 1054 ppm. Details of the measurement results are shown in Table 24.
(4) Printing Evaluation Regarding water-based ink prepared in Comparative Example E-1 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example E-1 (4). Using the same evaluation paper as in Example E-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example E-1 (4). The results of printing evaluation are shown in Table 23.

(5) Evaluation of ejection stability Using the same printer and water-based ink as in Comparative Example E-1 (4), the same evaluation method as in Example E-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 24.
(6) Storage Stability Evaluation For the water-based ink prepared in Comparative Example E-1 (2), the same evaluation method as in Example E-1 (6) was used, and the same as in Example E-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 24.

<Comparative Example E-2>
(1) Production of dispersion: Dispersion E10
In the production of Dispersion E10 used in Comparative Example E-2, organic pigment phthalocyanine green pigment (CI Pigment Green 7) was dispersed using Solsperse 27000 (manufactured by Avicia Co., Ltd.) which is a dispersion resin. .
C. I. 15 parts of Pigment Green 7, 5 parts of Solsperse 27000, 5 parts of diethanolamine, 0.5 part of 2-propanol, and 74.5 parts of ion-exchanged water were dispersed for 2 hours with a bead mill minizeta (manufactured by Ajisawa Co., Ltd.). The dispersion E10 used in Comparative Example E-2 containing 20% of the dispersion E10 (pigment: 15%, dispersion resin: 5%) was obtained.

(2) Adjustment of water-based ink In this comparative example E-2, water-based ink was adjusted using the dispersion liquid E10 obtained by the said comparative example E-2 (1). The specific composition of this comparative example is shown below.
In preparing the water-based ink, the dispersion E10 was added so that the content of the dispersion E10 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element E10 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the present Comparative Example E-2 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink as in Example E-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion E10 <150> ... 8.0%
Nonionic surfactant ... 1.0%
Ethylene glycol ... 5.0%
Glycerin ... 15.0%
Ion exchange water ...

  In the above composition, Neugen EA160 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of amount of polyvalent anion The aqueous ink prepared in Comparative Example E-2 (2) was measured by the method described in "Measurement of amount of polyvalent anion". The total amount was 1585 ppm. Details of the measurement results are shown in Table 24.
(4) Printing Evaluation Regarding water-based ink prepared in Comparative Example E-2 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example E-1 (4). Using the same evaluation paper as in Example E-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example E-1 (4). The results of printing evaluation are shown in Table 23.

(5) Evaluation of ejection stability Using the same printer and water-based ink as in Comparative Example E-2 (4), the same evaluation method as in Example E-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 24.
(6) Storage Stability Evaluation For the water-based ink prepared in Comparative Example E-2 (2), the same evaluation method as in Example E-1 (6) was used, and the same as in Example E-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 24.

As is apparent from the results of Tables 22 and 23, it is understood that the water-based ink used in the comparative example has poor print quality, and that the print quality is good when the water-based ink according to the present invention is used.
As described above, by using the water-based ink cartridge of the present invention, it is possible to obtain a high-quality print record in which bleeding is reduced for any paper type.

As is apparent from the results in Table 24, the amount of polyvalent anions in the liquid component of the water-based ink is set to 80.
It can be seen from Table 23 that the water-based ink according to the present invention suppressed to 0 ppm or less has excellent ejection stability and storage stability, and the printing quality is excellent from Table 23. It can also be seen that when the amount of the polyvalent anion is 600 ppm or less, the discharge stability and the storage stability are remarkably excellent. On the other hand, when the amount of polyvalent anion exceeds 1000 ppm as in the comparative example, it can be seen that the print quality, ejection stability, and storage stability are not at practical levels.
As can be seen from the above results, it can be seen that by using the water-based ink according to the present invention, good print quality and ejection stability can be obtained, and the storage stability of the water-based ink itself is excellent.

[Example F]
Next, examples of another preferred embodiment (f) according to the present invention will be described.
In addition, the Example described below does not limit the scope of the present invention. In addition, each measured value (amount of aromatic ring, average particle size, amount of monovalent cation, surface tension) obtained in this example was measured by the following method.

"Measurement of aromatic ring quantity"
A part of the dispersion obtained in each example or comparative example was taken out, 0.1 mol / L concentration HCl was added for acid precipitation, and only the dispersed polymer was taken out by Soxhlet extraction method using acetone. DMSO-d By measuring with ¹³ C-NMR and ¹ H-NMR (AMX400 manufactured by Bruker (Germany)) using ₆ , the amount of the aromatic ring relative to the total weight of the dispersed polymer was measured.
"Measurement of average particle size"
Dilute with ion-exchanged water so that the dispersion concentration of the water-based ink obtained in each Example or Comparative Example is 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement is slightly different depending on the water-based ink). The average particle size of the dispersed particles at 20 ° C. was measured with a particle size distribution meter (DLS-800 manufactured by Otsuka Electronics Co., Ltd.). The average particle diameter is shown in <> in nm (nanometer) in <>.

"Measurement of monovalent cation content"
A necessary amount of the water-based ink obtained in each Example or Comparative Example was taken out and centrifuged by a centrifugal ultrafiltration device (C-15; Millipore). As the filter, type NMWL10000 was used, and the centrifugation conditions were 2500 G × 60 minutes. The amount of monovalent cation was measured for the obtained filtrate by the ion chromatography method (column ionPac AS12A; Nippon Dionex Corporation DX-500).
"Measurement of surface tension"
The surface tension at 20 ° C. of the water-based ink obtained in each example or comparative example was measured with a surface tension meter (CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.).

Next, the method for producing a dispersion according to the present invention will be specifically described.
In this example, a pigment is included in a reactive dispersant, and emulsion polymerization is carried out in water in the presence of a catalyst to produce a dispersion.

<< Manufacture of Dispersion (Production Method I) >>
(Dispersion F1)
MA88 (manufactured by Mitsubishi Chemical Corporation), which is a carbon black pigment, was used for the production of dispersion F1. In a reaction vessel equipped with an ultrasonic generator, a stirrer, a dropping device, a water-cooled reflux condenser, and a temperature controller, 25 parts of carbon black pigment (hereinafter, simply indicated as part indicates part by weight), a polymerizable surfactant 6 parts of Adeka Soap SE-10N manufactured by Asahi Denka Co., Ltd. was added to 180 parts of ion-exchanged water, and ultrasonic waves were applied for 4 hours.
Next, a methyl ethyl ketone solution of 5 parts of styrene, 1.7 parts of α-methylstyrene and 0.5 part of azobisisobutyronitrile was further added, and a polymerization reaction was carried out at 60 ° C. for 8 hours. The pigment contained in the polymer was removed by centrifugal filtration, and further filtered through a 5 μm membrane filter to remove coarse particles.

Next, after the pigment solution contained in the polymer is loosened with a homogenizer, a methylethylketone solution of the pigment described above is further added to the reaction vessel, and 30 parts of ion-exchanged water and 0.05 part of sodium lauryl sulfate are added. 0.5 parts of potassium persulfate as a part and a polymerization initiator were added, and a nitrogen atmosphere was maintained at 70 ° C. Next, a mixed solution containing 25 parts of styrene, 1 part of tetrahydrofurfuryl methacrylate, 15 parts of butyl methacrylate, 5 parts of triethylene glycol methacrylate and 0.02 part of t-dodecyl mercaptan was dropped and reacted, and then a rotary evaporator was used. Methyl ethyl ketone and a part of water were distilled off, adjusted to pH 8.5 using a sodium hydroxide aqueous solution as a neutralizing agent, and then filtered through a 0.3 μm filter to obtain dispersion F1.
With respect to Dispersion F1, the ratio of aromatic rings to the total weight of the dispersed polymer was 39% when measured by the method described in "Measurement of Aromatic Ring Amount" above.

Dispersions F2 to F7 were obtained by the same method (Production Method I) as Dispersion F1. Dispersion F2 uses a phthalocyanine blue pigment (CI Pigment Blue 15: 4), Dispersion F3 uses an insoluble monoazo yellow pigment (CI Pigment Yellow 74), and Dispersion F4 uses an isoindolinone pigment ( CI Pigment Yellow 109), Dispersion F5 using anthraquinone yellow pigment (CI Pigment Yellow 147), and Dispersion F6 using benzimidazolone yellow pigment (CI Pigment Yellow 180) Dispersion F7 used was a mixture of quinacridone red pigment (CI Pigment Red 122) and dioxazine violet pigment (CI Pigment Bio Red 23) at a ratio of 9: 1.
In Table 25, it shows about the pigment of the dispersion F1-F7 manufactured with the manufacturing method I, the neutralizer, the ratio of a pigment and a dispersion polymer, and the amount of aromatic rings.

Next, production of dispersion F8 using a production method different from dispersion F1 will be described. ≪Production of dispersion (Production Method II) ≫
(Dispersion F8)
For the production of Dispersion F8, Color Black FW18 (manufactured by Degussa), which is a carbon black pigment, was used. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 21 parts of styrene, 5 parts of α-methylstyrene, 16 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t-dodecyl Add 0.3 part of mercaptan and heat to 70 ° C., separately prepared 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile. Was placed in a dropping funnel and the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.

40 parts of the above dispersion polymer solution, 30 parts of color black FW18 (manufactured by Degussa), carbon black, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 35 parts of methyl ethyl ketone are mixed, and stirred for 30 minutes with a homogenizer. Add 350 parts of exchange water and stir for another hour. Then, after the total amount of methyl ethyl ketone and a part of water were distilled off using a rotary evaporator, the mixture was adjusted to pH 7.5 using a mixed solution of aqueous sodium hydroxide and aqueous ammonia as a neutralizing agent, and then 0.3 μm. To obtain a dispersion F8.
With respect to Dispersion F8, the ratio of aromatic rings to the total weight of the dispersed polymer was measured by the method described in the above-mentioned “Measurement of Aromatic Ring Amount” and found to be 56%.

Dispersions F9 to F14 were obtained by the same method (Production Method II) as described above. Dispersion F9 uses an organic pigment phthalocyanine green pigment (CI Pigment Green 7), and Dispersion F10 uses an organic pigment condensed azo yellow pigment (CI Pigment Yellow 128). F11 is an organic pigment azo lake pigment (CI Pigment Red 53: 1), Dispersion F12 is an organic pigment perinone orange pigment (CI Pigment Orange 43), and Dispersion F13 is organic. The pigment benzimidazolone brown pigment (CI Pigment Brown 32) was used, and the dispersion F14 was an organic pigment, perylene red pigment (CI Pigment Red 178).
Table 26 shows the pigments, neutralizers, ratios of the pigment to the dispersion polymer, and the amount of aromatic rings of dispersions F8 to F14 produced by Production Method II.

(Preparation example of water-based ink)
Hereinafter, examples of the composition of the water-based ink suitable for the water-based ink jet recording will be described. The addition amount of each dispersion is shown as the solid content concentration (total amount of pigment and dispersion polymer surrounding it) converted by weight. <> Indicates the particle size of the pigment in nm units. The ion-exchanged water added as the remaining amount in this embodiment includes Proxel XL-2 for preventing corrosion of aqueous ink, benzotriazole for preventing corrosion of the aqueous inkjet head member, and metal ions in the aqueous ink system. EDTA (ethylenediaminetetraacetic acid) for reducing the influence was added and stirred so that the concentrations in the aqueous ink were 0.05%, 0.02%, and 0.01%, respectively.

(Example F-1)
The aqueous ink composition of Example F-1 is shown below.

Amount added (%)
Dispersion F1 ... 8.0
Olfin E1010 ... 0.5
TEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
1,5-pentanediol ... 2.5
Glycerin ... 9.0
Triethanolamine ... 0.5
Ion exchange water ...

  In the above composition, TEGmBE represents triethylene glycol monobutyl ether, and Orphine E1010 represents an acetylene glycol surfactant (trade name; manufactured by Nissin Chemical Industry Co., Ltd.).

"Quantification of monovalent cations"
The water-based ink prepared in Example F-1 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 120 ppm, 1300 ppm, 115 ppm, and 80 ppm, respectively. The total amount of monovalent cations was 1615 ppm.

(Example F-2)
The aqueous ink composition of Example F-2 is shown below.

Amount added (%)
Dispersion F2 ... 3.0
Surfinol TG ... 0.3
DEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Dipropylene glycol ... 5.0
Trimethylolethane ... 4.0
Triethanolamine ... 0.1
Ion exchange water ...

  In the above composition, Surfinol TG represents acetylene glycol surfactant (trade name; manufactured by Air Products Co., Ltd.), and DEGmBE represents diethylene glycol monobutyl ether.

"Quantification of monovalent cations"
The water-based ink prepared in Example F-2 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 135 ppm, 460 ppm, 160 ppm, and 710 ppm, respectively. The total amount of monovalent cations was 1465 ppm.

(Example F-3)
The aqueous ink composition of Example F-3 is shown below.

Amount added (%)
Dispersion F3 ... 5.0
Olphine STG ... 0.3
1,2-hexanediol ... 1.0
1,6-hexanezil ... 2.0
Triethylene glycol ... 10.0
Thiodiglycol ... 1.5
Triethanolamine ... 0.3
Potassium hydroxide ... 0.1
Ion exchange water ...

  In the above composition, Olfine STG represents an acetylene glycol surfactant (trade name; manufactured by Nissin Chemical Industry Co., Ltd.).

"Quantification of monovalent cations"
The water-based ink prepared in Example F-3 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 450 ppm, 1050 ppm, 640 ppm, and 240 ppm, respectively. The total amount of monovalent cations was 1920 ppm.

(Example F-4)
The aqueous ink composition of Example F-4 is shown below.

Amount added (%)
Dispersion F4 ... 6.5
Surfinol 104 ... 0.1
TEGmBE ... 3.0
1,2-pentanediol ... 5.0
1,5-pentanediol ... 2.0
Tetraethylene glycol ... 9.0
Dimethyl-2-imidazolidinone ... 2.0
Sodium benzoate 0.1
Triethanolamine 0.7
Ion exchange water ...

  In the above composition, Surfynol 104 represents an acetylene glycol surfactant (trade name; manufactured by Air Products Co., Ltd.).

"Quantification of monovalent cations"
The water-based ink prepared in Example F-4 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 80 ppm, 1390 ppm, 550 ppm, and 190 ppm, respectively. The total amount of monovalent cations was 2210 ppm.

(Example F-5)
The aqueous ink composition of Example F-5 is shown below.

Amount added (%)
Dispersion F5 ... 7.0
DPGmBE ... 2.0
DEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 7.0
Glycerin ... 5.0
Triethylene glycol ... 5.0
Trehalose ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Triethanolamine ... 0.2
LiOH ... 0.1
Ion exchange water ...

  In the above composition, DPGmBE represents dipropylene glycol monobutyl ether.

"Quantification of monovalent cations"
The water-based ink prepared in Example F-5 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 1800 ppm, 260 ppm, 150 ppm, and 250 ppm, respectively. The total amount of monovalent cations was 2460 ppm.

(Example F-6)
The aqueous ink composition of Example F-6 is shown below.

Amount added (%)
Dispersion F6 ... 7.0
Acetylenol EO ... 0.5
TEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
1,2-pentanediol ... 1.0
Glycerin ... 13.0
Thiodiglycol 2.0
2-Pyrrolidone ... 2.0
Triethanolamine ... 0.3
Ion exchange water ...

  In the above composition, acetylenol EO represents an acetylene glycol surfactant (trade name; manufactured by Kawaken Fine Chemical Co., Ltd.).

"Quantification of monovalent cations"
The water-based ink prepared in Example F-6 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ion, sodium ion, potassium ion, and ammonium ion were 460 ppm, 850 ppm, 1050 ppm, and 65 ppm, respectively. The total amount of monovalent cations was 2425 ppm.

(Example F-7)
The aqueous ink composition of Example F-7 is shown below.

Amount added (%)
Dispersion F7 ... 7.2
Surfinol 465 ... 0.5
Surfinol 61 ... 0.5
TEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 6.0
Glycerin ... 15.0
Trimethylolpropane ... 1.0
Trimethylolethane ... 1.0
Triethanolamine ... 0.1
NaOH ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.05
Ion exchange water ...

  In the above composition, Surfynol 465 represents an acetylene glycol surfactant (trade name; manufactured by Air Products Co., Ltd.), and Surfynol 61 represents an acetylene alcohol surfactant (trade name; manufactured by Air Products Co., Ltd.).

"Quantification of monovalent cations"
The water-based ink prepared in Example F-7 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 265 ppm, 500 ppm, 390 ppm, and 595 ppm, respectively. The total amount of monovalent cations was 1750 ppm.

(Example F-8)
The aqueous ink composition of Example F-8 is shown below.

Amount added (%)
Dispersion F8 ... 10.0
Surfinol 420 ... 0.5
PGmBE ... 2.0
DEGmBE ... 10.0
Tetrapropylene glycol ... 5.0
Glycerin ... 7.0
Diethylene glycol ... 5.0
Triethanolamine ... 0.1
NaOH ... 0.1
Ion exchange water ...

  In the above composition, Surfynol 420 represents an acetylene glycol surfactant (trade name; manufactured by Air Products Co., Ltd.), and PGmBE represents propylene glycol monobutyl ether.

"Quantification of monovalent cations"
The water-based ink prepared in Example F-8 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 90 ppm, 1000 ppm, 210 ppm, and 950 ppm, respectively. The total amount of monovalent cations was 2250 ppm.

(Example F-9)
The aqueous ink composition of Example F-9 is shown below.

Amount added (%)
Dispersion F9 ... 5.0
Surfinol 485 ... 1.5
DEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
1,5-pentanediol ... 5.0
Glycerin ... 9.0
1,4-cyclohexanedimethanol ・ 5.0
Triethanolamine ... 0.2
Ion exchange water ...

  In the above composition, Surfynol 485 represents an acetylene glycol surfactant (trade name; manufactured by Air Products Co., Ltd.).

"Quantification of monovalent cations"
The water-based ink prepared in Example F-9 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 950 ppm, 350 ppm, 290 ppm, and 510 ppm, respectively. The total amount of monovalent cations was 2100 ppm.

(Example F-10)
The aqueous ink composition of Example F-10 is shown below.

Amount added (%)
Dispersion F10 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Surfinol TG ... 0.3
DEGmBE ... 10.0
Dipropylene glycol ... 5.0
Triethanolamine ... 0.5
Ion exchange water ...

  In the above composition, Surfinol TG represents acetylene glycol surfactant (trade name; manufactured by Air Products Co., Ltd.), and DEGmBE represents diethylene glycol monobutyl ether.

"Quantification of monovalent cations"
The water-based ink prepared in Example F-10 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 330 ppm, 450 ppm, 250 ppm, and 350 ppm, respectively. The total amount of monovalent cations was 1380 ppm.

(Example F-11)
The aqueous ink composition of Example F-11 is shown below.

Amount added (%)
Dispersion F11 ... 4.5
Olphine STG ... 0.3
1,2-hexanediol ... 2.0
1,6-hexanezil ... 2.0
Diethylene glycol: 7.0
Thiodiglycol ... 1.5
Triethanolamine ... 0.2
Ion exchange water ...

  In the above composition, Olfine STG represents an acetylene glycol surfactant (trade name; manufactured by Nissin Chemical Industry Co., Ltd.).

"Quantification of monovalent cations"
The water-based ink prepared in Example F-11 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ion, sodium ion, potassium ion, and ammonium ion were 465 ppm, 560 ppm, 350 ppm, and 450 ppm, respectively. The total amount of monovalent cations was 1825 ppm.

(Example F-12)
The aqueous ink composition of Example F-12 is shown below.

Amount added (%)
Dispersion F12 ... 6.5
Surfinol 104 ... 0.1
TEGmBE ... 3.0
1,2-pentanediol ... 2.0
1,5-pentanediol ... 2.0
Tetraethylene glycol ... 9.0
Dimethyl-2-imidazolidinone ... 2.0
Sodium benzoate 0.1
Triethanolamine ... 0.5
Ion exchange water ...

  In the above composition, Surfynol 104 represents an acetylene glycol surfactant (trade name; manufactured by Air Products Co., Ltd.).

"Quantification of monovalent cations"
The water-based ink prepared in Example F-12 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 1200 ppm, 480 ppm, 220 ppm, and 90 ppm, respectively. The total amount of monovalent cations was 1950 ppm.

(Example F-13)
The aqueous ink composition of Example F-13 is shown below.

Amount added (%)
Dispersion F13 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Surfinol 465 ... 0.5
Surfinol TG ... 0.1
TEGmBE ... 2.0
1,2-hexanediol ... 2.0
Glycerin ... 5.0
Triethylene glycol ... 5.0
Trimethylolpropane ... 5.0
Tripropanolamine ... 0.1
Ion exchange water ...

"Quantification of monovalent cations"
The water-based ink prepared in Example F-13 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 350 ppm, 380 ppm, 980 ppm, and 290 ppm, respectively. The total amount of monovalent cations was 2000 ppm.

(Example F-14)
The aqueous ink composition of Example F-14 is shown below.

Amount added (%)
Dispersion F14 ... 8.5
Acetylenol EL ... 0.5
Acetylenol EO ... 0.1
TEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 6.0
1,2-pentanediol ... 1.0
Glycerin ... 15.0
Thiodiglycol 2.0
Triethanolamine ... 0.2
Ion exchange water ...

In the above composition, acetylenol EL represents an acetylene glycol surfactant (trade name; manufactured by Kawaken Fine Chemical Co., Ltd.).

"Quantification of monovalent cations"
The water-based ink prepared in Example F-14 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 750 ppm, 890 ppm, 710 ppm, and 100 ppm, respectively. The total amount of monovalent cations was 2450 ppm.

(Comparative Example F-1)
In Comparative Example F-1, Dispersion F1 was used as in Example F-1. Furthermore, in Comparative Example F-1, a water-based ink was prepared using water intentionally containing a large amount of monovalent cations.
The aqueous ink composition of Comparative Example F-1 is shown below.

Amount added (%)
Dispersion F1 ... 8.0
Ethylene glycol ... 5.0
Glycerin ... 10.0
Nonionic surfactant ... 1.0
Monovalent metal ion-containing water

  In the above composition, Epan 450 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

"Quantification of monovalent cations"
The water-based ink prepared in Comparative Example F-1 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 1350 ppm, 1640 ppm, 1090 ppm, and 1100 ppm, respectively. The total amount of monovalent cations was 5180 ppm.

(Comparative Example F-2)
In Comparative Example F-2, similarly to Example F-1, MA88 (manufactured by Mitsubishi Chemical Corporation), which is a carbon black pigment, was dispersed using Solsperse 27000 (manufactured by Avicia) as a dispersant.
Disperse 15 parts of MA88, 5 parts of Solsperse 27000 (manufactured by Avicia), 5 parts of diethanolamine, 0.5 part of 2-propanol, and 74.5 parts of ion-exchanged water with a bead mill mini-zeta (manufactured by Ajisawa Corporation) for 2 hours. Treatment was performed to obtain dispersion F15 used in Comparative Example F-2.
The aqueous ink composition of Comparative Example F-2 is shown below.

Amount added (%)
Dispersion F15 <120> ... 7.0
Glycerin ... 15.0
Dispersant ... 3.0
Nonionic surfactant ... 1.0
Ion exchange water ...

  In the above composition, Neugen EA160 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

"Quantification of monovalent cations"
The water-based ink prepared in Comparative Example F-2 was measured by the method described in “Measurement of monovalent cation amount”.
The amounts of lithium ions, sodium ions, potassium ions, and ammonium ions were 540 ppm, 810 ppm, 220 ppm, and 490 ppm, respectively. The total amount of monovalent cations was 2060 ppm.

Next, printing evaluation was performed for each of the water-based inks of Examples F-1 to 14 and Comparative Examples F-1 and F-2. For printing evaluation, a water-based ink jet printer PM-900C manufactured by Seiko Epson Corporation, which discharges water-based ink with a water-based ink jet head using a piezoelectric element (piezo element), was used as an evaluation paper. Common paper used is Conqueror paper, Favorit paper, Modo Copy paper, Rapid Copy paper, EPSON EPP paper, Xerox 4024 paper, Xerox 10 paper, Nenha Bond paper, Rcopyy 6200 paper, Yamaryo paper, Xerox paper.
Table 27 shows the bleeding evaluation results when characters are printed as the printing evaluation results.
In Table 27, A is very good, B is good, C is bad, and D is very bad.

As is clear from the results in Table 27, it can be seen that the aqueous ink used in the comparative example has poor print quality, and that the print quality is good when the aqueous ink of the present invention is used.
As described above, in the present invention, it is possible to provide a high-quality and practical water-based ink suitable for water-based inkjet recording in which bleeding of a printed image on a recording medium such as paper is reduced.
In addition, storage stability evaluation and ejection stability evaluation were performed for the aqueous inks of Examples F-1 to 14 and Comparative Examples F-1 and F-2.
Storage stability was evaluated by placing each water-based ink in a glass sample bottle and sealing it, and then leaving it at 60 ° C./1 week and −20 ° C./1 week, respectively. , Surface tension).

The amount of foreign matter generated is the amount of foreign matter after standing / initial amount of foreign matter, the viscosity is the viscosity after standing / initial viscosity, and the surface tension is the surface tension after standing / initial surface tension.
Discharge stability evaluation is based on the above-mentioned water-based ink jet printer PM-900C manufactured by Seiko Epson Corporation. A continuous printing of 200 pages on A4 size Xerox P paper is performed. B was 10 or more and less than 100 places and C was printed, and D was printed and printed 100 or more places.
Table 28 shows the quantification result of the monovalent cation, the storage stability evaluation result, and the ejection stability evaluation result of each of the aqueous inks of Examples F-1 to 14 and Comparative Examples F-1 and F2.

  As can be seen from the results in Tables 27 and 28, the water-based ink using the dispersion according to the present invention has good print quality, and is excellent in ejection stability and storage stability. It turns out that it becomes. Further, such a water-based ink can be suitably used for a water-based inkjet head using a piezoelectric element as in the above-described embodiment. Further, since a pigment is preferably used as the colorant, the water resistance has an effect that the printed matter is superior to the case of using a normal dye. In addition, the function of the polymer that coats the colorant can be freely changed by the polymerization monomer and other reactants, so it can have various functions (light resistance, gas resistance, colorability, glossiness, fixability, etc.). It also has the effect of being able to. When conventional dispersants are used as in the past, the dispersants are basically weakly adsorbed by the colorant and have a weak adsorption force, causing partial desorption. Since the viscosity is increased by the agent, the amount of the colorant added is limited, and it is difficult to obtain sufficient color development.

[Example G]
Next, examples of other preferred embodiment (g) according to the present invention will be described, but these do not limit the scope of the present invention. In addition, each measured value (amount of aromatic ring, average particle diameter, amount of monovalent anion, surface tension) obtained in this example was measured by the following method.

"Measurement of aromatic ring quantity"
A part of the dispersion obtained in each example or comparative example was taken out, 0.1 mol / L concentration HCl was added for acid precipitation, and only the dispersed polymer was taken out by Soxhlet extraction method using acetone. DMSO-d By measuring with ¹³ C-NMR and ¹ H-NMR (AMX400 manufactured by Bruker (Germany)) using ₆ , the amount of the aromatic ring relative to the total weight of the dispersed polymer was measured.
"Measurement of average particle size"
Dilute with ion-exchanged water so that the dispersion concentration of the water-based ink obtained in each Example or Comparative Example is 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement differs slightly depending on the ink), The average particle diameter at 20 ° C. of the dispersed particles was measured with a particle size distribution meter (ELS-800 manufactured by Otsuka Electronics Co., Ltd.). The average particle diameter is shown in <> in nm (nanometer) in <>.

"Measurement of monovalent anion amount"
A necessary amount of the water-based ink obtained in each Example or Comparative Example was taken out and centrifuged by a centrifugal ultrafiltration device (C-15; Millipore). As the filter, type NMWL10000 was used, and the centrifugation conditions were 2500 G × 60 minutes. The amount of monovalent anions was measured for the obtained filtrate by an ion chromatography method (column ionPac AS12A; Nippon Dionex Corporation DX-500).
"Measurement of surface tension"
The surface tension at 20 ° C. of the water-based ink obtained in each example or comparative example was measured with a surface tension meter (CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.).

Next, the method for producing a dispersion according to the present invention will be specifically described.
In this example, a pigment is included in a reactive dispersant, and emulsion polymerization is carried out in water in the presence of a catalyst to produce a dispersion.
<< Production of dispersion (Production Method I) >>
(Dispersion G1)
MA7 (manufactured by Mitsubishi Chemical Corporation), which is a carbon black pigment, was used for the production of dispersion G1. In a reaction vessel equipped with an ultrasonic generator, a stirrer, a dropping device, a water-cooled reflux condenser, and a temperature controller, 25 parts of carbon black pigment (hereinafter, simply indicated as part indicates part by weight), a polymerizable surfactant 6 parts of Adeka Soap SE-10N manufactured by Asahi Denka Co., Ltd. was added to 180 parts of ion-exchanged water, and ultrasonic waves were applied for 4 hours.
Next, 5 parts of styrene, 1.7 parts of α-methylstyrene, and azobisisobutyronitrile 0
. 5 parts of methyl ethyl ketone solution was further added and a polymerization reaction was carried out at 60 ° C. for 8 hours. The resulting solution was subjected to centrifugal filtration to remove the pigment contained in the polymer, and further filtered through a 5 μm membrane filter to obtain coarse particles. Was removed.

Next, after the pigment solution contained in the polymer is loosened with a homogenizer, a methylethylketone solution of the pigment described above is further added to the reaction vessel, and 30 parts of ion-exchanged water and 0.05 part of sodium lauryl sulfate are added. 0.5 parts of potassium persulfate as a part and a polymerization initiator were added, and a nitrogen atmosphere was maintained at 70 ° C. Next, a mixed solution containing 25 parts of styrene, 1 part of tetrahydrofurfuryl methacrylate, 15 parts of butyl methacrylate, 5 parts of triethylene glycol methacrylate and 0.02 part of t-dodecyl mercaptan was dropped and reacted, and then a rotary evaporator was used. Methyl ethyl ketone and a part of water were distilled off, adjusted to pH 8.5 using sodium hydroxide aqueous solution as a neutralizing agent, and then filtered through a 0.3 μm filter to obtain dispersion G1.
With respect to Dispersion G1, the ratio of aromatic rings to the total weight of the dispersed polymer was 45% when measured by the method described in "Measurement of Aromatic Ring Amount" above.

Dispersions G2 to G7 were obtained by the same method (Production Method I) as Dispersion G1. Dispersion G2 uses a phthalocyanine blue pigment (CI Pigment Blue 15: 4), Dispersion G3 uses an insoluble monoazo yellow pigment (CI Pigment Yellow 74), and Dispersion G4 uses an isoindolinone pigment ( CI Pigment Yellow 109), Dispersion G5 using anthraquinone yellow pigment (CI Pigment Yellow 147), and Dispersion G6 using benzimidazolone yellow pigment (CI Pigment Yellow 180) Dispersion G7 used was a mixture of quinacridone red pigment (CI Pigment Red 122) and dioxazine violet pigment (CI Pigment Bio Red 23) at 8: 2.
In Table 29, it shows about the pigment of the dispersion G1-G7 manufactured with the manufacturing method I, the neutralizing agent, ratio of a pigment and a dispersion polymer, and the amount of aromatic rings.

Next, production of the dispersion G8 using a production method different from the dispersion G1 will be described. << Production of dispersion (Production Method II) >>
(Dispersion G8)
For the production of the dispersion G8, color black FW18 (manufactured by Degussa), which is a carbon black pigment, was used. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 21 parts of styrene, 5 parts of α-methylstyrene, 16 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t-dodecyl Add 0.3 part of mercaptan and heat to 70 ° C., separately prepared 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile. Was placed in a dropping funnel and the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.

40 parts of the above dispersion polymer solution, 30 parts of color black FW18 (manufactured by Degussa), carbon black, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 35 parts of methyl ethyl ketone are mixed, and stirred for 30 minutes with a homogenizer. Add 350 parts of exchange water and stir for another hour. Then, after the total amount of methyl ethyl ketone and a part of water were distilled off using a rotary evaporator, the mixture was adjusted to pH 7.5 using a mixed solution of aqueous sodium hydroxide and aqueous ammonia as a neutralizing agent, and then 0.3 μm. To obtain a dispersion G8.
With respect to Dispersion G8, the ratio of the aromatic ring to the total weight of the dispersed polymer was measured by the method described in the above-mentioned “Measurement of the amount of aromatic rings” and found to be 56%.

Dispersions G9 to G14 were obtained by the same method (Production Method II) as described above. Dispersion G9 uses a phthalocyanine green pigment (CI Pigment Green 7) as an organic pigment, and Dispersion G10 uses a condensed azo yellow pigment (CI Pigment Yellow 128) as an organic pigment. G11 is an organic pigment azo lake pigment (CI Pigment Red 53: 1), Dispersion G12 is an organic pigment perinone orange pigment (CI Pigment Orange 43), and Dispersion G13 is organic. A benzimidazolone brown pigment (CI Pigment Brown 32) as a pigment was used, and a perylene red pigment (CI Pigment Red 178) as an organic pigment was used as the dispersion G14.
Table 30 shows the pigments, neutralizing agents, the ratio of the pigment to the dispersion polymer, and the amount of aromatic rings of dispersions G8 to G14 produced by Production Method II.

(Inkjet ink preparation example)
Examples of compositions suitable for ink jet recording are shown below for the water-based ink according to the present invention. The addition amount of each dispersion is shown as the solid content concentration (total amount of pigment and dispersion polymer surrounding it) converted by weight. <> Indicates the particle size of the pigment in nm units. In addition, the ion exchange water added as the remaining amount in this embodiment reduces the influence of Proxel XL-2 to prevent ink corrosion, benzotriazole to prevent ink jet head member corrosion, and metal ions in the ink system. EDTA (ethylenediaminetetraacetic acid) was added and stirred so that the concentrations in the ink were 0.05%, 0.02%, and 0.01%, respectively.

(Example G-1)
The ink composition of Example G-1 is shown below.

Amount added (%)
Dispersion G1 8.0
Olphin E1010 0.5
TEGmBE 5.0
1,5-pentanediol 2.5
Glycerin 9.0
Triethanolamine 0.5
Ion exchange water

  In the above composition, TEGmBE represents triethylene glycol monobutyl ether, and Orphine E1010 represents an acetylene glycol surfactant (trade name; manufactured by Nissin Chemical Industry Co., Ltd.).

"Quantification of monovalent anions"
The ink prepared in Example G-1 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 600 ppm, 100 ppm, 115 ppm and 40 ppm, respectively. The total amount of monovalent anions was 855 ppm.

(Example G-2)
The ink composition of Example G-2 is shown below.

Amount added (%)
Dispersion G2 3.0
Surfinol TG 0.3
DEGmBE 5.0
Dipropylene glycol 5.0
Trimethylolethane 4.0
Triethanolamine 0.1
Ion exchange water

  In the above composition, Surfinol TG represents acetylene glycol surfactant (trade name; manufactured by Air Products Co., Ltd.), and DEGmBE represents diethylene glycol monobutyl ether.

"Quantification of monovalent anions"
The ink prepared in Example G-2 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 735 ppm, 90 ppm, 160 ppm and 30 ppm, respectively. The total amount of monovalent anions was 1015 ppm.

(Example G-3)
The ink composition of Example G-3 is shown below.

Amount added (%)
Dispersion G3 5.0
Olfin STG 0.3
1,2-hexanediol 1.0
1,6-hexanediol 2.0
Triethylene glycol 10.0
Thiodiglycol 1.5
Triethanolamine 0.3
Potassium hydroxide 0.1
Ion exchange water

  In the above composition, Olfine STG represents an acetylene glycol surfactant (trade name; manufactured by Nissin Chemical Industry Co., Ltd.).

"Quantification of monovalent anions"
The ink prepared in Example G-3 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 490 ppm, 80 ppm, 40 ppm and 140 ppm, respectively. The total amount of monovalent anions was 750 ppm.

(Example G-4)
The ink composition of Example G-4 is shown below.

Amount added (%)
Dispersion G4 6.5
Surfinol 104 0.1
TEGmBE 3.0
1,2-pentanediol 5.0
1,5-pentanediol 2.0
Tetraethylene glycol 9.0
Dimethyl-2-imidazolidinone 2.0
Sodium benzoate 0.1
Triethanolamine 0.7
Ion exchange water

  In the above composition, Surfynol 104 represents an acetylene glycol surfactant (trade name; manufactured by Air Products).

"Quantification of monovalent anions"
The ink prepared in Example G-4 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 680 ppm, 190 ppm, 150 ppm and 90 ppm, respectively. The total amount of monovalent anions was 1110 ppm.

(Example G-5)
The ink composition of Example G-5 is shown below.

Amount added (%)
Dispersion G5 7.0
DPGmBE 2.0
DEGmBE 7.0
Glycerin 5.0
Triethylene glycol 5.0
Trehalose 5.0
Triethanolamine 0.8
Ion exchange water

  In the above composition, DPGmBE represents dipropylene glycol monobutyl ether.

"Quantification of monovalent anions"
The ink prepared in Example G-5 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 500 ppm, 65 ppm, 100 ppm and 55 ppm, respectively. The total amount of monovalent anions was 720 ppm.

(Example G-6)
The ink composition of Example G-6 is shown below.

Amount added (%)
Dispersion G6 7.0
Acetylenol EO 0.5
TEGmBE 5.0
1,2-pentanediol 1.0
Glycerin 13.0
Thiodiglycol 2.0
2-pyrrolidone 2.0
Triethanolamine 0.3
Ion exchange water

  In the above composition, acetylenol EO represents an acetylene glycol surfactant (trade name; manufactured by Kawaken Fine Chemical Co., Ltd.).

"Quantification of monovalent anions"
The ink prepared in Example G-6 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 460 ppm, 55 ppm, 80 ppm and 65 ppm, respectively. The total amount of monovalent anions was 660 ppm.

(Example G-7)
The ink composition of Example G-7 is shown below.

Amount added (%)
Dispersion G7 7.2
Surfinol 465 0.5
Surfinol 61 0.5
TEGmBE 6.0
Glycerin 15.0
Trimethylolpropane 1.0
Trimethylolethane 1.0
Triethanolamine 0.1
NaOH 0.05
Ion exchange water

  In the above composition, Surfynol 465 represents an acetylene glycol surfactant (trade name; manufactured by Air Products), and Surfynol 61 represents an acetylene alcohol surfactant (trade name; manufactured by Air Products).

"Quantification of monovalent anions"
The ink prepared in Example G-7 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 845 ppm, 60 ppm, 90 ppm and 45 ppm, respectively. The total amount of monovalent anions was 1040 ppm.

(Example G-8)
The ink composition of Example G-8 is shown below.

Amount added (%)
Dispersion G8 10.0
Surfinol 420 0.5
PGmBE 2.0
DEGmBE 10.0
Tetrapropylene glycol 5.0
Glycerin 7.0
Diethylene glycol 5.0
Triethanolamine 0.1
KOH 0.1
Ion exchange water

  In the above composition, Surfynol 420 represents an acetylene glycol surfactant (trade name; manufactured by Air Products), and PGmBE represents propylene glycol monobutyl ether.

