JP2010047727A - Ink for ink-jet recording, and recording method and recorded matter using the ink - Google Patents

Abstract

An ink for ink jet recording which can improve ejection failure due to a decrease in ink repellency due to adhesion or adhesion of dry ink and can be used in a highly reliable state, an ink jet recording method using the ink, and an ink cartridge And provision of records.
An ink used in an ink jet recording apparatus having at least an ink flying means for applying an stimulus to the ink and causing the ink to fly to record an image, wherein the ink includes at least a colorant pigment, resin emulsions A and B, fluorine An ink for ink-jet recording, comprising a surfactant, a water-soluble solvent, and water, wherein the resin emulsion A is an ester / ether urethane resin emulsion and the resin emulsion B is an ether urethane resin emulsion.
[Selection] Figure 1

Description

  The present invention relates to an ink for ink jet recording, an ink jet recording method using the ink, an ink cartridge, and a recorded matter.

Inks used for ink jet recording generally contain water as a main component and contain a colorant and a wetting agent. A dye is mainly used as the colorant. However, in the case of the dye-based ink, the light resistance and water resistance of the image are inferior, and there is a problem particularly with plain paper.
Therefore, in recent years, ink using a pigment as a colorant has begun to be used, and the above-mentioned defects such as light resistance have been greatly improved. However, pigment-based inks have a storage stability problem that, when left for a long period of time, sedimentation and viscosity increase occur due to aggregation of pigment particles.
In order to solve this problem, Patent Document 1 proposes an ink jet recording ink containing a fluorosurfactant and an ether urethane resin emulsion. However, although the storage stability is improved, the head of the ink jet recording apparatus is proposed. Since the problem that dry ink adheres (adheres) to the nozzle surface occurs, further improvement is necessary for practical use.

On the other hand, in the head of an ink jet recording apparatus, an ink repellent layer is formed on the ejection surface side of a nozzle to improve surface uniformity and ensure ejection stability. Although there are various materials for the ink repellent layer, an ink repellent layer with extremely high ink repellency is required for low surface tension ink or highly adhesive ink.
Therefore, an ink jet head in which a layer containing a fluorine-based silane coupling agent is formed as an ink repellent layer having high ink repellency is known (for example, Patent Document 2).
However, conventional inkjet recording inks containing the above-mentioned fluorine-based surfactant and ether-based urethane resin emulsion for an inkjet head having an ink-repellent layer containing such a fluorine-based silane coupling agent formed on the nozzle surface Ink will stick to the nozzle surface. This is because the fluorine-based surfactant in the ink is easily adsorbed to the ink-repellent layer composed of the same fluorine-based material (fluorine-based silane coupling agent), and the fluorine-based surfactant is adsorbed to the ink-repellent layer. It is considered that the ink repellency of the portion is lowered and the ether urethane resin emulsion is deposited there.

JP 2007-63316 A Japanese Patent Laid-Open No. 6-210857

  The present invention has been made in view of such a situation, and improves ink ejection failure due to a decrease in ink repellency associated with adhesion or fixation of dry ink, and can be used in a highly reliable state. In particular, an object of the present invention is to provide an ink for inkjet recording that is effective even for a nozzle ink repellent layer containing a fluorine-based silane coupling agent having extremely high ink repellency. It is another object of the present invention to provide an ink jet recording method, an ink cartridge, and a recorded matter using the ink.

上記式中、Ｒ^１は水素、アルキル基、アシル基の何れかを表し、Ｒｆは−ＣＦ_３、又は−ＣＦ_２ＣＦ_３を表し、ｍは１０〜３０の整数であり、ｎ、ｐはｎ＋ｐ＝４〜１０を満たす正の整数である。

上記式中、Ｍはアルカリ金属、アンモニウム、ホスホニウム、アルカノールアミンの何れかを表し、Ｒｆは−ＣＦ_３、又は−ＣＦ_２ＣＦ_３を表し、ｑは４〜１０の整数である。

上記式中、ｒは０〜１０の整数、ｓは０〜４０の整数である。
３） フッ素系樹脂からなる撥インク層を有するインクジェットヘッドを備えたインクジェット記録装置を用い、１）又は２）記載のインクジェット記録用インクを吐出することを特徴とするインクジェット記録方法。
４） １）又は２）記載のインクジェット記録用インクを収容したインクカートリッジ。
５） １）又は２）記載のインクジェット記録用インクを用いて記録された記録物。 The above problems are solved by the following inventions 1) to 5).
1) Contains at least a colorant pigment, resin emulsions A and B, a fluorosurfactant, a water-soluble solvent, and water. The resin emulsion A is an ester / ether urethane resin emulsion, and the resin emulsion B is an ether urethane. An ink for ink-jet recording comprising a resin emulsion.
2) The inkjet recording ink according to 1), wherein the fluorine-containing surfactant contains a compound represented by any one of the following structural formula (1), structural formula (2), and structural formula (3).

In the above formula, R ¹ represents any ^one of hydrogen, an alkyl group, and an acyl group, Rf represents —CF ₃ or —CF ₂ CF ₃ , m is an integer of 10 to 30, and n and p are n + p. = A positive integer satisfying 4-10.

In the above formula, M represents any one of alkali metal, ammonium, phosphonium, and alkanolamine, Rf represents —CF ₃ or —CF ₂ CF ₃ , and q is an integer of 4 to 10.

In the above formula, r is an integer of 0 to 10, and s is an integer of 0 to 40.
3) An ink jet recording method characterized by using an ink jet recording apparatus provided with an ink jet head having an ink repellent layer made of a fluorine-based resin and discharging the ink for ink jet recording described in 1) or 2).
4) An ink cartridge containing the ink for inkjet recording described in 1) or 2).
5) A recorded matter recorded using the ink for ink jet recording described in 1) or 2).

Hereinafter, the present invention will be described in detail.
As a result of intensive studies, the present inventors have been able to ensure storage stability by using a fluorosurfactant in combination with an ester / ether urethane resin emulsion A and an ether urethane resin emulsion B. It has been found that high-quality images can be realized without any disturbance because no sticking occurs even with an ink-jet head having an ink repellent layer containing a ring agent, and the present invention has been achieved.
In particular, by including the ester / ether urethane resin emulsion A in the ink, it is possible to prevent sticking from occurring even for an ink jet head having an ink repellent layer containing a fluorine-based silane coupling agent. . In addition, since the ester / ether urethane resin emulsion A also has the effect of improving the storage stability, the ether urethane resin emulsion B alone can achieve a much higher stability by supplementing the storage stability insufficient. .

