WO2014136569A1 - Ink composition, inkjet recording method and colored body - Google Patents

Abstract

Provided are: an ink composition which does not cause a mottling phenomenon even in cases where a recording is made on a record-receiving material that has a low ink absorbing capacity, and which provides a recorded image having a high print density; an inkjet recording method which uses this ink composition; and a colored body which is colored by this ink composition. An ink composition of the present invention contains a compound represented by formula (1), a coloring agent, a water-soluble organic solvent and water. The content of the compound represented by formula (1) in the total mass of the ink composition is 0.1-3% on a mass basis. In the formula, R₁ represents a hydroxy group, a hydroxyalkoxy group, an acyloxy group or an arylcarbonyloxy group; R₂ represents a hydrogen atom or an alkyl group; R₃ represents a hydrogen atom or an alkyl group; R₄ represents a hydrogen atom, a hydroxy group or an alkyl group; and R₅ represents an alkyl group.

Description

Ink composition, ink jet recording method, and colored body

The present invention relates to an ink composition used in an ink jet recording method, an ink jet recording method using the ink composition, and a colored body colored with the ink composition.

A recording method using an ink jet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to a recording material such as paper to perform recording. Due to recent advances in inkjet technology, inkjet recording methods have come to be used in the field of high-definition printing that has been realized by silver salt photography and offset printing.

In the ink jet recording method using water-based ink, in addition to a recording medium having an ink receiving layer such as ink jet dedicated paper; ink jet glossy paper; etc., recording not having an ink receiving layer such as general-purpose plain paper having a low ink absorption capability A medium is also used. Among these, since the ink hardly penetrates into the latter recording medium, a phenomenon called “mottling” may occur particularly when an aqueous pigment ink is used.

The mottling phenomenon is, for example, that when an image with a large amount of ink such as a solid image is recorded, the amount of ink adhering exceeds the ink absorption capacity of the material to be recorded, so that it is not uniformly absorbed by the material to be recorded. This is a phenomenon in which unabsorbed ink droplets are unevenly distributed and fixed on a recording material to cause irregular image unevenness. Since recording on a recording material not having an ink receiving layer is also actively performed, suppression of the mottling phenomenon is considered as one major issue.

In order to solve the above problems, attempts have been made to suppress the mottling phenomenon by adding a surfactant or penetrant to the ink.
Patent Document 1 discloses an ink capable of obtaining a high-quality image on a non-absorbent medium by adding a silicone-based or fluorine-based surfactant and an alkanediol such as 1,2-hexanediol. ing.
Patent Documents 2 and 3 disclose inks and recording liquids that control the permeability of ink into plain paper and are capable of obtaining high-quality images on plain paper.
Patent Document 4 discloses a paint containing a compound represented by the formula (1) described later as a film-forming aid.

International Publication No. 2008/105289 JP 2003-213179 A JP 2003-253167 A JP 2006-182943 A

The present invention relates to an ink composition that does not cause a mottling phenomenon even when recording on a recording material having a low ink absorption capability, and gives a recorded image with a high print density, an ink jet recording method using the ink composition, and It is an object to provide a colored body colored with the ink composition.

As a result of intensive studies to solve the above-described problems, the present inventors have at least a specific amount of the compound represented by the formula (1), a colorant, a water-soluble organic solvent, water, The present invention has been completed by finding that the above-mentioned problems can be solved by using an ink composition containing.

［式（１）中、Ｒ_１はヒドロキシ基、ヒドロキシ基を有するアルコキシ基、アシロキシ基、又はアリールカルボニルオキシ基を表し、Ｒ_２は水素原子又はアルキル基を表し、Ｒ_３は水素原子又はアルキル基を表し、Ｒ_４は水素原子、ヒドロキシ基、又はアルキル基を表し、Ｒ_５はアルキル基を表す。］
［２］
　上記式（１）において、Ｒ_１がヒドロキシ基又はヒドロキシ基を有するアルコキシ基である、上記［１］に記載のインク組成物。
［３］
　上記式（１）において、Ｒ_１がヒドロキシ基である、上記［１］に記載のインク組成物。
［４］
　上記式（１）において、Ｒ_１がヒドロキシ基であり、Ｒ_２がアルキル基であり、Ｒ_３がアルキル基であり、Ｒ_４が水素原子又はヒドロキシ基であり、Ｒ_５がアルキル基である、上記［１］に記載のインク組成物。
［５］
　上記式（１）において、Ｒ_１がヒドロキシ基であり、Ｒ_２が分岐鎖アルキル基であり、Ｒ_３が直鎖アルキル基であり、Ｒ_４が水素原子又はヒドロキシ基であり、Ｒ_５が分岐鎖アルキル基である、上記［１］に記載のインク組成物。
［６］
　上記［１］～［５］のいずれか一項に記載のインク組成物の液滴を、記録信号に応じて吐出させて被記録材に付着させることにより記録を行うインクジェット記録方法。
［７］
　上記被記録材が情報伝達用シートである上記［６］に記載のインクジェット記録方法。
［８］
　上記［１］～［５］のいずれか一項に記載のインク組成物により着色された着色体。
［９］
　上記［１］～［５］のいずれか一項に記載のインク組成物を含有する容器が装填されたインクジェットプリンタ。 That is, the present invention relates to the following [1] to [9].
[1]
An ink composition comprising a compound represented by the following formula (1), a colorant, a water-soluble organic solvent, and water, represented by the following formula (1) in the total mass of the ink composition: An ink composition having a content of 0.1 to 3% by mass.