"Quantification of monovalent anions"
The ink prepared in Example G-8 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion are 55 in order, respectively.
They were 0 ppm, 110 ppm, 75 ppm, and 100 ppm. The total amount of monovalent anions was 835 ppm.

(Example G-9)
The ink composition of Example G-9 is shown below.

Amount added (%)
Dispersion G9 5.0
Surfinol 485 1.5
DEGmBE 5.0
1,5-pentanediol 5.0
Glycerin 9.0
1,4-cyclohexanedimethanol 5.0
Triethanolamine 0.2
Ion exchange water

  In the above composition, Surfynol 485 represents an acetylene glycol surfactant (trade name; manufactured by Air Products).

"Quantification of monovalent anions"
The ink prepared in Example G-9 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 950 ppm, 250 ppm, 190 ppm and 105 ppm, respectively. The total amount of monovalent anions was 1495 ppm.

(Example G-10)
The ink composition of Example G-10 is shown below.

Amount added (%)
Dispersion G10 5.0
Surfinol TG 0.3
DEGmBE 10.0
Dipropylene glycol 5.0
Triethanolamine 0.9
Ion exchange water

  In the above composition, Surfinol TG represents acetylene glycol surfactant (trade name; manufactured by Air Products), and DEGmBE represents diethylene glycol monobutyl ether.

"Quantification of monovalent anions"
The ink prepared in Example G-10 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 630 ppm, 250 ppm, 120 ppm and 50 ppm, respectively. The total amount of monovalent anions was 1050 ppm.

(Example G-11)
The ink composition of Example G-11 is shown below.

Amount added (%)
Dispersion G11 4.5
Olfin STG 0.3
1,2-hexanediol 2.0
1,6-hexanediol 2.0
Diethylene glycol 7.0
Thiodiglycol 1.5
Triethanolamine 0.2
Ion exchange water

  In the above composition, Olfine STG represents an acetylene glycol surfactant (trade name; manufactured by Nissin Chemical Industry Co., Ltd.).

"Quantification of monovalent anions"
The ink prepared in Example G-11 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 465 ppm, 160 ppm, 135 ppm and 80 ppm, respectively. The total amount of monovalent anions was 840 ppm.

(Example G-12)
The ink composition of Example G-12 is shown below.

Amount added (%)
Dispersion G12 6.5
Surfinol 104 0.1
TEGmBE 3.0
1,2-pentanediol 2.0
1,5-pentanediol 2.0
Tetraethylene glycol 9.0
Dimethyl-2-imidazolidinone 2.0
Sodium benzoate 0.1
Triethanolamine 0.5
Ion exchange water

  In the above composition, Surfynol 104 represents an acetylene glycol surfactant (trade name; manufactured by Air Products).

"Quantification of monovalent anions"
The ink prepared in Example G-12 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion, and nitrate ion were 300 ppm, 280 ppm, 260 ppm, and 75 ppm, respectively. The total amount of monovalent anions was 915 ppm.

(Example G-13)
The ink composition of Example G-13 is shown below.

Amount added (%)
Dispersion G13 5.0
Surfinol 465 0.5
Surfinol TG 0.1
TEGmBE 2.0
1,2-hexanediol 2.0
Glycerin 5.0
Triethylene glycol 5.0
Trimethylolpropane 5.0
Tripropanolamine 0.1
Ion exchange water

"Quantification of monovalent anions"
The ink prepared in Example G-13 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 650 ppm, 80 ppm, 70 ppm and 30 ppm, respectively. The total amount of monovalent anions was 830 ppm.

(Example G-14)
The ink composition of Example G-14 is shown below.

Amount added (%)
Dispersion G14 8.5
Acetylenol EL 0.5
Acetylenol EO 0.1
TEGmBE 6.0
1,2-pentanediol 1.0
Glycerin 15.0
Thiodiglycol 2.0
Triethanolamine 0.2
Ion exchange water

  In the above composition, acetylenol EL represents an acetylene glycol surfactant (trade name; manufactured by Kawaken Fine Chemical Co., Ltd.).

"Quantification of monovalent anions"
The ink prepared in Example G-14 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 250 ppm, 190 ppm, 210 ppm and 150 ppm, respectively. The total amount of monovalent anions was 800 ppm.

(Comparative Example G-1)
In Comparative Example G-1, Dispersion G1 was used as in Example G-1. Furthermore, in Comparative Example G-1, the ink was prepared using water intentionally containing a large amount of monovalent anions.
The ink composition of Comparative Example G-1 is shown below.

Amount added (%)
Dispersion G1 8.0
Ethylene glycol 5.0
Glycerin 10.0
Nonionic surfactant 1.0
Monovalent metal ion-containing water

  In the above composition, Epan 450 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

"Quantification of monovalent anions"
The ink prepared in Comparative Example G-1 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 1250 ppm, 640 ppm, 590 ppm and 530 ppm, respectively. The total amount of monovalent anions was 3010 ppm.

(Comparative Example G-2)
In Comparative Example G-2, similarly to Example G-1, MA88 (manufactured by Mitsubishi Chemical Corporation), which is a carbon black pigment, was dispersed using Solsperse 27000 (manufactured by Avicia) as a dispersant.
Disperse 15 parts of MA88, 5 parts of Solsperse 27000 (manufactured by Avicia), 5 parts of diethanolamine, 0.5 part of 2-propanol, and 74.5 parts of ion-exchanged water with a bead mill mini-zeta (manufactured by Ajisawa Corporation) for 2 hours. Treatment was performed to obtain dispersion G15 used in Comparative Example G-2.
The ink composition of Comparative Example G-2 is shown below.

Amount added (%)
Dispersion G15 <120> 7.0
Glycerin 15.0
Dispersant 3.0
Nonionic surfactant 1.0
Ion exchange water

  In the above composition, Neugen EA160 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

"Quantification of monovalent anions"
The ink prepared in Comparative Example G-2 was measured by the method described in “Measurement of monovalent anion amount”.
The respective ion amounts of chlorine ion, bromine ion, iodine ion and nitrate ion were 660 ppm, 190 ppm, 120 ppm and 80 ppm, respectively. The total amount of monovalent anions was 1050 ppm.

Next, printing evaluation was performed for each ink of Examples G-1 to 14 and Comparative Examples G-1 and G2. In addition, for printing evaluation, an ink jet printer PM-900C manufactured by Seiko Epson Corporation, which ejects ink by an ink jet head using a piezoelectric element (piezo element), is commercially available as an evaluation paper in Europe, the United States, and Japan. As ordinary paper, Conqueror paper, Favorit paper, Modo Copy paper, Rapid Copy paper, EPSON EPP paper, Xerox 4024 paper, Xerox 10 paper, Nenha Bond paper, Rcopyy 6200 paper, Yamayori paper, XeroxR paper.
Table 31 shows the bleeding evaluation results when characters are printed as printing evaluation results. In Table 31, A is very good, B is good, C is bad, and D is very bad.

As apparent from the results in Table 31, it can be seen that the ink used in the comparative example has poor print quality, and that the print quality is good when the ink for ink jet recording used in the present invention is used.
As described above, according to the present invention, it is possible to provide a high-quality and practical ink-jet recording ink in which bleeding of a printed image on a recording medium such as paper is reduced.
In addition, the storage stability evaluation and the ejection stability evaluation were performed for the inks of Examples G-1 to 14 and Comparative Examples G-1 and G2.
Storage stability was evaluated by placing each ink in a glass sample bottle and sealing it, then leaving it at 60 ° C / 1 week and -20 ° C / 1 week, respectively. (Tension) was examined.
The amount of foreign matter generated is the amount of foreign matter after standing / initial amount of foreign matter, the viscosity is the viscosity after standing / initial viscosity, and the surface tension is the surface tension after standing / initial surface tension.

The ejection stability evaluation was performed by using the above-described inkjet printer PM-900C manufactured by Seiko Epson Corporation, and printing 200 pages continuously on A4 version Xerox P paper. Some were B and 10 or more and less than 100 printing disturbances were C, and 100 or more printing printing disturbances were D.
Table 32 shows the quantification result, the storage stability evaluation result, and the ejection stability evaluation result of the monovalent anion of each ink of Examples G-1 to 14 and Comparative Examples G-1 and G2.

  As can be seen from the results in Tables 31 and 32, the water-based ink using the dispersion according to the present invention has good print quality, and is a water-based ink suitable for ink jet recording excellent in ejection stability and storage stability. I understand that Further, such an ink can be suitably used for an ink jet head using a piezoelectric element as in the above embodiment. Further, since the pigment is used, the water resistance has an effect that the printed matter is superior to the case of using a normal dye. In addition, the function of the polymer that coats the colorant can be freely changed by the polymerization monomer and other reactants, so it can have various functions (light resistance, gas resistance, colorability, glossiness, fixability, etc.). It also has the effect of being able to. In the case of using an ordinary dispersant as in the past, in the dispersant, the adsorption force of the dispersant basically adsorbed on the pigment is weak and partial desorption occurs, and the desorbed material or the dispersant that has not been adsorbed As a result, the viscosity increases, so the amount of colorant added is limited and it is difficult to obtain a sufficient color.

[Example H]
Next, examples of other preferred embodiment (h) according to the present invention will be described, but these do not limit the scope of the present invention.
(Measurement method of aromatic ring amount, pigment: polymer ratio, average particle size, free polymer amount, and surface tension)
Each measured value (amount of aromatic ring, pigment: polymer ratio, average particle size, amount of free polymer, surface tension) obtained in this example was measured by the following method.

"Measurement of aromatic ring quantity"
A part of the dispersion polymer solution obtained in each example or comparative example was taken out, the solvent component was distilled off, and only the polymer component was taken out, dissolved in DMSO-d ₆ , ¹³ C-NMR and ¹ H-NMR ( The amount of aromatic rings in the polymer was measured using Bruker (Germany AMX400).
“Measurement of pigment: polymer ratio”
A part of the dispersion obtained in each Example or Comparative Example was taken out, 0.1 mol / l concentration HCl was added, and only the dispersion was acidified, and the dry weight was measured. Next, the pigment: polymer weight ratio was calculated by taking out only the dispersed polymer by Soxhlet extraction using acetone and measuring the dry weight.

"Measurement of average particle size"
Dilute with ion-exchanged water so that the dispersion concentration of the water-based ink obtained in each Example or Comparative Example is 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement differs slightly depending on the ink), The average particle diameter at 20 ° C. of the dispersed particles was measured with a particle size distribution meter (ELS-800 manufactured by Otsuka Electronics Co., Ltd.).
"Measurement of free polymer"
A necessary amount of the water-based ink obtained in each example or comparative example was taken out, and solid content such as a dispersion in the ink was precipitated as a precipitation component by centrifugal acceleration (condition: 2500 G × 60 minutes).
Next, the liquid component of the ink obtained as a supernatant component is heated under reduced pressure, the solvent component is evaporated, and the weight of the free polymer present in the liquid component is measured. Was measured.

"Measurement of surface tension"
The surface tension at 20 ° C. of the water-based ink obtained in each example or comparative example was measured with a surface tension meter (CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.).

<Example H-1>
(1) Production of dispersion: Dispersion H1
For the production of the dispersion H1 used in Example H-1, a carbon black pigment color black FW18 (manufactured by Degussa), which is an inorganic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, then 15 parts of methyl ethyl ketone, 21 parts of styrene, 5 parts of α-methyl styrene, 16 parts of butyl methacrylate, 10 parts of lauryl methacrylate, acrylic acid 2 parts, 0.3 part of t-dodecyl mercaptan is added and heated to 70 ° C., and separately prepared 100 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and azobis 3 parts of isobutyronitrile was placed in a dropping funnel and the dispersion polymer was subjected to a polymerization reaction while dropping into a reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 58%.

40 parts of the above dispersion polymer solution, 30 parts of carbon black pigment Color Black FW18 (manufactured by Degussa), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 35 parts of methyl ethyl ketone are mixed and dispersed with a homogenizer for 30 minutes or more. Then, 350 parts of ion exchange water is added and dispersed for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, filtration and washing are repeated using a Buchner funnel. Next, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added to the filtered pigment-encapsulated resin dispersion while stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm. As a result, a dispersion H1 containing 20% of the dispersion H1 (a dispersion in which a carbon black pigment is included by a polymer having an aromatic ring amount of 58%) was obtained.
Table 33 shows the pigment used in the dispersion H1, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Ink adjustment In Example H-1, the dispersion H1 obtained in Example H-1 (1), Olphine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant, Diethylene glycol monobutyl ether, which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol, which is 1,2-alkylene glycol, were used. A specific composition is shown below.
In preparing the ink, the dispersion H1 was added so that the content of the dispersion H1 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element H1 measured by the method described in "Measurement of Average Particle Size" above.
In addition, ion exchange water added as “remaining amount” in the ink composition of Example H-1 below includes Proxel XL-2 for preventing corrosion of the ink, Benzotriazole for preventing corrosion of the inkjet head member, In order to reduce the influence of metal ions in the ink system, EDTA · 2Na salt added to 0.01%, 0.01%, and 0.02% with respect to the total weight of the ink is used. It was.

Dispersion H1 <120> 8.0%
Olfine E1010 0.5%
Diethylene glycol monobutyl ether 3.0%
1,2-pentanediol 2.5%
Diethylene glycol 3.0%
Glycerin 11.5%
Trimethylolpropane 6.0%
Tripropanolamine 0.3%
Ion exchange water

(3) Measurement of free polymer amount When the ink prepared in Example H-1 (2) was measured by the method described in "Measurement of free polymer amount", the amount of free polymer relative to the total weight of the ink was 1. 18%.
(4) Print evaluation For print image evaluation, an ink jet printer PM-950C (manufactured by Seiko Epson Corporation) that discharges ink with an ink jet head using a piezoelectric element (piezo element) was used. Printing evaluation of the ink adjusted in 2) was performed.
As evaluation papers, (a) Conqueror paper, (b) Reymat paper, (c) Mode Copy paper, (d) Rapid Copy paper, (e) Xerox P paper , (F) Xerox 4024 paper, (g) Xerox 10 paper, (h) Neenha Bond paper, (i) Riccopy 6200 paper, and (j) Hammer mill Copy Plus paper.
In addition, evaluation was performed visually and was performed based on the following evaluation criteria.

A: The blur is not recognized in the characters at all points.
B: Slight bleeding is observed with characters of 5 points or less (practical level).
C: Characters of 5 points or less appear thick due to blurring.
D: Significant blurring and characters of 5 points or less cannot be identified.

  Table 34 shows the results of the print evaluation.

(5) Evaluation of ejection stability Using the same printer and ink as in Example H-1 (4), A4 version Xerox
200 pages were continuously printed on P paper, and the ejection stability was evaluated by observing the printing disorder.
In addition, evaluation was performed visually and was performed based on the following evaluation criteria.
A: Printing disorder does not occur at all.
B: Printing disorder was observed, but the number was less than 10 (practical level).
C: There is printing disorder in the range of 10 or more and less than 100.
D: Disturbance of printing occurred at 100 locations or more.

  Table 35 shows the results of the discharge stability evaluation.

(6) Storage stability evaluation After the ink prepared in Example H-1 (2) was put in a glass bottle and sealed, it was left at 60 ° C./1 week and −20 ° C./1 week, respectively. Foreign matter and physical property value fluctuation (viscosity, surface tension) were evaluated.
The evaluation was performed based on the following evaluation criteria.

A: The ratio of the amount of foreign matter / physical properties after standing at 60 ° C. or −20 ° C. to that before standing is in the range of 0.99 to 1.01.
B: The ratio is in the range of 0.95 to 0.99, or 1.01 to 1.05 (
Practical level).
C: The ratio is in the range of 0.90 to 0.95, or 1.05 to 1.10.
D: Ratio is less than 0.90 or greater than 1.10.

  The storage stability evaluation results are shown in Table 35.

<Example H-2>
(1) Production of dispersion: Dispersion H2
For the production of the dispersion H2 used in Example H-2, an insoluble monoazo yellow pigment (CI Pigment Yellow 74), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 12 parts of styrene, 9 parts of lauryl methacrylate, and 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 3 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 part of mercaptoethanol, heated to 70 ° C., 25 parts of styrene prepared separately, lauryl 30 parts of methacrylate, 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), 15 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toagosei Co., Ltd.), 10 parts of methacrylic acid, 20 parts of methyl ethyl ketone Dropwise to the reaction vessel over 4 hours putting 1.0 parts of mercaptoethanol to the dropping funnel and the dispersed polymer is the polymerization reaction. Next, methyl ethyl ketone was appropriately added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.

A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 26%.
40 parts of the above dispersion polymer solution, 30 parts of an insoluble monoazo yellow pigment (CI Pigment Yellow 74) as an organic pigment, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed, and 30 parts are mixed with a homogenizer. Disperse for at least minutes, add 380 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion H2 (insoluble monoazo). A dispersion H2 containing 20% of a dispersion in which a yellow pigment was included by a polymer having an aromatic ring content of 26% was obtained.
Table 33 shows the pigment used in the dispersion H2, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example H-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Ink adjustment In this Example H-2, the dispersion H2 obtained in Example H-2 (1), Surfynol 440 (produced by Air Products), which is an acetylene glycol surfactant, and Olfin STG are used. (Manufactured by Nissin Chemical Industry Co., Ltd.), triethylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the ink, the dispersion H2 was added so that the content of the dispersion H2 was 7.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element H2 measured by the method described in "Measurement of Average Particle Size" above.
In addition, the ion exchange water added as “remaining amount” in the ink composition of the following Example H-2 is similar to the above Example H-1 (2), and Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion H2 <120> 7.0%
Surfinol 440 0.2%
Olphine STG 0.2%
Triethylene glycol monobutyl ether 3.0%
1,2-pentanediol 2.0%
2-pyrrolidone 3.0%
Glycerin 13.5%
Trimethylolethane 5.0%
Triethanolamine 0.1%
Ion exchange water

(3) Measurement of free polymer amount The ink prepared in Example H-2 (2) was measured by the method described in the above-mentioned "Measurement of free polymer amount". 48%.
(4) Printing evaluation Using the ink jet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example H-1 (4), the ink prepared in Example H-2 (2) was Using the same evaluation paper as in Example H-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example H-1 (4). The print evaluation results are shown in Table 34.
(5) Evaluation of ejection stability Using the same printer and ink as in Example H-2 (4), the same evaluation method as in Example H-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 35. (6) Storage Stability Evaluation For the ink prepared in Example H-2 (2), the same evaluation method as in Example H-1 (6) was used, and the same as in Example H-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 35.

<Example H-3>
(1) Production of dispersion: Dispersion H3
For the production of the dispersion H3 used in Example H-3, quinacridone red pigment (CI Pigment Red 122), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 12 parts of styrene, 6 parts of styrene macromer (AS-6; manufactured by Toagosei Co., Ltd.), n-dodecyl methacrylate 3.5 Parts, N, N-dimethylaminoethyl methacrylate 12 parts, methoxypolyethylene glycol methacrylate (NK ester M40G; manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts, methyl ethyl ketone 5 parts, mercaptoethanol 0.3 part, and heated to 70 ° C. 15 parts of styrene prepared separately, 8 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 7 parts of n-dodecyl methacrylate, 20 parts of N, N-dimethylaminoethyl methacrylate, methoxypolyethylene glycol methacrylate (NK ester M40G) ; Shin-Nakamura Chemical Co., Ltd. 30 parts, 50 parts of methyl ethyl ketone, and the dispersion polymer dropwise into the reaction vessel over 4 hours and placed in a dropping funnel and 1.5 parts of azobisisobutyronitrile was polymerized reaction. Next, methyl ethyl ketone was appropriately added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.

A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 36%.
40 parts of the above dispersion polymer solution, 25 parts of an organic pigment, quinacridone red pigment (CI Pigment Red 122), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 40 parts of methyl ethyl ketone are mixed, and 30 minutes with a homogenizer. Dispersion treatment is performed as described above, and 380 parts of ion exchange water is added and further dispersed for 1 hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added while stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion H3 (quinacridone red A dispersion H3 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 36% was obtained.

  Table 33 shows the pigment used in the dispersion H3, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example H-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Ink adjustment In Example H-3, the dispersion H3 obtained in Example H-3 (1) above, Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant, Surfynol 104PG50 (manufactured by Air Products), triethylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-hexanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the ink, the dispersion H3 was added so that the content of the dispersion H3 was 7.5%. The value in <> shows the average particle size (unit: nm) of Dispersing Element H3 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the ink composition of the following Example H-3, the ion-exchanged water added as “remaining amount” is similar to Example H-1 (2) described above, with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion H3 <140> 7.5%
Olfin E1010 0.1%
Surfynol 104PG50 0.4%
Triethylene glycol monobutyl ether 1.0%
1,2-hexanediol 2.5%
Triethylene glycol 2.0%
2-pyrrolidone 4.0%
Glycerin 13.8%
Trimethylolpropane 6.0%
Ion exchange water

(3) Measurement of free polymer amount The ink prepared in Example H-3 (2) was measured by the method described in "Measurement of free polymer amount". 63%.
(4) Printing evaluation Using the ink jet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example H-1 (4), the ink prepared in Example H-3 (2) was Using the same evaluation paper as in Example H-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example H-1 (4). The print evaluation results are shown in Table 34.
(5) Evaluation of ejection stability Using the same printer and ink as in Example H-3 (4), the same evaluation method as in Example H-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 35. (6) Storage Stability Evaluation For the ink prepared in Example H-3 (2), the same evaluation method as in Example H-1 (6) was used, and the same as in Example H-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 35.

<Example H-4>
(1) Production of dispersion: Dispersion H4
For the production of the dispersion H4 used in Example H-4, a phthalocyanine blue pigment (CI Pigment Blue 15: 4), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 20 parts of styrene, 9 parts of lauryl methacrylate, and 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 10 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 n-dodecyl mercaptan And heated to 70 ° C., separately prepared 25 parts of styrene, 30 parts of lauryl methacrylate, 20 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), isobutyl methacrylate macromer (AW-6S; Toa) Synthetic strain 15 parts), 15 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 20 parts of methyl ethyl ketone, 1.5 parts of n-dodecyl mercaptan are placed in the dropping funnel and reacted for 4 hours. The dispersion polymer was subjected to a polymerization reaction while dropping into the container. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.

A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 49%.
40 parts of the above dispersion polymer solution, 40 parts of an organic pigment phthalocyanine blue pigment (CI Pigment Blue 15: 4), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed together. Disperse for 30 minutes or more, add 350 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion H4 (phthalocyanine blue A dispersion H4 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 49% was obtained.
Table 33 shows the pigment used in the dispersion H4, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example H-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of ink In Example H-4, the dispersion H4 obtained in Example H-4 (1), acetylenol E100 (produced by Kawaken Fine Chemical Co., Ltd.), which is an acetylene glycol surfactant, alkylene Propylene glycol monobutyl ether, which is glycol monoalkyl ether, and 1,2-hexanediol, which is 1,2-alkylene glycol, were used. A specific composition is shown below.
In preparing the ink, the dispersion H4 was added so that the content of the dispersion H4 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element H4 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the ink composition of the following Example H-4, ion-exchanged water added as “remaining amount” is similar to Example H-1 (2) described above, and Proxel XL- 2
In which 0.01% was added, 0.01% benzotriazole, and 0.02% EDTA · 2Na salt were used.

Dispersion H4 <100> 8.0%
Acetylenol E100 0.5%
Propylene glycol monobutyl ether 3.0%
1,2-hexanediol 1.0%
Triethylene glycol 3.0%
Glycerin 13.8%
Trimethylolpropane 5.2%
Tripropanolamine 0.2%
Ion exchange water

(3) Measurement of free polymer amount The ink prepared in Example H-4 (2) was measured by the method described in "Measurement of free polymer amount". It was 54%.
(4) Printing evaluation Using the inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example H-1 (4), the ink prepared in Example H-4 (2) was Using the same evaluation paper as in Example H-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example H-1 (4). The print evaluation results are shown in Table 34.
(5) Evaluation of ejection stability Using the same printer and ink as in Example H-4 (4), the same evaluation method as in Example H-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 35. (6) Storage Stability Evaluation For the ink prepared in Example H-4 (2), the same evaluation method as in Example H-1 (6) was used, and the same as in Example H-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 35.

<Example H-5>
(1) Production of dispersion: Dispersion H5
A perinone orange pigment (CI Pigment Orange 43) was used for the production of the dispersion H5 used in Example H-5. Otherwise, in the same manner as described in Example H-1 (1), 20% of dispersion H5 (dispersion containing a perinone orange pigment with a polymer having an aromatic ring content of 44%) is contained. Dispersion H5 was obtained.
Table 33 shows the pigment used in the dispersion H5, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example H-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Ink Adjustment In this Example H-5, the dispersion H5 obtained in Example H-5 (1), Surfynol 485 and Surfynol TG which are acetylene glycol surfactants (both are air products) Co., Ltd.), dipropylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol. A specific composition is shown below.
In preparing the ink, the dispersion H5 was added so that the content of the dispersion H5 was 10.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element H5 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the ink composition of the following Example H-5, ion-exchanged water added as “remaining amount” is similar to Example H-1 (2) described above with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion H5 <150> 10.0%
Surfynol 485 0.5%
Surfinol TG 0.2%
Dipropylene glycol monobutyl ether 2.0%
1,2-pentanediol 2.0%
N-methyl-2-pyrrolidone 5.0%
Glycerin 11.2%
Trehalose 5.8%
Ion exchange water

(3) Measurement of free polymer amount When the ink prepared in Example H-5 (2) was measured by the method described in "Measurement of free polymer amount", the amount of free polymer relative to the total weight of the ink was 1. 62%.
(4) Printing evaluation Using the ink jet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example H-1 (4), the ink prepared in Example H-5 (2) was Using the same evaluation paper as in Example H-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example H-1 (4). The print evaluation results are shown in Table 34.
(5) Evaluation of ejection stability Using the same printer and ink as in Example H-5 (4), the same evaluation method as in Example H-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 35. (6) Storage Stability Evaluation For the ink prepared in Example H-5 (2), the same evaluation method as in Example H-1 (6) was used, and the same as in Example H-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 35.

<Example H-6>
(1) Production of dispersion: Dispersion H6
A benzimidazolone brown pigment (CI Pigment Brown 32) was used for the production of the dispersion H6 used in Example H-6. Otherwise, 20% of dispersion H6 (dispersion containing benzimidazolone brown pigment with polymer having 70% aromatic ring content) was prepared in the same manner as described in Example H-1 (1). A dispersion H6 was obtained.
Table 33 shows the pigment used in the dispersion H6, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example H-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of ink In Example H-6, the dispersion H6 obtained in Example H-6 (1), Surfynol 420 which is an acetylene glycol surfactant, and alkylene glycol monoalkyl ether are used. Diethylene glycol monobutyl ether was used. A specific composition is shown below.
In preparing the ink, dispersion H6 was added so that the content of dispersion H6 was 5.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element H6 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the ink composition of the following Example H-6, the ion-exchanged water added as “remaining amount” is similar to Example H-1 (2), with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion H6 <140> 5.0%
Surfynol 420 0.1%
Diethylene glycol monobutyl ether 3.0%
1,6-hexanediol 2.0%
Tetraethylene glycol 5.5%
Glycerin 13.5%
Triethanolamine 0.5%
Ion exchange water

(3) Measurement of free polymer amount When the ink prepared in Example H-6 (2) was measured by the method described in "Measurement of free polymer amount", the amount of free polymer relative to the total weight of the ink was 1. It was 98%.
(4) Printing evaluation Using the inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example H-1 (4), the ink prepared in Example H-6 (2) was Using the same evaluation paper as in Example H-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example H-1 (4). The print evaluation results are shown in Table 34.
(5) Evaluation of ejection stability Using the same printer and ink as in Example H-6 (4), the same evaluation method as in Example H-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 35. (6) Storage Stability Evaluation For the ink prepared in Example H-6 (2), the same evaluation method as in Example H-1 (6) was used, and the same as in Example H-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 35.

<Example H-7>
(1) Production of dispersion: Dispersion H7
For the production of the dispersion H7 used in Example H-7, quinacridone violet pigment (CI Pigment Bio Red 19) was used as an organic pigment. Other than that, a dispersion containing 20% of dispersion H7 (a dispersion including a quinacridone violet pigment with a polymer having an aromatic ring content of 52%) was produced in the same manner as described in Example H-2 (1). A liquid H7 was obtained.
Table 33 shows the pigment used in the dispersion H7, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example H-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of ink In this Example H-7, the dispersion H7 obtained in Example H-7 (1), Surfynol 61 and Surfynol TG which are acetylene alcohol surfactants (both are air products) Co., Ltd.), triethylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2 alkylene glycol. A specific composition is shown below.
In preparing the ink, the dispersion H7 was added so that the content of the dispersion H7 was 6.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element H7 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the ink composition of the following Example H-7, the ion-exchanged water added as “remaining amount” is similar to Example H-1 (2) described above, with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion H7 <120> 6.0%
Surfynol 61 0.3%
Surfynol TG 0.1%
Triethylene glycol monobutyl ether 1.5%
1,2-pentanediol 2.0%
Diethylene glycol 2.0%
Thiodiglycol 4.0%
Glycerin 12.6%
Trimethylolethane 7.2%
Ion exchange water

(3) Measurement of free polymer amount The ink prepared in Example H-7 (2) was measured by the method described in "Measurement of free polymer amount". 39%.
(4) Printing Evaluation Regarding the ink prepared in Example H-7 (2) using the inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example H-1 (4), Using the same evaluation paper as in Example H-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example H-1 (4). The print evaluation results are shown in Table 34.
(5) Evaluation of ejection stability Using the same printer and ink as in Example H-7 (4), the same evaluation method as in Example H-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 35. (6) Storage Stability Evaluation For the ink prepared in Example H-7 (2), the same evaluation method as in Example H-1 (6) was used, and the same as in Example H-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 35.

<Example H-8>
(1) Production of dispersion: Dispersion H8
For the production of the dispersion H8 used in Example H-8, a phthalocyanine green pigment (CI Pigment Green 7), which is an organic pigment, was used. Otherwise, the dispersion containing 20% of dispersion H8 (dispersion containing phthalocyanine green pigment by a polymer having an aromatic ring content of 38%) in the same manner as described in Example H-3 (1) above A liquid H8 was obtained.
Table 33 shows the pigment used in the dispersion H8, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example H-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Ink adjustment In Example H-8, the dispersion H8 obtained in Example H-8 (1) above, Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant, Surfynol 104 (manufactured by Air Products), dipropylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the ink, the dispersion H8 was added so that the content of the dispersion H8 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element H8 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the ink composition of the following Example H-8, the ion-exchanged water added as “remaining amount” is similar to Example H-1 (2), with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion H8 <110> 8.0%
Olfine E1010 0.3%
Surfynol 104 0.1%
Dipropylene glycol monobutyl ether 1.0%
1,2-pentanediol 3.0%
Triethylene glycol 2.0%
Thiodiglycol 4.0%
Glycerin 13.8%
Trimethylolpropane 6.4%
Triethanolamine 0.1%
Ion exchange water

(3) Measurement of free polymer amount When the ink produced in Example H-8 (2) was measured by the method described in "Measurement of free polymer amount", the free polymer amount with respect to the total weight of the ink was 0. 72%.
(4) Printing Evaluation Regarding the ink prepared in Example H-8 (2) using the inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example H-1 (4), Using the same evaluation paper as in Example H-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example H-1 (4). The print evaluation results are shown in Table 34.
(5) Evaluation of ejection stability Using the same printer and ink as in Example H-8 (4), the same evaluation method as in Example H-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 35. (6) Storage Stability Evaluation For the ink prepared in Example H-8 (2), the same evaluation method as in Example H-1 (6) was used, and the same as in Example H-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 35.

<Comparative Example H-1>
(1) Production of dispersion: Dispersion H9
In this comparative example H-1, similarly to the example H-1 (1), the carbon black pigment color black FW18 (manufactured by Degussa Co., Ltd.), which is an inorganic pigment, was used, and the dispersion used in this comparative example H-1 was used. Liquid H9 was produced.
However, in Comparative Example H-1, since the amount of free polymer in the ink was changed to Example H-1, a dispersion was intentionally produced under conditions different from those of Example H-1 (1).
First, the reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 26 parts of styrene, 5 parts of α-methylstyrene, 15 parts of butyl methacrylate, 12 parts of lauryl methacrylate, 2 parts of acrylic acid, t -0.6 parts of dodecyl mercaptan was added and heated to 55 ° C in this comparative example. Separately, 160 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile were placed in a dropping funnel, and this comparison was made while dropping into the reaction vessel. In the example, the dispersion polymer was polymerized in 2 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 38%.

A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in the above-mentioned “Measurement of the amount of aromatic ring”. The amount was 20%.
40 parts of the above dispersion polymer solution, 30 parts of carbon black pigment Color Black FW18 (manufactured by Degussa), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 35 parts of methyl ethyl ketone are mixed and dispersed with a homogenizer for 30 minutes or more. Then, 350 parts of ion exchange water is added and dispersed for another hour. Then, after distilling off the total amount of methyl ethyl ketone and a part of water using a rotary evaporator, in this comparative example, without washing with a Buchner funnel, the pigment-encapsulated resin dispersion separated by filtration, ion-exchanged water, and A sodium hydroxide aqueous solution is appropriately added as a neutralizing agent with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion H9 (carbon black pigment having an aromatic ring amount of 20%). Dispersion H9 containing 20% of the dispersion (enclosed by the polymer)
Table 33 shows the pigment used in dispersion H9, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Ink adjustment In Comparative Example H-1, the ink was adjusted using the dispersion H9 obtained in Comparative Example H-1 (1). A specific composition is shown below.
In preparing the ink, the dispersion H9 was added so that the content of the dispersion H9 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element H9 measured by the method described in "Measurement of Average Particle Size" above.
In addition, the ion exchange water added as “remaining amount” in the ink composition of the following Comparative Example H-1 is similar to Proxel XL- with respect to the total weight of the ink, as in Example H-1 (2). 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion H9 <140> 8.0%
Nonionic surfactant 1.0%
Ethylene glycol 5.0%
Glycerin 15.0%
Ion exchange water

  In the above composition, Epan 450 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of free polymer amount When the ink prepared in Comparative Example H-1 (2) was measured by the method described in "Measurement of free polymer amount", the amount of free polymer relative to the total weight of the ink was 3. 02%.
(4) Printing evaluation Using the ink jet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example H-1 (4), the ink prepared in Comparative Example H-1 (2) was Using the same evaluation paper as in Example H-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example H-1 (4). The print evaluation results are shown in Table 34.
(5) Evaluation of ejection stability Using the same printer and ink as in Comparative Example H-1 (4), the same evaluation method as in Example H-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 35. (6) Storage Stability Evaluation For the ink prepared in Comparative Example H-1 (2), the same evaluation method as in Example H-1 (6) was used, and the same as in Example H-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 35.

<Comparative Example H-2>
(1) Production of dispersion: Dispersion H10
In the production of the dispersion H10 used in this comparative example H-2, an organic pigment phthalocyanine green pigment (CI Pigment Green 7) was dispersed using Solsperse 12000 (manufactured by Avicia Co., Ltd.).
Disperse 15 parts of phthalocyanine green pigment, 5 parts of Solsperse 12000, 5 parts of diethanolamine, 0.5 part of 2-propanol, and 74.5 parts of ion-exchanged water with a bead mill minizeta (manufactured by Ajisawa Co., Ltd.) for 2 hours. As a result, a dispersion H10 containing 20% of dispersion H10 used in Comparative Example H-2 (pigment: 15%, dispersion resin: 5%) was obtained.

(2) Ink adjustment In Comparative Example H-2, the ink was adjusted using the dispersion H10 obtained in Comparative Example H-2 (1). The specific composition of this comparative example is shown below.
In preparing the ink, the dispersion H10 was added so that the content of the dispersion H10 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element H10 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the ink composition of the following Comparative Example H-2, the ion-exchanged water added as the “remaining amount” is similar to Example H-1 (2) in the case of Proxel XL- with respect to the total weight of the ink. 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion H10 <150> 20.0%
Nonionic surfactant 1.0%
Ethylene glycol 5.0%
Glycerin 15.0%
Ion exchange water

  In the above composition, Neugen EA160 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of free polymer amount When the ink prepared in Comparative Example H-2 (2) was measured by the method described in "Measurement of free polymer amount", the amount of free polymer relative to the total weight of the ink was 4. It was 23%.
(4) Printing evaluation Using the ink jet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example H-1 (4), the ink prepared in Comparative Example H-2 (2) was Using the same evaluation paper as in Example H-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example H-1 (4). The print evaluation results are shown in Table 34.
(5) Evaluation of ejection stability Using the same printer and ink as in Comparative Example H-2 (4), the same evaluation method as in Example H-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 35. (6) Storage Stability Evaluation For the ink prepared in Comparative Example H-2 (2), the same evaluation method as in Example H-1 (6) was used, and the same as in Example H-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 35.

As is apparent from the results in Tables 33 and 34, it can be seen that the ink used in the comparative example has poor print quality, and that the print quality is good when the ink according to the present invention is used.
As described above, by using the water-based ink of the present invention, it is possible to obtain a high-quality printed image in which bleeding is reduced for any paper type.

As is apparent from the results in Table 35, the water-based ink according to the present invention in which the amount of free polymer in the ink is suppressed to 2% or less ensures excellent ejection stability and storage stability, and the print quality is superior to Table 34. I understand that. It can also be seen that when the amount of free polymer is 1% or less, the discharge stability and storage stability are remarkably improved. On the other hand, it can be seen that when the amount of free polymer exceeds 3% as in the comparative example, the print quality, ejection stability, and storage stability are not at practical levels.
As can be seen from the above results, it can be seen that by using the water-based ink according to the present invention, good printing quality and ejection stability can be obtained, and the storage stability is excellent.

[Example I]
Next, another preferred embodiment (i) according to the present invention will be described by the following examples. The scope of the present invention is not limited to such examples.
As an example of the colorant shown in the present invention, the following examples and comparative examples describe cases where some organic or inorganic pigments are used. Organic and inorganic pigments can be used. Each average particle diameter is shown in <> in nm (nanometer) units.
Further, in the pigment dispersion used in the aqueous ink set of the present invention, in addition to the experimental examples exemplified below, the pigment is dispersed with a reactive dispersant, and then emulsion polymerization is performed in water in the presence of a catalyst. It can also be obtained.

(Production of Black Dispersion I1)
As the black dispersion I1, Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant. A reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 30 parts of styrene, 10 parts of α-methylstyrene, 15 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t-dodecyl Add 0.3 part of mercaptan and heat to 70 ° C., separately prepared 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile. Was placed in a dropping funnel and the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 50%.

40 parts of the above dispersion polymer solution, 30 parts of Monarch 880 (manufactured by Cabot), carbon black, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed and stirred with a homogenizer for 30 minutes. Thereafter, 300 parts of ion-exchanged water was added and further stirred for 1 hour. Then, the whole amount of methyl ethyl ketone and a part of water were distilled off using a rotary evaporator, neutralized with 0.1 mol / L sodium hydroxide to adjust to pH 9, and filtered through a 0.3 μm membrane filter. Thus, a black dispersion I1 having a solid content (dispersion polymer and carbon black) of 20% was obtained.
A part of this dispersion was taken out, 0.1 mol / L HCl was added for acid precipitation, only the dispersion polymer was taken out by Soxhlet extraction using acetone, and ¹³ C-NMR using DMSO-d _6. And the amount of the aromatic ring relative to the total weight of the dispersed polymer as measured by ¹ H-NMR (AMX400 manufactured by Bruker (Germany)) was 50%.

