Photosensitive coloring composition, color filter, liquid crystal display device, organic el display device and solid-state imaging element

Abstract

To provide a photosensitive coloring composition which achieves both solvent resistance and good pattern shape (linearity and cross-sectional shape), even when containing a coloring agent with high concentration.SOLUTION: A photosensitive coloring composition contains a coloring agent (A), a dispersion agent (B), a binder resin (C), a polymerizable compound (D), and a photopolymerizable initiator (E), wherein the polymerizable compound (D) contains an isocyanurate ring-containing polymerizable compound (D1) having two or three polymerizable unsaturated groups, and a polymerizable compound (D2) having three alkyleneoxy chain-containing polymerizable unsaturated groups (provided that the polymerizable compound contains no ring structure), and a mass ratio of the polymerizable compound (D1) to the polymerizable compound (D2) is 10:90 to 50:50.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a photosensitive coloring composition that can be used for color filters and the like that constitute an image display device or the like.

Background Art

[0002] An organic EL (organic electroluminescence) display device is used for high-definition and small displays of about 0.5 inches such as head-mounted displays and electronic viewfinders (hereinafter referred to as microdisplays). Since the heat resistance of the organic light-emitting layer of the organic EL (organic electroluminescence) display device is low, when forming a color filter on the organic EL element by photolithography, it is necessary to perform post-baking on the film after development at a low temperature of 150°C or lower. However, when the post-baking temperature is lowered, curing becomes insufficient, and problems such as pixel peeling caused by the solvent contained in the applied coloring composition and unevenness on the pixel surface (hereinafter referred to as surface roughness) occur during pixel formation in the next process. On the other hand, when the exposure amount is increased, the reaction of the polymerizable compound contained in the pixel proceeds, but it is very difficult to form pixels of any size. In addition, when the concentration of the colorant is increased, there is a problem that the photocurability is inhibited and it is difficult to form a pattern with a good shape.

[0003] On the other hand, Patent Document 1 discloses a photosensitive coloring composition containing a colorant, dipentaerythritol hexaacrylate as a photopolymerizable compound, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 as a photopolymerization initiator, and the like. Patent Document 2 discloses a photosensitive coloring composition containing a colorant, at least one photopolymerizable compound selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate, at least one photopolymerization initiator selected from the group consisting of acetophenone-based compounds, biimidazole-based compounds, and triazine-based compounds, or a photosensitive coloring composition containing at least one photopolymerization initiator selected from the group consisting of acetophenone-based compounds and triazine-based compounds in addition to a biimidazole-based compound, and the like.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0005] However, conventional photosensitive coloring compositions have a problem that although the curability is improved and the solvent resistance is improved, it is difficult to form a pattern with a good shape.

[0006] An object of the present invention is to provide a photosensitive coloring composition that can achieve both solvent resistance and a good pattern shape (linearity, cross-sectional shape) even when containing a colorant at a high concentration.

Means for Solving the Problems

[0007] <1>The photosensitive coloring composition of the present invention contains a colorant (A), a dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E). The polymerizable compound (D) includes an isocyanurate ring-containing polymerizable compound (D1) having two or three polymerizable unsaturated groups and a polymerizable compound (D2) having three polymerizable unsaturated groups containing an alkyleneoxy chain (however, it does not include a ring structure), and the mass ratio of the polymerizable compound (D1) to the polymerizable compound (D2) is 10:90 to 50:50. <2>Regarding the photosensitive coloring composition of <1>, the content of the polymerizable compound (D) is 15 to 30% by mass in the non-volatile content of the photosensitive coloring composition. <3>Regarding the photosensitive coloring composition of <1> or <2>, the photopolymerization initiator (E) contains an oxime ester-based photopolymerization initiator. <4>Regarding a color filter formed from the photosensitive coloring composition of <1> to <3>. <5>Regarding a liquid crystal display device including the color filter of <4>. <6>Regarding an organic EL display device including the color filter of <4>. <7>Regarding a solid-state imaging device including the color filter of <4>.

Advantages of the Invention

[0008] According to the present invention described above, even when a colorant is contained at a high concentration, a photosensitive coloring composition capable of achieving both solvent resistance and a good pattern shape (linearity, cross-sectional shape) can be provided. Further, the present invention can provide a color filter, a liquid crystal display device, an organic EL display device, and a solid-state imaging device.

Brief Description of the Drawings

[0009]

Figure 1

Embodiments for Carrying Out the Invention

[0010] First, define the terms used in this specification. "(Meth)acryloyl" means "acryloyl and methacryloyl". "(Meth)acrylic" means "acrylic and methacrylic". "(Meth)acrylic acid" means "acrylic acid and methacrylic acid". "(Meth)acrylate" means "acrylate and methacrylate". The monomer is a polymerizable unsaturated group-containing monomer. The polymerizable unsaturated group is a vinyl group, a (meth)acryloyl group, or a (meth)allyl group. "C.I." means Color Index (C.I.).

[0011] The photosensitive coloring composition of the present invention contains a colorant (A), a dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E). The polymerizable compound (D) includes an isocyanurate ring-containing polymerizable compound (D1) having 2 or 3 polymerizable unsaturated groups, and a polymerizable compound (D2) (excluding a ring structure) having 3 alkyleneoxy chain-containing polymerizable unsaturated groups. The mass ratio of the polymerizable compound (D1) to the polymerizable compound (D2) is 10:90 to 50:50.

[0012] The photosensitive coloring composition of the present invention contains an isocyanurate ring-containing polymerizable compound (D1) and a polymerizable compound (D2) having an alkyleneoxy chain-containing polymerizable unsaturated group within a specific range. The film formed from the photosensitive coloring composition has a dense crosslinked structure derived from a rigid isocyanurate ring structure by exposure, and an appropriate alkyleneoxy chain with high hydrophilicity. It is presumed that this can solve the problem by improving the pattern shape (linearity, cross-sectional shape) because the unexposed portion after exposure is easily dissolved in an alkaline developer while having good solvent resistance.

[0013] <Colorant (A)> As the colorant (A), a pigment or a dye can be used. Among pigments, there are organic pigments and inorganic pigments, and organic pigments are preferred. The colorant (A) can be used alone or in combination of two or more.

[0014] The colorant (A) can be appropriately selected according to the color tone of the film. Hereinafter, organic pigments will be exemplified.

[0015] Examples of green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc. Among these, C.I. Pigment Green 7, 36, 58, 59, 62, 63 are preferred in terms of high contrast ratio and high brightness.

[0016] Examples of yellow pigments include C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, 231, etc. Among these, at least one selected from the group consisting of C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, 231 is preferred from the viewpoints of the contrast ratio and lightness of the filter segment, and C.I. Pigment Yellow 138, 139, 150, 185, 231 are more preferred.

[0017] Red pigments include, for example, C.I. Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 122, 146, 149, 166, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 268, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, diketopyrrolopyrrole pigments described in Japanese Patent Application Laid-Open No. 2011-523433, naphthol azo pigments described in Japanese Patent Application Laid-Open No. 2013-161025, and the like. Among these, C.I. Pigment Red 177, 242, 254, and 269 are preferred.

[0018] Blue pigments include, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 62, 63, 64, etc. Further, C.I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. can be used in combination as purple pigments. Among these, from the viewpoints of lightness and contrast ratio, C.I. Pigment Blue 15:1 and 15:6 are preferred.

[0019] <Dye> Dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. Further, derivatives of these dyes, or lake pigments obtained by lake-forming the dyes can also be used.

[0020] Acid dyes preferably have acidic groups such as sulfonic acid and carboxylic acid. Direct dyes preferably form salt compounds with inorganic salts of acid dyes or with nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds. Further, salt compounds that are salts of resin components having these functional groups and acid dyes are also preferable. Also, the salt compounds are easily made into photosensitive coloring compositions excellent in resistance (light resistance, solvent resistance) by sulfonamidation to be modified into sulfonic acid amide compounds. Also, salt compounds of acid dyes and compounds having an onium base are preferable because they are excellent in resistance (light resistance, solvent resistance). Note that as the compound having an onium base, a resin having a cationic group is preferable.

[0021] Basic dyes can be used as they are, but salt compounds formed by salt formation with organic acids, perchloric acid, or metal salts thereof are preferable. The salt compounds of basic dyes are preferable because they are excellent in resistance (light resistance, solvent resistance) and affinity with pigments. Also, as the anion component acting as a counterion in the salt compounds of basic dyes, anionic compounds having conjugated bases of organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, and organic acids having halogenated hydrocarbon groups, and salt compounds formed by salt formation with acid dyes are preferable. Note that the resistance is further improved when the salt compound contains a polymerizable unsaturated group in the molecule.

[0022] Dyes include, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes and indophenol dyes), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, and anthrapyridone dyes), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, and acridine dyes), quinoneimine dyes (such as oxazine dyes and thiazine dyes), azine dyes, polymethine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, and croconium dyes), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes, as well as metal complex dyes thereof, etc. Among these, from the viewpoints of color characteristics such as hue, difficulty in color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred.

[0023] The content of the colorant (A) is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 30% by mass or more in 100% by mass of the non-volatile content of the photosensitive coloring composition. Also, the upper limit of the content is preferably 70% by mass or less, and more preferably 60% by mass or less. When an appropriate amount of the colorant (A) is used, good color reproducibility is easily obtained even if the film is thin.

[0024] <Refinement of Pigment> When a pigment is used as the colorant (A) in this specification, it is preferably used after being micronized. The micronization method is not particularly limited, and for example, any of wet grinding, dry grinding, and solution precipitation methods can be used. Among these, salt milling treatment by the kneader method, which is a type of wet grinding, is preferred. The average primary particle diameter determined by TEM (transmission electron microscope) of the micronized pigment is preferably 5 to 90 nm. From the viewpoint of dispersibility, the average primary particle diameter is more preferably 10 to 70 nm.

