JP2022191835A - Coloring composition, ink, and coating - Google Patents

Abstract

To provide a coloring composition that has excellent low-temperature dispersion stability and light resistance.SOLUTION: Provided is a coloring composition containing dispersant and colorant, in which the dispersant is a polymer containing an alkyl chain-containing monomer unit having 6 or more carbon atoms, an acid monomer unit, and an ultraviolet-absorbing monomer unit. Here, the alkyl chain-containing monomer unit having 6 or more carbon atoms is preferably an α-olefin unit. Moreover, it is preferable that the dispersant is a polymer further containing an alkyleneoxy chain.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a coloring composition, an ink containing the same, and a coated article.

Pigments and dyes are processed into dispersions and used for coloring inks, moldings, and the like. Among these, water-based inks are expected to be applied to various printed materials because of their low environmental load. However, the use of a colorant with low lightfastness may cause problems in long-term storage of printed matter. On the other hand, although there are pigments that are excellent in light resistance, they have problems with their dispersibility in ink, making it difficult to achieve both light resistance and dispersibility.

Therefore, Patent Documents 1 and 2 disclose colored compositions using resins having UV-absorbing monomer units.

WO 1999/067337 WO 11/118557

However, conventional coloring compositions have a low level of compatibility between dispersion stability and light resistance. In particular, when the coloring composition is stored at a low temperature, its dispersion stability is lowered, and when it is used as an ink, for example, there is a problem that the quality is lowered.

An object of the present invention is to provide a coloring composition that is excellent in low-temperature dispersion stability and light resistance.

The present invention is a colored composition containing a dispersant and a colorant, wherein the dispersant is a polymer containing an alkyl chain-containing monomer unit having 6 or more carbon atoms, an acid monomer unit, and an ultraviolet absorbing monomer unit. It relates to a coloring composition.

ADVANTAGE OF THE INVENTION According to said invention, the coloring composition which is excellent in dispersion stability and light resistance at low temperature can be provided.

First, the terms used in this specification are defined. "C.I." means Color Index (C.I.). Monomers and monomers are ethylenically unsaturated group-containing monomers. (Poly)alkyleneoxy groups include both polyalkyleneoxy groups and alkyleneoxy groups. An alkyleneoxy group is, for example, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, and the like. A unit in the (anhydride) maleic acid unit means one of repeating units constituting a polymer obtained by polymerizing a (anhydride) maleic acid monomer. Other monomer units are the same as above. Dispersants are compounds used to disperse pre-micronized colorants. The coated colorant is a colorant that is finely divided together with a resin and at least a part of the surface of which is coated with the resin.

The colored composition of the present invention is a dispersant, a colored composition containing a colorant, wherein the dispersant contains an alkyl chain-containing monomer unit having 6 or more carbon atoms, an acid monomer unit, and an ultraviolet absorbing monomer unit. It is characterized by containing a polymer.
The colored composition is preferably used for, for example, inkjet recording inks, flexographic printing inks, paints, stationery, textile printing agents, and toners.

[Coloring agent]
The coloring agent of the present invention can be appropriately selected from inorganic pigments, organic pigments, and dyes.

Examples of inorganic pigments include carbon black, metal oxides, metal complex salts, and other inorganic pigments. Examples of carbon black include furnace black, thermal lamp black, acetylene black, channel black and the like.
Examples of metal oxides include titanium oxide, iron oxide, iron hydroxide, zirconia, and alumina.
Examples of other inorganic pigments include ultramarine blue, yellow lead, zinc sulfide, and cobalt blue.

Examples of organic pigments include azo pigments, diazo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, dioxazine pigments, perylene pigments, perinone pigments, thioindigo pigments, anthraquinone pigments, quinophthalone pigments, and the like.

Organic pigments, in terms of color index, include, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 32, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 147, 148, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 266, 269, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214,
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34,
36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73,
C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63,
C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 79, 80
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28
C. I. Pigment Black 1, 7
C. I. Pigment White 1, 2, 4, 5, 6, 7, 11, 12, 18, 19, 21, 22, 23, 26, 27, 28 and the like.

Among these, C.I. I. Pigment Red 31, 48:1, 48:2, 48:3, 48:4, 57:1, 122, 146, 147, 148, 150, 170, 176, 177, 184, 185, 202, 242, 254, 255, 264, 266, 269,
C. I. Pigment Yellow 12, 13, 14, 17, 74, 83, 108, 109, 120, 150, 151, 154, 155, 180, 185, 213
C. I. Pigment Orange 36, 38, 43, 64, 73
C. I. Pigment Green 7, 36, 37, 58, 62, 63,
C. I. Pigment Blue 15:1, 15:3, 15:6, 16, 22, 60, 66,
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Brown 25,
C. I. Pigment Black 1, 7
C. I. Pigment White 6 is preferred.

The dye is preferably a disperse dye. Disperse dyes are dyes that have the property of sublimating upon heating. Disperse dyes include, for example, C.I. I. Disperse Yellow 3, 7, 8, 23, 39, 51, 54, 60, 71, 86; C.I. I. Disperse Orange 1, 1:1, 5, 20, 25, 25:1, 33, 56, 76; C.I. I. Disperse Brown 2; C.I. I. Disperse Thread 11, 50, 53, 55, 55:1, 59, 60, 65, 70, 75, 93, 146, 158, 190, 190:1, 207, 239, 240, 343; I. Bat Red 41; C.I. I. Disperse Violet 8, 17, 23, 27, 28, 29, 36, 57; C.I. I. Disperse Blue 19, 26, 26:1, 35, 55, 56, 58, 60, 64, 64:1, 72, 72:1, 81, 81:1, 91, 95, 108, 131, 141, 145 , 165, 359, 360 and the like.

A coloring agent can be used individually or in combination of 2 or more types.

The average primary particle size of the colorant is usually 5 to 1,000 nm. Incidentally, the average primary particle size is, for example, the average value of about 20 arbitrary particles selected from an enlarged image selected from a range of 2,000 to 100,000 times using a transmission electron microscope. If the particles are elliptical, the longitudinal axis length is used.

[Dispersant]
The dispersant contains alkyl chain-containing monomer units having 6 or more carbon atoms, acid monomer units, and UV-absorbing monomer units.

[Alkyl chain-containing monomer unit having 6 or more carbon atoms]
The alkyl chain-containing monomer unit having 6 or more carbon atoms is not particularly limited as long as it is a monomer unit containing an alkyl chain having 6 or more carbon atoms. . Among these, α-olefins are preferable from the viewpoint of copolymerizability with acid monomers and UV-absorbing monomers, and adsorption to the surface of colorants.

The α-olefin is preferably an α-olefin having 6 to 52 carbon atoms, more preferably 8 to 38 carbon atoms, even more preferably 12 to 38 carbon atoms. The number of carbon atoms in the alkyl chain of the α-olefin unit is the number of carbon atoms in the entire α-olefin minus 2.
α-olefins include, for example, 1-octene (8 carbon atoms), 1-nonene (9 carbon atoms), 1-decene (10 carbon atoms), 1-dodecene (12 carbon atoms), 1-tetradecene (14 carbon atoms), ), 1-hexadecene (16 carbon atoms), 1-octadecene (18 carbon atoms), 1-eicosene (20 carbon atoms), 1-docosene (22 carbon atoms), 1-tetracosene (24 carbon atoms), 1-octacosene (28 carbon atoms), 1-triacontene (30 carbon atoms), 1-dotriacontene (32 carbon atoms), 1-tetratriacontene (34 carbon atoms), 1-hexatriacontene (36 carbon atoms), 1 -octatriacontene (38 carbon atoms) and the like.

The alkyl group of the alkyl (meth)acrylate is chain-shaped and preferably has 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms. Alkyl (meth)acrylates are, for example, 2-ethylhexyl (meth)acrylate, (iso)octyl (meth)acrylate, (iso)decyl (meth)acrylate, (iso)dodecyl (meth)acrylate, (iso)stearyl (meth)acrylate. ) acrylate, (iso)behenyl (meth)acrylate and the like.

The alkyl chain-containing monomer units having 6 or more carbon atoms can be used alone or in combination of two or more.

[Acid monomer unit]
The acid monomer unit is one or more selected from the group consisting of (meth)acrylic acid units, unsaturated fatty acid units, and unsaturated dibasic acid units. These units are formed by polymerization of (meth)acrylic acid, unsaturated fatty acids, and unsaturated dibasic acids, respectively. In particular, unsaturated fatty acids and unsaturated dibasic acids are preferred because of their excellent copolymerizability with α-olefins. The unsaturated dibasic acid includes unsaturated dibasic acid anhydride.

The unsaturated fatty acid is preferably, for example, an unsaturated fatty acid having 6 or more carbon atoms, more preferably an unsaturated fatty acid having a double bond of 6 or more carbon atoms at its terminal. Examples include oleic acid, ricinoleic acid, ricinoleic acid and undecylenic acid. Among these, undecylenic acid is preferable from the viewpoint of copolymerizability.

The unsaturated dibasic acid is preferably, for example, an unsaturated dibasic acid having 4 to 10 carbon atoms, such as (anhydrous) maleic acid, fumaric acid, halogenated maleic anhydride, itaconic acid, citraconic anhydride, From the viewpoint of copolymerizability, (anhydrous) maleic acid and itaconic acid are preferred, and (anhydrous) maleic acid is particularly preferred.

Formation of (anhydride) maleic acid units uses at least one of maleic acid and maleic anhydride. Among these, maleic anhydride is preferable in terms of excellent copolymerizability.

Acid monomer units can be used alone or in combination of two or more.

[Ultraviolet absorbing monomer unit]
The UV-absorbing monomer unit is a UV-absorbing monomer unit represented by the general formula (1). The UV-absorbing monomer unit is preferably formed by polymerization of one selected from the group consisting of a benzotriazole skeleton, a triazine skeleton, and a benzophenone skeleton in which U in the general formula (1) has UV absorption. Among these, a benzotriazole skeleton is preferable from the viewpoint of cost and industrial availability. The monomers are described below for each skeleton that absorbs ultraviolet rays.

