Coated colorant, dispersion and photosensitive colored composition

Abstract

To provide a coated colorant capable of preparing a dispersion and composition having good filterability and temporal viscosity stability even if a colorant is pulverized.SOLUTION: There is provided a coated colorant in which a surface of a colorant is coated with a resin (P), wherein the resin (P) has a first polymer moiety, a second polymer moiety and an acid dianhydride residue, the first polymer moiety contains a cyclic ester polymer and the second polymer moiety contains a vinyl polymer. Further, the resin (P) preferably has an acid value of 10 to 200 mgKOH / g.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a coating colorant.

[0002] In applications such as printing inks, inkjet inks, color filters, and paints, coloring compositions containing coating colorants using colorants such as pigments and dyes are widely used.

[0003] For color filter coloring compositions and inkjet inks for high-definition image display devices and printed images, etc., the refinement of colorants is important. However, when the colorants are refined, the colorants tend to aggregate with each other, resulting in problems such as a decrease in dispersibility and a deterioration in the temporal stability of the viscosity of the composition.

[0004] Also, when performing filtration during the production of the composition, if coarse particles remain, it is necessary to frequently replace the filtration filter, resulting in a decrease in productivity. Furthermore, due to the progress of the above high-definition, the pore diameter of the filtration filter tends to become smaller, and it is necessary to disperse the colorant more finely.

[0005] Patent Document 1 discloses a coating colorant using a block polymer or a graft polymer using an acrylic monomer.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, in the conventional composition, when the colorant was refined, aggregates were likely to occur and the filterability was low. Also, there was a problem in that the temporal stability of the viscosity of the composition was insufficient. In addition, the cyclic ester polymer has low heat resistance, and there is a problem that the heat resistance of the composition using the cyclic ester polymer decreases.

[0008] An object of the present invention is to provide a coated colorant capable of producing a dispersion / composition having good filterability even when the colorant is refined and excellent in temporal stability of viscosity and heat resistance.

Means for Solving the Problems

[0009] <1>The coated colorant of the present invention is a coated colorant in which the surface of the colorant is coated with a resin (P), and the resin (P) has a first polymer moiety, a second polymer moiety, and an acid dianhydride residue. The first polymer moiety includes a cyclic ester polymer, and the second polymer moiety includes a vinyl polymer. <2>The coated colorant according to <1>, wherein the resin (P) has an acid value of 10 to 200 mgKOH / g. <3>The coated colorant according to <1> or <2>, wherein the acid dianhydride residue is a residue having an aromatic ring. <4>The coated colorant according to <1> to <3>, wherein the cyclic ester polymer is a polymer containing polylactone. <5>The coated colorant according to <1> to <4>, wherein the resin (P) contains 20 to 80% by mass of the first polymer moiety. <6>A dispersion containing the coated colorant according to <1> to <5> and a binder resin (excluding the resin (P)). <7>A photosensitive coloring composition containing the dispersion according to <6>, a polymerizable compound, and a photopolymerization initiator.

Effects of the Invention

[0010] According to the present invention described above, it is possible to provide a coated colorant capable of producing a dispersion / composition having good filterability even when the colorant is refined and excellent in temporal stability of viscosity and heat resistance. Further, the present invention can also provide a dispersion, a photosensitive coloring composition, and the like.

Modes for Carrying Out the Invention

[0011] First, the terms used in this specification are defined. When expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, they represent "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. Also, in this specification, "C.I." means Color Index (C.I.). A vinyl monomer is a compound containing an ethylenically unsaturated group. An acid dianhydride is a compound having two acid anhydride groups. A dispersant is a compound used to disperse a previously micronized colorant. The molecular weight dispersity is the value of weight average molecular weight / number average molecular weight. A monomer is in an unreacted state. A monomer unit is in a state of constituting a part of a resin after polymerization of the monomer.

[0012] [Coated colorant] The coated colorant of the present invention is a coated colorant in which the surface of the colorant is coated with a resin (P). The colorant is a particle and coats all or part of the particles. The coating may be carried out to such an extent that the problem can be solved. The resin (P) has a first polymer moiety, a second polymer moiety, and an acid dianhydride residue. The first polymer moiety includes a cyclic ester polymer, and the second polymer moiety includes a vinyl polymer. In this specification, the coated colorant is in a particulate form.

[0013] The coated colorant of the present invention is preferably used in applications such as a colored composition for a color filter, an ink for inkjet, a flexographic ink, a toner, stationery, an ink for resist printing, a paint, and a resin molded body. Among these, the color filter application is preferred.

[0014] The coating colorant of the present invention can suppress the aggregates of the colorant because the resin (P) adsorbs on the surface of the colorant. As a result, even if the colorant is refined, the filterability of the composition is good, and the viscosity stability of the composition over time is good. The steric repulsion site derived from the cyclic ester polymer, which is the first polymer site of the resin (P), has a relatively narrow molecular weight dispersity compared to the vinyl polymer site, so that a steric repulsion with less variation in the molecular chain can be obtained. This compensates for the demerit of the vinyl polymer with a relatively wide molecular weight dispersity and contributes to the dispersion stability. The second polymer site of the resin (P) contains a vinyl polymer having high heat resistance with respect to the cyclic ester polymer, so that the heat resistance of the coating colorant is improved, and it is easy to maintain the dispersed state even during the heating process of the dispersion or the composition. Therefore, foreign matters derived from the colorant are less likely to occur. The acid dianhydride residue of the resin (P) strongly adsorbs by electrostatic interaction with the colorant. Therefore, in addition to the fact that the resin (P) is difficult to desorb from the colorant, the synergistic effect of the steric repulsion effect with the first polymer site and the second polymer site can suppress the formation of aggregates.

[0015] <Colorant> The colorant is in the form of particles and can be appropriately selected and used from, for example, inorganic pigments, organic pigments, and dyes.

[0016] Examples of the inorganic pigment include metal oxide powders such as barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, titanium oxide, and iron tetraoxide; metal sulfide powders; or metal powders. The inorganic pigment is used in combination with an organic pigment in order to ensure good coating properties, sensitivity, developability, etc. while taking a balance between chroma and lightness.

[0017] Examples of the organic pigment 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. As the pigment, an organic pigment having high color development and high thermal decomposition resistance is preferable. Specific examples of the organic pigment are shown by the Color Index number below.

[0018] Red pigments include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, etc. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, preferably C.I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296 are preferred, and C.I. Pigment Red 177, 254, 291, 295, 296 are more preferred.

[0019] Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73, etc.

[0020] Cyan pigments include, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferable, and C.I. Pigment Blue 15:6 is more preferable.

[0021] Magenta pigments include, for example, C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, C.I. Pigment Violet 19, or 23 is preferable, and C.I. Pigment Violet 23 is more preferable.

[0022] Green pigments include, for example, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63 and the like. Among these, from the viewpoint of transmittance, C.I. Pigment Green 36, 58, 59, 62, 63 are preferable.

[0023] Yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 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, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, etc. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233 are preferred.

[0024] <Dye> Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. Also, derivatives of these dyes, or lake pigments obtained by lake-forming the dyes, can also be used.

[0025] Acid dyes preferably have acidic groups such as sulfonic acid and carboxylic acid. Direct dyes are preferably inorganic salts of acid dyes, or salt-forming compounds of acid dyes and nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds. Also, salt-forming compounds that are salts of resin components having these functional groups and acid dyes are also preferred. Further, salt-forming compounds are likely to obtain a photosensitive coloring composition excellent in resistance (light resistance, solvent resistance) by sulfonamidation and modification to sulfonic acid amide compounds. Also, salt-forming compounds of acid dyes and compounds having an onium base are preferred because they are excellent in resistance (light resistance, solvent resistance). Note that the compound having an onium base is preferably a resin having a cationic group.

[0026] Basic dyes can be used as they are, but salt-forming compounds formed by salification with organic acids, perchloric acid or metal salts thereof are preferred. The salt-forming compounds of basic dyes are preferred because they have excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, among the salt-forming compounds of basic dyes, the anionic components that act as counterions are organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, and anionic compounds having a conjugated base of an organic acid having a halogenated hydrocarbon group, and salt-forming compounds formed by salifying with acid dyes are preferred. Note that the salt-forming compound has better resistance when it contains a polymerizable unsaturated group in the molecule.

[0027] In addition, when the dye has a polymerizable unsaturated group in the molecule, it becomes a dye with excellent resistance.

[0028] From the viewpoint of color characteristics such as hue, color separation property, and color unevenness, the chemical structure of the dye is preferably an azo dye, a xanthene dye, a cyanine dye, a triphenylmethane dye, an anthraquinone dye, a dipyrromethene dye, a squarylium dye, a quinophthalone dye, a phthalocyanine dye, a subphthalocyanine dye, and more preferably a xanthene dye, a cyanine dye, a triphenylmethane dye, an anthraquinone dye, a dipyrromethene dye, a phthalocyanine dye.

[0029] The colorant can be used alone or in combination of two or more.

[0030] [Resin (P)] In the coated colorant of the present invention, the resin (P) has a first polymer part, a second polymer part, and an acid dianhydride residue, the first polymer part includes a cyclic ester polymer, and the second polymer part includes a vinyl polymer. The first polymer part functions as a steric repulsion part of the coating colorant. When a cyclic ester is polymerized, a cyclic ester polymer with a narrow molecular weight distribution is produced. Since the first polymer part has a cyclic ester polymer with little variation in the length of the molecular chain, the dispersion using the coating colorant has good dispersion stability.