(Production of Black Dispersion I2)
The black dispersion I2 has the same composition as that of the black dispersion I1 except that 20 parts of Raven C (trade name; manufactured by Columbia Carbon Co., CI Pigment Black 7), which is carbon black, was used as a colorant. And manufactured by the method.
(Production of black dispersion I3)
Black Dispersion I3 was prepared as Black Dispersion I1 except that 46.7 parts of CI Pigment Black A (trade name; manufactured by BASF, CI Pigment Black 1) was used as the molecular color former. The same composition and method were used.

(Manufacture of yellow dispersion I1)
Yellow Dispersion I1 is a C.I. I. Except for using 30 parts of Pigment Yellow 180, it was produced by the same composition and method as the production of Black Dispersion I1.
(Production of yellow dispersion I2)
Yellow Dispersion I2 is a C.I. I. Except that 46.7 parts of Pigment Yellow 74 (insoluble monoazo pigment) was used, it was produced by the same composition and method as the production of Black Dispersion I1.
(Preparation of yellow dispersion I3)
Yellow Dispersion I3 is a C.I. I. Except that 80 parts of Pigment Yellow 128 (condensed azo pigment) was used, it was produced by the same composition and method as the production of Black Dispersion I1.

(Manufacture of magenta dispersion I1)
The magenta dispersion I1 is C.I. I. Except for using 30 parts of Pigment Violet 19 (quinacridone pigment), it was produced by the same composition and method as the production of Black Dispersion I1.
(Production of magenta dispersion I2)
The magenta dispersion I2 is C.I. I. Except that 46.7 parts of Pigment Red 202 (quinacridone pigment) was used, it was produced by the same composition and method as the production of the black colorant I1.
(Production of magenta dispersion I3)
The magenta dispersion I3 is C.I. I. Except for using 80 parts of Pigment Red 122 (dimethylquinacridone pigment), it was produced by the same composition and method as the production of Black Dispersion I1.

(Production of cyan dispersion I1)
Cyan dispersion I1 is a C.I. I. Except for using 30 parts of Pigment Blue 15: 3 (copper phthalocyanine pigment), it was produced by the same composition and method as the production of Black Dispersion I1.
(Production of cyan dispersion liquid I2)
Cyan dispersion liquid I2 is C.I. I. Except that 20 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment) was used, it was produced by the same composition and method as the production of Black Dispersion I1.
(Production of cyan dispersion I3)
Cyan dispersion I3 is a C.I. I. Except for using 13.3 parts of Pigment Blue 16 (metal-free phthalocyanine pigment), it was produced by the same composition and method as the production of Black Dispersion I1.

(Manufacture of red dispersion I1)
Red Dispersion I1 is a C.I. I. Pigment Red 190 (perylene pigment): Manufactured by the same composition and method as that of the black dispersion I1, except that 30 parts were used.
(Production of Blue Dispersion I1)
Blue dispersion I1 is C.I. I. Except for using 30 parts of Pigment Violet 23 (dioxazine pigment), it was manufactured by the same composition and method as the manufacture of Black Dispersion I1.
(Production of Green Dispersion I1)
Green dispersion I1 is C.I. I. Except for using 30 parts of Pigment Green 7 (highly chlorinated copper phthalocyanine pigment), it was produced by the same composition and method as the production of Black Dispersion I1.

(Preparation example of water-based ink)
Specific examples of ink compositions suitable for the aqueous ink set of the present invention are shown below. The addition amount of the pigment dispersion is shown as the solid content (solid content: the amount of the pigment and the dispersion polymer surrounding it) converted by weight. The numerical values in <> indicate that the pigment dispersions obtained in the following Examples and Comparative Examples have a pigment concentration of 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement varies slightly depending on the pigment). Thus, the value obtained by diluting with ion-exchanged water and measuring the “average particle diameter at 20 ° C.” of the dispersed particles with a particle size distribution meter (ELS-800 manufactured by Otsuka Electronics Co., Ltd.) is shown in nm units. In the ink composition examples shown below, the remaining amount of water indicates 0.05% of Proxel XL-2 for preventing corrosion of the ink, and 0.02% of benzotriazole for preventing corrosion of the ink jet head member. In order to reduce the influence of metal ions in the ink system, 0.04% each of EDTA · 2Na salt was added to ion-exchanged water.

(Composition Example I1: Black Ink I1)
Additive amount (%)
Black dispersion I1 <105> ... 10.0 (as solids)
DEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 2.0
Olphin E1010 ... 1.0
Olphine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.2
1,2-pentanediol ... 2.0
Glycerin ... 12.0
Tetraethylene glycol ... 5.0
2-pyrrolidone ... 2.0
Water ........................ Remaining amount

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether, and Olfine E1010 and Olfine STG represent acetylene glycol surfactants (both are trade names, manufactured by Nissin Chemical Industry Co., Ltd.).

(Composition example I2: Black ink I2)
Additive amount (%)
Black dispersion I2 <100> ... 10.0 (as solids)
Surfinol 465 ... 1.0
Glycerin ... 10.0
Tetraethylene glycol ... 5.0
Triethanolamine ... 0.3
Water ........................ Remaining amount

  In the above composition, Surfynol 465 represents an acetylene glycol surfactant (trade name, manufactured by Air Products (USA)).

(Composition Example I3: Black Ink I3)
Additive amount (%)
Black dispersion I3 <110> ... 10.0 (as solids)
Surfinol 61 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
DPGmBE ... 3.0
1,5-pentanediol ... 5.0
Maltose ... 3.0
Thiodiglycol ... 7
Water ........................ Remaining amount

  In the above composition, Surfynol 61 represents an acetylene alcohol surfactant (trade name, manufactured by Air Products (USA)), and DPGmBE represents dipropylene glycol monobutyl ether.

(Composition Example I4: Yellow Ink I1)
Additive amount (%)
Yellow dispersion I1 <90> ... 13.0 (as solids)
Surfinol 465 ... 1.0
Surfinol 61 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.3
DPGmBE ... 10.0
Diethylene glycol ... 5.0
2-pyrrolidone ... 1.0
Glycerin ... 5.0
Water ........................ Remaining amount

  In the above composition, Surfynol 465 is an acetylene glycol surfactant (trade name, manufactured by Air Products (USA)), and Surfynol 61 is an acetylene alcohol surfactant (trade name, Air Products (USA)). DPGmBE represents dipropylene glycol monobutyl ether.

(Composition Example I5: Yellow Ink I2)
Additive amount (%)
Yellow Dispersion I2 <80> ... 8.0 (as solids)
Olfine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
TEGmBE ... 1.0
1,2-hexanediol ... 3.0
2-pyrrolidone ... 2.0
Trimethylolpropane ... 8.0
Glycerin ... 15.0
Water ........................ Remaining amount

  In the above composition, Orphine STG represents acetylene glycol surfactant (trade name, manufactured by Nissin Chemical Industry Co., Ltd.), and TEGmBE represents triethylene glycol monobutyl ether.

(Composition Example I6: Yellow Ink I3)
Additive amount (%)
Yellow dispersion I3 <90> ... 10.0 (as solids)
DEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
DPGmBE ... 5.0
Ethylene glycol 2.0
2-pyrrolidone ... 1.0
Trimethylolpropane ... 10.0
Glycerin ... 5.0
Water ........................ Remaining amount

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether, and DPGmBE represents dipropylene glycol monobutyl ether.

(Composition Example I7: Magenta Ink I1)
Additive amount (%)
Magenta dispersion I1 <120> ... 8.0 (as solids)
1,2-hexanediol ... 5.0
DEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Diethylene glycol ... 5.0
Glycerin ... 10.0
Urea ... 2.0
Water ........................ Remaining amount

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether.

(Composition Example I8: Magenta Ink I2)
Additive amount (%)
Magenta dispersion I2 <90> ... 10.0 (as solids)
Surfinol 61 ... 1.0
Trimethylolethane ... 8
1,3-dimethyl-2-imidazolidinone ... 2.0
Triethylene glycol ... 10.0
28% ammonia water ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
Water ........................ Remaining amount

  In the above composition, Surfynol 61 represents an acetylene alcohol surfactant (trade name, manufactured by Air Products (USA)).

(Composition example I9: Magenta ink I3)
Additive amount (%)
Magenta dispersion I3 <140> ... 7.5 (as solids)
Olfin E1010 ... 0.1
Olfine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
TEGmBE ... 1.0
1,2-hexanediol ... 2.5
Triethylene glycol ... 2.0
2-Pyrrolidone ... 4.0
Trimethylolpropane ... 6.0
Glycerin ... 14.0
Water ........................ Remaining amount

  In the above composition, Olfine E1010 and Olfine STG are acetylene glycol surfactants (both trade names, manufactured by Nissin Chemical Industry Co., Ltd.), and TEGmBE is triethylene glycol monobutyl ether.

(Composition Example I10: Cyan Ink I1)
Additive amount (%)
Cyan Dispersion I1 <95> ... 6.0 (as solids)
DEGmBE ... 10.0
Diethylene glycol ... 3.0
N-methyl-2-pyrrolidone ... 1.0
Glycerin ... 10.0
Water ........................ Remaining amount

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether.

(Composition Example I11: Cyan Ink I2)
Additive amount (%)
Cyan Dispersion I2 <105> ... 8.0 (as solids)
Surfinol 465 ... 0.5
Olphine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.3
TEGmBE ... 1.0
1,2-hexanediol ... 3.0
Glycerin ... 17.0
Triethylene glycol ... 2.0
2-pyrrolidone ... 2.0
Water ........................ Remaining amount

  In the above composition, Surfynol 465 is an acetylene glycol surfactant (trade name, manufactured by Air Products (USA)), and Olfin STG is an acetylene glycol surfactant (trade name, manufactured by Nissin Chemical Industry Co., Ltd.). ), TEGmBE represents triethylene glycol monobutyl ether.

(Composition example I12: Cyan ink I3)
Additive amount (%)
Cyan Dispersion I3 <110> ... 10.0 (as solids)
Surfinol 61 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
PGmBE ... 5.0
Fructose ... 5.0
1,3-dimethyl-2-imidazolidinone ... 2.0
Tetraethylene glycol ... 10.0
Water ........................ Remaining amount

  In the above composition, Surfynol 61 represents an acetylene alcohol surfactant (trade name, manufactured by Air Products (USA)), and PGmBE represents propylene glycol monobutyl ether.

(Composition example I13: Red ink I1)
Additive amount (%)
Red dispersion I1 <130> ... 10.0 (as solids)
DEGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Olfine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
1,2-pentanediol ... 2.0
Glycerin ... 8.0
Tetraethylene glycol ... 5.0
Trimethylolethane ... 5.0
N-methyl-2-pyrrolidone ... 1.0
Triisopropanolamine ... 1.0
Water ........................ Remaining amount

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether, and orphine STG represents an acetylene glycol surfactant (trade name, manufactured by Nissin Chemical Industry Co., Ltd.).

(Composition Example I14: Blue Ink I1)
Additive amount (%)
Blue dispersion I1 <90> ... 7.5 (as solids)
Olphin E1010 ... 1.0
1,2-pentanediol ... 10.0
Thiodiglycol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 2.0
Ethylene glycol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Trimethylolpropane ... 10.0
1,3-dimethyl-2-imidazolidinone ... 2.0
Triethanolamine ... 0.5
Water ........................ Remaining amount

  In the above composition, Orphine E1010 represents an acetylene glycol surfactant (trade name, manufactured by Nissin Chemical Industry Co., Ltd.).

(Composition Example I15: Green Ink I1)
Additive amount (%)
Green dispersion I1 <120> ... 10.0 (as solids)
TEGmBE ... 5.0
Olphin E1010 ... 1.0
Olfine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
Surfinol 61 ... 0.2
1,2-hexanediol ... 2.0
Glycerin ... 5.0
Trimethylolpropane ... 5.0
Triethylene glycol ... 5.0
2-pyrrolidone ... 2.0
Trehalose ... 1.0
Water ........................ Remaining amount

  In the above composition, TEGmBE is triethylene glycol monobutyl ether, Olphine E1010 and Olphine STG are acetylene glycol surfactants (both are trade names, manufactured by Nissin Chemical Industry Co., Ltd.), and Surfynol 61 is acetylene alcohol. Surfactant (trade name, manufactured by Air Products (USA)) is shown.

  The water-based inks prepared in the composition examples described above were combined to form a water-based ink set, which was used for printing evaluation described later. The combinations of water-based ink sets are shown below.

(Example I-1: Water-based ink set I-1)
In this Example I-1, the four inks black ink I1, yellow ink I2, magenta ink I3, and cyan ink I2 prepared in the above composition example were combined to obtain an aqueous ink set I-1.
(Example I-2: Water-based ink set I-2)
In Example I-2, the four inks black ink I2, yellow ink I1, magenta ink I1, and cyan ink I1 prepared in the above composition example were combined to obtain an aqueous ink set I-2.
(Example I-3: Water-based ink set I-3)
In Example I-3, the four color inks black ink I3, yellow ink I3, magenta ink I2, and cyan ink I3 prepared in the above composition example were combined to obtain an aqueous ink set I-3.
(Example I-4: Water-based ink set I-4)
In this Example I-4, the seven inks black ink I1, yellow ink I2, magenta ink I3, cyan ink I2, red ink I1, blue ink I1, and green ink I1 prepared in the above composition example were combined. Was water-based ink set I-4.

(Comparative example)
(Comparative Example I-1: Preparation of water-based ink set I-5)
In Comparative Example I-1, the black black ink I4 of Comparative Example I-1 was prepared using the carbon black pigment used in the black dispersion I1 as the colorant and the polymer dispersant and the surfactant as the dispersant. . Its composition is shown below.

Additive amount (%)
Carbon black pigment <105> ... 7.0
Glycerin ... 10.0
Polymer dispersing agent ... 3.0
Nonionic surfactant ... 1.0
Ion exchange water

In the above composition, the carbon black pigment is Raben C (trade name, manufactured by Colombian Carbon Co., CI Pigment Black 7), and the nonionic surfactant is Neugen EA160 (trade name, Daiichi Kogyo Seiyaku Co., Ltd.). The polymer dispersant is Solsperse 27000 (trade name, manufactured by Avicia). The composition was subjected to a dispersion treatment for 2 hours using a bead mill mini-zeta (manufactured by Ajisawa Co., Ltd.) to prepare an aqueous inkjet ink according to Comparative Example I-1. In this comparative example, Proxel XL-2, EDTA.2Na salt, and benzotriazole were not added.
In the above composition, the carbon black pigment is C.I. I. A yellow ink I4 of Comparative Example I-1 was prepared in the same composition except that it was changed to CI Pigment Yellow 14 (insoluble disazo pigment).
In the above composition, the carbon black pigment is C.I. I. Magenta ink I4 of Comparative Example I-1 was prepared in the same composition except that it was changed to CI Pigment Red 81 (basic dye lake pigment).
In the above composition, the carbon black pigment is C.I. I. A cyan ink I4 of Comparative Example I-1 was prepared in the same composition except that it was changed to CI Pigment Blue 2 (basic dye lake pigment).
The black ink I4, the yellow ink I4, the magenta ink I4, and the cyan ink I4 prepared with the composition described above are combined to obtain an aqueous ink set I-5 of Comparative Example I-1.

(Comparative Example I-2)
In Comparative Example I-2, an aqueous ink set described in JP-A No. 2001-354886 was prepared. The composition of the pigment dispersion and the water-based ink using the same is shown below.
<Production of Black Dispersion I5>
Additive amount (%)
Carbon black pigment ... 20.0
Styrene-acrylic acid copolymer ... 10.0
Glycerin ... 10.0
Ion exchange water

The above additives were mixed and dispersed with Eiger motor mill M250 type (Eiger Japan Co., Ltd.) filled with 60% by volume of 0.3 mm zirconia beads for 2 hours under the condition of 5,000 rpm. A black dispersion I5 of Comparative Example I-2 was produced. The average particle diameter of the dispersed particles in the obtained black dispersion I5 was 90 nm.
In the above composition, the carbon black pigment is Raven C (trade name, CI Pigment Black 7 manufactured by Colombian Carbon Co.), and the styrene-acrylic acid copolymer is weight average molecular weight 7,000, acid value 150. The thing of was used.

<Preparation of black ink I5>
Using the black dispersion I5 produced by the above composition and method, a black ink I5 of this Comparative Example I-2 was prepared. The composition is shown below.

Additive amount (%)
Black dispersion I5 ... 4.5 (as solids)
Ethylene glycol ... 20.0
TEGmEE ... 5.0
Perex OP-T ... 0.2
Ion exchange water

  In the above composition, PELEX OP-T represents an anionic surfactant (trade name, manufactured by Kao Corporation), and TEGmEE represents triethylene glycol monoethyl ether. In addition to the above composition, 1.5% glycerin is contained as an additive to the black dispersion I5.

<Preparation of yellow dispersion I5>
Additive amount (%)
C. I. Pigment Yellow 128 ... 20.0
Styrene-acrylic acid copolymer ... 12.0
Diethylene glycol ... 15.0
Ion exchange water

The above additives were mixed, and dispersed with Eiger Motor Mill M250 type (Eiger Japan Co., Ltd.) filled with 0.3 mm zirconia beads at a volume ratio of 60% for 2 hours under the condition of 5,000 rpm. A yellow dispersion I5 of Comparative Example I-2 was produced. The average particle diameter of the dispersed particles in the obtained yellow dispersion I5 was 120 nm.
In the above composition, a styrene-acrylic acid copolymer having a weight average molecular weight of 10,000 and an acid value of 120 was used.

<Preparation of yellow ink I5>
A yellow ink I5 of Comparative Example I-2 was prepared using the yellow dispersion I5 produced by the above composition and method. The composition is shown below.

Additive amount (%)
Yellow Dispersion I5 ... 3.2 (as solids)
Ethylene glycol ... 25.0
DEGmME ... 15.0
Emulgen 120 ... 0.2
Ion exchange water

In the above composition, Emulgen 120 represents a nonionic surfactant (trade name, manufactured by Kao Corporation), and DEGmME represents diethylene glycol monomethyl ether. In addition to the above composition, 1.5% of diethylene glycol is contained as a component added to the yellow dispersion I5.

<Preparation of magenta dispersion I5>
Additive amount (%)
C. I. Pigment Red 122 ... 20.0
Styrene-acrylic acid copolymer ... 15.0
Glycerin ... 10.0
Ion exchange water

The above additives were mixed, and dispersed with Eiger Motor Mill M250 type (Eiger Japan Co., Ltd.) filled with 0.3 mm zirconia beads at a volume ratio of 60% for 2 hours under the condition of 5,000 rpm. A magenta dispersion I5 of Comparative Example I-2 was produced. The average particle diameter of the dispersed particles in the obtained magenta dispersion I5 was 100 nm.
In the above composition, a styrene-acrylic acid copolymer having a weight average molecular weight of 7,000 and an acid value of 150 was used.

<Preparation of magenta ink I5>
Using the magenta dispersion I5 produced by the above composition and method, a magenta ink I5 of Comparative Example I-2 was prepared. The composition is shown below.

Additive amount (%)
Magenta dispersion I5 7.0 (as solids)
Diethylene glycol ... 25.0
Ethylene glycol ... 10.0
LEVENOL WX ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.2
Ion exchange water

  In the above composition, Rebenol WX represents an anionic surfactant (trade name, manufactured by Kao Corporation). In addition to the above composition, 2.0% glycerin is contained as a component added to the magenta dispersion I5.

<Preparation of Cyan Dispersion I5>
Additive amount (%)
C. I. Pigment Blue 15: 3 ... 25.0
Jonkrill 61 ... 15.0 (as solids)
Glycerin ... 10.0
Ion exchange water

The above additives were mixed, and dispersed with Eiger Motor Mill M250 type (Eiger Japan Co., Ltd.) filled with 0.3 mm zirconia beads at a volume ratio of 60% for 2 hours under the condition of 5,000 rpm. Cyan dispersion I5 of Comparative Example I-2 was produced. The average particle diameter of the dispersed particles in the obtained cyan dispersion liquid I5 was 90 nm.
In the above composition, John Crill 61 represents a styrene-acrylic acid resin (trade name, manufactured by Johnson Polymer Co., Ltd.).

<Preparation of cyan ink I5>
Cyan ink I5 of Comparative Example I-2 was prepared using cyan dispersion I5 produced by the above composition and method. The composition is shown below.

Additive amount (%)
Cyan Dispersion I5 ... 4.0 (as solids)
Ethylene glycol ... 30.0
DEGmBE ... 10.0
Pluronic L-44 ... 1.0
Ion exchange water

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether, and Pluronic L-44 represents a surfactant (trade name, manufactured by Asahi Denka Co., Ltd.). In addition to the above composition, 1.0% of glycerin is contained as added to the cyan dispersion I5.

<Preparation of Red Dispersion I2>
Additive amount (%)
C. I. Pigment Red 177 ... 20.0
Styrene-acrylic acid copolymer ... 12.0
Diethylene glycol ... 15.0
Ion exchange water

The above additives were mixed and dispersed with Eiger motor mill M250 type (Eiger Japan Co., Ltd.) filled with 60% by volume of 0.3 mm zirconia beads for 2 hours under the condition of 5,000 rpm. A red dispersion I2 of Comparative Example I-2 was produced. The average particle diameter of the dispersed particles in the obtained red dispersion liquid I2 was 110 nm.
In the above composition, a styrene-acrylic acid copolymer having a weight average molecular weight of 10,000 and an acid value of 120 was used.

<Preparation of Red Ink I2>
A red ink I2 of Comparative Example I-2 was prepared using the red dispersion I2 produced by the above composition and method. The composition is shown below.

Additive amount (%)
Red dispersion I2 ... 6.4 (as solids)
Ethylene glycol ... 20.0
LEVENOL WX ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.2
Ion exchange water

  In the above composition, Rebenol WX represents an anionic surfactant (trade name, manufactured by Kao Corporation). In addition to the above composition, 3.0% of diethylene glycol is contained as a component added to the red dispersion liquid I2.

<Preparation of Green Dispersion I2>
Additive amount (%)
C. I. Pigment Green 7 ... 25.0
Jonkrill 61 ... 15.0 (as solids)
Ethylene glycol ... 10.0
Ion exchange water

The above additives were mixed, and dispersed with Eiger Motor Mill M250 type (Eiger Japan Co., Ltd.) filled with 0.3 mm zirconia beads at a volume ratio of 60% for 2 hours under the condition of 5,000 rpm. A green dispersion I2 of Comparative Example I-2 was produced. The average particle diameter of the dispersed particles in the obtained green dispersion liquid I2 was 110 nm.
In the above composition, John Crill 61 represents a styrene-acrylic acid resin (trade name, manufactured by Johnson Polymer Co., Ltd.).

<Preparation of green ink I2>
A green ink I2 of Comparative Example I-2 was prepared using the green dispersion I2 produced by the above composition and method. The composition is shown below.

Additive amount (%)
Green dispersion I2 ... 4.0 (as solids)
Ethylene glycol ... 30.0
Pluronic L-44 ... 1.0
Ion exchange water

In the above composition, Pluronic L-44 represents a surfactant (trade name, manufactured by Asahi Denka Co., Ltd.). In addition to the above composition, 1.0% of ethylene glycol is further included as added to the green dispersion I2.
The black ink I5, the yellow ink I5, the magenta ink I5, the cyan ink I5, the red ink I2, and the green ink I2 having the above-described composition are combined to obtain an aqueous ink set I-6 in this comparative example I-2.

(Evaluation of water-based ink set)
<Print quality of print image>
The aqueous ink set prepared in the above examples and comparative examples is mounted on an ink jet printer PM-950C (trade name, manufactured by Seiko Epson Corporation), and a full color image is printed on plain paper and glossy media. The print quality was evaluated. The plain papers used in this evaluation are ordinary papers that are commercially available in Europe, the United States and Japan. (1) Conqueror paper, (2) Reymat paper, (3) Mode Copy paper, (4) Rapid Copy paper, (5 ) Xerox P paper, (6) Xerox 4024 paper, (7) Xerox 10 paper, (8) Neenah Bond paper, (9) Ricopy 6200 paper, and (10) Hammer mill Copy Plus paper, glossy media in Europe and America And (11) Photo Print Paper 2, (12) MC Photo Paper (Both (11) and (12) are trade names, manufactured by Seiko Epson Corporation), and (13) Ink Jet Paper.
Photo Glossy Paper Super Photo Grade, (14) Ink Jet Paper Photo Paper High
Grade (Both (13) and (14) are trade names, manufactured by Fuji Photo Film Co., Ltd.), (15) Ink Jet Photographic Quality Paper Photo Weight (trade name, manufactured by Kodak), (16) Photo like QP QP20A4GH (trade name) , Manufactured by Konica Corporation. The evaluation was performed by visually observing the degree of bleeding of the printed image. The evaluation criteria are shown below. The evaluation results are shown in Table 36. Note that the circled numbers shown in “Print medium type” in Table 36 are the same as those given to the names of the above-mentioned plain paper and glossy media.

Evaluation A: Blur is not recognized even in the secondary color (red, blue, green) image portion.
B: Slight bleeding is observed in the secondary color (red, blue, green) image portion (practical level).
C: Blur is observed in the image portion of the primary color (black, yellow, magenta, cyan).
D: Bleeding is also severe in the primary color (black, yellow, magenta, cyan) image portion.

In the above evaluation, ink set I-1 of Example I-1, ink set I-2 of Example I-2, ink set I-3 of Example I-3, and ink set I of Comparative Example I-1 As for -5, red has a ratio of 1: 1 for magenta ink and yellow ink, blue has a ratio of 1: 1 for magenta ink and cyan ink, and green has a ratio of 1: 1 for yellow ink and cyan ink. Printed in proportion. For ink set I-4 of Example I-4, the red color was printed with red ink, the blue color with blue ink, and the green color with green ink. Further, for the ink set I-6 of Comparative Example I-2, the red color was printed with red ink, the blue color with magenta ink and cyan ink at a ratio of 1: 1, and the green color with green ink.

As is clear from the results in Table 36, images printed using the aqueous ink set I-5 of Comparative Example I-1 and the aqueous ink set I-6 of Comparative Example I-2 were particularly blurred on plain paper. However, the images printed using the water-based ink sets I-1 to I-4 of Examples I-1 to I-4 had little bleeding regardless of plain paper / glossy media. Among these, in particular, the red, blue, and green image portions printed using the water-based ink set I-4 of Example I-4 provide a clear and blur-free image regardless of plain paper or glossy media. It was.
As described above, according to the present invention, it is possible to provide a water-based ink for ink jet printing that is clear and bleed-free and has high quality and high practicality regardless of plain paper or glossy media.

<Saturation of printed image (C ^* )>
The water-based ink set prepared in the above examples and comparative examples is mounted on an ink jet printer PM-950C (trade name, manufactured by Seiko Epson Corporation), and is on a plain paper and glossy media in increments of 5% from 10% to 100%. Solid pattern printing with varying duty was performed, and the saturation (C ^* ) of the printed image was measured. The plain paper and glossy media used in this evaluation are the same as those used in the evaluation of the print quality of the printed image. Evaluation is made by measuring a printed image with an optical densitometer X-Rite 938 (manufactured by X-Rite Co., Ltd.), obtaining it with an L ^* a ^* b ^* display system defined by the CIE, and a saturation (C ^* ) By calculating.

C ^* = [(a ^* ) ² + (b ^* ) ² ] ^1/2

  The results were evaluated according to the following evaluation criteria. The evaluation results are shown in Table 37. Note that the circled numbers shown in “Print medium type” in Table 37 are the same as in Table 36.

Evaluation A: In all color image areas (yellow area, magenta area, cyan area, red area, blue area, and green area), the maximum saturation (C ^* ) is 50 or more for plain paper and 60 or more for glossy media. Indicates.
B: There is a color image region in which the maximum value of saturation (C ^* ) is 45 to less than 50 for plain paper and 55 to less than 60 for glossy media.
C: There is a color image area in which the maximum value of saturation (C ^* ) is 40 or more and less than 45 for plain paper and 50 or more and less than 60 for glossy media.
D: There is a color image area where the maximum value of saturation (C ^* ) is less than 40 for plain paper and less than 50 for glossy media.

  In the above evaluation, ink set I-1 of Example I-1, ink set I-2 of Example I-2, ink set I-3 of Example I-3, and ink set I of Comparative Example I-1 As for -5, red has a ratio of 1: 1 for magenta ink and yellow ink, blue has a ratio of 1: 1 for magenta ink and cyan ink, and green has a ratio of 1: 1 for yellow ink and cyan ink. Printed in proportion. In the ink set I-4 of Example I-4, the red color was printed with red ink, the blue color with blue ink, and the green color with green ink. Further, for the ink set I-6 of Comparative Example I-2, the red color was printed with red ink, the blue color with magenta ink and cyan ink at a ratio of 1: 1, and the green color with green ink.

As is clear from the results in Table 37, the water-based ink set I-5 of Comparative Example I-1 and the water-based ink set I-6 of Comparative Example I-2 had low saturation (C ^* ) on plain paper. The aqueous ink sets I-1 to I-4 of Examples I-1 to I-4 had high chroma (C ^* ) for both plain paper and glossy media, and were clear. In particular, in the ink set I-4 of Example I-4 using red ink, blue ink, and green ink, clear images with higher saturation in red, blue, and green were obtained.
As described above, according to the present invention, it is possible to provide a high-quality and practical water-based ink set for ink jet printing that can obtain a clear image with high saturation on not only glossy media but also plain paper. it can.

<Optical Density of Printed Image (OD Value)>
The water-based ink set prepared in the above examples and comparative examples is mounted on an ink jet printer PM-950C (trade name, manufactured by Seiko Epson Corporation), and 100% duty solid pattern printing is performed on plain paper and glossy media. The optical density (OD value) of the printed image was measured. The plain paper and glossy media used in this evaluation are the same as those used in the evaluation of the print quality of the printed image. The evaluation was performed by measuring the optical density (OD value) of the printed image with an optical densitometer X-Rite 938 (manufactured by X-Rite). The results were evaluated according to the following evaluation criteria. The evaluation results are shown in Table 38. Note that the circled numbers shown in “Print medium type” in Table 38 are the same as in Table 36.

Evaluation A: In all image areas (black area, yellow area, magenta area, cyan area, red area, blue area, green area), the optical density (OD value) is 1.2 or more on plain paper, and gloss The media shows 1.6 or more.
B: There is an image area where the optical density (OD value) is 1.1 to less than 1.2 for plain paper and 1.5 to less than 1.6 for glossy media.
C: There is an image area where the optical density (OD value) is 1.0 or more and less than 1.1 for plain paper and 1.4 or more and less than 1.5 for glossy media.
D: There is an image area where the optical density (OD value) is less than 1.0 for plain paper and less than 1.4 for glossy media.

  In the above evaluation, ink set I-1 of Example I-1, ink set I-2 of Example I-2, ink set I-3 of Example I-3, and ink set I of Comparative Example I-1 As for -5, red has a ratio of 1: 1 for magenta ink and yellow ink, blue has a ratio of 1: 1 for magenta ink and cyan ink, and green has a ratio of 1: 1 for yellow ink and cyan ink. Printed in proportion. For ink set I-4 of Example I-4, the red color was printed with red ink, the blue color with blue ink, and the green color with green ink. Further, for the ink set I-6 of Comparative Example I-2, the red color was printed with red ink, the blue color with magenta ink and cyan ink at a ratio of 1: 1, and the green color with green ink.

As is apparent from the results of Table 38, the optical density (OD value) of the aqueous ink set I-5 of Comparative Example I-1 and the aqueous ink set I-6 of Comparative Example I-2 was particularly on plain paper. However, the aqueous ink sets I-1 to I-4 of Examples I-1 to I-4 had high optical densities (OD values) for both plain paper and glossy media, and a dark and clear image was obtained. It was.
As described above, in the present invention, a clear image having a high optical density (OD value) can be obtained not only on glossy media but also on plain paper. An ink set can be provided.

<Fixability of printed matter>
The water-based ink set prepared in the above examples and comparative examples was mounted on an ink jet printer PM-950C (trade name, manufactured by Seiko Epson Corporation), printed on glossy media, and the fixability of the printed matter was evaluated. . The glossy media used in this evaluation is the same as that used in the evaluation of the print quality of the printed image. The evaluation was carried out by visually observing the shift / blurred state of characters after rubbing with a finger using a printed image dried under 20 to 25 ° C./40 to 60% RH for one hour after printing. The evaluation criteria are shown below. The evaluation results are shown in Table 39. Note that the circled numbers shown in “Print medium type” in Table 39 are the same as in Table 36.

Evaluation A: Misalignment and blurring are not recognized.
B: A slight deviation is recognized, but there is no practical problem.
C: Misalignment or fading is observed.
D: Displacement and faintness are severe, and characters are difficult to read.

  In the above evaluation, ink set I-1 of Example I-1, ink set I-2 of Example I-2, ink set I-3 of Example I-3, and ink set I of Comparative Example I-1 As for -5, red has a ratio of 1: 1 for magenta ink and yellow ink, blue has a ratio of 1: 1 for magenta ink and cyan ink, and green has a ratio of 1: 1 for yellow ink and cyan ink. Printed in proportion. For ink set I-4 of Example I-4, the red color was printed with red ink, the blue color with blue ink, and the green color with green ink. Further, for the ink set I-6 of Comparative Example I-2, the red color was printed with red ink, the blue color with magenta ink and cyan ink at a ratio of 1: 1, and the green color with green ink.

As is apparent from the results in Table 39, the water-based ink set I-5 of Comparative Example I-1 and the water-based ink set I-6 of Comparative Example I-2 lacked fixing ability. On the other hand, the water-based ink sets I-1 to I-4 of Examples I-1 to I-4 had good fixability. Among these, the water-based ink set I-4 of Example I-4 was particularly excellent in fixability for characters printed in red, blue and green colors.
As described above, the present invention provides a high-quality and highly practical water-based ink set for ink-jet printing that has excellent fixability not only on plain paper but also on glossy media such as glossy paper that is usually used for inkjet. can do.

<Storage stability and ejection stability of water-based ink>
The aqueous inks prepared in the composition examples and comparative examples in the above examples were put in glass sample bottles and sealed tightly, then left at 60 ° C. for 1 week. , Surface tension). The evaluation criteria are shown below. The evaluation results are shown in Table 40.

Evaluation A: The ratio of the amount of foreign matter / physical properties after standing at 60 ° C. to that before standing is in the range of 0.99 to 1.01.
B: The ratio is in the range of 0.95 to 0.99, or 1.01 to 1.05 (practical level).
C: The ratio is in the range of 0.90 to 0.95, or 1.05 to 1.10.
D: Ratio is less than 0.90 or greater than 1.10.

  Further, the ejection stability of the water-based ink sets prepared in the above examples and comparative examples was evaluated. The evaluation method is to visually observe printing irregularities when 100 pages are continuously printed on A4 version Xerox P paper by mounting each of the above water-based ink sets on an inkjet printer PM-950C (trade name, manufactured by Seiko Epson Corporation). Performed. The evaluation criteria are shown below. The evaluation results are shown in Table 40.

Evaluation A: Printing disorder does not occur at all.
B: Printing disorder was observed, but the number was less than 10 (practical level).
C: There is printing disorder in the range of 10 or more and less than 100.
D: Disturbance of printing occurred at 100 locations or more.

As is clear from the results in Table 40, the aqueous inks used in the aqueous ink sets of Comparative Examples I-1 and 2 were inferior in storage stability and ejection stability. In contrast, the water-based inks used in the water-based ink sets of Examples I-1 to I-4 had good storage stability in terms of foreign matter and physical properties, and also had good ejection stability.
On the other hand, in the ink composition shown in Composition Example I1 in the Examples, when the black dispersion I1 was changed to the black dispersion I4 of Comparative Example I-2 and the same experiment was conducted, the change in surface tension was small ( B) by the above evaluation criteria, a large amount of foreign matter is generated (D by the above evaluation criteria), the filterability is lowered, and the ink is thickened (D by the above evaluation criteria), so that stable storage stability is obtained. There wasn't.
As can be seen from the evaluation results described above, the water-based ink set for inkjet printing using the pigment dispersion according to the present invention has little blur regardless of whether it is plain paper or glossy media, and has good saturation, optical density, and fixability. It can be seen that the water-based ink set for ink jet printing exhibits excellent print quality and is excellent in ejection stability and storage stability.

<Evaluation of stability of water-based ink>
In the dispersion polymer used in the production of the black dispersion I1, the dispersion polymer is obtained by changing the ratio of styrene and α-methylstyrene, which are monomers containing aromatic rings, and other monomers, butyl methacrylate, lauryl methacrylate, and acrylic acid. Polymerization was performed to change the amount of the aromatic ring inside. Black dispersions I6 to I13 were produced using this dispersion polymer, and water-based inks were prepared by the same composition and method as in Composition Example I1 in the Examples. In the black dispersions I6 to I14, the carbon black pigment Monarch 880 (trade name, manufactured by Cabot, CI Pigment Black 7) used as a colorant and the weight ratio of the dispersion polymer are the same as those of the black dispersion I1. did. The compositions of the black dispersions I6 to I13 are shown below. Moreover, the result of measuring the amount of aromatic rings in the dispersion polymer by the same method as that for the black dispersion I1 is shown next to the dispersion name.