As described above, the ink of the present invention contains a colorant pigment, an ester / ether urethane resin emulsion, an ether urethane resin emulsion, a fluorosurfactant (penetrant), a water-soluble solvent, and water. Furthermore, you may contain a dispersing agent, acrylic resin emulsion, a water-soluble solvent (wetting agent), a mold release agent, a pH adjuster, and other additives.
Next, each component of the ink of the present invention will be described.
<Color material pigment>
Examples of the pigment used in the present invention include azo, phthalocyanine, anthraquinone, dioxazine, indigo, thioindigo, perylene, isoindolenone, aniline black, azomethine, rhodamine B lake pigment, and the like as organic pigments. Examples of the inorganic pigment include carbon black, iron oxide, titanium oxide, calcium carbonate, barium sulfate, aluminum hydroxide, barium yellow, bitumen, cadmium red, chrome yellow, and metal powder.

Specifically, carbon blacks (CI pigment black 7) such as furnace black, lamp black, acetylene black, channel black; copper oxide, iron oxide (CI pigment black 11) as black pigments ), Metal oxides such as titanium oxide; organic pigments such as aniline black (CI Pigment Black 1).
Examples of yellow pigments include C.I. I. Pigment Yellow 1 (Fast Yellow G), 2, 3, 12 (Disazo Yellow AAA), 13, 14, 16, 17, 20, 23, 24, 34, 35, 37, 42 (Yellow Iron Oxide), 53, 55 73, 74, 75, 81, 83 (disazo yellow HR), 86, 93, 95, 97, 98, 100, 101, 104, 108, 109, 110, 114, 117, 120, 125, 128, 129, 137, 138, 139, 147, 148, 150, 151, 153, 154, 155, 166, 168, 180, 185 and the like.

Examples of magenta pigments include C.I. I. Pigment Red 1, 2, 3, 5, 7, 9, 12, 17, 22 (Brilliant First Scarlet), 23, 31, 38, 48: 1 [Permanent Red 2B (Ba)], 48: 2 [Permanent Red 2B (Ca)], 48: 3 [permanent red 2B (Sr)], 48: 4 [permanent red 2B (Mn)], 49: 1, 52: 2, 53: 1, 57: 1 (brilliant carmine 6B), 60: 1, 63: 1, 63: 2, 64: 1, 81 (Rhodamine 6G rake), 83, 88, 92, 97, 101 (Bengara), 104, 105, 106, 108 (Cadmium red), 112, 114, 122 (dimethylquinacridone), 123, 146, 149, 166, 168, 170, 172, 175, 176, 178, 179, 180 184,185,190,192,193,202,209,215,216,217,219,220,223,226,227,228,238,240,254,255,272, and the like.
Examples of cyan pigments include C.I. I. Pigment Blue 1, 2, 3, 15 (copper phthalocyanine blue R), 15: 1, 15: 2, 15: 3 (phthalocyanine blue G), 15: 4, 15: 6 (phthalocyanine blue E), 16, 17: 1, 22, 56, 60, 63, 64, Bat Blue 4, Bat Blue 60, and the like.

Intermediate colors include red, green and blue for C.I. I. Pigment red 177, 194, 224, C.I. I. Pigment orange 16, 36, 43, 51, 55, 59, 61, 71, C.I. I. Pigment violet 3, 19, 23, 29, 30, 37, 40, 50, C.I. I. Pigment green 7, 36, and the like.
Among the above pigments, carbon black is particularly preferable as the black pigment. Carbon black produced by the furnace method and the channel method has an average primary particle size of 15 to 40 nm, and a specific surface area by the BET adsorption method of 50 to 50. 300m ² / g, DBP oil absorption amount 40 to 150/100 g, a volatile matter content of 0.5% to 10%, are used those PH2～9, especially pH6 following acidic carbon black is preferred in a high concentration.
As pigments, Pigment Yellow 13, 17, 55, 74, 93, 97, 98, 110, 128, 139, 147, 150, 151, 154, 155, 180, 185, Pigment Red 122, 202, 209, Pigment Blue 15: 3 and 15: 4 are preferred.

The average particle diameter of the pigment is not particularly limited, but is preferably 20 to 200 nm, more preferably 30 to 150 nm, and still more preferably 50 to 100 nm. When the average particle diameter exceeds 200 nm, not only the saturation of the printed image is lowered, but also thickening aggregation during ink storage and nozzle clogging during printing are likely to occur. Further, when the pigment particle size is less than 20 nm, not only the light resistance is lowered but also the storage stability tends to be deteriorated.
The average particle diameter of the pigment referred to in the present invention is a particle refractive index using a sample diluted with pure water so that the pigment concentration in the measurement sample becomes 0.01% by weight using Microtrack UPA-150 manufactured by Nikkiso Co., Ltd. It is a 50% average particle diameter (D50) measured at 23 ° C. using 1.51 and a particle density of 1.4 g / cm ³ and a pure water parameter as a solvent parameter.
The pigment concentration in the ink is preferably 2 to 15% by weight, more preferably 3 to 12% by weight, and still more preferably 4 to 10% by weight. If the amount is less than 2% by weight, the tinting strength is insufficient, so that the vividness of the image tends to be inferior. If the amount exceeds 15% by weight, not only the storage stability of the ink is lowered but also the image tends to be dull.

<Dispersant>
Usually, a dispersant is used to disperse the pigment. Examples of such a dispersant include nonionic or anionic surfactant-based dispersants, which can be appropriately selected according to the pigment type or ink formulation.
Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, and other polyoxyethylene alkyl ethers; polyoxyethylene octyl phenyl ether Polyoxyethylene alkylphenyl ethers such as polyoxyethylene nonylphenyl ether; polyoxyethylene-α-naphthyl ether, polyoxyethylene-β-naphthyl ether, polyoxyethylene monostyryl phenyl ether, polyoxyethylene distyryl phenyl ether, Polyoxyethylene alkyl naphthyl ether, polyoxyethylene monostyryl naphthyl ether, polyoxyethylene Examples include distyryl naphthyl ether and polyoxyethylene polyoxypropylene block copolymer.
Also used are surfactants in which a part of polyoxyethylene in the above surfactant is replaced with polyoxypropylene, and surfactants condensed with a compound having an aromatic ring such as polyoxyethylene alkylphenyl ether with formalin. it can.

上記構造式中、Ｒ^２は炭素数１〜２０のアルキル基、炭素数１〜２０のアラルキル基、又はアリル基を表し、ｌは０〜７の整数であり、ｋは２０〜８０の整数である。 The nonionic surfactant preferably has an HLB of 12 to 19.5, more preferably 13 to 19. If the HLB is less than 12, there is a tendency for the dispersion stability to deteriorate due to poor compatibility of the surfactant with the dispersion medium. If the HLB exceeds 19.5, the surfactant is less likely to be adsorbed to the pigment. There is a tendency for stability to deteriorate.
In the present invention, the nonionic dispersant represented by the following structural formula (4) is particularly excellent, and the storage stability of the pigment-dispersed ink can be improved.

In the structural formula, ^{R 2} represents an alkyl group, an aralkyl group having 1 to 20 carbon atoms, or an allyl group having 1 to 20 carbon atoms, l is an integer of 0 to 7, k is an integer of 20 to 80 is there.