[0025] <Dispersant (B)> As the dispersant (B), a known resin-type dispersant is preferred. The resin-type dispersant is a dispersant having an adsorption site that adsorbs to the colorant (A) and a steric repulsion site that stably disperses the colorant particles. Examples of the dispersant (B) include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, (partial) amine salts of polycarboxylic acids, ammonium salts of polycarboxylic acids, alkylamine salts of polycarboxylic acids, polysiloxanes, long-chain polyamino amidine salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides and their salts formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide / propylene oxide adduct compounds, phosphate ester-based ones, and the like. In addition, examples of the polymer dispersant having a basic functional group include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers having functional groups such as a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring in the side chain, and urethane-based polymer dispersants.

[0026] Commercially available resin dispersants include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS or Bykumen, etc. manufactured by BYK Chemie Japan; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. manufactured by Lubrizol Japan; EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF; and Ajisper-PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Inc.

[0027] The dispersant (B) is a resin-type dispersant, which is obtained by reacting an acid anhydride group in at least one acid anhydride selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound. It has a polyester moiety (X1) having a carboxyl group, a monomer (b1) having at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetanyl group, a tert-butyl group, and a blocked isocyanate group, and a vinyl polymer moiety (X2) formed by radical polymerization of a carboxyl group-containing monomer (b2). A dispersant (B1) is preferred. Since the thermally crosslinkable functional group of the dispersant (B1) reacts, its solvent resistance is further improved.

[0028] Hereinafter, the dispersant (B1) will be described in detail. In the dispersant (B1), the polyester moiety (X1) acts as a colorant adsorption site, and the vinyl polymer moiety (X2) acts as a steric repulsion site. Therefore, aggregation of the colorant (A) can be suppressed, and a dispersion having excellent dispersion stability can be produced.

[0029] Each component of the dispersant (B1) will be described. [Hydroxyl Group-Containing Compound Constituting the Polyester Moiety (X1) in the Dispersant (B1)] Examples of the hydroxyl group-containing compound constituting the polyester moiety (X1) include a compound having two hydroxyl groups and one thiol group in the molecule, a vinyl polymer having a hydroxyl group at one end, and a polyol. Among these, it is preferable to use at least one hydroxyl group-containing compound selected from the group consisting of a compound having two hydroxyl groups and one thiol group in the molecule and a vinyl polymer having a hydroxyl group at one end.

[0030] [Compound Having Two Hydroxyl Groups and One Thiol Group in the Molecule] Compounds having two hydroxyl groups and one thiol group in the molecule include, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol, etc.

[0031] [Vinyl polymer containing a hydroxyl group at one end] Although the details of the method for synthesizing the dispersant (B1) will be described later, there are a method of first synthesizing the polyester portion (X1) and then synthesizing the vinyl polymer portion (X2), and a method of first synthesizing the vinyl polymer portion (X2) and then synthesizing the polyester portion (X1). When first synthesizing the polyester portion (X1), a hydroxyl group-containing compound containing at least the above-described compound having two hydroxyl groups and one thiol group in the molecule is reacted with an acid anhydride. When first synthesizing the vinyl polymer portion (X2), in the presence of the above-described compound having two hydroxyl groups and one thiol group in the molecule, a monomer is polymerized to obtain a vinyl polymer portion (X2) in which a hydroxyl group derived from the compound having two hydroxyl groups and one thiol group in the molecule is introduced at the end. Therefore, when reacting with the acid anhydride during the synthesis of the next polyester portion (X1), it becomes the terminal hydroxyl group of the vinyl polymer portion (X2). That is, when first synthesizing the vinyl polymer portion (X2), the hydroxyl group-containing compound constituting the polyester portion (X1) also includes the vinyl polymer portion (X2) (vinyl polymer containing a hydroxyl group at one end) in which a hydroxyl group derived from the compound having two hydroxyl groups and one thiol group in the molecule is introduced at the end.

[0032] [Acid anhydride constituting the polyester portion (X1) in the dispersant (B1)] The acid anhydride constituting the polyester portion (X1) of the dispersant (B1) contains one or more selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides. By reacting the two anhydride groups of the tetracarboxylic dianhydride with the hydroxyl groups of the above-described hydroxyl group-containing compound, carboxyl groups serving as colorant adsorption groups can be regularly arranged in the main chain of the dispersant (B1), improving the dispersibility. When a tricarboxylic anhydride is used, it can react with a hydroxyl group to form an ester bond and leave a carboxyl group.

[0033] In addition, a dicarboxylic anhydride, which is a polycarboxylic anhydride other than tetracarboxylic dianhydride and tricarboxylic anhydride, and an anhydride of a compound having 5 or more carboxylic acids can also be used in combination.

[0034] 〔Tetracarboxylic Dianhydride〕 The tetracarboxylic dianhydride is preferably an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, ethylene glycol dianhydride trimellitate, propylene glycol dianhydride trimellitate, butylene glycol dianhydride trimellitate, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl propane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride and other aromatic tetracarboxylic dianhydrides. Among these, tetracarboxylic dianhydrides having two or more aromatic rings are more preferred.

[0035] [Tricarboxylic Anhydride] Examples of the tricarboxylic anhydride include aliphatic tricarboxylic anhydrides and aromatic tricarboxylic anhydrides. Among these, aromatic tricarboxylic anhydrides are preferred.

[0036] Examples of the aromatic tricarboxylic acid include benzenetricarboxylic anhydrides (such as 1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydrides (such as 1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenyl ether tricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, or 3,4,4'-biphenylsulfonetricarboxylic anhydride, etc. Among these, aromatic tricarboxylic anhydrides are preferred in terms of excellent adsorbability to the colorant.

[0037] [Monomer constituting the vinyl polymer moiety (X2) in the dispersant (B1)] The vinyl polymer moiety (X2) is preferably a radical polymer synthesized using monomers appropriately selected from monomers (b1) having at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetanyl group, a t-butyl group, and a blocked isocyanato group, carboxyl group-containing monomers (b2), and other monomers.

[0038] (Hydroxyl group-containing monomer) Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2(or 3)-hydroxypropyl (meth)acrylate, 2(or 3 or 4)-hydroxybutyl (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, etc.

[0039] (Oxetanyl group-containing monomer) Examples of the oxetanyl group-containing monomer include (vinyloxyalkyl) alkyloxetane, (meth)acryloyloxyalkyloxetane, [(meth)acryloyloxyalkyl] alkyloxetane, and the like. Among these, methyl (3-ethyloxetan-3-yl) methacrylate is preferable. Examples of commercially available products include ETERNACOLL OXMA (methyl (3-ethyloxetan-3-yl) methacrylate) (manufactured by Ube Industries, Ltd.).

[0040] (tert-Butyl group-containing monomer) Examples of the tert-butyl group-containing monomer include t-butyl methacrylate, t-butyl acrylate, and the like.

[0041] (Block isocyanato group-containing monomer) Examples of the block isocyanato group-containing monomer include 2-(0-[1'-methylpropylideneamino]carboxamido)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, and the like. Examples of commercially available products include KARENS MOI-BM (2-(0-[1'-methylpropylideneamino]carboxamido)ethyl methacrylate) (manufactured by Resona Co., Ltd.), KARENS MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (manufactured by Resona Co., Ltd.), and the like.

[0042] The content of the oxetanyl group-containing monomer, tert-butyl group-containing monomer, and block isocyanato group-containing monomer is preferably 5 to 90% by mass, more preferably 20 to 60% by mass, in the total monomers of the vinyl polymer. If it is 5% by mass or more, a photosensitive coloring composition excellent in resistance can be obtained due to the crosslinking effect, and if it is 90% by mass or less, the stability of the photosensitive coloring composition is further improved.

[0043] (Carboxyl group-containing monomer (b2)) Examples of the carboxyl group-containing monomer (b2) include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc. Among these, (meth)acrylic acid is preferred.

[0044] 〔Other monomers〕 Examples of other monomers include (meth)acrylates, nitrogen-containing group monomers, and vinyl monomers. (Meth)acrylates include, for example, alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, etc.; alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate, tertiary butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate; aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, etc.; heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate; alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate;

[0045] Examples of the nitrogen-containing group monomers include N-substituted (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, acryloylmorpholine, etc.; 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.

[0046] Vinyl monomers include, for example, styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0047] The content of the dispersant (B1) is preferably 0.01 to 100 parts by mass, more preferably 0.01 to 60 parts by mass, and still more preferably 5 to 40 parts by mass with respect to 100 parts by mass of the colorant (A). Appropriate content of the dispersant (B1) can further improve the dispersibility and solvent resistance.

[0048] The weight average molecular weight of the dispersant (B1) is preferably 2,000 to 100,000. Appropriate weight average molecular weight can further improve the dispersion stability. The acid value of the dispersant (B1) is preferably 5 to 200 mgKOH / g, more preferably 5 to 150 mgKOH / g, and still more preferably 5 to 100 mgKOH / g. Appropriate acid value can further improve the dispersibility and easily adjust the viscosity of the photosensitive coloring composition.

[0049] The dispersant (B) can be used alone or in combination of two or more.

[0050] <Dye derivative> The pigment derivative is preferably used as a dispersion aid. When the colorant (A) is an organic pigment, the pigment derivative adsorbs on the surface of the organic pigment, making the surface of the organic pigment polar and more likely to affinity with the dispersant (B), thereby further improving the dispersibility of the organic pigment. The pigment derivative is a known pigment derivative having an acidic group, a basic group, a neutral group, etc. in the organic pigment residue. For example, compounds having acidic substituents such as sulfo group, carboxy group, phosphate group, and amine salts thereof, compounds having basic substituents such as sulfonamide group and tertiary amino group at the end, and compounds having neutral substituents such as phenyl group and phthalimide alkyl group can be mentioned. Since the resin type dispersant used in combination has an acidic group, a pigment derivative having a basic group is preferred.

[0051] Examples of the organic pigment include diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, fluorene-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, polyazo, etc.

[0052] The pigment derivative can be used alone or in a mixture of two or more.

[0053] The content of the pigment derivative is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and still more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the colorant (A).

[0054] By adding a pigment derivative to the pigment and performing a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, solvent salt milling, etc., the pigment derivative adsorbs on the pigment surface, and the primary particles of the pigment can be made finer compared to the case where no pigment derivative is added.