（一般式（１）中、Ｒ_１１は、水素原子及びメチル基からなる群より選択されるいずれかを表し、Ｕは、紫外線を吸収する骨格を有する炭化水素基であり、ヘテロ原子を含んでもよい。） General formula (1)

(In the general formula (1), R ₁₁ represents any one selected from the group consisting of a hydrogen atom and a methyl group, U is a hydrocarbon group having a skeleton that absorbs ultraviolet rays, and may contain a heteroatom. good.)

The monomer units represented by formula (1) can be used singly or in combination of two or more.

(monomer containing benzotriazole skeleton)
In the general formula (1), when U is a benzotriazole skeleton, examples thereof include monomers represented by the following chemical formulas (a1-1) to (a1-3-32).

(monomer containing triazine skeleton)
In the general formula (1), when U is a triazine skeleton, monomers represented by the following chemical formulas (a1-4-1) to (a1-4-21) are exemplified. Incidentally, the triazine skeleton is preferably a triphenyltriazine skeleton.

(monomer containing benzophenone skeleton)
In general formula (1), when U is a benzophenone skeleton, the following monomers may be mentioned.
Monomers having a benzophenone skeleton include, for example, 4-acryloyloxybenzophenone, 4-methacryloyloxybenzophenone, 2-hydroxy-4-acryloyloxybenzophenone, 2-hydroxy-4-methacryloyloxybenzophenone, 2-hydroxy-4-( 2-acryloyloxy)ethoxybenzophenone, 2-hydroxy-4-(2-methacryloyloxy)ethoxybenzophenone, 2-hydroxy-4-(2-methyl-2-acryloyloxy)ethoxybenzophenone, 2,2'-dihydroxy-4 -Methacryloyloxybenzophenone and the like.

Among the monomers represented by the general formula (1), 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole has polymerization controllability, cost, and UV absorption. It is preferable because of its excellent balance.

[Other monomer units]
The dispersant can contain other monomeric units. Other monomer units are not particularly limited as long as they are compounds containing one double bond in the molecule, but are formed by copolymerization of (meth)allyl monomers, vinyl monomers, and (meth)acrylic ester monomers in terms of copolymerizability. is preferable. (Meth)allyl monomers are particularly preferred due to their copolymerizability with α-olefins and (anhydride) maleic acid.

[(Meth)allyl monomer]
The (meth)allyl monomer is not particularly limited as long as it contains a (meth)allyl group, but a (meth)allyl ether monomer represented by the following general formula (2) is particularly preferred.

In general formula (2), R ₁ represents a hydrogen atom or a methyl group. R ₂ O represents an alkyleneoxy group, and two or more types of alkyleneoxy groups may be added randomly or in blocks. The alkyleneoxy group represented by R ₂ O is preferably an alkyleneoxy group having 2 to 5 carbon atoms from the viewpoint of dispersion stability.
Examples of the alkyleneoxy group having 2 to 5 carbon atoms include ethyleneoxy group, propyleneoxy group, butyleneoxy group and tetramethyleneoxy group. Among these, from the viewpoint of dispersibility, single addition of an ethyleneoxy group or a propyleneoxy group, or block or random addition of an ethyleneoxy group and a propyleneoxy group is preferable, and single addition of a propyleneoxy group, or an ethyleneoxy group and propylene Block or random addition of oxy groups is more preferred.

In general formula (2), m is an average number of moles of alkyleneoxy groups added, and is 0 or an integer of 1-100. From the viewpoint of the copolymerizability of the monomer and the adsorption rate of the dispersant to the colorant, it is preferably 1 to 60, more preferably 3 to 50, even more preferably 5 to 40.

In general formula ( ₂ ), R3 represents a hydrogen atom, or a linear or branched alkyl group, saturated acyl group, or phenyl group optionally substituted with an alkyl group. The linear or branched alkyl group includes a linear or branched alkyl group having 1 to 20 carbon atoms, preferably a methyl group, an ethyl group, an isopropyl group, or the like.
The saturated acyl group includes saturated acyl groups having 1 to 10 carbon atoms, and substituents derived from ethanoic acid, butanoic acid, propionic acid and butyric acid are preferred.
The phenyl group optionally substituted with an alkyl group includes, for example, a phenyl group, a naphthyl group, p-methylphenyl and the like.
Among these, R ₃ is preferably a linear or branched alkyl group, and most preferably a methyl group from the viewpoint of dispersion stability.

The compounds represented by the general formula (2) include, for example, alkyl (meth)allyl ethers such as methyl (meth)allyl ether and ethyl (meth)allyl ether; phenyl (meth)allyl ether, cyclohexyl (meth)allyl ether, etc. ring-containing (meth)allyl ether; hydroxyalkyl (meth)allyl ether such as 2-hydroxyethyl (meth)allyl ether, 4-hydroxybutyl (meth)allyl ether, (meth)allyl propionate, hexanoic acid (meth) and (meth)allyl esters such as allyl and (meth)allyl cyclohexanepropionate.
Moreover, the compound represented by the general formula (2) preferably has a (poly)alkyleneoxy group. Examples thereof include (poly)alkyleneoxy group-containing (meth)allyl ethers such as polyalkylene glycol (meth)allyl ethers, alkyleneoxy glycol (meth)allyl ethers, and alkoxypolyalkylene glycol (meth)allyl ethers. Among these, from the viewpoint of dispersion stability, it is preferable that a (poly)alkyleneoxy group is included, and an alkoxypolyalkyleneglycol (meth)allyl ether is more preferable.

Specifically, methoxyethylene glycol (meth) allyl ether, methoxy polyethylene glycol (meth) allyl ether, methoxypropylene glycol (meth) allyl ether, methoxy polypropylene glycol (meth) allyl ether, ethoxyethylene glycol (meth) allyl ether, Ethoxypolyethylene glycol (meth) allyl ether, ethoxypropylene glycol (meth) allyl ether, ethoxypolypropylene glycol (meth) allyl ether, propoxyethylene glycol (meth) allyl ether, propoxypolyethylene glycol (meth) allyl ether, propoxypropylene glycol (meth) ) allyl ether, propoxypolypropylene glycol (meth)allyl ether, and the like. From the viewpoint of the dispersion stability of the coating colorant, methoxy polyethylene glycol (meth) allyl ether, methoxy polypropylene glycol (meth) allyl ether, and butoxy polypropylene glycol (meth) allyl ether are more preferable, and butoxy polypropylene glycol (meth) allyl ether is preferred. Most preferred.

[vinyl monomer]
A vinyl monomer is a compound having one vinyl group in the molecule, and examples thereof include styrene, vinylpyrrolidone, vinylsulfonic acid, acrylonitrile, and acrylamide.

[(Meth) acrylic ester monomer]
(Meth)acrylic ester monomers include, for example, methoxypolypropylene glycol (meth)acrylate, alkoxypolyalkylene glycol (meth)acrylates such as ethoxypolyethylene glycol (meth)acrylate, N,N-dimethyl (meth)acrylamide, N,N - diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, N-substituted (meth)acrylamides such as acryloylmorpholine, N,N-dimethylaminoethyl (meth)acrylate, N,N - amino group-containing (meth)acrylates such as diethylaminoethyl (meth)acrylate, and nitriles such as (meth)acrylonitrile.

Other monomer units can be used alone or in combination of two or more.

[Synthesis of Dispersant]
Synthesis of the dispersant includes, for example, emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like. Polymerization methods include, for example, random polymerization, alternating copolymerization, and block polymerization. Polymerization reactions include, for example, radical polymerization, anionic polymerization, and cationic polymerization. The dispersant herein can be synthesized by appropriately combining these techniques.
A preferred polymerization method is to add a radical polymerization initiator and, if necessary, a chain transfer agent to a monomer mixture containing an alkyl chain-containing monomer having 6 or more carbon atoms, an acid monomer, and an ultraviolet-absorbing monomer, and carry out solution polymerization. method.
For example, when an α-olefin, (anhydride) maleic acid, and an ultraviolet-absorbing monomer are polymerized by the above method, the resulting dispersant is essentially randomly arranged between the α-olefin units and the ultraviolet-absorbing monomer. It becomes an alternating polymer in which maleic anhydride units are arranged alternately.

The content of alkyl chain-containing monomer units having 6 or more carbon atoms is preferably 5 to 59 mol%, more preferably 15 to 50 mol%, and even more preferably 15 to 40 mol%, based on the total monomer units of the dispersant. When contained in an appropriate amount, the dispersant is easily adsorbed on the surface of the colorant, and the water resistance is further improved.

The content of acid monomer units is preferably 40 to 75 mol %, more preferably 45 to 70 mol %, and even more preferably 50 to 65 mol %, based on the total monomer units of the dispersant. When contained in an appropriate amount, the dispersion stability of the coating colorant is further improved.

The content of the UV-absorbing monomer units is preferably 1 to 55 mol %, more preferably 3 to 50 mol %, and even more preferably 5 to 30 mol %, based on the total monomer units of the dispersant. By containing an appropriate amount, both low-temperature dispersion stability and light resistance can be achieved at a high level.

The content of (meth)allyl monomer units, which are other monomer units, is preferably from 0 to 30 mol %, more preferably from 1 to 20 mol %, still more preferably from 2 to 15 mol %, based on the total monomer units of the dispersant. When contained in an appropriate amount, the affinity between the coating colorant and the binder resin or the like is improved, and the dispersion stability is further improved.

Radical polymerization initiators include azo compounds and peroxides.
Examples of azo compounds include azobisisobutyronitrile, azobis2,4-dimethylvaleronitrile, and the like. Peroxides are, for example, cumene hydroperoxide, t-butyl hydroperoxide, benzoyl peroxide, diisopropyl peroxycarbonate, di-t-butyl peroxide, lauroyl peroxide, t-butyl peroxybenzoate, t-butyl peroxy and oxy-2-ethylhexanoate.