Anionic surfactants include polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene monostyryl phenyl ether sulfate, polyoxyethylene distyryl phenyl ether sulfate, polyoxyethylene alkyl ether phosphorus Acid salt, polyoxyethylene alkyl phenyl ether phosphate, polyoxyethylene monostyryl phenyl ether phosphate, polyoxyethylene distyryl phenyl ether phosphate, polyoxyethylene alkyl ether carboxylate, polyoxyethylene alkyl phenyl ether Carboxylate, polyoxyethylene monostyryl phenyl ether carboxylate, polyoxyethylene distyryl phenyl ether carboxylate, naphthalene Sulfonate formalin condensate, melanin sulfonate formalin condensate, dialkyl sulfosuccinic acid ester salt, sulfosuccinic acid alkyl disalt, polyoxyethylene alkyl sulfosuccinic acid disalt, alkyl sulfoacetate, α-olefin sulphonate, alkylbenzene sulfone Examples thereof include acid salts, alkylnaphthalene sulfonates, alkyl sulfonates, N-acyl amino acid salts, acylated peptides, soaps and the like. Among these, sulfates or phosphates of polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyoxyethylene distyryl phenyl ether are particularly preferable.
The addition amount of the surfactant-based dispersant is preferably 10 to 50% by weight of the pigment. If it is less than 10% by weight, the storage stability of the pigment dispersion and the ink is lowered or it takes an extremely long time to disperse, and if it exceeds 50% by weight, the viscosity of the ink becomes too high and the discharge stability tends to be lowered. .

<Urethane resin emulsion A, B>
The urethane resin emulsion in the present invention is obtained by polymerizing at least polyisocyanate and polyether polyol, polyester polyol, polylactone polyol, polycarbonate polyol or the like.
Examples of polyisocyanates include aliphatic diisocyanate compounds such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate; isophorone diisocyanate, hydrogenated xylylene diisocyanate, 1,4-cyclohexane diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate. Cycloaliphatic diisocyanate compounds such as xylylene diisocyanate and tetramethylxylene diisocyanate; aromatic diisocyanate compounds such as toluylene diisocyanate and phenylmethane diisocyanate; Metamorphic materials, etc.).

Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol, polyhexamethylene ether glycol and the like.
Examples of the polyester polyol include polyethylene adipate, polybutylene adipate, polyneopentyl adipate, poly-3-methylpentyl adipate, polyethylene / butylene adipate, polyneopentyl / hexyl adipate, and the like.
Examples of the polylactone polyol include polycaprolactone diol and polyomega-hydroxycaproic acid polyol.
Polycarbonate polyols include 1,3-propanediol, 1,4-butanediol and / or 1,6-hexanediol, diols such as diethylene glycol, triethylene glycol or tetraethylene glycol, phosgene and diphenyl carbonate. Included are those known per se, such as products obtained from reaction with diaryl carbonates or cyclic carbonates such as ethylene or propylene carbonate. Also suitable are polyester carbonates obtained from the polyesters or polylactones described above and phosgene, diaryl carbonates or cyclic carbonates.

Among the above urethane resin emulsions, the urethane resin emulsion A needs to be an ester / ether type, and the urethane resin emulsion B needs to be an ether type.
When the urethane resin emulsion A is other than an ester / ether type, there arises a problem that the dried ink adheres to an ink jet head having an ink repellent layer containing a fluorine-based silane coupling agent. Since the dry ink fixed to the nozzle surface of the ink jet head cannot be removed by scraping off with a wiper, the ink repellency of that portion is lowered, and if it is close to the nozzle hole, the ejection direction is disturbed.
On the other hand, when the urethane resin emulsion B is other than the ether type, sufficient storage stability cannot be ensured, so that the ink tends to aggregate, increase in viscosity, or decrease in viscosity when stored at a high temperature.
As the urethane resin emulsion A or B, a self-emulsifying urethane resin emulsion having a hydrophilic group such as a sulfonyl group, a carboxyl group, or polyethylene oxide is preferable, and a self-emulsifying urethane resin emulsion having a carboxyl group is particularly preferable. By introducing a hydrophilic group into the urethane resin emulsion, the storage stability can be further improved. Examples of the method for introducing a hydrophilic group into the urethane resin emulsion include a method in which monomers such as dimethylolacetic acid, dimethylolbutanoic acid, dimethylolpropionic acid, and dimethylolbutyric acid are added and copolymerized during synthesis.

When a self-emulsifying urethane resin emulsion having a carboxyl group or a sulfonyl group is used, a basic compound may be contained in the ink in order to enhance the dispersibility of the urethane resin in an aqueous medium. Such a basic compound is not particularly limited as long as it can disperse the urethane resin in an aqueous medium to be described later by the blending thereof, and those commonly used can be used. Specific examples thereof include alkylamines such as butylamine and triethylamine; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine and triisopropanolamine; morpholine, aqueous ammonia, sodium hydroxide, lithium hydroxide, potassium hydroxide and aminomethyl. Examples thereof include propanediol, aminoethylpropanediol, choline and the like. Moreover, you may use buffer agents, such as a trishydroxymethylaminomethane and a good buffer, as a basic compound. These basic compounds can be used alone or in admixture of two or more.
The addition amount of the basic compound is appropriately set according to the physical properties and use amount of the urethane resin to be used and the pH suitable as the ink.

As a method for producing the urethane resin emulsion A or B, an isocyanate-terminated prepolymer is synthesized in a low boiling point solvent (acetone or the like) that does not react with an isocyanate group, a hydrophilic group is introduced with a diamine, a polyol or the like, and then diluted with water. Phase conversion, solvent method to obtain urethane dispersion solution method, prepolymer method in which isocyanate group-terminated prepolymer with hydrophilic group introduced is first synthesized, dispersed in water and then chain extended with amine, etc. Hot melt method, Method using urethane prepolymer in aqueous emulsifier as water as chain extender, Sulfonating aromatic ring of urethane prepolymer having free isocyanate group obtained from hydrophobic polyol and aromatic polyisocyanate A method of passing through a process, a method of using a blocked isocyanate, etc. It is known to people, but not particularly limited.
In addition, when adopting the prepolymer method, a polyhydroxy compound having a low molecular weight may be used. Examples thereof include the glycol and alkylene oxide low molar adducts mentioned as the raw material of the above polyester diol, glycerin, and trimethylol. Examples thereof include trihydric alcohols such as ethane and trimethylolpropane, and alkylene oxide low molar adducts thereof.
In the case of an aqueous urethane resin, a method is generally known in which a urethane prepolymer prepared in an organic solvent phase is phase-inverted and emulsified and further chain-extended in the aqueous phase. In this case, polyamines such as diamine are generally used as the chain extender. Specifically, after neutralizing the acid group derived from dimethylol alkanoic acid in the urethane prepolymer or with neutralization, water extension or di- or triamine extension is performed. Examples of polyamines used as a chain extender during amine extension include diamines and triamines, and specific examples thereof include hexamethylene diamine, isophorone diamine, hydrazine, and piperazine.