(Black dispersion I6; amount of aromatic ring in dispersion polymer: 0%)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 0 parts α-methylstyrene: 0 parts Butyl methacrylate: 46 parts Lauryl methacrylate: 30.7 parts Acrylic acid: 6.1 Parts t-dodecyl mercaptan: 0.3 parts styrene: 0 parts acrylic acid: 46 parts butyl methacrylate: 153.3 parts t-dodecyl mercaptan: 1 part azobisisobutyronitrile: 3 parts

(Black dispersion I7; amount of aromatic ring in dispersion polymer: 10%)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 6 parts α-methylstyrene: 2.3 parts Butyl methacrylate: 39.7 parts Lauryl methacrylate: 26.5 parts Acrylic acid : 5.3 parts t-dodecyl mercaptan: 0.3 parts Styrene: 30 parts Acrylic acid: 39.7 parts Butyl methacrylate: 132.4 parts t-dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

(Black dispersion I8; amount of aromatic ring in dispersion polymer: 20%)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 12 parts α-methylstyrene: 4.6 parts Butyl methacrylate: 33.5 parts Lauryl methacrylate: 22.3 parts Acrylic acid : 4.5 parts t-dodecyl mercaptan: 0.3 parts Styrene: 60 parts Acrylic acid: 33.5 parts Butyl methacrylate: 111.7 parts t-dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

(Black dispersion I9; amount of aromatic ring in dispersion polymer: 25%)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 15 parts α-methylstyrene: 5.8 parts Butyl methacrylate: 30.4 parts Lauryl methacrylate: 20.2 parts Acrylic acid : 4.1 parts t-dodecyl mercaptan: 0.3 parts styrene: 75 parts acrylic acid: 30.4 parts butyl methacrylate: 101.2 parts t-dodecyl mercaptan: 1 part azobisisobutyronitrile: 3 parts

(Black dispersion I10; amount of aromatic ring in dispersion polymer: 30%)
Monarch 880 (trade name; manufactured by Cabot Corporation, CI Pigment Black 7): 30 parts Styrene: 18 parts α-methylstyrene: 6.9 parts Butyl methacrylate: 27.2 parts Lauryl methacrylate: 18.2 parts Acrylic acid : 3.6 parts t-dodecyl mercaptan: 0.3 parts Styrene: 90 parts Acrylic acid: 27.2 parts Butyl methacrylate: 90.8 parts t-dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

(Black dispersion I11; amount of aromatic ring in dispersion polymer: 60%)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 36 parts α-Methylstyrene: 13.8 parts Butyl methacrylate: 8.5 parts Lauryl methacrylate: 5.7 parts Acrylic acid : 1.1 parts t-dodecyl mercaptan: 0.3 parts Styrene: 180 parts Acrylic acid: 8.5 parts Butyl methacrylate: 28.4 parts t-dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

(Black dispersion I12; amount of aromatic ring in dispersion polymer: 70%)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 42 parts α-methylstyrene: 16.1 parts Butyl methacrylate: 2.3 parts Lauryl methacrylate: 1.5 parts Acrylic acid : 0.3 part t-dodecyl mercaptan: 0.3 part Styrene: 210 parts Acrylic acid: 2.3 parts Butyl methacrylate: 7.6 parts t-dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

(Black dispersion I13; amount of aromatic ring in dispersion polymer: 73%)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 67 parts α-methylstyrene: 0 parts Butyl methacrylate: 0 parts Lauryl methacrylate: 0 parts Acrylic acid: 0 parts t-Dodecyl Mercaptan: 0.3 parts Styrene: 215 parts Acrylic acid: 0 parts Butyl methacrylate: 0 parts t-Dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

  The storage stability of the water-based ink using the dispersion prepared by the methods and materials described above was evaluated. In the evaluation method, the ink was put into a glass sample bottle and sealed, and then left to stand at 60 ° C. and 70 ° C./1 week, respectively. The evaluation criteria were the same as the storage stability evaluation shown in the storage stability and ejection stability of the water-based ink. The evaluation results are shown in Table 41.

From the results in Table 41, it can be seen that the storage stability can be secured when the amount of the aromatic ring in the dispersion polymer of the present invention is 20% or more and 70% or less. Furthermore, it can be seen that when it is 25% or more and 50% or less, there is no generation of foreign matter and no change in viscosity, which is a preferable form.
As described above, according to the present invention, it is possible to provide a high-quality and practical water-based ink for inkjet printing that is excellent in storage stability and ejection stability. In addition, by using an aqueous ink set in which such an aqueous ink is combined, any of the above-described chroma (C ^* ), optical density (OD value), and fixability of a printed image is evaluated. It can be seen that the evaluation shows excellent print quality characteristics not only on plain paper but also on glossy media usually used for inkjet printing.

Based on the above, penetrants (acetylene glycol surfactants, acetylene alcohols) that are preferred in the present invention when dispersed with conventional dispersants (eg, water-soluble polymer dispersants, surfactants) as described above It is difficult to use a surfactant, a silicon-based surfactant, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and one or more selected from 1,2-alkylene glycol), Therefore, sufficient print quality cannot be obtained. However, when the dispersion according to the present invention includes the dispersion polymer so that it can be dispersed in water and the amount of the benzene ring in the dispersion polymer is 20% or more and 70% or less of the dispersion polymer, Suitable for ink-jet printing that has sufficient color development (saturation, optical density) and fixability on both plain paper and glossy media, while maintaining storage stability and ejection stability, even with water-based inks containing penetrants. A water-based ink set can be provided. Further, since the pigment is used in the water-based ink of the present invention, it has an effect that a printed matter having excellent water resistance and light resistance can be obtained as compared with the case of using a dye that has been conventionally used as a colorant for ink for inkjet printers. Furthermore, since the function of the dispersion polymer for coating the colorant can be freely changed by the polymerization monomer and other reactants, various functions (further light resistance, gas resistance, colorability, gloss, It also has an effect that an improvement function such as fixing property can be provided. Conventionally, when using a dispersant that has been used to disperse a pigment in an aqueous system (for example, a water-soluble polymer dispersant, a surfactant, etc.), the adsorptive power of the dispersant to the pigment is basically weak. Therefore, partial detachment occurs. As a result, the viscosity of the ink increases due to the desorbed material and the dispersant that has not been adsorbed, so that the amount of colorant added is limited and it is difficult to obtain sufficient color development. In particular, when a penetrant that is preferred in the present invention is used, its desorption is significant.
The present invention should not be considered to be limited to these examples, and various modifications can be made without departing from the gist of the present invention.

[Example J]
Next, the present invention will be described in detail by examples. However, the present invention is not limited to such examples.
As an example of the colorant shown in the present invention, the following examples and comparative examples describe cases where some organic or inorganic pigments are used. Organic and inorganic pigments can be used. Each average particle diameter is shown in <> in nm (nanometer) units.
In addition to the experimental examples exemplified below, the dispersion used in the aqueous ink set of the present invention is obtained by dispersing a pigment with a reactive dispersant and then performing emulsion polymerization in water in the presence of a catalyst. You can also

(Production of Black Dispersion J1)
As the black dispersion J1, Monarch 880 (manufactured by Cabot), which is carbon black, was used as a colorant. The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 30 parts of styrene, 10 parts of α-methylstyrene, 15 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t-dodecyl Add 0.3 part of mercaptan and heat to 70 ° C., separately prepared 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile. Was placed in a dropping funnel and the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersed polymer solution having a concentration of 50%.
40 parts of the above dispersion polymer solution, 30 parts of Monarch 880 (manufactured by Cabot), carbon black, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 30 parts of methyl ethyl ketone were mixed and stirred with a homogenizer for 30 minutes. Thereafter, 300 parts of ion-exchanged water was added and further stirred for 1 hour. Then, the whole amount of methyl ethyl ketone and a part of water were distilled off using a rotary evaporator, neutralized with 0.1 mol / L sodium hydroxide to adjust to pH 9, and filtered through a 0.3 μm membrane filter. Thus, a black dispersion J1 having a solid content (dispersion polymer and carbon black) of 20% was obtained.
A part of this dispersion was taken out, acidified by adding 0.1 mol / L HCl, and only the dispersion polymer was taken out by Soxhlet extraction using acetone, and ¹³ C-NMR and DMSO-DM ₆ were used. The amount of the aromatic ring relative to the total weight of the dispersed polymer as measured by ¹ H-NMR (AMX400 manufactured by Bruker (Germany)) was 50%.

(Production of Black Dispersion J2)
The black dispersion J2 was the same as the production of the black dispersion J1, except that 20 parts of Raven C (trade name; manufactured by Columbia Carbon Co., Ltd., CI Pigment Black 7) was used as the colorant. Produced by composition and method.
(Production of Black Dispersion J3)
The black dispersion J3 was the same as the production of the black dispersion J1, except that 46.7 parts of pigment black A (trade name; manufactured by BASF, CI Pigment Black 1), which is carbon black, was used as a colorant. It was manufactured with various compositions and methods.
(Production of yellow dispersion J1)
Yellow dispersion J1 is C.I. I. Except for using 30 parts of Pigment Yellow 180, it was produced by the same composition and method as the production of Black Dispersion J1. (Manufacture of yellow dispersion J2)
Yellow dispersion J2 is C.I. I. Except that 46.7 parts of Pigment Yellow 74 (insoluble monoazo pigment) was used, it was produced by the same composition and method as the production of Black Dispersion J1.
(Production of yellow dispersion J3)
Yellow dispersion J3 is C.I. I. Except for using 80 parts of Pigment Yellow 128 (condensed azo pigment), it was produced by the same composition and method as the production of Black Dispersion J1.

(Production of magenta dispersion J1)
The magenta dispersion J1 is C.I. I. Except for using 30 parts of Pigment Violet 19 (quinacridone pigment), it was produced by the same composition and method as the production of Black Dispersion J1.
(Production of magenta dispersion J2)
The magenta dispersion J2 is C.I. I. Except for using 46.7 parts of Pigment Red 202 (quinacridone pigment), it was produced by the same composition and method as the production of Black Dispersion J1.
(Production of magenta dispersion J3)
The magenta dispersion J3 is C.I. I. Except for using 80 parts of Pigment Red 122 (dimethylquinacridone pigment), it was produced by the same composition and method as the production of Black Dispersion J1.

(Production of cyan dispersion J1)
Cyan dispersion J1 is a C.I. I. Except for using 30 parts of Pigment Blue 15: 3 (copper phthalocyanine pigment), it was produced by the same composition and method as the production of Black Dispersion J1.
(Production of cyan dispersion J2)
Cyan dispersion J2 is a C.I. I. Except for using 20 parts of Pigment Blue 15: 4 (copper phthalocyanine pigment), it was produced by the same composition and method as the production of Black Dispersion J1.
(Production of cyan dispersion J3)
Cyan dispersion J3 is a C.I. I. Except for using 13.3 parts of Pigment Blue 16 (metal-free phthalocyanine pigment), it was produced by the same composition and method as the production of Black Dispersion J1.

(Preparation example of water-based ink)
Specific examples of ink compositions suitable for the aqueous ink set of the present invention are shown below. The added amount of the dispersion is shown as the amount (solid content concentration: the total amount of the pigment and the dispersed polymer surrounding it) converted by weight. <> Indicates that the dispersion and aqueous ink obtained in each of the following Examples and Comparative Examples have a pigment concentration of 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement varies slightly depending on the pigment). The value obtained by diluting with ion-exchanged water and measuring the “average particle size at 20 ° C.” of the dispersed particles with a particle size distribution meter (ELS-800 manufactured by Otsuka Electronics Co., Ltd.) is shown in nm. In the present embodiment, the remaining amount of water is 0.05% by weight of Proxel XL-2 for preventing corrosion of the ink, and 0.02% by weight of benzotriazole for preventing corrosion of the inkjet head member. In order to reduce the influence of metal ions in the ink system, 0.04% by weight of EDTA · 2Na salt was added to ion-exchanged water.

<Composition Example J1: Dark Black Ink J1>
Additive Amount added (wt%)
Black dispersion J1 <105> ... 10.0
DEGmBE ... 2.0
Olphine E1010 ... 1.0
Olphine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.2
1,2-pentanediol ... 2.0
Glycerin ... 12.0
Tetraethylene glycol ... 5.0
2-Pyrrolidone ... 2.0
Water ........................ Remaining amount

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether, and Olfine E1010 and Olfine STG represent acetylene glycol surfactants (both are trade names, manufactured by Nissin Chemical Industry Co., Ltd.).

<Composition Example J2: Light Black Ink J1>
In Composition Example J2, a light black ink J1 was prepared with the same composition as Composition Example J1, except that the amount of black dispersion J1 added was 3.0% by weight in terms of solid content.

<Composition Example J3: Dark Black Ink J2>
Additive Amount added (wt%)
Black dispersion J2 <100> ... 10.0
Surfinol 465 ... 1.0
Glycerin ... 10.0
Tetraethylene glycol ... 5.0
Triethanolamine ... 0.3
Water ........................ Remaining amount

  In the above composition, Surfynol 465 represents an acetylene glycol surfactant (trade name, manufactured by Air Products (USA)).

<Composition Example J4: Dark Black Ink J3>
Additive Amount added (wt%)
Black dispersion J3 <110> ... 10.0
Surfinol 61 ... 0.5
DPGmBE ... 3.0
1,5-pentanediol ... 5.0
Maltose ... 3.0
Thiodiglycol 7.0
Water ........................ Remaining amount

  In the above composition, Surfynol 61 represents an acetylene alcohol surfactant (trade name, manufactured by Air Products (USA)), and DPGmBE represents dipropylene glycol monobutyl ether.

<Composition Example J5: Dark Yellow Ink J1>
Additive Amount added (wt%)
Yellow dispersion J1 <90> ・ ・ ・ ・ ・ 13.0
Surfinol 465 ... 1.0
Surfinol 61 ... 0.3
DPGmBE ... 10.0
Diethylene glycol ... 5.0
2-Pyrrolidone ... 1.0
Glycerin ... 5.0
Water ........................ Remaining amount

  In the above composition, Surfynol 465 is an acetylene glycol surfactant (trade name, manufactured by Air Products (USA)), and Surfynol 61 is an acetylene alcohol surfactant (trade name, Air Products (USA)). DPGmBE represents dipropylene glycol monobutyl ether.

<Composition Example J6: Dark Yellow Ink J2>
Additive Amount added (wt%)
Yellow dispersion J2 <80> ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 8.0
Olphine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
TEGmBE ... 1.0
1,2-hexanediol ... 3.0
2-Pyrrolidone ... 2.0
Trimethylolpropane ... 8.0
Glycerin ... 15.0
Water ........................ Remaining amount

  In the above composition, Orphine STG represents acetylene glycol surfactant (trade name, manufactured by Nissin Chemical Industry Co., Ltd.), and TEGmBE represents triethylene glycol monobutyl ether.

<Composition Example J7: Dark Yellow Ink J3>
Additive Amount added (wt%)
Yellow dispersion J3 <90> ... 10.0
DEGmBE ... 5.0
DPGmBE ... 5.0
Ethylene glycol ... 2.0
2-Pyrrolidone ... 1.0
Trimethylolpropane ... 10.0
Glycerin ... 5.0
Water ........................ Remaining amount

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether, and DPGmBE represents dipropylene glycol monobutyl ether.

<Composition Example J8: Light Yellow Ink J1>
In Composition Example J8, pale yellow ink J1 was prepared with the same composition as Composition Example J7, except that the amount of yellow dispersion J3 added was 2.0 wt% in terms of solid content.

<Composition Example J9: Dark Magenta Ink J1>
Additive Amount added (wt%)
Magenta dispersion J1 <120> ... 8.0
1,2-hexanediol ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
DEGmBE ... 5.0
Diethylene glycol ... 5.0
Glycerin ... 10.0
Urea ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 2.0
Water ........................ Remaining amount

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether.

<Composition Example J10: Light Magenta Ink J1>
In Composition Example J10, light magenta ink J1 was prepared with the same composition as Composition Example J9 except that the amount of magenta dispersion J1 added was 4.0% by weight in terms of solid content.

<Composition Example J11: Dark Magenta Ink J2>
Additive Amount added (wt%)
Magenta dispersion J2 <90> ... 10.0
Surfinol 61 ... 1.0
Trimethylolethane ... 8
1,3-dimethyl-2-imidazolidinone 2.0
Triethylene glycol ... 10.0
28% ammonia water 0.5
Water ........................ Remaining amount

  In the above composition, Surfynol 61 represents an acetylene alcohol surfactant (trade name, manufactured by Air Products (USA)).

<Composition Example J12: Light Magenta Ink J2>
In Composition Example J12, light magenta ink J2 was prepared with the same composition as Composition Example J11 except that the amount of magenta dispersion J2 added was 3.0% by weight in terms of solid content.

<Composition Example J13: Dark Magenta Ink J3>
Additive Amount added (wt%)
Magenta dispersion J3 <140> ・ ・ ・ ・ ・ 7.5
Olphine E1010 ... 0.1
Olphine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.5
TEGmBE ... 1.0
1,2-hexanediol ... 2.5
Triethylene glycol ... 2.0
2-Pyrrolidone ... 4.0
Trimethylolpropane ... 6.0
Glycerin ... 14.0
Water ........................ Remaining amount

  In the above composition, Olfine E1010 and Olfine STG are acetylene glycol surfactants (both trade names, manufactured by Nissin Chemical Industry Co., Ltd.), and TEGmBE is triethylene glycol monobutyl ether.

<Composition Example J14: Light Magenta Ink J3>
In Composition Example J14, light magenta ink J3 was prepared with the same composition as Composition Example J15 except that the amount of magenta dispersion J3 added was 2.0 wt% in terms of solid content.

<Composition Example J15: Dark Cyan Ink J1>
Additive Amount added (wt%)
Cyan dispersion J1 <95> ... 6.0
DEGmBE ... 10.0
Diethylene glycol ... 3.0
N-methyl-2-pyrrolidone ... 1.0
Glycerin ... 10.0
Water ........................ Remaining amount

  In the above composition, DEGmBE represents diethylene glycol monobutyl ether.

<Composition Example J16: Light Cyan Ink J1>
In Composition Example J16, light cyan ink J1 was prepared with the same composition as Composition Example J15 except that the amount of cyan dispersion J1 added was 1.2 wt% in terms of solid content.

<Composition Example J17: Dark Cyan Ink J2>
Additive Amount added (wt%)
Cyan dispersion J2 <105> ... 8.0
Surfinol 465 ... 0.5
Olphine STG ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 0.3
TEGmBE ... 1.0
1,2-hexanediol ... 3.0
Glycerin ... 17.0
Triethylene glycol ... 2.0
2-Pyrrolidone ... 2.0
Water ........................ Remaining amount

  In the above composition, Surfynol 465 is an acetylene glycol surfactant (trade name, manufactured by Air Products (USA)), and Olfin STG is an acetylene glycol surfactant (trade name, manufactured by Nissin Chemical Industry Co., Ltd.). ), TEGmBE represents triethylene glycol monobutyl ether.

<Composition Example J18: Light Cyan Ink J2>
In Composition Example J18, light cyan ink J2 was prepared with the same composition as Composition Example J17, except that the amount of cyan dispersion J2 added was 1.6 wt% in terms of solid content.

<Composition Example J19: Dark Cyan Ink J3>
Additive Amount added (wt%)
Cyan dispersion J3 <110> ... 10.0
Surfinol 61 ... 0.5
PGmBE ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ 5.0
Fructose ... 5.0
1,3-dimethyl-2-imidazolidinone 2.0
Tetraethylene glycol ... 10.0
Water ........................ Remaining amount

  In the above composition, Surfynol 61 represents an acetylene alcohol surfactant (trade name, manufactured by Air Products (USA)), and PGmBE represents propylene glycol monobutyl ether.

<Composition Example J20: Light Cyan Ink J3>
In Composition Example J20, light cyan ink J3 was prepared with the same composition as in Composition Example J19 except that the amount of cyan dispersion J3 added was 1.5 wt% in terms of solid content.
The water-based inks prepared in the composition examples described above were combined to form a water-based ink set, which was used for printing evaluation described later. The combinations of water-based ink sets are shown below.

<Example J-1: Water-based ink set J1>
In Example J-1, six inks, dark black ink J1, dark yellow ink J2, dark magenta ink J3, dark cyan ink J2, light magenta ink J1, and light cyan ink J1, prepared in the above composition example, were used. This was used as a water-based ink set J1.
<Example J-2: Water-based ink set J2>
In this Example J-2, six inks of dark black ink J2, dark yellow ink J1, dark magenta ink J1, dark cyan ink J1, light magenta ink J2, and light cyan ink J2 prepared in the above composition example were used. This was used as a water-based ink set J2.
<Example J-3: Water-based ink set J3>
In this Example J-3, six colors of ink, dark black ink J3, dark yellow ink J3, dark magenta ink J2, dark cyan ink J3, light magenta ink J3, and light cyan ink J3 prepared in the above composition example, were used. This was used as a water-based ink set J3.

<Example J-4: Water-based ink set J4>
In Example J-4, the dark black ink J1, dark yellow ink J1, dark magenta ink J1, dark cyan ink J1, light yellow ink J1, light magenta ink J1, and light cyan ink J1 prepared in the above composition example were used. Seven color inks were combined and used as water-based ink set J4.
<Example J-5: Water-based ink set J5>
In Example J-5, the dark black ink J2, dark yellow ink J2, dark magenta ink J2, dark cyan ink J2, light black ink J1, light magenta ink J2, and light cyan ink J2 prepared in the above composition example were used. Seven color inks were combined and used as water-based ink set J5.
<Example J-6: Water-based ink set J6>
In Example J-6, the dark black ink J3, dark yellow ink J3, dark magenta ink J3, dark cyan ink J3, light black ink J1, light yellow ink J1, light magenta ink J3, prepared in the above composition example, Eight colors of light cyan ink J3 were combined and used as water-based ink set J6.

(Comparative Example J)
<Comparative Example J-1: Preparation of water-based ink set J7>
In Comparative Example J-1, the dark black ink J4 of this Comparative Example J-1 was prepared using the carbon black pigment used in the black dispersion J1 as the colorant and the polymer dispersant and the surfactant as the dispersant. . Its composition is shown below.

Additive Amount added (wt%)
Carbon black pigment <105> ... 7.0
Glycerin ... 10.0
Polymer dispersing agent ... 3.0
Nonionic surfactant ... 1.0
Ion exchange water

In the above composition, the carbon black pigment is Raven C (trade name, manufactured by Colombian Carbon Co., Ltd., CI Pigment Black 7), and the nonionic surfactant is Neugen EA160 (trade name, Daiichi Kogyo Seiyaku). The polymer dispersant is Solsperse 27000 (trade name, manufactured by Avicia). The composition was subjected to a dispersion treatment for 2 hours with a bead mill mini-zeta (manufactured by Ajisawa Co., Ltd.) to prepare dark black ink J4 according to Comparative Example J-1. In this comparative example, Proxel XL-2, EDTA.2Na salt, and benzotriazole were not added.
In the above composition, the carbon black pigment is C.I. I. A dark yellow ink J4 of this comparative example J-1 was prepared with the same composition except that it was changed to Pigment Yellow 14 (insoluble disazo pigment).
In the above composition, the carbon black pigment is C.I. I. A dark magenta ink J4 of this comparative example J-1 was prepared with the same composition except that it was changed to CI Pigment Red 81 (basic dye lake pigment).
In the above composition, the carbon black pigment is C.I. I. A light magenta ink J4 of this comparative example J-1 was prepared with the same composition except that it was changed to CI Pigment Red 81 (basic dye lake pigment) and its addition amount was 2.0% by weight.

In the above composition, the carbon black pigment is C.I. I. A dark cyan ink J4 of this comparative example J-1 was prepared with the same composition except that it was changed to CI Pigment Blue 2 (basic dye lake pigment).
In the above composition, the carbon black pigment is C.I. I. A light cyan ink J4 of this comparative example J-1 was prepared with the same composition except that it was changed to CI Pigment Blue 2 (basic dye lake pigment) and added in an amount of 1.5% by weight.
An ink set combining six colors of dark black ink J4, dark yellow ink J4, dark magenta ink J4, dark cyan ink J4, light magenta ink J4, and light cyan ink J4 prepared with the composition described above is shown in this comparative example. Let it be J-1 aqueous ink set J7.

<Comparative Example J-2>
In Comparative Example J-2, a dispersion and an aqueous ink set described in JP-A-2002-30235 were produced. In this comparative example, a water-soluble resin was used as a dispersion polymer used for the dispersion. The composition of the dispersion and the water-based ink using the dispersion is shown below.

<Production of Black Dispersion J4>
Additive Amount added (wt%)
Carbon black pigment ... 20.0
Styrene-acrylic acid copolymer ... 10.0
Glycerin ... 10.0
Ion exchange water

The above additives were mixed and dispersed with Eiger motor mill M250 type (Eiger Japan Co., Ltd.) filled with 0.3 mm zirconia beads at a volume ratio of 60% for 2 hours under the condition of 5,000 rpm. A black dispersion J4 of Comparative Example J-2 was produced. The average particle diameter of the obtained black dispersion J4 was 75 nm.
In the above composition, the carbon black pigment is Raven C (trade name, CI Pigment Black 7 manufactured by Colombian Carbon Co., Ltd.), and the styrene-acrylic acid copolymer is 7,000 weight average molecular weight, acid value 150 were used.

<Preparation of dark black ink J5>
Using the black dispersion J4 produced by the above composition and method, a dark black ink J5 of this comparative example J-2 was prepared. The composition is shown below.

Additive Amount added (wt%)
Black dispersion J4 ... 10.0
Acrylic emulsion ... 8.0
Ethylene glycol ... 20.0
Diethylene glycol ... 10.0
Maltitol ... 5.0
Surfinol 465 ... 0.1
Ion exchange water

  In the above composition, the acrylic emulsion is Yodosol GD86B (trade name, manufactured by Japan NCS, glass transition temperature: 60 ° C., average particle size: 90 nm), and Surfynol 465 is an acetylene glycol surfactant (trade name, air). Product (USA)). In addition to the above composition, 1.0% by weight of glycerin is included as added to the black dispersion J4.

<Preparation of light black ink J2>
The light black ink J2 of this comparative example J-2 was prepared using the black dispersion J4 produced by the above composition and method. The composition is shown below.

Additive Amount added (wt%)
Black dispersion J4 ... 2.0
Acrylic emulsion ... 8.0
Ethylene glycol ... 25.0
Diethylene glycol ... 10.0
Maltitol ... 10.0
Surfinol 465 ... 0.1
Ion exchange water

  In the above composition, the acrylic emulsion is Yodosol GD86B (trade name, manufactured by Japan NCS, glass transition temperature: 60 ° C., average particle size: 90 nm), and Surfynol 465 is an acetylene glycol surfactant (trade name, air). Product (USA)). In addition to the above composition, 0.2% by weight of glycerin is included as added to the black dispersion J4.

<Preparation of yellow dispersion J4>
Additive Amount added (wt%)
C. I. Pigment Yellow 74 ... 20.0
Styrene-acrylic acid copolymer ... 12.0
Diethylene glycol ... 15.0
Ion exchange water

The above additives were mixed and dispersed with Eiger motor mill M250 type (Eiger Japan Co., Ltd.) filled with 0.3 mm zirconia beads at a volume ratio of 60% for 2 hours under the condition of 5,000 rpm. A yellow dispersion J4 of Comparative Example J-2 was produced. The average particle diameter of the obtained yellow dispersion J4 was 112 nm.
In the above composition, a styrene-acrylic acid copolymer having a weight average molecular weight of 10,000 and an acid value of 120 was used.

<Preparation of dark yellow ink J5>
Using the yellow dispersion J4 produced by the above composition and method, a dark yellow ink J5 of this comparative example J-2 was prepared. The composition is shown below.
Additive Amount added (wt%)
Yellow dispersion J4 ... 15.0
Acrylic emulsion ... 10.0
Ethylene glycol ... 20.0
Diethylene glycol ... 10.0
Maltitol ... 5.0
Surfinol 465 ... 0.1
Ion exchange water

  In the above composition, acrylic emulsion is Yodosol AD53 (trade name, manufactured by Japan NCS, glass transition temperature: 80 ° C., average particle size: 80 nm), and Surfynol 465 is an acetylene glycol surfactant (trade name, air). Product (USA)). In addition to the above composition, 2.25% by weight of diethylene glycol is contained as a component added to the yellow dispersion J4.

<Preparation of light yellow ink J2>
A pale yellow ink J2 of Comparative Example J-2 was prepared using the yellow dispersion J4 produced by the above composition and method. The composition is shown below.

Additive Amount added (wt%)
Yellow dispersion J4 ... 3.0
Acrylic emulsion ... 10.0
Ethylene glycol ... 25.0
Diethylene glycol ... 10.0
Maltitol ... 10.0
Surfinol 465 ... 0.1
Ion exchange water

In the above composition, acrylic emulsion is Yodosol AD53 (trade name, manufactured by Japan NCS, glass transition temperature: 80 ° C., average particle size: 80 nm), and Surfynol 465 is an acetylene glycol surfactant (trade name, air). Product (USA)). In addition to the above composition, 0.45% by weight of diethylene glycol is contained as a component added to the yellow dispersion J4.

<Preparation of magenta dispersion J4>
Additive Amount added (wt%)
C. I. Pigment Red 122 ... 25.0
Jonkrill 61J ... (as solid content) 18.0
Diethylene glycol ... 15.0
Ion exchange water

The above additives were mixed and dispersed with Eiger motor mill M250 type (Eiger Japan Co., Ltd.) filled with 0.3 mm zirconia beads at a volume ratio of 60% for 2 hours under the condition of 5,000 rpm. A magenta dispersion J4 of Comparative Example J-2 was produced. The average particle size of the obtained magenta dispersion J4 was 100 nm.
In the above composition, Joncrill 61J represents a styrene-acrylic acid copolymer (trade name, manufactured by Johnson Polymer Co., Ltd., concentration: 30.5% by weight, weight average molecular weight 10,000, acid value 195).

<Preparation of dark magenta ink J5>
A dark magenta ink J5 of this comparative example J-2 was prepared using the magenta dispersion J4 produced by the above composition and method. The composition is shown below.

Additive Amount added (wt%)
Magenta dispersion J4 ... 15.0
Styrene-acrylic emulsion ... 10.0
Ethylene glycol ... 20.0
Diethylene glycol ... 10.0
Maltitol ... 5.0
Surfinol 465 ... 0.1
Ion exchange water

  In the above composition, styrene-acryl emulsion is Microgel E-1002 (trade name, manufactured by Nippon Paint Co., Ltd., glass transition temperature: about 60 ° C., average particle size: 100 nm), and Surfynol 465 is acetylene glycol surfactant. The agent (trade name, manufactured by Air Products (USA)) is shown. In addition to the above composition, 2.25% by weight of diethylene glycol is contained as an additive to the magenta dispersion J4.

<Preparation of light magenta ink J5>
A light magenta ink J5 of this comparative example J-2 was prepared using the magenta dispersion J4 produced by the above composition and method. The composition is shown below.

Additive Amount added (wt%)
Magenta dispersion J4 ... 3.0
Styrene-acrylic emulsion ... 8.0
Ethylene glycol ... 25.0
Diethylene glycol ... 10.0
Maltitol ... 10.0
Surfinol 465 ... 0.1
Ion exchange water

In the above composition, the styrene-acryl emulsion is Microgel E-1002 (
Trade name, manufactured by Nippon Paint Co., Ltd., glass transition temperature: about 60 ° C., average particle size: 100 nm), Surfynol 465 indicates acetylene glycol surfactant (trade name, manufactured by Air Products (USA)). In addition to the above composition, 0.45% by weight of diethylene glycol is contained as an additive to the magenta dispersion J4.

<Preparation of cyan dispersion J4>
Additive Amount added (wt%)
C. I. Pigment Blue 15: 3 ... 25.0
Jonkrill 61J (as solids) 15.0
Glycerin ... 10.0
Ion exchange water

The above additives were mixed and dispersed with Eiger motor mill M250 type (Eiger Japan Co., Ltd.) filled with 0.3 mm zirconia beads at a volume ratio of 60% for 2 hours under the condition of 5,000 rpm. A cyan dispersion J4 of Comparative Example J-2 was produced. The average particle diameter of the obtained cyan dispersion J4 was 87 nm.
In the above composition, Joncrill 61J represents a styrene-acrylic acid copolymer (trade name, manufactured by Johnson Polymer Co., Ltd., concentration: 30.5% by weight, weight average molecular weight 10,000, acid value 195).

<Preparation of dark cyan ink J5>
Using the cyan dispersion J4 produced by the above composition and method, a dark cyan ink J5 of this comparative example J-2 was prepared. The composition is shown below.

Additive Amount added (wt%)
Cyan dispersion J4 ... 10.0
Acrylic emulsion ... 10.0
Ethylene glycol ... 20.0
Diethylene glycol ... 10.0
Maltitol ... 5.0
Surfinol 465 ... 0.1
Ion exchange water

  In the above composition, the acrylic emulsion is Yodosol GD86B (trade name, manufactured by Japan NCS, glass transition temperature: 60 ° C., average particle size: 90 nm), and Surfynol 465 is an acetylene glycol surfactant (trade name, air). Product (USA)). In addition to the above composition, 1.0% by weight of glycerin is included as added to the cyan dispersion J4.

<Preparation of light cyan ink J5>
A light cyan ink J5 of Comparative Example J-2 was prepared using the cyan dispersion J4 produced by the above composition and method. The composition is shown below.

Additive Amount added (wt%)
Cyan dispersion J4 ... 2.0
Acrylic emulsion ... 10.0
Ethylene glycol ... 20.0
Diethylene glycol ... 10.0
Maltitol ... 5.0
Surfinol 465 ... 0.1
Ion exchange water

In the above composition, the acrylic emulsion is Yodosol GD86B (trade name, manufactured by Japan NCS, glass transition temperature: 60 ° C., average particle size: 90 nm), and Surfynol 465 is an acetylene glycol surfactant (trade name, air). Product (USA)). In addition to the above composition, 0.2% by weight of glycerin is contained as added to the cyan dispersion J4.
Dark black ink J5, light black ink J2, dark yellow ink J5, light yellow ink J2, dark magenta ink J5, light magenta ink J5, dark cyan ink J5, and light cyan ink J5 prepared with the materials and compositions described above. These eight colors are combined to obtain a water-based ink set J8 of Comparative Example J-2.

(Evaluation of water-based ink set)
<(1) Evaluation of print quality on plain paper and glossy media>
The water-based ink set prepared in the above examples and comparative examples is mounted on a modified inkjet printer PM-950C (trade name, manufactured by Seiko Epson Corporation), and a full color image of a person is printed on plain paper and glossy media. The print quality due to bleeding and graininess of the printed image was evaluated. The plain papers used in this evaluation are commercially available plain papers in Europe, the United States and Japan (1) Conqueror paper, (2) Reymat paper, (3) Mode Copy paper, (4) Rapid Copy paper, (5 ) Xerox P paper, (6) Xerox 4024 paper, (7) Xerox 10 paper, (8) Neenah Bond paper, (9) Riccopy 6200 paper, and (10) Hammer mill Copyplus paper, glossy media are Europe and America (11) Photo print paper 2, (12) MC photo paper (Both (11) and (12) are trade names, manufactured by Seiko Epson Corporation), (13) Ink Jet Paper Photo Glossy Paper Super Photo Grade, 14) Ink Jet Paper Photo High Grade (trade names (13, 14), Fuji Photo Film Co., Ltd.), (15) Ink Jet photo Quality Paper Photo Weight (product name, Kodak Co., Ltd.), 16 ) Photolike QP QP20A4GH (trade name, manufactured by Konica Corporation). Evaluation was made visually. The evaluation criteria are shown below. The evaluation results are shown in Table 42. Note that the parenthesis numerals shown for the print medium types in Table 42 are the same as the parenthesis numerals assigned to the names of the above-mentioned plain paper and glossy media.

Evaluation A: Blur is not recognized in all image portions. The shadow on the person's skin looks smooth.
B: Slight bleeding is observed in an image portion where two or more colors of ink overlap. There is a slight graininess in the shadow area of human skin (practical level).
C: Slight blur is observed in the monochromatic image portion. There is a graininess in the shadows of the person's skin.
D: The blur is severe even in the monochromatic image portion. Graininess is remarkable in the shadow of the person's skin.

As is apparent from the results in Table 42, images printed using the water-based ink set J7 of Comparative Example J-1 and the water-based ink set J8 of Comparative Example J-2 have much blurring and poor graininess, particularly on plain paper. However, the images printed using the water-based ink sets J1 to J6 of Examples J-1 to 6 had less blur regardless of whether they were plain paper or glossy media. Among these, in particular, the image printed using the water-based ink set J5 or J6 gave a clear image with smooth gradation and no blur or graininess in the gray portion irrespective of plain paper / glossy media.
As described above, according to the present invention, it is possible to provide a high-quality and practical water-based ink for ink jet recording that is clear and bleed-free regardless of plain paper / glossy media.

<(2) Evaluation of glossiness on glossy media>
The water-based ink set created in the above examples and comparative examples is mounted on a modified inkjet printer PM-950C (trade name, manufactured by Seiko Epson Corporation), and the resolution is 720 dpi × 720 dpi on glossy media from 5%. A solid pattern with the duty changed in increments of 5% up to 100% was printed, and the glossiness of the printed matter was evaluated. The glossy media used in this evaluation are the glossy media (numbers (11) to (16)) used in <(1) Evaluation of print quality on plain paper and glossy media>. Evaluation was made visually. The evaluation criteria are shown below. The evaluation results are shown in Table 43. The parenthesized numerals shown in Table 43 for the print medium type are the same as those in Table 42.

Evaluation A: Glossiness is recognized in all solid patterns.
B: Although the printed part of 100% duty is slightly lacking in gloss, it is a level at which there is no practical problem.
C: Printed portion with 50% duty or more lacks gloss.
D: All the solid patterns lack gloss.

As is apparent from the results in Table 43, the water-based ink set J7 of Comparative Example J-1 and the water-based ink set J8 of Comparative Example J-2 lacked gloss and further had a low printing density. On the other hand, the water-based ink sets J1 to J6 of Examples J-1 to 6 were clear and glossy with high density.
As described above, the present invention provides a water-based ink set that is excellent in gloss, high-quality, and highly practical for inkjet recording even in glossy media such as glossy paper that is usually used for inkjet. Can do.

<(3) Evaluation of fixability of printed matter>
The water-based ink set prepared in the above examples and comparative examples is mounted on a modified inkjet printer PM-950C (trade name, manufactured by Seiko Epson Corporation), and characters are printed on plain paper and glossy media. The fixability of was evaluated. The plain paper and glossy media used in this evaluation were the same as those used in <(1) Evaluation of print quality on plain paper and glossy media>. The evaluation was performed by visually observing the misalignment / blurred state of characters after rubbing with a finger, using a printed matter dried at 20 to 25 ° C./40 to 60% RH for one hour after printing. The evaluation criteria are shown below. The evaluation results are shown in Table 44. Note that the parenthesis numerals shown for the print medium types in Table 44 are the same as those in Table 42.

Evaluation A: Misalignment and blurring are not recognized.
B: A slight deviation is recognized, but there is no practical problem.
C: Misalignment or fading is observed.
D: Displacement and faintness are severe, and characters are difficult to read.

As is clear from the results in Table 44, the water-based ink set J7 of Comparative Example J-1 and the water-based ink set J8 of Comparative Example J-2 lacked fixing properties particularly in glossy media. In contrast, the water-based ink sets J1 to J6 of Examples J-1 to 6 had good fixability for both plain paper and glossy media.
As described above, in the present invention, a high-quality and practical water-based ink set for ink-jet recording has excellent fixability not only on plain paper but also on glossy media such as glossy paper usually used for ink-jet. Can be provided.

<(4) Evaluation of storage stability and ejection stability of water-based ink>
The aqueous inks prepared in the composition examples and comparative examples in the above examples were put in glass sample bottles and sealed tightly, then left at 60 ° C. for 1 week. , Surface tension). The evaluation criteria are shown below. The evaluation results are shown in Table 45.

Evaluation A: The ratio of the amount of foreign matter / physical properties after standing at 60 ° C. to that before standing is in the range of 0.99 to 1.01.
B: The ratio is in the range of 0.95 to 0.99, or 1.01 to 1.05 (practical level).
C: The ratio is in the range of 0.90 to 0.95, or 1.05 to 1.10.
D: Ratio is less than 0.90 or greater than 1.10.

  Further, the ejection stability of the water-based ink sets prepared in the above examples and comparative examples was evaluated. The evaluation method is to visually observe printing irregularities when 100 pages are continuously printed on A4 version Xerox P paper by mounting each of the above water-based ink sets on a modified inkjet printer PM-950C (trade name, manufactured by Seiko Epson Corporation). It was done by doing. The evaluation criteria are shown below. The evaluation results are shown in Table 45.