A radical polymerization initiator can be used individually or in combination of 2 or more types.

Organic solvents used for solution polymerization include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone and the like. are used, but are not particularly limited to these. Two or more of these polymerization solvents may be mixed and used.

An organic solvent can be used individually or in combination of 2 or more types.

The (anhydride) maleic acid unit of the dispersant preferably has an ester bond site, an amide bond site, or an imide bond site, and more preferably has an ester bond site or an amide bond site. These binding sites are formed by reacting the acid anhydride groups with specific compounds. This further improves the dispersion stability of the coating colorant.
The ester bond site, amide bond site, or imide bond site is preferably formed at a ratio of 30 to 100 mol % in 100 mol % of the acid anhydride group. Esterification, amidation, or the like can impart a carboxyl group site to the dispersant, resulting in an excellent electrostatic repulsion effect. Especially when esterified, the compatibility with the binder is particularly improved.

A method of obtaining an esterified product or amidated product of a dispersant is, for example, polymerization of α-olefin, maleic anhydride and (meth)allyl ether, and copolymerization of α-olefin, maleic anhydride and (meth)allyl ether. A method of reacting an alcohol or an amine after obtaining is preferred.

Water or alcohol is preferably used to form the ester linkage site.
Alcohols are, for example, methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, tert-butanol, pentanol, amyl alcohol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, benzyl alcohol, α-oxybutyric acid, 12-hydroxystearic acid, lactic acid and the like. Among these, methanol, ethanol, propanol, and isopropanol are preferred in terms of reactivity.

(alcohol containing alkyleneoxy group)
The alcohol may also contain an alkyleneoxy group, preferably an alkyleneoxy group having 2 to 6 carbon atoms, more preferably an alkyleneoxy group having 2 to 3 carbon atoms. Specific examples thereof include compounds represented by the following general formula (2) or (3), and particularly preferred are compounds represented by the following general formula (2).

［一般式（２）中、Ｒ_１は水素原子、炭素原子数１～２０のアルキル基、又は炭素原子数１～９のアルキル基で置換されていてもよいフェニル基を表し、Ａ^１Ｏ及びＡ^２Ｏはそれぞれ独立して、炭素原子数２～６のアルキレンオキシ基を表し、ｍ及びｎはアルキレンオキシ基の平均付加モル数を表し、０～１００の整数であり、ｍ＋ｎは１以上を満たす。］ general formula (2)

[In general formula (2), R ₁ represents ^a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 9 carbon atoms; A ² O each independently represents an alkyleneoxy group having 2 to 6 carbon atoms, m and n represent the average number of added moles of the alkyleneoxy group and are integers of 0 to 100, and m+n is 1 or more. Fulfill. ]

［一般式（３）中、Ｒ_１は水素原子、炭素原子数１～２０のアルキル基、又は炭素原子数１～９のアルキル基で置換されていてもよいフェニル基を示し、Ａ^１Ｏ及びＡ^２Ｏはそれぞれ独立して、炭素数２～６のアルキレンオキシ基を表し、ｍ及びｎはアルキレンオキシ基の平均付加モル数を表し、０～１００の整数であり、ｍ＋ｎ＝１以上を満たす。］ General formula (3)

[In general formula (3), R ₁ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group optionally substituted with an alkyl group having 1 to 9 carbon atoms, and A ¹ O and A ² O each independently represents an alkyleneoxy group having 2 to 6 carbon atoms, m and n represent the average number of added moles of the alkyleneoxy group, are integers of 0 to 100, and satisfy m + n = 1 or more. . ]

In the general formulas (2) and (3) above, R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or a phenyl group in which the hydrogen atom may be substituted with an alkyl group having 1 to 9 carbon atoms. From the viewpoint of improving the dispersion stability of the colorant dispersion and the storage stability of the inkjet recording ink using the same, an alkyl group having 1 to 12 carbon atoms is preferable, and a methyl group is particularly preferable.

In the general formulas (2) and (3), m and n represent the average number of added moles of the alkyleneoxy group and are integers of 0 or more and 100 or less. m+n is preferably 4 or more and 100 or less, and 4 or more and 70 from the viewpoint of lowering the viscosity of the ink when the solvent is volatilized, improving the printability on highly hydrophobic substrates, and improving the storage stability and ejection properties of the ink. The following are more preferable, 9 or more and 40 or less are still more preferable, and 9 or more and 30 or less are most preferable. When m+n is in the range of 9 to 30, the dispersion stability during the production of the colorant dispersion and the ink for inkjet recording using the same is improved. In the general formulas (2) and (3), A ¹ O and A ² O are alkyleneoxy groups having 2 to 6 carbon atoms, which contribute to improving affinity with water and water-soluble solvents in the ink. In addition, in the colorant dispersion, the alkyleneoxy group spreads in the ink and acts as a steric hindrance group, contributing to stabilization and easy dispersibility of the colorant dispersion. From an industrial point of view, an ethyleneoxy group and a propyleneoxy group are preferred, and an ethyleneoxy group is particularly preferred.

The compound represented by the general formula (2) includes, for example, polyethylene glycol, polyalkylene glycol such as polypropylene glycol, polyoxyethylene monomethyl ether, polyoxypropylene monomethyl ether, polyoxyethylene-2-ethylhexyl ether, polyoxyethylene isodecyl Polyalkyleneoxyalkyl ethers such as ethers, diethylene glycol monoethyl ether and triethylene glycol monomethyl ether can be mentioned, and polyoxyethylene monomethyl ether is most preferable from the above viewpoint. Specific examples of commercially available UNIOX M-400, UNIOX M-550, and UNIOX M-1000 (manufactured by NOF CORPORATION) can be mentioned.

Examples of the compound represented by the general formula (3) include polyoxyethylene monolaurate, polyoxyethylene monostearate, and polyoxyethylene monooleate. Polyoxyethylene monolaurate is most preferable from the above viewpoint. Specific examples of commercially available general formula (3) include nonion L-2, nonion L-4, nonion S-4, and nonion O-4 (manufactured by NOF CORPORATION).

The compounds used for forming the ester bond site can be used alone or in combination of two or more.

Preferably, an amine is used to form the amide binding site.
Amines are, for example, methylamine, ethylamine, propylamine, isopropylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, aniline, o- toluidine, 2-ethylaniline, 2-fluoroaniline, o-anisidine, m-toluidine, m-anisidine, m-phenetidine, p-toluidine, 2,3-dimethylaniline, 5-aminoindane, aspartic acid, glutamic acid, γ - aminobutyric acid and the like. However, it is not particularly limited to these.

Amines can be used singly or in combination of two or more.

An imide binding site is obtained by forming an amide bond and then dehydrating it. It can also be obtained by polymerizing a monomer containing a maleimide structure that has been imidized in advance. Specific examples include maleimide monomers such as N-phenylmaleimide, N-dodecylmaleimide, o-methylphenylmaleimide and p-hydroxyphenylmaleimide.

The acid value of the dispersant is preferably 35-400 mgKOH/g, more preferably 50-350 mgKOH/g, and even more preferably 65-300 mgKOH/g. A moderate acid value further improves redispersibility and dispersion stability.

The number average molecular weight of the dispersant is preferably 2,000 to 35,000, more preferably 3,000 to 15,000. Having an appropriate number average molecular weight makes it easier to achieve both ease of coating with a colorant and redispersibility.

The molecular weight dispersity (Mw/Mn) of the dispersant is not particularly limited, but is preferably 1.0 to 5.0, more preferably 1.5 to 3.0, from the viewpoint of dispersibility.
Mw: mass average molecular weight Mn: number average molecular weight

The colored composition herein can be prepared, for example, by bead dispersion of a dispersant and a colorant. Also, in order to disperse the colorant to a high degree, it is preferable to prepare the coated colorant by, for example, a salt milling method. This allows part or all of the colorant to be coated with the dispersant. Needless to say, the coating colorant can also be formed by bead dispersion or the like.

<Production of coating colorant>
A method for producing a coated colorant includes, for example, kneading a mixture of a water-soluble solvent, a water-soluble inorganic salt, a colorant and a dispersant by a salt kneading method to coat the surface of the colorant with the dispersant, followed by water-soluble including the step of removing inorganic salts and water-soluble solvents.
Examples of kneading devices used in the salt milling method include kneaders, two-roll mills, three-roll mills, ball mills, attritors, horizontal sand mills, vertical sand mills and/or annular bead mills. Among these, a kneader is preferable because it can efficiently coat the surface of the colorant. The kneading conditions can be appropriately adjusted according to the type of colorant, the degree of fineness, and the like. Moreover, it can also be heated or cooled as needed.

The water-soluble inorganic salt acts as a crushing aid, and crushes the colorant by utilizing the high hardness of the water-soluble inorganic salt. Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, sodium sulfate and the like. It is preferable to use sodium chloride (table salt) from the viewpoint of price.

The water-soluble solvent wets the colorant and the water-soluble inorganic salt. A water-soluble solvent is a compound that dissolves (miscible in) water but does not dissolve a water-soluble inorganic salt.
Water-soluble solvents include, for example, glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; diols such as butanediol, pentanediol and hexanediol; propylene glycol laurate; ethers such as diethylene glycol monoethyl, diethylene glycol monobutyl, diethylene glycol monohexyl; glycol ethers such as cellosolve, including propylene glycol ether, dipropylene glycol ether, and triethylene glycol ether; methanol, ethanol, isopropyl alcohol, alcohols such as 1-propanol, 2-propanol, 1-butanol, 2-butanol, butyl alcohol and pentyl alcohol; sulfolane; lactones such as γ-butyrolactone; lactams such as N-(2-hydroxyethyl)pyrrolidone; glycerin and the like. Among these, glycols such as diethylene glycol and triethylene glycol are preferred.

A water-soluble solvent can be used individually or in combination of 2 or more types.

The amount of the water-soluble solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the colorant.
The amount of the soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, per 100 parts by mass of the colorant.
The amount of the dispersant used is preferably 5 to 100 parts by mass, preferably 10 to 80 parts by mass, per 100 parts by mass of the colorant. When used in an appropriate amount, dispersion stability and redispersibility are further improved.