[0031] <The first polymer part> The cyclic ester polymer forming the first polymer part has a hydroxyl group at its terminal part that can react with an acid dianhydride. The cyclic ester polymer can be synthesized into a cyclic ester polymer having a hydroxyl group at one end by ring-opening polymerization of a cyclic ester using an active hydrogen compound as an initiator. Since the polymerization reaction of the cyclic ester is controlled by the use of the initiator, a cyclic ester polymer with a narrow molecular weight distribution can be obtained.

[0032] The cyclic ester polymer preferably includes a polymer of lactone which is a cyclic ester (polylactone). Lactones include, for example, 3- to 16-membered cyclic esters such as α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valerolactone, ε-caprolactone, ζ-enanthrolactone, η-caprylolactone (=8-hydroxyoctanoic acid lactone), 12-hydroxydodecanoic acid lactone, 13-hydroxytetradecanoic acid lactone, 15-hydroxypentadecanoic acid lactone, etc. Among these, from the viewpoint of reaction control, δ-valerolactone and ε-caprolactone are preferred, and ε-caprolactone is more preferred. Note that as long as the problems of the present application can be solved, compounds other than lactone may be used for the cyclic ester polymer.

[0033] For the synthesis of the cyclic ester polymer, cyclic compounds copolymerizable with lactone can be used. Examples of the cyclic compound include lactide, trimethylene carbonate, glycolide, lactam, etc. In the mass of the cyclic ester polymer, polylactone is preferably 50% by mass or more, and preferably 70% by mass or more. Note that the mass is preferably 90% by mass or more, and more preferably 100% by mass.

[0034] The cyclic esters can be used alone or in combination of two or more kinds.

[0035] <Synthesis of the first polymer moiety> <Active hydrogen compound> The active hydrogen compound used for the synthesis of the cyclic ester polymer is not particularly limited as long as it can provide the active hydrogen contributing to the polymerization of the cyclic ester to the polymerization site. In the present specification, the active hydrogen compound is preferably a compound having at least one functional group selected from a hydroxyl group, a carboxyl group, a phosphate group, an amino group, and a thiol group. Among these, a compound having a hydroxyl group is preferable in terms of excellent reactivity, and a monoalcohol is more preferable from the viewpoint of reaction control.

[0036] Monoalcohols include, for example, aliphatic monoalcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1-heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldecanol, 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, oleyl alcohol; aromatic ring-containing monoalcohols such as benzyl alcohol, phenoxyethyl alcohol, p-cumylphenoxyethyl alcohol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monohexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether,Triethylene glycol mono-2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol monoethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, tetraethylene glycol dimethyl ether and other alkylene glycol monoalkyl ethers, 3-ethyl-3-oxetanemethanol, 3-ethyl-3-(4-hydroxybutyloxymethyl)oxetane and other reactive alcohols are mentioned. The monoalcohol can be used alone or in combination of two or more.

[0037] For ring-opening polymerization, it is preferable to use a monoalcohol having a molecular weight of 100 to 300. By setting the molecular weight to 300 or less, a cyclic ester polymer having a sharp (narrow) molecular weight distribution can be obtained. Thereby, the dispersibility of the coating colorant is improved. Further, by setting the molecular weight to 100 or more, ring-opening polymerization of the cyclic ester becomes possible at a high temperature, and the yield is improved.

[0038] The amount of the initiator used is preferably 0.1 to 100 moles per 100 moles of the cyclic ester. By controlling the molar ratio of the cyclic ester to the initiator, the molecular weight of the cyclic ester polymer can be adjusted.

[0039] For ring-opening polymerization, a polymerization catalyst can be used. When using a polymerization catalyst, the reaction temperature can be lowered and the reaction time can be shortened. Examples of the polymerization catalyst include quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide; quaternary phosphonium salts such as tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide; phosphorus compounds such as triphenylphosphine; organotin compounds such as monomethyltin oxide, monobutyltin oxide, monooctyltin oxide, dibutyltin oxide, dioctyltin dilaurate; organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, sodium benzoate; alkali metal alcoholates such as sodium alcoholate, potassium alcoholate, and other tertiary amines, organoaluminum compounds, organotitanate compounds, and zinc compounds such as zinc chloride, etc.

[0040] The usage amount of the polymerization catalyst is preferably 0.1 ppm to 3000 ppm based on the cyclic ester. When used within the above range, it is easy to obtain a cyclic ester polymer with a polymerization rate suitable for production and without coloring.

[0041] The polymerization temperature of the cyclic ester is preferably 100 °C to 220 °C. When polymerizing within the above range, it is easy to obtain a cyclic ester polymer with a polymerization rate suitable for production and with few by-products.

[0042] The weight average molecular weight of the cyclic ester polymer is preferably from 500 to 10,000, more preferably from 1,000 to 8,000, and still more preferably from 1,000 to 5,000. When the molecular weight is 500 or more, the pigment dispersibility can be further improved due to the steric repulsion effect. When the molecular weight is 10,000 or less, appropriate crystallinity and solvent solubility can be obtained, so that the dispersibility is further improved.

[0043] <Second polymer moiety> The second polymer moiety contains a vinyl polymer having excellent heat resistance. Therefore, the heat resistance of the resin (P) can be further improved. Further, the heat resistance of the vinyl polymer can be further improved, for example, by introducing a crosslinking group. The vinyl polymer forming the second polymer moiety has a hydroxyl group at its terminal that can react with an acid dianhydride. A vinyl polymer having a hydroxyl group at one end can be synthesized by polymerizing a vinyl monomer in the presence of a thiol group-containing alcohol compound.

[0044] The vinyl monomer is, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate, methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, or methoxypolyethylene glycol polypropylene glycol (meth) acrylate, etc., linear or branched alkyl (meth) acrylate; Cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, or isobornyl (meth)acrylate; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, or tetrafluoropropyl (meth)acrylate; (Meth)acryloxy-modified polydimethylsiloxane (silicone macromer); (Meth)acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth)acrylate, or glycidyl (meth)acrylate, 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane; (Meth)acrylates having an aromatic ring such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, or nonylphenoxypolyethylene glycol (meth)acrylate; (Meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, or ω-carboxypolycaprolactone (meth)acrylate, etc. (meth)acrylate having a carboxyl group; Vinyl such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; (Meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or N-substituted type (meth)acrylamide such as acryloylmorpholine; Amino group-containing (meth)acrylate such as N,N-dimethylaminoethyl (meth)acrylate or N,N-diethylaminoethyl (meth)acrylate; Nitrile such as (meth)acrylonitrile; (Meth)acrylate having a blocked isocyanate group such as 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate, 2-[0-(1'-methylpropylideneamino)carboxyamino]ethyl (meth)acrylate, etc.; may be mentioned.

[0045] The vinyl polymer preferably contains a thermally crosslinkable group such as a tert-butyl group, an oxetanyl group, or a blocked isocyanate group. The monomer having the thermally crosslinkable group is preferably a vinyl monomer having a tert-butyl group such as tert-butyl methacrylate or tert-butyl acrylate, a vinyl monomer having an oxetanyl group such as 3-ethyl-3-methacryloyloxymethyloxetane or 3-ethyl-3-acryloyloxymethyloxetane, or a vinyl monomer having a blocked isocyanate group such as 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl (meth)acrylate or 2-[0-(1'-methylpropylideneamino)carboxylamino]ethyl (meth)acrylate. The heat resistance of the coating colorant is improved by the reaction of these thermally crosslinkable groups with a crosslinking agent.

[0046] The amount of the vinyl monomer having a thermally crosslinkable group used is preferably 5 to 90% by mass, more preferably 20 to 60% by mass, based on the monomers used for the synthesis of the vinyl polymer. When used in an appropriate amount, a crosslinking effect can be obtained without impairing the polymerization stability.

[0047] <Thiol group-containing alcohol compound> The thiol group-containing alcohol compound is preferably a compound having one or more hydroxyl groups and a thiol group in the molecule, and more preferably a compound having two hydroxyl groups and one thiol group in the molecule. Thereby, the vinyl polymer can form a second polymer moiety by reaction with an acid dianhydride.

[0048] Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol. Examples of the compound having one hydroxyl group and one thiol group in the molecule include mercaptomethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-butanol, 2-mercapto-3-butanol, and the like. Among these, a compound having two hydroxyl groups and one thiol group in the molecule is preferable, and 3-mercapto-1,2-propanediol is more preferable from the viewpoints of polymerization control and odor.

[0049] The amount of the compound having two hydroxyl groups and one thiol group used is preferably 1 to 10 parts by mass, more preferably 2 to 9 parts by mass, and even more preferably 3 to 8 parts by mass with respect to 100 parts by mass of the total vinyl monomers. When used in an appropriate amount, a vinyl polymer having an appropriate molecular weight that functions as a steric repulsion site of the dispersant is easily obtained, and the viscosity stability is improved.

[0050] The polymerization temperature is preferably 40 to 150°C, more preferably 50 to 110°C. Polymerization at an appropriate temperature facilitates the control of the polymerization reaction and the adjustment of the molecular weight.

[0051] A polymerization initiator is used for the polymerization of the vinyl monomer. The amount of the polymerization initiator used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the monomer. Examples of the polymerization initiator include azo compounds and organic peroxides.

[0052] Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), or 2,2'-azobis[2-(2-imidazolin-2-yl)propane], etc.

[0053] Organic peroxides include, for example, benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, t-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, or diacetyl peroxide, etc.

[0054] The polymerization initiator can be used alone or in combination of two or more.

[0055] The weight average molecular weight of the vinyl polymer is preferably 1,000 to 20,000. Being in this range can obtain an appropriate steric repulsion effect and solvent solubility as a dispersant of the resin (P), and improve the dispersibility of the coating colorant.