[In formula (1), R ₁ represents a hydroxy group, an alkoxy group having a hydroxy group, an acyloxy group, or an arylcarbonyloxy group, R ₂ represents a hydrogen atom or an alkyl group, and R ₃ represents a hydrogen atom or an alkyl group. R ₄ represents a hydrogen atom, a hydroxy group, or an alkyl group, and R ₅ represents an alkyl group. ]
[2]
The ink composition according to the above [1], wherein in the formula (1), R ₁ is a hydroxy group or an alkoxy group having a hydroxy group.
[3]
The ink composition according to [1], wherein in formula (1), R ₁ is a hydroxy group.
[4]
In the above formula (1), R ₁ is a hydroxy group, R ₂ is an alkyl group, R ₃ is an alkyl group, R ₄ is a hydrogen atom or a hydroxy group, and R ₅ is an alkyl group. The ink composition according to the above [1].
[5]
In the above formula (1), R ₁ is a hydroxy group, R ₂ is a branched alkyl group, R ₃ is a linear alkyl group, R ₄ is a hydrogen atom or a hydroxy group, and R ₅ is branched. The ink composition according to the above [1], which is a chain alkyl group.
[6]
An ink jet recording method for performing recording by ejecting the droplets of the ink composition according to any one of [1] to [5] according to a recording signal and attaching the droplets to a recording material.
[7]
The inkjet recording method according to [6], wherein the recording material is an information transmission sheet.
[8]
A colored body colored with the ink composition according to any one of [1] to [5] above.
[9]
An inkjet printer loaded with a container containing the ink composition according to any one of [1] to [5] above.

According to the present invention, an ink composition that does not cause a mottling phenomenon even when recording on a recording material having a low ink absorption capability and gives a recorded image with a high print density, and an ink jet recording method using the ink composition And a colored body colored with the ink composition.

Hereinafter, the present invention will be described in detail.
In this specification, “CI” means “color index”. In addition, in this specification, “%” and “parts” including examples and the like are described on a mass basis unless otherwise specified.

In the above formula (1), examples of the alkoxy group having a hydroxy group in R ₁ include hydroxy C1-C6 alkoxy, preferably hydroxy C1-C4 alkoxy, more preferably hydroxy C2-C4 alkoxy. Examples of the alkoxy moiety include straight-chain, branched-chain, or cyclic alkoxy, preferably straight-chain or branched-chain, more preferably straight-chain. Specific examples thereof include hydroxymethoxy, 2-hydroxyethoxy, 2-hydroxy-n-propoxy, 3-hydroxy-n-propoxy, 2-hydroxy-n-butoxy, 3-hydroxy-n-butoxy, 4-hydroxy- n-butoxy, 2-hydroxy-n-pentoxy, 3-hydroxy-n-pentoxy, 4-hydroxy-n-pentoxy, 5-hydroxy-n-pentoxy, 2-hydroxy-n-hexyloxy, 3-hydroxy-n- Straight chain such as hexyloxy, 4-hydroxy-n-hexyloxy, 5-hydroxy-n-hexyloxy, 6-hydroxy-n-hexyloxy; 2-hydroxyisopropoxy, 2-hydroxyisobutoxy, 3-hydroxyisobutoxy, 2-hydroxyisopentoxy, 3-hydroxyisope Branched chain such as toxi, 4-hydroxyisopentoxy, 2-hydroxyisohexyloxy, 3-hydroxyisohexyloxy, 4-hydroxyisohexyloxy, 5-hydroxyisohexyloxy; 2-hydroxycyclopropoxy, 2 -Cyclic compounds such as hydroxycyclobutoxy, 3-hydroxycyclobutoxy, 2-hydroxycyclopentoxy, 3-hydroxycyclopentoxy, 2-hydroxycyclohexyloxy, 3-hydroxycyclohexyloxy, 4-hydroxycyclohexyloxy; etc. Can be mentioned. Of these, 2-hydroxyethoxy is preferred.

Examples of the acyloxy group in R ₁ include linear, branched or cyclic normal C1-C6 acyloxy, preferably C1-C5 acyloxy, more preferably C2-C5 acyloxy groups. Among these, a straight chain is preferable. In addition to the ester carbonyl of the acyloxy moiety, an acyloxy group having one more carbonyl group is preferred. Specific examples thereof include straight-chain compounds such as methylcarbonyloxy, ethylcarbonyloxy, n-propylcarbonyloxy, n-butylcarbonyloxy, n-pentylcarbonyloxy; isopropylcarbonyloxy, isobutylcarbonyloxy, t-butylcarbonyl Branched chain such as oxy, isopentylcarbonyloxy, 1-ethylpropylcarbonyloxy, 1,1-dimethylpropylcarbonyloxy, 2,2-dimethylpropylcarbonyloxy; cyclopentylcarbonyloxy, cyclobutylcarbonyloxy, cyclopentylcarbonyloxy Cyclic ones such as 1-oxoethylcarbonyloxy, 2-oxopropylcarbonyloxy, 2-oxobutylcarbonyloxy, 3-oxobutylcarbonyloxy 2-oxo-pentyl carbonyloxy, 3- oxopentyloxy carbonyloxy, 4-oxo-pentylcarbonyl oxy such as those having one more carbonyl groups; and the like. Of these, 1-oxoethylcarbonyloxy and 3-oxobutylcarbonyloxy are preferable.

