Photosensitive colored composition, color filter using the same, image display device, and solid-state image sensor

Abstract

To provide a photosensitive coloring composition capable of forming a color filter that has improved storage stability and is less prone to the occurrence of foreign matter and the deterioration of brightness.SOLUTION: A photosensitive coloring composition comprises a colorant (A), a dispersion resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). The dispersion resin (B) comprises a dispersion resin (B1) comprising an acidic group. The total content of Li, Na, K, Mg, Ca, Fe, and Cr in the photosensitive coloring composition is 500 mass ppm or less, and the content of water is 2.0 mass% or less.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive coloring composition, a color filter using the same, an image display device, a solid-state imaging device, and the like.

Background Art

[0002] Image display devices, solid-state imaging devices, etc. may need to be miniaturized and have higher pixel counts depending on the application. Therefore, a color filter, which is one type of optical filter incorporated in these devices, tends to have a smaller area per pixel and is also required to be made thinner. On the other hand, even when the color filter is made thinner, its spectral characteristics need to be maintained at the conventional level. Therefore, it is necessary to increase the concentration of the colorant contained in the pixels of the color filter. However, on the contrary, the content of the dispersion resin is suppressed, resulting in a problem of reduced storage stability of the photosensitive coloring composition used for pixel formation. In addition, during the manufacture of the color filter, foreign substances are generated in the post-baking process, causing problems such as a decrease in contrast and brightness. There is also a problem that when the color filter is incorporated into a liquid crystal display device and exposed to backlight, the brightness decreases (Non-Patent Document 1).

[0003] Therefore, for example, Patent Document 1 discloses a method for producing a pigment composition for a color filter using an ε-type phthalocyanine pigment and a phthalocyanine derivative. Patent Document 2 discloses an organic pigment composition for a color filter in which the total content ratio of Fe and Cr in the composition is less than 1000 ppm. Patent Document 3 discloses a photosensitive coloring composition in which the content of group 2 element ions with respect to the mass of a zinc phthalocyanine halide pigment is 30 to 300 mass ppm.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

[0005] [Non-Patent Document 1] Journal of Photopolymer Science and Technology, Volume 7, Number 1 (1994) p.151-158 [Summary of the Invention] [Problems to be Solved by the Invention]

[0006] However, the photosensitive coloring compositions described in Patent Documents 1 to 3 could not simultaneously improve the storage stability and the suppression of foreign matter generation. Further, the decrease in brightness due to the backlight was not taken into consideration.

[0007] An object of the present invention is to provide a photosensitive coloring composition capable of forming a color filter having excellent storage stability, less generation of foreign matter, and less decrease in brightness. [Means for Solving the Problems]

[0008] The present invention is a photosensitive coloring composition containing a coloring agent (A), a dispersion resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), where the dispersion resin (B) includes a dispersion resin (B1) having an acidic group, and relates to a photosensitive coloring composition in which the total amount of metals of Li, Na, K, Mg, Ca, Fe, and Cr contained in the photosensitive coloring composition is 500 mass ppm or less, and the water content is 2.0 mass% or less. [Effects of the Invention]

[0009] According to the above-described present invention, it is possible to provide a photosensitive coloring composition capable of forming a color filter having excellent storage stability, less generation of foreign matter, and less decrease in brightness. Further, the present invention can provide a color filter, a liquid crystal display device, and a solid-state imaging device. [Modes for carrying out the invention]

[0010] The following describes in detail embodiments for carrying out the photosensitive colored composition of the present invention. However, the present invention is not limited to the following embodiments and can be modified and implemented within the scope of solving the problem.

[0011] In this invention, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Also, "CI" means Color Index (CI; issued by The Society of Dyers and Colourists). A polymerizable unsaturated group is an ethylenically unsaturated double bond. Furthermore, regarding the molecular weight of the compounds in this invention, for low molecular weight compounds whose molecular weight can be determined, the value is calculated (formula weight) or measured by ESI-MS (electrospray ionization mass spectrometry), and for compounds with a molecular weight distribution, the weight-average molecular weight in polystyrene terms is measured by gel permeation chromatography using tetrahydrofuran as the solvent.

[0012] <Photosensitive coloring composition> The photosensitive colored composition of the present invention comprises a colorant (A), a dispersion resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). The dispersion resin (B) comprises a dispersion resin (B1) having an acidic group. The photosensitive coloring composition is characterized in that the total amount of metals Li, Na, K, Mg, Ca, Fe, and Cr contained in it is 500 ppm by mass or less, and the water content is 2.0% by mass or less.

[0013] [Coloring agent (A)] The photosensitive colored composition of the present invention comprises a colorant (A). The colorant (A) is not particularly limited and may be either a pigment or a dye, and can be used in combination.

[0014] (Pigment) The pigments are not particularly limited. Examples are given below.

[0015] Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179 ,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259, Examples include pigments 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in Japanese Patent Publication No. 2014-134712, pigments described in Japanese Patent Publication No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance, CI Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844 are preferred, and CI Pigment Red 177,254,291,295,296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844 are particularly preferred.

[0016] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0017] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 Examples include pigments described in JP 2012-226110, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the pigments described in JP 2012-226110. Among these, the pigments described in CI Pigment Yellow 138, 139, 150, 185, 231, 233 and Japanese Patent Publication No. 2012-226110 are preferred.

[0018] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, CI Pigment Green 36, 58, 59, 62, and 63 are preferred.

[0019] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

[0020] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 and 23 are preferred.

[0021] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31. Alternatively, a black coloring agent may be used, consisting of at least two pigments selected from red, yellow, blue, green, and purple pigments.

[0022] Examples of inorganic pigments include titanium dioxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

[0023] (dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Derivatives of these dyes, as well as lake pigments (dyes obtained by lake formation), are also examples.

[0024] Acid dyes preferably have acidic groups such as sulfonic acid or carboxylic acid. Salt compounds are also preferred, which are salts of acid dyes with nitrogen-containing compounds such as quaternary ammonium salts, tertiary amines, secondary amines, or primary amines. Salt compounds are also preferred, which are salts of resin components having these functional groups with acid dyes. Furthermore, by sulfonamidating the salt compounds to sulfonamide compounds, it is easy to obtain photosensitive compositions with excellent resistance (lightfastness, solvent resistance). Furthermore, salt-forming compounds of acid dyes and compounds containing an onium base are also preferred due to their excellent resistance (light resistance and solvent resistance). The compound containing the onium base is preferably a resin having a cationic group.

[0025] Basic dyes can be used as is, but salt-forming compounds that form salts with organic acids, perchloric acid, or their metal salts are preferred. Salt-forming compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in salt-forming compounds of basic dyes, preferred anionic components that act as counterions are salt-forming compounds obtained by salting with organic sulfonic acids, organic sulfuric acids, fluorine-containing phosphorus anionic compounds, fluorine-containing boron anionic compounds, cyano-containing nitrogen anionic compounds, anionic compounds having a conjugate base of an organic acid having a halogenated hydrocarbon group, and acid dyes. Note that the resistance of the salt-forming compound is further improved if it contains polymerizable unsaturated groups in its molecule.

[0026] The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), and azite dyes. Examples of dye structures derived from dyes selected from chloromethic acid dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0027] Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, a pigment structure derived from a pigment selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferred, and a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes is more preferred.

[0028] Coloring agent (A) can be used alone or in combination of two or more types.

[0029] When the photosensitive colored composition of the present invention uses both a halogenated phthalocyanine pigment and a quinophthalone pigment as colorants (A), it is more susceptible to brightness reduction caused by backlighting, and the brightness reduction suppression effect of the present invention can be expected to be more pronounced.

[0030] The halogenated phthalocyanine pigments are preferably CI Pigment Greens 36, 58, 59, 62, and 63, with CI Pigment Greens 58 and 59 being more preferred.

[0031] Quinophthalone pigments are preferably compounds represented by the following general formula (2). General formula (2) [ka]

[0032] In general formula (2), R1 to R 13 Each of these independently represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxyl group, or an optionally substituted aryl group. Adjacent groups R1-R4 and / or R5-R8 may together form an optionally substituted aromatic ring.

[0033] R1~R in general formula (2) 13 The substituents are described below.

[0034] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0035] Furthermore, alkyl groups that may have substituents include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl groups, as well as alkyl groups having substituents such as trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, and 2,4-dichlorobenzyl groups.

[0036] Furthermore, examples of alkoxyl groups that may have substituents include linear or branched alkoxyl groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutyloxy, tert-butyloxy, neopentyloxy, 2,3-dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy, as well as alkoxyl groups having substituents such as trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropyloxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy.

[0037] Furthermore, examples of aryl groups that may have substituents include aryl groups such as phenyl, naphthyl, and anthranyl groups, as well as aryl groups having substituents such as p-methylphenyl, p-bromophenyl, p-nitrophenyl, p-methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthraquinonyl, and 2-aminoanthraquinonyl groups.

[0038] In general formula (2), adjacent groups R1 to R4 and / or R5 to R8 form an aromatic ring which may have substituents. The aromatic ring referred to here includes hydrocarbon aromatic rings and heteroaromatic rings. Examples of hydrocarbon aromatic rings include benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings. Examples of heteroaromatic rings include pyridine rings, pyrazine rings, pyrrole rings, quinoline rings, quinoxaline rings, furan rings, benzofuran rings, thiophene rings, benzothiophene rings, oxazole rings, thiazole rings, imidazole rings, pyrazole rings, indole rings, and carbazole rings.

[0039] The quinophthalone pigment is preferably CI Pigment Yellow 138, or a quinophthalone pigment represented by the following general formulas (3) to (5). Here, R 14 ~R 28 , R 29 ~R 43 , R 44 ~R 60 In this formula, the hydrogen atom, halogen atom, optionally substituted alkyl group, optionally substituted alkoxyl group, and optionally substituted aryl group are equivalent to the groups described in general formula (2).

[0040] [ka] [ka]

[0041] In general formulas (3) to (5), R 14 ~R 28 、R 29 ~R 43 、R 44 ~R 60 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent.

[0042] Furthermore, in the quinophthalone pigment used in the coloring composition of the present invention, it is more preferable that R 14 ~R 28 、R 29 ~R 43 、R 44 ~R 60 is a hydrogen atom or a halogen atom.

[0043] The quinophthalone pigment represented by general formula (2) can be synthesized, for example, by the methods described in JP-A-4-226163 and JP-A-2012-226110.

[0044] The content of the colorant (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, in 100% by mass of the non-volatile components of the photosensitive coloring composition.

[0045] (Fine particle size of organic pigment) The organic pigment is preferably used after being made into fine particles. The method of making the particles fine is not particularly limited, and for example, any of wet grinding, dry grinding, and precipitation from solution can be used. Among these, salt milling treatment by a kneader method, which is one type of wet grinding, is preferable. The average primary particle diameter determined by TEM (transmission electron microscope) of the fine particles of the pigment is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0046] A resin may be added to the salt milling process as needed. The type of resin is not particularly limited and includes natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in the organic solvent. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of pigment.

[0047] [Dispersion resin (B)] (Dispersion resin containing acidic groups (B1)) The photosensitive colored composition of the present invention contains a dispersion resin (B1) having an acidic group as the dispersion resin (B). This makes it possible to obtain a photosensitive colored composition with excellent storage stability and low generation of foreign matter.

[0048] Examples of acidic groups include carboxyl groups, phosphate groups, and sulfonic acid groups. Among these, carboxyl groups and phosphate groups are preferred from the viewpoint of storage stability and suppression of foreign matter, with carboxyl groups being more preferred.

[0049] The dispersion resin (B1) having an acidic group preferably includes a dispersion resin having a carboxyl group. Examples include the dispersion resins shown in (B1-1) or (B1-2) below.

[0050] [Dispersion resin containing acidic groups (B1-1)] The acidic group-containing dispersion resin (B1-1) is a resin comprising a carboxyl group-containing polyester portion obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic dianhydrides and tricarboxylic anhydrides with a hydroxyl group in a hydroxyl group-containing compound, and a vinyl polymer portion obtained by radical polymerization of monomers. First, let's explain the polyester portion. The polyester portion is a region where multiple ester groups exist, resulting from the reaction between acid anhydride groups and hydroxyl groups.

