Colored composition, photosensitive colored composition, film, and optical filter

Abstract

To provide a colored composition which does not easily generate a phase difference and can form a film with an excellent chemical resistance.SOLUTION: The present invention relates to a colored composition including a colorant and a dispersant, the dispersant including an aromatic carboxylic acid moiety and a vinyl polymer moiety containing a polymerizable unsaturated group, and the vinyl polymer moiety including a monomer unit having a linear alkyl group with six or more carbon atoms. In this colored composition, it is preferable that the monomer unit having a linear alkyl group with at least six carbon atoms be contained in an amount of 2-40 mass% among all monomer units constituting the vinyl polymer moiety.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a colored composition for use in forming an optical filter. [Background technology]

[0002] Image display devices such as televisions and personal computers have a viewing angle dependency problem caused by the refractive index anisotropy of liquid crystal cells and polarizing plates. This problem results in differences in color and contrast when comparing an image viewed from the front of the liquid crystal display device with an image viewed from an oblique angle. To address this issue, retardation films are incorporated into liquid crystal display devices to compensate for the retardation. The color filters used in liquid crystal display devices have different phase differences depending on the RGB (red, green, blue) colored layers, so as the screen size of liquid crystal display devices increases, even if a phase difference film is used, compensation for the differences in phase differences between the colored layers of each color becomes insufficient. In particular, when displaying black, there is a problem in that the image appears reddish black or bluish black when viewed from an angle. Note that the same problem exists with color filters used in organic EL display devices, etc.

[0003] The viewing angle dependency of the black display of an image display device is caused by the difference in the phase difference between the RGB colored layers, and it is known that the dependency improves as the phase difference approaches zero. Therefore, Patent Document 1 discloses a coloring composition containing an additive having a specific structure. Furthermore, Patent Document 2 discloses a method for appropriately adjusting the glass transition temperature of a dispersant. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2013-82905 [Patent Document 2] Patent No. 5326848 Summary of the Invention [Problem to be solved by the invention]

[0005] However, although the conventional method improves the retardation, it has the problem of reducing the chemical resistance of the film.

[0006] An object of the present invention is to provide a coloring composition that can form a film that is less likely to cause retardation and has good chemical resistance. [Means for solving the problem]

[0007] The coloring composition of the present invention contains a colorant and a dispersant, The dispersant has an aromatic carboxylic acid moiety and a polymerizable unsaturated group-containing vinyl polymer moiety, and the vinyl polymer moiety has a chain alkyl group-containing monomer unit having 6 or more carbon atoms. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a coloring composition capable of forming a film that is less likely to cause retardation and has good chemical resistance. Furthermore, the present invention can provide a photosensitive coloring composition, a film, and an optical film. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present invention will be described in detail below. The terms used in this specification are defined below. Unless otherwise specified, the terms "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" respectively mean "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide." Furthermore, in this specification, "CI" means color index (CI). A monomer refers to the form before polymerization, and a monomer unit refers to the form that constitutes a resin after the monomer is polymerized. In this specification, the thickness direction retardation (Rth) of the colored layer is a value expressed by the following formula, where Nx is the refractive index in the fast axis direction (the direction in which the refractive index is smallest) in the plane of the colored layer, Ny is the refractive index in the slow axis direction (the direction in which the refractive index is largest), Nz is the refractive index in the thickness direction, and d (nm) is the thickness of the colored layer. Rth={(Nx+Ny) / 2-Nz}×d The Rth of the colored layer was measured using a retardation layer measuring device (Axoscan manufactured by AXOM ETRICS). TM The values ​​are measured using a Mueller Matrix Polarimeter. In the case of three colored layers of red, green, and blue, values ​​measured at three wavelengths of 620 nm (red colored layer), 550 nm (green colored layer), and 450 nm (blue colored layer) are used.

[0010] The present invention provides a coloring composition containing a colorant and a dispersant, The dispersant is a colored composition having an aromatic carboxylic acid moiety and a polymerizable unsaturated group-containing vinyl polymer moiety, and the vinyl polymer moiety has a chain alkyl group-containing monomer unit having 6 or more carbon atoms. The colored composition of the present invention can be used for applications such as ink, paint, colored molded article, color filter, etc. Among these, color filter is preferred.

[0011] In the coloring composition of the present invention, the dispersant has an aromatic carboxylic acid moiety that acts as a colorant adsorption site, and a vinyl polymer moiety that acts as a steric repulsion site. When the colorant is finely dispersed, the colorant simultaneously undergoes micronization and crystallization. It is speculated that crystal growth of the colorant, which has orientation, occurs during crystallization, and the resulting crystals are uniformly aligned throughout the film, resulting in the development of thickness-direction retardation. While the detailed mechanism is unknown, this specification speculates that the use of the dispersant reduces thickness-direction retardation by inhibiting crystal growth through the action of the linear alkyl group-containing monomer units with 6 or more carbon atoms in the vinyl polymer moiety, which act as steric repulsion sites. Furthermore, it is speculated that the polymerizable unsaturated groups in the vinyl polymer moiety fix the molecular arrangement of the colorant, whose crystal growth has been inhibited, after reaction (curing), thereby maintaining the reduced thickness-direction retardation. Furthermore, the curing of the polymerizable unsaturated groups provides the film with solvent resistance.

[0012] <Coloring agent> Colorants include pigments, dyes, and near-infrared absorbing dyes. Examples of pigments include organic pigments and inorganic pigments. Organic pigments with high color development and heat resistance are preferred. Specific examples of organic pigments are listed below using color index numbers.

[0013] Red pigments include, for example, CI 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, the pigments described in JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light fastness, and transmittance of the filter segment, preferred are CI Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, and 296, the pigments described in JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844, and more preferred are CI Pigment Red 177, 254, 291, 295, and 296, the pigments described in JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844. Examples of orange pigments include CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, and 73. Examples of blue pigments include CI 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, and 79. Among these, from the viewpoints of heat resistance, light fastness, and transmittance of the filter segment, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and CI Pigment Blue 15:6 is more preferred. Examples of purple pigments include CI 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, and 50. Among these, from the viewpoints of heat resistance, light fastness, and transmittance of the filter segment, CI Pigment Violet 19 or 23 is preferred, and CI Pigment Violet 23 is more preferred. Examples of green pigments include CI 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, and 63, and pigments described in JP-A-2017-111398. Among these, CI Pigment Green 36, 58, 59, 62, and 63, and the pigments described in JP-A-2017-111398 are preferred from the viewpoint of transmittance. Yellow pigments include, for example, CI 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, and 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, and the pigments described in JP-A-2012-226110. Preferred are CI Pigment Yellows 138, 139, 150, 185, 231, and 233, and the pigments described in JP-A-2012-226110. Examples of purple pigments include CI Pigment Violet 1 and 19, and CI Pigment Red 144, 146, 177, 169, and 81.

[0014] Examples of inorganic pigments include metal oxide powders, metal sulfide powders, and metal powders such as barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, titanium black, synthetic iron black, titanium oxide, and iron tetroxide. Inorganic pigments are used in combination with organic pigments to ensure good coatability, sensitivity, developability, and the like while maintaining a balance between saturation and brightness.

[0015] The content of the colorant is preferably 5 to 80 mass %, more preferably 7 to 70 mass %, based on 100 mass % of the nonvolatile content of the colored composition. When the colorant is contained in an appropriate amount, good color properties are easily obtained.