[0055] <Binder resin (C)> The photosensitive coloring composition of the present invention contains a binder resin (C). When forming a film with a thickness of 2 μm, the binder resin (C) is preferably a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm, and more preferably 95% or more. The binder resin (C) is preferably a thermoplastic resin or an alkali-soluble resin.

[0056] <Thermoplastic resin> Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.

[0057] <Alkali-soluble resin> When a color filter is manufactured by a photolithography method, the alkali-soluble resin imparts developability solubility to the film formed from the photosensitive coloring composition. The alkali-soluble resin is preferably a thermoplastic resin having an acidic group. Examples of the acidic group include a carboxyl group and a sulfone group. Examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or an isobutylene / (anhydrous) maleic acid copolymer. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable in terms of developability, heat resistance, and transparency, and an acrylic resin having an acidic group is more preferable. In addition, the alkali-soluble resin is preferably a chain random polymer. The chain includes a branched chain.

[0058] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000. Also, the value of Mw / Mn is preferably 10 or less. Appropriate Mw further improves the alkali developability solubility. The acid value of the alkali-soluble resin is preferably from 50 to 200 mgKOH / g, more preferably from 70 to 180 mgKOH / g, and even more preferably from 90 to 170 mgKOH / g. Having an appropriate acid value further improves the alkali developability.

[0059] Examples of the alkali-soluble resin include an alkali-soluble resin (C1) having no polymerizable unsaturated group (hereinafter referred to as alkali-soluble resin (C1)) and an alkali-soluble resin (C2) having a polymerizable unsaturated group (hereinafter referred to as alkali-soluble resin (C2)).

[0060] <Alkali-soluble resin (C2)> The alkali-soluble resin (C2) is preferably a resin synthesized by, for example, the following methods (i) or (ii). This further improves the crosslinking density by light irradiation of the film formed from the photosensitive coloring composition.

[0061] [Method (i)] Method (i) includes, for example, first synthesizing a polymer of an epoxy group-containing monomer and other monomers. Next, a carboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the generated hydroxyl group to obtain an alkali-soluble resin (C2).

[0062] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0063] Examples of the carboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted products of (meth)acrylic acid, etc.

[0064] Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc.

[0065] The monomer and the polybasic acid anhydride can be used alone or in combination of two or more.

[0066] Also, as a method similar to method (i), for example, a carboxyl group-containing monomer and other monomers are synthesized to produce a polymer. Then, an epoxy group-containing monomer is added to a part of the carboxyl groups of the polymer to obtain an alkali-soluble resin (C2).

[0067] [Method (ii)] Method (ii) is, for example, a method in which a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to produce a polymer. Then, the isocyanate group of an isocyanate group-containing monomer is reacted with the hydroxyl groups of the polymer.

[0068] As the hydroxyl group-containing monomer, the monomers already exemplified can be used. Among them, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferable in terms of being less likely to generate foreign substances in the film. Also, glycerol mono(meth)acrylate is preferable in terms of photosensitivity.

[0069] Examples of the monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate, etc.

[0070] <Alkali-soluble resin (C1)> The alkali-soluble resin (C1) includes, for example, the alkali-soluble resins already exemplified and the resins obtained by removing polymerizable unsaturated groups from the alkali-soluble resin (C2).

[0071] The binder resin (C) can be used alone or in combination of two or more.

[0072] The content of the binder resin is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the colorant (A). Since the film-forming property and various resistances are good, it is preferably 20 parts by mass or more, and since the colorant concentration is high and good color characteristics can be exhibited, it is preferably 400 parts by mass or less.

[0073] <Thermosetting compound> The photosensitive coloring composition can contain a thermosetting compound. Thereby, when producing a color filter, the crosslinking density is improved in the heating step after forming a pattern on the film by photolithography, so the heat resistance is improved. In addition, since the colorant (A) is less likely to aggregate in the heating step, the contrast ratio is further improved.

[0074] The thermosetting compound is a compound having no carboxyl group and is a compound different from the binder resin (C). Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0075] (Epoxy compound) Epoxy compounds include, for example, polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polymers of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethyl biphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like.

[0076] Commercially available products include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (above are trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (above are trade names; manufactured by Japan Epoxy Resins Co., Ltd.), TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade names; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; manufactured by Japan Epoxy Resins Co., Ltd.), JER 157S65, 157S70 (trade names; manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (above are trade names; manufactured by Japan Epoxy Resins Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (above are trade names; manufactured by Nippon Kayaku Co., Ltd.), Celloxide 2021, EHPE-3150 (above are trade names; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 (above are trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), and the like.

[0077] The content of the epoxy compound is preferably 0.5 to 20 parts by mass, more preferably 1.0 to 10 parts by mass, per 100 parts by mass of the non-volatile content of the photosensitive composition. When blended in an appropriate amount, the heat resistance of the film and the pattern shape are further improved.

[0078] (Oxetane compound) The oxetane compound is a compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

[0079] Functional oxetane compounds include, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, and the like. Commercially available products include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

[0080] The bifunctional oxetane compounds include, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO modified bisphenol F(3-ethyl-3-oxetanylmethyl)ether, and the like. Commercially available products include OXBP, OXTP manufactured by Ube Industries, Ltd., OXT-121, OXT-221 manufactured by Toagosei Co., Ltd., and the like.

[0081] Examples of those having a trifunctional or higher oxetane group include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing an oxetane group (for example, oxetane-modified phenol novolak resins described in Japanese Patent No. 3783462, etc.), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0082] The content of the oxetane compound is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in the non-volatile content of the photosensitive composition. When an appropriate amount is contained, the solvent resistance of the film is further improved.

[0083] (Curing agent) In this specification, a curing agent can be contained to assist the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like. The amine compounds include (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (for example, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (for example, dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and their salts (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.), etc.

[0084] The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound.

[0085] <Polymerizable compound (D)> The polymerizable compound (D) is a monomer or oligomer having a polymerizable unsaturated group. The polymerizable compound (D) is a compound that forms a film by the reaction of the polymerizable unsaturated group. In this specification, the polymerizable compound (D) includes a polymerizable compound (D1) having an isocyanurate skeleton (hereinafter also referred to as the polymerizable compound (D1)) and an alkyleneoxy chain-containing polymerizable compound (D2) (hereinafter also referred to as the polymerizable compound (D2)).

[0086] (Isocyanurate ring-containing polymerizable compound (D1) having 2 or 3 polymerizable unsaturated groups) The polymerizable compound (D1) includes, for example, a polymerizable compound (D1-1) having an isocyanurate skeleton represented by the following general formula (11).

[0087] General formula (11)

Chemical formula

[0088] [In general formula (11), R1, R2, and R3 are each independently a group represented by the following general formulas (12-1) to (12-3)]

[0089] Formula (12-1) -CH2-CH2-О-(X) l -CО-CH=CH2 Formula (12-2) -CH2-CH2-О-(X) m -CО-CH=CH2 Formula (12-3) -CH2-CH2-(X) n -Y In the above formulas, X is an alkylene group having 1 to 3 carbon atoms or a single bond, and Y is CH2=CH-CО-О- or ОH. [In general formulas (12-1) to (12-3), l, m, and n are each independently an integer from 0 to 3.

[0090] Commercially available products of the polymerizable compound (D1) include ethoxylated isocyanuric acid triacrylate (A-9300), (A-9300-1CL), A9300-3CL (all manufactured by Shin-Nakamura Chemical Co., Ltd.), etc.

[0091] The content of the polymerizable compound (D1) is preferably 5 to 400 parts by mass, more preferably 10 to 300 parts by mass, based on 100 parts by mass of the colorant (A). When contained in an appropriate amount, the photosensitivity is further improved.

[0092] (Polymerizable compound (D2) having three polymerizable unsaturated groups containing alkyleneoxy chains) The polymerizable compound (D2) having three polymerizable unsaturated groups containing alkyleneoxy chains is a polymerizable compound having three polymerizable unsaturated groups in its molecule and is a compound having no ring structure. Further, the polymerizable unsaturated group containing an alkyleneoxy chain means that the linking group directly or indirectly bonded to the polymerizable unsaturated group has an alkyleneoxy chain. In the present specification, when the photosensitive coloring composition contains the polymerizable compound (D2), the mobility of the ethylenically unsaturated group bonded to the alkyleneoxy chain is improved, and the curability of the film is further improved. Examples of the alkyleneoxy chain include an ethyleneoxy chain, a propyleneoxy chain, and a pentyleneoxy chain. Among these, a pentyleneoxy chain having high reactivity is preferable.

[0093] Commercially available products of the polymerizable compound (D2) include, for example, Aronix M-310, M-321, M-350, M-360 manufactured by Toagosei Co., Ltd., and A-TMPT, A-TMPT-9EO, AT-20E manufactured by Shin-Nakamura Chemical Co., Ltd.

[0094] In the present specification, the polymerizable compound (D1) and the polymerizable compound (D2) are used in combination. By the above-mentioned combined use, a pattern formed by the photolithography method has good linearity and a shape with a nearly vertical cross section can be obtained.

[0095] The mass ratio of the polymerizable compound (D1) to the polymerizable compound (D2) is 10:90 to 50:50, and more preferably 25:75 to 35:65.

[0096] <Photopolymerization initiator (E)> The photopolymerization initiator (E) preferably contains an oxime ester-based photopolymerization initiator. When the oxime ester-based photopolymerization initiator is used, high sensitivity can be maintained even in a film made from a photosensitive composition having a high pigment content. Therefore, high solvent resistance and a good pattern shape (linearity, cross-sectional shape) can be achieved simultaneously.