[0051] The tetracarboxylic dianhydrides mentioned above include, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid dianhydride, and bicyclo[2.2.Aliphatic tetracarboxylic dianhydrides such as [2]-octo-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride Substance, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic acid dianhydride, 1,2,3,4-furantetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride Hon dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid 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 Examples include aromatic tetracarboxylic dianhydrides such as 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 acid dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride. Among these, aromatic tetracarboxylic dianhydrides are preferred from the viewpoint of adsorption to pigments.

[0052] Tetracarboxylic acid dianhydrides are preferable because, upon reaction with hydroxyl group-containing compounds, they form a dispersion resin having two carboxyl groups per tetracarboxylic acid dianhydride unit, thus improving pigment adsorption.

[0053] The aforementioned tricarboxylic acid anhydride may be an aliphatic tricarboxylic acid anhydride or an aromatic tricarboxylic acid anhydride, etc.

[0054] Examples of the aliphatic tricarboxylic acid anhydrides include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1,2-anhydride, and 1,3,4-cyclopentanetricarboxylic acid anhydride.

[0055] Examples of the aromatic tricarboxylic acid anhydrides include benzenetricarboxylic acid anhydrides (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalentricarboxylic acid anhydrides (1,2,4-naphthalentricarboxylic acid anhydride, 1,4,5-naphthalentricarboxylic acid anhydride, 2,3,6-naphthalentricarboxylic acid anhydride, 1,2,8-naphthalentricarboxylic acid anhydride, etc.), 3,4,4'-benzophenonetricarboxylic acid anhydride, 3,4,4'-biphenylethertricarboxylic acid anhydride, 3,4,4'-biphenyltricarboxylic acid anhydride, 2,3,2'-biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, or 3,4,4'-biphenylsulfonetricarboxylic acid anhydride. Among these, aromatic tricarboxylic acid anhydrides are preferred from the viewpoint of adsorption to pigments.

[0056] The molar ratio of acid anhydride groups in one or more acid anhydrides selected from the tetracarboxylic dianhydrides and tricarboxylic anhydrides to hydroxyl groups in the hydroxyl group-containing compound is preferably acid anhydride groups / hydroxyl groups = 0.5 to 1.5. Reacting in an appropriate ratio makes it easier to obtain a dispersion resin with good dispersibility.

[0057] The hydroxyl group-containing compound can be a monool or a polyol, with polyol being preferred. The hydroxyl groups in the polyol function as bonding starting points with the vinyl polymer portion. Examples of polyols that serve as the starting point for bonding with the vinyl polymer portion include compounds having two hydroxyl groups and one thiol group in their molecule. Examples of compounds having two hydroxyl groups and one thiol group in their molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or 1-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.

[0058] Examples of dispersion resins having acidic groups (B1-1) include (B1-1-1) or (B1-1-2) below.

[0059] ≪Dispersion resin containing acidic groups (B1-1-1)≫ The vinyl polymer moiety of the acidic group-containing dispersion resin (B1-1-1) is obtained by radical polymerization of (i) a monomer having at least one thermally crosslinkable group selected from the group consisting of hydroxyl groups, oxetane groups, t-butyl groups, and blocked isocyanate groups, (ii) a carboxyl group-containing monomer, and optionally (iii) other monomers.

[0060] (i-1) [Hydroxyl group-containing monomer] The hydroxyl group-containing monomers used as thermally crosslinkable groups include hydroxyl group-containing (meth)acrylate monomers, such as hydroxyalkyl (meth)acrylates including 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. Alternatively, hydroxyl group-containing (meth)acrylamide monomers, such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)(meth)acrylamide, and other N-(hydroxyalkyl)(meth)acrylamides. Alternatively, hydroxyl group-containing vinyl ether monomers, such as hydroxyalkyl vinyl ethers including 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, and 2-(or 3- or 4-)hydroxybutyl vinyl ether, Alternatively, hydroxyl group-containing allyl ether monomers, such as hydroxyalkyl allyl ethers including 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, and 2-(or 3- or 4-)hydroxybutyl allyl ether, are used.

[0061] Monomers obtained by adding alkylene oxide and / or lactone to the above-mentioned hydroxyalkyl (meth)acrylate, alkyl-α-hydroxyalkyl acrylate, N-(hydroxyalkyl)(meth)acrylamide, hydroxyalkyl vinyl ether, or hydroxyalkyl allyl ether are also preferred. Examples of the alkylene oxide to be added include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide, and combinations of two or more of these. When two or more alkylene oxides are used in combination, the bonding configuration may be random or / or block. Examples of the lactone to be added include δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and combinations of two or more of these. It is also acceptable to add both alkylene oxide and lactone.

[0062] (i-2) [Oxetane group-containing monomers] Oxetane group-containing monomers include (vinyloxyalkyl)alkyl oxetane, (meth)acryloyloxyalkyl oxetane, and [(meth)acryloyloxyalkyl]alkyl oxetane. Among these, (3-ethyloxetan-3-yl)methyl methacrylate is particularly preferred. A commercially available example is ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate) (manufactured by Ube Industries, Ltd.).

[0063] (i-3) [t-butyl group-containing monomer] Examples of t-butyl group-containing monomers used as thermally crosslinkable functional groups include t-butyl methacrylate and t-butyl acrylate.

[0064] (i-4) [Blocked isocyanate group-containing monomer] Examples of monomers containing blocked isocyanate groups as thermally crosslinkable groups include 2-(0-[1'-methylpropylenedenamino]carboxyamino)ethyl methacrylate and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate. Examples of commercially available products include Karenz MOI-BM (2-(0-[1'-methylpropylenedenamino]carboxyamino)ethyl methacrylate) (manufactured by Showa Denko Co., Ltd.) and Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (manufactured by Showa Denko Co., Ltd.).

[0065] The content of oxetane group-containing monomers, t-butyl group-containing monomers, and blocked isocyanate group-containing monomers is preferably 5 to 90% by mass, and more preferably 20 to 60% by mass, of the total monomers. If the content is 5% by mass or more, it is possible to obtain a photosensitive colored composition with excellent resistance due to the effect of crosslinking, and if it is 90% by mass or less, the stability of the composition is also good, which is therefore preferable.

[0066] (ii) [Carboxyl group-containing monomers] Examples of carboxyl group-containing monomers include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Among these, (meth)acrylic acid is preferred because it has good copolymerizability and is readily available.

[0067] (iii) [Other monomers] In the vinyl polymer portion of the acidic group-containing dispersion resin (B1-1-1), other monomers other than thermally crosslinkable monomers and carboxyl group-containing monomers can be used. Other monomers include 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, trimethylcyclohexyl(meth)acrylate, and isobornyl(meth)acrylate; Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate; Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate; Alkoxy polyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate; 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, and acryloylmorpholine; Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; Other examples include nitriles such as (meth)acrylonitrile.

[0068] Other examples include 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.

[0069] ≪Dispersion resin containing acidic groups (B1-1-2)≫ The dispersion resin (B1-1-2) having acidic groups has polymerizable unsaturated groups in the vinyl polymer portion.

[0070] A method for producing an acidic dispersion resin (B1-1-2) can be, for example, by reacting a compound having a polymerizable unsaturated group, such as a (meth)acryloyl group, with a functional group, with a monomer polymer containing a functional group-containing monomer that reacts with the functional group. Examples include a reaction product of glycidyl methacrylate with a polymer having a hydroxyl group or a carboxyl group, and a reaction product of methacryloyloxyethyl isocyanate with a polymer having a hydroxyl group or a carboxyl group. Polymers having hydroxyl groups or carboxyl groups can also be obtained by ring-opening a polymer having a glycidyl group with an acid anhydride compound, or by ring-opening a polymer having an acid anhydride group. For example, the dispersion resin described in Japanese Patent Application Publication No. 2011-157416 is an example.

[0071] [Dispersion resins containing acidic groups (B1-2)] The dispersion resin having an acidic group (B1-2) is a dispersion resin represented by the following general formula (6), and specifically, it is the dispersion resin described in Japanese Patent Publication No. 2007-140487.

[0072] General formula (6) (HOOC-) m -R 2 -(-COO-[-R 4 -COO-] n -R 5 ) t (In general formula (6), R 2 R is a tetravalent tetracarboxylic acid compound residue, 5 is a monoalcoholic residue, R 4 (where m represents a lactone residue, m is 2 or 3, n is an integer from 1 to 50, and t represents (4-m).)

[0073] The acid value of the dispersion resin (B1) having an acidic group is preferably 20 to 250 mg KOH / g, and more preferably 30 to 200 mg KOH / g, from the viewpoint of storage stability and suppression of foreign matter.

[0074] The dispersion resin (B1) having an acidic group can be used alone or in combination of two or more types.

[0075] From the viewpoint of storage stability and suppression of foreign matter, the content of the dispersion resin (B1) having an acidic group is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the coloring agent (A).

[0076] [Dispersion resin containing basic groups (B2)] From the viewpoint of storage stability, the photosensitive colored composition of the present invention preferably further contains a dispersion resin (B2) having a basic group.

[0077] Basic groups include, for example, primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles and other groups containing nitrogen atoms.

[0078] The dispersion resin (B2) having a basic group preferably has one or more units selected from the group represented by the following general formulas (7), (8), and (9) as the basic group.

[0079] General formula (7) [ka]

[0080] (In general formula (7), R1 to R3 represent a hydrogen atom or a linear or cyclic hydrocarbon group which may have substituents, and two or more of R1 to R3 may be bonded to each other to form a cyclic structure. R4 represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y - (This indicates the paired anion.)

[0081] General formula (8) [ka] (In general formula (8), R5 and R6 represent a hydrogen atom or a substituted linear or cyclic hydrocarbon group, either mutually or independently, and R5 and R6 may bond to each other to form a cyclic structure. R4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group.)

[0082] General formula (9) [ka] (In general formula (9), R7 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxyradical group, or OR 12 Represents R 12 R8, R9, R 10 , R 11 Each of these independently represents a methyl group, an ethyl group, or a phenyl group. R4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

[0083] In general formula (7), R1 to R3 are more preferably alkyl groups having 1 to 4 carbon atoms, which may have substituents, or aralkyl groups having 7 to 16 carbon atoms, which may have substituents, and particularly preferably methyl, ethyl, propyl, butyl, or benzyl groups.

[0084] In general formula (8), R5 and R6 are more preferably alkyl groups having 1 to 4 carbon atoms, which may have substituents, and methyl, ethyl, propyl, and butyl groups are particularly preferred.

[0085] In R7 of general formula (9), the alkyl group having 1 to 18 carbon atoms can be, for example, linear, branched, or cyclic alkyl groups. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, cyclohexyl, n-octyl, and hexadecyl groups. Examples of aryl groups having 6 to 20 carbon atoms include phenyl groups, 1-naphthyl groups, and 2-naphthyl groups. Aralkyl groups having 7 to 12 carbon atoms include, for example, groups in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Examples include benzyl groups, phenethyl groups, α-methylbenzyl groups, and 2-phenylpropan-2-yl groups. Examples of acyl groups include alkanoyl groups and alloyl groups having 2 to 8 carbon atoms. Examples include acetyl groups and benzoyl groups. Among these, hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, and oxy radical groups are particularly preferred, hydrogen atoms and methyl groups are more preferred, and methyl groups are most preferred.

[0086] In general formulas (7) to (9), the divalent linking group X is, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, or -CONH-R 13 -,-COO-R 14 -(However, R 13 , and R 14 Examples include single bonds, methylene groups, C2-C10 alkylene groups, or C2-C10 ether groups (alkyloxyalkyl groups). Preferably -COO-R 14 -. Also, in general formula (7), the Y of the pair anion - For example, Cl - , Br - , I - ClO4 - BF4 - CH3COO - PF6 - These are some examples.