[0016] <Dispersant> The dispersant has an aromatic carboxylic acid moiety and a polymerizable unsaturated group-containing vinyl polymer moiety, and the vinyl polymer moiety has a chain alkyl group-containing monomer unit having 6 or more carbon atoms. The aromatic carboxylic acid moiety of the dispersant acts as a pigment adsorption site, and the vinyl polymer moiety acts as a steric repulsion site, so that aggregation of the pigment is suppressed and a dispersion with excellent dispersion stability can be obtained. Note that the aromatic carboxylic acid has a structure in which the aromatic ring and the carboxyl group are directly bonded. As described above, by having a chain alkyl group-containing monomer unit having 6 or more carbon atoms and a polymerizable unsaturated group in the vinyl polymer portion, the retardation in the thickness direction of the cured film can be reduced and the chemical resistance of the film can be improved.

[0017] (Method for synthesizing dispersants) The dispersant herein can be synthesized, for example, by the following method: a first step of producing an aromatic carboxylic acid moiety by reacting a compound having two hydroxyl groups and one thiol group in the molecule with an aromatic compound having two or more acid anhydride groups in the molecule; a second step of producing a compound having a vinyl polymer moiety by radically polymerizing a linear alkyl-containing monomer having 6 or more carbon atoms using the thiol group remaining in the aromatic carboxylic acid moiety as a chain transfer agent; and a third step of modifying the vinyl polymer moiety to a vinyl polymer moiety containing a polymerizable unsaturated group.

[0018] A method for synthesizing the dispersant will be described. (Synthesis of aromatic carboxylic acid moiety (first step)) The aromatic carboxylic acid moiety in the dispersant is synthesized by reacting a compound having two hydroxyl groups and one thiol group in the molecule with an aromatic compound having two or more acid anhydride groups in the molecule. A catalyst and an organic solvent can be used for the reaction.

[0019] (A compound with two hydroxyl groups and one thiol group in the molecule) Examples of compounds 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 (thioglycerin), 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, and 2-mercaptoethyl-2-ethyl-1,3-propanediol. The amount of the compound having two hydroxyl groups and one thiol group used in the second step is preferably 1 to 10% by mass, more preferably 2 to 9% by mass, and even more preferably 3 to 8% by mass, based on the total amount of monomers used in the second step. Using an appropriate amount makes it easy to obtain a vinyl polymer with an appropriate molecular weight that functions as a steric repulsion site when dispersing the pigment.

[0020] (Aromatic compounds with two or more acid anhydride groups in the molecule) Examples of aromatic compounds having two or more acid anhydride groups in the molecule include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7 ... Phthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic 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)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic) dianhydride, m-phenylene-bis(triphenylphthalic) dianhydride, bis(triphenylphthalic)-4,4'-diphenyl ter dianhydride, bis(triphenylphthalic)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

[0021] Examples of aromatic compounds having two or more acid anhydride groups in the molecule include aromatic tetracarboxylic dianhydrides represented by the following general formula (1) or (2).

[0022] General formula (1) [ka] [In general formula (1), k is 1 or 2.]

[0023] General formula (2) [ka] In general formula (2), Q1 is a direct bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following general formula (3), or a group represented by the following general formula (4).

[0024] General formula (3) [ka]

[0025] General formula (4): [ka]

[0026] Aromatic compounds having two or more acid anhydride groups in the molecule can be used alone or in combination. From the viewpoint of adsorption to colorants, aromatic tetracarboxylic dianhydrides are preferred, and pyromellitic dianhydride is more preferred.

[0027] The amount of the aromatic compound having two or more acid anhydride groups in the molecule is preferably 0.3 to 1, more preferably 0.5 to 1, and even more preferably 0.6 to 0.8, in terms of the molar ratio of acid anhydride groups to hydroxyl groups in the compound having two hydroxyl groups and one thiol group in the molecule (number of moles of acid anhydride groups / number of moles of hydroxyl groups).Using an appropriate amount increases the adsorption to the colorant and improves dispersibility. A catalyst and an organic solvent can be used when reacting a compound having two hydroxyl groups and one thiol group in the molecule with an aromatic compound having two or more acid anhydride groups in the molecule.

[0028] The catalyst is preferably a tertiary amine compound, such as triethylamine, triethylenediamine, N,N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo-[5.4.0]-7-undecene, or 1,5-diazabicyclo-[4.3.0]-5-nonene.

[0029] Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, acetonitrile, hexane, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0030] The reaction temperature for synthesis of the aromatic carboxylic acid moiety is preferably 50 to 180°C, more preferably 80 to 140°C.

[0031] (Synthesis of vinyl polymer portion (second step)) The synthesis of the vinyl polymer moiety is preferably carried out by radically polymerizing a monomer containing a chain alkyl group having 6 or more carbon atoms using the thiol group remaining in the aromatic carboxylic acid moiety produced in the first step as a chain transfer agent to produce the vinyl polymer moiety.

[0032] (monomers containing chain alkyl groups with 6 or more carbon atoms) Examples of chain alkyl monomers having 6 or more carbon atoms include hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, myristyl (meth)acrylate, isomyristyl (meth)acrylate, cetyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, arachidyl (meth)acrylate, and behenyl (meth)acrylate.

[0033] Of all the monomer units constituting the vinyl polymer moiety of the dispersant, the content of the monomer units containing a chain alkyl group having 6 or more carbon atoms is preferably 2 to 40% by mass, more preferably 2 to 30% by mass. When the content is 2% by mass or more, the oriented crystal growth of the pigment is further suppressed, making it easier to reduce the retardation in the thickness direction of the film. Furthermore, when the content is 40% by mass or less, the chemical resistance of the film is further improved. The chain alkyl group-containing monomer having 6 or more carbon atoms is preferably a chain alkyl group-containing monomer having 6 to 22 carbon atoms, more preferably a chain alkyl group-containing monomer having 8 to 22 carbon atoms, and even more preferably a chain alkyl group-containing monomer having 10 to 22 carbon atoms. When a chain alkyl group-containing monomer having 6 or more carbon atoms is used, crystal growth with molecular orientation of the colorant is suppressed, and the retardation in the thickness direction of the film is likely to be reduced.

[0034] (Other monomers) As the monomer constituting the vinyl polymer segment, other monomers than the chain alkyl group-containing monomer having 6 or more carbon atoms can be used. Examples of other monomers include alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, isoamyl (meth)acrylate, methoxy (meth)acrylate, and ethoxy (meth)acrylate; hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, and glycerin mono(meth)acrylate; alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate; N-(hydroxyalkyl)(meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, and N-(2-hydroxybutyl)(meth)acrylamide; hydroxyalkyl vinyl ethers such as 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, and 2-(or 3- or 4-)hydroxybutyl vinyl ether; hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, and 2-(or 3- or 4-)hydroxybutyl allyl ether; hydroxyl group-containing monomers obtained by adding alkylene oxides and / or lactones to the hydroxyalkyl(meth)acrylates, alkyl-α-hydroxyalkyl(meth)acrylates, N-(hydroxyalkyl)(meth)acrylamides, hydroxyalkyl vinyl ethers, and hydroxyalkyl allyl ethers; alkoxy-terminated polyalkylene glycol (meth)acrylates such as methoxypolyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, methoxypolytetramethylene glycol (meth)acrylate, and methoxypolyethylene glycol polypropylene glycol (meth)acrylate; cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate; (Meth)acryloxy-modified polydimethylsiloxanes (silicone macromers); (meth)acrylates having a heterocycle, such as glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and 3-methyl-3-oxetanyl (meth)acrylate; (meth)acrylic monomers having an aromatic ring, such as benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, and nonylphenoxypolyethylene glycol (meth)acrylate; (meth)acrylates having a carboxyl group, such as (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, and ω-carboxypolycaprolactone (meth)acrylate; Styrenic monomers such as styrene and α-methylstyrene; vinyl compounds such as vinyl acetate, vinyl (meth)acrylate, and allyl (meth)acrylate; (Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; Examples include nitriles such as (meth)acrylonitrile.