The arylcarbonyloxy group for R ₁ usually includes C6-C12 arylcarbonyloxy. Specific examples include phenylcarbonyloxy, naphthylcarbonyloxy, biphenylcarbonyloxy and the like. Among these, phenylcarbonyloxy is preferable.

Among the above, R ₁ is preferably a hydroxy group or an alkoxy group having a hydroxy group, more preferably a hydroxy group.

Examples of the alkyl group in R _{2 to} R ₅ include a normal C1-C6, preferably C1-C4 linear, branched, or cyclic alkyl group. Specific examples thereof include, for example, linear ones such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl; isopropyl, isobutyl, sec-butyl, t-butyl, isopentyl, t- Branched chain such as pentyl, isohexyl and t-hexyl; cyclic such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl; and the like.
Of these, R ₂ is preferably linear or branched, and more preferably branched. Among these, n-propyl, isopropyl and t-butyl are preferable, and isopropyl is particularly preferable.
R ₃ is preferably a straight chain, and methyl is particularly preferred among the above.
R ₄ is preferably linear or branched, and among these, n-propyl, isopropyl and t-butyl are preferable.
R ₅ is preferably linear or branched, and more preferably branched. Of these, ethyl, n-propyl, isopropyl and t-butyl are preferable, and isopropyl is particularly preferable.

Among the above, R ₁ is preferably a hydroxy group or an alkoxy group having a hydroxy group, more preferably a hydroxy group.
R ₂ is preferably an alkyl group, and more preferably a branched alkyl group.
R ₃ is preferably an alkyl group, and more preferably a linear alkyl group.
R ₄ is preferably a hydrogen atom or a hydroxy group.
R ₅ is preferably a branched alkyl group.

Of the above, a combination of preferable ones is more preferable, and a combination of more preferable ones is more preferable. The same applies to a combination of a preferable one and a more preferable one, a more preferable one, and a more preferable one.

Among the compounds represented by the above formula (1), a commercially available product is texanol manufactured by Eastman Chemical Company.

Specific examples of the compound represented by the formula (1) are listed in the following Table 1, but the present invention is not limited to these specific examples. Moreover, the abbreviations in Table 1 have the following meanings.
Ph: Phenyl i-Pr: Isopropyl n-Pr: Normal propyl t-Bu: Tertiary butyl Et: Ethyl

The content of the compound represented by the formula (1) in the total mass of the ink composition is usually 0.1 to 3%. If the content is less than 0.1%, the effect of improving the mottling phenomenon cannot be obtained. In particular, from the viewpoint of long-term storage stability, a content of 0.1 to 1.2% is preferable.
The ink composition may contain only one type of the compound represented by the formula (1), or may contain two or more types.

The colorant contained in the ink composition is not particularly limited, and pigments, disperse dyes, and the like can be used. Moreover, you may use these together as needed. However, the ink composition is an ink composition in which a colorant is dispersed, that is, a dispersed ink composition.

The pigment mainly includes inorganic pigments, organic pigments, extender pigments and the like, and any pigment can be used in the present invention. These pigments can also be combined. For example, extender pigments can be added to organic pigments.

Examples of inorganic pigments include carbon black; metal oxides, hydroxides, sulfides, ferrocyanides, and chlorides. In particular, carbon black is preferable as the black inorganic pigment. Examples of the carbon black include thermal black, acetylene black, oil furnace black, gas furnace black, lamp black, gas black, and channel black. One kind of these carbon blacks may be used, or a plurality of carbon blacks may be used in combination.

As the above carbon black, furnace black, lamp black, acetylene black, channel black and the like are preferable. Specific examples of the carbon black, for example, Raven760ULTRA, Raven780ULTRA, Raven790ULTRA, Raven1060ULTRA, Raven1080ULTRA, Raven1170, Raven1190ULTRA II, Raven1200, Raven1250, Raven1255, Raven1500, Raven2000, Raven2500ULTRA, Raven3500, Raven5000ULTRA II, Raven5250, Raven5750, Raven7000 (or, (Manufactured by Columbian Carbon); Monarch700, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Mona ch1300, Monarch1400, Regal1330R, Regal1400R, Regal1660R, Moguul L (above, manufactured by Cabot Corporation); Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW200C, Black Black FW200C , Printex U, Printex V, Printex 140U, Printex 140V, SpecIal Black 4, SpecIal Black 4A, SpecIal Black 5, Special Black 6 (manufactured by Degussa MA, 8) MA100, MA600, MCF-88, No. 25, no. 33, no. 40, no. 47, no. 52, no. 900, no. 2300 (manufactured by Mitsubishi Chemical Corporation);

Examples of organic pigments include soluble azo pigments, insoluble azo pigments, insoluble diazo pigments, condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, and A quinophthalone pigment is mentioned. One kind of these organic pigments may be used, or a plurality of organic pigments may be used in combination. Further, the above inorganic pigments can be used in combination. For example, an extender pigment may be used in combination for the purpose of improving the fluidity of the pigment.