[0087] Examples of quaternary ammonium base-containing monomers that form precursors or substructures of general formula (7) include alkyl (meth)acrylate-based quaternary ammonium salts such as (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride, and (meth)acryloyloxyethylmethylmorpholinoammonium chloride; alkyl (meth)acryloylamide-based quaternary ammonium salts such as (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, and (meth)acryloylaminoethyldimethylbenzylammonium chloride; dimethyldiallylammonium methyl sulfate; and trimethylvinylphenylammonium chloride.

[0088] The tertiary amine group-containing monomers that form precursors and substructures of general formula (8) are, for example, (meth)acrylates having a tertiary amino group, such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate; Examples include (meth)acrylamides having a tertiary amino group, such as N,N-dimethylaminoethyl(meth)acrylamide, N,N-diethylaminoethyl(meth)acrylamide, N,N-dimethylaminopropyl(meth)acrylamide, and N,N-diethylaminopropyl(meth)acrylamide.

[0089] Examples of monomers that serve as precursors or substructures of general formula (9) include compounds represented by the following general formulas (9-1) to (9-11).

[0090] [ka] [ka] [ka] [ka]

[0091] In general formulas (9-1) to (9-11), R4 represents hydrogen or a methyl group.

[0092] Of these, 2,2,6,6-tetramethylpiperidyl methacrylate (a compound in which R4 is a methyl group in general formula (9-1)) and 1,2,2,6,6-pentamethylpiperidyl methacrylate (a compound in which R4 is a methyl group in general formula (9-2)) are preferred, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is particularly preferred.

[0093] The units represented by general formulas (7) to (9) may be present individually or in combination of two or more types, and may be present in any form of random copolymerization, block copolymerization, or graft copolymerization, with the presence of block copolymerization being more preferable.

[0094] The units represented by general formulas (7) to (9) are not particularly limited as long as they are structures obtained by copolymerizing copolymerizable monomers, and can be appropriately selected depending on the application. The copolymerizable monomers are shown below.

[0095] For example, linear or branched alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth), tertiarybutyl(meth)acrylate, isoamyl(meth)acrylate, octyl(meth)acrylate, isooctyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, cetyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, isomiristyl(meth)acrylate, stearyl(meth)acrylate, and isostearyl(meth)acrylate; Cyclohexyl (meth)acrylates such as tertiary butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate; Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate; (Meth)acrylates having aromatic rings such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate (Poly)alkylene glycol monoalkyl ether (meth)acrylates such as methyl ether (meth)acrylate, tripropylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, polyethylene glycol monostearyl ether (meth)acrylate, and octoxy polyethylene glycol-polypropylene glycol (meth)acrylate; (Poly)alkylene glycol (meth)acrylates having aromatic rings, such as phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, and nonylphenoxypoly(ethylene glycol-propylene glycol) (meth)acrylate; (Meth)acrylates having alkyloxysilyl groups, such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate; (meth)acryloxy-modified polydimethylsiloxanes (silicone macromers); Examples include N-substituted (meth)acrylamides such as (meth)acrylamide, dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; and nitriles such as (meth)acrylonitrile. Other examples include styrene and styrene compounds such as 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 vinyl fatty acid compounds such as vinyl acetate and vinyl propionate.

[0096] Furthermore, carboxyl group-containing monomers can also be used in combination. Examples of carboxyl group-containing monomers include (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth)acrylate.

[0097] Furthermore, amino group-containing monomers other than those represented by general formulas (7) to (9) may be used in combination, as long as they do not impair the effects of the present invention.

[0098] Furthermore, a resin in which a portion of the basic groups of a dispersion resin (B2) having basic groups are bonded to a compound represented by the following general formula (10) or (11) to form a salt can also be suitably used.

[0099] General formula (10) [ka]

[0100] (In general formula (10), R 1 , and R 2 Each of these can independently be a hydrogen atom, a hydroxyl group, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl or benzyl group which may have substituents, or -OR 4 Represents R 4 R represents a (meth)acryloyl group via a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl or benzyl group, or an alkylene group having 1 to 4 carbon atoms. However, R 1 , and R 2 At least one of them is a group containing a carbon atom.

[0101] General formula (11) [ka]

[0102] (In general formula (11), R 3 This includes a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have substituents, or -OR 4 Represents R 4 This represents a (meth)acryloyl group via a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl or benzyl group, or an alkylene group having 1 to 4 carbon atoms.

[0103] Examples of compounds represented by the general formula (10) include monobutyl phosphate, dibutyl phosphate, methyl phosphate, dibenzyl phosphate, diphenyl phosphate, phenylphosphinic acid, phenylphosphonic acid, and dimethacryloyloxyethyl acid phosphate.

[0104] Examples of compounds represented by the general formula (11) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid, and mono-n-propylsulfuric acid. Hydrates such as p-toluenesulfonic acid monohydrate may also be used.

[0105] From the viewpoint of storage stability, the amine value of the dispersion resin (B2) having a basic group is preferably 20 to 250 mg KOH / g, and more preferably 30 to 150 mg KOH / g.

[0106] The dispersion resin (B2) having a basic group can be used alone or in combination of two or more types.

[0107] The mass ratio of the dispersion resin having an acidic group (B1) to the dispersion resin having a basic group (B2) is preferably 100:0 to 30:70, and more preferably 70:30 to 30:70, from the viewpoint of storage stability and suppression of foreign matter.

[0108] From the viewpoint of storage stability and suppression of foreign matter, the content of dispersion resin (B) is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of coloring agent (A).

[0109] [Polymerizable compound (C)] The photosensitive coloring composition of the present invention contains a polymerizable compound (C).

[0110] Polymerizable compounds (C) include monomers and oligomers having polymerizable unsaturated groups. Examples of polymerizable unsaturated groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and (meth)acryloyloxy groups. Examples of polymerizable compounds (C) include lactone-modified polymerizable compounds, polymerizable compounds having acidic groups, polymerizable compounds having urethane bonds, and other polymerizable compounds. Note that oligomers are compounds with a molecular weight of 1000 or more.

[0111] (Lactone-modified polymerizable compound) From the viewpoint of coating film resistance, the photosensitive coloring composition of the present invention preferably contains a lactone-modified polymerizable compound.

[0112] Lactone-modified polymerizable compounds are compounds that have a structure modified with lactone within their molecule. Lactone-modified polymerizable compounds are obtained by esterifying polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethythritol, tripentaerythritol, glycerin, diglycerol, and trimetrolmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compounds are preferably those represented by the following general formula (12).

[0113] General formula (12) [ka]

[0114] In general formula (12), all six Rs are groups represented by general formula (13), or one to five of the six Rs are groups represented by general formula (13) and the remaining ones are groups represented by general formula (14).

[0115] General formula (13) [ka]

[0116] In general formula (13), R 1 represents a hydrogen atom or a methyl group, m is an integer from 1 to 2, and * is a bond that connects to the oxygen atom in general formula (12).

[0117] General formula (14) [ka]

[0118] In general formula (14), R 1 represents a hydrogen atom or a methyl group, and * represents a bond that connects to the oxygen atom in general formula (12).

[0119] Lactone-modified polymerizable compounds are commercially available, for example, as the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd., such as DPCA-20 (where m=1 in the above general formulas (12) to (14), the number of groups represented in general formula (13) = 2, R 1 (A compound in which all atoms are hydrogen atoms), DPCA-30 (In the above general formulas (12) to (14), m=1, the number of groups represented in general formula (13) = 3, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-60 (in the above general formulas (12) to (14), m=1, number of groups represented in general formula (13)=6, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-120 (in the above general formulas (12) to (14), m=2, number of groups represented in general formula (13)=6, R 1 Examples include compounds in which all atoms are hydrogen atoms.

[0120] From the viewpoint of coating film resistance, the lactone-modified polymerizable compound has m=1 in the above general formulas (12) to (14), the number of groups represented in general formula (13) = 2 to 6, and R 1 Compounds in which all atoms are hydrogen atoms are preferred, and in the above general formulas (12) to (14), m=1, the number of groups represented in general formula (13) = 2 or 3, R 1 Compounds in which all atoms are hydrogen atoms are more preferable.

[0121] From the viewpoint of coating film resistance, the content of the lactone-modified polymerizable compound is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass, based on 100% by mass of polymerizable compound (C).

[0122] (Polymerizable compounds containing acidic groups) The photosensitive coloring composition of the present invention preferably contains a polymerizable compound having an acidic group, from the viewpoint of alkali developability and pattern formation. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups. Among these, carboxyl groups are preferred.

[0123] Examples of polymerizable compounds having acidic groups include esters of polyhydric alcohols and (meth)acrylic acid poly(meth)acrylates containing free hydroxyl groups with dicarboxylic acids; and esters of polyhydric acids with monohydroxyalkyl (meth)acrylates. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid. Examples of polycarboxylic acids include trimellitic acid and pyromellitic acid. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0124] Examples of commercially available polymerizable compounds containing acidic groups include Viscoat #2500P from Osaka Organic Chemicals Co., Ltd., and Aronics M-5300, M-5400, M-5700, M-510, M-520, and M-521 from Toagosei Co., Ltd.

[0125] From the viewpoint of alkali developability and pattern formation properties, the content of polymerizable compounds having acidic groups is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass, based on 100% by mass of polymerizable compound (C).

[0126] (Polymerizable compound containing urethane bonds) From the viewpoint of pattern-forming properties, the photosensitive coloring composition of the present invention preferably contains a polymerizable compound having a urethane bond as the polymerizable compound (C).

[0127] Polymerizable compounds having a urethane bond include, for example, urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting it with a hydroxyl group-containing (meth)acrylate.

[0128] Examples of the hydroxyl group-containing (meth)acrylates mentioned above include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylate.

[0129] Examples of the polyfunctional isocyanates mentioned above include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate, as well as their bilets, isocyanate nulates, and trimethylolpropane adducts.

[0130] Polymerizable compounds having urethane bonds may also have acidic groups from the viewpoint of developability. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups. Among these, carboxyl groups are preferred.

[0131] One method for introducing an acidic group into a polymerizable compound having a urethane bond is to first react the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then add a mercapto compound having a carboxyl group to the product.

[0132] Examples of mercapto compounds having the carboxyl group mentioned above include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0133] From the viewpoint of pattern formation, the number of polymerizable unsaturated groups in a polymerizable compound having a urethane bond is preferably 3 to 15, and more preferably 5 to 12.

[0134] From the viewpoint of pattern formation, the content of the polymerizable compound having a urethane bond is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and even more preferably 20 to 60% by mass, based on 100% by mass of polymerizable compound (C).

[0135] (Other polymerizable compounds) Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate Examples include acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, various acrylic acid esters and methacrylic acid esters such as (meth)acrylic acid esters of methylolated melamine, epoxy(meth)acrylate, urethane acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, etc.

[0136] Other commercially available polymerizable compounds include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330 from Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-32 from Toagosei Co., Ltd. 5, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 manufactured by Osaka Organic Co., Ltd., and OGSOL manufactured by Osaka Gas Chemical Co., Ltd. Examples include EA-0200, EA-0300, GA-5060P, GA-2800, Miramer HR6060, 6100, 6200 from Miwon Specialty Chemical Co., Ltd., NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4, A-9300 from Shin Nakamura Chemical Industry Co., Ltd., and EBECRYL40, 130, 140, 145 from Daicel Ornex Co., Ltd.

[0137] Polymerizable compound (C) can be used alone or in combination of two or more types.

[0138] From the viewpoint of coating film resistance and pattern formation, the polymerizable compound (C) preferably contains one or more selected from the group consisting of lactone-modified polymerizable compounds, polymerizable compounds having acidic groups, and polymerizable compounds having urethane bonds.

[0139] The content of polymerizable compound (C) is preferably 1 to 60% by mass, and more preferably 2 to 50% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0140] [Photopolymerization initiator (D)] The photosensitive colored composition of the present invention contains a photopolymerization initiator (D). This allows the photosensitive composition to be cured by irradiation with active energy rays.