The water-soluble inorganic salt and water-soluble solvent are then removed from the resulting mixture containing the coating colorant.
First, the mixture is taken out from the kneading device, ion-exchanged water is added, and the mixture is stirred to obtain a suspension. The amount of ion-exchanged water used is preferably 10 to 10,000 times the mass charged into the kneading device. The stirring temperature is preferably 25-90°C. Filtration is then carried out to obtain the coated colorant. Water-soluble solvents and water-soluble inorganic salts can be removed by these operations. In addition, a step of removing the ion-exchanged water may be performed. Drying treatment is preferable for removing water. Drying conditions include, for example, a method of drying at 80 to 120° C. under normal pressure for about 12 to 48 hours, and a method of drying at 25 to 80° C. under reduced pressure for about 12 to 60 hours. . A spray drying apparatus is preferable for the drying treatment. Moreover, the pulverization treatment can be performed simultaneously with the drying treatment or after the drying treatment.

The coloring composition of the present specification preferably further contains a basic compound and water, and particularly preferably further contains a cross-linking agent. Moreover, it is also preferable that a binder resin is included.

[Basic compound]
The basic compound neutralizes the carboxyl group derived from the dispersant and stably disperses the colorant and the coating colorant. Further, it is used to adjust the pH of the coloring composition to about 7-10.
Basic compounds include, for example, aqueous ammonia, organic amines such as dimethylaminoethanol, diethanolamine and triethanolamine; inorganic alkalis such as alkali metal hydroxides such as sodium hydroxide, lithium hydroxide and potassium hydroxide; organic acids; and mineral acids.

The degree of neutralization of the dispersant is preferably 10 to 100 mol% reaction of the basic compound with respect to the carboxyl group derived from the dispersant, from the viewpoint of the dispersion stability of the coloring composition, and 30 to 100 mol% reaction. It is more preferable to allow 50 to 100 mol % of reaction to occur, and it is particularly preferable to react 50 to 100 mol %.
Here, the degree of neutralization is obtained by dividing the molar equivalent of the basic compound by the molar amount of the carboxyl group of the dispersant. It can be obtained by the following formula.
{(weight of basic compound (g)/equivalent weight of basic compound)/[(acid value of dispersant (mg KOH/g) x weight of dispersant (g)/(56.1 x 1000)]} x 100

A basic compound can be used individually or in combination of 2 or more types.

[Crosslinking agent]
A cross-linking agent is used to cross-link the carboxyl groups derived from the dispersant. A cross-linking agent is a compound having two or more functional groups capable of reacting with a carboxyl group (hereinafter referred to as reactive functional groups). Crosslinking allows the dispersant to firmly cover the colorant, thereby further improving the dispersion stability of the coloring composition.
The reactive functional group is, for example, preferably an isocyanate group, an aziridine group, a carbodiimide group, an oxetane group, an oxazoline group or an epoxy group, more preferably an aziridine group, a carbodiimide group or an epoxy group, and still more preferably an epoxy group. Addition of a cross-linking agent is also preferable from the viewpoint of improving the dispersion stability of the ink for inkjet recording. Examples of specific cross-linking agents include isocyanate compounds, aziridine compounds, carbodiimide compounds, oxetane compounds, oxazoline compounds, and epoxy compounds.

Examples of isocyanate compounds include polyisocyanates and isocyanate group-terminated prepolymers. Polyisocyanates include aliphatic diisocyanates such as hexamethylene diisocyanate and 2,2,4-trimethylhexamethylene diisocyanate; aromatic diisocyanates such as tolylene-2,4-diisocyanate and phenylene diisocyanate; alicyclic diisocyanates; ; Modified products such as urethane modified products thereof can be mentioned. The isocyanate group-terminated prepolymer can be obtained by reacting a polyisocyanate or a modified product thereof with a low-molecular-weight polyol or the like.

Aziridine compounds include, for example, N,N'-diphenylmethane-4,4'-bis(1-aziridine carboxysite), N,N'-toluene-2,4-bis(1-aziridine carboxysite), bisisophthalo yl-1-(2-methylaziridine), tri-1-aziridinylphosphine oxide, N,N'-hexamethylene-1,6-bis(1-aziridinecarboxyte), 2,2'-bishydroxymethyl butanol-tris[3-(1-aziridinyl)propionate], trimethylolpropane tri-β-aziridinylpropionate, tetramethylolmethane tri-β-aziridinylpropionate, tris-2,4,6- (1-aziridinyl)-1,3,5-triazine, 4,4′-bis(ethyleneiminocarbonylamino)diphenylmethane and the like.

Carbodiimide compounds include, for example, high-molecular-weight polycarbodiimides produced by subjecting a diisocyanate compound to a decarboxylation condensation reaction in the presence of a carbodiimidation catalyst. Examples of such high-molecular-weight polycarbodiimides include the Carbodilite series manufactured by Nisshinbo.

Oxetane compounds such as 4,4′-(3-ethyloxetan-3-ylmethyloxymethyl)biphenyl (OXBP), 3-ethyl-3-hydroxymethyloxetane (EHO), 1,4-bis[{(3 -ethyl-3-oxetanyl)methoxy}methyl]benzene (XDO), di[1-ethyl(3-oxetanyl)]methyl ether (DOX), di[1-ethyl(3-oxetanyl)]methyl ether (DOE), 1,6-bis[(3-ethyl-3-oxetanyl)methoxy]hexane (HDB), 9,9-bis[2-methyl-4-{2-(3-oxetanyl)}butoxyphenyl]fluorene, 9, 9-bis[4-[2-{2-(3-oxetanyl)}butoxy]ethoxyphenyl]fluorene and the like.

The oxazoline compound is, for example, a compound in which 2 or more, preferably 2 to 3, oxazoline groups are bonded to an aliphatic group or an aromatic group, more specifically 2,2'-bis(2-oxazoline), 1 bisoxazoline compounds such as ,3-phenylenebisoxazoline and 1,3-benzobisoxazoline, and compounds having terminal oxazoline groups obtained by reacting these compounds with polybasic carboxylic acids.

Epoxy compounds include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, glycerin triglycidyl ether, glycerol polyglycidyl ether, polyglycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether, sorbitol polyglycidyl ether. polyglycidyl ether such as ether, pentaerythritol polyglycidyl ether, resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, and hydrogenated bisphenol A diglycidyl ether.

Among these, compounds having two or more epoxy groups in the molecule are preferred, and ethylene glycol diglycidyl ether and trimethylolpropane polyglycidyl ether are particularly preferred.

A crosslinking agent can be used individually or in combination of 2 or more types.

The molecular weight (formula weight or number average molecular weight Mn) of the cross-linking agent is preferably 100 to 2,000, more preferably 120 to 1,500, more preferably 150 to 1, from the viewpoint of ease of reaction and redispersibility. ,000 is particularly preferred. The number of reactive functional groups contained in the cross-linking agent is preferably 2 to 6 from the viewpoint of controlling the molecular weight of the cross-linked dispersant to improve redispersibility.

The cross-linking agent preferably has appropriate water solubility in terms of efficiently reacting with the carboxyl group of the dispersant in water. Regarding water solubility, the amount of the cross-linking agent dissolved in 100 g of water at 25° C. is preferably 0.1 to 50 g, more preferably 0.2 to 40 g, and even more preferably 0.5 to 30 g.

The amount of the cross-linking agent used is preferably about 10 to 150 mol% of the reactive functional group, more preferably 20 to 120 mol%, more preferably 30 to 100 mol%, relative to 100 mol% of the carboxyl group of the dispersant. preferable.

Examples of binder resins include (meth)acrylic resins, styrene-(meth)acrylic resins, polyurethane resins, styrene-butadiene resins, vinyl chloride resins, polyolefin resins, polyester resins, and polyurethane resins.

The content of the binder resin is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, based on the non-volatile content of the coloring composition.

A mixture containing the coating colorant and optionally water, a basic compound, and a cross-linking agent can be mixed and dispersed using a conventionally known device. For example, high-speed mixer, homogenizer, high-pressure homogenizer, planetary mixer, trimix, kneader, extruder, horizontal sand mill, vertical sand mill and/or annular bead mill, paint shaker, ball mill, disperser equipped with ultrasonic oscillator , a high-pressure disperser, a counter-impingement disperser, an oblique impingement disperser, a two-roll mill, a three-roll mill, and the like. When a bead dispersing machine such as a sand mill is used, the bead material can be selected from conventionally known materials such as zirconia, glass, steel, etc. Among them, zirconia is preferable. The bead diameter is preferably 0.01 mm to 10 mm. By mixing and dispersing using these devices, agglomeration of the coated colorant is crushed to the level of primary particles, and a colorant composition having desired properties can be produced.

<Method for preparing colored composition of bead mill dispersion>
In this specification, a bead mill dispersion method is exemplified as a method for producing a colored composition that does not use the salt milling method. In addition, it cannot be overemphasized that the coloring composition preparation method is not limited to the salt milling method and the bead mill method.
To prepare a bead mill dispersion, first, a coloring agent is added to an aqueous medium in which a dispersant, a basic compound, and water are mixed, mixed and dispersed, and if necessary, a foreign matter removal process such as centrifugation or magnetic separation is performed. to obtain the desired colored composition.

It is effective to carry out pre-mixing before the mixing/dispersion treatment carried out in the production of the coloring composition. That is, premixing may be performed by adding a coloring agent to an aqueous medium in which at least a dispersant and water are mixed. Such a premixing operation is preferable because it can improve the wettability of the colorant surface and promote the adsorption of the dispersant to the colorant surface.

Apparatuses used for the mixing/dispersion treatment include, for example, ball mills, roll mills, sand mills, bead mills and nanomizers. Among them, a bead mill is preferably used. Examples of such mills include super mill, sand grinder, agitator mill, grain mill, dyno mill, pearl mill and covol mill (all trade names).