[0097] <Oxime ester-based photopolymerization initiator> Oxime ester-based photoinitiators absorb ultraviolet light, causing the cleavage of the N-O bond in the oxime to generate iminyl radicals and alkoxy radicals. These radicals further decompose to generate highly active radicals, enabling the formation of patterns with a small exposure amount. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may decrease and the degree of curing of the coating film may become low. However, when an oxime ester-based photoinitiator is contained, the photocurability is improved, and thus the solvent resistance of the coating film is further improved. As the oxime ester-based photoinitiator, an oxime ester-based photoinitiator represented by the following general formula (2) or (3) is preferred, and an oxime ester-based photoinitiator represented by the general formula (2) is more preferred in terms of higher sensitivity.

[0098] (Oxime ester-based photoinitiator represented by general formula (2))

[0099] [Chemical formula]

[0100] In general formula (2), Z represents a direct bond or a -C(=O)- group, and R 1 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and R 2 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R 3 ~R 10 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group, or an R 11 -C(=O)- group. R 11 represents an aryl group which may have a substituent.

[0101] R 1 ~R 10 Examples of the alkyl group having 1 to 20 carbon atoms in R R 2 ~R11 Examples of the aryl group in [description] include a phenyl group, a naphthyl group, an anthracenyl group, and the like. Note that when Z is a direct bond, it means that Z has no atoms and the two atoms connected to Z in the general formula (2) are directly bonded.

[0102] The substituent that the alkyl group and the aryl group may have means that the alkyl group or the aryl group may have a substituent instead of a hydrogen atom it has. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; aryloxy groups such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group; acyloxy groups such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; acyl groups such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxysulfuryl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; alkylamino groups such as a methylamino group and a cyclohexylamino group; dialkylamino groups such as a dimethylamino group, a diethylamino group, a morpholino group, and a piperidino group; arylamino groups such as a phenylamino group and a p-tolylamino group; alkyl groups such as a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctadecyl group; aryl groups such as a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, and a phenanthryl group; heterocyclic groups such as a furyl group and a thienyl group, and in addition, a hydroxy group, a carboxy group, a formyl group, a mercapto group, a sulfo group, a mesyl group, a p-toluenesulfonyl group, an amino group, a nitro group, a cyano group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammoniumyl group, a dimethylsulfoniumyl group, and a triphenylphenacylphosphoniumyl group. In addition, one or more or one or more of these substituents may be present, and further, the hydrogen atoms of these substituents may be further substituted with other substituents.

[0103] In the oxime ester-based photopolymerization initiator represented by the general formula (2), Z is a direct bond or a -C(=O)- group, and R 1 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and R 2 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R 3 ~R 10 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group, or an R 11 -CO- group. Further, it is preferable that R 4 ~R 6 and R 8 ~R 10 are hydrogen atoms, R 7 is a hydrogen atom, or R 11 -CO- group, and it is more preferable that R 11 is an aryl group which may have a substituent.

[0104] As the oxime ester-based photopolymerization initiator represented by the general formula (2), a compound represented by the following chemical formula (2-1) or (2-2) is preferable.

[0105]

Chemical formula

[0106] (Oxime ester-based photopolymerization initiator represented by the general formula (3))

[0107]

Chemical formula

[0108] In the general formula (3), R 21 and R 22is, independently, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R 23 and R 24 are, independently, a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R 25 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, or R 26 -CO- group, and R 26 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group.)

[0109] R 21 ~R 26 The alkyl group having 1 to 20 carbon atoms in is the same as the alkyl group having 1 to 20 carbon atoms in the above R 1 ~R 10 . R 21 ~R 26 The aryl group in is the same as the aryl group in the above R 2 ~R 11 . R 26 Examples of the heterocyclic ring in the heterocyclic group of include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, benzofuran, thionaphthene, indole, carbazole, coumarin, quinoline, phthalazine, quinoxaline, etc. In addition, the substituents which the alkyl group and the aryl group may have are the same as the substituents in the general formula (2).

[0110] In the oxime ester-based photopolymerization initiator represented by the general formula (3), R 21 is an aryl group which may have a substituent, R 22 is an alkyl group having 1 to 20 carbon atoms which may have a substituent, R 23 and R 24 are hydrogen atoms, and R 25 is a hydrogen atom, or R26 It is preferably a -CO- group.

[0111] As the oxime ester-based photopolymerization initiator represented by the general formula (3), a compound represented by the following chemical formula (3-1) is preferred.

[0112] [Chemical formula]

[0113] (Other photopolymerization initiators) The photopolymerization initiator (C) can contain other photopolymerization initiators other than oxime ester-based photopolymerization initiators. Examples of other photopolymerization initiators include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 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)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal; benzophenone-based compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone;Triazine 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-(naphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthalen-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds, etc.

[0114] Commercially available products of the photopolymerization initiator include, for example, as acetophenone compounds, all are manufactured by BASF and include "IRGACURE 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "IRGACURE 369" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), "IRGACURE 379" 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; as phosphine compounds, all are manufactured by BASF and include "IRGACURE 819" (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide), "IRGACURE TPO" (2,4,6-trimethylbenzoyldiphenylphosphine oxide), etc.

[0115] The photopolymerization initiator (E) can be used alone or in combination of two or more.

[0116] The content of the photopolymerization initiator (E) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, per 100 parts by mass of the colorant (A). When the content is 2 parts by mass or more, the adhesion to the substrate is improved. When the content is 50 parts by mass or less, the resolution is further improved.

[0117] [Sensitizer] The photosensitive coloring composition of this embodiment can further contain a sensitizer. Examples of the sensitizer include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. Examples of the sensitizer include 2,4 - diethylthioxanthone, 2 - chlorothioxanthone, 2,4 - dichlorothioxanthone, 2 - isopropylthioxanthone, 4 - isopropylthioxanthone, 1 - chloro - 4 - propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N - ethylcarbazole, 3 - benzoyl - N - ethylcarbazole, 3,6 - dibenzoyl - N - ethylcarbazole, and the like.

[0118] Commercially available products of sensitizers include "KAYACURE DETX - S" (2,3 - diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.), "EAB - F" (4,4'-bis(diethylamino)benzophenone, manufactured by Hodogaya Chemical Co., Ltd.), and the like.

[0119] The sensitizer can be used alone or in combination of two or more.

[0120] The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator (E). When used in an appropriate amount, the photocurability and developability are improved.

[0121] [Chain transfer agent] The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, during radical polymerization after light irradiation, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated, improving the sensitivity of the photosensitive coloring composition.

[0122] As the thiol-based chain transfer agent, a polyfunctional thiol having two or more thiol groups (SH groups) is preferable. It is more preferable that the thiol-based chain transfer agent has four or more SH groups. As the number of functional groups increases, it becomes easier for the film to be photocured from the surface to the deepest part.

[0123] Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristthioglycolate, trimethylolpropane tristthiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristthiopropionate, pentaerythritol tetrakisthiopropionate, etc. are included.

[0124] The chain transfer agent can be used alone or in combination of two or more kinds.

[0125] The content of the chain transfer agent is preferably 1 to 10% by mass, more preferably 2.0 to 8.0% by mass in the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, the photosensitivity and pattern shape are further improved.

[0126] <Polymerization inhibitor> The photosensitive coloring composition can contain a polymerization inhibitor. This prevents photosensitivity due to diffracted light of the mask during exposure, making it easier to obtain a good pattern shape.

[0127] Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol; alkyl resorcinol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol; alkyl hydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide, triphenylphosphine oxide; phosphite compounds such as triphenyl phosphite, trisnonylphenyl phosphite; pyrogallol, phloroglucin, and the like.

[0128] The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass in the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, it is easier to obtain a good pattern shape.

[0129] <Ultraviolet absorber> The photosensitive coloring composition can contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

[0130] Commercially available products of benzotriazole compounds include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF, Adeka Stab LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA, KEMISORB 71, 73, 74, 79, 279 manufactured by Chemipro Kasei, RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

[0131] Commercially available products of triazine compounds include KEMISORB 102 manufactured by Chemipro Kasei, TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF, Adeka Stab LA-46, LA-F70 manufactured by ADEKA, CYASORB UV-1164 manufactured by Sankyo Chemical Co., Ltd., and the like.

[0132] Commercially available products of benzophenone compounds include KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei, SEESORB 101, 107 manufactured by Cipro Kasei, Adeka Stab 1413 manufactured by ADEKA, UV-12 manufactured by Sankyo Chemical Co., Ltd., and the like.

[0133] Examples of the salicylic acid ester compound include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

[0134] The content of the ultraviolet absorber is preferably 0.1 to 1.0% by mass in the non-volatile content of the photosensitive composition.

[0135] <Antioxidant> The photosensitive coloring composition can contain an antioxidant. Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, hydroxylamine compounds and the like. Note that the antioxidant is preferably a compound that does not contain a halogen atom.

[0136] Commercially available hindered phenol compounds include ADEKA STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA Corporation; KEMINOX 101, 179, 76, 9425 manufactured by Chemipro Kasei Co., Ltd.; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF SE; CYANOX CY-1790, CY-2777 manufactured by Sankyo Chemical Co., Ltd. and the like.

[0137] Commercially available hindered amine compounds include ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP manufactured by ADEKA Corporation; KAMISTAB 29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd.; Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, 5100 manufactured by BASF SE; CYASORB UV-3346, UV-3529, UV-3853 manufactured by Sankyo Chemical Co., Ltd. and the like.

[0138] Commercially available phosphorus compounds include ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA Corporation; IRGAFOS 168 manufactured by BASF SE; Hostanox P-EPQ manufactured by Clariant Chemicals (China) Co., Ltd. and the like.

[0139] Commercially available sulfur compounds include ADEKA STAB AO-412S, AO-503 manufactured by ADEKA Corporation; KEMINOX PLS manufactured by Chemipro Kasei Co., Ltd. and the like.

[0140] The antioxidant can be used alone or in combination of two or more.

[0141] The content of the antioxidant is preferably 0.5 to 5.0% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, the transmittance, spectral characteristics, and sensitivity are further improved.

[0142] <Leveling agent> The photosensitive coloring composition can contain a leveling agent. Thereby, the wettability with respect to the transparent substrate during film formation and the drying property of the film are further improved. Examples of the leveling agent include silicone surfactants, fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and the like.