In the urethane resin emulsion in the ink, the content of the urethane resin emulsion A is preferably not more than the content of the urethane resin emulsion B. The content in the present invention means the solid content concentration in the ink. If the B content is less than the A content, nozzle surface sticking may occur, resulting in ejection failure.
The content ratio of the urethane resin emulsions A and B is preferably A: B = 1: 1 to 1:10, more preferably 1: 1.5 to 1: 5. When the content ratio of B is less than 1: 1, the storage stability tends to decrease, and when the content ratio of B exceeds 1:10, it is difficult to prevent nozzle surface sticking.
The content of the urethane resin emulsion A with respect to the pigment is preferably 3 to 20% by weight, and more preferably 5 to 15% by weight. If it is less than 3% by weight, a sufficient effect of preventing nozzle surface sticking cannot be obtained, and if it exceeds 20% by weight, the viscosity of the ink becomes too high and the ejection stability tends to be inferior.

The total solid content concentration in the ink is preferably 6 to 25% by weight, more preferably 7 to 20% by weight, and still more preferably 8 to 15% by weight. When the total amount is less than 6% by weight, the blur of the printed image tends to increase, and when it exceeds 25% by weight, the storage stability tends to deteriorate.
The total amount of the solid content is the total amount of components that are not soluble in a mixture such as water or a water-soluble organic solvent contained in the ink, and includes pigments, resin emulsions, and the like. The method for determining the total amount of solid content in the ink is to centrifuge the ink to separate or float the solid content and measure the weight, or to add a flocculant to the ink to coagulate the solid content. And a method of measuring the weight by separating from the ink.

<Acrylic resin emulsion>
An acrylic resin emulsion may be used for the purpose of improving the scratch resistance and water resistance of an image when ink is printed on a medium such as paper. Examples thereof include resin emulsions obtained by polymerizing the following polymerizable monomers singly or in combination of two or more.
Polymerizable monomer: styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, α-methylstyrene, p-ethylstyrene, 2,4-dimethylstyrene, p-tert-butylstyrene, p-chlorostyrene, Vinyl aromatic hydrocarbons such as divinylbenzene; methyl acrylate, ethyl acrylate, butyl acrylate, acrylic acid-n-propyl, isopropyl acrylate, acrylic acid-n-butyl, acrylic acid isobutyl, acrylic acid-t- Butyl, acrylate-n-pentyl, isopentyl acrylate, neopentyl acrylate, 3- (methyl) butyl acrylate, 2-ethylhexyl acrylate, cyclohexyl acrylate, hexyl acrylate, octyl acrylate, nonyl acrylate, Decyl acrylate, acrylic Undecyl acrylate, dodecyl acrylate, phenyl acrylate, methyl methacrylate, -n-propyl methacrylate, isopropyl methacrylate, -n-butyl methacrylate, isobutyl methacrylate, -t-butyl methacrylate, methacrylic acid -n- Pentyl, isopentyl methacrylate, neopentyl methacrylate, 3- (methyl) butyl methacrylate, 2-ethylhexyl methacrylate, hexyl methacrylate, octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, dodecyl methacrylate (Meth) acrylic acid esters such as; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid; (meth) acrylamide, N-substituted maleimide, maleic anhydride, (meth) acrylonite Ril, vinyl ketone, vinyl acetate, vinylidene chloride, etc.

The acrylic resin emulsion exhibits excellent water dispersibility by containing an ionic group on the surface. Examples of such ionic groups include sulfonic acid groups, carboxylic acid groups, sulfuric acid groups, phosphoric acid groups, phosphonic acid groups and phosphinic acid groups, or alkali metal bases and ammonium bases thereof, or primary to tertiary. An amine group and the like can be mentioned, and an alkali metal carboxylate, an ammonium carboxylate, an alkali metal sulfonate, and an ammonium sulfonate are preferable. Particularly, an alkali metal sulfonate and an ammonium sulfonate are water dispersion stable. This is preferable. The introduction of the ionic group is performed by adding a monomer having an ionic group at the time of resin synthesis.
Examples of the salt include salts such as ammonium ions, Li, Na, K, Mg, Ca, Cu, and Fe ions, and preferred are Li, K, and Na salts.

<Penetration agent>
By adding a penetrant to the ink, surface tension is reduced, and penetration into the recording medium after the ink droplets have landed on the recording medium, such as paper, becomes faster, thus reducing feathering and color bleeding. it can. In the present invention, a fluorosurfactant is used as the penetrant, but the appropriate surface tension range is 20 to 30 mN / m.
The addition amount of the fluorosurfactant in the ink is 0.05 to 20% by weight, preferably 0.1 to 10% by weight, but is not particularly limited. Examples of fluorosurfactants include perfluoroalkyl sulfonates, perfluoroalkyl carboxylates, perfluoroalkyl phosphates, perfluoroalkyl ethylene oxide adducts, perfluoroalkyl betaines, perfluoroalkylamine oxide compounds. The structure represented by the structural formulas (1) to (3) is particularly preferable from the viewpoint of reliability.
As the alkyl group in R1 of the structural formula (1), a methyl group, an ethyl group, a propyl group, a butyl group, and an isobutyl group having up to 4 carbon atoms are useful, and as an acyl group, HCO- (formyl group), CH ₃ CO— (acetyl group), CH ₃ CH ₂ CO— (propynyl group), CH ₃ [CH ₂ ] ₂ CO— (butyryl group), (CH ₃ ) ₂ CHCO— (isobutyryl group) are useful.
Li, Na, and K are useful as alkali metals in M of the structural formula (2), and methanolamine and ethanolamine are useful as alkanolamines.

Commercially available fluorosurfactants include Surflon S-111, S-112, S-113, S121, S131, S132, S-141 and S-145 (manufactured by Asahi Glass Co., Ltd.), Fullrad FC- 93, FC-95, FC-98, FC-129, FC-135, FC-170C, FC-430, FC-431, FC-4430 (manufactured by Sumitomo 3M), MegaFuck F-470, F-1405 F474 (Dainippon Ink & Chemicals), Zonyl FS-300, FSN, FSN-100, FSO (DuPont), F-Top EF-351, 352, 801, 802 (Gemco) etc. are easily available Can be used in the present invention. Among these, Zonyl FS-300, FSN, FSN-100, FSO (manufactured by DuPont), polyfox PF-136A, PF-156A, and PF-151N (manufactured by Omninova) are particularly good in terms of reliability and color development improvement. It can be used suitably. These commercially available products are often a mixture of several molecular weights [m and n have a distribution in the structural formula (1)], but do not particularly affect the effects of the present invention.
These compounds can be used alone or in admixture of two or more, and can also be used in admixture with other various surfactants such as the following anionic, cationic and nonionic types. is there.