Evaluation A: No printing disturbance occurs in any water-based ink.
B: Although there was water-based ink in which printing disturbance was observed, it was less than 10 places (practical level).
C: There is a water-based ink having printing disorder in a range of 10 or more and less than 100.
D: There is a water-based ink in which printing disorder occurs at 100 or more locations.

As is clear from the results in Table 45, the aqueous inks used in the aqueous ink sets of Comparative Examples J-1 and J-2 were inferior in storage stability and ejection stability. On the other hand, the water-based inks used in the water-based ink sets of Examples J-1 to 6 had good storage stability in terms of both foreign matter and physical properties, and good discharge stability.
On the other hand, when the black dispersion J1 was replaced with the black dispersion J4 of Comparative Example J-2 with the ink composition shown in Composition Example J1 in the Examples, the change in surface tension was small ( B) by the above evaluation criteria, a large amount of foreign matter is generated (D by the above evaluation criteria), the filterability is lowered, and the ink is thickened (D by the above evaluation criteria), so that stable storage stability is obtained. There wasn't.
As can be seen from the evaluation results described above, the water-based ink set using the dispersion according to the present invention exhibits good print quality regardless of plain paper or glossy media, and is excellent in ejection stability and storage stability. It turns out that it becomes a water-based ink set suitable for inkjet recording.

<(5) Evaluation of stability of water-based ink>
In the dispersion polymer used in the production of the black dispersion J1, the dispersion polymer is obtained by changing the ratio of styrene and α-methylstyrene, which are monomers containing aromatic rings, and other monomers, butyl methacrylate, lauryl methacrylate, and acrylic acid. Polymerization was performed to change the amount of the aromatic ring inside. Black dispersions J5 to J12 were produced using this dispersion polymer, and water-based inks were prepared by the same composition and method as in composition example J1 in the examples. In the black dispersions J5 to J12, the carbon black pigment Monarch 880 (trade name, manufactured by Cabot, CI Pigment Black 7) used as the colorant and the weight ratio of the dispersion polymer were the same as those of the black dispersion J1. . The compositions of black dispersions J5 to J12 are shown below. Moreover, the result of measuring the amount of aromatic rings in the dispersion polymer by the same method as that for the black dispersion J1 is shown next to the dispersion name.

(Black dispersion J5; amount of aromatic ring in dispersion polymer: 0% by weight)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 0 parts α-methylstyrene: 0 parts Butyl methacrylate: 46 parts Lauryl methacrylate: 30.7 parts Acrylic acid: 6.1 Parts t-dodecyl mercaptan: 0.3 parts styrene: 0 parts acrylic acid: 46 parts butyl methacrylate: 153.3 parts t-dodecyl mercaptan: 1 part azobisisobutyronitrile: 3 parts

(Black dispersion J6; amount of aromatic ring in dispersion polymer: 10% by weight)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 6 parts α-methylstyrene: 2.3 parts Butyl methacrylate: 39.7 parts Lauryl methacrylate: 26.5 parts Acrylic acid : 5.3 parts t-dodecyl mercaptan: 0.3 parts Styrene: 30 parts Acrylic acid: 39.7 parts Butyl methacrylate: 132.4 parts t-dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

(Black dispersion J7; amount of aromatic ring in dispersion polymer: 20% by weight)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 12 parts α-methylstyrene: 4.6 parts Butyl methacrylate: 33.5 parts Lauryl methacrylate: 22.3 parts Acrylic acid : 4.5 parts t-dodecyl mercaptan: 0.3 parts Styrene: 60 parts Acrylic acid: 33.5 parts Butyl methacrylate: 111.7 parts t-dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

(Black dispersion J8; amount of aromatic ring in dispersion polymer: 25% by weight)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 15 parts α-methylstyrene: 5.8 parts Butyl methacrylate: 30.4 parts Lauryl methacrylate: 20.2 parts Acrylic acid : 4.1 parts t-dodecyl mercaptan: 0.3 parts styrene: 75 parts acrylic acid: 30.4 parts butyl methacrylate: 101.2 parts t-dodecyl mercaptan: 1 part azobisisobutyronitrile: 3 parts

(Black dispersion J9; amount of aromatic ring in dispersion polymer: 30% by weight)
Monarch 880 (trade name; manufactured by Cabot Corporation, CI Pigment Black 7): 30 parts Styrene: 18 parts α-methylstyrene: 6.9 parts Butyl methacrylate: 27.2 parts Lauryl methacrylate: 18.2 parts Acrylic acid : 3.6 parts t-dodecyl mercaptan: 0.3 parts Styrene: 90 parts Acrylic acid: 27.2 parts Butyl methacrylate: 90.8 parts t-dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

(Black dispersion J10; amount of aromatic ring in dispersion polymer: 60% by weight)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 36 parts α-Methylstyrene: 13.8 parts Butyl methacrylate: 8.5 parts Lauryl methacrylate: 5.7 parts Acrylic acid : 1.1 parts t-dodecyl mercaptan: 0.3 parts Styrene: 180 parts Acrylic acid: 8.5 parts Butyl methacrylate: 28.4 parts t-dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

(Black dispersion J11; amount of aromatic ring in dispersed polymer: 70% by weight)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 42 parts α-methylstyrene: 16.1 parts Butyl methacrylate: 2.3 parts Lauryl methacrylate: 1.5 parts Acrylic acid : 0.3 part t-dodecyl mercaptan: 0.3 part Styrene: 210 parts Acrylic acid: 2.3 parts Butyl methacrylate: 7.6 parts t-dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

(Black dispersion J12; amount of aromatic ring in dispersed polymer: 73% by weight)
Monarch 880 (trade name; manufactured by Cabot, CI Pigment Black 7): 30 parts Styrene: 67 parts α-methylstyrene: 0 parts Butyl methacrylate: 0 parts Lauryl methacrylate: 0 parts Acrylic acid: 0 parts t-Dodecyl Mercaptan: 0.3 parts Styrene: 215 parts Acrylic acid: 0 parts Butyl methacrylate: 0 parts t-Dodecyl mercaptan: 1 part Azobisisobutyronitrile: 3 parts

  The storage stability of the water-based ink using the dispersion prepared by the methods and materials described above was evaluated. In the evaluation method, the ink was put into a glass sample bottle and sealed, and then left to stand at 60 ° C. and 70 ° C./1 week, respectively, and the foreign matter and physical property value (viscosity) of the ink before and after being left were examined. The evaluation criteria were the same as the storage stability evaluation shown in <(4) Evaluation of storage stability and ejection stability of water-based ink> above. The evaluation results are shown in Table 46.

From the results in Table 46, it can be seen that the storage stability can be secured when the amount of the aromatic ring in the dispersion polymer of the present invention is in the range of 20 wt% to 70 wt%. Furthermore, it can be seen that a range of 25% by weight to 50% by weight is a preferable form with no foreign matter generation and no viscosity change.
As described above, according to the present invention, it is possible to provide a high-quality and practical water-based ink for ink-jet recording that is excellent in storage stability. In addition, by using the water-based ink set in combination with such water-based inks, when the print quality (bleeding, graininess) and fixability of the printed matter described above are evaluated, not only plain paper but also ink jet recording can be evaluated. It can also be seen that the glossy media usually used in the present invention exhibit excellent printed material properties.

Based on the above, penetrants (acetylene glycol surfactants, acetylene alcohols) that are preferred in the present invention when dispersed with conventional dispersants (eg, water-soluble polymer dispersants, surfactants) as described above It is difficult to use a surfactant, a silicon-based surfactant, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and one or more selected from 1,2-alkylene glycol), Therefore, sufficient print quality cannot be obtained. However, a dispersion was used in which the pigment according to the present invention was included in the dispersion polymer so as to be dispersible in water, and the amount of benzene rings in the dispersion polymer was in the range of 20% to 70% by weight of the dispersion polymer. In this case, water-based inks suitable for ink-jet recording that have sufficient printing quality and fixability for both plain paper and glossy media, while ensuring storage stability and ejection stability, even in the case of water-based inks containing the penetrant. Set can be provided. Further, since the pigment is used in the water-based ink of the present invention, it has an effect that a printed matter having excellent water resistance and light resistance can be obtained as compared with the case of using a dye that has been conventionally used as a colorant for ink for inkjet printers. In addition, since the function of the dispersion polymer that coats the colorant can be freely changed by the polymerization monomer and other reactants, various functions (further light resistance, gas resistance, colorability, glossiness, fixability of printed matter) Etc.) can be provided. Conventionally, when using a dispersant that has been used to disperse a pigment in an aqueous system (for example, a water-soluble polymer dispersant, a surfactant, etc.), the adsorptive power of the dispersant to the pigment is basically weak. Therefore, partial detachment occurs. As a result, the viscosity of the ink is increased by the desorbed material and the dispersant that has not been adsorbed, so that the amount of colorant added is limited and it is difficult to obtain sufficient color development. In particular, when a penetrant that is preferred in the present invention is used, its desorption is significant.
The present invention should not be considered to be limited to these examples, and various modifications can be made without departing from the gist of the present invention.

[Example K]
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention. Further, the physical properties (surface tension, average particle size) of the dispersion obtained in this example were measured by the following methods.
"Measurement of surface tension"
The surface tension at 20 ° C. of the pigment dispersions obtained in each Example or Comparative Example was measured with a surface tension meter (CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.).
"Measurement of average particle size"
The pigment dispersion obtained in each example or comparative example was diluted with ion-exchanged water so that the pigment concentration was 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement varies slightly depending on the pigment). The average particle size of the dispersed particles at 20 ° C. was measured with a particle size distribution meter (DLS-800 manufactured by Otsuka Electronics Co., Ltd.). The average particle diameter is shown in <> in nm (nanometer) in <>.

  In this example, a pigment is included in a reactive dispersant, and emulsion polymerization is carried out in water in the presence of a catalyst to produce a dispersion. Subsequently, a neutralizing agent and a dispersion accelerator were added to the produced dispersion and dispersed in water to obtain each dispersion.

The method for producing the dispersion according to the present invention will be specifically described below.
-Manufacturing process of dispersion (dispersion K1)
For the production of the dispersion K1, Monarch 880 (manufactured by Cabot Corporation), which is a carbon black pigment, was used.
The reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was purged with nitrogen, and then 20 parts of styrene, 5 parts of α-methylstyrene, 15 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t-dodecyl Add 0.3 part of mercaptan and heat to 70 ° C., separately prepared 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile. Was placed in a dropping funnel and the dispersion polymer was polymerized while being dropped into the reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
40 parts of the above dispersion polymer solution, 30 parts of carbon black Monarch 880 (manufactured by Cabot), 100 parts of a 0.1 mol / L aqueous sodium hydroxide solution and 30 parts of methyl ethyl ketone are mixed, stirred for 30 minutes with a homogenizer, and then subjected to ion exchange. Add 300 parts of water and stir for another hour. And after distiling the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, the dispersion K1 was obtained by filtering.

・ Production of dispersion (dispersion process)
(Dispersion K1)
Paint shaker with 15 parts of dispersion K1, 1.5 parts of Surfinol 485 (Air Products) as a dispersion accelerator, 0.5 parts of sodium hydroxide and 82.5 parts of ion-exchanged water as neutralizing agents (Glass beads used; beads filling rate = 60%; media diameter = 1.7 mm) were used until the dispersion was dispersed until the average particle diameter (secondary particle diameter) reached 95 nm, and the dispersion K1 (surface tension; 33 mN / m).
A part of this dispersion K1 was taken out, acidified by adding 0.1 mol / l HCl, only the dispersion polymer was taken out by Soxhlet extraction using acetone, and C ¹³ -NMR using DMSO-d _6. And the amount of the benzene ring relative to the total weight of the dispersed polymer as measured by H ¹ -NMR (AMX400 manufactured by Bruker (Germany)) was 36%.

  Dispersions K2 to K4 were obtained in the same manner as dispersion K1. Dispersion K2 uses an organic pigment phthalocyanine blue pigment (CI Pigment Blue 15: 4), and Dispersion K3 uses an organic pigment dimethylquinacridone pigment (CI Pigment Red 122). Dispersion K4 Used an organic pigment, quinacridone pigment (CI Pigment Violet 19). Table 47 shows the dispersion accelerators and neutralizers used in the production of these dispersions and the proportions added.

Next, production of the dispersion K5 using a production method different from the dispersion K1 will be described.・ Production of dispersion (dispersion K5)
Raven C (manufactured by Columbian Carbon Co., Ltd.), which is a carbon black pigment, was used for the production of dispersion K5.
In a reaction vessel equipped with an ultrasonic generator, a stirrer, a dropping device, a water-cooled reflux condenser, and a temperature controller, 25 parts of carbon black pigment (hereinafter, simply indicated as part indicates part by weight), a polymerizable surfactant Asahi Denka Co., Ltd. Adekaria Soap SE-10N was added to 180 parts of ion-exchanged water, and ultrasonic waves were applied for 4 hours.
Next, 5 parts of styrene, 1.6 parts of α-methylstyrene, 0.5 part of azobisisobutyronitrile and 3 parts of Adekalya soap SE-10N were further added, and a polymerization reaction was performed at 60 ° C. for 8 hours. The resulting solution was subjected to centrifugal filtration to take out the pigment included in the polymer, and further filtered through a 0.4 μm membrane filter to remove coarse particles.
Next, after loosening the pigment solution contained in the polymer with a homogenizer, 27 parts of ion-exchanged water and 0.05 part of sodium lauryl sulfate were further added to the reaction vessel, and 100 parts of ion-exchanged water and a polymerization initiator were added. 0.5 parts of potassium flow acid was added, and a nitrogen atmosphere was maintained at 70 ° C. Next, a mixed solution containing 25 parts of styrene, 1 part of tetrahydrofurfuryl methacrylate, 15 parts of butyl methacrylate, 5 parts of triethylene glycol methacrylate and 0.02 part of t-dodecyl mercaptan was dropped and reacted, and then a rotary evaporator was used. Dispersion K5 was obtained by distilling off part of methyl ethyl ketone and water and then filtering.

・ Production of dispersion (dispersion process)
(Dispersion K5)
15 parts of the dispersion K5, 0.5 part of acetylenol EH (manufactured by Kawaken Fine Chemical Co., Ltd.) and 2.5 parts of triethylene glycol monobutyl ether as a dispersion accelerator, and 0.5 part of sodium hydroxide as a neutralizing agent Then, 81 parts of ion-exchanged water was added until the average particle diameter (secondary particle diameter) of the dispersion reached 100 nm using a paint shaker (glass beads used; bead filling rate = 60%; media diameter = 1.7 mm). Dispersion was performed to obtain dispersion K5 (surface tension: 30 mN / m). In this production, two types of dispersion accelerators, acetylenol EH and TEGmBE, were used.
A part of this dispersion K5 was taken out, acidified by adding 0.1 mol / l HCl, and only the dispersion polymer was taken out by Soxhlet extraction using acetone, and C ¹³ -NMR using DMSO-d _6. And the amount of the benzene ring relative to the total weight of the dispersed polymer as measured by H ¹ -NMR (AMX400 manufactured by Bruker (Germany)) is 40%.
Dispersions K6 to K8 were obtained in the same manner as the dispersion K5. Dispersion K6 uses phthalocyanine green pigment (CI Pigment Green 7), Dispersion K7 uses condensed azo yellow pigment (CI Pigment Yellow 128), and Dispersion K8 uses benzimidazolone orange pigment (C I. Pigment Orange 36) was used. Table 48 shows the dispersion accelerators and neutralizers used in the production of these dispersions and the proportions added.

(Inkjet ink preparation example)
Specific examples of compositions suitable for the ink jet recording ink according to the present invention are shown below. The added amount of each dispersion is shown as the solid content concentration (total amount of pigment and the dispersion polymer surrounding it) converted by weight. <> Indicates the particle size of the pigment in nm units. In this embodiment, the remaining amount of water is 0.05% for Proxel XL-2 to prevent ink corrosion, and EDTA (ethylenediaminetetraacetic acid for reducing the influence of metal ions in the ink system. ) Was added to ion-exchanged water at 0.01% each.

(Example K-1)
The ink composition of Example K-1 is shown below.

Amount added (%)
Dispersion K1 40.0
Olphin E1010 0.5
TEGmBE 5.0
1,5-pentanediol 5.0
Glycerin 9.0
Triethanolamine 1.0
Ion exchange water

Orphine E1010 (acetylene glycol surfactant: manufactured by Nissin Chemical Industry Co., Ltd.) TEGmBE: triethylene glycol monobutyl ether

(Example K-2)
The ink composition of Example K-2 is shown below.

Amount added (%)
Dispersion liquid K2 30.0
Surfinol TG 0.3
DEGmBE 10.0
Dipropylene glycol 5.0
Triethanolamine 0.9
Ion exchange water

Surfynol TG (acetylene glycol surfactant: manufactured by Air Products (USA))
DEGmBE: Diethylene glycol monobutyl ether

(Example K-3)
The ink composition of Example K-3 is shown below.

Amount added (%)
Dispersion liquid K3 50.0
1,2-hexanediol 4.0
1,6-hexanediol 4.0
Olfin STG 0.3
Diethylene glycol 7.0
Thiodiglycol 1.5
Triethanolamine 1.0
Potassium hydroxide 0.1
Ion exchange water

Olphine STG (acetylene glycols: manufactured by Nissin Chemical Industry Co., Ltd.)

(Example K-4)
The ink composition of Example K-4 is shown below.

Amount added (%)
Dispersion liquid K4 60.0
Surfinol 104 0.5
TEGmBE 3.0
1,2-pentanediol 5.0
1,5-pentanediol 2.0
Tetraethylene glycol 9.0
Dimethyl-2-imidazolidinone 2.0
Sodium benzoate 0.1
Triethanolamine 0.7
Ion exchange water

  Surfynol 104 (acetylene glycols: manufactured by Air Products (USA))

(Example K-5)
The ink composition of Example K-5 is shown below.

Amount added (%)
Dispersion K5 50.0
DPGmBE 2.0
DEGmBE 7.0
Glycerol 14.0
Triethanolamine 0.9
Ion exchange water

DPGmBE: Dipropylene glycol monobutyl ether

(Example K-6)
The ink composition of Example K-6 is shown below.
Amount added (%)
Dispersion liquid K6 40.0
Acetylenol EO 0.1
TEGmBE 6.0
1,5-pentanediol 1.0
Glycerin 15.0
Thiodiglycol 2.0
Triethanolamine 0.9
Ion exchange water

(Example K-7)
The ink composition of Example K-7 is shown below.

Amount added (%)
Dispersion liquid K7 60.0
Surfinol 465 0.5
Surfinol 61 0.5
DEGmBE 8.0
Glycerin 15.0
Trimethylolpropane 1.0
Trimethylolethane 1.0
Triethanolamine 0.5
KOH 0.05
Ion exchange water

(Example K-8)
The ink composition of Example K-8 is shown below.

Amount added (%)
Dispersion liquid K8 40.0
Olphine STG 0.5
PGmBE 2.0
DEGmBE 10.0
Tetrapropylene glycol 5.0
Glycerin 7.0
Diethylene glycol 5.0
Triethanolamine 0.9
KOH 0.1
Ion exchange water

PGmBE: Propylene glycol monobutyl ether

(Comparative Example K-1)
In Comparative Example K-1, as in Example K-1, Raven C (produced by Columbian Carbon Co., Ltd.), which is a carbon black pigment, was dispersed using Solsperse 27000 (produced by Avicia) as a dispersant.
15 parts of Raven C, 4 parts of Solsperse 27000 (Avisia), 4 parts of diethanolamine, 0.5 part of 2-propanol, and 76.5 parts of ion-exchanged water for 2 hours using a bead mill minizeta (manufactured by Ajisawa Corporation) Dispersion treatment was performed to make dispersion liquid K9 used in Comparative Example K-1.
The ink composition of Comparative Example K-1 is shown below.

Amount added (%)
Dispersion liquid K9 <120> 7.0
Glycerin 10.0
Dispersant 3.0
Nonionic surfactant 1.0
Ion exchange water

Nonionic surfactant: Neugen EA160 (Daiichi Kogyo Seiyaku Co., Ltd.)

(Comparative Example K-2)
In Comparative Example K-2, Acid Blue 9, which is an acid dye, was used as a colorant.
The ink composition of Comparative Example K-2 is shown below.

Amount added (%)
Acid Blue 9 6.5
DEGmME 7.0
Diethylene glycol 10.0
2-pyrrolidone 5.0
Ion exchange water

  DEGmME: Diethylene glycol monomethyl ether

(Comparative Example K-3)
In Comparative Example K-3, Direct Black 154, which is a direct dye, was used as a colorant.
The ink composition of Comparative Example K-3 is shown below.

Amount added (%)
Direct Black 154 2.5
Diethylene glycol 10.0
Nonionic surfactant 1.0
Ion exchange water

Nonionic surfactant: Epan 450 (Daiichi Kogyo Seiyaku Co., Ltd.)

  Table 49 shows the bleeding evaluation results when characters are printed as the printing evaluation results. In Table 49, A is very good, B is good, C is bad, and D is very bad.

As apparent from the results in Table 49, it can be seen that the ink used in the comparative example has poor print quality, and that the print quality is good when the ink for ink jet recording used in the present invention is used.
These print evaluations were measured by using an ink jet printer PM-900C manufactured by Seiko Epson Corporation. The papers used for these evaluations are ordinary papers commercially available in Europe, America and Japan, such as Conqueror paper, Favorit paper, Modo Copy paper, Rapid Copy paper, EPSON EPP paper, Xerox 4024 paper, Xerox 10 paper, Neenha. Bond paper, Rcopyy 6200 paper, Yamayuri paper, Xerox R paper.
As described above, according to the present invention, it is possible to provide a high-quality and practical ink-jet recording ink in which bleeding of a printed image on a recording medium such as paper is reduced.
Further, after placing the inks of Examples K-1 to 8 in glass sample bottles and sealing them, they were left at 60 ° C./week for about 1 week, and the generated foreign matter and physical properties (viscosity, surface tension) before and after being left. Examined.
As a result, none of the inks generated foreign matter and the physical property value hardly changed, and the ink had good storage stability.
On the other hand, when the experiment was carried out in the same manner by changing the colorant to the pigment of Comparative Example K-1 with the composition of Example K-1, there was little change in surface tension, but foreign matter was generated and the filterability was reduced. A thickening phenomenon occurred and ejection stability could not be obtained.

Further, in the composition of Example K-1, other additives (acetylene glycols, acetylene alcohols, polysiloxanes, di (tri) ethylene glycol monobutyl ether, (di ) An additive (acetylene glycol) that may be used in the present invention for an ink prepared using propylene glycol monobutyl ether and a material comprising one or more selected from 1,2-alkylene glycol and the ink shown in Comparative Example K-1 , Acetylene alcohols, polysiloxanes, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and one or more substances selected from 1,2-alkylene glycol) Example K-9 in Table 50 18), similarly allowed to stand at 60 ° C. / 1 week, the ink generation foreign matter after standing, indicating the examination result of physical properties (viscosity, surface tension) and ejection stability in Table 50. The amount of foreign matter generated is the amount of foreign matter after standing at 60 ° C./initial amount of foreign matter, the viscosity is the viscosity after standing at 60 ° C./initial viscosity, and the surface tension is the value of surface tension after standing at 60 ° C./initial surface tension. Stability is 100 pages continuously printed on A4 version Xerox P paper by using an ink jet printer PM-900C manufactured by Seiko Epson Corporation. C having a print disorder of 10 or more and less than 100 is D, and D having a print disorder of 100 or more.

As can be seen from the results in Table 49 and Table 50, the ink for ink jet recording using the dispersion according to the present invention has good print quality, and becomes an ink for ink jet recording excellent in ejection stability and storage stability. I understand. Moreover, about Example K-2-8, when the test was done similarly changing the additive, the substantially same result was obtained.
Further, Table 51 shows the results of determining the relationship between the amount of benzene ring and storage stability by performing polymerization in which the amount of benzene ring of the dispersion polymer used in Example K-1 and Example K-5 was changed. Storage stability was determined by placing the inks of Examples K-1 to 8 in glass sample bottles and sealing them, and then leaving them at 60 ° C. and 70 ° C./1 week, respectively. Investigated about. The amount of foreign matter generated is the amount of foreign matter after standing at 60 ° C. and 70 ° C./initial amount of foreign matter, and the viscosity is the viscosity after standing at 60 ° C. and 70 ° C./initial viscosity.

As can be seen from the results in Table 51, it can be seen that the amount of the benzene ring in the dispersion polymer of the present invention is 20% to 70%, preferably 25% to 50%.
From the above, additives (acetylene glycols, acetylene alcohols, polysiloxanes, di (tri) ethylene glycol monobutyl ether, (di ) It is difficult to use a substance comprising at least one selected from propylene glycol monobutyl ether and 1,2-alkylene glycol), so that sufficient print quality cannot be obtained, but the pigment as in the present invention is polymerized. In which the amount of benzene rings in the polymer is 20% by weight or more and 70% or less of the polymer, while having sufficient color developability and storage stability. An ink for ink jet recording can be obtained which provides ejection stability. Further, since the pigment is used, the water resistance has an effect that the printed matter is superior to the case of using a normal dye (for example, Comparative Examples K-2 and 3). In addition, the function of the polymer that coats the colorant can be freely changed by the polymerization monomer and other reactants, so it can have various functions (light resistance, gas resistance, colorability, glossiness, fixability, etc.). It also has the effect of being able to. In the case of using an ordinary dispersant as in the past, in the dispersant, the adsorption force of the dispersant basically adsorbed on the pigment is weak and partial desorption occurs, and the desorbed material or the dispersant that has not been adsorbed As a result, the viscosity increases, so the amount of colorant added is limited and it is difficult to obtain a sufficient color.

[Example L]
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.
(Measurement method of aromatic ring amount, pigment: polymer ratio, average particle size, amount of polyvalent cation in dispersion, and surface tension)
Each measured value (amount of aromatic ring, pigment: polymer ratio, average particle size, amount of polyvalent cation in dispersion, surface tension) obtained in this example was measured by the following method.

"Measurement of aromatic ring quantity"
A part of the dispersion polymer solution obtained in each example or comparative example was taken out, the solvent component was distilled off, and only the polymer component was taken out, dissolved in DMSO-d ₆ , ¹³ C-NMR and ¹ H-NMR ( The amount of aromatic rings in the polymer was measured using Bruker (Germany AMX400).
“Measurement of pigment: polymer ratio”
A part of the dispersion obtained in each Example or Comparative Example was taken out, 0.1 mol / l concentration HCl was added, and only the dispersion was acidified, and the dry weight was measured. Next, the pigment: polymer weight ratio was calculated by taking out only the dispersed polymer by Soxhlet extraction using acetone and measuring the dry weight.
"Measurement of average particle size"
Dilute with ion-exchanged water so that the dispersion concentration of the water-based ink obtained in each Example or Comparative Example is 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement differs slightly depending on the ink), The average particle diameter at 20 ° C. of the dispersed particles was measured with a particle size distribution meter (DLS-800 manufactured by Otsuka Electronics Co., Ltd.).

"Measurement of polyvalent cation content in dispersion"
A required amount of the water-based ink obtained in each Example or Comparative Example was taken out and separated into a dispersion which is a solvent component and a solid content of the ink by a centrifugal separation process. The centrifugation condition was 2500 G × 60 minutes.
The obtained dispersion is taken in a quartz dish, added with a scavenger, incinerated, melted with potassium hydrogen sulfate, dissolved in dilute nitric acid, and subjected to ICP emission analysis (ICPS-8000; manufactured by Shimadzu Corporation). The amount of polyvalent cation in the dispersion was measured.
"Measurement of surface tension"
The surface tension at 20 ° C. of the water-based ink obtained in each example or comparative example was measured with a surface tension meter (CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.).

<Example L-1>
(1) Production of dispersion: Dispersion L1
For the production of the dispersion L1 used in Example L-1, a carbon black pigment color black FW18 (manufactured by Degussa Co., Ltd.), which is an inorganic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, then 15 parts of methyl ethyl ketone, 22 parts of styrene, 5 parts of α-methyl styrene, 16 parts of butyl methacrylate, 10 parts of lauryl methacrylate, acrylic acid 2 parts, 0.3 part of t-dodecyl mercaptan was added and heated to 70 ° C., and separately prepared 100 parts of styrene, 16 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and azobis 3 parts of isobutyronitrile was placed in a dropping funnel and the dispersion polymer was subjected to a polymerization reaction while dropping into a reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 57%.

40 parts of the above dispersion polymer solution, 30 parts of carbon black pigment Color Black FW18 (manufactured by Degussa), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 35 parts of methyl ethyl ketone are mixed and dispersed with a homogenizer for 30 minutes or more. Then, 350 parts of ion exchange water is added and dispersed for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and an aqueous sodium hydroxide solution as a neutralizing agent are added as appropriate while stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion L1 (carbon black A dispersion L1 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 57% was obtained.
Table 52 shows the pigment used in dispersion L1, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Ink adjustment In Example L-1, the dispersion L1 obtained in Example L-1 (1), Olphine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant, Diethylene glycol monobutyl ether, which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol, which is 1,2-alkylene glycol, were used. A specific composition is shown below.
In preparing the ink, the dispersion liquid L1 was added so that the content of the dispersion L1 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element L1 measured by the method described in "Measurement of Average Particle Size" above.
In addition, ion exchange water added as the “remaining amount” in the ink composition of Example L-1 below includes Proxel XL-2 for preventing ink corrosion, benzotriazole for preventing ink jet head member corrosion, In order to reduce the influence of metal ions in the ink system, EDTA · 2Na salt added to 0.01%, 0.01%, and 0.02% with respect to the total weight of the ink is used. It was.

Dispersion L1 <120> 8.0%
Olfine E1010 0.5%
Diethylene glycol monobutyl ether 3.0%
1,2-pentanediol 2.5%
Diethylene glycol 3.0%
Glycerin 11.5%
Trimethylolpropane 6.0%
Tripropanolamine 0.3%
Ion exchange water

(3) Measurement of amount of polyvalent cation in dispersion The ink prepared in Example L-1 (2) was measured by the method described in "Measurement of amount of polyvalent cation in dispersion". However, the total amount of polyvalent cations in the dispersion was 387 ppm. Details of the measurement results are shown in Table 54.

(4) Printing Evaluation For printing evaluation, an ink jet printer PM-950C (manufactured by Seiko Epson Corporation) that discharges ink with an ink jet head using a piezoelectric element (piezo element) was used, and Example L-1 (2 ) Was evaluated for the ink adjusted in (1).
As evaluation papers, (a) Conqueror paper, (b) Reymat paper, (c) Mode Copy paper, (d) Rapid Copy paper, (e) Xerox P paper , (F) Xerox 4024 paper, (g) Xerox 10 paper, (h) Neenha Bond paper, (i) Riccopy 6200 paper, and (j) Hammer mill Copy Plus paper.
In addition, evaluation was performed visually and was performed based on the following evaluation criteria.

A: The blur is not recognized in the characters at all points.
B: Slight bleeding is observed with characters of 5 points or less (practical level).
C: Characters of 5 points or less appear thick due to blurring.
D: Significant blurring and characters of 5 points or less cannot be identified.

  Table 53 shows the results of the print evaluation.

(5) Evaluation of ejection stability Using the same printer and ink as in Example L-1 (4), A4 version Xerox
200 pages were continuously printed on P paper, and the ejection stability was evaluated by observing the printing disorder.
In addition, evaluation was performed visually and was performed based on the following evaluation criteria.

A: Printing disorder does not occur at all.
B: Printing disorder was observed, but the number was less than 10 (practical level).
C: There is printing disorder in the range of 10 or more and less than 100.
D: Disturbance of printing occurred at 100 locations or more.

  Table 54 shows the results of the discharge stability evaluation.

(6) Storage stability evaluation After the ink prepared in Example L-1 (2) was put in a glass bottle and sealed, it was left at 60 ° C./1 week and −20 ° C./1 week, respectively. Foreign matter and physical property value fluctuation (viscosity, surface tension) were evaluated.
The evaluation was performed based on the following evaluation criteria.

A: The ratio of the amount of foreign matter / physical properties after standing at 60 ° C. or −20 ° C. to that before standing is in the range of 0.99 to 1.01.
B: The ratio is in the range of 0.95 to 0.99, or 1.01 to 1.05 (practical level).
C: The ratio is in the range of 0.90 to 0.95, or 1.05 to 1.10.
D: Ratio is less than 0.90 or greater than 1.10.

  The storage stability evaluation results are shown in Table 54.

<Example L-2>
(1) Production of dispersion: Dispersion L2
For the production of the dispersion L2 used in Example L-2, an insoluble monoazo yellow pigment (CI Pigment Yellow 74), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 12 parts of styrene, 9 parts of lauryl methacrylate, and 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 3 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 part of mercaptoethanol, heated to 70 ° C., 25 parts of styrene prepared separately, lauryl 30 parts of methacrylate, 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), 15 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toagosei Co., Ltd.), 10 parts of methacrylic acid, 20 parts of methyl ethyl ketone Dropwise to the reaction vessel over 4 hours putting 1.0 parts of mercaptoethanol to the dropping funnel and the dispersed polymer is the polymerization reaction. Next, methyl ethyl ketone was appropriately added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 40%.

40 parts of the above dispersion polymer solution, 30 parts of an insoluble monoazo yellow pigment (CI Pigment Yellow 74) as an organic pigment, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed, and 30 parts are mixed with a homogenizer. Disperse for at least minutes, add 380 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added while stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion L2 (insoluble monoazo A dispersion L2 containing 20% of a dispersion in which a yellow pigment was included by a polymer having an aromatic ring content of 40% was obtained.
Table 52 shows the pigment used in the dispersion L2, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example L-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Ink adjustment In this Example L-2, the dispersion L2 obtained in Example L-2 (1), Surfynol 440 (made by Air Products Co., Ltd.), which is an acetylene glycol surfactant, and Olfine STG (manufactured by Nissin Chemical Industry Co., Ltd.), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the ink, the dispersion liquid L2 was added so that the content of the dispersion L2 was 7.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element L2 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the ink composition of Example L-2 below, the ion-exchanged water added as “remaining amount” is similar to Example L-1 (2), with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion L2 <120> 7.0%
Surfinol 440 0.2%
Olphine STG 0.2%
Triethylene glycol monobutyl ether 3.0%
1,2-pentanediol 2.0%
2-pyrrolidone 3.0%
Glycerin 13.5%
Trimethylolethane 5.0%
Triethanolamine 0.1%
Ion exchange water

(3) Measurement of amount of polyvalent cation in dispersion The ink prepared in Example L-2 (2) was measured by the method described in "Measurement of amount of polyvalent cation in dispersion". However, the total amount of polyvalent cations in the dispersion was 272 ppm. Details of the measurement results are shown in Table 54.
(4) Printing evaluation Using the ink jet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example L-1 (4), the ink prepared in Example L-2 (2) was Using the same evaluation paper as in Example L-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example L-1 (4). The results of printing evaluation are shown in Table 53.
(5) Evaluation of ejection stability Using the same printer and ink as in Example L-2 (4), the same evaluation method as in Example L-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 54. (6) Storage Stability Evaluation For the ink prepared in Example L-2 (2), the same evaluation method as in Example L-1 (6) was used, and the same as in Example L-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 54.

<Example L-3>
(1) Production of dispersion: Dispersion L3
For the production of the dispersion L3 used in Example L-3, quinacridone red pigment (CI Pigment Red 122), which is an organic pigment, was used.
First, the reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 10 parts of styrene, 5 parts of styrene macromer (AS-6; manufactured by Toagosei Co., Ltd.), n-dodecyl methacrylate 3.5 Parts, N, N-dimethylaminoethyl methacrylate 10 parts, methoxypolyethylene glycol methacrylate (NK ester M40G; manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts, methyl ethyl ketone 5 parts, mercaptoethanol 0.3 part, and heated to 70 ° C. 15 parts of styrene prepared separately, 10 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of n-dodecyl methacrylate, 20 parts of N, N-dimethylaminoethyl methacrylate, methoxypolyethylene glycol methacrylate (NK ester M40G) ; Shin-Nakamura Chemical Co., Ltd. ) 30 parts, 50 parts of methyl ethyl ketone, and the dispersion polymer dropwise into the reaction vessel over 4 hours and placed in a dropping funnel and 1.5 parts of azobisisobutyronitrile was polymerized reaction. Next, methyl ethyl ketone was appropriately added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 28%.

40 parts of the above dispersion polymer solution, 25 parts of an organic pigment, quinacridone red pigment (CI Pigment Red 122), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 40 parts of methyl ethyl ketone are mixed, and 30 minutes with a homogenizer. Dispersion treatment is performed as described above, and 380 parts of ion exchange water is added and further dispersed for 1 hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm, whereby dispersion L3 (quinacridone red A dispersion L3 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 28% was obtained.
Table 52 shows the pigment used in the dispersion L3, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example L-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Ink adjustment In Example L-3, the dispersion L3 obtained in Example L-3 (1) above, Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant, Surfynol 104PG50 (manufactured by Air Products), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-hexanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the ink, the dispersion liquid L3 was added so that the content of the dispersion L3 was 7.5%. The value in <> shows the average particle size (unit: nm) of Dispersing Element L3 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the ink composition of Example L-3 below, the ion-exchanged water added as the “remaining amount” is similar to Example L-1 (2), with respect to the total weight of the ink, Proxel XL- 2
In which 0.01% was added, 0.01% benzotriazole, and 0.02% EDTA · 2Na salt were used.

Dispersion L3 <140> 7.5%
Olfin E1010 0.1%
Surfynol 104PG50 0.4%
Triethylene glycol monobutyl ether 1.0%
1,2-hexanediol 2.5%
Triethylene glycol 2.0%
2-pyrrolidone 4.0%
Glycerin 13.8%
Trimethylolpropane 6.0%
Ion exchange water

(3) Measurement of amount of polyvalent cation in dispersion The ink prepared in Example L-3 (2) was measured by the method described in "Measurement of amount of polyvalent cation in dispersion". However, the total amount of polyvalent cations in the dispersion was 527 ppm. Details of the measurement results are shown in Table 54.
(4) Printing evaluation Using the inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example L-1 (4), the ink prepared in Example L-3 (2) was Using the same evaluation paper as in Example L-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example L-1 (4). The results of printing evaluation are shown in Table 53.
(5) Evaluation of ejection stability Using the same printer and ink as in Example L-3 (4), using the same evaluation method as in Example L-1 (5), the Example L-1 The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 54. (6) Storage stability evaluation The ink prepared in Example L-3 (2) was evaluated in the same manner as in Example L-1 (6), and the same as in Example L-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 54.

<Example L-4>
(1) Production of dispersion: Dispersion L4
For the production of the dispersion L4 used in Example L-4, a phthalocyanine blue pigment (CI Pigment Blue 15: 4), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 20 parts of styrene, 10 parts of lauryl methacrylate, 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 10 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 n-dodecyl mercaptan And heated to 70 ° C., separately prepared 25 parts of styrene, 30 parts of lauryl methacrylate, 20 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), isobutyl methacrylate macromer (AW-6S; Toa) Composition 15 parts, 15 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 20 parts of methyl ethyl ketone, 1.5 parts of n-dodecyl mercaptan in a dropping funnel over 4 hours The dispersion polymer was polymerized while being dropped into the reaction vessel. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 45%.