[0141] The photopolymerization initiator (D) is, for example, an acetophenone compound such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; 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-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], or etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole3-yl]-,1-(O-acetyl oxime); Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.

[0142] Commercially available products include acetophenone compounds such as Omnirad907, 369E, and 379EG from IGM Resins; acylphosphine compounds such as Omnirad819 and TPO from IGM Resins; oxime compounds such as IRGACURE OXE-01, 02, 03, and 04 from BASF Japan; N-1919, NCI-730, 831, and 930 from ADEKA; and TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 from Changzhou Strong New Materials Co., Ltd. Examples include Omnirad 1312, 1314, and 1316 from Resins, SPI-02, 03, 04, 05, 06, and 07 from Samyang Corporation, and DFI-020, 306, and EOX-01 from Daito Chemix. Other examples include oxime compounds described in Japanese Patent Publication No. 2007-210991, Japanese Patent Publication No. 2009-179619, Japanese Patent Publication No. 2010-037223, Japanese Patent Publication No. 2010-215575, Japanese Patent Publication No. 2011-020998, International Publication No. 2015 / 036910, International Publication No. 2021 / 175855, etc.

[0143] (Compound (D1) represented by general formula (1)) From the viewpoint of suppressing foreign matter, the photosensitive colored composition of the present invention preferably contains a compound (D1) represented by the following general formula (1) as a photopolymerization initiator (D).

[0144] General formula (1) [ka] (In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent.)

[0145] R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Alkyl groups having 1 to 8 carbon atoms may be linear, branched, cyclic, or combined. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylmethyl groups. Of these, linear alkyl groups having 3 to 8 carbon atoms are preferred from the viewpoint of pattern shape, and linear alkyl groups having 4 to 6 carbon atoms are more preferred.

[0146] R3 represents a hydrogen atom or any monovalent substituent. Examples of monovalent substituents include C1-C20 alkyl groups such as methyl and ethyl groups; C1-C20 alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as F, Cl, Br, and I; C1-C20 acyl groups; C1-C20 alkyl ester groups; C1-C20 alkoxycarbonyl groups; C1-C20 halogenated alkyl groups, C4-C20 aromatic ring groups; amino groups; C1-C20 aminoalkyl groups; hydroxyl groups; nitro groups; cyano groups; benzoyl groups which may have substituents; and tenoyl groups which may have substituents. Examples of substituents that the benzoyl or tenoyl group may have include C1-C10 alkyl groups, C1-C10 alkoxy groups, and C1-C10 alkoxycarbonyl groups. Among these, hydrogen atoms and nitro groups are preferred from the viewpoint of radical generation efficiency, and hydrogen atoms are more preferred.

[0147] Examples of methods for producing compound (D1) represented by general formula (1) include those described in Japanese Patent Publication No. 2019-507108 and Japanese Patent Publication No. 2019-528331.

[0148] The following are specific examples of compounds (D1) represented by general formula (1). However, the present invention is not limited to these examples.

[0149] [ka] [ka]

[0150] Among the compounds of chemical formulas (15) to (18), the compound of chemical formula (15) is preferred from the viewpoint of suppressing foreign matter.

[0151] Compound (D1) represented by general formula (1) can be used alone or in combination of two or more types.

[0152] The content of the photopolymerization initiator (D) is preferably 2 to 50 parts by mass, and more preferably 2 to 30 parts by mass, per 100 parts by mass of the coloring agent (A), from the viewpoint of photocurability and developability.

[0153] [Copper salt (E) of a quinophthalone compound having a sulfo group] From the viewpoint of suppressing a decrease in brightness, the photosensitive coloring composition of the present invention preferably contains a copper salt (E) of a quinophthalone compound having a sulfo group.

[0154] Quinophthalone compounds are compounds having the structure represented by the following chemical formula (19). Specifically, examples include commercially available dyes such as CI Acid Yellow 3 and 5, and commercially available pigments and dyes such as CI Pigment Yellow 138, CI Solvent Yellow 33, 114, and 157, and CI Disperse Yellow 54, 64, and 67.

[0155] Chemical formula (19) [ka]

[0156] Quinophthalone compounds having a sulfo group are compounds obtained by sulfonating a compound having the structure represented by chemical formula (19) using known methods. Examples are given below, but the present invention is not limited to these.

[0157] [ka] [ka]

[0158] The copper salt (E) of a quinophthalone compound having a sulfo group can be obtained by counter-exchanging the -SO3H group of the above-mentioned example compound with a copper salt using a known method.

[0159] Copper salts (E) of quinophthalone compounds having a sulfo group can be used alone or in combination of two or more types.

[0160] From the viewpoint of suppressing a decrease in brightness, the content of the copper salt (E) of the quinophthalone compound having a sulfo group is preferably 1 to 40 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of the coloring agent (A).

[0161] Furthermore, the photosensitive coloring composition of the present invention may contain metal salts other than copper of the copper salt (E) of a quinophthalone compound having a sulfo group. Examples of metals include aluminum, zinc, nickel, and iron.

[0162] [Binder resin (F)] The photosensitive colored composition of the present invention may contain a binder resin (F). This improves the heat resistance, chemical resistance, and other properties of the cured film.

[0163] The binder resin (F) is not particularly limited, and any known resin can be used.

[0164] The binder resin (F) can be classified into non-photosensitive binder resins and photosensitive binder resins, and from the viewpoint of developability, it is preferable that it has alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, phosphate groups, sulfonic acid groups, hydroxyl groups, and phenolic hydroxyl groups, and among these, carboxyl groups are preferred. Furthermore, the binder resin (F) may contain thermosetting groups such as epoxy groups, oxetanyl groups, and isocyanate groups.

[0165] (Non-photosensitive binder resin) Examples of non-photosensitive binder resins include acrylic resins having acidic groups, α-olefin / (anhydride) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydride) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferred.

[0166] (Photosensitive binder resin) The photosensitive binder resin is a binder resin having polymerizable unsaturated groups. The photosensitive binder resin is preferably a resin synthesized by, for example, the method shown in (i) or (ii) below. Curing with active energy rays causes the resin to undergo three-dimensional crosslinking, improving the crosslinking density and thus improving chemical resistance.

[0167] [Method (i)] Method (i) is, for example, to first synthesize polymers of epoxy group-containing monomers and other monomers. Then, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the resulting hydroxyl group to obtain a photosensitive binder resin.

[0168] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methylglycidyl (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.

[0169] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy (Meth)acrylates such as diethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethylene oxide (EO)-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol; (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Styrene, or styrene compounds such as α-methylstyrene; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; Vinyl acetate or vinyl propionate, and other fatty acid vinyl compounds; Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichloro N-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzoimidazolyl)phenyl]maleimide, and 9-maleimidacridine; Examples of phosphate ester group-containing monomers include 2-(meth)acryloyloxyethyl acid phosphate and compounds obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer described later with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate.

[0170] Monocarboxyl group-containing monomers include, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid.

[0171] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Furthermore, if necessary, the remaining anhydride group can be hydrolyzed using tricarboxylic acid anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic anhydride.

[0172] Another method similar to method (i) involves synthesizing polymers of carboxyl group-containing monomers and other monomers. Subsequently, epoxy group-containing monomers are added to some of the carboxyl groups of the polymer to obtain a photosensitive binder resin.

[0173] [Method (ii)] Method (ii) involves synthesizing polymers of, for example, hydroxyl group-containing monomers, monocarboxyl group-containing monomers, and other monomers. Then, the hydroxyl group of the polymer is reacted with the isocyanate group of an isocyanate group-containing monomer.

[0174] Examples of hydroxyl group-containing monomers include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Also included are polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by adding polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred because they are less likely to produce foreign matter in the coating. Glycerol mono(meth)acrylate is also preferred in terms of light sensitivity.

[0175] Examples of isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0176] Monocarboxyl group-containing monomers and other monomers can be those described above.

[0177] The raw materials used in the synthesis of photosensitive binder resins can be used individually or in combination of two or more types.

[0178] The binder resin (F) can be used alone or in combination of two or more types.

[0179] The weight-average molecular weight (Mw) of the binder resin (F) is preferably 4,000 to 40,000, and more preferably 4,000 to 35,000, from the viewpoint of developability. Furthermore, the Mw / Mn value is preferably 10 or less. An appropriate weight-average molecular weight (Mw) improves adhesion to the substrate and developability.

[0180] The acid value of the binder resin (F) is preferably 30 to 200 mg KOH / g, and more preferably 40 to 180 mg KOH / g. An appropriate acid value improves adhesion to the substrate and developability.

[0181] The content of the binder resin (F) is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of the coloring agent (A).

[0182] [Sensitizer (G)] The photosensitive colored composition of the present invention may contain a sensitizer (G).

[0183] The sensitizer (G) is, for example, a polymethine dye such as chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyra Examples include din derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal allene complexes, organoruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acyl oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0184] Among the sensitizers (G), thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are preferred. Specific compounds that are preferred 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, and 3,6-dibenzoyl-N-ethylcarbazole.

[0185] The sensitizer (G) can be used alone or in combination of two or more types.

[0186] The sensitizer (G) content is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator (D). Including an appropriate amount improves photocurability and developability.

[0187] [Thermosetting compound (H)] The photosensitive colored composition of the present invention may contain a thermosetting compound (H). This allows the thermosetting compound (H) to react during the heating process, increasing the crosslinking density and thus improving heat resistance.

[0188] The thermosetting compound (H) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of thermosetting compounds (H) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0189] (Epoxy compound) Epoxy compounds include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnolbornene, tetrahydroindene, divinylbenzene, etc.). Examples include polymers of 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 (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins obtained by glycidylating alcohols, etc.

[0190] Commercially available products include, for example, Epicote 807, 815, 825, 827, 828, 190P, and 191P from Shell Epoxy Oil & Epoxy Corporation, and TECHMORE from Mitsui Chemicals. Examples include VG3101L, EPPN-201, 501H, 502H from Nippon Kayaku Co., Ltd., EOCN-102S, 103S, 104S, 1020 from Japan Epoxy Resin Co., Ltd., Epicote 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 from Daicel Chemical Industries, Ltd., Celoxide 2021, EHPE-3150 from Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 from Nagase ChemteX Corporation, and TEPIC-L, H, S from Nissan Chemical Industries, Ltd.

[0191] The epoxy compound content is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0192] (Oxetane compounds) Oxetane compounds are known compounds that have an oxetane group. Examples of oxetane compounds include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or multifunctional oxetane compounds.

[0193] Examples of monofunctional oxetane compounds include (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0194] Examples of commercially available products include OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

[0195] Examples of bifunctional oxetane compounds include 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 glycos(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl(3-ethyl- Examples include 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, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

[0196] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0197] Examples of oxetane compounds with three or more functionalities 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, and caprolactone-modified dipenta Examples include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0198] The oxetane compound content is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the nonvolatile content of the photosensitive colored composition.

[0199] Thermosetting compounds (H) can be used alone or in combination of two or more types.

[0200] [Hardening agent (hardening accelerator)] The photosensitive coloring composition of the present invention can be used in combination with a curing agent (curing accelerator) to assist in the curing of the thermosetting compound (H). Examples of curing agents include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. Examples of curing agents include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Examples include 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine), S-triazine derivatives (e.g., 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.).

[0201] The hardening agent can be used alone or in combination of two or more types.

[0202] The curing agent content is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermosetting compound (H).

[0203] [Thiol chain transfer agent (I)] The photosensitive colored composition of the present invention may contain a thiol-based chain transfer agent (I). When used in combination with a photopolymerization initiator (D), the thiol-based chain transfer agent (I) generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen during radical polymerization after light irradiation, thereby improving the photosensitivity of the photosensitive colored composition.

[0204] The thiol-based chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), and more preferably a polyfunctional thiol having four or more thiol groups. When the number of functional groups increases, it becomes easier to photocure from the surface to the deepest part of the film.

[0205] Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, 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 tristhiopropionate, pentaerythritol tetrakisthiopropionate, etc. are included.

[0206] The thiol-based chain transfer agent (I) can be used alone or in combination of two or more kinds.

