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

Abstract

To provide a photosensitive coloring composition which has little generation of wrinkles on a pattern surface, suppresses water stains after development, and has excellent pattern formation property (adhesion, shape, and residual film ratio).SOLUTION: A photosensitive coloring composition contains a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), in which the polymerizable compound (C) contains acid group-containing aromatic urethane (meth)acrylate (C1) and lactone-modified (meth)acrylate (C2).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive colored composition, a color filter using the same, an image display device, and a solid-state image sensor. [Background technology]

[0002] A color filter is formed by arranging two or more fine strip-shaped filter segments of different hues parallel to each other (in a stripe pattern) or intersecting each other on a transparent substrate such as a glass substrate, or by arranging two or more fine filter segments of different hues sequentially in both the vertical and horizontal directions. The filter segments have small dimensions ranging from a few microns to several hundred microns and are arranged neatly in a predetermined arrangement for each hue.

[0003] Currently, the manufacturing method for color filters involves the steps of: applying a photosensitive colored composition to a transparent substrate such as glass and removing the solvent from the coating by drying; irradiating and curing the coating through a photomask having a desired pattern shape (hereinafter referred to as exposure); then washing and removing the unexposed parts of the coating (hereinafter referred to as development); and then, if necessary, performing a heat treatment (hereinafter referred to as post-bake) to sufficiently harden the cured film to obtain the first color filter segment pattern. By performing the same operation, filter segment patterns of other colors are formed, and the color filter is completed.

[0004] The above development process uses an alkaline developer to wash and remove unexposed areas. However, this process had the problem of causing defects in the pattern shape, such as chipping or peeling of the exposed areas. In addition, when the coating film was exposed to the alkaline developer, a phenomenon called water staining occurred, which affected the coating film. Therefore, there is a need for a photosensitive coloring composition that does not cause defects in the pattern shape or water staining during the development process. Furthermore, there was also the problem that the film thickness of the coating film changed (hereinafter referred to as the residual film rate) due to the elution or vaporization of unreacted substances during the development and post-bake processes.

[0005] Furthermore, in recent years, the miniaturization and increased pixel count of image display devices have led to a trend of smaller area per pixel, prompting consideration of increasing the concentration of colorants in the color filter composition and increasing the film thickness. However, increasing the concentration of colorants or increasing the film thickness has resulted in the problem of wrinkles forming on the film surface during curing.

[0006] As an effort to improve water stains, Patent Document 1 discloses a resist composition containing a fluorine-based surfactant of a specific structure. Furthermore, as an effort to improve pattern defects during development, Patent Document 2 discloses a colored composition containing a polymerizable compound having an alkylene oxide structure. Furthermore, as an effort to improve pattern formation when containing high concentrations of colorants, Patent Document 3 discloses a colored photosensitive resin composition containing a polyfunctional thiol compound and an acetophenone compound. Furthermore, as an effort to improve wrinkles on the surface of the film, Patent Document 4 discloses a colored resin composition containing a photopolymerizable monomer having a double bond equivalent of 400 g / mol or less and having a bisphenol skeleton. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2016-102212 [Patent Document 2] Japanese Patent Publication No. 2014-142582 [Patent Document 3] Japanese Patent Publication No. 2004-83857 [Patent Document 4] Japanese Patent Publication No. 2019-183053 [Overview of the Initiative] [Problems that the invention aims to solve]

[0008] However, none of the compositions described in Patent Documents 1 to 4 satisfied all the requirements regarding water stain resistance, adhesion, and surface wrinkles. Furthermore, the residual film rate was not considered and was therefore unsatisfactory.

[0009] The present invention aims to provide a photosensitive coloring composition that exhibits minimal wrinkle formation on the pattern surface, suppresses water staining after development, and has excellent pattern-forming properties (adhesion, shape, and residual film rate). [Means for solving the problem]

[0010] The present invention relates to a photosensitive colored composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The present invention relates to a photosensitive coloring composition in which the polymerizable compound (C) comprises an acid group-containing aromatic urethane (meth)acrylate (C1) and a lactone-modified (meth)acrylate (C2). Regarding.

[0011] Furthermore, the present invention relates to the above-mentioned photosensitive coloring composition, wherein the total content of the acid group-containing aromatic urethane (meth)acrylate (C1) and the lactone-modified (meth)acrylate (C2) is 20% by mass or more of the polymerizable compound (C) by mass.

[0012] Furthermore, the present invention relates to the above-mentioned photosensitive coloring composition, wherein the polymerizable compound (C) further comprises at least one selected from the group consisting of aliphatic urethane (meth)acrylate (C3) and alicyclic urethane (meth)acrylate (C4).

[0013] Furthermore, the present invention relates to the above-mentioned photosensitive coloring composition, wherein the mass ratio of the acid group-containing aromatic urethane (meth)acrylate (C1) to the total amount of the aliphatic urethane (meth)acrylate (C3) and the alicyclic urethane (meth)acrylate (C4) is 90:10 to 50:50.

[0014] In addition, the present invention relates to the photosensitive coloring composition in which the photopolymerization initiator (D) contains an oxime-based compound (D1).

[0015] In addition, the present invention relates to the photosensitive coloring composition in which the oxime-based compound (D1) contains an oxime-based compound (D1-2) having two oxime groups in one molecule.

[0016] In addition, the present invention relates to the photosensitive coloring composition further containing a sensitizer (E).

[0017] In addition, the present invention relates to a color filter having a substrate and a filter segment formed using the above photosensitive coloring composition.