Specific examples of organic pigments include C.I. I. Pigment Yellow 1, 2, 3, 12, 13, 14, 16, 17, 24, 55, 73, 74, 75, 83, 93, 94, 95, 97, 98, 108, 114, 128, 129, 138, 139, 150, 151, 154, 155, 180, 185, 193, 199, 202, and other yellow pigments; I. Pigment Red 5, 7, 12, 48, 48: 1, 57, 88, 112, 122, 123, 146, 149, 166, 168, 177, 178, 179, 184, 185, 202, 206, 207, 254, Red pigments such as 255, 257, 260, 264, and 272; I. Pigment Blue 1, 2, 3, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 25, 60, 66, 80, and the like; C.I. I. Violet pigments such as Pigment Violet 19, 23, 29, 37, 38, 50; I. Pigment Orange 13, 16, 68, 69, 71, 73 and other orange-brown pigments; C.I. I. Pigment Green 7, 36, 54 and other green pigments; C.I. I. And black pigments such as Pigment Black 1.

Examples of extender pigments include silica, calcium carbonate, talc, clay, barium sulfate, and white carbon. These extender pigments are not used alone and are usually used in combination with inorganic pigments or organic pigments.

As the disperse dye, for example, a known disperse dye such as azobenzene or anthraquinone may be used alone, or two or more kinds may be used in combination for the purpose of adjusting the hue.

Suitable disperse dyes include, for example, C.I. I. Dispers Yellow 9, 23, 33, 42, 49, 54, 58, 60, 64, 66, 71, 76, 79, 83, 86, 90, 93, 99, 114, 116, 119, 122, 126, 149, 160 163, 165, 180, 183, 186, 198, 200, 211, 224, 226, 227, 231, 237; I. Dispers Red 60, 73, 88, 91, 92, 111, 127, 131, 143, 145, 146, 152, 153, 154, 167, 179, 191, 192, 206, 221, 258, 283: C.I. I. Dispers Orange 9, 25, 29, 30, 31, 32, 37, 38, 42, 44, 45, 53, 54, 55, 56, 61, 71, 73, 76, 80, 96, 97; C.I. I. Dispers Violet 25, 27, 28, 54, 57, 60, 73, 77, 79, 79: 1; I. Dispers Blue 27, 56, 60, 79: 1, 87, 143, 165, 165: 1, 165: 2, 181, 185, 197, 202, 225, 257, 266, 267, 281, 341, 353, 354, 358 364, 365, 368 and the like.

A single pigment or disperse dye may be used as the colorant. Further, for the purpose of adjusting the hue of an image to be recorded, three or more kinds of inorganic pigments, organic pigments, and / or disperse dyes may be used in combination.
Further, a surface-treated pigment (also referred to as a self-dispersing pigment) in which a dispersibility-imparting group is chemically introduced on the surface of the pigment particle can be used.

The content of the colorant in the total mass of the ink composition is usually 1 to 30%, preferably 1 to 10%, more preferably 2 to 7%.

Examples of the water-soluble organic solvent contained in the ink composition include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, 1,2-hexanediol, and 1,6-hexanediol. C1-C6 alkanols such as trimethylolpropane; carboxylic acid amides such as N, N-dimethylformamide and N, N-dimethylacetamide; 2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one Lactams such as 1, cyclic ureas such as 1,3-dimethylimidazolidin-2-one and 1,3-dimethylhexahydropyrimido-2-one; acetone, 2-methyl-2-hydroxypentan-4-one , Ketones such as ethylene carbonate or keto alcohols; tetrahydro Cyclic ethers such as run and dioxane; ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol , Triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, mono-, oligo-, or polyalkylene glycols or thioglycols having C2-C6 alkylene units such as polypropylene glycol, thiodiglycol, dithiodiglycol; Polyol (triol) such as glycerin, hexane-1,2,6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monoallyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, propylene glycol monopropyl ether And C1-C4 alkyl ethers of polyhydric alcohols such as triethylene glycol monobutyl ether; γ-butyrolactone, dimethyl sulfoxide; polyethylene glycols having a molecular weight of 400, 800, 1540, or higher. These organic solvents may be used alone or in combination of two or more.
Among these, isopropanol, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,2-propylene glycol, glycerin, ethylene glycol monoallyl ether, ethylene glycol monoisopropyl ether, diethylene glycol monomethyl ether, propylene glycol monopropyl ether, etc. Is preferred.

The ink composition preferably further contains a dispersant in order to stabilize the dispersion state.

Examples of the dispersant include styrene and derivatives thereof; vinyl naphthalene and derivatives thereof; aliphatic alcohol esters of α, β-ethylenically unsaturated carboxylic acid, etc .; acrylic acid and derivatives thereof; maleic acid and derivatives thereof; itaconic acid and derivatives thereof Fumaric acid and derivatives thereof; vinyl acetate, vinyl alcohol, vinyl pyrrolidone, acrylamide, and derivatives thereof; at least two monomers selected from the group consisting of monomers; preferably at least one of which is A hydrophilic monomer), for example, a block copolymer, a random copolymer, a graft copolymer, and / or a salt thereof. Moreover, you may use together said various copolymer and / or those salts.
The weight average molecular weight of the dispersant is about 1000 to 30000, preferably about 1250 to 25000, more preferably about 1500 to 20000. The acid value is about 80 to 300, preferably 90 to 275, more preferably about 100 to 250.
The dispersant can also be obtained as a commercial product, and specific examples thereof include Jonkrill ^TM 61J, 67, 68, 450, 55, 555, 586, 678, 680, 682, all manufactured by BASF. 683, 690; B-36;
In the present specification, the superscript “TM” means a trademark.