Furthermore, in the above premixing and mixing/dispersion treatment of the colorant, the dispersant may be dissolved or dispersed only in water or dissolved or dispersed in a mixed solvent of water-soluble solvent and water. good.

<Method for producing a colored composition containing a cross-linking agent>
Methods for producing a colored composition containing a cross-linking agent include the following methods, but the present invention is not limited thereto.
First, the coating colorant, dispersant, basic compound and water are mixed and the pH of the whole mixture is adjusted to 7-10. The cross-linking agent is then mixed and cross-linked. The cross-linking temperature may be 25°C, but preferably 40 to 95°C. The cross-linking time is preferably about 0.5 to 10 hours.

It is preferable to adjust the non-volatile content of the coloring composition with water to the extent of 5 to 80% by mass.

The content of the colorant and dispersant is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, based on 100% by mass of the coloring composition. If it is contained in an appropriate amount, the storage stability is further improved.

The D50 average particle size (median size) of the colorant of the coloring composition is preferably 20 to 200 nm, more preferably 25 to 150 nm, still more preferably 30 to 130 nm, and particularly preferably 35 to 90 nm. When the particles have an appropriate particle size, the ejection stability from the nozzle is improved, and the storage stability of the coloring composition is further improved. A laser diffraction/scattering method is used to measure the D50 average particle size.

<Application of Coloring Composition>
Applications of the coloring composition include, for example, inks and toners. Among these, ink is preferred.

<Ink>
Inks include inkjet recording inks, flexographic printing inks, paints, stationery, and textile printing agents. A preferred application is, for example, an ink containing water, particularly preferably an ink for inkjet recording.

<Ink for inkjet recording>
The ink for inkjet recording of this specification contains a coloring composition, water, and a water-soluble solvent.
The ink for inkjet recording of the present specification uses water as a solvent (medium), and it is preferable to use a water-soluble solvent together in order to prevent drying of the ink. In addition, since the dispersion stability of the coloring composition is improved, the penetrability and wetting spreadability into the substrate after printing are improved.

Examples of water-soluble solvents include polyhydric alcohols, polyhydric alcohol alkyl ethers, polyhydric alcohol aryl ethers, nitrogen-containing heterocyclic compounds, amides, amines, sulfur-containing compounds, propylene carbonate, ethylene carbonate, and others. Water-soluble solvents and the like are included.

Polyhydric alcohols include, for example, glycerin, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, 1,2-propanediol, 1,3-propanediol, dipropylene glycol, tripropylene glycol, polypropylene glycol. , 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,3-hexanediol, 1,4-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 3-methyl-1,3-butanediol, trimethylolethane, trimethylolpropane, 1,2,6-hexanetriol, 1,2,4-butanetriol, 1,2,3-butanetriol, petriol, 2-ethyl-2-methyl-1,3-propanediol, 3 ,3-dimethyl-1,2-butanediol, 2,2-diethyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-dimethyl-2,4- pentanediol, 2,5-dimethyl-2,5-hexanediol, 5-hexene-1,2-diol, 2-ethyl-1,3-hexanediol and the like. Among these, 2-ethyl-1,3-hexanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,2-propanediol, 1,2-butanediol, 1,3-butanediol , 1,2-pentanediol, 1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol and 1,2-heptanediol are preferred.

Examples of polyhydric alcohol alkyl ethers include 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, and propylene glycol monobutyl ether. etc.
Examples of polyhydric alcohol aryl ethers include ethylene glycol monophenyl ether, diethylene glycol monophenyl ether, tetraethylene glycol chlorophenyl ether, ethylene glycol monobenzyl ether, and ethylene glycol monoallyl ether.

Nitrogen-containing heterocyclic compounds include, for example, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidinone, ε-caprolactam, γ-butyrolactone and the like. be done.
Amides include, for example, formamide, N-methylformamide, N,N-dimethylformamide and the like.
Examples of amines include monoethanolamine, diethanolamine, triethanolamine, monoethylamine, diethylamine, triethylamine and the like.
etc.
Examples of sulfur-containing compounds include dimethylsulfoxide, sulfolane, thiodiethanol and the like.

Other water-soluble solvents are preferably sugars. Sugars include monosaccharides, disaccharides, oligosaccharides (including trisaccharides and tetrasaccharides), polysaccharides, and the like. Sugars include glucose, mannose, fructose, ribose, xylose, arabinose, galactose, maltose, cellobiose, lactose, sucrose, trehalose, maltotriose and the like. As used herein, polysaccharides mean sugars in a broad sense, and include substances that exist widely in nature, such as α-cyclodextrin and cellulose. Further, these saccharide derivatives are represented by, for example, reducing sugars of the above saccharides (for example, sugar alcohols [general formula: HOCH ₂ (CHOH) _n CH ₂ OH (where n = an integer of 2 to 5). , oxidized sugars (eg, aldonic acid, uronic acid, etc.), amino acids, thioacids, etc. Among these, sugar alcohols are preferred, and maltitol and sorbitol are more preferred.

A water-soluble solvent can be used individually or in combination of 2 or more types.

The content of the water-soluble solvent is preferably 3 to 60% by mass, more preferably 3 to 50% by mass, in the ink for inkjet recording. The content of water is preferably 10 to 90% by mass, more preferably 30 to 80% by mass in the ink for inkjet recording. When the water-soluble solvent is appropriately contained, the ink ejection stability from the head is improved.

The ink for inkjet recording preferably contains a binder resin. This improves the water resistance, solvent resistance, abrasion resistance, glossiness, etc. of the printed coating film. Examples of binder resins include acrylic resins, polyester resins, alkyd resins, fluororesins, urethane resins, silicone-containing resins, etc. containing crosslinkable functional groups.

The ink for inkjet recording of this specification can contain an additive as needed. Additives include surfactants, antifoaming agents, preservatives and the like. The content of the additive is preferably 0.05 to 10% by mass, more preferably 0.2 to 5% by mass, in the ink for inkjet recording.

The inkjet recording ink of the present specification can be used in various inkjet printers. The inkjet method includes, for example, a charge control type, a continuous injection type such as a spray type, and an on-demand type such as a piezo method, a thermal method, and an electrostatic suction method.

<Flexographic printing ink>
The flexographic printing inks herein contain a coloring composition. The flexographic printing ink preferably further contains a binder resin. Examples of binder resins include acrylic resins and urethane resins. Flexographic printing inks can also contain additives, solvents and crosslinkers.

(acrylic resin)
Acrylic resins include acrylic copolymers, acrylic acid-styrene copolymer resins, acrylic acid-maleic acid resins, acrylic acid-styrene-maleic acid resins, and the like. The acrylic copolymer is a copolymer using two or more monomers selected from (meth)acrylic acid and (meth)acrylic acid ester. The two or more monomers may be selected from (meth)acrylic acid esters.

The acrylic resin preferably has a weight average molecular weight of 200,000 to 800,000. If the weight-average molecular weight is less than 200,000, the strength of the resin film may be lowered, and the adhesion to the substrate, water abrasion resistance, scratch resistance, and blocking resistance of the laminate may be lowered. On the other hand, if it exceeds 800,000, the mobility of the molecular chains will decrease, and under low-temperature drying conditions, the fusion between the ink layers will be insufficient, and there is a risk that the adhesion to the substrate and the resistance to water rubbing of the laminate will decrease. There is In addition, the re-solubility tends to decrease.

The glass transition temperature (Tg) of the acrylic resin is preferably about -30°C to 30°C. Appropriate Tg further improves water friction resistance, blocking resistance, and adhesion to substrates.

(urethane resin)
In the present invention, as the urethane resin, a polyurethane-urea resin can be used in addition to the polyurethane resin. From the viewpoint of film-forming properties, the urethane resin preferably has an acid value. The weight average molecular weight of the urethane resin is preferably 10,000 to 100,000. Adhesion to substrates, water rubbing resistance, scratch resistance, and blocking resistance are further improved by having an appropriate molecular weight.

The acid value of the binder resin is preferably 20-180 mgKOH/g, more preferably 40-150 mgKOH/g. An appropriate acid value further improves re-solubility in printing, adhesion to substrates, water rubbing resistance, and blocking resistance. The acid value refers to milligrams of potassium hydroxide required to neutralize acidic components contained in 1 g of resin.

The amount of the binder resin contained in the flexographic printing ink is preferably 10-40% by mass. When contained in an appropriate amount, the strength of the ink coating film is improved, and the adhesion to the substrate and water rubbing resistance are further improved.

Flexographic printing inks can optionally contain additives. Additives include leveling agents, wetting agents, water repellents, antifoaming agents, waxes, cross-linking agents and the like.

Solvents used in flexographic printing inks include water, the aforementioned water-soluble solvents, and the like. A solvent can be used individually or in combination of 2 or more types.

The content of the coloring composition is preferably an amount sufficient to ensure the density and coloring power of the flexographic printing ink, that is, 1 to 50% by mass of the total amount of the flexographic printing ink. The viscosity of the flexographic printing ink composition should be in the range of 10 mPa·s or more from the viewpoint of preventing sedimentation of the coloring composition and appropriately dispersing it, and 1000 mPa·s or less from the viewpoint of work efficiency during ink production and printing. is preferred. The above viscosity is measured at 25° C. with a B-type viscometer manufactured by Tokimec.

Flexographic printing inks can be prepared by mixing and dispersing the aforementioned ingredients. For example, in addition to the coloring composition of the present invention, a wax, a wetting agent, and the like may be added as optional components and mixed with stirring to prepare an aqueous flexographic ink. For dispersion and stirring, for example, high-speed mixer, homogenizer, planetary mixer, trimix, kneader, extruder, horizontal sand mill, vertical sand mill and/or annular bead mill, paint shaker, ball mill, etc., equipped with an ultrasonic oscillator. A disperser, a two-roll mill, a three-roll mill, and the like can be mentioned.