[0018] In addition, the present invention relates to an image display device having the above color filter.

[0019] In addition, the present invention relates to a solid-state imaging device having the above color filter.

Effects of the Invention

[0020] According to the present invention described above, it is possible to provide a photosensitive coloring composition with less generation of wrinkles on the surface of the pattern film, suppression of water stains after development, and excellent pattern forming properties (adhesion, shape, residual film ratio). Further, the present invention can provide a color filter, an image display device, and a solid-state imaging device.

Modes for Carrying Out the Invention

[0021] Hereinafter, modes for carrying out the photosensitive coloring composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be implemented with modifications within the range capable of solving the problems.

[0022] 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 identified, the value is calculated 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.

[0023] <Photosensitive coloring composition> The present invention relates to a photosensitive colored composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The polymerizable compound (C) is a photosensitive coloring composition comprising an acid group-containing aromatic urethane (meth)acrylate (C1) and a lactone-modified (meth)acrylate (C2).

[0024] [Coloring agent (A)] The photosensitive colored composition of the present invention contains a colorant (A).

[0025] The coloring agent (A) is not particularly limited and may be either a pigment or a dye, but since color filters require lightfastness, heat resistance, and solvent resistance, a pigment is preferred.

[0026] (Pigment) The pigments are not particularly limited; for example, compounds classified as pigments in the color index can be used.

[0027] The red pigments that can be used in this invention include, specifically, 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 described in JP 2014-134712, JP 6368844, JP 260, JP 262, JP 263, JP 264, JP 265, JP 266, JP 267, JP 268, JP 269, JP 270, JP 271, JP 272, JP 273, JP 274, JP 275, JP 276, JP 277, JP 278, JP 279, JP 280, JP 281, JP 282, JP 283, JP 284, JP 285, JP 286, JP 287, JP 291, JP 295, JP 296, JP 2014-134712, JP 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.

[0028] Examples of orange pigments that can be used in this invention include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0029] The yellow pigments that can be used in this invention are specifically 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, 11 Examples include pigments described in 9, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and Japanese Patent Publication No. 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.

[0030] Specific examples of green pigments that can be used in the present invention 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.

[0031] The blue pigments that can be used in the present invention include, specifically, 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, 79, etc. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

[0032] The purple pigments that can be used in the present invention include, specifically, 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.

[0033] Specific examples of black pigments that can be used in this invention include CI Pigment Black 1, 6, 7, 12, 20, 31, and the like.

[0034] The photosensitive colored composition of the present invention may also use inorganic pigments as the colorant (A). Examples 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.

[0035] (dye) The dyes are not particularly limited and include, for example, acid dyes, direct dyes, basic dyes, salt-making dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Derivatives of these dyes, or in the form of lake pigments obtained by lake-forming dyes, are also acceptable.

[0036] Furthermore, in the case of acidic dyes having acidic groups such as sulfonic acid or carboxylic acid, or in the form of direct dyes, it is preferable to use inorganic salts of the acidic dye, or salt compounds formed by combining the acidic dye with nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds, or to use them as salt compounds by chlorinating them using resin components having these functional groups, or to use them as sulfonamide compounds by sulfonamide formation, as this results in a colored composition with excellent durability. Furthermore, salt-forming compounds of acid dyes and compounds containing an onium base are also preferred due to their excellent durability, and more preferably, the compound containing the onium base is a resin having a cationic group in its side chain.

[0037] In the case of basic dyes, they can be used after being chlorinated using organic acids, perchloric acid, or their metal salts. Among these, salt compounds of basic dyes are preferred because they have excellent resistance and compatibility with pigments. Furthermore, it is even more preferable to use salt compounds obtained by saturating a basic dye with an organic sulfonic acid, organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye, which act as a counter ion.

[0038] Furthermore, if the pigment skeleton has polymerizable unsaturated groups, it can be used to produce a dye with excellent resistance, which is preferable.

[0039] Examples of dye chemical structures include 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.), azine dyes, polymer dyes, etc. Examples of dye structures derived from dyes selected from tin-based dyes (oxonol-based dyes, merocyanine-based dyes, allylidene-based dyes, styryl-based dyes, cyanine-based dyes, squarylium-based dyes, croconium-based dyes, etc.), quinophthalone-based dyes, phthalocyanine-based dyes, subphthalocyanine-based dyes, perinone-based dyes, indigo-based dyes, thioindigo-based dyes, quinoline-based dyes, nitro-based dyes, nitroso-based dyes, rhodamine-based dyes, and metal complex dyes thereof can be cited, but are not limited to these.

[0040] Among these pigment structures, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, pigment structures derived from pigments selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and pigment structures derived from pigments selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes are more preferred. Specific pigment compounds that can form pigment structures are described in "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), and "Pigment Handbook" (edited by Okawara et al.; Kodansha, 1986), among others.

[0041] The coloring agent (A) can be used alone or in combination of two or more types.

[0042] The content of the coloring agent (A) is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0043] (Pigment refinement) It is preferable to use the pigment after it has been finely milled. The milling method is not particularly limited, and for example, wet milling, dry milling, or dissolution milling can all be used. Among these, salt milling by the kneader method, which is a type of wet milling, is preferred. The average primary particle size of the finely milled pigment, as determined by TEM (transmission electron microscopy), is preferably 5 to 90 nm. However, from the viewpoint of dispersibility and contrast ratio, an average primary particle size of 10 to 70 nm is more preferable.