The amount of the dispersant used relative to the colorant is usually 0.1 to 1 part, preferably 0.1 to 0.6 part, more preferably 0.2 to 0.4 part, with 1 part of the colorant. If the amount of the dispersant used is too small or too large, problems such as a decrease in the stability of the dispersion; deterioration of the image of the printed matter;

The pH of the ink composition is preferably pH 5 to 11 and more preferably pH 7 to 10 for the purpose of improving storage stability. The surface tension of the ink composition is preferably 10 to 50 mN / m, more preferably 20 to 40 mN / m. Furthermore, the viscosity of the ink composition is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less.

When the ink composition is used as an ink for inkjet recording, the content of inorganic impurities such as metal cation chloride (for example, sodium chloride) and sulfate (for example, sodium sulfate) contained in the ink composition of the present invention. Is preferably used in a small amount. In general, inorganic impurities are often contained in colorants obtained as commercial products. The standard of the inorganic impurity content is about 1% or less with respect to the total mass of the colorant, and the lower limit may be the detection limit of the analytical instrument or less, that is, 0%. As a method for obtaining a colorant having a small amount of inorganic impurities, for example, a method using a reverse osmosis membrane; a dry product of a colorant or a wet cake is suspended and stirred in a mixed solvent of (C1-C4) alcohol such as methanol and water; Desalting treatments such as a method of filtering and separating a colored body and drying; a method of exchanging and adsorbing inorganic impurities with an ion exchange resin;

In the preparation of the ink composition, for example, antiseptic / antifungal agent, pH adjuster, chelating reagent, rust preventive agent, water-soluble UV absorber, water-soluble polymer compound, antioxidant, surfactant, and further necessary Accordingly, an ink preparation agent such as a water-dispersible resin can be used as necessary.

Specific examples of the preservative include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloaryl sulfone, iodopropargyl, haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzo Thiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone , Benzyl bromacetate compounds, inorganic salt compounds and the like. Specific examples of organic halogen compounds include sodium pentachlorophenol, and specific examples of pyridine oxide compounds include, for example, sodium 2-pyridinethiol-1-oxide. Specific examples of isothiazoline compounds Are, for example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2 -Methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like. Specific examples of the other antiseptic / antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, trade name, Proxel ^TM GXL (S), Proxel ^TM XL-2 (S), and the like.

Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and salts thereof. .

As the pH adjuster, any substance can be used as long as it can control the pH within the above range without adversely affecting the prepared ink composition. Specific examples thereof include, for example, alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxide (ammonia water) Alkaline metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate and potassium carbonate; alkali metal salts of organic acids such as sodium silicate and potassium acetate; inorganic bases such as disodium phosphate;

Specific examples of the chelating reagent include, for example, disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.

Specific examples of the rust preventive include, for example, acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite and the like.

Specific examples of water-soluble ultraviolet absorbers include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

Specific examples of the water-soluble polymer compound include polyethylene glycol, polyvinyl alcohol, cellulose derivatives, polyamine, polyimine and the like.

As specific examples of the antioxidant, for example, various organic and metal complex anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocyclic rings. .

Specific examples of the surfactant include known surfactants such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a silicone surfactant, and a fluorine surfactant. Is mentioned.

Anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, polyoxyethylene alkyl ether sulfates, N-acyl amino acids or salts thereof, N-acyl methyl taurate salts , Alkyl sulfate polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethyl sulfosuccinate, diethylhexyl sulfosuccinate, dioctyl sulfosuccinate and the like, specific examples of those commercially available, for example, HITENOL ^{TM LA-10,} L -12, LA-16, neo HITENOL ^{TM ECL-30S, ECL-45} ( or more, Dai-ichi Kogyo Seiyaku Co., Ltd.).

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, imidazoline derivatives, etc. Is mentioned.

Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl -1-hexyne-3-acetylene glycol (alcohol) -based ol; Nissin Chemical Industry Co. trade name Surfynol ^RTM 104,105PG50,82,420,440,465,485, Olfine ^RTM STG; polyglycol ether (e.g. SIGMA-ALDRICH Corp. TergItol ^TM 15-S-7 and the like); and the like.

Examples of silicone surfactants include polyether-modified siloxane and polyether-modified polydimethylsiloxane. Commercially available products include BYK-345, BYK-348, BYK-3455 (manufactured by BYK Chemie, polyether-modified). Polydimethylsiloxane), BYK-347, BYK-349 (same as polyether-modified siloxane), and the like.

Examples of the fluorosurfactant include a perfluoroalkyl sulfonic acid compound, a perfluoroalkyl carboxylic acid compound, a perfluoroalkyl phosphate compound, a perfluoroalkyl ethylene oxide adduct, and a perfluoroalkyl ether group in the side chain. Examples of commercially available products include Zonyl TBS, FSP, FSA, FSN-100, FSN, FSO-100, FSO, FS-300, Capstone FS-30, FS-31 (and above). DuPont), PF-151N, PF-154N (Omnova), F-114, F-410, F-444, EXP. TF-2066, EXP. TF-2148, EXP. TF-2149, F-430, F-477, F-552, F-553, F-554, F-555, F-556, F-557, F-558, F-559, F-561, F- 562, R-40, R-41, RS-72-K, RS-75, RS-76-E, RS-76-NS, RS-77, EXP. TF-1540, EXP. Examples thereof include TF-1760 (manufactured by DIC), BYK-3440, BYK-3441 (manufactured by BYK Chemie).