[0056] The resin (P) is synthesized by reacting a first polymer site and a second polymer site with different compositions with an acid dianhydride. Also, in the said reaction, the acid dianhydride residue is such that the acid anhydride group binds to the terminal hydroxyl groups of the first polymer site and the second polymer site, so that the carboxyl groups are regularly arranged and become strong adsorption groups for the colorant. Thereby, the resin (P) can adsorb and be stably dispersed in a wide range of materials, regardless of organic particles or inorganic particles.

[0057] <Acid dianhydride residue> In the coating colorant of the present invention, the resin (P) has an acid dianhydride residue. The acid dianhydride residue is generated by reacting the terminal hydroxyl group of the aforementioned first polymer site or the second polymer site with an acid dianhydride.

[0058] <Acid dianhydride> Examples of the acid dianhydride include aliphatic tetracarboxylic acid dianhydrides, aromatic tetracarboxylic acid dianhydrides, or polycyclic tetracarboxylic acid dianhydrides.

[0059] Aliphatic tetracarboxylic dianhydrides include, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 2,3,5,6-tetracarboxycyclohexane dianhydride, 2,3,5,6-tetracarboxynorbornane dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2,2,2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and the like.

[0060] Aromatic tetracarboxylic dianhydrides include, for example, pyromellitic dianhydride, ethylene glycol dianhydride trimellitate, propylene glycol dianhydride trimellitate, butylene glycol dianhydride trimellitate, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 2,2',3,3'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl propane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, M-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl] fluorene dianhydride, and the like.

[0061] Polycyclic tetracarboxylic dianhydrides include, for example, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride, and the like.

[0062] Among these, from the viewpoints of reactivity and adsorptivity to pigments, aliphatic tetracarboxylic dianhydrides and aromatic tetracarboxylic dianhydrides are more preferable, and aromatic tetracarboxylic dianhydrides are even more preferable. That is, the acid anhydride residue preferably has a residue having an aromatic ring.

[0063] <Method for producing resin (P)> In this specification, the resin (P) only needs to have the first polymer moiety, the second polymer moiety, and the acid dianhydride residue as already described, and its synthesis method is not limited. In the production of the resin (P) in this specification, for example, in the presence of a polymer containing a cyclic ester polymer having a hydroxyl group at one end, a thiol group-containing alcohol and a vinyl monomer are reacted to synthesize a vinyl polymer having a hydroxyl group at one end (step (1)), Subsequently, it preferably has a step (2) of reacting an acid dianhydride with these polymers to synthesize a resin (P) having a first polymer moiety containing a cyclic ester polymer, a second polymer moiety containing a vinyl polymer, and an acid dianhydride residue.

[0064] In the step (1), in the presence of the cyclic ester polymer synthesized as already described, a thiol group-containing alcohol and a vinyl monomer are reacted to synthesize a vinyl polymer having a hydroxyl group at one end. Since the cyclic ester polymer functions as a reaction solvent during the polymerization of the vinyl monomer, polymerization can be carried out without using an organic solvent. Note that the above description does not exclude the use of an organic solvent during the polymerization. The synthesis of the vinyl polymer is as already described.

[0065] The acid dianhydride used in the step (2) is as already described.

[0066] When the total amount of hydroxyl groups in the cyclic ester polymer and the vinyl polymer is 1 mol, the amount of the dianhydride used is preferably 0.5 to 1.5 mol, more preferably 0.6 to 1.2 mol, and even more preferably 0.7 to 1.0 mol. By carrying out the reaction with an appropriate amount, a resin (P) can be obtained in which the dianhydride residue at the pigment adsorption site and the first polymer site and the second polymer site at the steric repulsion site are appropriately bonded.

[0067] In the step (2), an esterification reaction catalyst can be used. The esterification reaction catalyst is preferably a tertiary amine. Examples of the tertiary amine include triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0068] During the reaction in the step (2), a terminal capping agent (for example, a monoalcohol or a monoamine) can be reacted with the acid anhydride group to form a capping site. Thereby, the storage stability of the resin (P) is improved.

[0069] The capping site can be formed by introducing the terminal capping agent at the timing when 70 to 98% of the acid anhydride groups have reacted and reacting them. It should be noted that it is more preferable to introduce the terminal capping agent at the timing when 75 to 95% of the acid anhydride groups have reacted.

[0070] When the amount of the terminal capping agent used is based on 100 mol% of the acid anhydride groups present when the terminal capping agent is introduced, an amount corresponding to 40 to 90 mol% is preferable, an amount corresponding to 50 to 90 mol% is more preferable, and an amount corresponding to 60 to 85 mol% is even more preferable. Introducing an appropriate amount can suppress unreacted acid anhydride groups, so that the storage stability of the resin (P) itself and the dispersion is further improved.

[0071] Monoalcohols include, for example, monohydric alcohols such as methanol, ethanol, 1-butanol, 2-butanol, isobutanol, tert-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, methylcyclohexanol, Monoalcohols having an ether group such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, Monoalcohols having a carbonyl group such as methyl lactate, ethyl lactate, diacetone alcohol, etc. can be mentioned.

[0072] The monoalcohol is preferably a compound having an ether group or a carbonyl group. The acid dianhydride residue portion of the resin (P) can have an ether group or a carbonyl group, improving the affinity with various solvents contained in the dispersion, such as acetate solvents like propylene glycol monomethyl ether acetate, and enhancing the dispersibility of the resin (P). Among these, the monoalcohol is preferably 3-methoxybutanol, propylene glycol monomethyl ether, or diacetone alcohol.

[0073] From the viewpoint of reaction control, the monoamine is preferably a secondary amine. By using a secondary amine, side reactions such as crosslinking reactions with acid dianhydrides can be suppressed. Examples of secondary amines include aliphatic secondary amines such as dimethylamine, diethylamine, ethylmethylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-s-butylamine, di-tert-butylamine, N-methylbutylamine, N-ethylbutylamine, di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-2-ethylhexylamine, di-n-decylamine, di-n-undecylamine, di-n-dodecylamine (dilaurylamine), di-n-tridecylamine, di-n-tetradecylamine (dimyristylamine), di-n-hexadecylamine (dipalmitylamine), di-n-stearylamine, diisostearylamine; alicyclic secondary amines such as N-methylcyclopentylamine, N-ethylcyclopentylamine, N-propylcyclopentylamine, N-methylcyclohexylamine, N-ethylcyclohexylamine, N-propylcyclohexylamine, N-isopropylcyclohexylamine; Examples of the aromatic secondary amines include N-methylaniline, N-ethylaniline, N-propylaniline, N-isopropylaniline, N-butylaniline, N-isobutylaniline, N-methylbenzylamine, N-ethylbenzylamine, N-propylbenzylamine, N-isopropylbenzylamine, N-butylbenzylamine, 1-(methylaminomethyl)naphthalene, 9-(methylamino)methylanthracene, and the like.

[0074] The terminal capping material is more preferably a monoalcohol. This facilitates the reaction control during the synthesis of the resin (P). In addition, the dispersibility and the solubility in propylene glycol monomethyl ether acetate (PGMAc) are further improved.

[0075] In the resin (P), the content of the first polymer moiety is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 40 to 65% by mass. When the resin (P) contains 20% by mass or more of the first polymer moiety, the solvent solubility and the crystallinity are improved in a well-balanced manner, and the resin (P) can easily coat the colorant and is difficult to detach from the colorant. Therefore, the viscosity stability and the filterability of the dispersion are improved. When the resin (P) has the first polymer moiety at 80% by mass or less, the solvent solubility and the heat resistance are further improved, and the viscosity stability and the heat resistance of the composition are improved.

[0076] In the resin (P), the content of the second polymer moiety is preferably 5 to 70% by mass, more preferably 10 to 65% by mass, and even more preferably 20 to 60% by mass. When the resin (P) contains 5% by mass or more of the second polymer moiety, the heat resistance is improved, and the temporal stability of the viscosity of the composition is improved. When the resin (P) has the second polymer moiety at 70% by mass or less, the viscosity decreases, and it becomes easier to coat the surface of the colorant with the resin (P). Thereby, the dispersibility is improved.

[0077] When the ratio of the first polymer part to the second polymer part in the resin (P) is such that the second polymer part is taken as 1, the first polymer part is preferably 0.3 to 5.0, more preferably 0.4 to 4.0, and even more preferably 0.5:1 to 3.0. By setting it within the above range, the dispersibility of the coated colorant is improved. [Molecular weight] The weight average molecular weight of the resin (P) is preferably 2,000 to 35,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. When it has an appropriate molecular weight, in addition to the dispersion stability of the dispersion containing the coated colorant being further improved due to the steric repulsion effect of the first polymer part and the second polymer part, the heat resistance is also further improved. That is, when it has an appropriate weight average molecular weight, it is easier to achieve both the dispersibility and the dispersion stability of the coated colorant.

[0078] [Acid value] The acid value of the resin (P) is preferably 10 to 200 mgKOH / g, more preferably 20 to 150 mgKOH / g, even more preferably 30 to 120 mgKOH / g, and particularly preferably 30 to 110 mgKOH / g. When the acid value is 10 mgKOH / g or more, the adsorptivity to the colorant is improved and the dispersibility is further improved. On the other hand, when it is 200 mgKOH / g or less, the viscosity stability of the dispersion is improved. The acid value is the number of milligrams of potassium hydroxide required to neutralize the acidic components contained in 1 g of the resin.

[0079] The amount of the resin (P) used is preferably 5 to 100 parts by mass, more preferably 10 to 80 parts by mass, based on 100 parts by mass of the colorant. When used in an appropriate amount, the dispersion stability and the filterability are further improved.