[0044] Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, etc., and then washed with water to remove the water-soluble inorganic salt and water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain pigments with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0045] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from a cost standpoint. The amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of pigment, considering both processing efficiency and production efficiency.

[0046] The water-soluble organic solvent serves to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is prone to evaporation, a high-boiling-point solvent with a boiling point of 120°C or higher is preferred from a safety standpoint. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, and more preferably 50 to 500 parts by mass, per 100 parts by mass of pigment.

[0047] 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.

[0048] [Alkali-soluble resin (B)] The photosensitive composition of the present invention contains an alkali-soluble resin (B). This improves the heat resistance, chemical resistance, and other properties of the cured film.

[0049] The alkali-soluble resin (B) is not particularly limited, and any known resin can be used.

[0050] Alkali-soluble resins (B) can be classified into non-photosensitive alkali-soluble resins and photosensitive alkali-soluble resins. From the viewpoint of developability, alkali-soluble resins (B) preferably have 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 alkali-soluble resin (B) may contain thermosetting groups such as epoxy groups or oxetanyl groups.

[0051] (Non-photosensitive alkali-soluble resin) Examples of non-photosensitive alkali-soluble 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.

[0052] (Photosensitive alkali-soluble resin) Photosensitive alkali-soluble resins are alkali-soluble resins having polymerizable unsaturated groups. Preferably, the photosensitive alkali-soluble resin is synthesized by, for example, the method shown in (i) or (ii) below. Curing with active energy rays causes three-dimensional crosslinking of the resin, improving the crosslink density and thus improving chemical resistance.

[0053] [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 alkali-soluble resin.

[0054] 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.

[0055] 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. These can be used alone or in combination of two or more.

[0056] 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, and can be used alone or in combination of two or more.

[0057] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride, which can be used individually or in combination of two or more. Furthermore, if necessary, the remaining anhydride group can be hydrolyzed using tricarboxylic acid dianhydrides such as trimellitic anhydride or tetracarboxylic acid dianhydrides such as pyromellitic anhydride.

[0058] 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 alkali-soluble resin.

[0059] [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.

[0060] 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. These can be used individually or in combination of two or more. 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.

[0061] Examples of isocyanate group-containing monomers include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate, which can be used alone or in combination of two or more.

[0062] Monocarboxyl group-containing monomers and other monomers can be those described above.

[0063] Alkali-soluble resin (B) can be synthesized using the above-mentioned monomers individually or in combination of two or more types.

[0064] The weight-average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 300,000, and particularly preferably 4,000 to 20,000, from the viewpoint of developability. Furthermore, the ratio (Mw / Mn) to the number-average molecular weight (Mn) is preferably 10 or less. An appropriate weight-average molecular weight (Mw) improves adhesion to the substrate and alkali-developable solubility.

[0065] The acid value of the alkali-soluble resin (B) is preferably 50 to 200 mg KOH / g, more preferably 70 to 180 mg KOH / g, and even more preferably 90 to 170 mg KOH / g. An appropriate acid value improves adhesion to the substrate and alkali development solubility.

[0066] Alkali-soluble resin (B) can be used alone or in combination of two or more types.

[0067] The content of alkali-soluble resin (B) is preferably 20 to 400 parts by mass, and more preferably 50 to 250 parts by mass, per 100 parts by mass of colorant (A).

[0068] [Polymerizable compound (C)] The photosensitive coloring composition of the present invention comprises an acid group-containing aromatic urethane (meth)acrylate (C1) and a lactone-modified (meth)acrylate (C2) as polymerizable compounds (C). Here, the acid group can be, for example, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. The inclusion of acid-group-containing aromatic urethane (meth)acrylate (C1) is thought to suppress shrinkage during curing by the highly rigid aromatic ring structure of the urethane bond portion, thereby reducing wrinkle formation. Furthermore, the acid group improves the solubility of the alkaline developer, allowing development to be completed in a short time and thus reducing chipping and peeling of the cured film. In addition, the inclusion of lactone-modified (meth)acrylate (C2) is thought to improve the residual film rate by reducing the affinity between water and the film during alkaline development through the highly hydrophobic and thermally stable lactone structure portion, thereby suppressing water staining and reducing decomposition during post-bake. By combining these factors, it is presumed that a photosensitive colored composition was obtained that exhibits less wrinkle formation on the pattern surface, suppresses water staining after development, and has excellent pattern-forming properties (adhesion, shape, and residual film rate).

[0069] (Acid group-containing aromatic urethane (meth)acrylate (C1)) The acid group-containing aromatic urethane (meth)acrylate (C1) is not particularly limited, and known ones can be used. For example, a compound obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate having an aromatic ring structure, and then adding a mercapto compound having a carboxyl group to the product, Compounds obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate having an aromatic ring structure, then reacting it with a (meth)acrylate having a hydroxyl group, and subsequently adding a mercapto compound having a carboxyl group to the product, Examples include compounds obtained by reacting a polyhydric alcohol having a carboxyl group with a polyfunctional isocyanate having an aromatic ring structure, and then reacting it with a (meth)acrylate having a hydroxyl group.

[0070] Examples of the above-mentioned (meth)acrylates having hydroxyl groups 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, hydroxyl group-containing polyol polyacrylate, and the like.

[0071] Examples of polyfunctional isocyanates having the above aromatic ring structure include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyli isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenedi isocyanate, 1,4-phenylenedi isocyanate, 2,4-tollylene diisocyanate, 2,6-tollylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatemethyl)benzene. Other examples include these biuret compounds, isocyanate nulate compounds, and trimethylolpropane adduct compounds.