<Paint>
A paint herein contains a coloring composition. The paint preferably further contains a binder resin, and more preferably contains a cross-linking agent. The paint is preferably a water-based paint containing a coloring composition and a binder resin. The ratio of the coloring composition to the binder resin varies depending on the intended use and is not particularly limited.

(binder resin)
Examples of binder resins include acrylic resins, polyester resins, alkyd resins, fluororesins, urethane resins, silicone-containing resins, and the like, which contain crosslinkable functional groups. Examples of cross-linking agents include melamine resins, urea resins, polyisocyanate compounds, blocked polyisocyanate compounds, epoxy compounds, carboxyl group-containing compounds, acid anhydrides, alkoxysilane group-containing compounds, and the like. Among these, the combined use of an acrylic resin and a melamine resin is preferred.

The paint may further contain water, organic solvent, rheology control agent, pigment dispersant, anti-settling agent, curing catalyst, anti-foaming agent, antioxidant, UV absorber, surface control agent, cross-linking agent, extender pigment. etc. can be included as appropriate.

The paint can be prepared by mixing and dispersing the above materials.

Paints can be applied to a variety of substrates. Substrates include, for example, metal substrates such as iron, stainless steel, aluminum, etc. and surface-treated products thereof; cement-based substrates such as cements, limes, gypsum; polyvinyl chlorides, polyesters, polycarbonates, acrylics and plastic base materials such as

Examples of the coating method include brush coating, roller coating, and spray coating. After coating, the coating is dried at room temperature or by heating to form a coating. The thickness of the coating is usually about 5-70 μm.

<Stationery>
The stationery of the present specification contains the coloring composition and can be used for applications such as writing instruments, recorders, and printers. The stationery preferably contains water and a binder in addition to the coloring composition. Stationery can optionally contain water-soluble organic solvents, thickeners, dispersants, lubricants, rust inhibitors, antiseptics, antibacterial agents, etc. . The ratio of the coloring composition to the binder resin varies depending on the intended use and is not particularly limited.

The stationery is preferably prepared by preparing a highly concentrated aqueous dispersion of the coloring composition, further diluting it with water, and adding the binder resin and, if necessary, other additives. The method for dispersing the coloring composition is not particularly limited, and the known dispersion method described above may be used.
For stationery, for example, thixotropic ink (eg gel ink water-based ballpoint pen ink) and Newtonian ink (eg low-viscosity water-based ballpoint pen ink) are more preferably used.
The pH (25° C.) of the stationery is preferably adjusted to 5 to 10 with a pH adjuster or the like from the viewpoints of usability, safety, stability of the ink itself, and compatibility with the ink container. ~9.5 is more preferred.

The content of the coloring composition can be appropriately adjusted according to the drawing density of the stationery, and is preferably about 0.1 to 40% by mass based on the total amount of the ink composition for stationery.

<Printing agent>
The printing agent of this specification preferably contains a coloring composition, water, and a binder resin. Textile printing agents can record images such as letters, pictures, and designs on fabrics such as woven fabrics, nonwoven fabrics, and knitted fabrics. The ratio of the covering colorant to the binder resin varies depending on the intended use, and is not particularly limited.

The binder resin described above can be used as the binder resin. The binder resin can be used in any form such as water-dispersed particles and water-soluble resin. Examples of binder resins include urethane resins and acrylic resins.

After preparing an aqueous dispersion of the coloring composition, the printing agent is mixed with water, a binder resin, and other additives as necessary, and is subjected to a preferred treatment method such as impregnation or printing depending on the fiber to be colored. A printing agent can be produced by combining them.
The printing agent for screen recording preferably contains additives such as preservatives, viscosity modifiers, pH modifiers, chelating agents, antioxidants, ultraviolet absorbers, flame retardants and cross-linking agents. The colorant concentration of the printing agent for screen recording is preferably 1 to 10 mass %.
The printing agent for dip-dyeing preferably contains additives such as preservatives, viscosity modifiers, pH modifiers, chelating agents, antioxidants, ultraviolet absorbers, flame retardants, and cross-linking agents. It is preferable to use a printing agent for dyeing with a colorant concentration in the range of 1 to 10% by weight. The viscosity of the printing agent for impregnation is arbitrarily set within the range of 1 mPa·s to 100 mPa·s in accordance with the printing apparatus.
The printing agent for spray printing preferably contains viscosity modifiers, pH modifiers, chelating agents, plasticizers, antioxidants, UV absorbers, etc. as additives. The colorant concentration of the printing agent for spray recording is preferably 1% by mass to 10% by mass. The viscosity of the printing agent for spray recording is arbitrarily set in the range of 1 mPa·s to 100 mPa·s according to the apparatus.
The textile printing agent for inkjet recording preferably contains additives such as preservatives, viscosity modifiers, pH modifiers, chelating agents, antioxidants, ultraviolet absorbers and flame retardants. The colorant concentration of the textile printing agent for inkjet recording is preferably 1% by mass to 20% by mass. The additive is preferably added to the aqueous dispersion of the coloring composition together with the binder resin.
Preservatives include, for example, sodium benzoate, pentachlorophenol sodium, 2-pyridinethiol-1-oxide sodium, sodium sorbate, sodium dehydroacetate, 1,2-dibenzisothiazolin-3-one (Arch Chemicals Proxel GXL, Proxel XL-2, Proxel LV, Proxel AQ, Proxel BD20, Proxel DL) and the like.
Specific examples of viscosity modifiers include mainly water-soluble natural or synthetic polymers such as carboxymethylcellulose, sodium polyacrylate, polyvinylpyrrolidone, gum arabic, and starch.
Examples of pH adjusters include collidine, imidazole, phosphoric acid, 3-(N-morpholino)propanesulfonic acid, tris(hydroxymethyl)aminomethane, boric acid and the like.
Chelating agents are, for example, ethylenediaminetetraacetic acid, ethylenediaminediacetic acid, nitrilotriacetic acid, 1,3-propanediaminetetraacetic acid, diethylenetriaminepentaacetic acid, N-hydroxyethylethylenediaminetriacetic acid, iminodiacetic acid, uramyldiacetic acid, 1, 2-diaminocyclohexane-N,N,N',N'-tetraacetic acid, malonic acid, succinic acid, glutaric acid, maleic acid, salts thereof (including hydrates), and the like.
Antioxidants include, for example, hindered phenol compounds, hydroquinone compounds, phosphite compounds and their substituted compounds, copper halides, alkali metal halides and the like. Examples of the ultraviolet absorber include organic compound ultraviolet absorbers such as benzotriazole and benzophenone; inorganic compound ultraviolet absorbers such as titanium oxide and zinc oxide; and the like.
When the textile printing agent is applied to an inkjet recording method, it is preferable to adjust the surface tension to 20 mN/m or more and 60 mN/m or less. More preferably, it is 20 mN or more and 45 mN/m or less, and still more preferably 20 mN/m or more and 40 mN/m or less. When the surface tension is less than 20 mN/m, the liquid overflows onto the nozzle surface, and normal printing may not be possible. On the other hand, if it exceeds 60 mN/m, there is a tendency for repelling to occur easily on the non-absorbent substrate. The viscosity is preferably 1.2 mPa s or more and 20.0 mPa s or less, more preferably 2.0 mPa s or more and less than 15.0 mPa s, still more preferably 3.0 mPa s or more and 12.0 mPa. - less than s. Within this range of viscosity, excellent dischargeability and maintenance of good jettability over a long period of time can be achieved. The surface tension can be appropriately adjusted with the surfactant.

The printing agent of the present invention can be used for printing on fabrics, artificial leathers, natural leathers and the like. In particular, it is excellent in printing on cloth.
The fabric is preferably a medium composed of fibers, and may be a non-woven fabric as well as a woven fabric. Materials include, for example, cotton, silk, wool, hemp, nylon, polyester, polyurethane, and rayon.

<Toner>
The toner herein contains a coloring composition. Further, the toner can be appropriately selected from binder resins, release agents, charge control agents, lubricants, fluidity improvers, abrasives, conductivity-imparting agents, image peeling prevention agents, and the like.

(Binder resin)
As the binder resin, it is preferable to use a colorless, transparent, white, or light-colored resin so as not to impair the hue of each colored composition.

Binder resins include, for example, homopolymers of styrene and substituted products thereof such as polystyrene, poly-p-chlorostyrene and polyvinyltoluene; Vinyl naphthalene copolymer, styrene-acrylate copolymer, styrene-methacrylate copolymer, styrene-α-methyl chloromethacrylate copolymer, styrene-acrylonitrile copolymer, styrene-vinyl methyl ether copolymer styrene-based copolymers such as styrene-vinyl ethyl ether copolymers, styrene-vinyl methyl ketone copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers, styrene-acrylonitrile-indene copolymers; Crosslinked styrenic copolymer; polyvinyl chloride, phenolic resin, natural modified phenolic resin, natural resin modified maleic acid resin, acrylic resin, methacrylic resin, polyvinyl acetate, silicone resin, polyester resin, polyurethane, polyamide resin, furan resins, epoxy resins, xylene resins, polyvinyl butyral, terpene resins, coumarone-indene resins, petroleum-based resins, and the like. Among these, polyester resins and styrene copolymers are preferred.

The glass transition temperature (Tg) of the binder resin is preferably 50-70°C. In the present invention, the glass transition temperature (Tg) is measured with a differential scanning calorimeter (DSC-60 manufactured by Shimadzu Corporation) at a heating rate of 10° C./min. , the value at the intersection with the tangent line of the endothermic curve near Tg is obtained and measured.

Further, the binder resin preferably has a softening temperature Ts of 60 to 90° C. measured by a flow tester. This is an effective numerical value for enhancing the compatibility with the colorant.

In the present invention, the softening temperature Ts was measured using a flow tester CFT-500D manufactured by Shimadzu Corporation with a starting temperature of 40°C and a heating rate of 6.0°C/min. , a test load of 20 kg, a preheating time of 300 seconds, a die hole diameter of 0.5 mm, and a die length of 1.0 mm.