[0080] [Manufacture of coated colorant] For the step of coating the resin (P) on the surface of the colorant, a conventionally known manufacturing method can be adopted. For example, the salt milling method, the wet dispersion method (e.g., the ball mill method, the sand mill method), the dry co-grinding method (e.g., the two-roll method, the three-roll method), etc. can be mentioned. Among these, the salt milling method, which can more firmly coat the resin (P) while making the colorant finer, is preferred.

[0081] <Dye derivative> When producing a coated colorant, a dye derivative can be used as necessary. As a result, the colorant can be dispersed into finer particles, so that the dispersibility of the coated colorant is further improved. A dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Dye derivatives include, for example, compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group (hereinafter referred to as an acidic derivative), and amine salts thereof, sulfonamide groups, or compounds having a basic substituent such as a tertiary amino group at the terminal (hereinafter referred to as a basic derivative), and compounds having a neutral substituent such as a phenyl group or a phthalimidalkyl group. Organic dyes include, for example, diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, fluorene-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, polyazo, etc. Among these, basic derivatives are preferred.

[0082] In the coated colorant of the present invention, the blending amount of the dye derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the colorant. When an appropriate amount of the dye derivative is used, the dispersibility is improved without reducing the coloring power.

[0083] <Salt milling method> The salt milling method includes a step of kneading a water-soluble solvent, a water-soluble inorganic salt, a colorant, and a resin (P) to coat the surface of the colorant with the resin (P), and then removing the water-soluble inorganic salt and the water-soluble solvent. First, a water-soluble solvent, a water-soluble inorganic salt, a colorant, and a resin (P) are kneaded to coat the surface of the colorant with the resin (P).

[0084] The kneading apparatus used in the salt milling method includes, for example, a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a horizontal sand mill, a vertical sand mill, and / or an annular bead mill, etc. Among these, a kneader is preferred in terms of being able to efficiently coat the surface of the colorant. The kneading conditions can be appropriately adjusted according to the type of colorant, the degree of refinement, etc. Also, heating or cooling can be carried out as necessary.

[0085] 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 the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate, etc. It is preferable to use sodium chloride (table salt) from the viewpoint of price.

[0086] The amount of the water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass with respect to 100 parts by mass of the colorant.

[0087] The water-soluble solvent wets the colorant and the water-soluble inorganic salt. The water-soluble solvent is a compound that dissolves (mixes) in water but does not dissolve the 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; glycol esters such as propylene glycol laurate; ethers such as diethylene glycol monoethyl, diethylene glycol monobutyl, and diethylene glycol monohexyl; glycol ethers such as cellosolve including propylene glycol ether, dipropylene glycol ether, and triethylene glycol ether; alcohols such as methanol, ethanol, isopropyl alcohol, 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; and glycerin. Among these, glycols such as diethylene glycol and triethylene glycol are preferred.

[0088] The water-soluble solvent can be used alone or in combination of two or more.

[0089] The amount of the water-soluble solvent used is preferably 5 to 1,000 parts by mass with respect to 100 parts by mass of the colorant.

[0090] Next, the water-soluble inorganic salt and the water-soluble solvent are removed from the obtained mixture containing the coated colorant. First, take out the mixture from the kneading device, add ion-exchanged water and stir to obtain a suspension. The amount of ion-exchanged water used is preferably 10 to 10,000 times the mass input into the kneading device. The stirring temperature is preferably 25 to 90°C. Next, perform filtration to obtain the coated colorant. By these operations, water-soluble solvents and water-soluble inorganic salts can be removed. Additionally, a step of further removing ion-exchanged water may be performed. The removal of water is preferably by a drying treatment. Examples of the drying conditions include a method of drying at 80 to 120°C for about 12 to 48 hours under normal pressure, and a method of drying at 25 to 80°C for about 12 to 60 hours under reduced pressure. The drying treatment is preferably performed using a spray dryer. Also, a grinding treatment can be performed simultaneously with or after the drying treatment.

[0091] The coated state of the obtained coated colorant can be confirmed by measuring the free amount (free rate) of the resin (P) by washing with the following organic solvents. The smaller the free amount, the more the colorant is coated.

[0092] <Dispersion> The dispersion of the present invention contains a coated colorant and a binder resin (excluding resin (P)). Further, the dispersion of the present invention can contain a dye derivative and a dispersion resin as required.

[0093] The content of the coated colorant in the dispersion is preferably 0.01 to 99% by mass, more preferably 0.01 to 60% by mass, and even more preferably 5 to 40% by mass in the non-volatile matter of the dispersion. When contained in an appropriate amount, a good dispersion effect can be obtained, and a dispersion with an appropriate viscosity is easily obtained.

[0094] The dispersion of the present invention can be used in applications where pigment dispersions such as color filters, flexographic inks, inkjet inks, and toners are used. Hereinafter, the color filter application will be described as an example.

[0095] <Binder resin> The binder resin is preferably a resin with a transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region when forming a film with a thickness of 2 μm. Examples of the resin include thermoplastic resins and photosensitive resins.

[0096] Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, acrylic resin, alkyd resin, polystyrene, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene, polybutadiene, or polyimide resin, etc. Note that thermosetting resins can also be used. Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, or phenol resin, etc.

[0097] The photosensitive resin is preferably a resin obtained by reacting a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group with a (meth)acrylic compound or cinnamic acid having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group to introduce a photocrosslinkable group such as a (meth)acryloyl group or a styryl group into the polymer. Also preferred is a resin obtained by half-esterifying a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer with a (meth)acrylic compound having a hydroxyl group such as hydroxyalkyl (meth)acrylate.

[0098] Considering pattern formation by photolithography, the binder resin is preferably an alkali-soluble resin. The alkali-soluble resin is a resin that dissolves in an aqueous alkali solution, and is, for example, a resin having an acidic functional group such as a carboxyl group or a sulfone group and a weight average molecular weight of 1,000 to 500,000, preferably 5,000 to 100,000. Examples of the alkali-soluble resin include acrylic resins having acidic functional groups, α-olefin / (anhydrous) maleic acid copolymers, styrene / (anhydrous) maleic acid copolymers, styrene / styrenesulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydrous) maleic acid copolymers. Among these, acrylic resins having acidic functional groups, α-olefin / (anhydrous) maleic acid copolymers, styrene / (anhydrous) maleic acid copolymers, and styrene / styrenesulfonic acid copolymers are preferred.

[0099] The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the coated colorant. When contained in an appropriate amount, a film can be easily formed and good color characteristics are easily obtained.

[0100] <Solvent> The dispersion of the present invention can contain a solvent. The solvent is, for example, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate,Dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, or dibasic acid ester, etc. may be mentioned. The solvent can be used alone or in combination of two or more kinds.

[0101] The dispersion of the present invention can contain a dye derivative if necessary. The dye derivative may be used when producing the coating colorant or when producing the dispersion. The content of the dye derivative is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 25 parts by mass with respect to 100 parts by mass of the coating colorant. When an appropriate amount of the dye derivative is contained, the dispersibility is improved without reducing the coloring power.

[0102] The dispersion is prepared, for example, by adding a coating colorant, a binder resin, a solvent, etc. and performing a dispersion treatment. When preparing the dispersion, a dye derivative and a dispersant can be blended. The timing of blending each material is arbitrary. Also, the dispersion step can be performed multiple times.

[0103] Examples of the disperser for performing the dispersion treatment include a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor, etc.

[0104] After preparing the dispersion, it is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means such as centrifugation, sintered filters, and membrane filters.

[0105] <Dispersed resin> Dispersed resins include, for example, styrene-maleic anhydride copolymers, olefin-maleic anhydride copolymers, poly(meth)acrylates, styrene-(meth)acrylic acid copolymers, (meth)acrylic acid-(meth)acrylic acid alkyl ester copolymers, (meth)acrylic acid-polyvinyl-based macromer copolymers, phosphate ester group-containing acrylic resins, aromatic carboxyl group-containing acrylic resins, polystyrene sulfonates, acrylamide-(meth)acrylic acid copolymers, carboxymethyl cellulose, polyurethanes having a carboxyl group, formalin condensates of naphthalene sulfonates, or anionic resin-type pigment dispersants such as sodium alginate; Nonionic resin-type pigment dispersants such as polyvinyl alcohol, polyalkylene polyamines, polyacrylamide, or polymer starches; Examples of cationic resin-type pigment dispersants include polyethyleneimine, aminoalkyl (meth)acrylate copolymers, polyvinylimidazoline, polyurethanes having an amino group, reaction products of poly(lower alkyleneimine) and a polyester having a free carboxyl group, or satokinsan. The dispersed resin is preferably a resin having a comb structure or a block structure. On the other hand, the binder resin is preferably a chain-like random polymer. The chain includes branched chains.

[0106] Commercially available dispersion resins include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc., manufactured by BYK-Chemie Japan; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., manufactured by Lubrizol Japan; EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., manufactured by BASF Japan; and Ajisper PA111, PB711, PB821, PB822, PB824, etc., manufactured by Ajinomoto Fine-Techno Co., Inc.

[0107] The amount of the dispersion resin used is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, per 100 parts by mass of the colorant. Using an appropriate amount of other dispersants can further improve the dispersibility.

[0108] The D50 average particle diameter (median diameter) of the coated colorant in the dispersion is preferably 20 to 200 nm, more preferably 30 to 150 nm, still more preferably 40 to 130 nm, and particularly preferably 50 to 90 nm. When it has an appropriate particle diameter, the dispersion stability of the dispersion is further improved. The measurement of the D50 average particle diameter uses the dynamic light scattering method.

[0109] The photosensitive coloring composition of the present invention preferably contains a dispersion, a polymerizable compound, and a photopolymerization initiator.