40 parts of the above dispersion polymer solution, 40 parts of an organic pigment phthalocyanine blue pigment (CI Pigment Blue 15: 4), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed together. Disperse for 30 minutes or more, add 350 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm, whereby dispersion L4 (phthalocyanine blue A dispersion L4 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 45% was obtained.
Table 52 shows the pigment used in the dispersion L4, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example L-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of ink In this Example L-4, the dispersion L4 obtained in Example L-4 (1), acetylenol E100 (produced by Kawaken Fine Chemical Co., Ltd.), which is an acetylene glycol surfactant, alkylene Propylene glycol monobutyl ether, which is glycol monoalkyl ether, and 1,2-hexanediol, which is 1,2-alkylene glycol, were used. A specific composition is shown below.
In preparing the ink, the dispersion liquid L4 was added so that the content of the dispersion L4 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element L4 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the ink composition of the following Example L-4, the ion-exchanged water added as the “remaining amount” is similar to Example L-1 (2) above, with Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion L4 <100> 8.0%
Acetylenol E100 0.5%
Propylene glycol monobutyl ether 3.0%
1,2-hexanediol 1.0%
Triethylene glycol 3.0%
Glycerin 13.8%
Trimethylolpropane 5.2%
Tripropanolamine 0.2%
Ion exchange water

(3) Measurement of amount of polyvalent cation in dispersion The ink prepared in Example L-4 (2) was measured by the method described in "Measurement of amount of polyvalent cation in dispersion". However, the total amount of polyvalent cations in the dispersion was 172 ppm. In this example, 9300 ppm of copper ion was detected, but the copper ion forms a pigment molecular skeleton and does not elute into the ink, so it is contained in the dispersion according to the present invention. Not applicable to polyvalent cations. Therefore, it is not added to the total amount of the polyvalent cations. Details of the measurement results are shown in Table 54.
(4) Printing Evaluation Regarding the ink prepared in Example L-4 (2) using an inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example L-1 (4), Using the same evaluation paper as in Example L-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example L-1 (4). The results of printing evaluation are shown in Table 53.
(5) Evaluation of ejection stability Using the same printer and ink as in Example L-4 (4), using the same evaluation method as in Example L-1 (5), the Example L-1 The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 54. (6) Storage Stability Evaluation For the ink prepared in Example L-4 (2), the same evaluation method as in Example L-1 (6) was used, and the same as in Example L-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 54.

<Example L-5>
(1) Production of dispersion: Dispersion L5
A perinone orange pigment (CI Pigment Orange 43) was used for the production of the dispersion L5 used in Example L-5. Otherwise, in the same manner as described in Example L-1 (1), 20% of dispersion L5 (dispersion containing a perinone orange pigment with a polymer having an aromatic ring content of 56%) is contained. Dispersion L5 was obtained.
Table 52 shows the pigment used in the dispersion L5, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example L-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Ink adjustment In this Example L-5, the dispersion L5 obtained in Example L-5 (1), Surfynol 485 and Surfynol TG which are acetylene glycol surfactants (both are air products) Co., Ltd.), dipropylene glycol monobutyl ether, which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol, which is a 1,2-alkylene glycol. A specific composition is shown below. In preparing the ink, the dispersion liquid L5 was added so that the content of the dispersion L5 was 10.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element L5 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the ink composition of the following Example L-5, ion exchange water added as “remaining amount” is similar to Example L-1 (2), with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion L5 <150> 10.0%
Surfynol 485 0.5%
Surfinol TG 0.2%
Dipropylene glycol monobutyl ether 2.0%
1,2-pentanediol 2.0%
N-methyl-2-pyrrolidone 5.0%
Glycerin 11.2%
Trehalose 5.8%
Ion exchange water

(3) Measurement of polyvalent cation amount in dispersion The ink prepared in Example L-5 (2) was measured by the method described in "Measurement of polyvalent cation amount in dispersion". However, the total amount of polyvalent cations in the dispersion was 610 ppm. Details of the measurement results are shown in Table 54.
(4) Printing evaluation Using the ink jet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example L-1 (4), the ink prepared in Example L-5 (2) was Using the same evaluation paper as in Example L-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example L-1 (4). The results of printing evaluation are shown in Table 53.
(5) Evaluation of ejection stability Using the same printer and ink as in Example L-5 (4), the same evaluation method as in Example L-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 54. (6) Storage Stability Evaluation For the ink prepared in Example L-5 (2), the same evaluation method as in Example L-1 (6) was used, and the same as in Example L-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 54.

<Example L-6>
(1) Production of dispersion: Dispersion L6
A benzimidazolone brown pigment (CI Pigment Brown 32) was used for the production of the dispersion L6 used in Example L-6. Otherwise, by the same method as described in Example L-1 (1) above, 20% of dispersion L6 (dispersion containing benzimidazolone brown pigment by a polymer having an aromatic ring content of 69%) A dispersion L6 was obtained.
Table 52 shows the pigment used in the dispersion L6, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example L-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of ink In Example L-6, the dispersion L6 obtained in Example L-6 (1), Surfynol 420 which is an acetylene glycol surfactant, and alkylene glycol monoalkyl ether are used. Diethylene glycol monobutyl ether was used. A specific composition is shown below.
In the adjustment of the ink, the dispersion L6 was added so that the content of the dispersion L6 was 5.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element L6 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the ink composition of Example L-6 below, ion exchange water added as “remaining amount” is similar to Example L-1 (2), with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion L6 <140> 5.0%
Surfynol 420 0.1%
Diethylene glycol monobutyl ether 3.0%
1,6-hexanediol 2.0%
Tetraethylene glycol 5.5%
Glycerin 13.5%
Triethanolamine 0.5%
Ion exchange water

(3) Measurement of amount of polyvalent cation in dispersion The ink prepared in Example L-6 (2) was measured by the method described in "Measurement of amount of polyvalent cation in dispersion". However, the total amount of polyvalent cations in the dispersion was 797 ppm. Details of the measurement results are shown in Table 54.
(4) Printing evaluation Using the ink jet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example L-1 (4), the ink prepared in Example L-6 (2) was Using the same evaluation paper as in Example L-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example L-1 (4). The results of printing evaluation are shown in Table 53.
(5) Evaluation of ejection stability Using the same printer and ink as in Example L-6 (4), the same evaluation method as in Example L-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 54. (6) Storage Stability Evaluation For the ink prepared in Example L-6 (2), the same evaluation method as in Example L-1 (6) was used, and the same as in Example L-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 54.

<Example L-7>
(1) Production of dispersion: Dispersion L7
In the production of the dispersion L7 used in Example L-7, quinacridone violet pigment (CI Pigment Bio Red 19) was used as an organic pigment. Otherwise, a dispersion containing 20% of dispersion L7 (a dispersion containing quinacridone violet pigment with a polymer having an aromatic ring content of 21%) in the same manner as described in Example L-1 (1). A liquid L7 was obtained.
Table 52 shows the pigment used in the dispersion L7, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example L-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Ink adjustment In this Example L-7, the dispersion L7 obtained in Example L-7 (1), Surfynol 61 and Surfynol TG which are acetylene alcohol surfactants (both are air products) Co., Ltd.), triethylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2 alkylene glycol. A specific composition is shown below.
In preparing the ink, the dispersion liquid L7 was added so that the content of the dispersion L7 was 6.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element L7 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the ink composition of Example L-7 below, the ion-exchanged water added as “remaining amount” is similar to Example L-1 (2), with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion L7 <120> 6.0%
Surfynol 61 0.3%
Surfynol TG 0.1%
Triethylene glycol monobutyl ether 1.5%
1,2-pentanediol 2.0%
Diethylene glycol 2.0%
Thiodiglycol 4.0%
Glycerin 12.6%
Trimethylolethane 7.0%
Ion exchange water

(3) Measurement of amount of polyvalent cation in dispersion The ink prepared in Example L-7 (2) was measured by the method described in "Measurement of amount of polyvalent cation in dispersion". However, the total amount of polyvalent cations in the dispersion was 742 ppm. Details of the measurement results are shown in Table 54.
(4) Printing evaluation Using the inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example L-1 (4), the ink prepared in Example L-7 (2) was Using the same evaluation paper as in Example L-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example L-1 (4). The results of printing evaluation are shown in Table 53.
(5) Evaluation of ejection stability Using the same printer and ink as in Example L-7 (4), the same evaluation method as in Example L-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 54. (6) Storage Stability Evaluation For the ink prepared in Example L-7 (2), the same evaluation method as in Example L-1 (6) was used, and the same as in Example L-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 54.

<Example L-8>
(1) Production of dispersion: Dispersion L8
For the production of the dispersion L8 used in Example L-8, a phthalocyanine green pigment (CI Pigment Green 7), which is an organic pigment, was used. Otherwise, a dispersion containing 20% of dispersion L8 (dispersion including a phthalocyanine green pigment with a polymer having an aromatic ring content of 30%) in the same manner as described in Example L-1 (1). A liquid L8 was obtained.
Table 52 shows the pigment used in the dispersion L8, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example L-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Ink adjustment In Example L-8, the dispersion L8 obtained in Example L-8 (1) above, Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant, Surfynol 104 (manufactured by Air Products Co., Ltd.), dipropylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the ink, the dispersion liquid L8 was added so that the content of the dispersion L8 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element L8 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the ink composition of Example L-8 below, the ion-exchanged water added as “remaining amount” is similar to Example L-1 (2), with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion L8 <110> 8.0%
Olfine E1010 0.3%
Surfynol 104 0.1%
Dipropylene glycol monobutyl ether 1.0%
1,2-pentanediol 3.0%
Triethylene glycol 2.0%
Thiodiglycol 4.0%
Glycerin 13.8%
Trimethylolpropane 6.0%
Triethanolamine 0.1%
Ion exchange water

(3) Measurement of amount of polyvalent cation in dispersion The ink prepared in Example L-8 (2) was measured by the method described in "Measurement of amount of polyvalent cation in dispersion". However, the total amount of polyvalent cations in the dispersion was 588 ppm. In this example, 8600 ppm of copper ion was detected. However, since the copper ion forms a pigment molecular skeleton and does not elute into the ink, it is contained in the dispersion according to the present invention. It does not correspond to a valent cation. Therefore, it is not added to the total amount of the polyvalent cations. Details of the measurement results are shown in Table 54.
(4) Printing evaluation Using the inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example L-1 (4), the ink prepared in Example L-8 (2) was Using the same evaluation paper as in Example L-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example L-1 (4). The results of printing evaluation are shown in Table 53.
(5) Evaluation of ejection stability Using the same printer and ink as in Example L-8 (4), the same evaluation method as in Example L-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 54. (6) Storage Stability Evaluation For the ink prepared in Example L-8 (2), the same evaluation method as in Example L-1 (6) was used, and the same as in Example L-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 54.

<Comparative Example L-1>
(1) Production of dispersion: Dispersion L9
In Comparative Example L-1, the quinacridone red pigment (CI Pigment Red 122), which is the organic pigment of Example L-3 (1), was used. However, the pigment used in this comparative example was intentionally pulverized in the above-described pigment pulverization process over a period of time more than usual. Otherwise, a dispersion containing 20% of dispersion L9 (a dispersion containing a quinacridone red pigment with a polymer having an aromatic ring content of 20%) in the same manner as described in Example L-3 (1). A liquid L9 was obtained.
Table 52 shows the pigment used in dispersion L9, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Ink adjustment In Comparative Example L-1, the ink was adjusted using the dispersion L9 obtained in Comparative Example L-1 (1). A specific composition is shown below.
In preparing the ink, the dispersion liquid L9 was added so that the content of the dispersion L9 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element L9 measured by the method described in "Measurement of Average Particle Size" above.
In addition, the ion-exchanged water added as “remaining amount” in the ink composition of the present Comparative Example L-1 described below is similar to Example L-1 (2) in the case of Proxel XL- with respect to the total weight of the ink. 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion L9 <140> 8.0%
Nonionic surfactant 1.0%
Ethylene glycol 5.0%
Glycerin 15.0%
Ion exchange water

  In the above composition, Epan 450 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of amount of polyvalent cation in dispersion The ink prepared in Comparative Example L-1 (2) was measured by the method described in "Measurement of amount of polyvalent cation in dispersion". However, the total amount of polyvalent cations in the dispersion was 1055 ppm. Details of the measurement results are shown in Table 54.
(4) Printing evaluation Using the ink jet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example L-1 (4), the ink prepared in Comparative Example L-1 (2) was Using the same evaluation paper as in Example L-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example L-1 (4). The results of printing evaluation are shown in Table 53.
(5) Evaluation of ejection stability Using the same printer and ink as in Comparative Example L-1 (4), the same evaluation method as in Example L-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 54. (6) Storage Stability Evaluation For the ink prepared in Comparative Example L-1 (2), the same evaluation method as in Example L-1 (6) was used, and the same as in Example L-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 54.

<Comparative Example L-2>
(1) Production of dispersion: Dispersion L10
In this comparative example, quinacridone violet pigment (CI Pigment Bio Red 19), which is an organic pigment, was dispersed using Solsperse 12000 (manufactured by Avisia Corporation).
Disperse 15 parts of quinacridone violet pigment, 5 parts of Solsperse 12000, 5 parts of diethanolamine, 0.5 part of 2-propanol, and 74.5 parts of ion-exchanged water with a bead mill mini-zeta (manufactured by Ajisawa Corporation) for 2 hours. The dispersion L10 used in Comparative Example L-2 containing 20% of the dispersion L10 (pigment: 15%, dispersion resin: 5%) was obtained.

(2) Ink adjustment In Comparative Example L-2, the ink was adjusted using the dispersion L10 obtained in Comparative Example L-2 (1). The specific composition of this comparative example is shown below.
In the preparation of the ink, the dispersion liquid L10 was added so that the content of the dispersion L10 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element L10 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the ink composition of the following Comparative Example L-2, the ion-exchanged water added as the “remaining amount” is similar to Example L-1 (2), with respect to the total weight of the ink, Proxel XL- 2 was added to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0.02%.

Dispersion L10 <150> 8.0%
Nonionic surfactant 1.0%
Ethylene glycol 5.0%
Glycerin 15.0%
Ion exchange water

In the above composition, Neugen EA160 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of polyvalent cation amount in dispersion The ink prepared in Comparative Example L-2 (2) was measured by the method described in "Measurement of polyvalent cation amount in dispersion". However, the total amount of polyvalent cations in the dispersion was 1393 ppm. Details of the measurement results are shown in Table 54.
(4) Printing evaluation Using the inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example L-1 (4), the ink prepared in Comparative Example L-2 (2) was Using the same evaluation paper as in Example L-1 (4), printing evaluation was performed according to the same evaluation criteria as in Example L-1 (4). The results of printing evaluation are shown in Table 53.
(5) Evaluation of ejection stability Using the same printer and ink as in Comparative Example L-2 (4), the same evaluation method as in Example L-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as in (5). The results of the discharge stability evaluation are shown in Table 54. (6) Storage stability evaluation For the ink prepared in Comparative Example L-2 (2), the same evaluation method as in Example L-1 (6) was used, and the same as in Example L-1 (6). Storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 54.

As is apparent from the results of Tables 52 and 53, it can be seen that the ink used in the comparative example has poor print quality, and that the print quality is good when the ink according to the present invention is used.
As described above, by using the water-based ink of the present invention, it is possible to obtain a high-quality print record in which bleeding is reduced for any paper type.

As is apparent from the results in Table 54, the amount of polyvalent cation in the ink dispersion was 800 pp.
It can be seen from Table 53 that the water-based ink according to the present invention suppressed to m or less ensures excellent ejection stability and storage stability, and the printing quality is excellent from Table 53. It can also be seen that when the amount of polyvalent cation is 550 ppm or less, the ejection stability and storage stability are significantly improved. On the other hand, when the amount of polyvalent cation exceeds 1000 ppm as in the comparative example, it is understood that the print quality, ejection stability, and storage stability are not at practical levels.
As can be seen from the above results, it can be seen that by using the water-based ink according to the present invention, good print quality and ejection stability can be obtained, and the storage stability is also excellent.

[Example M]
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.
(Measurement method of aromatic ring amount, pigment: polymer ratio, average particle size, amount of polyvalent anion in dispersion, and surface tension)
Each measured value (amount of aromatic ring, pigment: polymer ratio, average particle size, amount of polyvalent anion in dispersion, surface tension) obtained in this example was measured by the following method.

"Measurement of aromatic ring quantity"
A part of the dispersion polymer solution obtained in each example or comparative example was taken out, the solvent component was distilled off, and only the polymer component was taken out, dissolved in DMSO-d ₆ , ¹³ C-NMR and ¹ H-NMR ( The amount of aromatic rings in the polymer was measured using Bruker (Germany AMX400).
“Measurement of pigment: polymer ratio”
A part of the dispersion obtained in each Example or Comparative Example was taken out, 0.1 mol / l concentration HCl was added, and only the dispersion was acidified, and the dry weight was measured. Next, the pigment: polymer weight ratio was calculated by taking out only the dispersed polymer by Soxhlet extraction using acetone and measuring the dry weight.
"Measurement of average particle size"
Dilute with ion-exchanged water so that the dispersion concentration of the water-based ink obtained in each Example or Comparative Example is 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement is slightly different depending on the water-based ink). The average particle size of the dispersed particles at 20 ° C. was measured with a particle size distribution meter (DLS-800 manufactured by Otsuka Electronics Co., Ltd.).

"Measurement of polyvalent anion content in dispersion"
A required amount of the water-based ink obtained in each example or comparative example was taken out and separated into a dispersion that is a solid component and a solvent component of the water-based ink by centrifugal separation. The centrifugation condition was 2500 G × 60 minutes.
The obtained dispersion is taken in a quartz dish, added with a scavenger, incinerated, melted with potassium hydrogen sulfate, dissolved in dilute nitric acid, and subjected to ICP emission analysis (ICPS-8000; manufactured by Shimadzu Corporation). The amount of polyvalent anions in the dispersion was measured.
"Measurement of surface tension"
The surface tension at 20 ° C. of the water-based ink obtained in each example or comparative example was measured with a surface tension meter (CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.).

<Example M-1>
(1) Production of dispersion: Dispersion M1
For the production of the dispersion M1 used in Example M-1, color black FW18 (manufactured by Degussa), which is an inorganic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 15 parts of methyl ethyl ketone, 22 parts of styrene, 5 parts of α-methyl styrene, 16 parts of butyl methacrylate, 10 parts of lauryl methacrylate, acrylic acid 2 parts, 0.3 part of t-dodecyl mercaptan is added and heated to 70 ° C., and separately prepared 100 parts of styrene, 16 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and azobis 3 parts of isobutyronitrile was placed in a dropping funnel and the dispersion polymer was subjected to a polymerization reaction while dropping into a reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 57%.

40 parts of the above dispersion polymer solution, 30 parts of carbon black pigment Color Black FW18 (manufactured by Degussa), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 35 parts of methyl ethyl ketone are mixed and dispersed with a homogenizer for 30 minutes or more. Then, 350 parts of ion exchange water is added and dispersed for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are added as appropriate while stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion M1 (carbon black A dispersion M1 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 57% was obtained.
Table 55 shows the pigment used in the dispersion M1, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Preparation of water-based ink In this Example M-1, the dispersion M1 obtained in Example M-1 (1) above, Olphine E1010 (made by Nissin Chemical Industry Co., Ltd.) which is an acetylene glycol surfactant. Diethylene glycol monobutyl ether, which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol, which is a 1,2-alkylene glycol, were used. A specific composition is shown below.
In preparing the aqueous ink, the dispersion M1 was added so that the content of the dispersion M1 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element M1 measured by the method described in "Measurement of Average Particle Size" above.
In addition, ion exchange water added as the “remaining amount” in the aqueous ink composition of Example M-1 below is used to prevent corrosion of the aqueous ink to prevent corrosion of Proxel XL-2 and the aqueous inkjet head member. In order to reduce the influence of benzotriazole and metal ions in the aqueous ink system, the EDTA · 2Na salt should be 0.01%, 0.01% and 0.02%, respectively, based on the total weight of the aqueous ink. What was added was used.

Dispersion M1 <120> 8.0%
Olfine E1010 0.5%
Diethylene glycol monobutyl ether 3.0%
1,2-pentanediol 2.5%
Diethylene glycol 3.0%
Glycerin 11.5%
Trimethylolpropane 6.0%
Tripropanolamine 0.3%
Ion exchange water

(3) Measurement of amount of polyvalent anion in dispersion The aqueous ink prepared in Example M-1 (2) was measured by the method described in "Measurement of amount of polyvalent anion in dispersion". As a result, the total amount of polyvalent anions in the dispersion was 402 ppm. Details of the measurement results are shown in Table 57.

(4) Printing Evaluation For printing evaluation, an aqueous ink jet printer PM-950C (manufactured by Seiko Epson Corporation) that discharges aqueous ink by an aqueous ink jet head using a piezoelectric element (piezo element) was used. Printing evaluation of the water-based ink prepared in 1 (2) was performed.
As evaluation papers, (a) Conqueror paper, (b) Reymat paper, (c) Mode Copy paper, (d) Rapid Copy paper, (e) Xerox P paper , (F) Xerox 4024 paper, (g) Xerox 10 paper, (h) Neenha Bond paper, (i) Rcopy 6200 paper, and (j) Hammer mill.
Copy Plus paper was used.
In addition, evaluation was performed visually and was performed based on the following evaluation criteria.

A: The blur is not recognized in the characters at all points.
B: Slight bleeding is observed with characters of 5 points or less (practical level).
C: Characters of 5 points or less appear thick due to blurring.
D: Significant blurring and characters of 5 points or less cannot be identified.

  Table 56 shows the results of the print evaluation.

(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example M-1 (4), 200 pages are continuously printed on A4 size Xerox P paper, and the disorder of printing is observed. In addition, discharge stability was evaluated in addition. Evaluation was performed visually and based on the following evaluation criteria.

A: Printing disorder does not occur at all.
B: Printing disorder was observed, but the number was less than 10 (practical level).
C: There is printing disorder in the range of 10 or more and less than 100.
D: Disturbance of printing occurred at 100 locations or more.

  Table 57 shows the results of the discharge stability evaluation.

(6) Storage stability evaluation The water-based ink prepared in Example M-1 (2) was placed in a glass bottle and sealed, then left at 60 ° C./1 week and −20 ° C./1 week, respectively. The generated foreign matter and physical property value fluctuation (viscosity, surface tension) were evaluated.
The evaluation was performed based on the following evaluation criteria.

A: The ratio of the amount of foreign matter / physical properties after standing at 60 ° C. or −20 ° C. to that before standing is in the range of 0.99 to 1.01.
B: The ratio is in the range of 0.95 to 0.99, or 1.01 to 1.05 (practical level).
C: The ratio is in the range of 0.90 to 0.95, or 1.05 to 1.10.
D: Ratio is less than 0.90 or greater than 1.10.

  The storage stability evaluation results are shown in Table 57.

<Example M-2>
(1) Production of dispersion: Dispersion M2
For the production of the dispersion M2 used in Example M-2, an insoluble monoazo yellow pigment (CI Pigment Yellow 74), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 12 parts of styrene, 9 parts of lauryl methacrylate, and 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 3 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 part of mercaptoethanol, heated to 70 ° C., 25 parts of styrene prepared separately, lauryl 30 parts of methacrylate, 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), 15 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toagosei Co., Ltd.), 10 parts of methacrylic acid, 20 parts of methyl ethyl ketone Dropwise to the reaction vessel over 4 hours putting 1.0 parts of mercaptoethanol to the dropping funnel and the dispersed polymer is the polymerization reaction. Next, methyl ethyl ketone was appropriately added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 40%.

40 parts of the above dispersion polymer solution, 30 parts of an insoluble monoazo yellow pigment (CI Pigment Yellow 74) as an organic pigment, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed, and 30 parts are mixed with a homogenizer. Disperse for at least minutes, add 380 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, followed by filtration with a membrane filter having an average pore size of 5 μm, thereby obtaining dispersion M2 (insoluble monoazo). A dispersion M2 containing 20% of a dispersion in which a yellow pigment was included by a polymer having an aromatic ring content of 40% was obtained.
Table 55 shows the pigment used in the dispersion M2, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example M-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example M-2, the dispersion M2 obtained in Example M-2 (1), Surfynol 440 (produced by Air Products Co., Ltd.), which is an acetylene glycol surfactant, Orphine STG (manufactured by Nissin Chemical Industry Co., Ltd.), triethylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion M2 was added so that the content of the dispersion M2 was 7.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element M2 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example M-2 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example M-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion M2 <120> 7.0%
Surfinol 440 0.2%
Olphine STG 0.2%
Triethylene glycol monobutyl ether 3.0%
1,2-pentanediol 2.0%
2-pyrrolidone 3.0%
Glycerin 13.5%
Trimethylolethane 5.0%
Triethanolamine 0.1%
Ion exchange water

(3) Measurement of amount of polyvalent anion in dispersion The aqueous ink prepared in Example M-2 (2) was measured by the method described in "Measurement of amount of polyvalent anion in dispersion". As a result, the total amount of polyvalent anions in the dispersion was 225 ppm. Details of the measurement results are shown in Table 57.
(4) Evaluation of printing Regarding water-based ink prepared in Example M-2 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example M-1 (4). Using the same evaluation paper as in Example M-1 (4), print evaluation was performed according to the same evaluation criteria as in Example M-1 (4). The results of printing evaluation are shown in Table 56.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example M-2 (4), using the same evaluation method as in Example M-1 (5), Example M- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 57.
(6) Storage Stability Evaluation For the water-based ink prepared in Example M-2 (2), the same evaluation method as in Example M-1 (6) was used, as in Example M-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 57.

<Example M-3>
(1) Production of dispersion: Dispersion M3
In the production of the dispersion M3 used in Example M-3, quinacridone red pigment (CI Pigment Red 122), which is an organic pigment, was used.
First, the reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 10 parts of styrene, 5 parts of styrene macromer (AS-6; manufactured by Toagosei Co., Ltd.), n-dodecyl methacrylate 3.5 Parts, N, N-dimethylaminoethyl methacrylate 10 parts, methoxypolyethylene glycol methacrylate (NK ester M40G; manufactured by Shin-Nakamura Chemical Co., Ltd.) 25 parts, methyl ethyl ketone 5 parts, mercaptoethanol 0.3 part, and heated to 70 ° C. 15 parts of styrene prepared separately, 10 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of n-dodecyl methacrylate, 20 parts of N, N-dimethylaminoethyl methacrylate, methoxypolyethylene glycol methacrylate (NK ester M40G) ; Shin-Nakamura Chemical Co., Ltd. ) 30 parts, 50 parts of methyl ethyl ketone, and the dispersion polymer dropwise into the reaction vessel over 4 hours and placed in a dropping funnel and 1.5 parts of azobisisobutyronitrile was polymerized reaction. Next, methyl ethyl ketone was appropriately added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 28%.

40 parts of the above dispersion polymer solution, 25 parts of an organic pigment, quinacridone red pigment (CI Pigment Red 122), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 40 parts of methyl ethyl ketone are mixed, and 30 minutes with a homogenizer. Dispersion treatment is performed as described above, and 380 parts of ion exchange water is added and further dispersed for 1 hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm, whereby dispersion M3 (quinacridone red A dispersion M3 containing 20% of a dispersion in which the pigment was covered with a polymer having an aromatic ring content of 28% was obtained.
Table 55 shows the pigment used in the dispersion M3, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example M-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example M-3, the dispersion M3 obtained in Example M-3 (1) above, Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant. And Surfynol 104PG50 (produced by Air Products), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-hexanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion M3 was added so that the content of the dispersion M3 was 7.5%. The value in <> shows the average particle size (unit: nm) of Dispersing Element M3 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example M-3 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example M-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt to 0.02% was used.

Dispersion M3 <140> 7.5%
Olfin E1010 0.1%
Surfynol 104PG50 0.4%
Triethylene glycol monobutyl ether 1.0%
1,2-hexanediol 2.5%
Triethylene glycol 2.0%
2-pyrrolidone 4.0%
Glycerin 13.8%
Trimethylolpropane 6.0%
Ion exchange water

(3) Measurement of amount of polyvalent anion in dispersion The aqueous ink prepared in Example M-3 (2) was measured by the method described in "Measurement of amount of polyvalent anion in dispersion". As a result, the total amount of polyvalent anions in the dispersion was 287 ppm. Details of the measurement results are shown in Table 57.
(4) Evaluation of printing Regarding water-based ink prepared in Example M-3 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example M-1 (4). Using the same evaluation paper as in Example M-1 (4), print evaluation was performed according to the same evaluation criteria as in Example M-1 (4). The results of printing evaluation are shown in Table 56.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example M-3 (4), Example M
-1 (5), the ejection stability was evaluated according to the same evaluation criteria as in Example M-1 (5). The results of the discharge stability evaluation are shown in Table 57.
(6) Storage Stability Evaluation For the water-based ink prepared in Example M-3 (2), the same evaluation method as in Example M-1 (6) was used, and the same as in Example M-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 57.

<Example M-4>
(1) Production of dispersion: Dispersion M4
For the production of the dispersion M4 used in Example M-4, a phthalocyanine blue pigment (CI pigment blue 15: 4), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 20 parts of styrene, 10 parts of lauryl methacrylate, 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 10 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 n-dodecyl mercaptan And heated to 70 ° C., separately prepared 25 parts of styrene, 30 parts of lauryl methacrylate, 20 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), isobutyl methacrylate macromer (AW-6S; Toa) Composition 15 parts, 15 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 20 parts of methyl ethyl ketone, 1.5 parts of n-dodecyl mercaptan in a dropping funnel over 4 hours The dispersion polymer was polymerized while being dropped into the reaction vessel. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 45%.

40 parts of the above dispersion polymer solution, 40 parts of an organic pigment phthalocyanine blue pigment (CI Pigment Blue 15: 4), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed together. Disperse for 30 minutes or more, add 350 parts of ion exchange water, and disperse for another hour.
And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm, whereby dispersion M4 (phthalocyanine blue) A dispersion M4 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 45% was obtained.
Table 55 shows the pigment used in the dispersion M4, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example M-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example M-4, the dispersion M4 obtained in Example M-4 (1), acetylenol E100 (made by Kawaken Fine Chemical Co., Ltd.), which is an acetylene glycol surfactant, Propylene glycol monobutyl ether which is alkylene glycol monoalkyl ether and 1,2-hexanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion M4 was added so that the content of the dispersion M4 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element M4 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example M-4 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example M-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt to 0.02% was used.

Dispersion M4 <100> 8.0%
Acetylenol E100 0.5%
Propylene glycol monobutyl ether 3.0%
1,2-hexanediol 1.0%
Triethylene glycol 3.0%
Glycerin 13.8%
Trimethylolpropane 5.2%
Tripropanolamine 0.2%
Ion exchange water

(3) Measurement of amount of polyvalent anion in dispersion The aqueous ink prepared in Example M-4 (2) was measured by the method described in "Measurement of amount of polyvalent anion in dispersion". As a result, the total amount of polyvalent anions in the dispersion was 375 ppm. Details of the measurement results are shown in Table 57.
(4) Evaluation of printing Regarding water-based ink prepared in Example M-4 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example M-1 (4). Using the same evaluation paper as in Example M-1 (4), print evaluation was performed according to the same evaluation criteria as in Example M-1 (4). The results of printing evaluation are shown in Table 56.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example M-4 (4), using the same evaluation method as in Example M-1 (5), Example M- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 57.
(6) Storage Stability Evaluation For the water-based ink prepared in Example M-4 (2), the same evaluation method as in Example M-1 (6) was used, and the same as in Example M-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 57.

<Example M-5>
(1) Production of dispersion: Dispersion M5
A perinone orange pigment (CI Pigment Orange 43) was used for the production of the dispersion M5 used in Example M-5. Otherwise, in the same manner as described in Example M-1 (1), 20% of dispersion M5 (dispersion containing a perinone orange pigment with a polymer having an aromatic ring content of 56%) is contained. Dispersion M5 was obtained.
Table 55 shows the pigment used in dispersion M5, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example M-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example M-5, the dispersion M5 obtained in Example M-5 (1), Surfynol 485 and Surfynol TG which are acetylene glycol surfactants (both are air) Products), dipropylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol. A specific composition is shown below.
In preparing the water-based ink, the dispersion M5 was added so that the content of the dispersion M5 was 10.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element M5 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example M-5 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example M-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt to 0.02% was used.

Dispersion M5 <150> 10.0%
Surfynol 485 0.5%
Surfinol TG 0.2%
Dipropylene glycol monobutyl ether 2.0%
1,2-pentanediol 2.0%
N-methyl-2-pyrrolidone 5.0%
Glycerin 11.2%
Trehalose 5.8%
Ion exchange water

(3) Measurement of amount of polyvalent anion in dispersion The aqueous ink prepared in Example M-5 (2) was measured by the method described in "Measurement of amount of polyvalent anion in dispersion". As a result, the total amount of polyvalent anions in the dispersion was 248 ppm. Details of the measurement results are shown in Table 57.
(4) Printing Evaluation About water-based ink prepared in Example M-5 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example M-1 (4). Using the same evaluation paper as in Example M-1 (4), print evaluation was performed according to the same evaluation criteria as in Example M-1 (4). The results of printing evaluation are shown in Table 56.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example M-5 (4), using the same evaluation method as in Example M-1 (5), Example M- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 57.
(6) Storage Stability Evaluation For the water-based ink prepared in Example M-5 (2), the same evaluation method as in Example M-1 (6) was used, and the same as in Example M-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 57.

<Example M-6>
(1) Production of dispersion: Dispersion M6
A benzimidazolone brown pigment (CI Pigment Brown 32) was used for the production of the dispersion M6 used in Example M-6. Otherwise, in the same manner as described in Example M-1 (1), 20% of dispersion M6 (dispersion containing benzimidazolone brown pigment by a polymer having an aromatic ring content of 69%) A dispersion M6 was obtained.
Table 55 shows the pigment used in dispersion M6, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example M-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example M-6, the dispersion M6 obtained in Example M-6 (1), Surfynol 420 which is an acetylene glycol surfactant, and alkylene glycol monoalkyl ether Some diethylene glycol monobutyl ether was used. A specific composition is shown below.
In preparing the water-based ink, the dispersion M6 was added so that the content of the dispersion M6 was 5.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element M6 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the following Example M-6, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example M-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt to 0.02% was used.

Dispersion M6 <140> 5.0%
Surfynol 420 0.1%
Diethylene glycol monobutyl ether 3.0%
1,6-hexanediol 2.0%
Tetraethylene glycol 5.5%
Glycerin 13.5%
Triethanolamine 0.5%
Ion exchange water

(3) Measurement of amount of polyvalent anion in dispersion The water-based ink prepared in Example M-6 (2) was measured by the method described in "Measurement of amount of polyvalent anion in dispersion". As a result, the total amount of polyvalent anions in the dispersion was 515 ppm. Details of the measurement results are shown in Table 57.
(4) Printing Evaluation Regarding water-based ink prepared in Example M-6 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example M-1 (4). Using the same evaluation paper as in Example M-1 (4), print evaluation was performed according to the same evaluation criteria as in Example M-1 (4). The results of printing evaluation are shown in Table 56.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example M-6 (4), using the same evaluation method as in Example M-1 (5), Example M- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 57.
(6) Storage Stability Evaluation For the water-based ink prepared in Example M-6 (2), the same evaluation method as in Example M-1 (6) was used, and the same as in Example M-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 57.

<Example M-7>
(1) Production of dispersion: Dispersion M7
For the production of the dispersion M7 used in Example M-7, quinacridone violet pigment (CI Pigment Bio Red 19) was used as an organic pigment. Otherwise, dispersion containing 20% of dispersion M7 (dispersion containing quinacridone violet pigment with polymer having 21% aromatic ring) in the same manner as described in Example M-1 (1) above A liquid M7 was obtained.
Table 55 shows the pigment used in dispersion M7, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example M-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example M-7, the dispersion M7 obtained in Example M-7 (1), Surfynol 61 and Surfynol TG which are acetylene alcohol surfactants (both air Products), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2 alkylene glycol. A specific composition is shown below.
In the preparation of the water-based ink, the dispersion M7 was added so that the content of the dispersion M7 was 6.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element M7 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example M-7 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example M-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion M7 <120> 6.0%
Surfynol 61 0.3%
Surfynol TG 0.1%
Triethylene glycol monobutyl ether 1.5%
1,2-pentanediol 2.0%
Diethylene glycol 2.0%
Thiodiglycol 4.0%
Glycerin 12.6%
Trimethylolethane 7.0%
Ion exchange water

(3) Measurement of amount of polyvalent anion in dispersion The water-based ink prepared in Example M-7 (2) was measured by the method described in "Measurement of amount of polyvalent anion in dispersion". As a result, the total amount of polyvalent anions in the dispersion was 351 ppm. Details of the measurement results are shown in Table 57.
(4) Printing Evaluation Regarding water-based ink prepared in Example M-7 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example M-1 (4). Using the same evaluation paper as in Example M-1 (4), print evaluation was performed according to the same evaluation criteria as in Example M-1 (4). The results of printing evaluation are shown in Table 56.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example M-7 (4), using the same evaluation method as in Example M-1 (5), Example M- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 57.
(6) Storage Stability Evaluation For the water-based ink prepared in Example M-7 (2), the same evaluation method as in Example M-1 (6) was used, and the same as in Example M-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 57.

<Example M-8>
(1) Production of dispersion: Dispersion M8
A phthalocyanine green pigment (CI Pigment Green 7), which is an organic pigment, was used for the production of the dispersion M8 used in Example M-8. Otherwise, dispersion containing 20% of dispersion M8 (dispersion containing phthalocyanine green pigment with a polymer having an aromatic ring content of 30%) in the same manner as described in Example M-1 (1) above A liquid M8 was obtained.
Table 55 shows the pigment used in dispersion M8, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example M-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example M-8, the dispersion M8 obtained in Example M-8 (1), Olphine E1010 (made by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant. And Surfynol 104 (produced by Air Products), dipropylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion M8 was added so that the content of the dispersion M8 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element M8 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the following Example M-8, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example M-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt to 0.02% was used.

Dispersion M8 <110> 8.0%
Olfine E1010 0.3%
Surfynol 104 0.1%
Dipropylene glycol monobutyl ether 1.0%
1,2-pentanediol 3.0%
Triethylene glycol 2.0%
Thiodiglycol 4.0%
Glycerin 13.8%
Trimethylolpropane 6.0%
Triethanolamine 0.1%
Ion exchange water

(3) Measurement of amount of polyvalent anion in dispersion The water-based ink prepared in Example M-8 (2) was measured by the method described in "Measurement of amount of polyvalent anion in dispersion". As a result, the total amount of polyvalent anions in the dispersion was 568 ppm. Details of the measurement results are shown in Table 57.
(4) Printing Evaluation Regarding water-based ink prepared in Example M-8 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example M-1 (4). Using the same evaluation paper as in Example M-1 (4), print evaluation was performed according to the same evaluation criteria as in Example M-1 (4). The results of printing evaluation are shown in Table 56.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example M-8 (4), using the same evaluation method as in Example M-1 (5), the Example M- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 57.
(6) Storage Stability Evaluation For the water-based ink prepared in Example M-8 (2), the same evaluation method as in Example M-1 (6) was used, and the same as in Example M-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 57.