Examples of the anionic surfactant include polyoxyethylene alkyl ether acetate, dodecyl benzene sulfonate, laurate, polyoxyethylene alkyl ether sulfate, and the like. Nonionic surfactants include, for example, Examples include polyol, glycol ether, polyoxyethylene alkyl ether, polyoxyethylene alkyl ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkylamine, polyoxyethylene alkylamide, and acetylene glycol. Examples of acetylene glycol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, And acetylene glycols such as 5-dimethyl-1-hexyn-3-ol (for example, Surfynol 104, 82, 465, 485 or TG manufactured by Air Products (USA)).
In the present invention, in particular, a polyol having 8 to 11 carbon atoms, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol and the like are shared with the above-mentioned surfactant. Then, more excellent permeability can be obtained.

<Water-soluble solvent (wetting agent)>
The ink of the present invention uses water as a liquid medium, but a water-soluble organic solvent is used as a wetting agent for the purpose of preventing the ink from drying and improving the dispersion stability.
Specific examples of the water-soluble organic solvent include the following, but a plurality of these may be used in combination.
Glycerin, 1,3-butanediol, 3-methyl-1,3-butanediol, trimethylolethane, trimethylolpropane, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene Glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2, Polyhydric alcohols such as 3-butanetriol and petriol;
Polyhydric alcohol alkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, tetraethylene glycol monomethyl ether, propylene glycol monoethyl ether;
Polyhydric alcohol aryl ethers such as ethylene glycol monophenyl ether and ethylene glycol monobenzyl ether;
Nitrogen-containing heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone;
Amides such as formamide, N-methylformamide, N, N-dimethylformamide;
Amines such as monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine;
Sulfur-containing compounds such as dimethyl sulfoxide, sulfolane, thiodiethanol;
Propylene carbonate, ethylene carbonate and the like.

As other wetting agents, those containing sugar are preferable. Examples of saccharides include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides) and polysaccharides, preferably glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, Examples include lactose, sucrose, trehalose, and maltotriose. Here, the polysaccharide means a saccharide in a broad sense, and is used to include a substance that exists widely in nature such as α-cyclodextrin and cellulose.
Examples of derivatives of these saccharides include reducing sugars of the aforementioned saccharides [for example, sugar alcohol [general formula HOCH ₂ (CHOH) nCH ₂ OH (n = 2 to 5)]], oxidized sugar (for example, aldone). Acid, uronic acid, etc.), amino acids, thioacids and the like. Among them, sugar alcohols are preferable, and specific examples include D-sorbitol, sorbitan, maltitol, erythritol, lactitol, xylitol and the like.
In particular, in the present invention, as a wetting agent, glycerin, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,6-hexanediol, propylene glycol, 1,5-pentanediol, dipropylene glycol, trimethylolpropane, By using 3-methyl-1,3-butanediol, D-sorbitol, and xylitol, an ink having excellent storage stability and ejection stability can be produced.

The ratio of pigment to wetting agent has a great influence on the stability of ink ejection from the head. If the blending amount of the wetting agent is small even though the pigment solid content is high, water evaporation near the ink meniscus of the nozzle proceeds and discharge failure occurs.
The blending amount of the wetting agent in the ink is 10 to 50% by weight, and the ratio of the wetting agent solid content to the solid content in the ink such as the colorant particles is preferably 0.5 to 12.5. More preferably, it is 1.0-6.0, Most preferably, it is the range of 2.0-5.0. Ink within this range has very good drying, storage and reliability tests.

<Release agent>
The polyether-modified silicone oil has a releasing action, and has an action of preventing the dried ink from sticking to the ink jet nozzle surface having a silicone resin water-repellent layer. However, in some cases, the ink jet head surface having an ink repellent layer containing a fluorine-based silane coupling agent may not provide a sufficient effect of preventing the adhesion of dry ink.
Commercially available products can be used as the polyether-modified silicone oil, and examples of available polyether-modified silicone oil include KF-351, KF-352, KF-353, KF-354L, KF-355A, KF-615A, KF-945, KF-618, KF-6011, KF-6015 (manufactured by Shin-Etsu Chemical Co., Ltd.), SF-8427, SF-8428, SH-3749, SH-8400, FZ-2101, FZ-2104, FZ -2118, FZ-2203, FZ-2207 (manufactured by Dow Corning Toray), BYK-345, BYK-346, BYK-348 (manufactured by Big Chemie Japan).

<PH adjuster>
By adding a pH adjusting agent to keep it alkaline, the dispersion state can be stabilized and the ejection can be stabilized. In addition, when the pH is 11 or more, the amount of the ink jet head and the ink supply unit that melts out is large, and problems such as ink deterioration, leakage, and ejection failure occur. The pH adjuster is preferably added when the pigment is kneaded and dispersed in water together with the dispersant, rather than being added together with additives such as a wetting agent and a penetrating agent after kneading and dispersing. This is because dispersion may be destroyed by adding some pH adjusters.
As the pH adjuster, those containing at least one kind of alcohol amines, alkali metal hydroxides, ammonium hydroxides, phosphonium hydroxides, and alkali metal carbonates are preferable.
Examples of alcohol amines include diethanolamine, triethanolamine, 2-amino-2-ethyl-1,3-propanediol, and the like. Examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide and the like. Examples of the ammonium hydroxide include ammonium hydroxide and quaternary ammonium hydroxide. Examples of the phosphonium hydroxide include quaternary phosphonium hydroxide. Examples of the alkali metal carbonate include lithium carbonate, sodium carbonate, potassium carbonate and the like.

<Other additives>
In addition to the above-mentioned materials, known additives such as antiseptic / antifungal agents, chelating reagents, and rust inhibitors can be added to the ink of the present invention.
Examples of antiseptic / antifungal agents include sodium dehydroacetate, sodium sorbate, sodium 2-pyridinethiol-1-oxide, sodium benzoate, sodium pentachlorophenol and the like.
Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uramil diacetate and the like.
Examples of the rust inhibitor include acidic sulfites, sodium thiosulfate, ammonium thiodiglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.

Next, the ink jet head will be described.
FIG. 1 is an enlarged view of an example of an inkjet head. Each ink jet head is of a piezo type, and includes an ink supply port (not shown), a frame 10 formed with an engraving serving as a common liquid chamber 1b, a fluid resistance portion 2a, and a pressurized liquid chamber 2b formed with engraving. , A flow path plate 20 having a communication port 2c communicating with the nozzle 3a, a nozzle plate 30 having a large number of nozzles 3a, and a laminated piezoelectric element fixed to the base 40 and applied with a driving waveform from the head driver. An element 50, a vibration plate 60 having a convex portion 6 a bonded to the multilayer piezoelectric element 50, a diaphragm portion 6 b, and an ink inlet 6 c, and an adhesive layer 70 for bonding the multilayer piezoelectric element 50 and the vibration plate 60 are provided. . Each inkjet head is not limited to a piezo type, but may be a thermal type, an electrostatic type, or the like.
The nozzle plate 30 is formed of a metal material, for example, an Ni plating film by an electroforming method. The ink repellent layer 3b (liquid repellent layer) according to the present invention is formed on the ink discharge surface side surface (droplet discharge surface side surface) of the nozzle plate 30.