[0110] <Polymerizable compound> The polymerizable compound is a monomer or oligomer having a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)acryloyl group, a (meth)allyl group, etc. The number of polymerizable unsaturated groups of the polymerizable compound is 1 or more, preferably 2 or more and 20 or less.

[0111] Examples of the polymerizable compound include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol-propylene glycol) di(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) di(meth)acrylate, poly(propylene glycol-tetramethylene glycol) di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, or 2-ethyl, 2-butyl-propanediol di(meth)acrylate, etc. (poly)alkylene glycol di(meth)acrylate; Di(meth)acrylate such as dimethylol dicyclopentane di(meth)acrylate, neopentyl glycol di(meth)acrylate hydroxypivalate, pentaerythritol di(meth)acrylate stearate-modified, bisphenol A di(meth)acrylate ethylene oxide-modified, bisphenol A di(meth)acrylate propylene oxide-modified, bisphenol A di(meth)acrylate tetramethylene oxide-modified, bisphenol F di(meth)acrylate ethylene oxide-modified, bisphenol F di(meth)acrylate propylene oxide-modified, bisphenol F di(meth)acrylate tetramethylene oxide-modified, zinc diacrylate, triacrylate phosphate ethylene oxide-modified, or glycerol di(meth)acrylate; (Meth)acrylate having a tertiary amino group such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, or diethylaminopropyl (meth)acrylate; Polyfunctional (meth)acrylate having trifunctionality or more such as glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, or dipentaerythritol hexa(meth)acrylate; Glycerol triglycidyl ether-(meth)acrylic acid adduct, glycerol diglycidyl ether-(meth)acrylic acid adduct, polyglycerol polyglycidyl ether-(meth)acrylic acid adduct, 1,6-butanediol diglycidyl ether, alkyl glycidyl ether-(meth)acrylic acid adduct, allyl glycidyl ether-(meth)acrylic acid adduct, phenyl glycidyl ether-(meth)acrylic acid adduct, styrene oxide-(meth)acrylic acid adduct, bisphenol A diglycidyl ether-(meth)acrylic acid adduct, propylene oxide modified bisphenol A diglycidyl ether-(meth)acrylic acid adduct, bisphenol F diglycidyl ether-(meth)acrylic acid adduct, epichlorohydrin modified phthalic acid-(meth)acrylic acid adduct, epichlorohydrin modified hexahydrophthalic acid-(meth)acrylic acid adduct, ethylene glycol diglycidyl ether-(meth)acrylic acid adduct, polyethylene glycol diglycidyl ether-(meth)acrylic acid adduct, propylene glycol diglycidyl ether-(meth)acrylic acid adduct, polypropylene glycol diglycidyl ether-(meth)acrylic acid adduct, phenol novolac type epoxy resin-(meth)acrylic acid adduct, cresol novolac type epoxy resin-(meth)acrylic acid adduct, or other epoxy resin-(meth)acrylic acid adducts, etc. epoxy (meth)acrylate; (Meth)acryloyl modified isocyanurate, (meth)acryloyl modified polyurethane, (meth)acryloyl modified polyester, (meth)acryloyl modified melamine, (meth)acryloyl modified silicone, (meth)acryloyl modified polybutadiene, or (meth)acryloyl modified rosin, etc. (meth)acryloyl modified resin oligomers; Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, or allyl (meth)acrylate; Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether; Amides such as (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, or N-vinylformamide; or acrylonitrile, etc. may be mentioned. The polymerizable compound can be used alone or in admixture of two or more.

[0112] The content of the polymerizable compound is preferably 2 to 50% by mass, more preferably 2 to 30% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition. When blended in an appropriate amount, the photocurability and developability are further improved.

[0113] <Photopolymerization initiator> Examples of the photopolymerization initiator include acetophenone-based photopolymerization initiators such as 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, or 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one; Benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; Benzophenone-based photopolymerization initiators such as benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl-4'-methyldiphenyl sulfide; Thioxanthone-based photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, or 2,4-diisopropylthioxanthone; Triazine-based photoinitiators such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine; borate-based photoinitiators; carbazole-based photoinitiators; imidazole-based photoinitiators; oxime ester-based photoinitiators, etc. Among these, oxime ester-based photoinitiators are preferred in terms of photocurability.

[0114] Commercially available oxime ester-based photoinitiators include IRGACURE OXE-01, 02, 03, 04 manufactured by BASF Japan; Adeka Arcles N-1919T, NCI-730, NCI-831E, NCI-930 manufactured by ADEKA; TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Qiangli New Materials; Omnirad1312, 1314, 1316 manufactured by IGM Resins; SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation; DFI-020, 306, EOX-01 manufactured by Daito Chemicals, etc.

[0115] The photoinitiator can be used alone or in a mixture of two or more.

[0116] The content of the photoinitiator is preferably 5 to 200% by mass, more preferably 10 to 150% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition.

[0117] The photosensitive coloring composition of the present invention can use a sensitizer in combination with a photoinitiator. Thereby, the photoreactivity is improved. Examples of the sensitizer include α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, or 4,4'-diethylaminobenzophenone and the like.

[0118] The content of the sensitizer is preferably 0.1 to 60 parts by mass with respect to 100 parts by mass of the photoinitiator.

[0119] The photosensitive coloring composition can be prepared, for example, by blending a dispersion, a polymerizable compound, and a photoinitiator and performing a dispersion treatment. Needless to say, the timing of blending each material is arbitrary.

[0120] Examples of the dispersion device used for the dispersion treatment include a disper, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor and the like.

[0121] After the preparation of the photosensitive coloring composition, it is preferable to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust by means such as centrifugation, a sintered filter, or a membrane filter.

[0122] One of the uses of the photosensitive coloring composition is an optical filter. Among optical filters, a color filter is preferable.

[0123] <Color filter> The color filter preferably has a filter segment formed from a base material (also referred to as a substrate) and the above photosensitive coloring composition. The color filter preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of coloring agent to be used. Further, the color filter can have a magenta filter segment, a cyan filter segment, and a yellow filter segment instead of or in addition to the color filter segments. Note that a transparent substrate or a reflective substrate can be used as the substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0124] It is preferable that the color filter first forms a black matrix on a substrate and then forms filter segments. Note that a thin film transistor (TFT) can be formed in advance on the substrate and then the black matrix can be formed. Examples of the black matrix include an inorganic film such as chromium, a multilayer film of chromium / chromium oxide, titanium nitride, and a resin film in which a light-shielding agent is dispersed.

[0125] The formation of the filter segments can be performed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like. In this specification, the most preferable photolithography method will be described.

[0126] Examples of the substrate include a glass plate having a high transmittance for visible light, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate.

[0127] In the photolithography method, for example, a coloring composition having a coloring agent of a certain color tone is applied onto a transparent substrate so as to form a film with a dry film thickness of about 0.2 to 5 μm. The obtained film (hereinafter referred to as the first film) is exposed (irradiated with light) through a mask having a predetermined pattern. Next, development is carried out by immersing it in a solvent or an alkaline developer or spraying the developer such as by spraying, and the uncured portion is removed to obtain a desired pattern. By performing this process in the same manner using a photosensitive coloring composition having a coloring agent of another color tone, a color filter having filter segments of each color can be manufactured. Further, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. As a result, since the first film does not come into contact with oxygen, the exposure sensitivity is further improved. In addition, the color filter can be heated (post-baked) to cure the uncured polymerizable compound in the filter segment.

[0128] Coating apparatuses include, for example, spray coating, spin coating, slit coating, roll coating, etc. A drying process can be performed during coating. Drying apparatuses include, for example, hot air ovens, infrared heaters, etc.

[0129] Examples of the developer as an alkaline developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; organic alkalis such as dimethylbenzylamine and triethanolamine. Further, the developer can contain an antifoaming agent and a surfactant.

[0130] The post-bake temperature is preferably about 80 to 230°C. In recent years, low-temperature curing at 150°C or lower is more preferable in order to address environmental issues. The low-temperature curing post-bake time is about 30 minutes to 1 hour.

[0131] An image display device can be manufactured using the color filter of the present invention. The manufacturing of an image display device involves bonding a counter substrate using a sealant, injecting liquid crystal through an injection port provided in the seal portion, sealing the injection port after injection, and laminating a polarizing film or a retardation film on the outside of the substrate as necessary, thereby obtaining a liquid crystal display device which is a type of image display device. This liquid crystal display device can be used in a liquid crystal display mode for colorization using color filters such as Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), and Optically Compensated Bend (OCB).

[0132] In addition to liquid crystal display devices, the above-mentioned image display devices include organic EL display devices, quantum dot display devices, electronic paper, head-mounted displays, and the like.

[0133] The dispersion in this specification can be used in flexographic printing inks.

[0134] <Flexographic printing ink> Examples of the binder resin used in the flexographic printing ink in this specification include acrylic resins and urethane resins. Further, the flexographic printing ink can contain additives, solvents, and crosslinking agents.

[0135] (Acrylic resin) Examples of acrylic resins include acrylic copolymers, acrylic acid-styrene copolymer resins, acrylic acid-maleic acid resins, acrylic acid-styrene-maleic acid resins, etc. Note that the acrylic copolymer is a copolymer using two or more monomers selected from (meth)acrylic acid and (meth)acrylic acid esters. Note that the two or more monomers may be selected from (meth)acrylic acid esters.