[0035] The other monomers can be used alone or in combination of two or more.

[0036] The polymerization initiator used for the polymerization includes azo compounds and organic peroxides. Examples of azo compounds 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), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

[0037] Examples of organic peroxides include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl)peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxypivalate, (3,5,5-trimethylhexanoyl)peroxide, dipropionyl peroxide, and diacetyl peroxide.

[0038] The polymerization initiators can be used alone or in combination of two or more.

[0039] The amount of the polymerization initiator used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of all the monomers used in the synthesis of the vinyl polymer segment.

[0040] The synthesis of the vinyl polymer is preferably carried out by bulk polymerization or solution polymerization. In the case of solution polymerization, examples of the polymerization solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. The polymerization solvent can be used alone or in combination of two or more.

[0041] (Modification to a vinyl polymer containing a polymerizable unsaturated group (third step)) The third step may be, for example, a method of reacting a modifier having a polymerizable unsaturated group with a vinyl polymer moiety, as follows. [1] A method of reacting an epoxy group in a vinyl polymer moiety with a carboxyl group in a carboxylic acid compound having a polymerizable unsaturated group. [2] A method of reacting a carboxyl group in a vinyl polymer moiety with an epoxy group in an epoxy compound having a polymerizable unsaturated group. [3] A method of reacting a carboxyl group or a hydroxyl group in a vinyl polymer moiety with a vinyl ether group in a vinyl ether compound having a polymerizable unsaturated group. [4] A method of reacting a hydroxyl group in a vinyl polymer moiety with an isocyanate group in an isocyanate compound having a polymerizable unsaturated group.

[0042] Examples of the modifying agent having a polymerizable unsaturated group include carboxylic acid compounds such as (meth)acrylic acid and succinic acid mono[2-(meth)acryloyloxyethyl]; epoxy compounds such as glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether and 3,4-epoxycyclohexylmethyl (meth)acrylate; vinyl ether compounds such as 2-(2-vinyloxyethoxy)ethyl (meth)acrylate; and isocyanate group-containing (meth)acrylates such as 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxymethyl]ethyl isocyanate. Among these, the modifying agent is preferably a compound having one isocyanate group and one or more polymerizable unsaturated groups in the molecule, and more preferably 2-(meth)acryloyloxyethyl isocyanate.

[0043] The amount of the compound having one isocyanate group and one or more polymerizable unsaturated groups in the molecule is preferably 0.1 to 1, more preferably 0.3 to 1, and even more preferably 0.5 to 1, in terms of the molar ratio (number of moles of isocyanate groups / number of moles of hydroxyl groups) of the hydroxyl group in the hydroxyl group-containing monomer used in the second step to the isocyanate group in the compound having one isocyanate group and one or more polymerizable unsaturated groups in the molecule. When the molar ratio is 0.1 or more, curability is easily improved, making it easier to achieve both chemical resistance and reduced retardation in the thickness direction. When the molar ratio is 1 or less, unreacted isocyanate groups are less likely to remain in the dispersant, making it easier to maintain the storage stability of the dispersant and colored composition.

[0044] The reaction temperature is preferably 40 to 150° C., more preferably 60 to 120° C. If the reaction temperature is 40° C. or higher, the reaction proceeds efficiently, and if the reaction temperature is 150° C. or lower, decomposition of the generated urethane groups is easily suppressed.

[0045] In the third step, an organic solvent can be newly added. Examples of organic solvents include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate. The organic solvents can be used alone or in combination of two or more.

[0046] (molecular weight) The weight-average molecular weight (Mw) of the dispersant is preferably 8,000 to 50,000, more preferably 8,000 to 25,000. When Mw is 8,000 or more, the steric repulsion effect is enhanced, making it easier to suppress pigment aggregation and further improving pigment dispersibility. When Mw is 50,000 or less, the pigment dispersibility can be maintained due to a sufficient steric repulsion effect, and the chemical resistance of the film also tends to improve.

[0047] (unsaturated double bond equivalent) The unsaturated double bond equivalent of the dispersant is preferably 300 to 3600 g / mol, more preferably 300 to 2500 g / mol. When the unsaturated double bond equivalent is 300 g / mol or more, the storage stability of the dispersant and the coloring composition is easily maintained. When the unsaturated double bond equivalent is 3600 g / mol or less, the curability is improved, and it becomes easier to achieve both chemical resistance of the film and reduced retardation in the thickness direction. The unsaturated double bond equivalent of the dispersant is expressed as (non-volatile content of the dispersant [g]) / (mol number of moles of polymerizable unsaturated groups in the dispersant [mol]).

[0048] (acid number) The acid value of the dispersant is preferably 5 to 200 mgKOH / g, more preferably 10 to 180 mgKOH / g, and even more preferably 20 to 150 mgKOH / g. When the acid value is 5 mgKOH / g or more, the adsorption ability to the pigment is improved, and the dispersibility is further improved. When the acid value is 200 mgKOH / g or less, the interaction between the resins is weakened, and the viscosity of the colored composition can be kept low.

[0049] The content of the dispersant is preferably 0.01 to 200 parts by mass, more preferably 0.01 to 150 parts by mass, and even more preferably 5 to 100 parts by mass, relative to 100 parts by mass of the colorant. When the content of the dispersant is 0.01 part by mass or more, a good colorant dispersion effect is obtained, while when the content is 200 parts by mass or less, the interaction between the resins is weakened, allowing the viscosity of the colored composition to be kept low. Furthermore, by setting the content within the above range, it becomes easier to achieve both chemical resistance of the film and reduced retardation in the thickness direction.

[0050] The photosensitive coloring composition of the present invention can contain a coloring composition, a polymerizable compound, and a photopolymerization initiator.

[0051] <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, and a (meth)allyl group. The number of polymerizable unsaturated groups in the photopolymerizable compound is 1 or more, and preferably 2 to 20.

[0052] The polymerizable compound may be, in addition to the monomers that can be used in the synthesis of the vinyl polymer portion, for example, 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)alkylene glycol di(meth)acrylates such as 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, and 2-ethyl-2-butylpropanediol di(meth)acrylate; Di(meth)acrylates such as dimethyloldicyclopentane di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, stearic acid-modified pentaerythritol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, tetramethylene oxide-modified bisphenol A di(meth)acrylate, ethylene oxide-modified bisphenol F di(meth)acrylate, propylene oxide-modified bisphenol F di(meth)acrylate, tetramethylene oxide-modified bisphenol F di(meth)acrylate, zinc diacrylate, ethylene oxide-modified phosphate triacrylate, and glycerol di(meth)acrylate; (meth)acrylates having a tertiary amino group, such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and diethylaminopropyl (meth)acrylate; trifunctional or higher polyfunctional (meth)acrylates such as glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and 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 p) Epoxy (meth)acrylates such as acrylic acid adducts, epichlorohydrin-modified phthalic acid-(meth)acrylic acid adducts, epichlorohydrin-modified hexahydrophthalic acid-(meth)acrylic acid adducts, ethylene glycol diglycidyl ether-(meth)acrylic acid adducts, polyethylene glycol diglycidyl ether-(meth)acrylic acid adducts, propylene glycol diglycidyl ether-(meth)acrylic acid adducts, polypropylene glycol diglycidyl ether-(meth)acrylic acid adducts, phenol novolac epoxy resin-(meth)acrylic acid adducts, cresol novolac epoxy resin-(meth)acrylic acid adducts, and other epoxy resin-(meth)acrylic acid adducts; (meth)acryloyl-modified resin oligomers such as (meth)acryloyl-modified isocyanurate, (meth)acryloyl-modified polyurethane, (meth)acryloyl-modified polyester, (meth)acryloyl-modified melamine, (meth)acryloyl-modified silicone, (meth)acryloyl-modified polybutadiene, and (meth)acryloyl-modified rosin; and the like.