[0072] 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.

[0073] Examples of polyhydric alcohols having the carboxyl group mentioned above include compounds obtained by reacting the polyhydric alcohol with a polybasic acid or its anhydride (e.g., succinic acid, succinic anhydride, fumaric acid, fumaric anhydride, tetrahydrophthalic anhydride, etc.) with dimethylolpropionic acid.

[0074] The number of polymerizable unsaturated groups in the acid group-containing aromatic urethane (meth)acrylate (C1) is preferably 3 to 15, and more preferably 5 to 12, from the viewpoint of suppressing wrinkles and pattern formation.

[0075] The molecular weight of the acid group-containing aromatic urethane (meth)acrylate (C1) is preferably 500 to 5,000, and more preferably 500 to 3,000, from the viewpoint of suppressing wrinkles and pattern formation.

[0076] Acid group-containing aromatic urethane (meth)acrylate (C1) can be used alone or in combination of two or more types.

[0077] (Lactone-modified (meth)acrylate (C2)) Lactone-modified (meth)acrylates (C2) are not particularly limited as long as they have a structure modified with a lactone within the molecule, but can be 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 lactones. Among these, compounds represented by the following general formula (1) are preferred.

[0078] General formula (1) [ka] (In general formula (1), all six R groups are either groups represented by general formula (2) below, or 1 to 5 of the six R groups are groups represented by general formula (2) below, and the remaining group is a group represented by general formula (3) below.)

[0079] General formula (2) [ka] (In general formula (2), R 1 (where m represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * represents a bond.)

[0080] General formula (3) [ka] (In the formula, R 1 (where * represents a hydrogen atom or a methyl group, and * represents a bonding bond.)

[0081] Lactone-modified (meth)acrylate (C2) is commercially available, for example, as the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd., and DPCA-20 (in general formulas (1) to (3), m=1, number of groups represented in general formula (2)=2, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-30 (in general formulas (1) to (3), m=1, number of groups represented in general formula (2)=3, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-60 (in general formulas (1) to (3), m=1, number of groups represented in general formula (2)=6, R 1 Compounds in which all atoms are hydrogen atoms), DPCA-120 (in general formulas (1) to (3), m=2, number of groups represented in general formula (2)=6, R 1 Examples include compounds in which all atoms are hydrogen atoms.

[0082] Lactone-modified (meth)acrylate (C2) is considered to have the following characteristics from the viewpoint of suppressing water stains and pattern formation: in general formulas (1) to (3), m=1, the number of groups represented in general formula (2) = 2 to 6, and R 1Compounds in which all atoms are hydrogen atoms are preferred, and in general formulas (1) to (3), m=1, the number of groups represented in general formula (2) = 2 or 3, R 1 Compounds in which all atoms are hydrogen atoms are more preferable.

[0083] The total content of acid group-containing aromatic urethane (meth)acrylate (C1) and lactone-modified (meth)acrylate (C2) is preferably 20% by mass or more, more preferably 30-80% by mass, and particularly preferably 40-70% by mass, of 100% by mass of polymerizable compound (C), from the viewpoint of suppressing wrinkles, suppressing water stains, and pattern formation.

[0084] The mass ratio of acid group-containing aromatic urethane (meth)acrylate (C1) to lactone-modified (meth)acrylate (C2) is preferably 80:20 to 20:80, and more preferably 70:30 to 30:70, from the viewpoint of suppressing wrinkles, suppressing water stains, and pattern formation.

[0085] Lactone-modified (meth)acrylate (C2) can be used alone or in combination of two or more types.

[0086] (Aliphatic urethane (meth)acrylate (C3) and alicyclic urethane (meth)acrylate (C4)) The photosensitive coloring composition of the present invention preferably further contains, as a polymerizable compound (C), at least one selected from the group consisting of aliphatic urethane (meth)acrylate (C3) and alicyclic urethane (meth)acrylate (C4), from the viewpoint of suppressing wrinkles. By using at least one selected from the group consisting of highly flexible aliphatic or alicyclic aliphatic urethane (meth)acrylate (C3) and alicyclic urethane (meth)acrylate (C4) in combination with an acid group-containing aromatic urethane (meth)acrylate (C1) having a highly rigid aromatic structure, shrinkage during curing can be further suppressed.

[0087] In particular, from the viewpoint of suppressing wrinkles, it is more preferable to include aliphatic urethane (meth)acrylate (C3).

[0088] The aliphatic urethane (meth)acrylate (C3) is not particularly limited, and known types can be used. Examples include compounds obtained by reacting a hydroxyl group-containing (meth)acrylate with an aliphatic structure-containing polyfunctional isocyanate, and compounds obtained by reacting a polyhydric alcohol with an aliphatic structure-containing polyfunctional isocyanate, and then reacting it with a hydroxyl group-containing (meth)acrylate.

[0089] Examples of the above-mentioned (meth)acrylates having hydroxyl groups 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, hydroxyl group-containing polyol polyacrylate, and the like.

[0090] Examples of polyfunctional isocyanates having the above-mentioned aliphatic structure include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropyl diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Other examples include their biuret derivatives, isocyanate nulate derivatives, and trimethylolpropane adduct derivatives.