[0136] The weight average molecular weight of the acrylic resin is preferably in the range of 200,000 to 800,000. When the weight average molecular weight is less than 200,000, the strength of the resin film may decrease, and the adhesion to the substrate, water friction resistance, scratch resistance, and blocking resistance of the laminate may decrease. On the other hand, when it exceeds 800,000, the mobility of the molecular chain decreases. Therefore, under low-temperature drying conditions, the fusion between the ink film layers may be insufficient, and the adhesion to the substrate and water friction resistance of the laminate may decrease. Also, the re-dissolvability tends to decrease.

[0137] The glass transition temperature (Tg) of the acrylic resin is preferably about -30°C to 30°C. With an appropriate Tg, the water friction resistance, blocking resistance, and adhesion to the substrate are further improved.

[0138] (Urethane resin) In the present invention, as the urethane resin, in addition to the polyurethane resin, a polyurethane-urea resin can be used. 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. Having an appropriate molecular weight further improves the adhesion to the substrate, water friction resistance, scratch resistance, and blocking resistance.

[0139] The acid value of the binder resin is preferably 20 to 180 mgKOH / g. An appropriate acid value further improves the re-dissolvability in printing, adhesion to the substrate, water friction resistance, and blocking resistance.

[0140] The content of the binder resin is preferably 10 to 40% by mass in the non-volatile content of the flexographic printing ink. When contained appropriately, the strength of the ink coating film is improved, and the adhesion to the substrate and water friction resistance are further improved.

[0141] The flexographic printing ink can contain additives as needed. Examples of the additives include leveling agents, wetting agents, water repellents, defoaming agents, waxes, crosslinking agents, and the like.

[0142] Solvents used in flexographic printing inks include water, or the aforementioned water-soluble solvents, etc. The solvents can be used alone or in combination of two or more kinds.

[0143] The content of the coating colorant is preferably 1 to 50% by mass in the flexographic printing ink. From the viewpoint of preventing sedimentation of the coating colorant and appropriately dispersing it, the viscosity of the flexographic printing ink is preferably 10 mPa·s or more and 1000 mPa·s or less. The above viscosity is the viscosity measured at 25°C with a B-type viscometer manufactured by Tokimec Co., Ltd.

[0144] The flexographic printing ink can be prepared by blending predetermined materials and then performing stirring and mixing or dispersion treatment. Stirring devices and dispersion devices include, for example, high-speed mixers, homogenizers, planetary mixers, trimixers, kneaders, extruders, horizontal sand mills, vertical sand mills, and / or annular bead mills, paint shakers, ball mills, etc., dispersers equipped with ultrasonic oscillators, two-roll mills, three-roll mills, etc.

Examples

[0145] Hereinafter, the present invention will be described more specifically with reference to examples. However, it goes without saying that the present invention is not limited to the examples. Hereinafter, "parts" means "parts by mass" and "%" means "% by mass".

[0146] (Weight average molecular weight (Mw)) The weight average molecular weight (Mw) was measured in terms of polystyrene using a TSK-GEL SUPER HZM-N column (manufactured by Tosoh Corporation) at a column temperature of 40°C with a GPC (manufactured by Tosoh Corporation, HLC-8320GPC) equipped with an RI detector, using tetrahydrofuran (THF) as the eluent at a flow rate of 0.35 ml / min.

[0147] (Acid value) Precisely weigh about 1 g of the sample into a triangular flask, add 50 ml of a distilled water / dioxane (weight ratio: distilled water / dioxane = 1 / 9) mixed solution, and dissolve it. Using a potential difference measuring device (manufactured by Kyoto Electronics Industry Co., Ltd., device name "Automatic Potentiometric Titrator AT-710M"), titrate the above sample solution with a 0.1 mol / L potassium hydroxide-ethanol solution (titer F), and measure the amount (α (mL)) of the potassium hydroxide-ethanol solution required until the titration end point.

[0148] As the value of the resin in the dry state, the acid value (mgKOH / g) was determined by the following formula. Acid value (mgKOH / g) = {(5.611 × α × F) / S} / (non-volatile content concentration / 100) However, S: Sampling amount of the sample (g) α: Consumption amount (ml) of 0.1 mol / L potassium hydroxide-ethanol solution F: Titer of 0.1 mol / L potassium hydroxide-ethanol solution

[0149] (Reaction rate of acid dianhydride groups) To 0.5 - 1.0 g of the sample, add 30 ml of a mixed solution of 1,4-dioxane and water (10:1), stir to dissolve uniformly. Then, add 10 ml of the following hexylamine adjustment solution, stir for 5 minutes to obtain a measurement sample solution. Next, using a 0.02 mol / L perchloric acid (1,4-dioxane) solution as the titrant, titrate using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) to obtain the titration volume (B ml). Similarly, titrate only 10 ml of the hexylamine adjustment solution to obtain the blank titration volume (C ml). Then, calculate the reaction rate of the acid dianhydride groups of the resin according to the following calculation formula. Hexylamine adjustment solution: A mixed solution of 0.79 g of hexylamine and 400 g of 1,4-dioxane S: Sampling amount of the sample (g) A: Amount of amine compound contained in the sample (mmol / g) = Amount of amine in the resin non-volatile content (%) / Amine molecular weight Measured acid dianhydride value of the resin (mmol / g) = {((Blank titration volume C × 0.02) - (Sample titration volume B × 0.02 - S × Non-volatile content concentration × A))} / (S × Non-volatile content concentration) Charge amount of acid dianhydride (mmol / g) = Amount of acid dianhydride charged in acidic dispersant (wt%) / Molecular weight of acid dianhydride × Number of acid dianhydride groups in acid dianhydride Reaction rate of acid dianhydride group (mol%) = {1 - (Measured acid dianhydride value / Charged acid dianhydride value)} × 100

[0150] (Non-volatile content) The non-volatile content was calculated from the weight ratio before and after drying for 10 minutes in an electric oven at 170°C atmosphere after weighing 1.0 g of the sample in an aluminum container. Non-volatile content % = (Weight of sample after drying) / (Weight of sample before drying) × 100

[0151] (Production of resin (P)) (Production Example 1) Into a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 7.9 parts of benzyl alcohol, 62.2 parts of ε-caprolactone, and 0.05 part of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, it was heated and stirred at 120°C for 4 hours. It was confirmed by non-volatile content measurement that 98% or more had reacted, and a cyclic ester polymer was obtained.

[0152] Next, the above reaction product was cooled to 40°C, 35.0 parts of tert-butyl acrylate, 31.5 parts of methyl methacrylate, 3.5 parts of methacrylic acid, and 5.0 parts of 3-mercapto-1,2-propanediol (1-thioglycerol) were charged, and stirred well. Further, 0.084 part of dimethyl 2,2'-azobis(2-methylpropionate) was charged as an initiator, the temperature was raised to 85°C, and reacted for 7 hours. It was confirmed that the non-volatile content reached 95% or more, and a vinyl polymer was obtained (however, it is a mixture with the cyclic ester polymer).

[0153] Next, while maintaining the internal temperature at 85°C, 14.4 parts of pyromellitic dianhydride were added to the above reaction product, and the temperature was raised to 100°C with stirring. Then, 0.13 part of N,N-dimethylbenzylamine was added, and the reaction was carried out at 120°C for 3 hours and further at 100°C for 2 hours. It was confirmed by measuring the reaction rate of the dianhydride group that 95% or more of the acid anhydride was half-esterified, and resin (P-1) was obtained. The obtained resin (P-1) became a wax-like solid at room temperature (25°C) and was a resin with fluidity at 80°C. The resin (P-1) had a weight average molecular weight of 4,900 and an acid value of 71 mgKOH / g.

[0154] (Production Examples 2 to 15) Synthesis was carried out in the same manner as resin (P-1) except that the raw materials and charged amounts in Production Example 1 were changed as described in Table 1-1 and Table 1-2, and resins (P-2) to (P-15) were obtained respectively. The molecular weight of the resin was adjusted by appropriately changing the amounts of the radical polymerization initiator and the chain transfer agent used.

[0155]

Table 1-1

[0156]

Table 1-2

[0157] The abbreviations in the table are as follows. 〔Monoalcohol〕 ·BzA: Benzyl alcohol ·DGME: Carbitol (diethylene glycol monoethyl ether) ·DA: 1-Dodecanol 〔Cyclic ester〕 ·ε-CL: ε-Caprolactone ·δ-VL: δ-Valerolactone ·M-LA: meso-Lactide 〔Vinyl monomer〕 ·t-BA: tert-Butyl acrylate ·MMA: Methyl methacrylate ·MAA: Methacrylic acid ·OXMA: (3-Ethyloxetan-3-yl)methyl methacrylate

[0158] [Chain transfer agent] ·1-TG: 1-Thioglycerol [Dianhydride] ·PMA: Pyromellitic dianhydride ·BPDA: 3,3',4,4'-Biphenyltetracarboxylic dianhydride ·BTA: 1,2,3,4-Butanetetracarboxylic dianhydride

[0159] (Production example of Resin P-16, for comparative example) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 11.2 parts of benzyl alcohol, 88.8 parts of ε-caprolactone, and 0.1 part of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was heated and stirred at 120 °C for 4 hours. It was confirmed by non-volatile content measurement that 98% of the reaction had occurred, and a cyclic ester polymer was obtained. Next, while maintaining the internal temperature at 85 °C, 11.3 parts of pyromellitic dianhydride were added to the above reaction product, and the temperature was raised to 100 °C with stirring. Then, 0.13 part of N,N-dimethylbenzylamine was added, and the reaction was carried out at 120 °C for 3 hours and further at 100 °C for 2 hours. It was confirmed by measuring the reaction rate of the acid anhydride groups that 95% or more of the acid anhydride was half-esterified, and Resin (P-16) was obtained. The obtained dispersant was a wax-like solid at room temperature and a thermoplastic resin with fluidity at 80 °C. The weight average molecular weight was 3,500 and the acid value was 62 mgKOH / g.