The water-dispersible resin has a function of fixing the colorant in the ink composition to the recording material by forming a film at room temperature. The resin used for the water dispersible resin is not particularly limited, and examples thereof include urethane resins, polyester resins, acrylic resins, vinyl acetate resins, vinyl chloride resins, acrylic styrene resins, acrylic silicone resins, and the like. Can be mentioned.
The water-dispersible resin is used, for example, in the state of a resin emulsion dispersed in water as a continuous phase.
Some resin emulsions are commercially available. Specific examples thereof include, for example, Superflex ^™ 126, 150, 170, 210, 420, 470, 820, 830, 890 (urethane resin emulsion, manufactured by Daiichi Kogyo Seiyaku); Hydran ^™ HW-350, HW- 178, HW-163, HW-171, AP-20, AP-30, WLS-201, WLS-210 (urethane resin emulsion, manufactured by DIC); 0569, 0850Z, 2108 (styrene-butadiene resin emulsion, JSR) AE980, AE981A, AE982, AE986B, AE104 (acrylic resin emulsion, manufactured by Etec);
When the water-dispersible resin is used, the content of the water-dispersible resin in the total mass of the ink composition is usually 0.5 to 20%, preferably 1 to 15% in terms of solid content. When the amount is less than this range, it is difficult to obtain sufficient fixability for the recording material, and when the amount is more, normal ejection of ink droplets in ink jet recording may be hindered.

The above ink preparation agents can be used alone or in combination.
Among the ink preparation agents, preferred are nonionic, silicone, and fluorine surfactants. Specific examples thereof include Surfinol ^TM 104PG50, Surfinol ^TM 420, Surfinol ^TM 440, Surfinol ^TM 465, BYK-345, BYK-348, Capstone FS-30, FS-31 and the like. These surfactants may be used alone or in combination of two or more.

When the ink composition contains a surfactant, the total content of the surfactant is usually 0.1 to 3%, preferably 0.3 to 1%, based on the total mass of the ink composition. If it is 0.1% or less, the effect as a surfactant cannot be obtained, and if it is 3% or more, there is a problem in the dispersion stability of the pigment.

As a method for preparing the ink composition, for example, the pigment is stirred and mixed using a sand mill (also referred to as a bead mill), a roll mill, a ball mill, a paint shaker, an ultrasonic disperser, a microfluidizer, or the like. Add an aqueous colorant dispersion in which a colorant is dispersed using a known method, a water-soluble organic solvent, water, and an ink preparation agent as necessary, and mix by stirring, or use a homogenizer or the like. And a method of mixing and preparing each component by a known method such as mixing. The order of mixing each component is not particularly limited.

In the above ink composition, impurities can be removed by microfiltration using a membrane filter, glass filter paper or the like, if necessary. When the ink composition is used for inkjet recording, microfiltration is preferably performed. The pore diameter of the filter for performing microfiltration is usually 1 to 0.1 μm, preferably 0.8 to 0.1 μm.

The ink composition of the present invention can be used in various printing fields. For example, it is suitable for water-based ink for writing, water-based printing ink, information recording ink, textile printing, etc., particularly preferably used as ink for ink-jet recording, and it is preferably used in the ink-jet recording method described later.

The ink jet recording method of the present invention is a method for recording by ejecting droplets of the ink composition according to a recording signal and attaching them to a recording material. The ink nozzles used for recording are not particularly limited and can be appropriately selected according to the purpose.

The ink jet recording method may be any known method. For example, a charge control method that ejects ink using electrostatic attraction force; a drop-on-demand method that uses vibration pressure of a piezo element (also called a pressure pulse method); And an acoustic ink jet method in which ink is ejected using the radiation pressure; a thermal ink jet in which ink is heated to form bubbles and the generated pressure is used, that is, a bubble jet (registered trademark) method;
In the inkjet recording method, a method called a photo ink, in which a large number of inks having a low colorant content in the ink are ejected in a small volume; the content of the colorant in the ink having substantially the same hue. Including a method for improving image quality using a plurality of different inks; a method for improving the fixability of a colorant to a recording material by using a colorless and transparent ink and an ink containing a colorant in combination. .

The colored body means a material colored by the ink composition or an ink set containing the ink composition, and preferably includes a recording material colored by an ink jet recording method using an ink jet printer. The recording material is not particularly limited, but an information transmission sheet is preferable, and a non-hardly absorbable recording material is particularly preferable. Specific examples thereof include coated paper, and examples include finely coated paper, art paper, coated paper, matte paper, and cast paper.
Coated paper is paper whose surface is coated with a paint to enhance aesthetics and smoothness. Examples of the paint include a mixture of various clays such as talc, pyrophyllite, and kaolin, titanium oxide, magnesium carbonate, calcium carbonate, and the like, and starch and / or polyvinyl alcohol.
The paint can be applied to the paper using a coater in the paper manufacturing process, for example. There are two types of coaters: an inline system in which papermaking and coating are performed in one process by being directly connected to a papermaking machine, and an off-line system in which the process is separate from papermaking.
The finely coated paper refers to a recording paper having a coating amount of paint of 12 g / m ² or less. Art paper refers to recording paper obtained by applying a coating of about 40 g / m ^{2 to} high-grade recording paper (quality paper, paper with a chemical pulp usage rate of 100%). Coated paper and matte paper refer to recording paper coated with a paint of about 20 to 40 g / m ² . The cast paper refers to a recording paper obtained by finishing art paper or coated paper by applying pressure to the surface with a machine called a cast drum so that the gloss and the recording effect are further enhanced.
The effect obtained by the present invention is very suitably exhibited when such a non-hardly absorbable recording material is used.