[0091] The alicyclic urethane (meth)acrylate (C4) is not particularly limited, and known types can be used. For example, it can be obtained by changing the polyfunctional isocyanate having an aliphatic structure in the above-mentioned aliphatic urethane (meth)acrylate (C3) to a polyfunctional isocyanate having an alicyclic structure.

[0092] Examples of polyfunctional isocyanates having the above-mentioned alicyclic structure include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanate-methyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanate-methyl)cyclohexane. Furthermore, examples include their biuret forms, isocyanate nulate forms, and trimethylolpropane adduct forms.

[0093] The number of polymerizable unsaturated groups in aliphatic urethane (meth)acrylate (C3) and alicyclic urethane (meth)acrylate (C4) is preferably 4 to 15, and more preferably 6 to 12, from the viewpoint of suppressing wrinkles and pattern formation.

[0094] The molecular weight of the aliphatic urethane (meth)acrylate (C3) and alicyclic urethane (meth)acrylate (C4) is preferably 500 to 5,000, and more preferably 500 to 3,000, from the viewpoint of wrinkle suppression and pattern formation.

[0095] Aliphatic urethane (meth)acrylate (C3) and alicyclic urethane (meth)acrylate (C4) can contain acid groups. The method for containing acid groups can be the same as that used for acid group-containing aromatic urethane (meth)acrylate (C1) described above.

[0096] The mass ratio of acid group-containing aromatic urethane (meth)acrylate (C1) to the total amount of aliphatic urethane (meth)acrylate (C3) and alicyclic urethane (meth)acrylate (C4) is preferably 90:10 to 50:50, and more preferably 85:15 to 65:35, from the viewpoint of wrinkle suppression and pattern formation.

[0097] Aliphatic urethane (meth)acrylate (C3) and alicyclic urethane (meth)acrylate (C4) can each be used individually or in combination of two or more types.

[0098] ((C1)~(C4) other polymerizable compounds (C5)) The photosensitive colored composition of the present invention may contain polymerizable compounds other than (C1) to (C4) (hereinafter also referred to as other polymerizable compounds (C5)).

[0099] Other polymerizable compounds (C5) 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, and tricyclodecane. Dimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]ful orange 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( Metha)acrylate, isocyanurate EO modified tri(meth)acrylate, ditrimethylolpropanetetra(meth)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, dipenta Examples include erythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated melamine (meth)acrylate (meth)acrylate, various acrylic acid esters and methacrylic acid esters such as epoxy(meth)acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile. Among these, those with 5 or more polymerizable unsaturated groups are preferred from the viewpoint of pattern formation.

[0100] Other commercially available polymerizable compounds (C5) 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 from Toagosei Co., Ltd. M-321, M-325, 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, M-5300, M-5400, M-5700, M-510, M-520, M-521, 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., Viscoat #2500P from Osaka Organic Chemicals, NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4 from Shin Nakamura Chemical Industry, and EBECRY40, 130, 140, 145 from Daicel Ornex.

[0101] The polymerizable compound (C) content is preferably 5 to 50% by mass, and more preferably 5 to 30% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0102] [Photopolymerization initiator (D)] The photosensitive colored composition of the present invention contains a photopolymerization initiator (D). By containing the photopolymerization initiator (D), the photosensitive colored composition can be cured by ultraviolet irradiation to form a cured film.

[0103] The photopolymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating the polymerization of the polymerizable compound (C) by light, and known photopolymerization initiators can be used. For example, acetophenone compounds 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. Among these, from the viewpoint of pattern formation, oxime compounds (D1) and acetophenone compounds (D2) are preferred, with oxime compounds (D1) being more preferred.

[0104] (Oxime compound (D1)) Oxime compounds (D1) include oxime compounds (D1-1) containing one oxime group per molecule and oxime compounds (D1-2) containing two oxime groups per molecule. From the viewpoint of pattern formation, oxime compounds (D1-2) containing two oxime groups per molecule are particularly preferred.

[0105] [Oxime compounds containing one oxime group per molecule (D1-1)] Examples of oxime compounds (D1-1) containing one oxime group per molecule include IRGACURE OXE-01, 02, 03, 04 from BASF, ADEKA Arcules N-1919, NCI-730, 831, 930 from ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 358, 380, 365, 610, 3054, 3057 from Changzhou Strong New Materials, OMNIRAD 1312, 1314, 1316 from IGM Resins, SPI-02, 03, 04, 05, 06, 07 from Samyang Corporation, and DFI-020, 036, EOX-01 from Daito Chemix.

[0106] [Oxime compounds containing two oxime groups in one molecule (D1-2)] Oxime compounds (D1-2) containing two oxime groups in one molecule include, for example, the compounds described in Japanese Patent Publication No. 2005-215378, Japanese Patent Publication No. 2011-105713, and Japanese Patent Publication No. 2017-523465. Among these, compounds represented by the following general formula (4) are preferred.

[0107] General formula (4) [ka] (In general formula (4), X1 and X2 each independently represent a carbonyl bond (-CO-) or a single bond. R1 represents an alkyl group having 1 to 20 carbon atoms, and R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R4 and R5 each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.)

[0108] In general formula (4), X1 and X2 each independently represent a carbonyl bond (-CO-) or a single bond. In particular, from the viewpoint of solubility in organic solvents, it is preferable that at least one of X1 and X2 is a carbonyl bond (-CO-), and it is more preferable that X1 and X2 are both carbonyl bonds (-CO-).

[0109] In general formula (4), R1 represents an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, amino group, nitro group, etc. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group. Among these, ethyl group, propyl group, and isopropyl group are preferred.