[0207] The content of the thiol-based chain transfer agent (I) is preferably 1 to 10% by mass, and more preferably 2 to 8% by mass with respect to 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, the photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[0208] [Polymerization inhibitor (J)] The photosensitive coloring composition of the present invention can contain a polymerization inhibitor (J).

[0209] Polymerization inhibitor (J) is, for example, alkylcatechol 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-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n- Examples include alkylresorcinol compounds such as butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0210] The polymerization inhibitor (J) content is preferably 0.01 to 0.4% by mass of 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0211] [UV absorber (K)] The photosensitive colored composition of the present invention may contain an ultraviolet absorber (K).

[0212] UV absorbers (K) are organic compounds that have UV absorption function, and examples include benzotriazole organic compounds, triazine organic compounds, benzophenone organic compounds, salicylate ester organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds.

[0213] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, and 2-[2-hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, a mixture of 3-(2H-benzotriazole2-yl)-(1,1-dimethylethyl)-4-hydroxy,C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazole2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl Reaction product of 3-(3-(2H-benzotriazole2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole2-yl)-6-t-butyl Examples include 4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate.

[0214] Examples of commercially available products include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 from BASF Japan; ADEKA LA-29, LA-31RG, LA-32, and LA-36 from ADEKA Corporation; KEMISORB 71, 73, 74, 79, and 279 from Chemipro Chemical Co., Ltd.; and RUVA-93 from Otsuka Chemical Co., Ltd.

[0215] Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the resulting compounds include 2,4-bis"2-hydroxy-4-butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0216] Examples of commercially available products include KEMISORB 102 from Chemipro Chemical Co., Ltd., TINUVIN 400, 405, 460, 477, 479, and 1577ED from BASF Japan, ADEKA LA-46 and LA-F70 from ADEKA Corporation, and CYASORB UV-1164 from Sun Chemical Co., Ltd.

[0217] Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid 3-hydrobenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0218] Examples of commercially available products include KEMISORB 10, 11, 11S, 12, and 111 from Chemipro Chemical Co., Ltd., SEESORB 101 and 107 from Cipro Chemical Co., Ltd., ADEKA Stab 1413 from ADEKA Corporation, and UV-12 from Sun Chemical Co., Ltd.

[0219] Examples of salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0220] The amount of ultraviolet absorber (K) is preferably 5 to 70% by mass of the total mass of photopolymerization initiator (D) and ultraviolet absorber (K).

[0221] [Antioxidant (L)] The photosensitive colored composition of the present invention may contain an antioxidant (L).

[0222] The antioxidant (L) prevents yellowing caused by oxidation of the photopolymerization initiator (D) and thermosetting compound (H) in the photosensitive coloring composition due to the heat process during thermal curing or ITO aneeling. In particular, when the colorant (A) concentration of the photosensitive coloring composition is high, the content of polymerizable compound (C) decreases relatively, so increasing the amount of photopolymerization initiator (D) or adding thermosetting compounds makes the cured film prone to yellowing. Therefore, including an antioxidant prevents yellowing of the cured film due to oxidation during the heating process. The antioxidant (L) is preferably a compound that does not contain halogen atoms.

[0223] Antioxidants (L) include, for example, hindered phenol, hindered amine, phosphorus, sulfur, and hydroxylamine compounds. Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred.

[0224] Hindered phenol antioxidants, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 1,3,5-Tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-Tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-Methylenebis(6-t-butyl-4-ethylphenol), 2,2'-Thiodiethylbis-(3,5-di- t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4, 6-Bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediolbis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2 Examples include 2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethylphenol), 2,2'-methylene-bis-(6-(1-methylcyclohexyl)-p-cresol), and 2,4-dimethyl-6-(1-methylcyclohexyl)-phenol.

[0225] Examples of commercially available products include ADEKA's ADEKA stub AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330; Chemipro's KEMINOX 101, 179, 76, 9425; BASF Japan's IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565; and Sun Chemical's Cyanox CY-1790, CY-2777.

[0226] Hindered amine antioxidants include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidine-4-yl)carbonate, and 1,2,2,6,6-pentamethyl-4-piperidyl. Tamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1- Ester of piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester of decandioate, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3,5-bi (1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonatemethyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,Examples include 6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0227] Commercially available products include, for example, AdekaStab 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 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan Ltd.; and Cyasorb UV-3346, UV-3529, UV-3853 manufactured by Sankyo Chemical Co., Ltd., etc.

[0228] Phosphorus-based antioxidants include, for example, di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra(C12~C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, and diphenyl mono (2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyldiphosphonate, tris(tridecyl) phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, phenyldi(tridecyl) phosphite, diphenylisooctyl phosphite, diphenyltridecyl phosphite, 4,4'-isopropylide Diphenolalkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)benzene, and ethylbis(2,4-di-t-butyl-6-methylphenyl) phosphite.

[0229] Examples of commercially available products include ADEKA's ADEKA Stub PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP; BASF Japan's IRGAFOS168; and Clariant Chemicals' Hostanox P-EPQ.

[0230] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0231] Examples of commercially available products include ADEKA's ADEKA stub AO-412S and AO-503, and KEMINOXPLS from Chemipro Chemical Co., Ltd.

[0232] Antioxidants (L) can be used alone or in combination of two or more types.

[0233] The antioxidant (L) content is preferably 0.5 to 5.0% by mass of 100% by mass of the non-volatile content of the photosensitive coloring composition. An appropriate amount improves transmittance, spectral characteristics, and sensitivity.

[0234] [Leveling agent (M)] The photosensitive colored composition of the present invention may contain a leveling agent (M). This further improves the wettability and drying properties on the substrate during coating.

[0235] Examples of leveling agents (M) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0236] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0237] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from Bic Chemie, and FZ-7002, 211 from Toray Dow Corning. Examples include 0, 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s 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, etc.

[0238] Examples of fluorinated surfactants include surfactants or leveling agents having fluorocarbon chains.

[0239] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 from AGC Seimi Chemical; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, as well as R-40-LM, R-41, RS-72-K, and DS-21 from DIC; FC-4430 and 4432 from Sumitomo 3M; EF-PP31N09, EF-PP33G1, and EF-PP32C1 from Mitsubishi Materials Electronic Chemicals; and Futergent 602A from Neos.

[0240] Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc.

[0241] Commercially available products include, for example, Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, L S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW- L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amit 102, Examples include 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA's Adekapluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Kyoeisha Chemical's (meth)acrylic acid-based (co)polymer Polyflow-No.75, No.90, No.95.

[0242] Cationic surfactants include, for example, alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0243] Examples of commercially available products include Acetamine 24, Cotamin 24P, 60W, and 86P Concentrate, all manufactured by Kao Corporation.

[0244] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

[0245] Examples of commercially available products include Neos's Futergent 100 and 150, and ADEKA's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, and EC-8600.

[0246] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0247] Examples of commercially available products include Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N, manufactured by Kao Corporation.

[0248] Leveling agent (M) can be used alone or in combination of two or more types.

[0249] The leveling agent (M) content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the nonvolatile content of the photosensitive colored composition. Including an appropriate amount further improves the balance between the coatability and adhesion of the photosensitive colored composition.

[0250] [Storage stabilizer (N)] The photosensitive colored composition of the present invention may contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive colored composition over time.

[0251] Storage stabilizers (N) include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organophosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphates.

[0252] The storage stabilizer (N) content is preferably 0.1 to 10 parts by mass per 100 parts by mass of coloring agent (A).

[0253] [Adhesion enhancer (O)] The photosensitive colored composition of the present invention may contain an adhesion enhancer (O). This improves the adhesion between the cured film and the substrate. It also makes it easier to form narrow patterns using photolithography.

[0254] Adhesion enhancer (O) is, for example, a silane coupling agent. Examples of silane coupling agents include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and N-2-(aminoethyl) Silane coupling agents include aminosilanes such as -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatetopropyltriethoxysilane.

[0255] Adhesion enhancers (O) can be used alone or in combination of two or more types.

[0256] The content of the adhesion enhancer (O) is preferably 0.01 to 10 parts by mass, and more preferably 0.05 to 5 parts by mass, per 100 parts by mass of the coloring agent (A).

[0257] [Organic solvent (P)] The photosensitive coloring composition of the present invention may contain an organic solvent (P).

[0258] Organic solvents (P) include, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy- 3-Methylbutylacetate, 3-Methoxybutanol, 3-Methoxybutylacetate, 4-Heptanone, m-Xylene, m-Diethylbenzene, m-Dichlorobenzene, N,N-Dimethylacetamide, N,N-Dimethylformamide, n-Butyl alcohol, n-Butylbenzene, n-Propylacetate, N-Methylpyrrolidone, o-Xylene, o-Chloritolene, o-Diethylbenzene, o-Dichlorobenzene, p-Chloritolene, p-Diethylbenzene, sec-Butylbenzene, tert-Butylbenzene, γ-Butyl Lactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,Examples include dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, and the like. Among these, from the viewpoint of pigment dispersibility and alkali-soluble resin solubility, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0259] From an environmental standpoint, the photosensitive coloring composition of the present invention preferably contains substantially no organic solvents, such as aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.). Substantially no organic solvents means that the concentration is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less in the photosensitive coloring composition.

[0260] Organic solvents (P) can be used alone or in combination of two or more types.

[0261] [Content of specific metallic elements] The photosensitive colored composition of the present invention has a total amount of metals Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive colored composition of 500 ppm by mass or less.

[0262] When the total amount of specific metal elements in a photosensitive colored composition falls within the above range, it exhibits excellent dispersion stability and sensitivity even after storage over time. Furthermore, color filters made using a photosensitive colored composition with a total amount of specific metal elements within the above range exhibit excellent heat resistance, generate less foreign matter even when heated, and suppress brightness reduction due to backlighting.

[0263] The total amount of specific metal elements contained in the photosensitive colored composition is more preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass or less. Furthermore, while there is no particular lower limit to the total amount of specific metal elements, it is preferably 1 ppm by mass or more, and more preferably 5 ppm by mass or more. Within the above range, a photosensitive colored composition can be obtained that suppresses costs, has excellent storage stability, and can form a color filter with minimal generation of foreign matter and reduction in brightness.

[0264] The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less. Furthermore, among the specific metal elements, the content of Li, which has high reactivity with the photopolymerization initiator (D), is preferably 30 ppm by mass or less, and more preferably 15 ppm by mass or less.

[0265] The method for reducing specific metal elements contained in the photosensitive colored composition is not particularly limited, but since specific metal elements are present in large quantities in the colorant (A), it is preferable to remove the specific metal elements from the colorant (A). Furthermore, since contamination also occurs from the equipment used to manufacture the photosensitive colored composition, it is also preferable to suppress contamination from the equipment.

[0266] The method for reducing or removing specific metal elements contained in the coloring agent (A) is not particularly limited, and known methods can be used. For example, as a method to avoid contamination from equipment during the manufacturing process, the method described in Japanese Patent Publication No. 2010-83997, Japanese Patent Publication No. 2018-36521, etc., can be cited. Also, as a method for removing specific metal elements from the coloring agent (A), for example, the method described in Japanese Patent Publication No. Hei 7-198928, Japanese Patent Publication No. Hei 8-333521, Japanese Patent Publication No. 2009-7432, Japanese Patent Publication No. 2010-83997, etc., can be cited. Among these, a method of washing the coloring agent (A) with water that has a low content of specific metal elements, such as ion-exchanged water, is preferred.

[0267] There are no particular restrictions on the method of washing the coloring agent (A), and known methods can be used. For example, the synthesized coloring agent (A) is placed in a container containing deionized water and stirred. After stirring for a certain period of time, the mixture is filtered using a filter press to separate the coloring agent (A) from the deionized water. This process is repeated until the amount of the specific metal element reaches the desired value. It is preferable to perform the washing while heating. After that, the coloring agent (A) is dried with hot air and pulverized.

[0268] The content of specific metal elements can be measured by inductively coupled plasma atomic emission spectroscopy (ICP).