The release agent improves, for example, release properties (anti-offset properties) during heat roll fixing. Release agents include, for example, aliphatic hydrocarbons, fatty acid metal salts, higher fatty acids, fatty acid esters or partially saponified products thereof, silicone oils, and various waxes. Among these, waxes such as ethylene homopolymer, low-molecular-weight polyethylene, low-molecular-weight polypropylene, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax having a weight average molecular weight (Mw) of about 500 to 8,000 are preferred. These are usually added at a ratio of about 0.5 to 10% by mass based on 100 parts by mass of the toner base particles.

A charge control agent is used to impart triboelectrification properties to a toner for the purpose of improving the sharpness of images obtained by development. By using a charge control agent, it can be adjusted to have an appropriate amount of charge. As the charge control agent, a positive charge control agent or a negative charge control agent is used depending on the toner.

Positive charge control agents include, for example, quaternary ammonium salt compounds (eg, tributylbenzylammonium-1-hydroxy-4-naphthosulfonate, tetrabutylbenzylammonium tetrafluoroborate), quaternary ammonium salts, organotin oxides (eg, dibutyltin oxide, dioctyltin oxide, dicyclohexyltin oxide), diorganotin borate (dibutyltin borate, dioctyltin borate, dicyclohexyltin borate), polymers having amino groups, and the like.

Examples of negative charge control agents include zinc salts, calcium salts, and chromium salts of aromatic hydroxycarboxylic acids; divalent or trivalent metal salts and metal chelates (complexes) of aryloxycarboxylic acids such as salicylic acid and salicylic acid derivatives; fatty acid soaps, naphthenic acid metal salts, and the like. The charge control agent is preferably used in an amount of 0.1 to 10 parts by mass, more preferably 0.5 to 8 parts by mass, per 100 parts by mass of the binder resin.

The toner is preferably a pulverized toner obtained by a melt-kneading method from the viewpoint of productivity and dispersibility of the coloring composition. The pulverized toner by the melt-kneading method is obtained by, for example, uniformly mixing raw materials such as a coloring composition, a binder resin, and a charge control agent in a mixer such as a Henschel mixer, followed by a closed kneader and a single-screw or twin-screw extruder. , melt kneading with an open roll type kneader or the like, cooling, pulverizing, and classifying. The content of the coloring composition is preferably 10 to 70% by weight in the toner from the viewpoint of productivity and dispersibility of the coloring agent.

The toner used herein is in the form of particles, and preferably has a weight average particle size of 3 to 15 μm, more preferably 5 to 10 μm. The particle size distribution of the toner can be measured using, for example, a Coulter counter (Multisizer 3, manufactured by Beckman Coulter, Inc.).

The coated article of the present invention comprises a substrate and a printed layer formed from the above ink. is preferred.
Examples of the substrate include paper substrates such as woodfree paper, recycled paper, coated paper, art paper, cast paper, lightly coated paper, and synthetic paper, polyvinyl chloride sheets, polyester films, polypropylene films, and polyethylene films. etc. Also, the substrate may be a laminate obtained by laminating a plurality of materials.
The base material has a thickness of about 20 to 300 μm and a basis weight of about 30 to 300 g/m ² .
The thickness of the printed layer is preferably 0.01 to 5 μm, more preferably 0.1 to 4 μm, further preferably 0.5 to 3 μm. By setting the thickness of the printed layer within the above range, it is possible to sufficiently evaporate the solvent in the drying process during the preparation of the printed layer and form a strong film while obtaining sufficient color development as a printed matter.
The printing layer may be formed using a printing machine suitable for each ink, such as an inkjet printing machine, a flexographic printing machine, a gravure printing machine, an offset printing machine, or the like.
After printing the ink, an optional drying step can be added. Dryers used in the drying step include, for example, hot air dryers and infrared heaters.

The ink set of the present invention can be used for applications such as inkjet, flexo ink, offset ink, and gravure ink. The ink set of the present invention preferably contains, for example, two or more colors of cyan ink, magenta ink, yellow ink and black ink. It is preferred that one or more of these inks contain the coloring composition of the present specification. In addition, if necessary, inks such as red ink, orange ink, and green ink can be added to form an image (printing layer) with higher color reproducibility. The pigment concentration, viscosity, dynamic viscoelasticity, surface tension, coating order, evaporation rate of volatile matter, etc. of each ink are design items, and can be appropriately adjusted according to desired properties.

Colorants already exemplified can be used for each ink. Preferred coloring agents are exemplified below.
Cyan ink contains C.I. I. Pigment Blue 15:1, 15:3, 15:4, 15:6.
The magenta ink used C.I. as a coloring agent. I. Pigment Red 31, 122, 146, 147, 150, 176, 177, 179, 184, 185, 202, 242, 254, 269, 291, C.I. I. Pigment Violet 1, 19, 23 is preferably included.
Yellow ink contains C.I. I. Pigment Yellow 12, 13, 14, 74, 138, 150, 155, 174, 180, 185, 213.
Black ink contains C.I. I. Pigment Black 1,7 is preferably included.
Orange ink contains C.I. I. PigmentOrange 34, 38, 43, 62, 64, 71, 73 is preferred.
The green ink contains C.I. as a coloring agent. I. Pigment Green 7, 36, 58, 59, 62, 63 is preferably included.

EXAMPLES The present invention will now be described more specifically with reference to examples and comparative examples. It goes without saying that the present invention is not limited to the examples. Hereinafter, "part" is "mass part" and "%" is "mass%".

(Mass average molecular weight (Mw), number average molecular weight (Mn))
Mass average molecular weight (Mw) and number average molecular weight (Mn) were measured using a TSK-GELSUPERHZM-N column (manufactured by Tosoh Corporation) at a column temperature of 40 ° C. GPC equipped with an RI detector (manufactured by Tosoh Corporation , HLC-8320GPC) using THF as a developing solvent at a flow rate of 0.35 ml/min.

(dispersion degree)
The degree of dispersion is obtained from the following formula.
Dispersity=mass average molecular weight (Mw)/number average molecular weight (Mn)

(acid number)
About 1 g of a sample is precisely weighed into an Erlenmeyer flask, and dissolved in 50 ml of a mixture of distilled water/dioxane (weight ratio: distilled water/dioxane=1/9). A 0.1 mol/L potassium hydroxide/ethanol solution (titer F) was applied to the above sample solution using a potentiometric measuring device (manufactured by Kyoto Electronics Industry Co., Ltd., device name “automatic potentiometric titrator AT-710M”). Titration was performed, and the amount (α (mL)) of the potassium hydroxide/ethanol solution required until the end point of the titration was measured. The acid value (mgKOH/g) was determined by the following formula as the value of the resin in a dry state.
Acid value (mgKOH/g) = {(5.611 x α x F)/S}/(non-volatile concentration/100)
However, S: sample collection amount (g)
α: consumption of 0.1 mol/L potassium hydroxide ethanol solution (ml)
F: Potency of 0.1 mol/L potassium hydroxide/ethanol solution

Table 1 shows the (meth)allyl monomers used in synthesizing the dispersants. (Meth)allyl monomers can be prepared according to known synthesis methods such as those disclosed in JP-A-01-000109.
The number of added moles of the alkyleneoxy group in the (meth)allyl monomer represents the average number of added moles.

<Production of dispersant>
(Production example 1)
19.2 parts (26 mol%) of 1-octene, 38.6 parts (60 mol%) of maleic anhydride, and a benzotriazole skeleton monomer were placed in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser and a stirrer. 21.2 parts (10 mol %), 21.0 parts (4 mol %) of monomer M3, 100 parts of xylene, and 0.6 parts of octyl thioglycolate as a chain transfer agent were charged into a flask, and the flask was purged with nitrogen. It was heated and stirred at 100°C. A mixture of 1.0 part of t-butylperoxy-2-ethylhexanoate as a radical polymerization initiator and 20 parts of xylene was added dropwise thereto over 2 hours while stirring. After that, while the temperature was maintained at 100° C., the mixture was further stirred for 1 hour to react. Then, after confirming that the polymerization conversion rate was 95 to 100%, the reaction temperature was lowered to 60° C., and 37.8 parts of methanol was used as an anhydride site-modifying compound, and diazabicycloundecene was used as a catalyst. was added, and the mixture was heated to 80°C while stirring, maintained for 4 hours, and then cooled to room temperature to complete the reaction. The organic solvent was completely removed by concentration under reduced pressure to obtain a dispersant (P-1). The obtained dispersant (P-1) had a number average molecular weight of 5,500.

(Production Examples 2 to 30)
Synthesized in the same manner as dispersant (P-1) except that the raw materials and charging amounts of Production Example 1 were changed as described in Tables 2-1, 2-2, 2-3, and 2-4. was carried out to obtain dispersants (P-2) to (P-33). Further, the molecular weight of the dispersant was appropriately adjusted by changing the amount of the radical polymerization initiator and the chain transfer agent used.