[0053] The polymerizable compounds can be used alone or in combination of two or more kinds.

[0054] The content of the polymerizable compound is preferably 5 to 500 parts by mass, more preferably 10 to 400 parts by mass, relative to 100 parts by mass of the colorant. When an appropriate amount is added, the curability and developability are further improved.

[0055] From the viewpoint of suppressing foreign matter, the copper ion concentration in the polymerizable compound is preferably 100 ppm or less, more preferably 50 ppm or less.

[0056] An example of a commercially available polymerizable compound having a copper ion concentration of 100 ppm or less is TJ-DP8 manufactured by TOA-JET CHEMICAL CO., LTD.

[0057] <Polymerization initiator> The photosensitive coloring composition of the present invention may contain a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Among these, a photopolymerization initiator is preferred.

[0058] Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; triazine-based compounds 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-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; and carbazole compounds.

[0059] Commercially available products include acetophenone compounds such as Omnirad 907, 369E, 379EG, 127, 184, 1173, and 2959 manufactured by IGM Resins, acylphosphine compounds such as Omnirad 819 and TPO manufactured by IGM Resins, oxime compounds such as IRGACURE OXE-01, 02, 03, 04, and 05 manufactured by BASF Japan, ADEKA ARKULES N-1919, NCI-730, 831E, and 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., and IGM Examples include Omnirad 1312, 1314, and 1316 manufactured by Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 306, and EOX-01 manufactured by Daito Chemiks. Further, compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, JP 2019-507108 A, JP 2019-528331 A, WO 2021 / 175855, JP 2022-5115524 A, etc., can also be mentioned.

[0060] (oxime compounds) In this specification, the photopolymerization initiator preferably contains an oxime compound from the viewpoint of suppressing the generation of foreign matter.

[0061] Specific examples of oxime compounds are shown below, but the present invention is not limited to these.

[0062] [ka]

[0063] [ka]

[0064] [ka]

[0065] The oxime compounds can be used alone or in combination of two or more.

[0066] From the viewpoint of suppressing the generation of foreign matter, the oxime compound preferably contains at least one selected from the compounds represented by the above (C1-1) to (C1-7).

[0067] (Compound represented by general formula (5)) The photopolymerization initiator preferably contains a compound represented by general formula (5).

[0068] General formula (5) [ka]

[0069] In general formula (5), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and R3 represents a hydrogen atom or a monovalent substituent.

[0070] The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylmethyl group, etc. Of these, a linear alkyl group having 3 to 8 carbon atoms is preferred, and a linear alkyl group having 4 to 6 carbon atoms is more preferred.

[0071] Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl groups; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy groups; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; optionally substituted benzoyl groups; and optionally substituted thenoyl groups. Substituents that the benzoyl and thenoyl groups may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred.

[0072] Examples of methods for producing the compound represented by general formula (5) include those described in JP-T-2019-507108 and JP-T-2019-528331.

[0073] Specific examples of the compound represented by formula (5) are shown below, but the present invention is not limited to these.

[0074] [ka]

[0075] Examples of the thermal polymerization initiator include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. pinacol-based compounds such as silane, 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); Examples of the organic peroxide include methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic peroxide, and benzoyl peroxide.

[0076] The polymerization initiators can be used alone or in combination of two or more.

[0077] The content of the polymerization initiator is preferably from 0.1 to 20% by mass, and more preferably from 0.5 to 10% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0078] The photosensitive coloring composition of the present invention can use a sensitizer in combination with the photopolymerization initiator. This improves photocurability. Examples of sensitizers include α-acyloxyester, acylphosphine oxide, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 4,4'-diethylaminobenzophenone.

[0079] The sensitizers can be used alone or in combination of two or more.

[0080] The content of the sensitizer is preferably 0.1 to 60 parts by mass relative to 100 parts by mass of the photopolymerization initiator. When an appropriate amount is added, the curability and developability are further improved.

[0081] <Leveling agent> The photosensitive coloring composition of the present invention can contain a leveling agent, which improves the wettability of the composition to the transparent substrate during film formation and the drying property of the film. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

[0082] The leveling agents can be used alone or in combination of two or more.

[0083] The content of the leveling agent is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the balance between the coatability, pattern adhesion, and transmittance of the photosensitive coloring composition is further improved.

[0084] Examples of leveling agents include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; and amphoteric surfactants such as alkyl betaines such as alkyldimethylaminoacetic acid betaine and alkyl imidazolines.

[0085] Commercially available leveling agents include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie, and FZ-7002 and 211 manufactured by Toray Dow Corning Co., Ltd. 0, 2122, 2123, 2191, 5609, silicone surfactants such as X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.; Examples of fluorine-based surfactants include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation, FC-4430 and 4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A manufactured by Neos Corporation.

[0086] The content of the leveling agent is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, relative to 100 parts by mass of the colorant. When an appropriate amount is contained, dispersibility is further improved.

[0087] <Solvent> The coloring composition of the present invention may contain a solvent. Examples of the solvent include 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, and 3-methoxymethyl-2-methyl-1-propanediol. Butyl 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 ethanol, 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,Examples of the solvent include 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, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. The solvents can be used alone or in combination.

[0088] The content of the solvent is preferably 100 to 10,000 parts by mass, and more preferably 500 to 5,000 parts by mass, relative to 100 parts by mass of the colorant. By including a solvent, it becomes easier to adjust the viscosity of the coloring composition, and therefore it becomes easier to form a film with a smooth surface.

[0089] <Binder resin> The coloring composition of the present invention may contain a binder resin. The binder resin is a resin that, when formed into a film having a thickness of 2 μm, has a transmittance of preferably 80% or more, more preferably 95% or more, over the entire wavelength range of 400 to 700 nm in the visible light region. Examples of the resin include thermoplastic resins and photosensitive resins.

[0090] Examples of thermoplastic resins include butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, and polyimide resins.

[0091] 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 having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group, or with cinnamic acid, thereby introducing 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 a hydroxyalkyl (meth)acrylate.

[0092] When the photosensitive coloring composition is used herein to form a film pattern by photolithography, the binder resin is preferably an alkali-soluble resin. The alkali-soluble resin is preferably a resin having an acidic functional group such as a carboxyl group or a sulfonic group and a weight-average molecular weight of 1,000 to 500,000, more preferably 5,000 to 100,000. Examples of alkali-soluble resins include acrylic resins having acidic functional groups, α-olefin / maleic acid (anhydride) copolymers, styrene / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having acidic functional groups, α-olefin / maleic acid (anhydride) copolymers, styrene / maleic acid (anhydride) copolymers, and styrene / styrene sulfonic acid copolymers are preferred because of their high heat resistance and transparency. The alkali-soluble resin may also be a photosensitive resin.

[0093] The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, per 100 parts by mass of the colorant. When an appropriate amount is contained, a film can be easily formed and good color characteristics can be easily obtained.

[0094] The alkali-soluble resin may have a structural unit derived from a compound containing a phenolic hydroxyl group. When the alkali-soluble resin has such a structural unit, the interaction with other materials is strengthened by the π-π interaction of the aromatic ring and the hydrogen bond of the hydroxyl group. This can reduce problems with the voltage holding ratio caused by the ionic compound in the photosensitive coloring composition described below.

[0095] The content of the structural units derived from the compound containing a phenolic hydroxyl group is preferably from 5 to 70 mass %, and more preferably from 15 to 70 mass %, of all the structural units of the alkali-soluble resin.