<Comparative Example M-1>
(1) Production of dispersion: Dispersion M9
In this comparative example M-1, the quinacridone red pigment (CI Pigment Red 122), which is the organic pigment of Example M-3 (1), was used. However, the pigment used in this comparative example was intentionally pulverized in the above-described pigment pulverization process over a period of time more than usual. Otherwise, a dispersion containing 20% of dispersion M9 (a dispersion containing quinacridone red pigment with a polymer having an aromatic ring content of 20%) in the same manner as described in Example M-3 (1) above A liquid M9 was obtained.
Table 55 shows the pigment used in dispersion M9, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Preparation of water-based ink In this comparative example M-1, water-based ink was prepared using the dispersion M9 obtained in the comparative example M-1 (1). A specific composition is shown below.
In the preparation of the water-based ink, the dispersion M9 was added so that the content of the dispersion M9 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element M9 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the present Comparative Example M-1, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example M-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt to 0.02% was used.

Dispersion M9 <140> 8.0%
Nonionic surfactant 1.0%
Ethylene glycol 5.0%
Glycerin 15.0%
Ion exchange water

  In the above composition, Epan 450 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of amount of polyvalent anion in dispersion The aqueous ink prepared in Comparative Example M-1 (2) was measured by the method described in "Measurement of amount of polyvalent anion in dispersion". As a result, the total amount of polyvalent anions in the dispersion was 848 ppm. Details of the measurement results are shown in Table 57.
(4) Print evaluation About water-based ink prepared in Comparative Example M-1 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example M-1 (4). Using the same evaluation paper as in Example M-1 (4), print evaluation was performed according to the same evaluation criteria as in Example M-1 (4). The results of printing evaluation are shown in Table 56.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Comparative Example M-1 (4), the same evaluation method as in Example M-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 57.
(6) Storage stability evaluation About the water-based ink adjusted by the said comparative example M-1 (2), it is the same evaluation method as the said Example M-1 (6), and is the same as the said Example M-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 57.

<Comparative Example M-2>
(1) Production of dispersion: Dispersion M10
In this comparative example M-, quinacridone violet pigment (CI Pigment Bio Red 19), which is an organic pigment, was dispersed using Solsperse 12000 (Avisia Corporation).
15 parts of quinacridone violet pigment (CI Pigment Bio Red 19), 5 parts of Solsperse 12000, 5 parts of diethanolamine, 0.5 part of 2-propanol, and 74.5 parts of ion-exchanged water were added to bead mill mini-zeta (Ajisawa). The dispersion M10 used in Comparative Example M-2 containing 20% of the dispersion M9 (pigment: 15%, dispersion resin: 5%) was obtained by carrying out a dispersion treatment for 2 hours.

(2) Adjustment of water-based ink In this comparative example M-2, the water-based ink was adjusted using the dispersion liquid M10 obtained by the said comparative example M-2 (1). The specific composition of this comparative example is shown below.
In preparation of the water-based ink, the dispersion M10 was added so that the content of the dispersion M9 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element M9 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the water-based ink composition of the present Comparative Example M-2 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example M-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt to 0.02% was used.

Dispersion M9 <150> 8.0%
Nonionic surfactant 1.0%
Ethylene glycol 5.0%
Glycerin 15.0%
Ion exchange water

  In the above composition, Neugen EA160 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of amount of polyvalent anion in dispersion The aqueous ink prepared in Comparative Example M-2 (2) was measured by the method described in "Measurement of amount of polyvalent anion in dispersion". As a result, the total amount of polyvalent anions in the dispersion was 1386 ppm. Details of the measurement results are shown in Table 57.
(4) Printing Evaluation Regarding water-based ink prepared in Comparative Example M-2 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example M-1 (4). Using the same evaluation paper as in Example M-1 (4), print evaluation was performed according to the same evaluation criteria as in Example M-1 (4). The results of printing evaluation are shown in Table 56.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Comparative Example M-2 (4), the same evaluation method as in Example M-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 57.
(6) Storage Stability Evaluation For the water-based ink prepared in Comparative Example M-2 (2), the same evaluation method as in Example M-1 (6) was used, and the same as in Example M-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 57.

As is apparent from the results in Tables 55 and 56, it is understood that the water-based ink used in the comparative example has poor print quality, and that the print quality is good when the water-based ink according to the present invention is used.
As described above, by using the water-based ink of the present invention, it is possible to obtain a high-quality print record in which bleeding is reduced for any paper type.

As is apparent from the results in Table 57, the aqueous ink according to the present invention in which the amount of polyvalent anions in the aqueous ink dispersion is suppressed to 600 ppm or less ensures excellent ejection stability and storage stability. It can be seen that the print quality is also excellent. It can also be seen that when the amount of polyvalent anions is 400 ppm or less, the discharge stability and storage stability are significantly improved. On the other hand, when the amount of polyvalent anions exceeds 800 ppm as in the comparative example, it is understood that the print quality, ejection stability, and storage stability are not at practical levels.
As can be seen from the above results, it can be seen that by using the water-based ink according to the present invention, good print quality and ejection stability can be obtained, and the storage stability is also excellent.

[Example N]
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.
(Measurement method of aromatic ring amount, pigment: polymer ratio, average particle size, amount of monovalent cation in dispersion, and surface tension)
Each measured value (amount of aromatic ring, pigment: polymer ratio, average particle diameter, amount of monovalent cation in dispersion, surface tension) obtained in this example was measured by the following method.

"Measurement of aromatic ring quantity"
A part of the dispersion polymer solution obtained in each example or comparative example was taken out, the solvent component was distilled off, and only the polymer component was taken out, dissolved in DMSO-d ₆ , ¹³ C-NMR and ¹ H-NMR ( The amount of aromatic rings in the polymer was measured using Bruker (Germany AMX400).
“Measurement of pigment: polymer ratio”
A part of the dispersion obtained in each Example or Comparative Example was taken out, 0.1 mol / l concentration HCl was added, and only the dispersion was acidified, and the dry weight was measured. Next, the pigment: polymer weight ratio was calculated by taking out only the dispersed polymer by Soxhlet extraction using acetone and measuring the dry weight.
"Measurement of average particle size"
Dilute with ion-exchanged water so that the dispersion concentration of the water-based ink obtained in each Example or Comparative Example is 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement is slightly different depending on the water-based ink). The average particle size of the dispersed particles at 20 ° C. was measured with a particle size distribution meter (DLS-800 manufactured by Otsuka Electronics Co., Ltd.).

"Measurement of monovalent cation content in dispersion"
A required amount of the water-based ink obtained in each example or comparative example was taken out and separated into a dispersion that is a solid component and a solvent component of the water-based ink by centrifugal separation. The centrifugation condition was 2500 G × 60 minutes.
After the centrifugal treatment, the obtained dispersion was diluted with pure water, and the amount of monovalent cation in the dispersion was measured by ICP emission analysis (ICPS-8000, manufactured by Shimadzu Corporation). "Measurement of surface tension"
The surface tension at 20 ° C. of the water-based ink obtained in each example or comparative example was measured with a surface tension meter (CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.).

<Example N-1>
(1) Production of dispersion: Dispersion N1
For the production of the dispersion N1 used in Example N-1, a carbon black pigment color black FW18 (manufactured by Degussa Co., Ltd.), which is an inorganic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, then 15 parts of methyl ethyl ketone, 21 parts of styrene, 5 parts of α-methyl styrene, 16 parts of butyl methacrylate, 10 parts of lauryl methacrylate, acrylic acid 2 parts, 0.3 part of t-dodecyl mercaptan was added and heated to 70 ° C., and separately prepared 100 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and azobis 3 parts of isobutyronitrile was placed in a dropping funnel and the dispersion polymer was subjected to a polymerization reaction while dropping into a reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 59%.

40 parts of the above dispersion polymer solution, 30 parts of carbon black pigment Color Black FW18 (manufactured by Degussa), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 35 parts of methyl ethyl ketone are mixed and dispersed with a homogenizer for 30 minutes or more. Then, 350 parts of ion exchange water is added and dispersed for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore diameter of 5 μm to obtain dispersion N1 (carbon black A dispersion N1 containing 20% of a dispersion in which the pigment is covered with a polymer having an aromatic ring content of 59% was obtained.
Table 58 shows the pigment used in the dispersion N1, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Preparation of water-based ink In Example N-1, the dispersion N1 obtained in Example N-1 (1), Olphine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant. Diethylene glycol monobutyl ether which is alkylene glycol monoalkyl ether and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion N1 was added so that the content of the dispersion N1 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element N1 measured by the method described in "Measurement of Average Particle Size" above.
In addition, ion exchange water added as the “remaining amount” in the aqueous ink composition of Example N-1 described below is used to prevent corrosion of water-based ink, Proxel XL-2, and water-based inkjet head member. In order to reduce the influence of benzotriazole and metal ions in the aqueous ink system, the EDTA · 2Na salt should be 0.01%, 0.01%, and 0.02%, respectively, based on the total weight of the aqueous ink. What was added was used.

Dispersion N1 <120> 8.0%
Olfine E1010 0.5%
Diethylene glycol monobutyl ether 3.0%
1,2-pentanediol 2.5%
Diethylene glycol 3.0%
Glycerin 11.5%
Trimethylolpropane 6.0%
Tripropanolamine 0.3%
Ion exchange water

(3) Measurement of monovalent cation amount in dispersion The aqueous ink prepared in Example N-1 (2) was measured by the method described in "Measurement of monovalent cation amount in dispersion". As a result, the total amount of monovalent cations was 1788 ppm. Details of the measurement results are shown in Table 60.

(4) Printing evaluation For printing evaluation, an aqueous inkjet printer PM-950C (manufactured by Seiko Epson Corporation) that discharges aqueous ink by an aqueous inkjet head using a piezoelectric element (piezo element) was used. Printing evaluation of the water-based ink prepared in 1 (2) was performed.
As evaluation papers, (a) Conqueror paper, (b) Reymat paper, (c) Mode Copy paper, (d) Rapid Copy paper, (e) Xerox P paper , (F) Xerox 4024 paper, (g) Xerox 10 paper, (h) Neenha Bond paper, (i) Riccopy 6200 paper, and (j) Hammer mill Copy Plus paper.
In addition, evaluation was performed visually and was performed based on the following evaluation criteria.

A: The blur is not recognized in the characters at all points.
B: Slight bleeding is observed with characters of 5 points or less (practical level).
C: Characters of 5 points or less appear thick due to blurring.
D: Significant blurring and characters of 5 points or less cannot be identified.

  Table 59 shows the results of printing evaluation.

(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example N-1 (4), 200 pages are continuously printed on A4 size Xerox P paper, and the printing disorder is observed. The ejection stability was evaluated.
In addition, evaluation was performed visually and was performed based on the following evaluation criteria.

A: Printing disorder does not occur at all.
B: Printing disorder was observed, but the number was less than 10 (practical level).
C: There is printing disorder in the range of 10 or more and less than 100.
D: Disturbance of printing occurred at 100 locations or more.

  Table 60 shows the results of the discharge stability evaluation.

(6) Storage stability evaluation The water-based ink prepared in Example N-1 (2) was placed in a glass bottle and sealed, then left at 60 ° C./1 week and −20 ° C./1 week, respectively. The generated foreign matter and physical property value fluctuation (viscosity, surface tension) were evaluated.
The evaluation was performed based on the following evaluation criteria.

A: The ratio of the amount of foreign matter / physical properties after standing at 60 ° C. or −20 ° C. to that before standing is in the range of 0.99 to 1.01.
B: The ratio is in the range of 0.95 to 0.99, or 1.01 to 1.05 (practical level).
C: The ratio is in the range of 0.90 to 0.95, or 1.05 to 1.10.
D: Ratio is less than 0.90 or greater than 1.10.

  The storage stability evaluation results are shown in Table 60.

<Example N-2>
(1) Production of dispersion: Dispersion N2
For the production of the dispersion N2 used in Example N-2, an insoluble monoazo yellow pigment (CI Pigment Yellow 74), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 12 parts of styrene, 9 parts of lauryl methacrylate, and 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 3 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 part of mercaptoethanol, heated to 70 ° C., 25 parts of styrene prepared separately, lauryl 30 parts of methacrylate, 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), 15 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toagosei Co., Ltd.), 10 parts of methacrylic acid, 20 parts of methyl ethyl ketone Dropwise to the reaction vessel over 4 hours putting 1.0 parts of mercaptoethanol to the dropping funnel and the dispersed polymer is the polymerization reaction. Next, methyl ethyl ketone was appropriately added to the reaction vessel to prepare a 35% concentration dispersion polymer solution.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in the above-mentioned “Measurement of the amount of aromatic ring”. The amount was 25%.

40 parts of the above dispersion polymer solution, 30 parts of an insoluble monoazo yellow pigment (CI Pigment Yellow 74) as an organic pigment, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed, and 30 parts are mixed with a homogenizer. Disperse for at least minutes, add 380 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore diameter of 5 μm, whereby dispersion N2 (insoluble monoazo A dispersion N2 containing 20% of a dispersion in which a yellow pigment was included by a polymer having an aromatic ring content of 25% was obtained.
Table 58 shows the pigment used in the dispersion N2, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example N-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of aqueous ink In Example N-2, the dispersion N2 obtained in Example N-2 (1), Surfynol 440 (produced by Air Products Co., Ltd.), which is an acetylene glycol surfactant, and Orphine STG (manufactured by Nissin Chemical Industry Co., Ltd.), triethylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion N2 was added so that the content of the dispersion N2 was 7.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element N2 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the water-based ink composition of Example N-2 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example N-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion N2 <120> 7.0%
Surfinol 440 0.2%
Olphine STG 0.2%
Triethylene glycol monobutyl ether 3.0%
1,2-pentanediol 2.0%
2-pyrrolidone 3.0%
Glycerin 13.5%
Trimethylolethane 5.0%
Triethanolamine 0.1%
Ion exchange water

(3) Measurement of monovalent cation amount in dispersion The water-based ink prepared in Example N-2 (2) was measured by the method described in "Measurement of monovalent cation amount in dispersion". As a result, the total amount of monovalent cations was 1085 ppm. Details of the measurement results are shown in Table 60.
(4) Printing Evaluation Regarding aqueous ink prepared in Example N-2 (2) using an aqueous inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example N-1 (4). Using the same evaluation paper as in Example N-1 (4), print evaluation was performed according to the same evaluation criteria as in Example N-1 (4). The print evaluation results are shown in Table 59.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example N-2 (4), using the same evaluation method as in Example N-1 (5), the Example N- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 60.
(6) Storage Stability Evaluation For the water-based ink prepared in Example N-2 (2), the same evaluation method as in Example N-1 (6) was used, as in Example N-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 60.

<Example N-3>
(1) Production of dispersion: Dispersion 3
For the production of the dispersion N3 used in Example N-3, quinacridone red pigment (CI Pigment Red 122), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 12 parts of styrene, 6 parts of styrene macromer (AS-6; manufactured by Toagosei Co., Ltd.), n-dodecyl methacrylate 3.5 70 parts by adding 12 parts of N, N-dimethylaminoethyl methacrylate, 25 parts of methoxypolyethylene glycol methacrylate (NK ester M40G; manufactured by Shin-Nakamura Chemical Co., Ltd.), 5 parts of methyl ethyl ketone, and 0.3 part of azobisisobutyronitrile. 15 parts of styrene prepared separately, 8 parts of styrene macromer (AS-6; manufactured by Toagosei Co., Ltd.), 7 parts of n-dodecyl methacrylate, 20 parts of N, N-dimethylaminoethyl methacrylate, methoxypolyethylene glycol methacrylate (NK Ester M40G; Shin-Nakamura Chemical Co., Ltd. Company Ltd.) 30 parts Methyl ethyl ketone 50 parts, the dispersion polymer dropwise into the reaction vessel over 4 hours and placed in a dropping funnel and 1.5 parts of azobisisobutyronitrile was polymerized reaction. Next, methyl ethyl ketone was appropriately added to the reaction vessel to prepare a 38% concentration dispersion polymer solution.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 40%.

40 parts of the above dispersion polymer solution, 25 parts of an organic pigment, quinacridone red pigment (CI Pigment Red 122), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 40 parts of methyl ethyl ketone are mixed, and 30 minutes with a homogenizer. Dispersion treatment is performed as described above, and 380 parts of ion exchange water is added and further dispersed for 1 hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm, whereby dispersion N3 (quinacridone red A dispersion N3 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 40% was obtained.
Table 58 shows the pigment used in the dispersion N3, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example N-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example N-3, the dispersion N3 obtained in Example N-3 (1), Olphine E1010 (made by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant, is used. And Surfynol 104PG50 (produced by Air Products), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-hexanediol which is 1,2-alkylene glycol. A specific composition is shown below.
In the preparation of the water-based ink, the dispersion N3 was added so that the content of the dispersion N3 was 7.5%. The value in <> shows the average particle size (unit: nm) of Dispersing Element N3 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example N-3 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example N-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt to 0.02% was used.

Dispersion N3 <140> 7.5%
Olfin E1010 0.1%
Surfynol 104PG50 0.4%
Triethylene glycol monobutyl ether 1.0%
1,2-hexanediol 2.5%
Triethylene glycol 2.0%
2-pyrrolidone 4.0%
Glycerin 13.8%
Trimethylolpropane 6.0%
Ion exchange water

(3) Measurement of monovalent cation amount in dispersion The water-based ink prepared in Example N-3 (2) was measured by the method described in "Measurement of monovalent cation amount in dispersion". As a result, the total amount of monovalent cations was 1484 ppm. Details of the measurement results are shown in Table 60.
(4) Printing Evaluation Regarding water-based ink prepared in Example N-3 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example N-1 (4). Using the same evaluation paper as in Example N-1 (4), print evaluation was performed according to the same evaluation criteria as in Example N-1 (4). The print evaluation results are shown in Table 59.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example N-3 (4), using the same evaluation method as in Example N-1 (5), Example N- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 60.
(6) Storage Stability Evaluation For the water-based ink prepared in Example N-3 (2), the same evaluation method as in Example N-1 (6) was used, as in Example N-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 60.

<Example N-4>
(1) Production of dispersion: Dispersion N4
For the production of the dispersion N4 used in Example N-4, a phthalocyanine blue pigment (CI Pigment Blue 15: 4), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 20 parts of styrene, 9 parts of lauryl methacrylate, and 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 10 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 n-dodecyl mercaptan And heated to 70 ° C., separately prepared 25 parts of styrene, 30 parts of lauryl methacrylate, 20 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), isobutyl methacrylate macromer (AW-6S; Toa) Synthetic strain 15 parts), 15 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 20 parts of methyl ethyl ketone, 1.5 parts of n-dodecyl mercaptan are placed in the dropping funnel and reacted for 4 hours. The dispersion polymer was subjected to a polymerization reaction while dropping into the container. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 46%.

40 parts of the above dispersion polymer solution, 40 parts of an organic pigment phthalocyanine blue pigment (CI Pigment Blue 15: 4), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed together. Disperse for 30 minutes or more, add 350 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore diameter of 5 μm, whereby dispersion N4 (phthalocyanine blue A dispersion N4 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 46% was obtained.
Table 58 shows the pigment used in the dispersion N4, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example N-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of aqueous ink In Example N-4, the dispersion N4 obtained in Example N-4 (1), acetylenol E100 (produced by Kawaken Fine Chemical Co., Ltd.), which is an acetylene glycol surfactant, Propylene glycol monobutyl ether, which is an alkylene glycol monoalkyl ether, and 1,2-hexanediol, which is 1,2-alkylene glycol, were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion N4 was added so that the content of the dispersion N4 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element N4 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the water-based ink composition of Example N-4 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example N-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt to 0.02% was used.

Dispersion N4 <100> 8.0%
Acetylenol E100 0.5%
Propylene glycol monobutyl ether 3.0%
1,2-hexanediol 1.0%
Triethylene glycol 3.0%
Glycerin 13.8%
Trimethylolpropane 5.2%
Tripropanolamine 0.2%
Ion exchange water

(3) Measurement of monovalent cation amount in dispersion The water-based ink prepared in Example N-4 (2) was measured by the method described in "Measurement of monovalent cation amount in dispersion". As a result, the total amount of monovalent cations was 1208 ppm. Details of the measurement results are shown in Table 60.
(4) Evaluation of printing Regarding water-based ink prepared in Example N-4 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example N-1 (4). Using the same evaluation paper as in Example N-1 (4), print evaluation was performed according to the same evaluation criteria as in Example N-1 (4). The print evaluation results are shown in Table 59.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example N-4 (4), Example N
-1 (5), the ejection stability was evaluated according to the same evaluation criteria as in Example N-1 (5). The results of the discharge stability evaluation are shown in Table 60.
(6) Storage Stability Evaluation For the water-based ink prepared in Example N-4 (2), the same evaluation method as in Example N-1 (6) was used, as in Example N-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 60.

<Example N-5>
(1) Production of dispersion: Dispersion N5
A perinone orange pigment (CI Pigment Orange 43) was used for the production of the dispersion N5 used in Example N-5. Other than that, by the same method as described in Example N-1 (1), the dispersion N5 (a dispersion containing a perinone orange pigment with a polymer having an aromatic ring content of 56%) is contained 20%. Dispersion N5 was obtained.
Table 58 shows the pigment used in the dispersion N5, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example N-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of aqueous ink In this Example N-5, the dispersion N5 obtained in Example N-5 (1), Surfynol 485 and Surfynol TG which are acetylene glycol surfactants (both are air) Products), dipropylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol. A specific composition is shown below. In preparing the water-based ink, the dispersion N5 was added so that the content of the dispersion N5 was 10.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element N5 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example N-5 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example N-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt to 0.02% was used.

Dispersion N5 <150> 10.0%
Surfynol 485 0.5%
Surfinol TG 0.2%
Dipropylene glycol monobutyl ether 2.0%
1,2-pentanediol 2.0%
N-methyl-2-pyrrolidone 5.0%
Glycerin 11.2%
Trehalose 5.8%
Ion exchange water

(3) Measurement of monovalent cation amount in dispersion The aqueous ink prepared in Example N-5 (2) was measured by the method described in "Measurement of monovalent cation amount in dispersion". As a result, the total amount of monovalent cations was 1040 ppm. Details of the measurement results are shown in Table 60.
(4) Printing Evaluation Regarding water-based ink prepared in Example N-5 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example N-1 (4). Using the same evaluation paper as in Example N-1 (4), print evaluation was performed according to the same evaluation criteria as in Example N-1 (4). The print evaluation results are shown in Table 59.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example N-5 (4), using the same evaluation method as in Example N-1 (5), the Example N- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 60.
(6) Storage Stability Evaluation For the water-based ink prepared in Example N-5 (2), the same evaluation method as in Example N-1 (6) was used, and the same as in Example N-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 60.

<Example N-6>
(1) Production of dispersion: Dispersion N6
A benzimidazolone brown pigment (CI Pigment Brown 32) was used in the production of the dispersion N6 used in Example N-6. Otherwise, by the same method as described in Example N-1 (1) above, 20% of dispersion N6 (dispersion containing benzimidazolone brown pigment by a polymer having an aromatic ring content of 67%) A dispersion N6 was obtained.
Table 58 shows the pigment used in the dispersion N6, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example N-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example N-6, the dispersion N6 obtained in Example N-6 (1), Surfynol 420 which is an acetylene glycol surfactant, and alkylene glycol monoalkyl ether Some diethylene glycol monobutyl ether was used. A specific composition is shown below.
In preparing the water-based ink, the dispersion N6 was added so that the content of the dispersion N6 was 5.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element N6 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example N-6 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example N-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion N6 <140> 5.0%
Surfynol 420 0.1%
Diethylene glycol monobutyl ether 3.0%
1,6-hexanediol 2.0%
Tetraethylene glycol 5.5%
Glycerin 13.5%
Triethanolamine 0.5%
Ion exchange water

(3) Measurement of monovalent cation amount in dispersion The water-based ink prepared in Example N-6 (2) was measured by the method described in "Measurement of monovalent cation amount in dispersion". As a result, the total amount of monovalent cations was 1780 ppm. Details of the measurement results are shown in Table 60.
(4) Printing Evaluation Regarding water-based ink prepared in Example N-6 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example N-1 (4). Using the same evaluation paper as in Example N-1 (4), print evaluation was performed according to the same evaluation criteria as in Example N-1 (4). The print evaluation results are shown in Table 59.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example N-6 (4), the same evaluation method as in Example N-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 60.
(6) Storage Stability Evaluation For the water-based ink prepared in Example N-6 (2), the same evaluation method as in Example N-1 (6) was used, and the same as in Example N-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 60.

<Example N-7>
(1) Production of dispersion: Dispersion N7
In the production of the dispersion N7 used in Example N-7, quinacridone violet pigment (CI Pigment Bio Red 19) was used as an organic pigment. Otherwise, dispersion containing 20% of dispersion N7 (a dispersion containing quinacridone violet pigment with a polymer having an aromatic ring content of 21%) in the same manner as described in Example N-1 (1) above A liquid N7 was obtained.
Table 58 shows the pigment used in the dispersion N7, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example N-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In this Example N-7, the dispersion N7 obtained in Example N-7 (1), Surfynol 61 and Surfynol TG which are acetylene alcohol surfactants (both are air) Products), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2 alkylene glycol. A specific composition is shown below.
In preparing the water-based ink, the dispersion N7 was added so that the content of the dispersion N7 was 6.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element N7 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example N-7 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example N-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion N7 <120> 6.0%
Surfynol 61 0.3%
Surfynol TG 0.1%
Triethylene glycol monobutyl ether 1.5%
1,2-pentanediol 2.0%
Diethylene glycol 2.0%
Thiodiglycol 4.0%
Glycerin 12.6%
Trimethylolethane 7.0%
Ion exchange water

(3) Measurement of monovalent cation amount in dispersion The aqueous ink prepared in Example N-7 (2) was measured by the method described in "Measurement of monovalent cation amount in dispersion". As a result, the total amount of monovalent cations was 1123 ppm. Details of the measurement results are shown in Table 60.
(4) Printing Evaluation Regarding water-based ink prepared in Example N-7 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example N-1 (4). Using the same evaluation paper as in Example N-1 (4), print evaluation was performed according to the same evaluation criteria as in Example N-1 (4). The print evaluation results are shown in Table 59.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example N-7 (4), using the same evaluation method as in Example N-1 (5), the Example N- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 60.
(6) Storage Stability Evaluation For the water-based ink prepared in Example N-7 (2), the same evaluation method as in Example N-1 (6) was used, and the same as in Example N-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 60.

<Example N-8>
(1) Production of dispersion: Dispersion N8
A phthalocyanine green pigment (CI Pigment Green 7), which is an organic pigment, was used for the production of the dispersion N8 used in Example N-8. Otherwise, dispersion containing 20% of dispersion N8 (dispersion containing a phthalocyanine green pigment with a polymer having an aromatic ring content of 30%) in the same manner as described in Example N-1 (1) above A liquid N8 was obtained.
Table 58 shows the pigment used in the dispersion N8, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic ring in the polymer and the pigment: polymer ratio are the same as in Example N-1 (1), as described in the above-mentioned “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example N-8, the dispersion N8 obtained in Example N-8 (1), Olfine E1010 (made by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant, is used. And Surfynol 104 (produced by Air Products Co., Ltd.), dipropylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparation of the water-based ink, the dispersion N8 was added so that the content of the dispersion N8 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element N8 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example N-8 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example N-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion N8 <110> 8.0%
Olfine E1010 0.3%
Surfynol 104 0.1%
Dipropylene glycol monobutyl ether 1.0%
1,2-pentanediol 3.0%
Triethylene glycol 2.0%
Thiodiglycol 4.0%
Glycerin 13.8%
Trimethylolpropane 6.0%
Triethanolamine 0.1%
Ion exchange water

(3) Measurement of monovalent cation amount in dispersion The water-based ink prepared in Example N-8 (2) was measured by the method described in "Measurement of monovalent cation amount in dispersion". As a result, the total amount of monovalent cations was 2387 ppm. Details of the measurement results are shown in Table 60.
(4) Printing Evaluation Regarding water-based ink prepared in Example N-8 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example N-1 (4). Using the same evaluation paper as in Example N-1 (4), print evaluation was performed according to the same evaluation criteria as in Example N-1 (4). The print evaluation results are shown in Table 59.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example N-8 (4), using the same evaluation method as in Example N-1 (5), the Example N- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 60.
(6) Storage Stability Evaluation For the water-based ink prepared in Example N-8 (2), the same evaluation method as in Example N-1 (6) was used, as in Example N-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 60.

<Comparative Example N-1>
(1) Production of dispersion: Dispersion N9
In this comparative example N-1, the carbon black pigment color black FW18 (manufactured by Degussa Co., Ltd.), which is an inorganic pigment, was used as in the case of the example N-1 (1).
However, in this comparative example N-1, the ultrafiltration process implemented in the said Example N-1 (1) was not implemented.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was purged with nitrogen, and then 25 parts of styrene, 5 parts of α-methylstyrene, 15 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t -0.5 part of dodecyl mercaptan was added and heated to 60 ° C in this comparative example. Separately, 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile were placed in a dropping funnel, and this comparison was made while dropping into the reaction vessel. In the example, the dispersion polymer was polymerized in 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 40%.

40 parts of the above dispersion polymer solution, 30 parts of carbon black pigment Color Black FW18 (manufactured by Degussa), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 35 parts of methyl ethyl ketone are mixed and dispersed with a homogenizer for 30 minutes or more. Then, 350 parts of ion exchange water is added and dispersed for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, in this comparative example, without performing ultrafiltration treatment, while stirring sodium hydroxide aqueous solution as ion-exchange water and neutralizing agent After appropriately adjusting to pH 7.5 and filtering through a membrane filter having an average pore diameter of 5 μm, dispersion N9 (a dispersion in which a carbon black pigment is contained by a polymer having an aromatic ring content of 40%) is 20%. A dispersion N9 containing was obtained.
Table 58 shows the pigment used in the dispersion N9, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Preparation of water-based ink In this comparative example N-1, a water-based ink was prepared using the dispersion N9 obtained in the comparative example N-1 (1). A specific composition is shown below.
In preparation of the water-based ink, the dispersion N9 was added so that the content of the dispersion N9 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element N9 measured by the method described in "Measurement of Average Particle Size" above.
Further, in the water-based ink composition of Comparative Example N-1 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example N-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion N9 <140> 8.0%
Nonionic surfactant 1.0%
Ethylene glycol 5.0%
Glycerin 15.0%
Ion exchange water

  In the above composition, Epan 450 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of monovalent cation amount in dispersion The aqueous ink prepared in Comparative Example N-1 (2) was measured by the method described in "Measurement of monovalent cation amount in dispersion". As a result, the total amount of monovalent cations was 3678 ppm. Details of the measurement results are shown in Table 60.
(4) Printing Evaluation Regarding water-based ink prepared in Comparative Example N-1 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example N-1 (4). Using the same evaluation paper as in Example N-1 (4), print evaluation was performed according to the same evaluation criteria as in Example N-1 (4). The print evaluation results are shown in Table 59.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Comparative Example N-1 (4), the same evaluation method as in Example N-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 60.
(6) Storage Stability Evaluation For the water-based ink prepared in Comparative Example N-1 (2), the same evaluation method as in Example N-1 (6) was used, as in Example N-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 60.

<Comparative Example N-2>
(1) Production of dispersion: Dispersion N10
In the production of the dispersion N10 used in this comparative example N-2, an organic pigment phthalocyanine green pigment (CI Pigment Green 7) was dispersed using a dispersion resin Solsperse 27000 (manufactured by Avicia Co., Ltd.). did.
Disperse 15 parts of phthalocyanine green pigment, 5 parts of Solsperse 27000, 5 parts of diethanolamine, 0.5 part of 2-propanol, and 74.5 parts of ion-exchanged water with a bead mill mini-zeta (manufactured by Ajisawa Corporation) for 2 hours. A dispersion N10 containing 20% of dispersion N10 used in Comparative Example N-2 (pigment: 15%, dispersion resin: 5%) was obtained.

(2) Preparation of water-based ink In this comparative example N-2, water-based ink was prepared using the dispersion N10 obtained in the comparative example N-2 (1). The specific composition of this comparative example is shown below.
In preparing the water-based ink, the dispersion N10 was added so that the content of the dispersion N10 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element N10 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of this Comparative Example N-2 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example N-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion N10 <150> 8.0%
Nonionic surfactant 1.0%
Ethylene glycol 5.0%
Glycerin 15.0%
Ion exchange water

  In the above composition, Neugen EA160 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of monovalent cation amount in dispersion The water-based ink prepared in Comparative Example N-2 (2) was measured by the method described in "Measurement of monovalent cation amount in dispersion". As a result, the total amount of monovalent cations was 4304 ppm. Details of the measurement results are shown in Table 60.
(4) Printing Evaluation Regarding water-based ink prepared in Comparative Example N-2 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example N-1 (4). Using the same evaluation paper as in Example N-1 (4), print evaluation was performed according to the same evaluation criteria as in Example N-1 (4). The print evaluation results are shown in Table 59.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Comparative Example N-2 (4), the same evaluation method as in Example N-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 60.
(6) Storage Stability Evaluation For the water-based ink prepared in Comparative Example N-2 (2), the same evaluation method as in Example N-1 (6) was used, as in Example N-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 60.

As is apparent from the results of Tables 58 and 59, the water-based ink used in the comparative example has poor print quality, and it can be seen that the print quality is good when the water-based ink according to the present invention is used.
As described above, by using the water-based ink of the present invention, it is possible to obtain a high-quality print record in which bleeding is reduced for any paper type.

As is apparent from the results in Table 60, the water-based ink according to the present invention in which the amount of monovalent cation contained in the dispersion is suppressed to 2500 ppm or less ensures excellent ejection stability and storage stability. It can be seen that the print quality is also superior. It can also be seen that when the amount of monovalent cation is 1500 ppm or less, the discharge stability and storage stability are significantly improved. On the other hand, it can be seen that when the amount of monovalent cation exceeds 3500 ppm as in the comparative example, the print quality, ejection stability, and storage stability are not at practical levels.
As can be seen from the above results, it can be seen that by using the water-based ink according to the present invention, good printing quality and ejection stability can be obtained, and the storage stability is also excellent.

[Example P]
EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these do not limit the scope of the present invention.
(Measurement method of aromatic ring amount, pigment: polymer ratio, average particle size, monovalent anion amount in dispersion, and surface tension)
Each measured value (amount of aromatic ring, pigment: polymer ratio, average particle size, amount of monovalent anion in dispersion, surface tension) obtained in this example was measured by the following method.

"Measurement of aromatic ring quantity"
A part of the dispersion polymer solution obtained in each example or comparative example was taken out, the solvent component was distilled off, and only the polymer component was taken out, dissolved in DMSO-d ₆ , ¹³ C-NMR and ¹ H-NMR ( The amount of aromatic rings in the polymer was measured using Bruker (Germany AMX400).
“Measurement of pigment: polymer ratio”
A part of the dispersion obtained in each Example or Comparative Example was taken out, 0.1 mol / l concentration HCl was added, and only the dispersion was acidified, and the dry weight was measured. Next, the pigment: polymer weight ratio was calculated by taking out only the dispersed polymer by Soxhlet extraction using acetone and measuring the dry weight.
"Measurement of average particle size"
Dilute with ion-exchanged water so that the dispersion concentration of the water-based ink obtained in each Example or Comparative Example is 0.001 to 0.01% by weight (because the optimum concentration at the time of measurement is slightly different depending on the water-based ink). The average particle size of the dispersed particles at 20 ° C. was measured with a particle size distribution meter (DLS-800 manufactured by Otsuka Electronics Co., Ltd.).

"Measurement of monovalent anion amount in dispersion"
A required amount of the water-based ink obtained in each example or comparative example was taken out and separated into a dispersion that is a solid component and a solvent component of the water-based ink by centrifugal separation. The centrifugation condition was 2500 G × 60 minutes.
The obtained dispersion is taken in a quartz dish, added with a scavenger, incinerated, melted with potassium hydrogen sulfate, dissolved in dilute nitric acid, and ICP emission analysis (ICPS-8000, manufactured by Shimadzu Corporation). Was used to measure the amount of monovalent anions in the dispersion.
"Measurement of surface tension"
The surface tension at 20 ° C. of the water-based ink obtained in each example or comparative example was measured with a surface tension meter (CBVP-A3 manufactured by Kyowa Interface Science Co., Ltd.).

<Example P-1>
(1) Production of dispersion: Dispersion P1
For the production of the dispersion P1 used in Example P-1, carbon black pigment color black FW18 (Degussa) was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 15 parts of methyl ethyl ketone, 22 parts of styrene, 5 parts of α-methyl styrene, 16 parts of butyl methacrylate, 10 parts of lauryl methacrylate, acrylic acid 2 parts, 0.3 part of t-dodecyl mercaptan is added and heated to 70 ° C., and separately prepared 100 parts of styrene, 16 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and azobis 3 parts of isobutyronitrile was placed in a dropping funnel and the dispersion polymer was subjected to a polymerization reaction while dropping into a reaction vessel over 4 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 56%.

40 parts of the above dispersion polymer solution, 30 parts of carbon black pigment Color Black FW18 (manufactured by Degussa), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 35 parts of methyl ethyl ketone are mixed and dispersed with a homogenizer for 30 minutes or more. Then, 350 parts of ion exchange water is added and dispersed for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion P1 (carbon black A dispersion P1 containing 20% of a dispersion in which the pigment is covered with a polymer having an aromatic ring content of 56% was obtained.
Table 61 shows the pigment used in dispersion P1, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Preparation of water-based ink In Example P-1, the dispersion P1 obtained in Example P-1 (1), Olphine E1010 (made by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant, is used. Diethylene glycol monobutyl ether which is alkylene glycol monoalkyl ether and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion P1 was added so that the content of the dispersion P1 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element P1 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the ion exchange water added as “remaining amount” in the aqueous ink composition of Example P-1 below, Proxel XL-2 and aqueous inkjet head member are prevented from corroding to prevent corrosion of the aqueous ink. In order to reduce the influence of benzotriazole and metal ions in the aqueous ink system, the EDTA · 2Na salt should be 0.01%, 0.01%, and 0.02%, respectively, based on the total weight of the aqueous ink. What was added was used.

Dispersion P1 <120> 8.0%
Olfine E1010 0.5%
Diethylene glycol monobutyl ether 3.0%
1,2-pentanediol 2.5%
Diethylene glycol 3.0%
Glycerin 11.5%
Trimethylolpropane 6.0%
Tripropanolamine 0.3%
Ion exchange water

(3) Measurement of monovalent anion amount in dispersion The aqueous ink prepared in Example P-1 (2) was measured by the method described in "Measurement of monovalent anion amount in dispersion". As a result, the total amount of monovalent anions was 2570 ppm. Details of the measurement results are shown in Table 63.