[0160] (Production example of Resin P-17, for comparative example) Into a four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube, and a reflux condenser, 400 parts of methyl ethyl ketone, 10 parts of acrylic acid, 45 parts of styrene, 5 parts of n-butyl acrylate, 30 parts of methyl methacrylate, and 6 parts of 2,2'-azobisisobutyronitrile (AIBN) were charged, and the mixture was maintained at an internal temperature of 80 °C for 20 hours under a nitrogen atmosphere. After heat preservation, the reflux condenser was replaced with a distillation tube, and the residual monomers and solvents in the system were removed under normal pressure and appropriately reduced pressure until the internal temperature reached 95 °C to obtain a resin (P-17). The weight average molecular weight (Mw) of the obtained resin (P-17) was 5,500, and the acid value was 123.0 mgKOH / g.

[0161] <Method for producing binder resin> (Preparation of acrylic resin solution 1) 70.0 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirring device, and the temperature was raised to 80 °C. After purging the inside of the reaction vessel with nitrogen, a mixture of 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of para-cumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 0.4 part of 2,2'-azobisisobutyronitrile was added dropwise from a dropping tube over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, the resin solution was sampled to measure the non-volatile content, and propylene glycol monoethyl ether acetate was added so that the non-volatile content became 20% by mass to prepare acrylic resin solution 1.

[0162] The dye derivatives used in the examples are shown below.

[0163] · Dye derivative 1 [Chemical formula] · Dye derivative 2 [Chemical formula] · Dye derivative 3 [Chemistry] · Pigment Derivative 4 [Chemistry] · Pigment Derivative 5 [Chemistry]

[0164] [Production of Coated Colorant] (Example 2-1) As the colorant, 90 parts of diketopyrrolopyrrole-based red pigment C.I. Pigment Red 254 (Irgazin Red L 3660 HD manufactured by BASF), 10 parts of pigment derivative 1, 50 parts of resin (P-1), 1000 parts of sodium chloride, and 200 parts of diethylene glycol as a water-soluble solvent were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 6 hours. This mixture was poured into 10,000 parts of water and stirred with a high-speed mixer for about 1 hour while heating to about 40°C to form a slurry. Filtration and washing with water were repeated to remove sodium chloride and the water-soluble solvent, and it was dried at 40°C under reduced pressure to obtain coated colorant 1.

[0165] [Examples 2-2 to 2-19, Comparative Examples 2-1 to 2-2] (Production of Coated Colorants 2 to 21) Coated colorants 2 to 21 were produced in the same manner as in Example 2-1 except that the compounding compositions shown in Table 2 were changed.

[0166] (Heat Resistance) The heat resistance of coating colorants 1 to 21 was evaluated as follows. Using a differential thermal and thermogravimetric simultaneous measurement device (TG-DTA8122 type manufactured by Rigaku Corporation), the temperature was raised from 40°C to 500°C at a heating rate of 10°C / min in the atmosphere to measure the TG-DTA curve. Then, the temperature at which the measured sample had a 50% weight loss was defined as Td50, and comparisons were made. The higher the temperature of Td50, the better the heat resistance, indicating that it is easier to maintain the dispersed state during the heating process of the dispersion or composition, and thus foreign substances derived from the colorant can be suppressed. Note that the evaluation of coating colorants 1 to 19 and coating colorant 21 was based on coating colorant 20 using a resin (P-16) with low heat resistance. 〇: Compared with coating colorant 20, Td50 is 30°C or higher (very good) △: Compared with coating colorant 20, Td50 is 10°C or higher (good) ×: Compared with coating colorant 20, the difference in Td50 is less than 10°C or equal or less (poor)

[0167] (Evaluation of coating degree) 10 g of the obtained coating colorant was put into 100 g of propylene glycol monomethyl ether acetate and shaken at room temperature for 3 hours using a shaker. Then, the pigment was sedimented using a centrifuge at 80,000 rpm for 5 hours, and the non-volatile content of the supernatant was determined by the drying method. The mass of the resin (P) released from the colorant was determined, and the release rate (%) was calculated from the ratio to the mass of the resin (P) used in the initial treatment. The smaller the value of the release rate, the more the colorant is coated. 〇: Release rate is less than 10% △: Release rate is 10% or more and less than 30% ×: Release rate is 30% or more

[0168]

Table 2

[0169] <Manufacture of pigment dispersion> [Example 3-1] (Preparation of pigment dispersion 1) After stirring and mixing the following mixture to make it uniform, it was dispersed for 3 hours using a 0.5 mm diameter zirconia bead in an Eiger mill (Mini Model M-250MKII manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 5.0 μm to prepare a pigment dispersion 1 with a non-volatile content of 28%. · Coating colorant 1: 18.0 parts · Acrylic resin solution 1: 10.0 parts (non-volatile content 2.0%) · Propylene glycol monomethyl ether acetate: 72.0 parts

[0170] [Examples 3-2 to 3-19, Comparative Examples 3-1 to 3-2] (Preparation of pigment dispersions 2 to 19, 22 to 23) Pigment dispersions 2 to 19 and 22 to 23 were prepared in the same manner as pigment dispersion 1, except that the formulation of pigment dispersion 1 was changed as shown in Table 3.

[0171] [Example 3-20] (Preparation of pigment dispersion 20) After stirring and mixing the following mixture to make it uniform, it was stirred in a dissolver equipped with a toothed disk of 4 cm at 70 °C and 5000 rpm for 180 minutes to prepare a pigment dispersion 20 with a non-volatile content of 20%. · Coating colorant 1: 18.0 parts · Acrylic resin solution 1: 10.0 parts (non-volatile content 2.0%) · Propylene glycol monomethyl ether acetate: 72.0 parts

[0172] [Example 3-21] (Preparation of pigment dispersion 21) After stirring and mixing the following mixture to make it uniform, it was dispersed for 3 hours using a 0.5 mm diameter zirconia bead in an Eiger mill (Mini Model M-250MKII manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 5.0 μm to prepare a pigment dispersion 21 with a non-volatile component content of 20%. · C.I. Pigment Red 254 ("Irgazin Red L 3660 HD" manufactured by BASF): 10.8 parts · Dye derivative 1: 1.2 parts · Resin (P-1): 6.0 parts · Acrylic resin solution 1: 10.0 parts (non-volatile content 2.0%) · Propylene glycol monomethyl ether acetate (PGMAc): 72.0 parts

[0173] <Evaluation of pigment dispersion> The obtained pigment dispersion was evaluated for dispersibility, viscosity stability, generation of foreign substances on the coating film, and filterability.

[0174] <Evaluation of dispersibility> When producing the above pigment dispersion, in-line sampling was performed when the dispersion time was 1 hour, and the average particle diameters of the sample dispersed for 1 hour and the sample dispersed for 3 hours were compared. The average particle diameter was measured as follows. The obtained pigment dispersion was diluted 100-fold with PGMAc, and about 5 ml of the diluted solution was measured for the average particle diameter by the dynamic light scattering measurement method (measurement device: NanotracWave (manufactured by Microtrac Bell Corporation)), and the average particle diameter (D50) was measured. Based on the obtained average particle diameter value, the dispersity was defined by the following formula. The smaller the value of the dispersity, the higher the dispersibility because the dispersion progresses in a shorter time. (Dispersity) = (average particle diameter of the product dispersed for 3 hours) / (average particle diameter of the product dispersed for 1 hour) ◎: Dispersity is 0.7 or more 〇: Dispersity is 0.65 or more and less than 0.7 ×: Dispersity is less than 0.65

[0175] (Stability of viscosity over time) The stability of the viscosity of the obtained dispersion over time was evaluated by the following method. The initial viscosity on the day after preparing the dispersion and the viscosity over time after 1 month at 13°C were measured at 25°C under the condition of a rotation speed of 50 rpm using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., "ELD-type viscometer"). From the values of this initial viscosity and viscosity over time, the viscosity change rate was calculated by the following formula, and the stability of the viscosity over time was evaluated in three levels. [Viscosity change rate over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| × 100 ◎: Viscosity change rate less than 5% (good) 〇: Viscosity change rate 5% or more and less than 20% (practicable) ×: Viscosity change rate 20% or more (not practicable)

[0176] (Foreign matter evaluation) The obtained dispersion was coated on a transparent glass substrate to a dry film thickness of 2.0 μm, and then heated in an oven at 230 °C for 1 hour to prepare a test substrate. The coating film of the test substrate was observed on the surface at a magnification of 500 times using a metallurgical microscope "BX60" (manufactured by Olympus Corporation) in transmission, and the number of foreign matters was measured in any 5 fields of view and evaluated according to the following criteria. ◎: Number of foreign matters less than 3 (excellent) ○: Number of foreign matters 3 or more and less than 20 (good) △: Number of foreign matters 21 or more and less than 100 (practicable) ×: Number of foreign matters 100 or more (not practicable)

[0177] (Filtration property evaluation) 10 parts of the obtained dispersion was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number; 39115221) under a nitrogen pressure of (0.3 MPa), and the mass that could be filtered was measured and evaluated according to the following criteria. ◎: Filtration amount 8.0 parts or more (good) 〇: Filtration amount 6.0 parts or more and less than 8.0 parts (practicable) ×: Filtration amount less than 6.0 parts (not practicable)

[0178]