Examples of the recording material include plain paper that does not have an ink receiving layer, media used for gravure printing, offset printing, and the like; ink jet dedicated paper that has an ink receiving layer, ink jet dedicated film, glossy paper, or gloss film Fiber and cloth (cellulose, nylon, wool, etc.); leather; base material for color filter; Here, among plain papers and the like that do not have an ink receiving layer, there are papers having low ink receptivity similar to the above-mentioned non-absorptive recording material. Even when such plain paper is used, the effects obtained by the present invention are exhibited very suitably.

In order to record on a recording material such as an information transmission sheet by the ink jet recording method of the present invention, for example, a container containing the above ink composition is set at a predetermined position of the ink jet printer, and recording is performed by the above recording method. Record it on the material.
In the ink jet recording method of the present invention, the ink composition of the present invention can be used in combination with an ink composition of each color such as green, blue (or violet), red (or orange), if necessary.
The ink composition of each color is poured into each container, and each container may be loaded into a predetermined position of the ink jet printer and used for ink jet recording in the same manner as the container containing the ink composition.

By using the ink composition of the present invention, not only inkjet special paper and general-purpose plain paper, but also a non-hardly absorbable recording material does not cause a mottling phenomenon and achieves a high print density. A recorded image can be obtained. In addition, an ink dot on the medium has high roundness, smoothness, and an image that does not impair glossiness. Furthermore, it is possible to obtain a recorded image excellent in various fastness properties such as scratch resistance, water resistance, light resistance, heat resistance, oxidation gas resistance (for example, ozone gas resistance).

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples.

[Preparation Example 1]: Preparation of Dispersion 1 11.3 parts of Joncryl 68 (MW: 13000) and 6 parts of triethanolamine were dissolved in 95.2 parts of ion-exchanged water and stirred for 1 hour. To the resulting solution, C.I. I. 37.5 parts of Pigment Blue 15: 3 (manufactured by Dainichi Seika Kogyo Co., Ltd., cyanine blue A220J) was added, and dispersion treatment was performed with a sand grinder at 1500 rpm for 20 hours. After 150 parts of ion-exchanged water was added dropwise to the obtained dispersion, this liquid was filtered to remove the dispersion beads, thereby obtaining a dispersion having a solid content of 19.2%. The resulting dispersion is referred to as “Dispersion 1”.

[Example 2]: Preparation of Ink of the Present Invention To the dispersion 1 obtained in Preparation Example 1, the components listed in Table 2 below were added and mixed with sufficient stirring. Thereafter, impurities were filtered off with a membrane filter having a pore size of 3 μm to obtain an ink composition for an evaluation test. The obtained ink composition is referred to as “ink composition of Example 2”.
In Table 2, the numerical value of each component means the number of copies. “Remainder” means that the total amount of the ink composition is adjusted to 100 parts by adding ion exchange water.

[Comparative Examples 1 to 4]: Preparation of Comparative Inks Comparative ink compositions of Comparative Examples 1 to 4 were prepared in the same manner as in Example 2 except that the components shown in Table 2 were used. .

[(A) Inkjet recording]
Using the ink compositions of Example 2 and Comparative Examples, respectively, with an ink-jet printer manufactured by Seiko Epson Corporation, trade name PX205, as a recording material for Pearl Coat N (Mitsubishi Paper: 127.9 g / m ² ) Inkjet recording was performed to obtain a colored product. Recording on the recording material was performed as a 100% duty image.
Each of the obtained colored bodies was used as a test piece, and the following evaluation test was performed.

[(B) Mottling test]
The state of mottling of each test piece obtained in [(A) Inkjet recording] was visually observed and evaluated according to the following three-stage evaluation criteria A to C. The evaluation results are shown in Table 3 below.
A: The mottling phenomenon is suppressed and the formed image is at a level with no problem in image performance.
B: Fine color unevenness of the image due to the Mottling phenomenon can be visually recognized.
C: The occurrence of the mottling phenomenon is conspicuous even visually, the formed image is non-uniform and the color unevenness is conspicuous.

[(C) Print density test]
The printing density of each test piece obtained in the above [(A) Inkjet recording] was measured with a densitometer manufactured by X-rite Co., Ltd., trade name: Spectro Eye. The measurement was performed under the conditions of an observation light source of D50, an observation field of view of 2 °, and a concentration of ANSI A. As a test piece, a solid printed matter in a state where 24 hours had passed after ink jet recording was used, and the reflection density Dc value of the recorded image was measured. The evaluation results are shown in Table 3 below.

As is apparent from the results in Table 3, the ink composition of the present invention containing the compound represented by the formula (1) has an excellent effect of suppressing the mottling phenomenon with respect to each of the comparative examples. High print density was shown.