<Nozzle plate>
An ink repellent layer is provided on the nozzle plate surface of the inkjet head in order to maintain sufficient ink repellency even for highly penetrating ink with low surface tension. The ink repellent layer is coated on the nozzle plate with PTFE / Ni eutectoid plating, fluororesin electrodeposition coating, evaporation of fluororesin (such as fluorinated pitch), and application of silicone resin or fluororesin (spin coating) , Roll coating, dipping, etc.), printing, etc.
As a material for the ink repellent layer, a fluorine-based water repellent agent, particularly a fluorine-based silane coupling agent is preferable because it has extremely high ink repellency. Further, an inorganic oxide layer may be provided between the nozzle substrate and the ink repellent layer in order to improve adhesion by making many hydroxyl groups serving as bonding points with the fluorine-based silane coupling agent. The inorganic oxide layer _SiO 2, TiO _2, etc. is used, the film thickness is preferably from 10～2000A, more preferably from 100 to 1000 Å.
The type of fluorine-based silane coupling agent is not particularly limited, but a preferred example is modified perfluoropolyoxetane (Optool DSX manufactured by Daikin Industries). In this case, the film thickness is preferably 1 to 200 mm, more preferably 10 to 100 mm.
The ink-repellent layer made of a fluorinated silane coupling agent has a chemical bond with the underlying layer, so it has high mechanical durability, but it is resistant to chemical hazards that break the bond like ink contact. Therefore, the ink wettability is greatly improved by using the ink of the present invention.

In addition to fluorine surfactants and ether urethane resin emulsions, inks that contain ester / ether urethane resin emulsions also contain repellents that contain fluorine silane coupling agents compared to inks that do not contain ester / ether urethane resin emulsions. Ink does not adhere to the nozzle surface on which the ink layer is formed, and as a result, ejection is also stabilized.
This is because the ester / ether urethane resin emulsion has a particularly strong interaction with the fluorosurfactant, so when the resin emulsion deposited on the nozzle surface is scraped off by wiping, the fluorine adsorbed on the nozzle surface This is considered to be because the fluorosurfactant can also be peeled off together and the fluorosurfactant does not remain on the nozzle surface.
Therefore, according to the present invention, ink jet recording ink that can be used in a highly reliable state with improved ejection failure due to a decrease in ink repellency associated with adhesion or adhesion of dry ink, particularly extremely high ink repellency. An ink for ink jet recording can be provided which is effective even for a nozzle ink repellent layer containing a fluorine-based silane coupling agent having the above. In addition, an ink jet recording method, an ink cartridge, and a recorded matter using the ink can be provided.
Further, according to the invention of claim 2, since the effect of preventing the ink sticking to the nozzle is great, there is no disturbance in ejection.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated further more concretely, this invention is not limited by these Examples. “Part”, “% solid content”, and “% aqueous dispersion” are all based on weight.

・イオン交換水 ８０．０部 [Preparation of pigment dispersion]
<Pigment dispersion C1>
Using a material having the following formulation, a dispersant represented by the following structural formula (5) was added to water, dissolved, and mixed and stirred with HELIOGENBlue D7079. (WAB) was filled with φ0.5 mm zirconia beads and kneaded at 2000 rpm for 60 minutes. The mill base was taken out and filtered through a 1 μm filter to obtain a pigment dispersion C1.
Pigment: HELIOGENBlue D7079 15.0 parts (CI Pigment Blue 15: 3, manufactured by BASF Japan)
-5.0 parts of a dispersant represented by the following structural formula (5)

・ Ion exchange water 80.0 parts

<Pigment dispersion C2>
The pigment dispersion is the same as the pigment dispersion C1, except that the dispersant is changed to the one represented by the following structural formula (6) (in the above structural formula (4), 1 = 0, k = 50). C2 was produced.

<Pigment dispersion Y1>
A pigment dispersion Y1 was produced in the same manner as the pigment dispersion C1, except that the pigment was changed to TONER YELLOW 3GP (CI Pigment Yellow 155, manufactured by Clariant Japan).

<Pigment dispersion Y2>
Except that the pigment was changed to HANSA Yellow 5GX01 (CI Pigment Yellow 74, manufactured by Clariant Japan) and the dispersant was changed to the one represented by the structural formula (6), the same as in the pigment dispersion C1. Thus, a pigment dispersion Y2 was produced.

<Pigment dispersion M1>
Pigment was treated with HOSTAPERM PINK EB Trans. (C.I. Pigment Red 122, manufactured by Clariant Japan), except that the dispersant was changed to that represented by the structural formula (6), the pigment dispersion M1 was changed in the same manner as the pigment dispersion C1. Produced.

<Pigment dispersion M2>
Except that the pigment was changed to CINQUASIA PACIFIC Red 2020 (CI Pigment Violet 19, manufactured by Ciba Specialty Chemicals) and the dispersant was changed to that represented by the structural formula (6), pigment dispersion C1 and Similarly, a pigment dispersion M2 was produced.

Example 1
Using materials of the following formulation, materials other than the pigment dispersion C1 are dissolved in ion-exchanged water, a vehicle is prepared and sufficiently stirred, then mixed with the pigment dispersion C1, filtered through a 1 μm filter, and inkjet A cyan ink for recording was obtained.
<Ink prescription>
・ Pigment dispersion C1 30 parts ・ Superflex 150 3 parts (Ester / ether urethane resin emulsion, solid content 30%, manufactured by Daiichi Kogyo Seiyaku)
・ Superflex 110 5 parts (ether urethane resin emulsion, solid content 30%, manufactured by Daiichi Kogyo Seiyaku)
· FTERGENT 110 1 part (fluorine surfactant _{C 12 H 4 F 11 -O-} SO 3 Na, Ltd. Neos)
・ Glycerin 12 parts ・ D-sorbitol 12 parts ・ Triethanolamine 0.1 part ・ Proxel LV (manufactured by Avecia, antiseptic / antifungal agent) 0.1 part ・ Ion-exchanged water 36.8 parts

Example 2
A yellow ink for ink jet recording was obtained in the same manner as in Example 1 using materials having the following formulation.
<Ink prescription>
・ Pigment dispersion Y1 30 parts ・ Superflex 126 2 parts (Ester / ether urethane resin emulsion, solid content 30%, manufactured by Daiichi Kogyo Seiyaku)
・ W-6061 3 parts (ether urethane resin emulsion, solid content 35%, manufactured by Mitsui Takeda Chemical)
Poly Fox PF-156A 2 parts [structural formula _{(2), Rf: -CF 2} CF 3, M: ammonium, q = 6, 30% solids
(Omnova)
-Glycerin 5 parts-1,5-pentanediol 15 parts-2-amino-2-ethyl-1,3-propanediol 0.2 parts-Proxel LV (Abesia, antiseptic / antifungal agent) 0.1 parts Ion-exchanged water 42.7 parts