[0110] In general formula (4), R2 and R3 independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocycle having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, amino group, nitro group, etc. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group. Among these, pentyl group, hexyl group, heptyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group are preferred. Examples of heterocyclic groups having 2 to 30 carbon atoms include pyridyl, pyrimidyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidyl, oxazolidyl, piperidyl, and morpholinyl groups. Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and anthuryl groups, and aryl groups substituted with halogen atoms, amino groups, nitro groups, etc. Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl groups, and may also be arylalkyl groups substituted with halogen atoms, amino groups, nitro groups, etc.

[0111] Among these, R2 and R3 are preferably at least one linear alkyl group having 1 to 20 carbon atoms from the viewpoint of solubility in organic solvents, and more preferably one linear alkyl group having 1 to 20 carbon atoms and the other a cyclic alkyl group having 1 to 20 carbon atoms from the viewpoint of solubility in organic solvents and suppression of water stains.

[0112] In general formula (4), R4 and R5 each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, amino group, nitro group, etc. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, cyclopentyl group, cyclopentylmethyl group, and cyclohexyl group. Among these, methyl group, ethyl group, propyl group, and isopropyl group are preferred from the viewpoint of reactivity. Examples of heterocyclic groups having 2 to 30 carbon atoms include pyridyl, pyrimidyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidyl, oxazolidyl, piperidyl, and morpholinyl groups. Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and anthuryl groups. They may also be aryl groups substituted with halogen atoms, amino groups, nitro groups, etc. Among these, the phenyl group is preferred from the viewpoint of reactivity. Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl groups. They may also be arylalkyl groups substituted with halogen atoms, amino groups, nitro groups, etc.

[0113] Among these, R4 and R5 are preferably methyl, ethyl, or phenyl groups from the viewpoint of reactivity, with methyl or ethyl groups being more preferred.

[0114] The method for producing the compound represented by general formula (4) is not particularly limited, and known methods can be used. For example, the method described in Japanese Patent Publication No. 2017-523465 can be used.

[0115] The following are specific examples of oxime compounds (D1-2) containing two oxime groups in one molecule. However, the present invention is not limited to these examples.

[0116] Chemical formula (5) [ka]

[0117] Chemical formula (6) [ka]

[0118] Chemical formula (7) [ka]

[0119] Chemical formula (8) [ka]

[0120] The photopolymerization initiator (D) can be used alone or in combination of two or more types.

[0121] The content of the photopolymerization initiator (D) is preferably 0.5 to 50 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 10% by mass, per 100 parts by mass of the coloring agent (A), from the viewpoint of photocurability and pattern formation.

[0122] [Sensitizer (E)] From the viewpoint of pattern-forming properties, the photosensitive coloring composition of the present invention preferably contains a sensitizer (E).

[0123] The sensitizer (E) is, for example, polymethine dyes such as chalcone compounds, unsaturated ketones represented by dibenzalacetone, 1,2-diketone compounds represented by benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, and azulenium compounds. Examples include compounds such as squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyradinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxaliloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyririum compounds, thiopyrillium compounds, tetraphylline compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organoruthenium complexes, or benzophenone compounds. Among these, from the viewpoint of pattern formation, thioxanthone compounds (E1) or benzophenone compounds (E2) are preferred, and benzophenone compounds (E2) are more preferred.

[0124] (Thioxanthone compound (E1)) Examples of thioxanthone compounds (E1) include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, and 1-chloro-4-propoxythioxanthone. Among these, 2,4-diethylthioxanthone is preferred.

[0125] (Benzophenone compounds (E2)) Examples of benzophenone compounds (E2) include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, and 2-aminobenzophenone. Among these, 4,4'-bis(diethylamino)benzophenone is preferred.

[0126] The sensitizer (E) can be used alone or in combination of two or more types.

[0127] From the viewpoint of suppressing water stains and pattern formation, the content of the sensitizer (E) is preferably 150 to 400 parts by mass, and more preferably 150 to 300 parts by mass, per 100 parts by mass of the photopolymerization initiator (D).

[0128] [Dye derivative (F)] The photosensitive colored composition of the present invention may contain a dye derivative (F).