[Examples 3 to 5]
An ink composition for an evaluation test was obtained in the same manner as in Example 2 except that the content of the compound represented by the above formula (1) was changed as described in Table 4 below. The obtained ink compositions are referred to as ink compositions of Examples 3 to 5, respectively.
In Table 4, the numerical value of each component means the number of copies. “Remainder” means that the total amount of the ink composition is adjusted to 100 parts by adding ion exchange water.

Using each of the ink compositions of Examples 3 to 5 obtained as described above, “(A) Inkjet recording”, “(B) Mottling test”, and “(C) Print density test are the same as described above. ”To evaluate its performance. The results are shown in Table 5 below.

From the results shown in Table 5, the printing density of Example 5 was equivalent to that of Comparative Example 2, but as for the effect of suppressing the mottling phenomenon, all of Examples showed results superior to those of Comparative Examples.
Further, when the ink composition of each example was allowed to stand overnight, in the ink compositions of examples 4 and 5, oil droplet-like separations were observed. This separation disappeared when the ink composition was re-stirred, but was observed in the same manner upon re-standing. This isolate was hardly observed when the content of the compound represented by the above formula (1) was 1.2%, but was observed when the content was 1.5%. Therefore, from the viewpoint of storage stability, the upper limit of the content of the compound represented by the above formula (1) is preferably 1.2%.

[Preparation Example 2]: Preparation of Dispersion 2 A block copolymer described in Synthesis Example 3 of International Publication No. 2013/115071 was prepared, and 6 parts of the resulting polymer dispersant was dissolved in 30 parts of 2-butanone. To obtain a uniform solution. A solution prepared by dissolving 0.44 parts of sodium hydroxide in 41 parts of ion-exchanged water was added to this liquid and stirred for 1 hour to prepare an emulsified solution. At this time, no crystals were precipitated. In addition, C.I. I. 20 parts of Pigment Blue 15: 3 (Cyanine Blue A220J manufactured by Dainichi Seika Kogyo Co., Ltd.) was added, and dispersion was performed with a sand grinder. Dispersion was performed at 1500 rpm for 15 hours. Thereafter, 100 parts of ion-exchanged water was added dropwise and filtered to remove the dispersing beads. Then, 2-butanone and water were distilled off under reduced pressure using an evaporator to obtain a cyan dispersion having a pigment solid content of 11.6%. . The solid content in the aqueous solution was measured by dry weight method using MS-70 manufactured by A & D Corporation. At this time, the pH was 9.3, the average particle size of the pigment was 106 nm, and the viscosity was 6.2 mPa · s. The resulting colored dispersion is referred to as “Dispersion 2”.

[Examples 6 and 7]: Preparation of Ink of the Present Invention To the dispersion liquid 2 obtained in Preparation Example 2, the components shown in Table 6 below were added and mixed with sufficient stirring. Thereafter, impurities were filtered off with a membrane filter having a pore size of 3 μm to obtain an ink for evaluation test.
In Table 6, the numerical value of each component means the number of copies. In addition, the remainder means that pure water was added to adjust the total amount of the ink composition to 100 parts.

Using each ink composition of Examples 6 and 7 obtained as described above, “(A) Inkjet recording”, “(B) Mottling test”, and “(C) Print density test” were performed in the same manner as described above. ”To evaluate its performance. The results are shown in Table 7 below.

As is clear from the results in Table 7, the ink composition of the present invention exhibited extremely excellent performance.

Since the ink composition of the present invention exhibits an effect of suppressing the mottling phenomenon and a high printing density, it is used for various recording inks, particularly for ink jet recording with respect to non-hardly absorbable recording materials that do not have an ink receiving layer. It is extremely useful as an ink.

Claims (9)

An ink composition comprising a compound represented by the following formula (1), a colorant, a water-soluble organic solvent, and water, represented by the following formula (1) in the total mass of the ink composition: An ink composition having a content of 0.1 to 3% by mass.

[In formula (1), R ₁ represents a hydroxy group, an alkoxy group having a hydroxy group, an acyloxy group, or an arylcarbonyloxy group, R ₂ represents a hydrogen atom or an alkyl group, and R ₃ represents a hydrogen atom or an alkyl group. R ₄ represents a hydrogen atom, a hydroxy group, or an alkyl group, and R ₅ represents an alkyl group. ] The ink composition according to claim 1, wherein, in the formula (1), R ₁ is a hydroxy group or an alkoxy group having a hydroxy group. The ink composition according to claim ₁ , wherein R ₁ in the formula (1) is a hydroxy group. In the above formula (1), R ₁ is a hydroxy group, R ₂ is an alkyl group, R ₃ is an alkyl group, R ₄ is a hydrogen atom or a hydroxy group, and R ₅ is an alkyl group. The ink composition according to claim 1. In the above formula (1), R ₁ is a hydroxy group, R ₂ is a branched alkyl group, R ₃ is a linear alkyl group, R ₄ is a hydrogen atom or a hydroxy group, and R ₅ is branched. The ink composition according to claim 1, which is a chain alkyl group. An ink jet recording method for performing recording by ejecting the droplets of the ink composition according to any one of claims 1 to 5 in accordance with a recording signal and attaching the droplets to a recording material. The ink jet recording method according to claim 6, wherein the recording material is an information transmission sheet. A colored body colored with the ink composition according to any one of claims 1 to 5. An ink jet printer loaded with a container containing the ink composition according to any one of claims 1 to 5.