[0096] <Method of producing colored composition> The coloring composition of the present invention is prepared by, for example, performing a dispersion treatment using a colorant, a dispersant, a solvent, and the like. When the colorant is an organic pigment, the organic pigment can be dispersed more finely by using a dispersing aid such as a dye derivative during the dispersion treatment. Furthermore, when the colorant has high solubility in the solvent, the dispersion treatment may not be necessary. When two or more colorants are used in combination, coloring compositions can be prepared for each colorant and then mixed. Alternatively, a coloring composition can be prepared by using multiple colorants at once. Next, a polymerizable compound, a photopolymerization initiator, etc. are further blended and mixed to obtain a photosensitive coloring composition. It goes without saying that the timing of blending each material is arbitrary.

[0097] The dispersion treatment can be carried out using a dispersion device such as 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.

[0098] After preparing the colored composition, 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 using means such as centrifugation, a sintered filter, or a membrane filter.

[0099] <Other dispersants> In the present specification, in addition to the dispersant described above, other dispersants may be used in combination, such as resin-type dispersants other than the dispersant used in the present invention, surfactants, etc.

[0100] Examples of the resin-type dispersant include anionic resin-type pigment dispersants such as styrene-maleic anhydride copolymer, olefin-maleic anhydride copolymer, poly(meth)acrylate, styrene-(meth)acrylic acid copolymer, (meth)acrylic acid-(meth)acrylic acid alkyl ester copolymer, (meth)acrylic acid-polyvinyl macromer copolymer, phosphate group-containing acrylic resin, aromatic carboxyl group-containing acrylic resin, polystyrene sulfonate, acrylamide-(meth)acrylic acid copolymer, carboxymethyl cellulose, polyurethane having a carboxyl group, formalin condensate of naphthalene sulfonate, and sodium alginate; a nonionic resin-based pigment dispersant such as polyvinyl alcohol, polyalkylene polyamine, polyacrylamide, or polymer starch; or Examples include polyethyleneimine, aminoalkyl(meth)acrylate copolymers, polyvinylimidazoline, polyurethanes having amino groups, reaction products of poly(lower alkyleneimine)s with polyesters having free carboxyl groups, and cationic resin-type pigment dispersants such as Satokinsan. Commercially available resin-type dispersants 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, and 2155 manufactured by BYK Japan. Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS, or Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, manufactured by Lubrizol Japan Corporation; 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., and EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4442, etc. manufactured by BASF Japan. 02, 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., and Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0101] Examples of the surfactant include the compounds already exemplified as the leveling agent.

[0102] The amount of the other dispersant used is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, relative to 100 parts by mass of the colorant.

[0103] <Dye derivatives> The coloring composition herein may contain a dye derivative. This allows for more finely dispersed colorants. The dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in the organic dye residue. Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group (hereinafter referred to as "acidic derivatives"), as well as amine salts thereof, sulfonamide groups, or compounds having basic substituents such as a tertiary amino group at the terminal (hereinafter referred to as "basic derivatives"), and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.

[0104] Examples of organic dyes include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo. Among these, basic derivatives are preferred.

[0105] The amount of the dye derivative used 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, per 100 parts by mass of the colorant. When the dye derivative is 1% by mass or more, the colorant can be easily finely dispersed. When the amount is 50% by mass or less, the heat resistance and light resistance are less likely to decrease.

[0106] Specific examples of basic derivatives are shown below, but are not limited to these.

[0107] [ka] JPEG2025168214000011.jpg37149JPEG2025168214000012.jpg5667JPEG2025168214000013.jpg6774

[0108] The film of the present invention is formed from a photosensitive coloring composition. The film is preferably used for optical filters. Examples of optical filters include color filters, near-infrared transmitting filters, and near-infrared blocking filters.

[0109] <Color filter> The color filter of the present invention has a base material (also referred to as a substrate) and filter segments formed from a photosensitive coloring composition. The color filter preferably has red filter segments, green filter segments, and blue filter segments by appropriately selecting the type of colorant used. Furthermore, the color filter may have magenta filter segments, cyan filter segments, and yellow filter segments instead of or in addition to the color filter segments. The substrate may be a transparent substrate or a reflective substrate. Examples of transparent substrates include glass substrates. Examples of reflective substrates include substrates that use aluminum electrodes or thin metal films as the reflective surface.

[0110] <Color filter manufacturing method> It is preferable to form a color filter by first forming a black matrix on a substrate and then forming filter segments. Alternatively, thin film transistors (TFTs) can be formed on the substrate before forming the black matrix. Examples of the black matrix include a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light-blocking agent is dispersed.

[0111] The filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, etc. In this specification, the most preferred method is the photolithography method.

[0112] Examples of the substrate include a glass plate having high transmittance to visible light, and a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate.

[0113] In photolithography, for example, a coloring composition containing a colorant of a certain color tone is applied to a transparent substrate to form a film with a dry film thickness of approximately 0.2 to 5 μm. The resulting film (hereinafter referred to as the "first film") is exposed (irradiated with light) through a mask having a predetermined pattern. The film is then developed by immersing it in a solvent or alkaline developer or by spraying the developer onto the film using a sprayer or the like, and the uncured portions are removed to obtain the desired pattern. This process can be similarly performed using photosensitive coloring compositions containing colorants of other colors to produce color filters having filter segments of each color. Furthermore, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first film from coming into contact with oxygen, thereby further improving exposure sensitivity. Furthermore, the color filter can be heated (post-baked) to cure any uncured photopolymerizable compound in the filter segments.

[0114] Examples of the coating device include spray coating, spin coating, slit coating, and roll coating. A drying step can be carried out during coating. Examples of the drying device include a hot air oven and an infrared heater.

[0115] The developer may be an alkaline developer, such as an inorganic alkali such as sodium carbonate or sodium hydroxide, or an organic alkali such as dimethylbenzylamine or triethanolamine. The developer may also contain an antifoaming agent or a surfactant. The dry film thickness of the filter segments and black matrix is ​​preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coated film, a reduced pressure dryer, convection oven, IR oven, hot plate, etc. may be used.

[0116] The post-baking temperature is preferably about 80 to 230°C.

[0117] In the present specification, the image display device preferably includes a color filter obtained by the above-described manufacturing method. To manufacture an image display device, a liquid crystal display (LCD) is obtained by laminating a substrate with an opposing substrate using a sealant, injecting liquid crystal through an injection port provided in the seal, sealing the injection port, and laminating polarizing films and retardation films to the outside of the substrate as needed. This LCD can be used in LCD display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convencive bend (OCB).

[0118] [Example of embodiment] Examples of embodiments of the present invention are given below: The present invention is not limited to the following.

[0119] In this specification, the image display device can be used for applications such as organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays in addition to liquid crystal display devices. <1> The present invention provides a coloring composition containing a colorant and a dispersant, The dispersant relates to a colored composition, wherein the dispersant has an aromatic carboxylic acid moiety and a polymerizable unsaturated group-containing vinyl polymer moiety, and the vinyl polymer moiety has a chain alkyl group-containing monomer unit having 6 or more carbon atoms. <2> Among all the monomer units constituting the vinyl polymer segment, monomer units containing a chain alkyl group having 6 or more carbon atoms account for 2 to 40 mass %. <1> A coloring composition. <3> The dispersant has an unsaturated double bond equivalent of 300 to 3600 g / mol. <1> or <2> A coloring composition. <4> The weight average molecular weight of the dispersant is 8,000 to 50,000. <1> ~ <3> Any of the coloring compositions. <5> <1> ~ <4> A photosensitive coloring composition comprising any one of the coloring compositions, a polymerizable compound, and a photopolymerization initiator. <6> <5> A film formed from the photosensitive coloring composition. <7> Substrate and <6> An optical filter having a film of <8> <7> An image display device having an optical filter. [Example]

[0120] The present invention will be described below based on examples. However, the present invention is not limited to these examples. In addition, "parts" means "parts by mass" and "%" means "% by mass".