[0129] The dye derivative (F) is not particularly limited and can include dye derivatives having acidic groups, basic groups, neutral groups, etc., in the organic dye residue. Examples of dye derivatives (F) include compounds having acidic substituents such as sulfo groups, carboxyl groups, and phosphate groups, as well as amine salts thereof, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminal, and compounds having neutral substituents such as phenyl groups or phthalimidoalkyl groups. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0130] Specifically, diketopyrrolopyrrole dye derivatives include JP 2001-220520, International Publication No. 2009 / 081930, International Publication No. 2011 / 052617, International Publication No. 2012 / 102399, and JP 2017-156397; phthalocyanine dye derivatives include JP 2007-226161, International Publication No. 2016 / 163351, JP 2017-165820, and Patent No. 5753266; and anthraquinone dye derivatives include JP Sho 63-264 Japanese Patent Publication No. 674, Japanese Patent Publication No. 09-272812, Japanese Patent Publication No. 10-245501, Japanese Patent Publication No. 10-265697, Japanese Patent Publication No. 2007-079094, International Publication No. 2009 / 025325, as quinacridone-based dye derivatives, Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, Japanese Patent Publication No. 2000-273383, as dioxazine-based dye derivatives, Japanese Patent Publication No. 2011-162662, as thiaidine-indigo-based dye derivatives, Japanese Patent Publication No. 2007-314785, triazine Examples of benzoindole-based dye derivatives include Japanese Patent Publication No. 61-246261, Japanese Patent Publication No. 11-199796, Japanese Patent Publication No. 2003-165922, Japanese Patent Publication No. 2003-168208, Japanese Patent Publication No. 2004-217842, and Japanese Patent Publication No. 2007-314681. Examples of benzoisoindole-based dye derivatives include Japanese Patent Publication No. 2009-57478. Examples of quinophthalone-based dye derivatives include Japanese Patent Publication No. 2003-167112, Japanese Patent Publication No. 2006-291194, Japanese Patent Publication No. 2008-31281, and Japanese Patent Publication No. 2012-226 Examples of known dye derivatives include those described in Japanese Patent Publication No. 110, Japanese Patent Publication No. 2012-208329 and Japanese Patent Publication No. 2014-5439 as naphthol-based dye derivatives, Japanese Patent Publication No. 2001-172520 and Japanese Patent Publication No. 2012-172092 as azo-based dye derivatives, Japanese Patent Publication No. 2004-307854 as an acidic substituent, and Japanese Patent Publication No. 2002-201377, Japanese Patent Publication No. 2003-171594, Japanese Patent Publication No. 2005-181383 and Japanese Patent Publication No. 2005-213404 as basic substituents.In addition, these documents may refer to dye derivatives as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, but compounds having substituents such as acidic groups, basic groups, or neutral groups on the aforementioned organic dye residues are synonymous with dye derivatives.

[0131] The dye derivative (F) can be used alone or in combination of two or more types.

[0132] The content of the pigment derivative (F) is preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the coloring agent (A).

[0133] [Dispersion resin (G)] The photosensitive composition of the present invention may optionally contain a dispersion resin (G). The dispersion resin (G) is preferably a resin having an adsorption group that has a high affinity for the colorant (A). The adsorption group preferably has one or more basic groups and acidic groups, and from the viewpoint of developability, it is preferable that it has an acidic group.

[0134] Basic groups include, for example, primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonia bases, and nitrogen-containing heterocyclic groups and other groups containing nitrogen atoms.

[0135] 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 adsorption to pigments and developability.

[0136] Examples of the resin types of the dispersed resin (G) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester systems, modified polyacrylate systems, ethylene oxide / propylene oxide adduct compounds, and phosphate ester systems.

[0137] Examples of the structure of the dispersed resin (G) include random structures, block structures, graft structures, comb structures, and star structures. Among these, block structures or comb structures are preferred from the viewpoint of dispersion stability.

[0138] Commercially available dispersion resins (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 21 SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 325, etc. manufactured by Lubrizol Japan, including 64, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen. 50, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500 etc., BASF Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 45 Examples of resins include 1,453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajisuper PA111, PB711, PB821, PB822, PB824 etc. manufactured by Ajinomoto Fine Techno Co., Ltd., and resins described in Japanese Patent Publication No. 2008-029901, Japanese Patent Publication No. 2009-155406, Japanese Patent Publication No. 2010-185934, Japanese Patent Publication No. 2011-157416, etc.

[0139] The dispersion resin (G) can be used alone or in combination of two or more types.

[0140] From the viewpoint of dispersion stability, the content of the dispersion resin (G) 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).

[0141] [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.

[0142] 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.

[0143] (Epoxy compound (H1)) Epoxy compounds (H1) include, for example, 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) and phenols. Examples include polymers of phenols (such as divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (such as benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (such as 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.

[0144] 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.

[0145] From the viewpoint of the heat resistance of the cured film, the content of the epoxy compound (H1) is preferably 0.5 to 300 parts by mass, and more preferably 1.0 to 50 parts by mass, per 100 parts by mass of the coloring agent (A).

[0146] (Oxetane compound (H2)) Oxetane compounds (H2) are known compounds having an oxetane group. Examples of oxetane compounds include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or multifunctional oxetane compounds.

[0147] 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.

[0148] 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.

[0149] 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.

[0150] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0151] 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.

[0152] The content of the oxetane compound (H2) 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.

[0153] Melamine compounds are compounds having a melamine ring structure. Methylol-type and ether-type melamine compounds are preferred, and melamine compounds with an average of 5.0 or more methylol and / or ether groups per melamine ring are more preferred. Having a moderate number of methylol and ether groups makes it easier to obtain adequate heat resistance.

[0154] Examples of commercially available products include Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 from Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 from Nippon Cytec Industries Co., Ltd.

[0155] Among these, Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 from Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, 350 from Nippon Cytec Industries Co., Ltd. are preferred in that they can increase the crosslinking density, as they have an average of 5.0 or more methylol groups and / or ether groups per melamine ring.

[0156] Thermosetting compounds (H) can be used alone or in combination of two or more types.

[0157] [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.).

[0158] The hardening agent can be used alone or in combination of two or more types.

[0159] The curing agent content is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermosetting compound (H).

[0160] [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.

[0161] The thiol-based chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). More preferably, the thiol-based chain transfer agent has four or more SH groups. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

[0162] Polyfunctional thiols include, for example, 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 Examples include lithritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferably, examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0163] Thiol chain transfer agents (I) can be used alone or in combination of two or more types.

[0164] The content of thiol-based chain transfer agent (I) is preferably 1 to 10% by mass, and more preferably 2 to 8% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. Including an appropriate amount improves photosensitivity and makes it less likely for wrinkles to form on the pattern surface.