[0143] Examples of the silicone surfactant include chain polymers having a siloxane bond and modified siloxane polymers having an organic group introduced into the side chain or the terminal.

[0144] Commercially available products of silicone surfactants include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345 / 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK Chemie GmbH; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning Co., Ltd.; 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, KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0145] The fluorosurfactant is a compound having a fluorocarbon chain.

[0146] Commercially available fluorosurfactants include Surflon S-242, S-243, S-420, S-611, S-651, S-386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21 manufactured by DIC Corporation, FC-4430, FC-4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., Ftergent 602A manufactured by Neos Corporation, and the like.

[0147] The surfactant can be used alone or in combination of two or more.

[0148] The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass in the nonvolatile content of the photosensitive coloring composition. Within this range, the balance of the coatability, pattern adhesion, and transmittance of the photosensitive coloring composition is further improved.

[0149] <Storage Stabilizer> The photosensitive coloring composition can contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphites.

[0150] The content of the storage stabilizer is preferably 0.1 to 10% by mass with respect to 100 parts by mass of the colorant (A).

[0151] <Adhesion Improver> The photosensitive coloring composition can contain an adhesion improver. Thereby, the adhesion between the film and the substrate is further improved. Also, it becomes easier to form a pattern with a narrow width by the photolithography method. Examples of the adhesion improver include silane coupling agents.

[0152] Silane coupling agents include, for example, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; amino silanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercapto silanes such as 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane; styryl silanes such as p-styryltrimethoxysilane; ureido silanes such as 3-ureidopropyltriethoxysilane; sulfide silanes such as bis(triethoxysilylpropyl)tetrasulfide; isocyanate silanes such as 3-isocyanatopropyltriethoxysilane and the like.

[0153] The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the colorant (A). When contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the film is further improved, and the resolution of the pattern is also further improved.

[0154] <Solvent> The photosensitive coloring composition can contain a solvent. This makes it easy to adjust the viscosity of the photosensitive coloring composition, so that it is easy to form a film with a smooth surface. The solvent may be appropriately selected according to the purpose of use and may be contained in an appropriate amount.

[0155] Examples of the solvent include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0156] The solvent is preferably a solvent having a boiling point of 120°C or higher and 180°C or lower at 1 atm in terms of coatability and drying properties. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone and the like are more preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are even more preferable.

[0157] The solvent can be used alone or in combination of two or more.

[0158] <Preparation of Photosensitive Coloring Composition> For example, the photosensitive coloring composition can be prepared by performing a dispersion treatment using a colorant (A), a dispersant (B), etc. to prepare a colorant dispersion. Then, the colorant dispersion, a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E) can be mixed. The timing of blending each material is arbitrary. Also, the dispersion step can be performed multiple times.

[0159] For the dispersion treatment, for example, a dispersing 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 can be used.

[0160] <Removal of Coarse Particles> In this specification, it is preferable to remove the contained coarse particles after the stage of the colorant dispersion or after preparing the photosensitive coloring composition. Thereby, foreign matters can be removed from the film, making it easier to form a fine pattern. The removal is preferably performed by a method such as centrifugation, a sintered filter, or a membrane filter. Thereby, foreign matters such as coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more can be removed. Thus, the photosensitive coloring composition preferably does not contain substantially particles of 0.5 μm or more and preferably does not contain particles of 0.3 μm or less.

[0161] <Color Filter> In this specification, the color filter includes a base material (also referred to as a transparent substrate) and filter segments formed from a photosensitive coloring composition. The color filter segments (hereinafter also referred to as filter segments) preferably have red filter segments, green filter segments, and blue filter segments by appropriately selecting the type of the colorant (A) to be used. Further, the color filter can have magenta filter segments, cyan filter segments, and yellow filter segments instead of or in addition to the color filter segments. Note that a reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0162] <Method for Manufacturing Color Filter> It is preferable to form a black matrix on a substrate first and then form filter segments. Note that a thin-film transistor (TFT) can be formed on the substrate in advance and then the black matrix can be formed. Examples of the black matrix include inorganic films such as chromium, multi-layer films of chromium / chromium oxide, titanium nitride, and resin films in which a light-shielding agent is dispersed.

[0163] The formation of filter segments can be carried out, for example, by printing, electrodeposition, transfer, inkjet, photolithography, etc. Hereinafter, the most preferable photolithography method will be described.

[0164] In the photolithography method, for example, a photosensitive coloring composition containing a coloring agent of a certain color tone is applied onto a transparent substrate so that the dry film thickness becomes about 0.2 to 5 μm to form a film. The obtained film (hereinafter referred to as the first film) is exposed (light irradiated) through a mask having a predetermined pattern. Then, development is carried out by immersing it in a solvent or an alkaline developer or spraying the developer such as by spraying to remove the uncured portion to obtain a desired pattern. By performing this process in the same manner using a photosensitive coloring composition having a coloring agent of another color tone, a color filter having filter segments of each color can be manufactured. Further, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, so the exposure sensitivity is further improved. Also, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment.

[0165] Examples of the coating device include spray coating, spin coating, slit coating, roll coating, etc. A drying process can be carried out during coating. Examples of the drying device include a hot air oven, an infrared heater, etc.

[0166] The developing solution is an alkaline developing solution, and examples of the alkaline developing solution include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. Further, an antifoaming agent and a surfactant can be added to the developing solution.

[0167] In this specification, after forming a color filter, a color filter is bonded to a counter substrate using a sealing agent, liquid crystal is injected from an injection port provided in the sealing portion, and then the injection port is sealed. Then, a polarizing film and a retardation film are bonded to the outside of the substrate as necessary, thereby a liquid crystal display device can be manufactured. Examples of this liquid crystal display device include Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Aligned (VA), Optically Compensated Bend (OCB), and the like.

[0168] In this specification, the color filter can be used for applications such as solid-state imaging devices, organic EL display devices, quantum dot display devices, and electronic paper, in addition to liquid crystal display devices.

[0169] <Liquid Crystal Display Device> The liquid crystal display device in this specification includes a color filter. The liquid crystal display device includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED. In the present invention, it is preferable to use a white LED in terms of expanding the red reproduction region. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 including the color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 arranged to face each other with a gap therebetween, and liquid crystal LC is enclosed therebetween.

[0170] The liquid crystal LC is aligned according to driving modes such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and OCB (Optically Compensated Birefringence). On the inner surface of the first transparent substrate 11, a TFT (Thin Film Transistor) array 12 is formed, and on top of that, a transparent electrode layer 13 made of, for example, ITO is formed. An alignment layer 14 is provided on the transparent electrode layer 13. Also, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0171] On the other hand, on the inner surface of the second transparent substrate 21, the color filter 22 of the present invention is formed. The red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

[0172] Covering the color filter 22, a transparent protective film (not shown) is formed as needed, and on top of that, a transparent electrode layer 23 made of, for example, ITO is formed, and an alignment layer 24 is provided covering the transparent electrode layer 23.

[0173] Also, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

[0174] White LED light sources include, for example, those formed by forming a fluorescent filter on the surface of a blue LED or those containing a phosphor in the resin package of a blue LED. They have a wavelength (λ3) at which the emission intensity reaches a maximum within the range of 430 nm to 485 nm, a wavelength (λ4) at which the emission intensity reaches a maximum within the range of 530 nm to 580 nm, and a wavelength (λ5) at which the emission intensity reaches a maximum within the range of 600 nm to 650 nm. Also, the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less. A white LED light source (LED1) having such spectral characteristics or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity within the range of 530 nm to 580 nm, and the ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 being 0.2 or more and 0.7 or less is preferred.

[0175] LED1 includes, for example, specifically, NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.), NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.), and the like.

[0176] LED2 includes, for example, specifically, NSSW440 (manufactured by Nichia Chemical Industries, Ltd.), NSSW304D (manufactured by Nichia Chemical Industries, Ltd.), and the like.

Examples

[0177] Hereinafter, the present invention will be described based on production examples and examples. However, the present invention is not limited to the examples. Note that "parts" means "parts by mass" and "%" means "% by mass".

[0178] Hereinafter, the method for measuring physical property values will be described.

[0179] (Weight average molecular weight (Mw)) The weight-average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used for the apparatus. Two separation columns were connected in series, and for both packing materials, two "TSK-GEL SUPER HZM-N" were connected in series and used. The measurement was carried out at an oven temperature of 40 °C, using tetrahydrofuran (THF) as the eluent at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and 20 microliters were injected. All molecular weights are in terms of polystyrene conversion values.

[0180] (Acid value of the resin) The acid value of the resin is the value obtained by converting the measured acid value (mgKOH / g) to a non-volatile content basis in accordance with the potentiometric titration method of JIS K 0070.

[0181] <Preparation of micronized pigment> (Manufacture of micronized red pigment (R-1)) 100 parts of a diketopyrrolopyrrole-based red pigment C.I. Pigment Red 254 ("Irgaphor Red B-CF" manufactured by BASF Japan), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60 °C for 10 hours. Next, the kneaded mixture was poured into warm water, stirred for 1 hour while heating to about 80 °C to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 °C for a whole day and night and pulverized to obtain the micronized pigment (R-1).

[0182] (Manufacture of micronized pigment (R-2)) Anthraquinone-based red pigment C.I. Pigment Red 177 (Chromophthal Red A2B manufactured by BASF Japan): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a 1-gallon stainless steel kneader and kneaded at 120 °C for 8 hours. Next, this kneaded product was put into 5 liters of warm water and stirred for 1 hour while heating to 70 °C to make it into a slurry state. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night to obtain a micronized pigment (R-2).