Example 3
A black ink for ink jet recording was obtained in the same manner as in Example 1 using materials having the following formulation.
<Ink prescription>
-50 parts of CAB-O-JET300 (self-dispersing carbon black dispersion, manufactured by Cabot Corporation)
・ Superflex 361 3 parts (Ester / ether urethane resin emulsion, solid content 25%, manufactured by Daiichi Kogyo Seiyaku)
・ Superflex 110 3 parts (ether urethane resin emulsion, solid content 30%, manufactured by Daiichi Kogyo Seiyaku)
Poly Fox PF-156A 3 parts [structural formula _{(2), Rf: -CF 2} CF 3, M: ammonium, q = 6, 30% solids
(Omnova)
・ Glycerin 5 parts ・ Propylene glycol 15 parts ・ Johncrill 632 3 parts (acrylic resin emulsion, solid content 42%, manufactured by BASF Japan)
・ Lithium hydroxide 0.1 part ・ Proxel LV (manufactured by Avecia, antiseptic / antifungal agent) 0.1 part ・ Ion-exchanged water 17.8 parts

Example 4
A magenta ink for ink jet recording was obtained in the same manner as in Example 1 using materials having the following formulation.
<Ink prescription>
・ Pigment dispersion M1 50 parts ・ Superflex 150H 1.5 parts (Ester / ether urethane resin emulsion, solid content 30%, manufactured by Daiichi Kogyo Seiyaku)
・ W-5661 1.5 parts (ether urethane resin emulsion, solid content 35%, manufactured by Mitsui Takeda Chemical Co., Ltd.)
・ Zonyl FS-300 2 parts [Structural Formula (3), r = 1-7, s = 1, solid content 40%, manufactured by DuPont]
・ Urea 7 parts ・ Tetramethylolpropane 14 parts ・ 2,2,4-trimethyl-1,3-pentanediol 2 parts ・ Proxel LV (manufactured by Avecia, antiseptic / antifungal agent) 0.1 part ・ Ion-exchanged water 21. 9 copies

Example 5
A magenta ink for ink jet recording was obtained in the same manner as in Example 1 using materials having the following formulation.
<Ink prescription>
・ Pigment dispersion M2 50 parts ・ Superflex 126 3 parts (Ester / ether urethane resin emulsion, solid content 30%, manufactured by Daiichi Kogyo Seiyaku)
・ Superflex 110 5 parts (ether urethane resin emulsion, solid content 30%, manufactured by Daiichi Kogyo Seiyaku)
・ Zonyl FS-300 2.5 parts [Structural Formula (3), r = 1-7, s = 1, solid content 40%, manufactured by DuPont]
・ Glycerin 8 parts ・ Diethylene glycol monobutyl ether 24 parts ・ Johncrill 7100 5 parts (styrene-acrylic resin emulsion, solid content 48%, manufactured by BASF Japan)
・ Proxel LV 0.1 part ・ Ion-exchanged water 2.4 part

Example 6
A cyan ink for ink jet recording was obtained in the same manner as in Example 1 using materials having the following formulation.
<Ink prescription>
-Pigment dispersion C2 30 parts-Superflex 126 1.5 parts (Ester / ether urethane resin emulsion, solid content 30%, manufactured by Daiichi Kogyo Seiyaku)
・ W-5661 2.5 parts (ether urethane resin emulsion, solid content 35%, manufactured by Mitsui Takeda Chemical Co., Ltd.)
Poly Fox PF-136A 1.5 parts [structural formula _{(2), Rf: -CF 3} , M: ammonium, q = 6, 30% solids
(Omnova)
・ Glycerin 5 parts ・ 3-methyl-1,3-butanediol 15 parts ・ 2-ethyl-1,3-hexanediol 2 parts ・ Lumiflon FE4500 2 parts (fluorine resin emulsion, solid content 50%, manufactured by Asahi Glass Co., Ltd.)
・ Triethanolamine 0.1 part ・ Proxel LV (manufactured by Avecia, antiseptic / antifungal agent) 0.1 part ・ Ion-exchanged water 40.3 part

Example 7
A yellow ink for ink jet recording was obtained in the same manner as in Example 1 using materials having the following formulation.
<Ink prescription>
-Pigment dispersion Y2 30 parts-Superflex 126 1.5 parts (Ester / ether urethane resin emulsion, solid content 30%, manufactured by Daiichi Kogyo Seiyaku)
・ W-5661 4 parts (ether urethane resin emulsion, solid content 35%, manufactured by Mitsui Takeda Chemical Co., Ltd.)
Poly Fox PF-151N 1 part [structural formula (1) ^{R 1} is _{H, Rf: -CF 2 CF 3} , m = 20, n + p = 4~8,
(50% solid content, made by Omninova)
・ Glycerin 12 parts ・ 1,6-hexanediol 18 parts ・ 2,2,4-trimethyl-1,3-pentanediol 2 parts ・ DOW CORNING TORAY L-7604 1 part (Polyether-modified silicone oil, Toray Dow Corning (Made by company)
2-amino-2-ethyl-1,3-propanediol 0.2 part Proxel LV 0.1 part Ion-exchanged water 30.2 parts

Example 8
A magenta ink for ink jet recording was obtained in the same manner as in Example 1 using materials having the following formulation.
<Ink prescription>
・ Pigment dispersion M1 50 parts ・ Superflex 126 2 parts (Ester / ether urethane resin emulsion, 30% aqueous dispersion, manufactured by Daiichi Kogyo Seiyaku)
-W-5661 3 parts (ether urethane resin emulsion, 35% aqueous dispersion, manufactured by Mitsui Takeda Chemical Co., Ltd.)
Poly Fox PF-151N 1 part [structural formula (1) ^{R 1} is _{H, Rf: -CF 2 CF 3} , m = 20, n + p = 4~8,
(50% solid content, made by Omninova)
・ Glycerol 7 parts ・ 1,3-butanediol 21 parts ・ 2-ethyl-1,3-hexanediol 2 parts ・ AP4710 3 parts (acrylic silicone resin emulsion, manufactured by Showa Polymer Co., Ltd.)
・ KF-353 1 part (Polyether-modified silicone oil, manufactured by Shin-Etsu Chemical Co., Ltd.)
・ 0.2 parts of 2-amino-2-ethyl-1,3-propanediol ・ 0.1 part of Proxel LV (manufactured by Avecia, antiseptic / antifungal agent) 9.7 parts of ion-exchanged water

Comparative Example 1
A magenta ink for ink-jet recording is obtained in the same manner as in Example 4 except that Zonyl FS-300 of Example 4 is changed to Dispanol TOC (polyoxyalkylene derivative, solid content: 100%, manufactured by NOF Corporation). It was.

Comparative Example 2
For inkjet recording in the same manner as in Example 7 except that Polyfox PF-151N in Example 7 was changed to Surfynol 465 (acetylene surfactant, solid content: 100%, manufactured by Nissin Chemical Industry). A yellow ink was obtained.

Comparative Example 3
A cyan ink for ink jet recording was obtained in the same manner as in Example 6 except that W-5661 (ether urethane resin emulsion) of Example 6 was not added.