Table 3

[0179] <Preparation of other dispersions> (Preparation of coloring composition (RP-50)) The following mixture was stirred and mixed uniformly, and then dispersed using zirconia beads with a diameter of 0.5 mm in an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) for 5 hours, and then filtered through a filter with a pore size of 5.0 μm to prepare a coloring composition (RP-50) with a non-volatile content of 40%. C.I. Pigment Red 177 (Manufactured by Sinic Co., Ltd., "Sinilex Red SR3C") 12.0 parts Resin (P-1) 12.0 parts Acrylic resin solution 1 16.0 parts Propylene glycol monomethyl ether acetate 55.0 parts Propylene glycol monomethyl ether 5.0 parts

[0180] <Preparation of photosensitive coloring composition> [Example 4-1] (Manufacture of coloring composition 1) Pigment dispersion 1 16.28 parts Coloring composition (RP-50) 33.72 parts Thermosetting compound (Epoxy compound "EHPE-3150" manufactured by Daicel Corporation) 0.16 part Polymerizable compound ("Aronix M402" manufactured by Toagosei Co., Ltd.) 1.16 parts Polymerizable compound ("Aronix M350" manufactured by Toagosei Co., Ltd.) 1.45 parts Photoinitiator (Oxime ester-based compound "NCI-831" manufactured by ADEKA Corporation) 0.05 part Photoinitiator (Oxime ester-based compound "OXE-04" manufactured by BASF SE) 0.05 part Photoinitiator (Compound represented by the following formula (31)) 0.30 part Sensitizer (Thioxanthone-based compound "KAYACURE DETX-S" manufactured by Nippon Kayaku Co., Ltd.) 0.05 part Thiol compound (Pentaerythritol tetrakis(thiopropionate)) 0.20 part Leveling agent (Silicone-based compound "BYK-330" manufactured by BYK-Chemie GmbH) 0.025 part Leveling agent (1% PGMAc solution of silicone-based compound DOWSIL FZ-2122 (manufactured by Dow Corning Toray Co., Ltd.)) 0.025 part Benzotriazole-based ultraviolet absorber ("Tinuvin 326" manufactured by BASF SE) 0.04 part Propylene glycol monomethyl ether acetate 22.84 parts 10.00 parts of ethyl 3 - ethoxypropionate 10.00 parts of propylene glycol monomethyl ether

[0181] Formula (31)

Chemical formula

[0182] [Examples 4 - 2 to 4 - 21, Comparative Examples 4 - 1 to 4 - 2] (Preparation of Coloring Compositions 2 to 23) Coloring Compositions 2 to 23 were prepared in the same manner as Coloring Composition 1, except that the pigment dispersion of Coloring Composition 1 was changed as shown in Table 4.

[0183] (Evaluation of Photosensitive Coloring Composition) The photosensitive coloring composition was evaluated for the temporal stability of viscosity, foreign matters, and heat resistance. The evaluation of the temporal stability of viscosity and foreign matters was carried out in the same manner as above.

[0184] (Heat Resistance Evaluation) The obtained coloring composition was coated on a glass substrate with a size of 100 mm in length × 100 mm in width and 1.1 mm in thickness using a spin coater so that the chromaticity under a C light source was y = 0.100. Then it was dried at 60 °C for 5 minutes and then heated at 230 °C for 20 minutes. After cooling to room temperature, a test substrate was obtained. The chromaticity ([L*(1), a*(1), b*(1)]) under a C light source of the prepared test substrate was measured using a micro - spectrophotometer ("OSP - SP100" manufactured by Olympus Optical Co., Ltd.). Then, as a heat resistance test, it was heated at 230 °C for 1 hour, and the chromaticity ([L*(2), a*(2), b*(2)]) under a C light source was measured. The color difference ΔEab* was calculated by the following formula from the chromaticity before and after heating, and the heat resistance was evaluated according to the following criteria. ΔEab* = √((L*(2) - L*(1))2+(a*(2) - a*(1))2+(b*(2) - b*(1))2 ) ◎: ΔEab* is less than 3.5 (excellent) 〇: ΔEab* is 3.5 or more and less than 5.0 (good) △: ΔEab* is 5.0 or more and less than 6.5 (usable) ×: ΔEab* is 6.5 or more (not usable)

[0185]

Table 4

[0186] (Flexographic printing ink) (Production of polyurethane resin (1)) While introducing nitrogen gas into a reaction vessel equipped with a thermometer, a stirrer, a reflux condenser, and a nitrogen gas introduction tube, 121.8 parts of PTG-3000SN (polytetramethylene glycol manufactured by Hodogaya Chemical Co., Ltd., number of functional groups 2, hydroxyl value 37 mgKOH / g, number average molecular weight 3000), 24.4 parts of PEG#2000 (polyethylene glycol manufactured by NOF Corporation, number of functional groups 2, hydroxyl value 56 mgKOH / g, number average molecular weight 2000), 32.7 parts of 2,2-dimethylolpropionic acid, and 66.9 parts of isophorone diisocyanate were charged and reacted at 90 °C for 3 hours to synthesize a water-soluble resin. After cooling, a mixed solution of 16.6 parts of 25% aqueous ammonia and 73.0 parts of ion-exchanged water was gradually added dropwise to the obtained water-soluble resin and neutralized to make it water-soluble, thereby obtaining an aqueous solution of polyurethane resin (1). The acid value of the obtained polyurethane resin (1) was 55 mgKOH / g, and the weight average molecular weight (Mw) was 36000.

[0187] (Production of flexographic printing ink) [Example 5-1] 25 parts of coating colorant 1, 0.6 part of potassium hydroxide, 35.0 parts of polyurethane resin (1), 0.1 part of nonionic surfactant (Surfynol 104PA, manufactured by Air Products), 2.0 parts of n-propanol, 2.0 parts of polyethylene wax (Aquapelto DP2502B, manufactured by Toyochem Co., Ltd.), 0.2 part of antifoaming agent (Tegoformex 1488, manufactured by Evonik), and 35 parts of ion-exchanged water were added, heated to 70 °C, and stirred with a high-speed mixer to obtain 100 parts of flexographic printing ink 1.

[0188] (Comparative Examples 5-1, 5-2) (Preparation of Flexographic Printing Inks 2 and 3) Flexographic printing inks 2 and 3 were prepared in the same manner as flexographic printing ink 1, except that the coating colorant of flexographic printing ink 1 was changed as shown in Table 5.

[0189] (Evaluation of Flexographic Printing Inks) For the obtained flexographic printing inks, the particle size distribution and the storage stability of viscosity over time were evaluated. Furthermore, the evaluation of coarse particles of the flexographic ink was carried out. The results are shown in Table 5.

[0190] (Evaluation of Coarse Particles) The obtained flexographic printing ink was evaluated for the presence or absence of coarse particles using a grind gauge (conforming to JIS K5600-2-5). The evaluation criteria are as follows. 〇: Less than 60 μm (good) △: 60 μm or more and less than 90 μm (practicable) ×: 90 μm or more (impractical)

[0191] (Storage Stability of Particle Size Distribution) The particle size distribution of the flexographic printing ink was measured by diluting with ion-exchanged water using Nanotrac Wave (manufactured by Microtrac Bell Co., Ltd.) to measure the D50 volume average particle diameter. Furthermore, after storing the flexographic printing ink in a constant temperature machine at 40 °C for one week, the particle size distribution was measured in the same manner, and the change rate was determined. The evaluation criteria are as follows. 〇: The change rate of the particle size distribution (D50) before and after storage at 40 °C for one week is less than ±10% (good) △: The change rate of the particle size distribution (D50) before and after storage at 40 °C for one week is ±10% or more and less than ±20% (no problem in practice) ×: The change rate of the particle size distribution (D50) before and after storage at 40 °C for one week is ±20% or more (impractical)

[0192] (Storage Stability of Viscosity) The viscosity of the flexographic printing ink at 25 °C was measured using a Zahn cup (No. 44). Furthermore, after storing in a constant temperature machine at 40 °C for one week to allow aging, the change rate of the viscosity before and after aging was determined. The evaluation criteria are as follows. 〇: The viscosity change rate before and after storage at 40°C for one week is less than ±10% (good). △: The viscosity change rate before and after storage at 40°C for one week is ±10% or more and less than ±15% (no practical problem). ×: The viscosity change rate before and after storage at 40°C for one week is ±15% or more (not practical).

[0193]

Table 5

[0194] From the results of Tables 3 to 5, the coating colorant of the examples is excellent in dispersibility, and the storage stability and filterability of the dispersion are good. Since the resin (P) has a carboxyl group derived from an acid dianhydride residue, it has a high adsorption ability for the colorant. Due to the steric repulsion effect of the first polymer site and the second polymer site, the coated colorant is easily dispersed, and a color composition excellent in dispersion stability and filterability can be obtained. On the other hand, the comparative examples had poor dispersibility, dispersion stability, and filterability.

Claims

Claim 1 A coated colorant in which the surface of a colorant is coated with a resin (P), wherein the resin (P) has a first polymer moiety, a second polymer moiety, and an acid dianhydride residue, the first polymer moiety includes a cyclic ester polymer, and the second polymer moiety includes a vinyl polymer, the coated colorant. Claim 2 The coated colorant according to claim 1, wherein the resin (P) has an acid value of 10 to 200 mgKOH / g. Claim 3 The coated colorant according to claim 1, wherein the acid dianhydride residue is a residue having an aromatic ring. Claim 4 The coated colorant according to claim 1, wherein the cyclic ester polymer is a polymer including polylactone. Claim 5 The coated colorant according to claim 1, wherein the resin (P) contains 20 to 80% by mass of the first polymer moiety. Claim 6 A dispersion including the coated colorant according to any one of claims 1 to 5 and a binder resin (excluding the resin (P)). Claim 7 A photosensitive coloring composition including the dispersion according to claim 6, a polymerizable compound, and a photopolymerization initiator.

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