[0183] (Production of micronized pigment (R-3)) 24.2 parts of 3-amino-4-methoxybenz anilide was added to 294 parts of water as a base component, stirred to prepare a suspension, and further 137 parts of ice was added to adjust the temperature to 5 °C or lower. 31.6 parts of 35% hydrochloric acid was added thereto and stirred for 30 minutes. Then, an aqueous solution prepared by adding 7.1 parts of sodium nitrite to 14 parts of water was added and diazotization was carried out by stirring for 1 hour. 2 parts of sulfamic acid was added to the reaction mixture to disappear nitrous acid. A buffer solution composed of a mixture of 36.5 parts of 25% aqueous sodium hydroxide solution, 36.5 parts of ice, and 37.7 parts of 80% acetic acid was added thereto to make a solution containing a diazo component. On the other hand, 33.4 parts of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthamide as a coupler component was added to a mixture of 66.8 parts of water and 66.8 parts of dimethyl sulfoxide and stirred and suspended for 15 minutes. 32.6 parts of 25% aqueous sodium hydroxide solution was added thereto and further stirred for 30 minutes, and 66.8 parts of water was added to make a coupler solution. This solution was added to the solution containing the diazo component over 20 minutes to carry out a coupling reaction. After stirring for 1 hour, the slurry was heated to 30 °C and further stirred for 30 minutes. This slurry was further heated to 50 °C and stirred for 30 minutes, and then filtered and washed with water to obtain a press cake of the pigment. This press cake was dried under the conditions of 90 °C for 18 hours and then pulverized to obtain a micronized red pigment (R-3) of C.I. Pigment Red 269 (PR269).

[0184] (Production of micronized yellow pigment (Y-1)) 100 parts of an isoindoline-based yellow pigment C.I. Pigment Yellow 139 (Irgalite Yellow 2R-CF manufactured by BASF Japan), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader and kneaded at 60 °C for 10 hours. Next, this mixture was poured into 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80 °C for 1 day and night to obtain a micronized pigment (Y-1).

[0185] (Production of micronized yellow pigment (Y-2)) 100 parts of a metal complex-based yellow pigment (C.I. Pigment Yellow 150, Yellow Pigment E4GN manufactured by Lanxess), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader and kneaded at 60 °C for 10 hours. Next, this mixture was poured into 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80 °C for 1 day and night to obtain a micronized pigment (Y-2).

[0186] (Production of micronized yellow pigment (Y-3)) 500 parts of yellow pigment C.I. Pigment Yellow 185 (Paritol Yellow D1155 manufactured by BASF Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader and kneaded at 120 °C for 8 hours. Next, this kneaded product was poured into 5 liters of warm water and stirred for 1 hour while heating to 70 °C to form a slurry. After repeating filtration and washing to remove sodium chloride and diethylene glycol, it was dried at 80 °C for 1 day and night to obtain a micronized pigment (Y-3).

[0187] (Production of micronized green pigment (G-1)) 100 parts of phthalocyanine-based green pigment C.I. Pigment Green 58 ("FASTGEN GREEN A110" manufactured by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader and kneaded at 70°C for 6 hours. This kneaded product was put into 3000 parts of warm water, stirred for 1 hour while heating to 70°C to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for one day and night to obtain a micronized pigment (G-1).

[0188] (Production of micronized green pigment (G-2)) 100 parts of phthalocyanine-based green pigment C.I. Pigment Green 36 ("CF-G-6YK" manufactured by Toyo Color Co., Ltd.), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader and kneaded at 70°C for 6 hours. This kneaded product was put into 3000 parts of warm water, stirred for 1 hour while heating to 70°C to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for one day and night to obtain a micronized pigment (G-2).

[0189] (Production of micronized blue pigment (B-1)) 500 parts of copper phthalocyanine-based blue pigment C.I. Pigment Blue 15:6 (PB15:6) ("Leonol Blue ES" manufactured by Toyo Color Co., Ltd.), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader and kneaded at 120°C for 12 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating to 70°C to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for one day and night to obtain a micronized pigment (B-1).

[0190] (Production of micronized blue pigment (B-2)) A micronized pigment (B-2) was obtained in the same manner as in the preparation of the micronized pigment (B-1), except that LIONOL BLUE FG-7330 (C.I. Pigment Blue15:3) manufactured by Toyo Color Co., Ltd. was used instead of PB15:6.

[0191] (Production of Fine Purple Pigment (V-1)) 500 parts of dioxazine-based purple pigment C.I. Pigment Violet 23 (PV23) ("Fast Violet RL" manufactured by Clariant), 2500 parts of sodium chloride, and 250 parts of polyethylene glycol were charged into a 1-gallon stainless steel kneader and kneaded at 120°C for 12 hours. Next, this mixture was poured into about 5 liters of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry, then filtered and washed with water to remove sodium chloride and diethylene glycol, and dried at 80°C for a whole day and night to obtain the finely processed pigment (V-1).

[0192] (Method for Producing Dispersant) (Dispersant 1) 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were charged into a reaction vessel equipped with a gas introduction tube, thermometer, condenser, and stirrer, replaced with nitrogen gas, and then heated and stirred at 120°C for 4 hours. After confirming by non-volatile content measurement that 98% had reacted, 73.3 parts of pyromellitic dianhydride were added and reacted at 120°C for 2 hours. The reaction was terminated after confirming by acid value measurement that 98% or more of the acid anhydride had been half-esterified. A 50% non-volatile content dispersant 1 solution was obtained by adjusting the non-volatile content.

[0193] (Dispersant 2) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 10 parts of methacrylic acid, 20 parts of methyl methacrylate, 90 parts of 2-methoxyethyl methacrylate, 40 parts of t-butyl methacrylate, 20 parts of n-butyl acrylate, 20 parts of t-butyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate were charged. While stirring, heating was started while purging with nitrogen gas. When the internal temperature of the reaction vessel reached 50 °C, 12 parts of 3-mercapto-1,2-propanediol were added. When the internal temperature reached 90 °C, a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate was added, and the reaction was carried out for 7 hours. It was confirmed by non-volatile content measurement that 95% of the reaction had occurred. Next, 19 parts of pyromellitic dianhydride, 50 parts of propylene glycol monomethyl ether acetate, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added to the reaction vessel, and the reaction was carried out at 100 °C for 7 hours. Sampling was performed, and it was confirmed by acid value measurement that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. Next, propylene glycol monomethyl ether acetate was added to adjust the non-volatile content to 50%, and Dispersant 2 was obtained.

[0194] (Dispersants 3 to 6) (Production Examples 3 to 6) Synthesis was carried out in the same manner as for Dispersant 2, except that the formulation of Dispersant 2 was changed to the raw materials and amounts used described in Table 1, and Dispersants 3 to 6 were obtained.

[0195]

Table 1

[0196] <Dye Derivative> The following dye derivatives were used. (Dye Derivative 1)

Chem.

[0197] (Pigment Derivative 3) The compound represented by the following general formula (103) General formula (103) [Chemistry]

[0198] In the above general formula (103), M1 = Cu, R 106 is the general formula (150), m is an integer from 1 to 3, X1 is -SO2-, o is 3, R 107 = H, n = 1. Note that Pigment Derivative 3 is a mixture of compounds having 1 to 3 R 106 groups.

[0199] General formula (150) [Chemistry]

[0200] In general formula (150), R 150 and R 151 represent an alkyl group having 4 carbon atoms. X1 is -SO2-, o is 3.

[0201] (Pigment Derivative 4) The compound represented by the above general formula (103) In the above general formula (103), M1 is Cu, R 106 is the following general formula (151), m is an integer from 1 to 3, R 107 is H, n is 1. In general formula (151), X1 is -CH2-, R 105 , R 151 each independently represents an alkyl group having 4 carbon atoms. Note that Pigment Derivative 4 is a mixture of compounds having 1 to 3 R 106 groups.

[0202] General formula (151) [Chemistry] In the above general formula (151), R 150 and R 151 are, similar to the above general formula (150), R 105 , R 151 are each independently an alkyl group having 4 carbon atoms, and X1 is -CH2-.

[0203] (Dye derivative 5) The compound represented by the above general formula (103) In general formula (103), M1 is Cu, R 106 is the above general formula (150), m is an integer from 1 to 3, X1 is -SO2-, and o represents 3. In the above general formula (150), R 150 , R 151 are each an alkyl group having 1 carbon atom, R 107 is H, and n represents 1. Note that the dye derivative 5 is a mixture of compounds having 1 to 3 R 106 .

[0204] (Dye derivative 6) The compound represented by the following general formula (107)

[0205] General formula (107) [Chemical formula]

[0206] In general formula (107), R 110 is general formula (153), and m represents 2. In general formula (153), Y1, Y2 and Y3 are direct bonds, R 157 , R 158 each independently represent general formula (156). In the following general formula (156), Z1 is NH, Z2 is a propylene group, R 150 , R 151 represents an ethyl group. General formula (153) [Chemical formula] General formula (156) JPEG2025103374000015.jpg2544 General formula (106)

Chem.

[0207] (Dye derivative 7) The compound represented by the above general formula (106) In general formula (106), R 109 represents general formula (150), and m represents an integer from 1 to 3. In general formula (150), R 150 , R 151 represents an ethyl group. X1 is -SO2-, and o represents 3. Note that dye derivative 7 is a mixture of compounds having 1 to 3 R 109 groups.

[0208] (Dye derivative 8) The compound represented by the following general formula (110) General formula (110)

Chem.

[0209] (Dye derivative 9) The compound represented by the following general formula (109) General formula (109)

Chem.

Chem.

[0210] In general formula (109), R112 is represented by the above general formula (159), m is an integer from 1 to 3, X2 is -SO2NH-, R 165 is represented by the above general formula (153). Note that the dye derivative 9 is a mixture of compounds having 1 to 3 R 112 . In the general formula (159), X2 is -SO2NH-, R 165 is represented by the above general formula (153). R 163 , R 164 , R 166 , R 167 represents H. In the general formula (153), R 157 is -OH, R 158 represents the general formula (150). Y1 and Y2 are a direct bond, and Y3 represents -NH-. In the general formula (150), R 150 , R 151 represents a butyl group. X1 is a direct bond, and o represents 3.

[0211] (Dye Derivative 10) The compound represented by the above general formula (110) In the general formula (110), R 112 represents the general formula (150), and m is an integer from 1 to 3. In the general formula (150), R 150 , R 151 represents a butyl group. X1 is -SO2-, and o represents 2. Note that the dye derivative 10 is a mixture of compounds having 1 to 3 R 112 .