[0121] (resin weight average molecular weight (Mw)) Weight-average molecular weight (Mw) was measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8320GPC (Tosoh Corporation). Two separation columns were connected in series, with both columns packed with "TSK-GEL SUPER HZM-N" in series. Measurements were performed at an oven temperature of 40°C, a THF solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 0.1 wt% of the above eluent, and 20 microliters was injected. All molecular weights are expressed in terms of polystyrene.

[0122] (Non-volatile content of resin) The nonvolatile content was calculated from the weight ratio before and after drying 1.0 g of the sample in an aluminum container in an electric oven at 200°C for 10 minutes. Nonvolatile content % = (weight of resin after drying) / (weight of resin before drying) x 100

[0123] (resin acid value) To 0.5-1.0 parts of the resin solution, 40 ml of pyridine and 5 ml of water were added and stirred to dissolve uniformly. The acid value of the resin solution was measured by titration using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L potassium hydroxide-ethanol aqueous solution as the titrant. The acid value per unit of nonvolatile content of the resin was then calculated from the acid value of the resin solution and the concentration of nonvolatile content of the resin solution. The acid value (mgKOH / g) of the dispersant in a dry state was calculated using the following formula. Acid value (mgKOH / g) = {(5.611 × α × F) / S} / (non-volatile content / 100) Where S: sample amount (g) α: Amount of 0.1 mol / L potassium hydroxide ethanol solution consumed (ml) F: Potency of 0.1 mol / L potassium hydroxide ethanol solution

[0124] (Example of manufacturing dispersant solution X1) A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 7 parts of 3-mercapto-1,2-propanediol, 10 parts of pyromellitic dianhydride, 0.06 parts of N,N-dimethylbenzylamine as a catalyst, and 69 parts of propylene glycol monomethyl ether acetate. After purging with nitrogen gas, the mixture was reacted at 120°C for 5 hours. Acid value measurement confirmed that 95% or more of the acid anhydride had been half-esterified. Next, 20 parts of n-hexyl acrylate, 25 parts of methyl methacrylate, 10 parts of tert-butyl methacrylate, 40 parts of 2-hydroxyethyl methacrylate, 5 parts of methacrylic acid, and 48 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel, which was then heated to 80°C. 0.2 parts of 2,2'-azobisisobutyronitrile was added, and the mixture was allowed to react for 10 hours. Measurement of the nonvolatile content confirmed that at least 95% had reacted. Subsequently, 39 parts of 2-acryloyloxyethyl isocyanate, 0.2 parts of hydroquinone as a polymerization inhibitor, 0.02 parts of dioctyltin dilaurate as a catalyst, and 40 parts of propylene glycol monomethyl ether acetate were charged, and the mixture was heated at 70°C while blowing in nitrogen gas and air. IR measurement revealed a peak of 2270 cm based on the isocyanate group. -1 After the disappearance of the peak was confirmed, propylene glycol monomethyl ether acetate was added to adjust the nonvolatile content to 45%, thereby obtaining a dispersant solution X1 having an acid value of 54 mg KOH / g, a weight average molecular weight of 12,000, and an unsaturated double bond equivalent of 565 g / mol.

[0125] (Production examples of dispersant solutions X2 to X17, and production examples of comparative dispersant solutions X19 and X20) Synthesis was carried out in the same manner as in the production example for dispersant solution X1, except that the raw materials and charged amounts shown in Table 1 were used, to obtain dispersant solutions X2 to X17 and comparative dispersant solutions X19 and X20.

[0126] (Example of manufacturing comparative dispersant solution X18) A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 7 parts of 3-mercapto-1,2-propanediol, 10 parts of pyromellitic dianhydride, 0.06 parts of N,N-dimethylbenzylamine as a catalyst, and 69 parts of propylene glycol monomethyl ether acetate. After purging with nitrogen gas, the mixture was reacted at 120°C for 5 hours. Acid value measurement confirmed that 95% or more of the acid anhydride had been half-esterified. Next, 20 parts of lauryl methacrylate, 65 parts of methyl methacrylate, 10 parts of tert-butyl methacrylate, 40 parts of 2-hydroxyethyl methacrylate, 5 parts of methacrylic acid, and 48 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel, heated to 80°C, and 0.2 parts of 2,2'-azobisisobutyronitrile was added. The reaction was allowed to proceed for 10 hours. Measurement of the nonvolatile content confirmed that more than 95% had reacted. Subsequently, propylene glycol monomethyl ether acetate was added to adjust the nonvolatile content to 45%, yielding comparative dispersant solution X18 with an acid value of 72 mgKOH / g and a weight-average molecular weight of 12,000.

[0127] [Table 1-1]

[0128] [Table 1-2]

[0129] The abbreviations in Table 1 are as follows: (Aromatic compounds with two or more acid anhydride groups in the molecule) PMDA: Pyromellitic dianhydride (A compound with two hydroxyl groups and one thiol group in the molecule) TG: 3-mercapto-1,2-propanediol (monomers containing chain alkyl groups with 6 or more carbon atoms) HA: n-hexyl acrylate OA: n-octyl acrylate 2EHMA: 2-Ethylhexyl methacrylate LMA: Lauryl methacrylate SA: Stearyl acrylate ·VA: Behenyl acrylate (Hydroxyl group-containing monomer) HEMA: 2-hydroxyethyl methacrylate (Other monomers) MMA: Methyl methacrylate tBMA: tert-butyl methacrylate ·MAA: methacrylic acid BA: n-butyl acrylate CHMA: Cyclohexyl methacrylate (Polymerization initiator) AIBN: 2,2'-azobisisobutyronitrile (denaturant) AOI: 2-Acryloyloxyethyl isocyanate MOI: 2-methacryloyloxyethyl isocyanate

[0130] <Method for producing binder resin> (Preparation of acrylic resin solution (E-1)) 262.0 parts of propylene glycol monomethyl ether was placed in a reaction vessel equipped with a separable four-neck flask thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer, and the vessel was heated to 120°C while nitrogen gas was injected into the vessel. At the same temperature, a mixture of 49.7 parts of 2-ethylhexyl acrylate (hereinafter, 2-EHA), 99.4 parts of glycidyl methacrylate (hereinafter, GMA), 6.6 parts of dicyclopentanyl methacrylate, 19.0 parts of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, and PGMAc was added dropwise from the dropping tube over 2.5 hours. After the dropwise addition was complete, the mixture was stirred for an additional 2 hours at 120°C to obtain a precursor. The atmosphere in the flask was then replaced with air, and 50.4 parts of acrylic acid (hereinafter referred to as AA) as a modifying compound, 0.6 parts of triphenylphosphine as catalysts, and 0.2 parts of methylhydroquinone were added, followed by a reaction at 110°C for 10 hours. This yielded a monomer unit (hereinafter referred to as GMA+AA) in which the epoxy group of GMA reacted with the carboxyl group of AA, and introduced a polymerizable unsaturated group-containing monomer unit. Next, 21.3 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) was added as a modifying compound and reacted at 110°C for 4 hours. This caused a portion of the hydroxyl groups of GMA + AA to react with THPA. Subsequently, PGMAc was added so that the nonvolatile content was 40% by mass, preparing acrylic resin solution (E-1). Acrylic resin solution (E-1) had an acid value of 38 mg KOH / g and a weight-average molecular weight of 12,000.