Comparative Example 4
A cyan ink for inkjet recording was obtained in the same manner as in Example 6 except that Superflex 126 (ester / ether urethane resin emulsion) of Example 6 was not added.

Comparative Example 5
A yellow ink for inkjet recording was obtained in the same manner as in Example 2 except that Superflex 126 (ester / ether urethane resin emulsion) in Example 2 was not added.

Comparative Example 6
A black ink for ink jet recording was obtained in the same manner as in Example 3 except that Superflex 361 (ester / ether urethane resin emulsion) of Example 3 was not added.

Table 1 shows the ink physical properties of Examples 1 to 8 and Comparative Examples 1 to 6. The measurement method is as follows.
(1) Viscosity Using RC-500 manufactured by Toki Sangyo, ink was measured at 25 ° C. immediately after preparation (initial) and after being left at 50 ° C. for 1 month (time). The change rate in the table is the change rate (%) of the viscosity with time relative to the initial viscosity. If the rate of change is within ± 10%, the storage stability is good, and if it exceeds ± 10%, it can be judged that the storage stability is poor.
(2) Surface tension Using a CBVP-Z type manufactured by Kyowa Interface Science, the ink immediately after preparation (initial) was measured at 25 ° C.
(3) pH
Measurement was performed at 25 ° C. for the ink immediately after preparation (initial stage) using Shin Dengen Kogyo pH BOY-P2.

Example α
The nozzle plate of the printer head is formed on a polyimide film (without DuPont Kapton particles added) by forming a SiO ₂ layer having a thickness of about 10 mm by sputtering, and then modified perfluoropolyoxetane having a thickness of about 50 mm by vacuum evaporation. An ink repellent layer of (Optool DSX manufactured by Daikin Industries, Ltd.) was formed, and nozzle holes were processed with an excimer laser from the polyimide film side.

Comparative Example α
On the surface of the Ni electroforming nozzle, a silicone resin (SR 2411 manufactured by Toray Dow Corning Silicone Co., Ltd.) was applied with a dispenser to form a silicone layer having a thickness of 1.2 μm.
At this time, the nozzle hole and the back surface of the nozzle plate were masked with a water-soluble resin, and after the silicone layer was formed, it was peeled and removed, and then left to stand at room temperature for 2 days and cured to form an ink repellent layer.

The nozzle plate produced by the above method is set in a printer (IPSiO G707 manufactured by Ricoh), the ink for ink jet recording of Examples and Comparative Examples is filled and set in an ink cartridge, and the ejection stability and nozzle surface are as follows. Adhesion evaluation was performed.

<Discharge stability evaluation>
Print continuously for 10 minutes using the printer with the nozzle plate set, put a moisturizing cap with the ink on the head surface, leave the printer in a 50 ° C 60% RH environment for 1 month, and then clean it. Implemented and returned to the same level as before. Thereafter, an intermittent printing test was conducted under the following conditions to evaluate the discharge stability.
That is, after printing the following print pattern charts continuously for 20 sheets, the printer is put into a pause state in which printing is not performed for 20 minutes. This is repeated 50 times, and after a total of 1000 sheets are printed, the same chart is printed again. The presence or absence of streaks, white spots, and jet disturbances in the 5% chart solid part was examined. The evaluation was performed visually according to the following criteria. In addition, the printing pattern printed each ink at 100% duty in a chart in which each color printing area is 5% in the entire area of the paper. The printing conditions were a recording density of 360 dpi and one-pass printing.
The evaluation criteria are as follows, and only rank A is an allowable range. The evaluation results are shown in Table 2.
〔Evaluation criteria〕
A: There are no streaks, white spots, or jet disturbance in the solid part.
B: Streaks, white spots, and jet disturbance are slightly observed in the solid portion.
C: Streaks, white spots, and jet turbulence are observed throughout the solid portion.

<Nozzle surface adhesion evaluation>
Put the printer in a constant temperature and humidity chamber, set the environment in the bath to a temperature of 32 ° C and a humidity of 30%. After printing the following print pattern charts continuously for 20 sheets, put the printer into a resting state in which printing is not performed for 20 minutes. It was repeated 50 times, and after a total of 1,000 copies were printed, the nozzle plate was observed with a microscope to determine the presence or absence of sticking.
In addition, the printing pattern printed each ink at 100% duty in a chart in which each color printing area is 5% in the entire area of the paper. The printing conditions were a recording density of 300 dpi and one-pass printing. The evaluation criteria are as follows, and only rank A is an allowable range. The evaluation results are shown in Table 2.
〔Evaluation criteria〕
A: No sticking near the nozzle
B: There is sticking near the nozzle
C: Adhering to the entire surface of the nozzle plate

  Based on the above results, the inks of Examples 1 to 8 are those of Comparative Examples 1 and 2 that do not contain a fluorosurfactant, with respect to the inkjet head having an ink repellent layer made of a fluororesin (modified perfluoropolyoxetane). Compared with ink, it has superior ejection stability and sticking evaluation, and it has superior ejection stability compared with the ink of Comparative Example 3 that does not contain an ether-based urethane resin emulsion. Furthermore, it is an ester / ether-based urethane resin emulsion. As compared with the inks of Comparative Examples 4 to 6 that do not contain, it was found that the ejection stability and the adhesion evaluation were excellent.

It is an element enlarged view showing an example of an ink jet head.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1b Common liquid chamber 2a Fluid resistance part 2b Pressurized liquid chamber 2c Communication port 3a Nozzle 6a Convex part 6b Diaphragm part 6c Ink inlet 10 Frame 20 Channel plate 30 Nozzle plate 40 Base 50 Multilayer piezoelectric element 60 Vibration plate 70 Adhesive layer

Claims (5)

  Contains at least a colorant pigment, resin emulsions A and B, a fluorosurfactant, a water-soluble solvent, and water, the resin emulsion A is an ester / ether urethane resin emulsion, and the resin emulsion B is an ether urethane resin emulsion An ink for ink-jet recording, comprising: The ink for inkjet recording according to claim 1, wherein the fluorine-based surfactant contains a compound represented by any one of the following structural formula (1), structural formula (2), and structural formula (3).

In the above formula, R ¹ represents any ^one of hydrogen, an alkyl group, and an acyl group, Rf represents —CF ₃ or —CF ₂ CF ₃ , m is an integer of 10 to 30, and n and p are n + p. = A positive integer satisfying 4-10.

In the above formula, M represents any one of alkali metal, ammonium, phosphonium, and alkanolamine, Rf represents —CF ₃ or —CF ₂ CF ₃ , and q is an integer of 4 to 10.

In the above formula, r is an integer of 0 to 10, and s is an integer of 0 to 40.   An ink jet recording method comprising: discharging an ink for ink jet recording according to claim 1 or 2 using an ink jet recording apparatus including an ink jet head having an ink repellent layer made of a fluorine resin.   An ink cartridge containing the ink for ink jet recording according to claim 1 or 2.   A recorded matter recorded using the ink for ink jet recording according to claim 1.

Images