[0269] In the photosensitive colored composition of the present invention, it is preferable to reduce the content of metal elements other than the specified metal elements, from the viewpoint of storage stability, suppression of foreign matter generation, and suppression of brightness reduction. Examples of metals other than the specified metal elements include Mn, Cs, Ti, Co, Si, Pd, etc.

[0270] [Water content] The photosensitive colored composition of the present invention has a water content of 2.0% by mass or less.

[0271] If the water content of the photosensitive coloring composition is within the above range, it exhibits excellent dispersion stability and sensitivity even after storage over time.

[0272] The water content in the photosensitive colored composition is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less. Furthermore, the lower limit of the water content is preferable as much as possible, but there are no particular restrictions. Within the above range, the dispersion stability and sensitivity are excellent even after storage over time.

[0273] There are no particular restrictions on the method for controlling the water content, and known methods can be used. For example, methods include manufacturing the photosensitive colored composition while blowing in dry air, an inert gas, or a mixture thereof, or adding molecular sieves after manufacturing to dehydrate the composition. Among these, the method of manufacturing while blowing in dry air, an inert gas, or a mixture thereof is preferred.

[0274] The water content can be measured by known methods such as the Karl Fischer method.

[0275] The mechanism by which the above-described photosensitive colored composition can solve the problems of the present invention is not clear, but we speculate as follows.

[0276] It is presumed that reducing the amount of specific metal elements and water suppressed the ionization of the specific metal elements, thereby inhibiting their reaction with the photopolymerization initiator during storage over time. Furthermore, it is presumed that the dispersion resin having acidic groups formed salts with the ionized specific metal elements, thereby inhibiting their reaction with the photopolymerization initiator during storage over time.

[0277] [Zirconium compound content] The photosensitive colored composition of the present invention preferably contains a zirconium compound content of 800 ppm by mass or less.

[0278] The zirconium compound is a pulverized dispersion media used in the dispersion process when dispersing the colorant (A). It is presumed that these pulverized particles act as nuclei, causing the generation of foreign matter upon heating. Therefore, it is preferable to reduce the amount of zirconium compound contained in the photosensitive colored composition.

[0279] If the zirconium compound content of the photosensitive colored composition is within the above range, a color filter with less foreign matter generation upon heating can be obtained.

[0280] The zirconium compound content in the photosensitive colored composition is more preferably 700 ppm by mass or less, and particularly preferably 600 ppm by mass or less. The lower limit of the zirconium compound content is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 5 ppm by mass or more. Within the above range, costs can be suppressed, and a color filter with less foreign matter generation during heating can be obtained.

[0281] There are no particular limitations on the method for reducing the zirconium compound content, and known methods can be used. Examples include dispersion methods using a dispersion media-less disperser, methods to suppress wear by reducing the shear during dispersion or shortening the dispersion time, and methods of centrifugal separation after dispersion.

[0282] The zirconium compound content can be measured by inductively coupled plasma atomic emission spectroscopy (ICP).

[0283] [Method for producing a photosensitive colored composition] The photosensitive colored composition of the present invention is produced by adding, for example, a colorant (A), a dispersion resin having an acidic group (B1), and an organic solvent (P), preferably a copper salt of a quinophthalone compound having a sulfo group (E), and dispersing them under a dry, inert gas atmosphere to produce a dispersion. Subsequently, under a dry, inert gas atmosphere, a polymerizable compound (C), a photopolymerization initiator (D), and a binder resin (F) are added to the dispersion and mixed. The timing of adding each material is arbitrary. Furthermore, to avoid contamination with water from the atmosphere, it is preferable to work in a place where humidity is controlled.

[0284] Examples of distributed processing machines include two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, or attritors.

[0285] The average dispersed particle size (secondary particle size) of the pigment in the dispersion is preferably 30 to 200 nm, and more preferably 40 to 200 nm. Having an appropriate particle size makes it easier to obtain a photosensitive colored composition with high dispersion stability.

[0286] The method for measuring the average dispersed particle diameter (secondary particle diameter) is, for example, to use Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power-spectrum method), with particle permeability set to absorption mode, particle shape to non-spherical, and D50 particle diameter as the average diameter. The diluent solvent for measurement is the same organic solvent used for dispersion, and it is preferable to measure immediately after sample preparation of ultrasonically treated samples to obtain results with less variation.

[0287] The photosensitive colored composition is preferably subjected to filtration by means of a sintered filter or membrane filter to remove coarse particles of 5 μm or larger, preferably 1 μm or larger, more preferably 0.5 μm or larger, and any mixed dust. The photosensitive colored composition of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

[0288] <Color Filter> The color filter of the present invention comprises a substrate and filter segments formed from the photosensitive coloring composition of the present invention. The color filter segments preferably have red, green, and blue filter segments by appropriately selecting the type of colorant (A) used. In addition, the color filter may have magenta, cyan, and yellow filter segments instead of or in addition to the above color filter segments. Examples of substrates include transparent substrates and reflective substrates. Transparent substrates include, for example, glass substrates. Reflective substrates include, for example, substrates that use aluminum electrodes or thin metal films as reflective surfaces.

[0289] [How to manufacture color filters] The method for manufacturing a color filter is not particularly limited, and for example, it can be manufactured by performing the steps of: (1) applying a photosensitive colored composition onto a substrate to form a layer of the composition; (2) exposing the layer in a patterned manner through a mask; (3) alkaline developing the unexposed areas to form a patterned cured film; and (4) heat-treating the pattern (post-bake).

[0290] The manufacturing method of color filters will be described in detail below. (Process (1)) Step (1) of forming a layer of composition involves applying the photosensitive colored composition onto a substrate by methods such as rotary coating, roll coating, slit coating, casting coating, or inkjet coating, and drying (pre-baking) it at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, hot plate, etc., if necessary. Examples of the substrate include glass substrates, resin substrates, and silicon substrates. Examples of resin substrates include polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamide-imide substrates, and polyimide substrates. An organic light-emitting layer may be formed on these substrates. For example, an image sensor such as a CCD or CMOS may be formed on the surface of the silicon substrate. In addition, a primer layer may be provided on the substrate as needed to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the substrate surface. The thickness of the layer is preferably 0.05 to 10.0 μm, and more preferably 0.3 to 5.0 μm.

[0291] (Process (2)) In the exposure process, the layer obtained in step (1) is exposed to a specific pattern through a mask using an exposure device such as a stepper. This results in a cured film. Examples of radiation used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). Furthermore, exposure may be performed by continuously irradiating with light, or by repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less) (pulse exposure).

[0292] (Step (3)) The cured film obtained in step (2) is subjected to alkaline development, which causes the unexposed portion of the composition to dissolve in the alkaline aqueous solution, leaving only the cured portion and resulting in a patterned cured film. Examples of developing solutions include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrol, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The developer concentration is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11-13, and more preferably 11.5-12.5. Using a moderate pH suppresses pattern roughness and peeling, and improves the residual film rate after development.

[0293] Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0294] (Step (4)) The heat treatment (post-bake) involves thoroughly hardening the patterned cured film obtained in step (3) by heating. The heating temperature for post-bake is preferably 100 to 300°C. The heating time is preferably 2 minutes to 1 hour.

[0295] <Image display device> The image display device of the present invention is equipped with the color filter of the present invention. The form used in the image display device is not particularly limited, as long as it functions as an image display device. For example, the configuration described in "Next-Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) is one such example. For definitions of image display devices and details of various image display devices, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989).

[0296] <Solid-state image sensor> The solid-state image sensor of the present invention is equipped with the color filter of the present invention. The form used for the solid-state image sensor is not particularly limited, but for example, it may have a substrate on which a plurality of photodiodes constituting the light-receiving area of ​​the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like are provided, a light-shielding film with an opening only for the light-receiving portion of the photodiode is provided on the photodiode and transfer electrodes, a device protective film made of silicon nitride or the like is provided on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a color filter on the device protective film. Furthermore, it may have a configuration in which a light-gathering means (e.g., a microlens, etc.; the same applies hereinafter) is provided on the device protective film and below the color filter (on the side closer to the substrate), or a configuration in which the light-gathering means is provided on the color filter. In addition, the color filter may have a structure in which a hardened film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, it is preferable that the partitions have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used not only in digital cameras and electronic devices with imaging functions (mobile phones, smartphones, etc.), but also in in-vehicle cameras and surveillance cameras. [Examples]

[0297] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" refers to "parts by mass" and "%" refers to "mass percent". In the present invention, nonvolatile content or nonvolatile content concentration refers to the mass residue after standing in an oven at 230°C for 30 minutes.

[0298] Prior to the examples, each measurement method will be described.

[0299] (Average molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with a radioisotope detector. An HLC-8220GPC (Tosoh Corporation) was used, with two separation columns connected in series. Both columns were packed with two TSK-GEL SUPER HZM-N columns. Measurements were performed at an oven temperature of 40°C, using tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. Molecular weights are expressed on a polystyrene basis.

[0300] (Acid value of resin) 0.5 to 1 g of resin solution was mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mg KOH / g). The acid value per unit of non-volatile content of the resin was then calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution.

[0301] (Amine value of resin) The amine value of the resin is calculated by converting the total amine value (mgKOH / g), which was measured according to the ASTM D 2074 method, into a non-volatile content value.

[0302] (Measurement of the content of specific metal elements) The content of Li, Na, K, Mg, Ca, Fe, and Cr in the photosensitive colored composition was measured using an ICP emission spectrometer (ICPE-9800, Shimadzu Corporation).

[0303] (Measuring water content) The water content in the photosensitive colored composition was measured using a Karl Fischer titrator (a volumetric titration type moisture analyzer, model KF-06, manufactured by Mitsubishi Chemical Corporation).

[0304] (Measurement of zirconium compound content) The zirconium content in the photosensitive colored composition was measured using an ICP mass spectrometer (ICPMS-2030, Shimadzu Corporation).

[0305] <Manufacturing of coloring agent (A)> (Micronized coloring agent (A-1)) In a 300 mL flask, 91 parts sulfuryl chloride, 109 parts aluminum chloride, 15 parts sodium chloride, 30 parts zinc phthalocyanine, and 59 parts bromine were charged. The mixture was heated to 130°C over 40 hours, then removed from the flask with water and filtered to obtain a zinc halide phthalocyanine compound with an average of 12.71 halogen atoms per molecule, of which an average of 10.22 bromine atoms and an average of 2.49 chlorine atoms. 100 parts of the zinc halide phthalocyanine compound, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 6 hours. Next, this kneaded mixture was added to 3,000 parts of deionized water, stirred for 1 hour while heating at 70°C, and then filtered (washing step). After repeating this washing step three times, the mixture was dried at 80°C overnight to obtain a finely ground coloring agent (A-1).

[0306] (Micronized coloring agent (A-2)) An aluminum phthalocyanine halide compound having an average of 10.1 bromine atoms was obtained according to the synthesis method of Example 15 in Japanese Patent Publication No. 2016-145349. 100 parts of the aluminum phthalocyanine halide compound, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 6 hours. Next, this kneaded mixture was added to 3,000 parts of deionized water, stirred for 1 hour while heating at 70°C, and then filtered (washing step). After repeating this washing step three times, the mixture was dried at 80°C overnight to obtain a finely ground coloring agent (A-2).

[0307] (Micronized coloring agent (A-3)) A quinophthalone compound represented by the following chemical formula (20) was obtained according to the synthesis method of Example 8 in Japanese Patent Publication No. 2012-226110. 100 parts of a quinophthalone compound represented by chemical formula (20), 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, 3,000 parts of deionized water were added to this mixture, and after stirring for 1 hour while heating to 70°C, it was filtered (washing step). After repeating this washing step three times, it was dried at 80°C overnight to obtain a finely ground coloring agent (A-3). Chemical formula (22) [ka]

[0308] (Micronized coloring agent (A-4)) In a 300 mL flask, 91 parts sulfuryl chloride, 109 parts aluminum chloride, 15 parts sodium chloride, 30 parts zinc phthalocyanine, and 59 parts bromine were charged. The mixture was heated to 130°C over 40 hours, then removed from the flask with water and filtered to obtain a zinc halide phthalocyanine compound with an average of 12.71 halogen atoms per molecule, of which an average of 10.22 bromine atoms and an average of 2.49 chlorine atoms. 100 parts of the zinc halide phthalocyanine compound, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 6 hours. Next, 3,000 parts of tap water were added to this mixture, stirred at room temperature for 1 hour, and then filtered. After that, it was dried at 80°C overnight to obtain a finely ground coloring agent (A-4).