[0212] <Production of Binder Resin (C) Solution> (Preparation of Binder Resin (C1) Solution) 70.0 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer, and the temperature was raised to 80°C. After purging the inside of the reaction vessel with nitrogen, a mixture of 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), and 0.4 part of 2,2'-azobisisobutyronitrile was added dropwise from a dropping tube over 2 hours and reacted. After completion of the dropwise addition, the reaction was continued for another 3 hours and then cooled to room temperature. Next, sampling was performed and propylene glycol monomethyl ether acetate was added to adjust the non-volatile content to 20% by mass to obtain a binder resin (C1) solution. The weight average molecular weight was 26,000.

[0213] (Preparation of Binder Resin (C2) Solution) 560 parts of cyclohexanone was placed in a reaction vessel, heated to 80°C while injecting nitrogen gas into the vessel, and a mixture of 34.0 parts of methacrylic acid, 23.0 parts of methyl methacrylate, 45.0 parts of n-butyl methacrylate, 47.0 parts of glycerol monomethacrylate, and 4.0 parts of 2,2'-azobisisobutyronitrile was added dropwise from a dropping tube over 1 hour to carry out a polymerization reaction at the same temperature. After completion of the dropwise addition, the reaction was further carried out at 80°C for 3 hours, and then a mixture of 1.0 part of azobisisobutyronitrile dissolved in 55 parts of cyclohexanone was added, and the reaction was continued at 80°C for 1 hour to obtain a copolymer. Next, to 338 parts of the obtained copolymer solution, a mixture of 32.0 parts of 2-methacryloylethyl isocyanate, 0.4 part of dibutyltin laurate, and 120.0 parts of cyclohexanone was added dropwise at 70°C over 3 hours and the reaction was continued, and then cooled to room temperature. Next, sampling was performed and propylene glycol monomethyl ether acetate was added, and cyclohexanone was added so that the non-volatile content became 20% by mass to obtain a binder resin (B2) solution of a photosensitive resin. The weight average molecular weight of the binder resin (C2) was 12,000.

[0214] (Preparation of Binder Resin (C3) Solution) (Step 1: Polymerization of Resin Main Chain) 100 parts of propylene glycol monomethyl ether acetate (PGMAC) was placed in a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer, and the mixture was heated to 120 °C while injecting nitrogen gas into the flask. Next, a mixture of 14 parts of styrene, 29 parts of dicyclopentanyl methacrylate, 57 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile as a catalyst was added dropwise over 2.5 hours through a dropping funnel, and a polymerization reaction was carried out while maintaining the temperature at 120 °C.

[0215] (Step 2: Reaction with epoxy groups) Next, the inside of the flask was purged with air, 29 parts of acrylic acid, 0.3 part of tris(dimethylaminomethyl)phenol as a catalyst, and 0.3 part of hydroquinone were added, and the mixture was reacted at 120 °C for 5 hours to obtain a resin solution having a weight average molecular weight (Mw) of about 10,500. Since the added acrylic acid forms an ester bond at the epoxy group terminal of the glycidyl methacrylate structural unit, the resin structure does not have a carboxyl group.

[0216] (Step 3: Reaction with hydroxyl groups) Next, 46 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst were added to the flask, and the mixture was reacted at 120 °C for 4 hours. One of the two carboxyl groups generated by the cleavage of the anhydrous carboxylic acid moiety of the added tetrahydrophthalic anhydride forms an ester bond with the hydroxyl group in the resin structure, and the other generates a carboxyl group terminal.

[0217] (Step 4: Adjustment of non-volatile content) Propylene glycol monomethyl ether acetate was added so that the non-volatile content became 20% by weight to obtain a binder resin (C3) solution.

[0218] (Preparation of binder resin (C4) solution) 145 parts of propylene glycol monomethyl ether acetate (PGMAC) was placed in a flask equipped with a stirring device, a dropping tube, a condenser, a thermometer, and a gas introduction tube. The mixture was stirred while purging with nitrogen and heated to 120 °C. Next, 10.1 parts (6.0 parts) of azobisisobutyronitrile was charged into a monomer mixture consisting of 20.0 parts (0.1 mol) of monomethacrylate having a dicyclopentadiene skeleton (FA-512M manufactured by Hitachi Chemical Co., Ltd.), 108.0 parts (1.5 mol) of methacrylic acid, and 31.0 parts (0.2 mol) of benzyl methacrylate per 100 parts of the monomer mixture. The resulting mixture was dropped from the dropping tube into the flask over 2 hours to carry out a polymerization reaction. After completion of the dropping, the mixture was continuously stirred at 120 °C for 2 hours to carry out the polymerization reaction. Next, the inside of the flask was replaced with air, and 0.9 part of tris(dimethylaminomethyl)phenol and 0.145 part of hydroquinone were added to 122.3 parts (0.9 mol, 60 mol% of methacrylic acid) of glycidyl methacrylate, and the reaction was carried out at 120 °C for 6 hours. Sampling was performed, and the reaction was terminated when the acid value in terms of non-volatile content became 1.0 mgKOH / g or less. Propylene glycol monomethyl ether acetate was added so that the non-volatile content became 20% by weight to obtain a binder resin (C4) solution.

[0219] <Preparation of Coloring Composition> (Production of Pigment Dispersion (Single Color: PR-1)) The following mixture was stirred and mixed uniformly, and then dispersed using zirconia beads with a diameter of 0.5 mm for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 5.0 μm to prepare a coloring composition (PR-1) having a non-volatile component of 20% by mass. 14.0 parts of micronized red pigment (R-1) 1.0 part of dye derivative 1 6.0 parts of dispersant 2 (non-volatile content 50% solution) 10.0 parts of binder resin (C1: non-volatile content 20.0% solution) 69.0 parts of PGMAc

[0220] (Production of Pigment Dispersion (PR-2 to PR-4 and PY1 to PY3)) A colored composition was prepared in the same manner as the colored composition (PR-1), except that the composition shown in Table 2 was changed.

[0221] [Table 2]

[0222] (Production of Pigment Dispersions (PG-1 to PG-7)) A colored composition was prepared in the same manner as the colored composition (PR-1), except that the composition shown in Table 3 was changed. [Table 3]

[0223] (Production of Pigment Dispersions (PB-1 to PB-4 and PV-1 to PV-3)) A colored composition was prepared in the same manner as the colored composition (PR-1), except that the composition shown in Table 4 was changed. [Table 4]

[0224] [Synthesis of Photoinitiators E1 to E4] [Synthesis of Photoinitiator (E1)] 100.0 g of N-benzoylcarbazole was dissolved in 1000 parts of chloroform, and 85.0 g of aluminum chloride was further added. While stirring at 0 °C, a solution prepared by dissolving 32.0 g of propionyl chloride in 500 parts of chloroform was added dropwise over 2 hours for reaction. After completion of the dropwise addition, the mixture was stirred at 25 °C for 4 hours for reaction. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, the drying agent was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 113.0 parts of intermediate compound (a1). Next, when 100.0 parts of compound (a1) was dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, 38.4 parts of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature for reaction. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours for reaction. The reaction solution was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts × 3 times), dried over magnesium sulfate, the drying agent was filtered, the solvent was distilled off, and the residue was washed with n-hexane to obtain 99.8 parts of precursor compound (b1). Next, when 30.0 parts of compound (b1) was stirred in 300 parts of ethyl acetate, 6.3 parts of acetic anhydride and 10.6 parts of sodium acetate were added, and the mixture was heated to reflux for 3 hours for reaction. Thereafter, the reaction solution was poured into 500 parts of ice water, the resulting product was extracted with ethyl acetate, the organic layer was washed with water (300 parts × 3 times), dried over magnesium sulfate, the drying agent was filtered, the solvent was distilled off, and the residue was recrystallized from ethyl acetate-hexane to obtain the oxime ester-based photopolymerization initiator (E1).

[0225] Photopolymerization initiator (E1) [Synthesis of photopolymerization initiator (E2)]

[0226] [Synthesis of photopolymerization initiator (E2)] 100.0 parts of N-benzoylcarbazole were dissolved in 1000 ml of chloroform, and 84.0 parts of aluminum chloride were further added. While stirring at 0 °C, a solution prepared by dissolving 36.8 parts of butanoyl chloride in 500 parts of chloroform was added dropwise over 2 hours for reaction. After completion of the dropwise addition, the mixture was stirred at 25 °C for 4 hours for reaction. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and after filtering off the drying agent, the residue was recrystallized from chloroform / methanol to obtain 109.3 parts of intermediate compound (a2). Next, when 100.0 parts of compound (a2) was dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, 43.1 parts of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature for reaction. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts × 3 times), dried over magnesium sulfate, the drying agent was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to obtain 89.3 parts of precursor compound (b2). Next, when 30.0 parts of compound (b2) was stirred in 300 parts of ethyl acetate, 6.1 parts of acetic anhydride and 10.3 parts of sodium acetate were added, and the mixture was heated to reflux for 3 hours for reaction. Thereafter, the reaction solution was poured into 500 parts of ice water, the resultant product was extracted with ethyl acetate, the organic layer was washed with water (300 parts × 3 times), dried over magnesium sulfate, the drying agent was filtered off, the solvent was distilled off, and the residue was recrystallized from ethyl acetate-hexane to obtain the oxime ester-based photopolymerization initiator (E2).