[0131] (Preparation of acrylic resin solution (E-2)) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 188 parts of propylene glycol monomethyl ether acetate. The mixture was stirred while purging with nitrogen gas and heated to 120°C. Next, a monomer mixture consisting of 58.8 parts of p-hydroxyphenyl methacrylate, 7.1 parts of dicyclopentanyl methacrylate, 17.7 parts of methacrylic acid, and 51.1 parts of 2-EHA, plus 11.2 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, was added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was stirred at 120°C for 2 hours to allow polymerization. After polymerization, PGMAc was added to adjust the nonvolatile content to 40% by mass to prepare acrylic resin solution (E-2). The acrylic resin solution (E-2) had a weight-average molecular weight of 8,000.

[0132] (Preparation of acrylic resin solution (E-3)) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 188 parts of propylene glycol monomethyl ether acetate, and the mixture was stirred while purging with nitrogen gas and heated to 120°C. Next, a mixture of 68.5 parts of p-hydroxyphenyl methacrylate (hereinafter referred to as PQMA) and 91.6 parts of GMA, plus 11.2 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator, was added dropwise from the dropping funnel to the flask. After the addition was complete, the mixture was stirred at 120°C for 2 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 0.05 parts of hydroquinone, 0.1 parts of tris(dimethylaminomethyl)phenol, and 44.9 parts of acrylic acid were added, followed by a reaction at 80°C for 6 hours. Next, 22.3 parts of THPA was added as a modifying compound, and the mixture was allowed to react at 110°C for 4 hours. PGMAc was added so that the non-volatile content was 40% by mass, and an acrylic resin solution (E-3) was prepared. The acrylic resin solution (E-3) had a weight average molecular weight of 10,000.

[0133] (Preparation of acrylic resin solutions (E-4 to E-7)) Alkali-soluble resin solutions (E-4 to E-7) were obtained in the same manner as for the acrylic resin solution (E-3), except that the amounts of raw materials used were changed as shown in Table 1-3.

[0134] (Preparation of acrylic resin solution (E-8)) (First stage: copolymerization reaction) A flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube was charged with 188 parts of propylene glycol monomethyl ether acetate, and the mixture was stirred while purging with nitrogen gas and heated to 120°C. Next, a mixture of 67.7 parts of PQMA and 69.2 parts of AA, to which 11.2 g of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was added, was added dropwise from the dropping funnel to the flask. After the dropwise addition, the mixture was stirred at 120°C for 2 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 90.5 parts of GMA, 0.45 parts of triphenylphosphine as a catalyst, and 0.3 parts of methylhydroquinone as a polymerization inhibitor were added, and the reaction was carried out at 120°C for 5 hours. After that, propylene glycol monomethyl ether acetate was added as a solvent so that the nonvolatile content was 40% by mass, and an acrylic resin solution (E-8) was prepared. The acrylic resin solution (E-8) had a weight average molecular weight of 10,000.

[0135] (Preparation of acrylic resin solution (E-9)) An alkali-soluble resin solution (E-9) was obtained in the same manner as in the preparation of acrylic resin solution (E-8), except that the amounts of raw materials used were changed as shown in Table 1-3.

[0136] [Table 1-3]

[0137] The abbreviations in Table 1-3 are as follows: PQMA: 4-hydroxyphenyl methacrylate (number of phenolic hydroxyl groups: 1) DA-AA: Dopamine acrylamide (number of phenolic hydroxyl groups: 2) GA-GMA: Ester compound of glycidyl methacrylate (GMA) and gallic acid, synthesized by the applicant (number of phenolic hydroxyl groups: 3) DCPMA: dicyclopentanyl methacrylate AA: acrylic acid GMA: Glycidyl methacrylate 2EHA: 2-ethylhexyl acrylate THPA: Tetrahydrophthalic anhydride

[0138] <Production of pigment dispersion> [Example 1-1] (Pigment Dispersion 1) The following mixture was stirred and mixed until uniform, and then dispersed for 3 hours in an Eiger mill (Mini Model M-250MKII, manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce Pigment Dispersion 1 with a non-volatile content of 20% by mass. PR254 (CI Pigment Red 254 "Irgazin RED 3630" manufactured by BASF Japan): 10.8 parts Dye derivative 1: 1.2 parts Dispersant solution x1: 17.8 parts Solvent (propylene glycol monomethyl ether acetate (PGMAc)): 70.2 parts

[0139] [Examples 1-2 to 1-26, Comparative Examples 1-1 to 1-6] (Pigment Dispersion 2-32) Pigment dispersions 2 to 32 were prepared in the same manner as in Example 1-1, except that the raw materials and amounts were changed as shown in Table 2.

[0140] [ka] JPEG2025168214000018.jpg62141JPEG2025168214000019.jpg6774

[0141] <Evaluation of pigment dispersion> The obtained pigment dispersion was evaluated for dispersibility, viscosity stability, generation of foreign matter on the film, and filterability.

[0142] (Stability of viscosity over time) The viscosity stability over time of the resulting dispersions was evaluated using the following method. The initial viscosity on the day after the dispersion was prepared and the viscosity over time after one month at 13°C were measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and 50 rpm. The viscosity change rate was calculated from the initial viscosity and viscosity over time values ​​using the following formula, and the viscosity stability over time was evaluated using a three-point scale. [Change in viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| x 100 ◎: Viscosity change rate less than 5% (good) 〇: Viscosity change rate is 5% or more but less than 20% (practical) ×: Viscosity change rate of 20% or more (not practical)

[0143] [Table 2]

[0144] <Production of Photosensitive Coloring Composition> [Example 2-1] (Photosensitive coloring composition 1) The following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition 1. The nonvolatile content was 15% by mass. Pigment dispersion 1: 25.0 parts Pigment dispersion 4: 25.0 parts Resin (E-1) solution: 4.6 parts Polymerizable compound (B1): 3.0 parts Oxime compounds: 0.15 parts Leveling agent (D1) solution: 1.0 part Organic solvent: 41.3 parts

[0145] The abbreviations in the table are as follows: Polymerizable compound (B1): Aronix M-402 manufactured by Toagosei Co., Ltd. Oxime compound: Irgacure OXE-04 manufactured by BASF Japan Ltd. Leveling agent (D1) solution: 1% PGMAc solution of BYK-330 (manufactured by BYK-Chemie) Organic solvent: methoxypropyl acetate

[0146] [Examples 2-2 to 2-31, Comparative Examples 2-1 to 2-4] (Photosensitive coloring composition 2-35) Photosensitive coloring compositions 2 to 35 were prepared in the same manner as in Example 2-1, except that the photosensitive coloring composition 1 in Example 2-1 was changed to the raw materials and amounts shown in Tables 3-1 to 3-4.

[0147] [Table 3-1]

[0148] [Table 3-2]

[0149] [Table 3-3]

[0150] [Table 3-4]

[0151] <Evaluation of Photosensitive Coloring Compositions for Color Filters in Examples> The obtained photosensitive coloring compositions 1 to 35 were evaluated for "measurement of retardation (Rth) in the thickness direction of the photosensitive coloring composition," "viscosity stability," and "evaluation of chemical resistance of film." The results are shown in Table 4. (Measurement of Retardation (Rth) in the Thickness Direction of Photosensitive Coloring Composition) The viewing angle dependency of the black display of the image display device is caused by differences in the retardation of each of the RGB colored layers, and improves as the retardation approaches zero. Therefore, the retardation (Rth) in the thickness direction of the colored layers was measured for each color. The obtained photosensitive coloring compositions were applied to glass substrates by spin coating, and then pre-baked on a hot plate at 80°C for 3 minutes. Then, after the substrates were cooled to room temperature, they were irradiated with an ultra-high pressure mercury lamp with an integrated light intensity of 150 mJ / cm. 2 The substrate was then alkali-developed, dried, and post-baked in an oven at 230°C for 20 minutes to obtain a colored layer of each color. The thickness of each film after drying was 2.0 μm. The Rth of the obtained colored layer was measured using the Rth measurement method described above. ⊚: Rth is less than ±3, which is a very good level. ◯: Rth is ±3 or more and less than ±5, which is a good level. △: Rth is ±5 or more and less than ±15, and is at a feasible level. ×: Rth is ±15 or more, which is extremely poor and not suitable for practical use.