[0309] (Micronized coloring agent (A-5)) A quinophthalone compound represented by chemical formula (20) was obtained according to the synthesis method of Example 8 in Japanese Patent Publication No. 2012-226110. 100 parts of a quinophthalone compound represented by chemical formula (20), 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, 3,000 parts of tap water were added to this mixture, stirred at room temperature for 1 hour, and then filtered. After that, it was dried at 80°C overnight to obtain a finely ground coloring agent (A-5).

[0310] <Manufacturing of Dispersed Resin (B)> (Solution of a dispersion resin (B1-1) containing acidic groups) In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts i-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts PGMAc were charged and purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts 2,2'-azobisisobutyronitrile added to 90 parts propylene glycol monomethyl ether acetate (hereinafter, PGMAc). Non-volatile content measurement confirmed that 95% had reacted. 19 parts pyromellitic anhydride, 50 parts PGMAc, 50 parts cyclohexanone, and 0.4 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. After confirming that more than 98% of the acid anhydride had undergone half-esterification by measuring the acid value, the reaction was terminated. The solution was then diluted by adding PGMAc to achieve a non-volatile content of 30% by measuring the non-volatile content, yielding a dispersion resin (B1-1) solution with an acid value of 70 mgKOH / g and a weight-average molecular weight of 8,500.

[0311] (Solution of a dispersion resin (B1-1-2) containing acidic groups) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after purging with nitrogen gas, the mixture was reacted at 120°C for 5 hours (first step). Acid value measurement confirmed that more than 95% of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step (on a non-volatile content basis), 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added, and the mixture was reacted for 12 hours (second step). Non-volatile content measurement confirmed that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and IR measurement showed 2270 cm⁻¹ based on the isocyanate group. -1 The reaction was carried out until the peak disappeared (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with PGMAc to obtain a dispersion resin (B1-1-2) solution with acidic groups and a non-volatile content of 30%. The acid value of the obtained dispersion resin (B1-1-2) with acidic groups was 68 mgKOH / g, the unsaturated double bond equivalent was 1,593, and the weight-average molecular weight was 13,000.

[0312] (Basic dispersion resin (B2-1) solution) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 30 parts methyl methacrylate, 30 parts n-butyl methacrylate, 20 parts hydroxyethyl methacrylate, and 13.2 parts tetramethylethylenediamine were charged. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts ethyl bromoisobutyrate, 5.6 parts cuprous chloride, and 133 parts PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to start polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate was 98% or higher. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Funcryl FA-711MM) were added to the reaction apparatus as the monomer for the second block (block A). The reaction was continued by stirring while maintaining a temperature of 110°C and a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and its non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or higher, and the reaction solution was cooled to room temperature to stop the polymerization. The solution was diluted by adding PGMAc to achieve a non-volatile content of 30%, obtaining a basic dispersion resin (B2-1) solution with an amine value of 57 mgKOH / g per non-volatile content and a number average molecular weight of 4,500 (Mn).

[0313] (Solution of a basic dispersion resin (B2-2)) 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of the initiator dimethylketene methyltrimethylsilyl acetal were added to a 500 mL round-bottom, four-neck separable flask equipped with a condenser, an additive funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, via the additive funnel, and the flask was thoroughly purged with nitrogen. 0.5 parts by mass of a 1 mol / L acetonitrile solution of the catalyst tetrabutylammonium m-chlorobenzoate was injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate, 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate, all solubility-dependent blocking monomers, were added dropwise over 60 minutes using the additive funnel. The reaction flask was cooled in an ice bath to maintain the temperature below 40°C. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, a monomer for blocking colorant adsorption, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, and purified by filtration and vacuum drying. Next, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of PGMAc in a 100 mL round-bottom flask, and 1.1 parts by mass of phenylphosphinic acid (0.5 molar equivalent relative to dimethylaminopropyl methacrylamide), which is a salt-forming component, was added. The mixture was stirred at a reaction temperature of 30°C for 20 hours, and PGMAc was added to adjust the solution to obtain a dispersion resin (B2-2) solution with a basic pH and a non-volatile content of 30%.

[0314] <Production of polymerizable compound (C)> (Polymerizable compound (C-4) containing urethane bonds) A five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts dipentaerythritol pentaacrylate, 100 parts PGMAc, and 0.5 parts N,N-dimethylbenzylamine. The temperature was raised to 70°C, and a mixture of 66 parts toluene diisocyanate and 66 parts PGMAc was added dropwise from the dropping tube over 2 hours. After addition, the mixture was reacted at a temperature of 50-70°C for 8 hours, and the reaction was measured at 2180 cm⁻¹ by infrared (IR). -1The disappearance of the absorption of the isocyanate was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted at a temperature of 50-60°C for 6 hours. The non-volatile content was adjusted to 50% by mass to obtain a polymerizable compound (C-4) solution having a urethane bond.

[0315] <Preparation of metal salt (E) of quinophthalone compounds containing a sulfo group> (Copper salt of a quinophthalone compound having a sulfo group (E-1)) Thirty parts of CI Pigment Yellow 138 (BASF Japan's "Pariotol Yellow K0960-HD"), a quinophthalone compound, were dissolved in 300 parts of 101% sulfuric acid, and the mixture was stirred at 70°C for 8 hours to carry out the sulfonation reaction. The endpoint of the reaction was determined by measuring the spectral spectrum of the sulfuric acid solution, and the point at which no change in the spectrum was observed was reached. Next, this reaction solution was poured into 3,000 parts of ice water, the precipitate was filtered off, washed with water, and dried at 80°C to obtain a quinophthalone compound containing a sulfo group. Next, 10 g of a quinophthalone compound having a sulfo group was added to 500 parts of water and stirred at 25°C for 2 hours to redisperse it. Then, 4.8 parts of copper(II) sulfate pentahydrate were gradually added to this solution and reacted at 60°C for 2 hours. The reaction product was filtered off, added to deionized water, stirred at 70°C for 1 hour while heating, and then filtered (washing step). After repeating this washing step three times, the mixture was dried at 80°C to obtain the copper salt (E-1) of the quinophthalone compound having a sulfo group represented by the following chemical formula (21). Chemical formula (21) [ka]

[0316] <Manufacturing of binder resin (F)> (Binder resin (F-1) solution) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 100 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 37.2 parts n-butyl methacrylate, 12.9 parts 2-hydroxyethyl methacrylate, 12.0 parts methacrylic acid, 20.7 parts paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 1.1 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the addition was complete, the reaction was continued for another 3 hours to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. PGMAc was then added to the previously synthesized resin solution to prepare a binder resin (F-1) solution so that the non-volatile content was 20% by mass. The weight-average molecular weight (Mw) was 26,000.

[0317] (Binder resin (F-2) solution) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 100 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 20 parts methacrylic acid, 20 parts paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 45 parts methyl methacrylate, 8.5 parts 2-hydroxyethyl methacrylate, and 1.33 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition was complete, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the entire amount of the obtained copolymer solution was stirred while injecting dry air for 1 hour after stopping the nitrogen gas supply, and then cooled to room temperature. After that, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Kalenz MOI, Showa Denko Co., Ltd.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70°C for 3 hours. After the dropwise addition was complete, the reaction was continued for another hour to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Cyclohexanone was then added to the previously synthesized resin solution so that the non-volatile content was 20% by mass to prepare a binder resin (F-2) solution. The weight-average molecular weight (Mw) was 18,000.

[0318] (Binder resin (F-3) solution) 200 parts of cyclohexanone were placed in a separable four-necked flask equipped with a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirrer. The temperature was raised to 80°C, and the flask was purged with nitrogen. Then, a mixture of 18 parts of paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition, the mixture was reacted at 100°C for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 20 parts of cyclohexanone was added. The reaction was then continued at 100°C for another hour. Next, the container was purged with air, and 9.3 parts of acrylic acid (100% of the glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the container. The reaction was continued at 120°C for 6 hours until the non-volatile acid value reached 0.5, at which point the reaction was terminated. Subsequently, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and the mixture was reacted at 120°C for 3.5 hours to obtain a resin solution. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. PGMAc was then added to the previously synthesized resin solution to achieve a non-volatile content of 20% by mass to prepare a binder resin (F-3) solution. The weight-average molecular weight (Mw) was 19,000.

[0319] (Binder resin (F-4) solution) A separable flask with a condenser was prepared as the reaction vessel, and a monomer dropping vessel was prepared by thoroughly stirring and mixing 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butyl peroxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), and 40 parts of PGMAc. A chain transfer agent dropping vessel was prepared by thoroughly stirring and mixing 8 parts of n-dodecanethiol and 32 parts of PGMAc. 200 parts of PGMAc were placed in the reaction vessel, and after purging with nitrogen, the vessel was heated in an oil bath while stirring to raise the temperature to 90°C. Once the temperature of the reaction vessel stabilized at 90°C, dropwise addition was started from the monomer dropping vessel and the chain transfer agent dropping vessel. Dropwise addition was carried out over 135 minutes each, while maintaining the temperature at 90°C. 60 minutes after the completion of dropwise addition, the temperature was raised to 110°C. After maintaining 110°C for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of an oxygen / nitrogen = 5 / 95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were placed in the reaction vessel, and the reaction was carried out at 110°C for 12 hours. Subsequently, 150 parts of PGMAc were added and the mixture was cooled to room temperature. Approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. PGMAc was then added to the previously synthesized resin solution to obtain a binder resin (F-4) solution, with the non-volatile content reaching 20% ​​by mass. The weight-average molecular weight of the resin was 18,000, and the acid value per non-volatile content was 2 mgKOH / g.

[0320] (Binder resin (F-5) solution) In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 150 parts of PGMAc were introduced, and the atmosphere inside the flask was changed from air to nitrogen. After raising the temperature to 100°C, a solution consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 164 parts of PGMAc, to which 3.6 parts of azobisisobutyronitrile was added, was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was then stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 43.0 parts [0.5 mol, (100 mol%) of methacrylic acid (relative to the glycidyl groups of the glycidyl methacrylate used in this reaction)], 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110°C for 6 hours until the non-volatile acid value reached 1 mg KOH / g, at which point the reaction was terminated. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the mixture was reacted at 120°C for 3.5 hours to obtain a resin solution with an acid value of 80 mg KOH / g. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. PGMAc was then added to the previously synthesized resin solution to a non-volatile content of 20% by mass to prepare a binder resin (F-5) solution. The weight-average molecular weight (Mw) was 12,000.

[0321] (Binder resin (F-6) solution) In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 150 parts of PGMAc were introduced, and the atmosphere inside the flask was changed from air to nitrogen. After raising the temperature to 100°C, a solution consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 136 parts of PGMAc, to which 3.6 parts of azobisisobutyronitrile was added, was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was then stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 35.5 parts [0.25 mol, (50 mol% relative to the carboxyl groups of the methacrylic acid used in this reaction)] of glycidyl methacrylate, 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110°C for 6 hours to obtain a resin solution with an acid value of 79 mg KOH / g. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. PGMAc was then added to the previously synthesized resin solution to prepare a binder resin (F-6) solution with a non-volatile content of 20% by mass. The weight-average molecular weight (Mw) was 13,000.

[0322] <Dispersion manufacturing> (Dispersion 1) After stirring and mixing the following raw materials until uniform, the mixture was dispersed for 3 hours using an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") with a 0.5 mm diameter zirconia bead, and then filtered through a 1.0 μm pore size filter to prepare dispersion 1. The organic solvent (P-1) is PGMAc. Micronized coloring agent (A1-1): 10.0 parts Solution of acidic dispersion resin (B1-1-2): 10.0 parts Basic dispersion resin (B2-1) solution: 7.0 parts Binder resin (F-1) solution: 10.0 parts Organic solvent (P-1): 63.0 parts

[0323] (Dispersion 2~10) Dispersions 2-10 were prepared in the same manner as dispersion 1, except that the raw materials and quantities listed in Table 1 were changed.