The contents of the abbreviations in Tables 2-1, 2-2, 2-3 and 2-4 are as follows.
C8: 1-octene C16: 1-hexadecene C30: 1-triacontene LMA: lauryl methacrylate VA: behenyl acrylate MAA: methacrylic acid MeOH: methanol IPA: isopropyl alcohol

The terms in Tables 2-1, 2-2, 2-3, and 2-4 are as follows.
Benzotriazole skeleton:
2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole triazine skeleton: compound (a1-4-1)
Benzophenone skeleton: 4-acryloyloxybenzophenone

<Production of coating colorant>
(Example 1)
C.I. I. Pigment Blue 15: 3 (LIONOGEN BLUE FG-7358G manufactured by Toyocolor Co., Ltd.) 35.0 parts, 175.0 parts of sodium chloride, 12.25 parts of dispersant (P-1), 35.0 parts of diethylene glycol as a water-soluble solvent, stainless steel It was charged in a gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80° C. for 3 hours. This mixture was poured into 1,000 parts of water, heated to about 40°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and water-soluble solvent, and dried under reduced pressure. Drying at 40° C. gave the coated colorant.
A coated colorant set 1 (C, M, Y, K) was obtained by using the same method except that the following pigments were used.
Magenta: Clariant Chemicals Toner Magenta E (C.I. Pigment Red 122)
Yellow: LIONOL YELLOW TT1405G (C.I. Pigment Yellow 14) manufactured by Toyocolor Co., Ltd.
Black: Printex85 (carbon black, manufactured by Orion Engineered Carbons)

<Production of coloring composition>
An aqueous solution of potassium hydroxide having a concentration of 10% was added to 20 parts of the obtained coating colorant so that the degree of neutralization of the acid value of the dispersant was 100%. Then, 0.03 part of PROXELGXL (S) (manufactured by Lonza) was added as an antiseptic, and ion-exchanged water was added so that the non-volatile content was 22%. Then, the mixture was stirred with a disper for about 1 hour while being heated in an oil bath at 70°C. Then, using an ultrasonic homogenizer with an output of 600 W, treatment was performed for 5 minutes while adjusting the internal temperature to 15°C.
Next, Denacol EX321 (an epoxy group-containing compound, manufactured by Nagase ChemteX Corporation, non-volatile content of 100%, epoxy equivalent of 140 g/eq) was added as a crosslinking agent at room temperature (25°C) at a molar ratio to the carboxyl groups of the dispersant. Added to 0.8 eq. Then, while heating in an oil bath at 70 ° C., stir with a disper for about 1 hour, adjust with ion-exchanged water so that the non-volatile content is 22%, Coloring composition set 1 (C, M, Y, K) got

<Production of Ink Set for Inkjet Recording Containing Coloring Composition>
33.3 parts of the resulting colored composition, 6.3 parts of Joncryl 780 (aqueous acrylic emulsion, manufactured by BASF Japan, 48% nonvolatile content) as a binder resin (3 parts as nonvolatile content), 16 parts of propylene glycol .65 parts, 16.65 parts of 1,2-hexanediol, 0.1 part of Surfynol DF110D (manufactured by Air Products Japan Co., Ltd.) as a leveling agent, and further adjusted with ion-exchanged water so that the total is 100 parts. , ink set 1 (C, M, Y, K) for inkjet recording was produced.

(Examples 2 to 32, Comparative Examples 1 to 4)
A coating colorant, a coloring composition, and an ink for inkjet recording were obtained in the same manner as in Example 1, except that the colorant and dispersant used were changed according to Table 3.

<Production of colored composition of bead mill dispersion>
(Example 33)
C.I. I. Pigment Blue 15:3 (LIONOGEN BLUE FG-7358G manufactured by Toyocolor Co., Ltd.) C.I. I. Pigment Red 122 (manufactured by Clariant Chemicals Co., Ltd., "Toner Magenta E") 20 parts, dispersant (P-2) 7 parts, potassium hydroxide aqueous solution with a concentration of 10% so that the degree of neutralization of the acid value of the dispersant is 100%. was added and mixed. Further, water was added and mixed so that the non-volatile content became 22%. After pre-mixing this with a stirrer, main dispersion was carried out using a Dyno mill with a volume of 0.6 L filled with 1800 g of zirconia beads with a diameter of 0.5 mm to obtain a colored composition.
A coated colorant set 33 (C, M, Y, K) was obtained by using the same method except that the following pigments were used.
Magenta: Clariant Chemicals Toner Magenta E (C.I. Pigment Red 122)
Yellow: LIONOL YELLOW TT1405G (C.I. Pigment Yellow 14) manufactured by Toyocolor Co., Ltd.
Black: Printex85 (carbon black, manufactured by Orion Engineered Carbons)

<Production of Ink Set for Inkjet Recording Containing Coloring Composition of Bead Mill Dispersion>
33.3 parts of the resulting colored composition, 6.3 parts of Joncryl 780 (aqueous acrylic emulsion, manufactured by BASF Japan, 48% nonvolatile content) as a binder resin (3 parts as nonvolatile content), 16 parts of propylene glycol .65 parts, 16.65 parts of 1,2-hexanediol, 0.1 part of Surfynol DF110D (manufactured by Air Products Japan Co., Ltd.) as a leveling agent, and further adjusted with ion-exchanged water so that the total is 100 parts. , an ink set for inkjet recording (C, M, Y, K) was produced.

(Examples 34 and 35, Comparative Examples 5 to 8)
A coloring composition, a coloring composition set, and an inkjet recording ink set were obtained in the same manner as in Example 33, except that the dispersant used was changed according to Table 4.

(Low temperature coarse particle amount test)
In order to evaluate the amount of coarse grains at low temperatures, the following tests were carried out. First, the produced colored composition was allowed to stand in a storage cabinet at 5°C for one month. Thereafter, the coloring composition was diluted 100 times with water, and about 5 ml of the diluted solution was evaluated for average dispersed particle diameter D99 using Microtrac UPA-EX150 (trade name, manufactured by Nikkiso Co., Ltd.).
○ (good): D99 is less than 500 nm △ (practically no problem): D99 is 500 nm or more and less than 1 μm × (not practical): D99 is 1 μm or more

(Light fastness test of colored composition)
The coloring composition was diluted 1000 times with water, placed in a 10 mm x 10 mm x 50 mm glass cell and sealed. This was placed in a xenon weatherometer XL75 [manufactured by Suga Test Instruments Co., Ltd.] so that the direction of light irradiation was perpendicular to the short side of the glass cell. for 100 hours.
The colored composition before and after irradiation, using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, model number: V-650), at room temperature (25 ° C.) UV-visible absorption spectrum (wavelength range of 300 ~ 750 nm) was measured. , the molar extinction coefficient at the maximum absorption wavelength was measured. The colorant residual ratio was calculated from the obtained molar extinction coefficient and evaluated according to the following four-level criteria.
◎ (very good): colorant residual rate is 95% or more ○ (good): colorant residual rate is 90% or more and less than 95% △ (practically no problem): colorant residual rate is 85% or more and less than 90% × (impossible to use): coloring agent residual rate is less than 85%

[Calculation formula for colorant residual ratio]
Percentage of coloring agent remaining=(molar extinction coefficient after test/molar extinction coefficient before test)×100 (%).

(Evaluation of clogging of discharge nozzles of low-temperature storage products)
The prepared inkjet recording ink was allowed to stand in a storage at 5°C for one month. After that, an ink jet printer (manufactured by EPSON, trade name PX-504A) was filled with initial filling, and an initial filling operation to the head was performed. After that, a nozzle check was performed to confirm whether ink could be ejected from all the nozzles of the head.
Then, after standing still for 24 hours, solid printing was performed as a 100% duty image on PPC paper (TPPAPER, NBS Ricoh). Ejection stability during printing was evaluated to what extent continuous ejection was possible without pin chipping.
◯ (Good): The number of sheets that can be discharged continuously is 80 or more.
Δ (practically no problem): The number of sheets that can be discharged continuously is 20 or more and less than 80 sheets.
x (unpractical): The number of sheets that can be ejected continuously is less than 20, and there are many missing pins. Alternatively, ink was not ejected from all nozzles in the initial filling evaluation.

(Ink lightfastness test)
Inkjet recording is performed on glossy paper (manufactured by Canon Inc., product name: Canon photo paper platinum grade (PT-201)) using an inkjet printer (manufactured by Canon Inc., product name: PIXUSip7230). and obtained a record.

Using a holder, this test piece was placed in a Xenon Weatherometer XL75 [manufactured by Suga Test Instruments Co., Ltd.] and irradiated for 100 hours at a temperature of 24°C, a humidity of 60% RH, and an illuminance of 100 klux. Colorimetric. The reflection color density was measured using a colorimeter manufactured by X-rite under the trade name of SpectroEye. The colorimetry was performed under the conditions of ANSIA as a density standard, a viewing angle of 2 degrees, and a light source of D50. The colorant residual ratio was calculated from the obtained transmission color density.
◎ (very good): colorant residual rate is 95% or more ○ (good): colorant residual rate is 90% or more and less than 95% △ (practically no problem): colorant residual rate is 85% or more and less than 90% × (impossible to use): coloring agent residual rate is less than 85%

[Calculation formula for colorant residual ratio]
Percentage of coloring agent remaining=(reflection density after test/reflection density before test)×100 (%).

From the results of Tables 3 and 4, the coloring composition of the present invention is excellent in low-temperature dispersion stability and light resistance.
Since the dispersant contains alkyl chain-containing monomer units with 6 or more carbon atoms, it has high adsorption capacity for colorants, and the acid monomer unit in the dispersant exhibits excellent dispersibility, and UV absorption in the dispersant. The monomer unit not only improved UV absorption but also improved dispersion stability at low temperature. Inkjet recording inks, flexographic printing inks, paints, stationery, and textile printing agents containing the coloring composition can realize inks and coated materials that are excellent in low-temperature dispersion stability and lightfastness.

Claims (9)

A coloring composition comprising a dispersant and a coloring agent,
The coloring composition, wherein the dispersant is a polymer containing an alkyl chain-containing monomer unit having 6 or more carbon atoms, an acid monomer unit, and an ultraviolet absorbing monomer unit. The coloring composition according to claim 1, wherein the alkyl chain-containing monomer unit having 6 or more carbon atoms is an α-olefin unit. 3. The coloring composition according to claim 1, wherein said dispersant is a polymer further containing an alkyleneoxy chain. A coloring composition according to any one of claims 1 to 3, wherein the acid monomer units are (anhydride) maleic acid units. The coloring composition according to any one of claims 1 to 4, further comprising a cross-linking agent. 6. The coloring composition according to claim 5, wherein the cross-linking agent contains at least one group selected from the group consisting of isocyanate groups, aziridinyl groups, carbodiimide groups, oxetane groups, oxazoline groups and epoxy groups. An ink comprising the coloring composition according to any one of claims 1 to 6. A coated article comprising a substrate and a printed layer formed from the ink according to claim 7. An ink set comprising a cyan ink, a magenta ink and a yellow ink, wherein one or more of said inks is the ink of claim 7.