(4) Printing Evaluation For printing evaluation, an aqueous ink jet printer PM-950C (manufactured by Seiko Epson Corporation) that discharges aqueous ink by an aqueous ink jet head using a piezoelectric element (piezo element) was used. Printing evaluation of the water-based ink prepared in 1 (2) was performed.
As evaluation papers, (a) Conqueror paper, (b) Reymat paper, (c) Mode Copy paper, (d) Rapid Copy paper, (e) Xerox P paper , (F) Xerox 4024 paper, (g) Xerox 10 paper, (h) Neenha Bond paper, (i) Riccopy 6200 paper, and (j) Hammer mill Copy Plus paper.
In addition, evaluation was performed visually and was performed based on the following evaluation criteria.

A: The blur is not recognized in the characters at all points.
B: Slight bleeding is observed with characters of 5 points or less (practical level).
C: Characters of 5 points or less appear thick due to blurring.
D: Significant blurring and characters of 5 points or less cannot be identified.

  Table 62 shows the results of the print evaluation.

(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example P-1 (4), 200 pages are continuously printed on A4 size Xerox P paper, and the printing disorder is observed. In addition, discharge stability was evaluated in addition. Evaluation was performed visually and based on the following evaluation criteria.
A: Printing disorder does not occur at all.
B: Printing disorder was observed, but the number was less than 10 (practical level).
C: There is printing disorder in the range of 10 or more and less than 100.
D: Disturbance of printing occurred at 100 locations or more.
Table 63 shows the results of the discharge stability evaluation.

(6) Storage stability evaluation The water-based ink prepared in Example P-1 (2) was placed in a glass bottle and sealed, then left at 60 ° C./1 week and −20 ° C./1 week, respectively. The generated foreign matter and physical property value fluctuation (viscosity, surface tension) were evaluated.
The evaluation was performed based on the following evaluation criteria.
A: The ratio of the amount of foreign matter / physical properties after standing at 60 ° C. or −20 ° C. to that before standing is in the range of 0.99 to 1.01.
B: The ratio is in the range of 0.95 to 0.99, or 1.01 to 1.05 (practical level).
C: The ratio is in the range of 0.90 to 0.95, or 1.05 to 1.10.
D: Ratio is less than 0.90 or greater than 1.10.
Table 63 shows the storage stability evaluation results.

<Example P-2>
(1) Production of dispersion: Dispersion P2
In the production of the dispersion P2 used in Example P-2, an insoluble monoazo yellow pigment (CI Pigment Yellow 74), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 12 parts of styrene, 9 parts of lauryl methacrylate, and 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 3 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 part of mercaptoethanol, heated to 70 ° C., 25 parts of styrene prepared separately, lauryl 30 parts of methacrylate, 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), 15 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toagosei Co., Ltd.), 10 parts of methacrylic acid, 20 parts of methyl ethyl ketone Dropwise to the reaction vessel over 4 hours putting 1.0 parts of mercaptoethanol to the dropping funnel and the dispersed polymer is the polymerization reaction. Next, methyl ethyl ketone was appropriately added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 26%.

40 parts of the above dispersion polymer solution, 30 parts of an insoluble monoazo yellow pigment (CI Pigment Yellow 74) as an organic pigment, 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed, and 30 parts are mixed with a homogenizer. Disperse for at least minutes, add 380 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion P2 (insoluble monoazo). A dispersion P2 containing 20% of a dispersion in which a yellow pigment was included by a polymer having an aromatic ring content of 26% was obtained.
Table 61 shows the pigment used in dispersion P2, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example P-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example P-2, the dispersion P2 obtained in Example P-2 (1), Surfynol 440 (produced by Air Products), which is an acetylene glycol surfactant, and Orphine STG (manufactured by Nissin Chemical Industry Co., Ltd.), triethylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion P2 was added so that the content of the dispersion P2 was 7.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element P2 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example P-2 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example P-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion P2 <120> 7.0%
Surfinol 440 0.2%
Olphine STG 0.2%
Triethylene glycol monobutyl ether 3.0%
1,2-pentanediol 2.0%
2-pyrrolidone 3.0%
Glycerin 13.5%
Trimethylolethane 5.0%
Triethanolamine 0.1%
Ion exchange water

(3) Measurement of amount of monovalent anion in dispersion The aqueous ink prepared in Example P-2 (2) was measured by the method described in "Measurement of amount of monovalent anion in dispersion". As a result, the total amount of monovalent anions was 1179 ppm. Details of the measurement results are shown in Table 63.
(4) Printing Evaluation Regarding water-based ink prepared in Example P-2 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example P-1 (4). Using the same evaluation paper as in Example P-1 (4), print evaluation was performed according to the same evaluation criteria as in Example P-1 (4). The print evaluation results are shown in Table 62.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example P-2 (4), using the same evaluation method as in Example P-1 (5), the Example P- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 63.
(6) Storage Stability Evaluation For the water-based ink prepared in Example P-2 (2), the same evaluation method as in Example P-1 (6) was used, as in Example P-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 63.

<Example P-3>
(1) Production of dispersion: Dispersion 3
For the production of the dispersion P3 used in Example P-3, quinacridone red pigment (CI Pigment Red 122), which is an organic pigment, was used.
First, the reaction vessel equipped with a stirrer, thermometer, reflux tube and dropping funnel was replaced with nitrogen, and then 10 parts of styrene, 5 parts of styrene macromer (AS-6; manufactured by Toagosei Co., Ltd.), n-dodecyl methacrylate 3.5 70 parts by adding 10 parts of N, N-dimethylaminoethyl methacrylate, 25 parts of methoxypolyethylene glycol methacrylate (NK ester M40G; manufactured by Shin-Nakamura Chemical Co., Ltd.), 5 parts of methyl ethyl ketone, and 0.3 part of azobisisobutyronitrile. 15 parts of styrene prepared separately, 10 parts of styrene macromer (AS-6; manufactured by Toagosei Co., Ltd.), 5 parts of n-dodecyl methacrylate, 20 parts of N, N-dimethylaminoethyl methacrylate, methoxypolyethylene glycol methacrylate (NK ester M40G; Shin-Nakamura Chemical Co., Ltd. Company Ltd.) 30 parts Methyl ethyl ketone 50 parts, the dispersion polymer dropwise into the reaction vessel over 4 hours and placed in a dropping funnel and 1.5 parts of azobisisobutyronitrile was polymerized reaction. Next, methyl ethyl ketone was appropriately added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 38%.

40 parts of the above dispersion polymer solution, 25 parts of an organic pigment, quinacridone red pigment (CI Pigment Red 122), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 40 parts of methyl ethyl ketone are mixed, and 30 minutes with a homogenizer. Dispersion treatment is performed as described above, and 380 parts of ion exchange water is added and further dispersed for 1 hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added with stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion P3 (quinacridone red A dispersion P3 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 38% was obtained.
Table 61 shows the pigment used in the dispersion P3, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example P-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example P-3, the dispersion P3 obtained in Example P-3 (1), Olfine E1010 (manufactured by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant. And Surfynol 104PG50 (produced by Air Products), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-hexanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In preparing the water-based ink, the dispersion P3 was added so that the content of the dispersion P3 was 7.5%. The value in <> shows the average particle size (unit: nm) of Dispersing Element P3 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example P-3 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example P-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion P3 <140> 7.5%
Olfin E1010 0.1%
Surfynol 104PG50 0.4%
Triethylene glycol monobutyl ether 1.0%
1,2-hexanediol 2.5%
Triethylene glycol 2.0%
2-pyrrolidone 4.0%
Glycerin 13.8%
Trimethylolpropane 6.0%
Ion exchange water

(3) Measurement of monovalent anion amount in dispersion The water-based ink prepared in Example P-3 (2) was measured by the method described in "Measurement of monovalent anion amount in dispersion". As a result, the total amount of monovalent anions was 1008 ppm. Details of the measurement results are shown in Table 63.
(4) Printing Evaluation Regarding water-based ink prepared in Example P-3 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example P-1 (4). Using the same evaluation paper as in Example P-1 (4), print evaluation was performed according to the same evaluation criteria as in Example P-1 (4). The print evaluation results are shown in Table 62.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example P-3 (4), using the same evaluation method as in Example P-1 (5), the Example P- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 63.
(6) Storage Stability Evaluation For the water-based ink prepared in Example P-3 (2), the same evaluation method as in Example P-1 (6) was used, and the same as in Example P-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 63.

<Example P-4>
(1) Production of dispersion: Dispersion P4
In the production of the dispersion P4 used in Example P-4, a phthalocyanine blue pigment (CI Pigment Blue 15: 4), which is an organic pigment, was used.
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was replaced with nitrogen, and then 20 parts of styrene, 10 parts of lauryl methacrylate, 15 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.) , 5 parts of isobutyl methacrylate macromer (AW-6S; manufactured by Toa Gosei Co., Ltd.), 10 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 5 parts of methyl ethyl ketone, 0.3 n-dodecyl mercaptan And heated to 70 ° C., separately prepared 25 parts of styrene, 30 parts of lauryl methacrylate, 20 parts of methoxypolyethylene glycol methacrylate (NK ester M90G; manufactured by Shin-Nakamura Chemical Co., Ltd.), isobutyl methacrylate macromer (AW-6S; Toa) Composition 15 parts, 15 parts of styrene macromer (AS-6; manufactured by Toa Gosei Co., Ltd.), 5 parts of methacrylic acid, 20 parts of methyl ethyl ketone, 1.5 parts of n-dodecyl mercaptan in a dropping funnel over 4 hours The dispersion polymer was polymerized while being dropped into the reaction vessel. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in “Measurement of the amount of aromatic rings” described above. The amount was 45%.

40 parts of the above dispersion polymer solution, 40 parts of an organic pigment phthalocyanine blue pigment (CI Pigment Blue 15: 4), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution, and 40 parts of methyl ethyl ketone are mixed together. Disperse for 30 minutes or more, add 350 parts of ion exchange water, and disperse for another hour. And after distilling off the whole amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration with a fractional molecular weight of 100,000 was carried out with millitan (manufactured by Millipore) of an ultrafiltration system while adding water appropriately. . Finally, ion-exchanged water and a sodium hydroxide aqueous solution as a neutralizing agent are appropriately added while stirring to adjust the pH to 7.5, and then filtered through a membrane filter having an average pore size of 5 μm to obtain dispersion P4 (phthalocyanine blue A dispersion P4 containing 20% of a dispersion in which the pigment is contained by a polymer having an aromatic ring content of 45% was obtained.
Table 61 shows the pigment used in the dispersion P4, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example P-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of aqueous ink In Example P-4, the dispersion P4 obtained in Example P-4 (1), acetylenol E100 (produced by Kawaken Fine Chemical Co., Ltd.), which is an acetylene glycol surfactant, Propylene glycol monobutyl ether, which is an alkylene glycol monoalkyl ether, and 1,2-hexanediol, which is 1,2-alkylene glycol, were used. A specific composition is shown below.
In the preparation of the water-based ink, the dispersion P4 was added so that the content of the dispersion P4 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element P4 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example P-4 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example P-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion P4 <100> 8.0%
Acetylenol E100 0.5%
Propylene glycol monobutyl ether 3.0%
1,2-hexanediol 1.0%
Triethylene glycol 3.0%
Glycerin 13.8%
Trimethylolpropane 5.2%
Tripropanolamine 0.2%
Ion exchange water

(3) Measurement of amount of monovalent anion in dispersion The aqueous ink prepared in Example P-4 (2) was measured by the method described in "Measurement of amount of monovalent anion in dispersion". As a result, the total amount of monovalent anions was 1982 ppm. Details of the measurement results are shown in Table 63.
(4) Printing Evaluation Regarding water-based ink prepared in Example P-4 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example P-1 (4). Using the same evaluation paper as in Example P-1 (4), print evaluation was performed according to the same evaluation criteria as in Example P-1 (4). The print evaluation results are shown in Table 62.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example P-4 (4), using the same evaluation method as in Example P-1 (5), the Example P- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 63.
(6) Storage Stability Evaluation For the water-based ink prepared in Example P-4 (2), the same evaluation method as in Example P-1 (6) was used, and the same as in Example P-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 63.

<Example P-5>
(1) Production of dispersion: Dispersion P5
A perinone orange pigment (CI Pigment Orange 43) was used in the production of the dispersion P5 used in Example P-5. Otherwise, by the same method as described in Example P-1 (1) above, 20% of dispersion P5 (a dispersion containing a perinone orange pigment with a polymer having an aromatic ring content of 56%) is contained. Dispersion P5 was obtained.
Table 61 shows the pigment used in the dispersion P5, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example P-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example P-5, the dispersion P5 obtained in Example P-5 (1), Surfynol 485 and Surfynol TG, which are acetylene glycol surfactants (both are air) Products), dipropylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol. A specific composition is shown below. In preparing the water-based ink, the dispersion P5 was added so that the content of the dispersion P5 was 10.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element P5 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example P-5 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example P-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion P5 <150> 10.0%
Surfynol 485 0.5%
Surfinol TG 0.2%
Dipropylene glycol monobutyl ether 2.0%
1,2-pentanediol 2.0%
N-methyl-2-pyrrolidone 5.0%
Glycerin 11.2%
Trehalose 5.8%
Ion exchange water

(3) Measurement of monovalent anion amount in dispersion The aqueous ink prepared in Example P-5 (2) was measured by the method described in "Measurement of monovalent anion amount in dispersion". As a result, the total amount of monovalent anions was 2406 ppm. Details of the measurement results are shown in Table 63.
(4) Printing Evaluation Regarding water-based ink prepared in Example P-5 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example P-1 (4). Using the same evaluation paper as in Example P-1 (4), print evaluation was performed according to the same evaluation criteria as in Example P-1 (4). The print evaluation results are shown in Table 62.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example P-5 (4), using the same evaluation method as in Example P-1 (5), the Example P- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 63.
(6) Storage Stability Evaluation For the water-based ink prepared in Example P-5 (2), the same evaluation method as in Example P-1 (6) was used, and the same as in Example P-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 63.

<Example P-6>
(1) Production of dispersion: Dispersion P6
A perylene brown pigment (CI Pigment Brown 26) was used for the production of the dispersion P6 used in Example P-6. Otherwise, a dispersion containing 20% of dispersion P6 (a dispersion in which a perylene brown pigment is contained by a polymer having an aromatic ring content of 67%) is performed in the same manner as described in Example P-1 (1). A liquid P6 was obtained.
Table 61 shows the pigment used in dispersion P6, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example P-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example P-6, the dispersion P6 obtained in Example P-6 (1), Surfynol 420 which is an acetylene glycol surfactant, and alkylene glycol monoalkyl ether are used. Some diethylene glycol monobutyl ether was used. A specific composition is shown below.
In preparing the water-based ink, the dispersion P6 was added so that the content of the dispersion P6 was 5.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element P6 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the following Example P-6, ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example P-1 (2). XL-2 0.01%, benzotriazole 0.01%, and EDTA · 2Na salt 0
. What was added so that it might become 02% was used.

Dispersion P6 <140> 5.0%
Surfynol 420 0.1%
Diethylene glycol monobutyl ether 3.0%
1,6-hexanediol 2.0%
Tetraethylene glycol 5.5%
Glycerin 13.5%
Triethanolamine 0.5%
Ion exchange water

(3) Measurement of amount of monovalent anion in dispersion The water-based ink prepared in Example P-6 (2) was measured by the method described in "Measurement of amount of monovalent anion in dispersion". As a result, the total amount of monovalent anions was 2563 ppm. Details of the measurement results are shown in Table 63.
(4) Printing Evaluation Regarding water-based ink prepared in Example P-6 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example P-1 (4). Using the same evaluation paper as in Example P-1 (4), print evaluation was performed according to the same evaluation criteria as in Example P-1 (4). The print evaluation results are shown in Table 62.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example P-6 (4), using the same evaluation method as in Example P-1 (5), the Example P- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 63.
(6) Storage Stability Evaluation For the water-based ink prepared in Example P-6 (2), the same evaluation method as in Example P-1 (6) was used, and the same as in Example P-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 63.

<Example P-7>
(1) Production of dispersion: Dispersion P7
In the production of the dispersion P7 used in Example P-7, quinacridone violet pigment (CI Pigment Bio Red 19) was used as an organic pigment. Otherwise, by the same method as described in Example P-1 (1) above, a dispersion containing 20% of dispersion P7 (a dispersion containing quinacridone violet pigment with a polymer having an aromatic ring content of 21%) A liquid P7 was obtained.
Table 61 shows the pigment used in dispersion P7, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example P-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example P-7, the dispersion P7 obtained in Example P-7 (1), Surfynol 61 and Surfynol TG which are acetylene alcohol surfactants (both are air) Products), triethylene glycol monobutyl ether which is an alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2 alkylene glycol. A specific composition is shown below.
In preparing the water-based ink, the dispersion P7 was added so that the content of the dispersion P7 was 6.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element P7 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example P-7 below, the ion-exchanged water added as “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example P-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion P7 <120> 6.0%
Surfynol 61 0.3%
Surfynol TG 0.1%
Triethylene glycol monobutyl ether 1.5%
1,2-pentanediol 2.0%
Diethylene glycol 2.0%
Thiodiglycol 4.0%
Glycerin 12.6%
Trimethylolethane 7.0%
Ion exchange water

(3) Measurement of amount of monovalent anion in dispersion The aqueous ink prepared in Example P-7 (2) was measured by the method described in "Measurement of amount of monovalent anion in dispersion". As a result, the total amount of monovalent anions was 2927 ppm. Details of the measurement results are shown in Table 63.
(4) Printing Evaluation Regarding water-based ink prepared in Example P-7 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example P-1 (4). Using the same evaluation paper as in Example P-1 (4), print evaluation was performed according to the same evaluation criteria as in Example P-1 (4). The print evaluation results are shown in Table 62.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example P-7 (4), using the same evaluation method as in Example P-1 (5), the Example P- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 63.
(6) Storage Stability Evaluation For the water-based ink prepared in Example P-7 (2), the same evaluation method as in Example P-1 (6) was used, and the same as in Example P-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 63.

<Example P-8>
(1) Production of dispersion: Dispersion P8
For the production of the dispersion P8 used in Example P-8, a violanthrone green pigment (CI Pigment Green 47), which is an organic pigment, was used. Otherwise, by the same method as described in Example P-1 (1) above, 20% of dispersion P8 (dispersion containing violanthrone green pigment by a polymer having an aromatic ring content of 30%) is contained. A dispersion P8 was obtained.
Table 61 shows the pigment used in dispersion P8, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The amount of aromatic rings in the polymer and the pigment: polymer ratio are the same as in Example P-1 (1), as described in “Measurement of aromatic ring amount” and “Measurement of pigment: polymer ratio”. Measured by the method.

(2) Preparation of water-based ink In Example P-8, the dispersion P8 obtained in Example P-8 (1), Olfine E1010 (made by Nissin Chemical Industry Co., Ltd.), which is an acetylene glycol surfactant, is used. And Surfynol 104 (produced by Air Products Co., Ltd.), dipropylene glycol monobutyl ether which is alkylene glycol monoalkyl ether, and 1,2-pentanediol which is 1,2-alkylene glycol were used. A specific composition is shown below.
In the preparation of the water-based ink, the dispersion P8 was added so that the content of the dispersion P8 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element P8 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of Example P-8 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink, as in Example P-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion P8 <110> 8.0%
Olfine E1010 0.3%
Surfynol 104 0.1%
Dipropylene glycol monobutyl ether 1.0%
1,2-pentanediol 3.0%
Triethylene glycol 2.0%
Thiodiglycol 4.0%
Glycerin 13.8%
Trimethylolpropane 6.0%
Triethanolamine 0.1%
Ion exchange water

(3) Measurement of monovalent anion amount in dispersion The water-based ink prepared in Example P-8 (2) was measured by the method described in "Measurement of monovalent anion amount in dispersion". As a result, the total amount of monovalent anions was 3429 ppm. Details of the measurement results are shown in Table 63.
(4) Printing Evaluation Regarding water-based ink prepared in Example P-8 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) in the same manner as in Example P-1 (4). Using the same evaluation paper as in Example P-1 (4), print evaluation was performed according to the same evaluation criteria as in Example P-1 (4). The print evaluation results are shown in Table 62.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Example P-8 (4), using the same evaluation method as in Example P-1 (5), the Example P- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 63.
(6) Storage Stability Evaluation For the water-based ink prepared in Example P-8 (2), the same evaluation method as in Example P-1 (6) was used, and the same as in Example P-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 63.

<Comparative Example P-1>
(1) Production of dispersion: Dispersion P9
In this comparative example P-1, a carbon black pigment color black FW18 (manufactured by Degussa Co., Ltd.), which is an inorganic pigment, was used as in the case of the example P-1 (1).
In Comparative Example P-1, the dispersion polymer was intentionally polymerized under polymerization conditions different from those of Example P-1 (1).
First, a reaction vessel equipped with a stirrer, a thermometer, a reflux tube and a dropping funnel was purged with nitrogen, and then 25 parts of styrene, 5 parts of α-methylstyrene, 15 parts of butyl methacrylate, 10 parts of lauryl methacrylate, 2 parts of acrylic acid, t -0.5 part of dodecyl mercaptan was added and heated to 65 ° C in this comparative example. Separately, 150 parts of styrene, 15 parts of acrylic acid, 50 parts of butyl methacrylate, 1 part of t-dodecyl mercaptan, 20 parts of methyl ethyl ketone and 3 parts of azobisisobutyronitrile were placed in a dropping funnel, and this comparison was made while dropping into the reaction vessel. In the example, the dispersion polymer was polymerized in 2 hours. Next, methyl ethyl ketone was added to the reaction vessel to prepare a dispersion polymer solution having a concentration of 40%.
A part of this dispersion polymer solution was taken out, the solvent component was distilled off, and the ratio of the aromatic ring to the total weight was measured by the method described in the above-mentioned “Measurement of the amount of aromatic ring”. The amount was 20%.

40 parts of the above dispersion polymer solution, 30 parts of carbon black pigment Color Black FW18 (manufactured by Degussa), 100 parts of a 0.1 mol / L sodium hydroxide aqueous solution and 35 parts of methyl ethyl ketone are mixed and dispersed with a homogenizer for 30 minutes or more. Then, 350 parts of ion exchange water is added and dispersed for another hour. And after distilling off the total amount of methyl ethyl ketone and a part of water using a rotary evaporator, ultrafiltration is not carried out in this comparative example, and ion hydroxide water and sodium hydroxide aqueous solution as a neutralizing agent are appropriately stirred. In addition, the pH is adjusted to 7.5, and then filtered through a membrane filter having an average pore diameter of 5 μm, thereby containing 20% of dispersion P9 (a dispersion in which a carbon black pigment is contained by a polymer having an aromatic ring content of 20%). A dispersion P9 was obtained.
Table 61 shows the pigment used in dispersion P9, the amount of aromatic rings in the dispersion polymer, and the pigment: polymer ratio. The pigment: polymer ratio was measured by the method described in “Measurement of pigment: polymer ratio” above.

(2) Adjustment of water-based ink In this comparative example P-1, the water-based ink was adjusted using the dispersion liquid P9 obtained by the said comparative example P-1 (1). A specific composition is shown below.
In the preparation of the water-based ink, the dispersion P9 was added so that the content of the dispersion P9 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element P9 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the present comparative example P-1 below, the ion-exchanged water added as the “remaining amount” is similar to the above-mentioned Example P-1 (2), with the proxel relative to the total weight of the water-based ink. What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion P9 <140> 8.0%
Nonionic surfactant 1.0%
Ethylene glycol 5.0%
Glycerin 15.0%
Monovalent anion-containing water

  In the above composition, Epan 450 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of the amount of monovalent anions in the dispersion The water-based ink prepared in Comparative Example P-1 (2) was measured by the method described in "Measurement of the amount of monovalent anions in the dispersion". As a result, the total amount of monovalent anions was 5059 ppm. Details of the measurement results are shown in Table 63.
(4) Evaluation of printing Regarding water-based ink prepared in Comparative Example P-1 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example P-1 (4). Using the same evaluation paper as in Example P-1 (4), print evaluation was performed according to the same evaluation criteria as in Example P-1 (4). The print evaluation results are shown in Table 62.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Comparative Example P-1 (4), with the same evaluation method as in Example P-1 (5), the Example P- The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 63.
(6) Storage stability evaluation About the water-based ink adjusted by the said comparative example P-1 (2), it is the same evaluation method as the said Example P-1 (6), and is the same as the said Example P-1 (6) The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 63.

<Comparative Example P-2>
(1) Production of dispersion: Dispersion P10
For the production of the dispersion P10 used in this comparative example P-2, Violanthrone Green pigment (CI Pigment Green 47), which is an organic pigment, was dispersed using Solsperse 12000 (Avisia Corporation). .
Disperse 15 parts of violanthrone green pigment, 5 parts of Solsperse 12000, 5 parts of diethanolamine, 0.5 part of 2-propanol, and 74.5 parts of ion-exchanged water with a bead mill minizeta (manufactured by Ajisawa Corporation) for 2 hours. Treatment was performed to obtain a dispersion P10 containing 20% of dispersion P9 (pigment: 15%, dispersion resin: 5%) used in Comparative Example P-2.

(2) Adjustment of water-based ink In this comparative example P-2, the water-based ink was adjusted using the dispersion liquid P10 obtained by the said comparative example P-2 (1). The specific composition of this comparative example is shown below.
In the preparation of the water-based ink, the dispersion P10 was added so that the content of the dispersion P9 was 8.0%. The value in <> shows the average particle size (unit: nm) of Dispersing Element P9 measured by the method described in "Measurement of Average Particle Size" above.
In addition, in the water-based ink composition of the present comparative example P-2 below, the ion-exchanged water added as the “remaining amount” is proxel with respect to the total weight of the water-based ink as in the case of the example P-1 (2). What added XL-2 to 0.01%, benzotriazole 0.01%, and EDTA.2Na salt to 0.02% was used.

Dispersion P10 <150> 20.0%
Nonionic surfactant 1.0%
Ethylene glycol 5.0%
Glycerin 15.0%
Ion exchange water

  In the above composition, Neugen EA160 (trade name; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was used as a nonionic surfactant.

(3) Measurement of amount of monovalent anion in dispersion The water-based ink prepared in Comparative Example P-2 (2) was measured by the method described in "Measurement of amount of monovalent anion in dispersion". As a result, the total amount of monovalent anions was 5393 ppm. Details of the measurement results are shown in Table 63.
(4) Printing Evaluation Regarding water-based ink prepared in Comparative Example P-2 (2) using a water-based inkjet printer PM-950C (manufactured by Seiko Epson Corporation) as in Example P-1 (4). Using the same evaluation paper as in Example P-1 (4), print evaluation was performed according to the same evaluation criteria as in Example P-1 (4). The print evaluation results are shown in Table 62.
(5) Evaluation of ejection stability Using the same printer and water-based ink as in Comparative Example P-2 (4), the same evaluation method as in Example P-1 (5) was used. The ejection stability was evaluated according to the same evaluation criteria as 1 (5). The results of the discharge stability evaluation are shown in Table 63.
(6) Storage Stability Evaluation For the water-based ink prepared in Comparative Example P-2 (2), the same evaluation method as in Example P-1 (6) was used, as in Example P-1 (6). The storage stability was evaluated according to the evaluation criteria. The results of the storage stability evaluation are shown in Table 63.

As is clear from the results in Tables 61 and 62, the water-based ink cartridge used in the comparative example has poor print quality, and it can be seen that the print quality is good when the water-based ink cartridge according to the present invention is used.
As described above, by using the water-based ink cartridge of the present invention, it is possible to obtain a high-quality print record in which bleeding is reduced for any paper type.

As is apparent from the results in Table 63, the water-based ink according to the present invention in which the amount of monovalent anions contained in the dispersion is suppressed to 3500 ppm or less ensures excellent ejection stability and storage stability. It can be seen that the print quality is also excellent. It can also be seen that when the amount of monovalent anion is 2500 ppm or less, the ejection stability and storage stability are significantly improved. On the other hand, it can be seen that when the amount of monovalent anion exceeds 5000 ppm as in the comparative example, the print quality, ejection stability, and storage stability are not at practical levels.
As can be seen from the above results, it can be seen that by using the water-based ink according to the present invention, good printing quality and ejection stability can be obtained, and the storage stability is also excellent.

Claims (66)

A water-based ink comprising a dispersion in which a colorant is included in a polymer and is dispersible in water, wherein the amount of aromatic rings in the polymer is 20% by weight or more and 70% by weight or less of the polymer Aqueous ink. The water-based ink according to claim 1, wherein a weight ratio of the colorant to the polymer is in a range of 10:90 to 90:10. The weight ratio of the colorant to the polymer is 40:60 to 90:10 for a black colorant, 50:50 to 90:10 for a yellow colorant, and 50:50 for a red colorant. 2. The water-based ink according to claim 1, wherein the water-based ink is in a range of 50 to 90:10 and 20 to 80 to 30:30 in the case of a blue colorant. 2. The aqueous ink according to claim 1, further comprising polymer fine particles, wherein an absolute value of a zeta potential in a mixed state of the dispersion and the polymer fine particles is 30 millivolts or more. The absolute value of the zeta potential of the dispersion and the polymer fine particle is independently 30 millivolts or more, and the difference between the value of the zeta potential of the dispersion and the value of the zeta potential of the polymer fine particle is ± 10 millivolts The water-based ink according to claim 4, wherein: The water-based ink according to claim 4 or 5, wherein ions of the polymer fine particles have the same polarity as that of the dispersion. The aqueous ink according to claim 1, wherein the total amount of polyvalent metal ions contained in the liquid component of the aqueous ink is 200 ppm or less. 2. The aqueous ink according to claim 1, wherein each of the amounts of ions of Si, Ca, Mg, Fe, Cr, Ni, and Zr contained in the liquid component of the aqueous ink is 50 ppm or less. The aqueous ink according to claim 1, wherein the total amount of polyvalent anions contained in the liquid component of the aqueous ink is 1000 ppm or less. The aqueous ink according to claim 9, wherein the polyvalent anion is a sulfate ion, a phosphate ion, or a low molecular weight polycarboxylate ion. The aqueous ink according to claim 1, wherein the total amount of monovalent cations contained in the liquid component of the aqueous ink is 5000 ppm or less. The water-based ink according to claim 1, wherein the monovalent cation is an alkali metal ion. 13. The aqueous ink according to claim 12, wherein the alkali metal ion is any one of lithium ion, sodium ion, and potassium ion. The aqueous ink according to claim 11, wherein the monovalent cation is an ammonium ion. The aqueous ink according to claim 1, wherein the total amount of monovalent anions contained in the liquid component of the aqueous ink is 3000 ppm or less. The aqueous ink according to claim 15, wherein the monovalent anion is a halogen ion. The aqueous ink according to claim 16, wherein the halogen ion is any one of a chlorine ion, a bromine ion, and an iodine ion. The aqueous ink according to claim 1, wherein the amount of free polymer contained in the liquid component of the aqueous ink is 3% or less. The total amount of polyvalent metal ions contained in the liquid component of the water-based ink is 200 ppm or less, the total amount of polyvalent anions is 1000 ppm or less, and the total amount of monovalent cations is 5000 ppm or less. 2. The aqueous ink according to claim 1, wherein the total amount of valent anions is 3000 ppm or less, and the amount of free polymer is 2% or less. The polymer including the colorant in the dispersion is one selected from the group consisting of polyacrylic acid ester, styrene-acrylic acid copolymer, polystyrene, polyester, polyamide, polyimide, silicon-containing polymer, and sulfur-containing polymer, or The water-based ink according to any one of claims 1 to 19, wherein there are two or more kinds. The aqueous ink according to claim 1, further comprising a surfactant. The aqueous ink according to claim 21, wherein the surfactant is at least one selected from an acetylene glycol surfactant, an acetylene alcohol surfactant, and a silicon surfactant. The aqueous ink according to claim 1 or 21, further comprising an alkylene glycol monoalkyl ether and / or 1,2-alkylene glycol. The water-based ink according to claim 23, wherein the alkylene glycol monoalkyl ether is an alkylene glycol having 10 or less repeating units and an alkyl ether having 4 to 10 carbon atoms. The aqueous ink according to claim 24, wherein the alkylene glycol monoalkyl ether is di (tri) ethylene glycol monobutyl ether and / or (di) propylene glycol monobutyl ether. The aqueous ink according to claim 23, wherein the 1,2-alkylene glycol is 1,2-hexanediol and / or 1,2-pentanediol. A water-based ink containing a substance composed of one or more selected from di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol, wherein the added amount of the substance is 0.5 2. The water-based ink according to claim 1, wherein the water-based ink is at least 30% by weight. The addition amount of one or more substances selected from the acetylene glycol surfactants, acetylene alcohol surfactants, and silicon surfactants is 0.1 wt% or more and 5 wt% or less. 23. The nk according to claim 22. At least one selected from acetylene glycol surfactants, acetylene alcohol surfactants and silicon surfactants, di (tri) ethylene glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2- The aqueous ink according to claim 1, comprising at least one selected from alkylene glycol. The addition amount of one or more selected from the acetylene glycol surfactants, acetylene alcohol surfactants and silicon surfactants is 0.01 wt% to 0.5 wt%, and di (tri) ethylene 30. The aqueous ink according to claim 29, wherein the addition amount of one or more selected from glycol monobutyl ether, (di) propylene glycol monobutyl ether and 1,2-alkylene glycol is 1% by weight or more. The water-based ink according to any one of claims 23, 26, 27, 29 and 30, wherein the amount of the 1,2-alkylene glycol added is 10% by weight or less. The addition amount of one or more selected from the acetylene glycol surfactant, acetylene alcohol surfactant and silicon surfactant is 0.5% by weight or more, and the addition amount with the 1,2-alkylene glycol 30. The water-based ink according to claim 29, wherein the ratio (hereinafter simply referred to as a ratio indicates the weight ratio of the added amount) is 1: 0 to 1:50. 31. The water-based ink according to claim 25, 27, 29 or 30, comprising 10% by weight or less of (di) propylene glycol monobutyl ether. The addition amount of one or more selected from the acetylene alcohol surfactants, acetylene glycol surfactants and silicon surfactants is 0.5% by weight or more, and the ratio of (di) propylene glycol monobutyl ether is 30. The water-based ink according to claim 29, which is 1: 0 to 1:10. 31. The water-based ink according to claim 25, 27, 29 or 30, comprising 20% by weight or less of the di (tri) ethylene glycol monobutyl ether. The addition amount of one or more selected from the acetylene alcohol surfactants, acetylene glycol surfactants and silicon surfactants is 0.5% by weight or more, and di (tri) ethylene glycol monobutyl ether 30. The water-based ink according to claim 29, wherein the ratio is 1: 0 to 1:50. The water-based ink according to any one of claims 1 to 36, wherein the colorant is a pigment. The pigment is C.I. I. Pigment black, C.I. I. Pigment yellow, C.I. I. Pigment Red, C.I. I. Pigment violet, C.I. I. Pigment blue, C.I. I. Pigment orange, C.I. I. Pigment Green, C.I. I. 38. The water-based ink according to claim 37, wherein the water-based ink is one or more selected from the group consisting of Pigment Brown. The pigment is a group consisting of carbon black pigment, phthalocyanine pigment, quinacridone pigment, monoazo pigment, azo lake pigment, condensed azo pigment, isoindolinone pigment, quinophthalone pigment, anthraquinone pigment, benzimidazolone pigment, dioxazine pigment, perylene pigment, perinone pigment. The water-based ink according to claim 37, wherein the water-based ink is one or more selected from the group consisting of: An aqueous ink set comprising at least a black aqueous ink, a yellow aqueous ink, a magenta aqueous ink, and a cyan aqueous ink, each aqueous ink including a dispersion in which a colorant is included in a polymer to be dispersible in water; An aqueous ink set, wherein the amount of aromatic rings in the polymer is 20% by weight or more and 70% by weight or less of the polymer. 41. The water-based ink set according to claim 40, wherein the water-based ink set further comprises a red water-based ink. The water-based ink set according to claim 40 or 41, wherein the water-based ink set further comprises a blue water-based ink. 43. The water-based ink set according to any one of claims 40 to 42, wherein the water-based ink set further comprises a green water-based ink. A water-based ink set comprising a combination of a dark water-based ink and a light water-based ink, wherein the dark water-based ink is at least a dark black water-based ink, a dark yellow water-based ink, a dark magenta water-based ink, and a dark cyan water-based ink, The ink is at least a light magenta water-based ink and a light cyan water-based ink, and each water-based ink includes a dispersion in which a colorant is included in a polymer and is dispersible in water, and the amount of the aromatic ring in the polymer is A water-based ink set characterized by being 20 wt% or more and 70 wt% or less of the polymer. The water-based ink set according to claim 44, wherein the water-based ink set further comprises a light black water-based ink as a light water-based ink. 46. The water-based ink set according to claim 44 or 45, wherein the water-based ink set further comprises a light yellow water-based ink as a light water-based ink. The water-based ink according to any one of claims 1 to 39 or the water-based ink set according to any one of claims 40 to 46 is energized and discharged from a recording head, and is attached to a recording medium for printing. An aqueous inkjet recording method characterized by the above. A process for producing a dispersion comprising two steps of a dispersion process in which a colorant is included in a polymer and dispersible in water, and a dispersion process in which the dispersion is dispersed in an aqueous medium, A method, wherein the amount of aromatic rings in the polymer is 20% by weight or more and 70% by weight or less of the polymer. 49. The method according to claim 48, wherein the dispersing step is a step of dispersing in a mixed liquid state of at least the dispersion, water, and a dispersion accelerator. The method according to claim 48 or 49, wherein a surface tension of the mixed liquid in the dispersing step is 40 mN / m or less. The method according to any one of claims 48 to 50, wherein the concentration of the dispersion in the mixed solution in the dispersion step is 50% by weight or less. The dispersion accelerator is one or two or more substances selected from the group consisting of acetylene glycols, acetylene alcohols, polysiloxanes, glycol ethers, and alkylene glycols. 51. The method according to any one of 51. The method according to claim 48, wherein the amount of polyvalent cation contained in the dispersion is 1000 ppm or less. The method according to claim 48, wherein the amount of polyvalent anions contained in the dispersion is 800 ppm or less. The method according to claim 48, wherein the amount of monovalent cations contained in the dispersion is 3500 ppm or less. 56. The method of claim 55, wherein the monovalent cation is an alkali metal ion and / or an ammonium ion. 57. The method according to claim 56, wherein the alkali metal ion is any one of a lithium ion, a sodium ion, and a potassium ion. The method according to claim 48, wherein the amount of monovalent anions contained in the dispersion is 5000 ppm or less. 59. The method of claim 58, wherein the monovalent anion is a halogen ion. The method according to claim 59, wherein the halogen ion is any one of chlorine ion, bromine ion and iodine ion. A dispersion produced by the method according to any one of claims 48 to 60. 62. The dispersion according to claim 61, wherein the total amount of polyvalent metal ions contained in the liquid component of the dispersion is 500 ppm or less. 62. The dispersion according to claim 61, wherein each of the amounts of ions of Si, Ca, Mg, Fe, Cr, Ni, and Zr contained in the liquid component of the dispersion is 100 ppm or less. The dispersion according to any one of claims 61 to 63, wherein the colorant is a pigment. The pigment dispersion according to claim 64, wherein the content of the polymer including the pigment in the dispersion is in the range of 10 wt% to 70 wt%. An aqueous ink containing the dispersion according to any one of claims 61 to 65.