[0324] [Table 1]

[0325] <Manufacturing of photosensitive colored compositions> [Example 1] (Photosensitive coloring composition 1) The following raw materials were added to a container while blowing dry nitrogen gas into it, and the mixture was stirred for 2 hours. After that, the mixture was filtered through a 1.0 μm pore size filter to obtain photosensitive colored composition 1. Dispersion 1: 30.0 parts Dispersion 3: 12.5 parts Dispersion 4: 12.5 parts Polymerizable compound (C): 5.0 parts Compound represented by general formula (1) (D1-1): 0.7 parts Photopolymerization initiator (D2-1): 0.3 parts Binder resin (F): 8.0 parts Sensitizer (G): 0.2 parts Thermosetting compound (H): 1.0 part Thiol chain transfer agent (I): 0.1 part Polymerization inhibitor (J): 0.1 part UV absorber (K): 0.1 part Antioxidant (L): 0.1 part Leveling agent (M): 1.5 parts Storage stabilizer (N): 0.1 part Organic solvent (P): 27.8 parts

[0326] The obtained photosensitive colored composition 1 was subjected to centrifugal separation using a centrifuge (himacCP-NX manufactured by Hitachi Koki Co., Ltd.).

[0327] The content of specific metal elements, water, and zirconium compounds in the obtained photosensitive colored composition 1 was measured.

[0328] [Examples 2-6, Comparative Examples 1 and 2] (Photosensitive colored compositions 2-6, 8 and 9) Photosensitive colored compositions 2-6, 8, and 9 were prepared in the same manner as in Example 1, except that the photosensitive colored composition 1 of Example 1 was changed to the raw materials and quantities listed in Table 2. The content of specific metal elements, water, and zirconium compounds was then measured.

[0329] [Example 7, Comparative Example 3] (Photosensitive colored compositions 7 and 10) The photosensitive colored composition 7 of Example 7 was prepared in the same manner as the photosensitive colored composition 1 of Example 1, except that centrifugation was not performed. Similarly, the photosensitive colored composition 10 of Comparative Example 3 was prepared in the same manner as the photosensitive colored composition 1 of Example 1, except that dry air was not blown into the mixture during preparation.

[0330] [Table 2]

[0331] The ingredients listed in Table 2 are as follows:

[0332] [Polymerizable compound (C)] (C-1): Arronix M-521 (manufactured by Toagosei Co., Ltd., an acrylate with an acidic group) (C-2): KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd., lactone-modified acrylate) (C-3): KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) (C-4): Solution of polymerizable compound (C-4) having the above-mentioned urethane bond. Equal amounts of (C-1) to (C-4) were mixed to obtain polymerizable compound (C).

[0333] [Photopolymerization initiator (D)] (Compound (D1) represented by general formula (1)) (D1-1): Compound of the above chemical formula (15)

[0334] (Compounds other than compound (D1) represented by general formula (1) (D2)) (D2-1):TRONLY TR-PBG-354 (manufactured by Changzhou Strong New Materials Co., Ltd.) (D2-2): Omnirad 369 (manufactured by IGM Resins)

[0335] [Binder resin (F) solution] Equal amounts of binder resins (F-1) to (F-6) were mixed to form binder resin (F) solution.

[0336] [Sensitizer (G)] (G-1): Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (G-2):CHEMARK DEABP (manufactured by Chemark Chemical) As described above, (G-1) and (G-2) were mixed in equal amounts to form the sensitizer (G).

[0337] [Thermosetting compound (H)] (H-1): EHPE-3150 (manufactured by Daicel Corporation) (H-2): Denacol EX611 (manufactured by Nagase ChemteX Corporation) (H-3): Triglycidyl isocyanurate Equal amounts of (H-1) to (H-3) were mixed to obtain thermosetting compound (H).

[0338] [Thiol chain transfer agent (I)] (I-1): Trimethylol-ethantris(3-mercaptobutyrate) (I-2): Trimethylolpropantris (3-mercaptobutyrate) (I-3): Pentaerythritol tetrakis(3-mercaptopropionate) (I-4): Trimethylolpropantris (3-mercaptopropionate) (I-5): Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate The above (I-1) to (I-5) were mixed in equal amounts to form thiol chain transfer agent (I).

[0339] [Polymerization inhibitor (J)] (J-1): 4-methylcatechol (J-2): Methylhydroquinone (J-3): t-butylhydroquinone The above (J-1) to (J-3) were mixed in equal amounts to form polymerization inhibitor (J).

[0340] [UV absorber (K)] (K-1): TINUVIN400 (manufactured by BASF Japan) (K-2): TINUVIN900 (manufactured by BASF Japan) As described above, (K-1) and (K-2) were mixed in equal amounts to form the ultraviolet absorber (K).

[0341] [Antioxidant (L)] (L-1): Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (L-2): 3,3'-Dioctadecyl Thiodipropanoate (L-3): Tris[2,4-di-(t)-butylphenyl]phosphine (L-4): Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (L-5): p-octylphenyl salicylate The above (L-1) to (L-5) were mixed in equal amounts to form antioxidant (L).

[0342] [Leveling agent (M)] (M-1): BYK-330 (manufactured by Big Chemie Co.) (M-2): Megafuck F-554 (manufactured by DIC Corporation) As described above, (M-1) and (M-2) were mixed in 1 part each and dissolved in 98 parts PGMAc to form a mixed solution which was used as the leveling agent (M).

[0343] [Storage stabilizer (N)] (N-1): 2,6-bis(1,1-dimethylethyl)-4-methylphenol (N-2): Triphenylphosphine As described above, (N-1) and (N-2) were mixed in equal amounts to form the storage stabilizer (N).

[0344] [Organic solvent (P)] (P-1): Propylene glycol monomethyl ether acetate 30 parts (P-2): Cyclohexanone 30 parts (P-3): 10 parts of 3-ethoxypropionate ethyl ethoxypropionate (P-4): Propylene glycol monomethyl ether 10 parts (P-5): Cyclohexanol acetate 10 parts (P-6): Dipropylene glycol methyl ether acetate 10 parts The above-mentioned parts by mass of (P-1) to (P-6) were mixed to obtain the organic solvent (P).

[0345] <Evaluation of photosensitive colored compositions> The following evaluations were performed on the obtained photosensitive colored compositions 1 to 10. The evaluation results are shown in Table 3.

[0346] [Storage stability evaluation: Viscosity change rate] The obtained photosensitive colored compositions were placed in sealed containers and stored at 40°C for one week. The rate of change in viscosity before and after storage was calculated and evaluated using the following formula. Viscosity was measured using an E-type viscometer (ELD-type viscometer manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. A viscosity of 2 or higher is considered practical. [Percentage change in viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| × 100 3: Those with a change rate of less than 5% 2: Those with a change rate of 5% or more but less than 10% 1: Those with a change rate of 10% or more

[0347] [Foreign object detection] The obtained photosensitive colored composition was applied to a glass substrate using a spin coater so that the chromaticity value of the coating after heat treatment was y=0.60 under a C light source. Next, it was dried at 70°C for 20 minutes, and then irradiated at 30 mW / cm using a predetermined mask and an ultra-high pressure mercury lamp. 2 50 mJ / cm² 2 After exposure, the image was spray-developed with a sodium carbonate aqueous solution at 23°C, washed with deionized water, and air-dried to form pattern pixels. Subsequently, the material was heat-treated in an oven at 230°C for 40 minutes, and the number of foreign objects on the glass substrate between pattern pixels was measured. For evaluation, surface observation was performed using a metallurgical microscope "BX60" (manufactured by Olympus Systems). The magnification was set to 500x, and the number of foreign objects observable in any five fields of view using transmission was calculated cumulatively. A count of 3 or higher is considered practical. 5: The number of foreign objects is less than 5. 4: Number of foreign objects is 5 or more but less than 10. 3: Number of foreign objects is 10 or more but less than 20. 2: Number of foreign objects is 20 or more but less than 50. 1: Number of foreign objects is 50 or more

[0348] [Brightness evaluation] The obtained photosensitive colored composition was applied to a glass substrate using a spin coater so that the chromaticity value of the coating film after heat treatment was y=0.60 under a C light source, and then dried at 70°C for 20 minutes. Next, an illuminance of 30 mW / cm² was applied using an ultra-high pressure mercury lamp. 2 50 mJ / cm² 2 After exposure, the substrate was spray-developed with a sodium carbonate aqueous solution at 23°C, washed with deionized water, air-dried, and then heat-treated in an oven at 230°C for 40 minutes to form a colored composition layer on the glass substrate. Next, an overcoat agent was applied to the colored composition layer using a spin coater, and the organic solvent was removed using a vacuum dryer. After that, it was baked on a hot plate at 90°C for 2 minutes, followed by heat treatment at 230°C for 60 minutes to obtain a substrate for brightness evaluation. The initial brightness of the obtained brightness evaluation substrate in the XYZ color system was measured using an LVmicroZ (LambdaVision). Subsequently, a 470W / m² test was performed. 2After irradiating with ultraviolet light for 200 hours using a xenon lamp, the brightness was measured again. The rate of change in brightness was calculated using the following formula. A value of 3 or higher is considered practical. Brightness change rate = |Brightness after 200 hours - Initial brightness| / Initial brightness × 100 5: Less than 3% 4: 3% or more, less than 5% 3: 5% or more, less than 10% 2: 10% or more, less than 15% 1: 15% or more

[0349] [Table 3]

Claims

1. The material comprises a colorant (A), a dispersion resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). A photosensitive coloring composition, The dispersion resin (B) comprises a dispersion resin (B1) having an acidic group. The dispersion resin (B1) having an acidic group comprises a dispersion resin (B1-1) which includes a polyester portion having a carboxyl group obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group of tetracarboxylic dianhydrides and tricarboxylic anhydrides with a hydroxyl group in a hydroxyl group-containing compound, and a vinyl polymer portion obtained by radical polymerization of monomers. The photopolymerization initiator (D) comprises a compound (D1) represented by the following general formula (1), A photosensitive coloring composition wherein the total amount of metals Li, Na, K, Mg, Ca, Fe, and Cr contained in the photosensitive coloring composition is 500 ppm by mass or less, and the water content is 2.0% by mass or less. General formula (1) 【Chemistry 1】 (In general formula (1), R １ , R ２ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ３ (This represents a hydrogen atom or a monovalent substituent.)

2. A photosensitive coloring composition comprising a colorant (A), a dispersion resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and a copper salt (E) of a quinophthalone compound having a sulfo group, The dispersion resin (B) comprises a dispersion resin (B1) having an acidic group. The photopolymerization initiator (D) comprises a compound (D1) represented by the following general formula (1), A photosensitive coloring composition wherein the total amount of metals Li, Na, K, Mg, Ca, Fe, and Cr contained in the photosensitive coloring composition is 500 ppm by mass or less, and the water content is 2.0% by mass or less. General formula (1) 【Chemistry 2】 (In general formula (1), R １ , R ２ Each of these independently comprises a hydrogen atom or a carbon atom with 1 to 8 carbon atoms. Represents an alkyl group. ３ (This represents a hydrogen atom or a monovalent substituent.)

3. Furthermore, the zirconium compound content in the photosensitive coloring composition is 800 p by mass. The photosensitive colored composition according to claim 1 or 2, wherein the particle size is less than or equal to pm.

4. Furthermore, the photosensitive coloring composition according to any one of claims 1 to 3, wherein the dispersion resin (B) comprises a dispersion resin (B2) having a basic group.

5. A color filter comprising a substrate and a filter segment formed using a photosensitive colored composition according to any one of claims 1 to 4.

6. A liquid crystal display device comprising the color filter described in claim 5.

7. A solid-state image sensor comprising the color filter described in claim 5.

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