[0227] Photopolymerization initiator (E2)

Chemical formula

[0228] [Synthesis of photopolymerization initiator (E3)] 100.0 parts of N-(p-nitrophenyl)carbazole was dissolved in 1000 parts of chloroform, and 101.8 parts of aluminum chloride was further added. While stirring at 0 °C, a solution prepared by dissolving 44.3 parts of butanoyl chloride in 500 parts of chloroform was added dropwise over 2 hours for reaction. After completion of the dropwise addition, the mixture was stirred at 25 °C for 4 hours for reaction. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and after filtering off the drying agent, the residue was recrystallized from chloroform / methanol to obtain 113.6 parts of intermediate compound (a3). Next, when 100.0 parts of compound (a3) was dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, 43.1 parts of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature for reaction. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours for reaction. The reaction solution was poured into 1600 parts of ice water and extracted with 1500 parts of chloroform. The organic layer was washed with water (500 parts × 3 times), dried over magnesium sulfate, the drying agent was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to obtain 107.2 parts of precursor compound (b3). Next, when 50.0 parts of compound (b3) was stirred in 500 parts of ethyl acetate, 19.9 parts of acetic anhydride and 11.7 parts of sodium acetate were added, and the mixture was heated to reflux for 3 hours for reaction. Thereafter, the reaction solution was poured into 500 parts of ice water, the resulting product was extracted with ethyl acetate, the organic layer was washed with water (500 parts × 3 times), dried over magnesium sulfate, the drying agent was filtered off, the solvent was distilled off, and the residue was recrystallized from ethyl acetate - hexane to obtain the oxime ester-based photoinitiator (E3).

[0229] Photoinitiator (E3) [Chemical Structure]

[0230] [Synthesis of Photoinitiator (E4)] 100.0 parts of N-benzoyl-1,3-dimethylcarbazole were dissolved in 1000 parts of chloroform, and 78.6 parts of aluminum chloride were further added. With stirring at 0 °C, a solution prepared by dissolving 29.6 parts of propionyl chloride in 500 parts of chloroform was added dropwise over 2 hours for reaction. After completion of the dropwise addition, the mixture was stirred at 25 °C for 4 hours for reaction. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and after filtering off the desiccant, the residue was recrystallized from chloroform / methanol to obtain 111.8 parts of intermediate compound (a4). Next, when 100.0 parts of compound (a4) were dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, 35.7 parts of tert-butyl nitrite were added dropwise over 1 hour with stirring at room temperature for reaction. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours for reaction. The reaction solution was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to obtain 98.3 parts of precursor compound (b4). Next, when 30.0 parts of compound (b4) were stirred in 300 parts of ethyl acetate, 5.9 parts of acetic anhydride and 10.0 parts of sodium acetate were added, and the mixture was heated to reflux for 3 hours for reaction. Thereafter, the reaction solution was poured into 500 parts of ice water, the resulting product was extracted with ethyl acetate, the organic layer was washed with water (300 parts × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was recrystallized from ethyl acetate - hexane to obtain 31.2 parts of photopolymerization initiator (E4).

[0231] Photopolymerization initiator (E4)

Chemical formula

[0232] Photopolymerization initiator (E5) (「IRGACURE OXE-02」manufactured by BASF)

Chemical formula

[0233] Photopolymerization initiator (E6) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Irgacure 379 (manufactured by BASF Japan Ltd.)] Photopolymerization initiator (E7) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Irgacure 907 (manufactured by BASF Japan Ltd.)]

[0234] (Production of photosensitive coloring composition) [Example 1] (Preparation of coloring composition (SG-1)) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (S-1) with a nonvolatile content of 20.0%. Coloring composition PG-2: 54.7 parts of a 20.0% nonvolatile liquid Coloring composition PY-3: 12.0 parts of a 20.0% nonvolatile liquid Binder solution C1: 11.1 parts of a 20.0% nonvolatile liquid Polymerizable compound D1-1 1.2 parts Polymerizable compound D2-1 2.8 parts Photopolymerization initiator E2 0.4 part PGMAc 17.8 parts

[0235] [Examples 2 to 35, Comparative Examples 1 to 3] (Preparation of photosensitive coloring compositions (SG-2 to SG-28, SR-1 to SR-4, SB-1 to SB-6)) Photosensitive coloring compositions were prepared in the same manner as in Example 1, except that the types of the coloring composition and the binder resin solution in Example 1 were changed as described in Tables 5 to 8. In the tables, the colorant content is the colorant content in the nonvolatile content of the photosensitive coloring composition.

[0236] [Table 5]

[0237] [Table 6]

[0238]

Table 7

[0239]

Table 8

[0240] The symbols in the table are as follows <Polymerizable compound (D)> ·Isocyanurate ring-containing polymerizable compound (D1) having 2 or 3 polymerizable unsaturated groups (D1-1) Triacrylate of ethoxylated isocyanuric acid [A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] (D1-2) Tris-(2-acryloxyethyl) isocyanurate containing a pentyleneoxy chain [A-9300-1CL (manufactured by Shin-Nakamura Chemical Co., Ltd.)] ·Polymerizable compound (D2) having 3 polymerizable unsaturated groups containing an alkyleneoxy chain (D2-1) Trimethylolpropane triacrylate having an ethyleneoxy chain as a linking group [Aronix M350 (manufactured by Toagosei Co., Ltd.)] (D2-2) Trimethylolpropane triacrylate having a propyleneoxy chain as a linking group [Aronix M321 (manufactured by Toagosei Co., Ltd.)] (D2-3) Trimethylolpropane triacrylate having a total of 20 ethyleneoxy chains as linking groups in the molecule [AT-20E (manufactured by Shin-Nakamura Chemical Co., Ltd.)] ·Other polymerizable compounds (D3-1) Trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)]

[0241] <Pixel shape (linearity)> The obtained photosensitive composition was coated on a silicon wafer substrate with a diameter of 200 mm using a spin coater to a thickness of 1.50 μm after drying, and dried at 70 °C for 1 minute to obtain a substrate. Next, using an i-line stepper exposure apparatus FPA-3000i4 (manufactured by Canon), exposure was performed at a wavelength of 365 nm with an exposure of 8000 J / m2. The exposure was performed through a photomask having a square opening with sides of 400 μm. The film after exposure was developed by paddle development with 2.38% TMAH (a 2.38% aqueous solution of tetramethylammonium hydroxide manufactured by Tama Chemical Industry Co., Ltd.) for 1 minute. After paddle development, rinsing was performed with pure water in a spin shower for 20 seconds and spin-dried. The linearity of the pixels formed by the openings was observed using a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following criteria. Paddle development was performed for 1 minute with . After paddle development, rinsing was performed with pure water in a spin shower for 20 seconds and spin-dried. The linearity of the pixels formed by the openings was observed using a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following criteria. ○: The linearity of the pixels is good throughout (a practically preferable level) △: The linearity of the pixels is partially good (a practically usable level) ×: The linearity of the pixels is poor throughout (a level not suitable for practical use)

[0242] <Pixel shape (cross section)> The obtained photosensitive composition was coated on a silicon wafer substrate with a diameter of 200 mm using a spin coater to a thickness of 1.50 μm after drying, and dried at 70 °C for 1 minute to obtain a substrate. Next, using an i-line stepper exposure apparatus FPA-3000i4 (manufactured by Canon), exposure was performed at a wavelength of 365 nm with an exposure of 8000 J / m2. The exposure was performed through a photomask having a square opening with sides of 5 mm. The film after exposure was developed by paddle development with 2.38% TMAH (a 2.38% aqueous solution of tetramethylammonium hydroxide manufactured by Tama Chemical Industry Co., Ltd.) for 1 minute. After paddle development, rinsing was performed with pure water in a spin shower for 20 seconds and spin-dried. The pixels formed by the openings were cut out, and the cross section was observed using a scanning electron microscope ("S-3000N" manufactured by Hitachi High-Technologies Corporation) and evaluated according to the following criteria. ○: The angle between the wafer and the pixel edge is 90 to 110° (a practically preferable level) △: The angle between the wafer and the pixel edge is 111 to 120° ×: The angle between the wafer and the pixel end is 120° or more (not suitable for practical use)

[0243] <Solvent resistance> The obtained photosensitive composition was spin-coated on a glass substrate using a spin coater to a dry film thickness of 0.9 μm and dried at 70 °C for 20 minutes. Next, the dried coating film was exposed to 200 mJ / cm2 using an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm2 through a photomask with a 6-μm square pattern mask pattern arranged. The pattern-exposed coating film was developed with an unexposed portion using a 2 mass% aqueous potassium hydroxide solution and then washed with pure water. After that, water droplets were blown off with high-pressure air, the substrate was naturally dried, and post-baked on a hot plate at 170 °C for 10 minutes to form a pattern on the glass substrate. The spectral transmittance of the patterned portion of the glass substrate was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Then, it was immersed in an aqueous solution in which TMAH (tetramethylammonium hydroxide) was dissolved at a concentration of 1.0 wt% in water, and the spectral transmittance was promoted again. The change in transmittance at 400 nm before and after immersion in the TMAH aqueous solution was evaluated. The evaluation ranks are as follows. 〇: Less than 1.0% (preferred level for practical use) △: 1.0% or more and less than 5.0% (usable level) ×: 5.0% or more (not suitable for practical use)

[0244] The above evaluation results are shown in Table 9. In the table, the "content of the polymerizable compound" is the content of the polymerizable compound in the non-volatile matter of the photosensitive coloring composition.

Table 9

Explanation of symbols

[0245] 10 Liquid crystal display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims

1. A photosensitive coloring composition containing a colorant (A), a dispersant (B), a binder resin (C), a polymerizable compound (D), and a photopolymerization initiator (E), wherein the polymerizable compound (D) includes an isocyanurate ring-containing polymerizable compound (D1) having two or three polymerizable unsaturated groups and a polymerizable compound (D2) (excluding those containing a ring structure) having three polymerizable unsaturated groups containing an alkyleneoxy chain, and the mass ratio of the polymerizable compound (D1) to the polymerizable compound (D2) is from 10:90 to 50:

50. The photosensitive coloring composition.

2. The photosensitive coloring composition according to claim 1, wherein the content of the polymerizable compound (D) is 15 to 35% by mass in the nonvolatile matter of the photosensitive coloring composition.

3. The photosensitive coloring composition according to claim 1, wherein the photopolymerization initiator (E) contains an oxime ester-based photopolymerization initiator.

4. A color filter formed from the photosensitive coloring composition according to any one of claims 1 to 3.

5. A liquid crystal display device including the color filter according to claim 4.

6. An organic EL display device including the color filter according to claim 4.

7. A solid-state imaging device including the color filter according to claim 4.

Images