[0152] (viscosity stability) The obtained photosensitive coloring composition was measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25 ° C. and a rotation speed of 50 rpm. The initial viscosity was measured. Separately, the photosensitive coloring composition was left standing in a sealed glass container at 40 ° C. for 24 hours, and then the viscosity was measured in the same manner as above, and was taken as the viscosity over time. ◯: The viscosity change rate was less than ±10%, and no sediment was formed. △: The viscosity change rate was ±10% or more and less than 20%, and no sediment was formed. ×: The viscosity change rate was ±20% or more, or sediment was formed even when the viscosity change rate was less than ±20%.

[0153] (Chemical resistance evaluation of membrane) The obtained photosensitive coloring composition was applied to a glass substrate of 100 mm length x 100 mm width and 1.1 mm thickness using a spin coater, and pre-baked on a hot plate at 80°C for 3 minutes. Then, after cooling the substrate to room temperature, an ultra-high pressure mercury lamp was used to irradiate the substrate with an integrated light dose of 150 mJ / cm. 2 The film was exposed to UV light at 400°C and developed in an alkaline developer at 23°C. The film was then heated at 230°C for 20 minutes and allowed to cool to prepare a substrate for evaluation. The film thickness was adjusted to 2 μm after heat treatment at 230°C. The evaluation substrate was measured after heat treatment at 230°C using a spectrophotometer (OSP-SP200, manufactured by Olympus Optical Co., Ltd.). The chromaticity ([L*(1), a*(1), b*(1)]) of the resulting film under Illuminant C was measured using a microspectrophotometer (OSP-SP100, manufactured by Olympus Optical Co., Ltd.). The chemical resistance test was then performed by immersing the film in NMP for 30 minutes. The chromaticity ([L*(2), a*(2), b*(2)]) under Illuminant C was measured. The color difference ΔEab* was calculated using the following formula and evaluated using the following three-point scale. ◯ indicates a good level, △ indicates a practically acceptable level, and × indicates a level that is not practically acceptable. ΔEab* = √((L*(2)- L*(1))2+ (a*(2)- a*(1))2+( b*(2)- b*(1))2) ○: ΔEab* is less than 1.5 △: ΔEab* is 1.5 or more and less than 3.0 ×: ΔEab* is 3.0 or more and 5.0 or more

[0154] [Table 4]

[0155] From the results in Table 4, it can be seen that the colored composition of the present invention can solve all of the problems, while the comparative examples could not solve all of the problems.

[0156] [Examples 2-32 to 2-51] (Photosensitive coloring composition 36~55) Photosensitive coloring compositions 36 to 55 were prepared in the same manner as in Example 2-1, except that the photosensitive coloring composition 1 in Example 2-1 was changed to the raw materials and amounts shown in Tables 3-5 and 3-6.

[0157] [Table 3-5]

[0158] [Table 3-6]

[0159] The abbreviations in the table are as follows: Polymerizable compound (B1): Aronix M-402 manufactured by Toagosei Co., Ltd. Polymerizable compound (B2): TJ-DP8 TOA-JET CHEMILAL CO.,LTD Oxime compound: Irgacure OXE-04 manufactured by BASF Japan Ltd. Leveling agent (D1) solution: 1% PGMAc solution of BYK-330 (manufactured by BYK-Chemie) Organic solvent: methoxypropyl acetate

[0160] <Evaluation of Photosensitive Coloring Compositions for Color Filters in Examples> The obtained photosensitive coloring compositions 36 to 55 were evaluated in the same manner as above for "measurement of retardation (Rth) in the thickness direction of the photosensitive coloring composition," "viscosity stability," and "evaluation of chemical resistance of the film." Furthermore, the following evaluations were performed. The results are shown in Table 5.

[0161] (Evaluation of the voltage holding rate of the film) [Voltage holding ratio evaluation] The obtained colored composition was applied using a spin coater onto a glass substrate having an ITO transparent electrode with an effective electrode size of 10 mm x 10 mm so that the coating film would be 2.0 μm thick after drying and heat treatment, the coating film on the electrode part was wiped off with a solvent, and then the substrate was exposed to ultraviolet light at an integrated dose of 50 mJ / cm2 and developed with an alkaline developer at 23°C to obtain a coated substrate. Next, the substrate was heated at 230°C for 20 minutes and allowed to cool, and two sample coated substrates for measurement were prepared. Two sample-coated glass substrates were placed facing each other with the ITO transparent electrode surfaces facing each other, and a small cell was fabricated using a sealant to create a cell gap of 9 μm. A liquid crystal solution was injected into this small cell across the cell gap to create an evaluation sample. A voltage of 5 V was applied to the resulting evaluation sample at 50°C for 60 μs over a span of 167 ms. The voltage holding ratio (VHR) (%) was measured 167 ms after the voltage was removed using a Toyo Corporation Model 6254 liquid crystal physical property evaluation system. The measured voltage holding ratio was evaluated using the following three-point scale: ◎: very good; ◯: good; △: acceptable; and ×: not acceptable. ◎: 95% or more ○: 85% or more, less than 95% △: 80% or more, less than 85% ×: Less than 80%

[0162] [Table 5]

[0163] From the results in Table 5, it can be seen that the colored composition using the resin into which the phenolic hydroxyl group has been introduced not only solves all the problems but also improves the voltage holding ratio to a very good level.

[0164] (Production of color filters) A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition 4 was applied to the substrate using a spin coater to form a colored film. A 150 mJ / cm 2 light was applied to the film using an ultra-high pressure mercury lamp through a photomask. 2 The substrate was then spray-developed with an alkaline developer consisting of a 0.2 wt% aqueous solution of sodium carbonate to remove the unexposed portions, washed with ion-exchanged water, and heated at 230°C for 20 minutes to form a red filter segment. The red filter segment, after heat treatment at 230°C, was adjusted to a chromaticity of x = 0.655, y = 0.325 under Illuminant C (hereinafter, this also applies to green and blue). Similarly, the green filter segment was adjusted to a chromaticity of x = 0.290, y = 0.600 using photosensitive coloring composition 31, and the blue filter segment was adjusted to a chromaticity of x = 0.139, y = 0.095 using photosensitive coloring composition 29. Each filter segment was then formed to obtain a color filter. From the above results, it was confirmed that the colored composition of the present invention has good viscosity stability and can provide a color filter that has both a low retardation in the thickness direction and chemical resistance.

Claims

1. A coloring composition containing a colorant and a dispersant, the dispersant has an aromatic carboxylic acid moiety and a polymerizable unsaturated group-containing vinyl polymer moiety, and the vinyl polymer moiety has a chain alkyl group-containing monomer unit having 6 or more carbon atoms.

2. The colored composition according to claim 1, wherein the vinyl polymer moiety contains 2 to 40% by mass of a monomer unit containing a chain alkyl group having 6 or more carbon atoms in all monomer units constituting the vinyl polymer moiety.

3. 2. The coloring composition according to claim 1, wherein the dispersant has an unsaturated double bond equivalent of 300 to 3600 g / mol.

4. 2. The colored composition according to claim 1, wherein the dispersant has a weight average molecular weight of 8,000 to 50,000.

5. A photosensitive coloring composition comprising the coloring composition according to any one of claims 1 to 4, a polymerizable compound, and a polymerization initiator.

6. A film formed from the photosensitive coloring composition according to claim 5.

7. An optical filter comprising a substrate and the film according to claim 6.

8. An image display device comprising the optical filter according to claim 7.

Images