[0165] [Polymerization inhibitor (J)] The photosensitive colored composition of the present invention may contain a polymerization inhibitor (J).

[0166] Polymerization inhibitors (J) include 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 trybenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0167] 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.

[0168] [UV absorber (K)] The photosensitive colored composition of the present invention may contain an ultraviolet absorber (K).

[0169] 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.

[0170] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 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, and 5% 2-methoxy-1-methylphenyl A mixture of tyl acetate and 95% benzenepropanoic acid, 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, methyl3-(3-(2H-benzotriazole2-yl) Reaction product of (-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-4-methylpheno Examples include 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.

[0171] 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.

[0172] 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.

[0173] Examples of commercially available products include KEMISORB102 from Chemipro Chemical Co., Ltd., TINUVIN400, 405, 460, 477, 479, and 1577ED from BASF Japan, ADEKA LA-46 and LA-F70 from ADEKA, and CYASORB UV-1164 from Sun Chemical Co., Ltd.

[0174] 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.

[0175] Examples of commercially available products include KEMISORB10, 11, 11S, 12, and 111 from Chemipro Chemical Co., Ltd., SEESORB101 and 107 from Cipro Chemical Co., Ltd., ADEKA Stab 1413 from ADEKA Corporation, and UV-12 from Sun Chemical Co., Ltd.

[0176] Examples of salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0177] 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).

[0178] [Antioxidant (L)] The photosensitive colored composition of the present invention may contain an antioxidant (L). The antioxidant (L) prevents the photopolymerization initiator (D) and thermosetting compound (I) contained in the photosensitive colored composition from yellowing due to oxidation during the thermal process of heat curing or ITO aneeling. In particular, when the colorant (A) concentration of the photosensitive colored composition is high, the content of polymerizable compound (C) decreases relatively, so if the amount of photopolymerization initiator (D) is increased or the thermosetting compound (I) is added, the cured film is prone to yellowing. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented.

[0179] Examples of antioxidants (L) include hinder-dophenol, hindered amine, phosphorus, sulfur, and hydroxylamine compounds. In this invention, the antioxidant is preferably a compound that does not contain halogen atoms.

[0180] Among these, hinder-dophenol antioxidants, hinder-amine antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0181] 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, Examples include 2,2'-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.

[0182] 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.

[0183] 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 and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide.

[0184] Examples of commercially available products include ADEKA's ADEKA Stab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP; KAMISTAB29, 62, 77, 94 from Chemipro Chemical; Tinuvin111FDL, 123, 144, 249, 292, 5100 from BASF Japan; and SiaSove UV-3346, UV-3529, UV-3853 from Sun Chemical.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] Examples of commercially available products include ADEKA's ADEKA stub AO-412S and AO-503, and KEMINOXPLS from Chemipro Chemical Co., Ltd.

[0189] Antioxidants (L) can be used alone or in combination of two or more types.

[0190] 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.

[0191] [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 to the substrate during coating. Examples of leveling agents (M) include silicon-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0192] Silicone-based surfactants include, for example, linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0193] 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.

[0194] Examples of fluorinated surfactants include surfactants or leveling agents having fluorocarbon chains.

[0195] 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.

[0196] 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.

[0197] 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.

[0198] 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.

[0199] Examples of commercially available products include Acetamine 24, Cotamin 24P, 60W, and 86P Concentrate, all manufactured by Kao Corporation.

[0200] 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.

[0201] 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.

[0202] 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.

[0203] Examples of commercially available products include Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N, manufactured by Kao Corporation.

[0204] Leveling agent (M) can be used alone or in combination of two or more types.

[0205] 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 non-volatile content of the photosensitive colored composition. Within this range, the balance between the applicability and adhesion of the photosensitive colored composition is further improved.

[0206] [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. Examples of storage stabilizers (N) include benzyltrimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphates.

[0207] The storage stabilizer (N) content is preferably 0.1 to 10 parts by mass per 100 parts by mass of coloring agent (A).

[0208] [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.

[0209] 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.

[0210] Adhesion enhancers (O) can be used alone or in combination of two or more types.

[0211] 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).

[0212] [Organic solvent (P)] The photosensitive composition of the present invention may contain an organic solvent (P).

[0213] 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 benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0214] Organic solvents (P) can be used alone or in combination of two or more types.

[0215] [Method for producing a photosensitive colored composition] The photosensitive colored composition of the present invention can be produced by dispersing a dispersion by adding, for example, a colorant (A), an alkali-soluble resin (B), a dispersion resin (G), a dye derivative (F), and an organic solvent (P). Subsequently, a polymerizable compound (C), a photopolymerization initiator (D), etc., are added to the dispersion and mixed. The timing of adding each material is arbitrary. Furthermore, the dispersion process can be performed multiple times.

[0216] Distributed processing machines include, for example, two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, or attritors.

[0217] 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.

[0218] 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.

[0219] The photosensitive colored composition is preferably subjected to centrifugation, sintering filter filtration or membrane filter filtration to remove coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, more preferably coarse particles of 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.

[0220] <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.

[0221] [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).

[0222] 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 and silicon 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 layer thickness is preferably 0.05 to 10.0 μm after drying, and more preferably 0.3 to 5 μm.

[0223] (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, h-rays, and i-rays.

[0224] (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.

[0225] Development methods include, for example, the dip method, spray method, and pador method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0226] (Step (4)) The heat treatment (post-bake) is used to fully harden the patterned cured film obtained in step (3) by heating. The heating temperature for post-bake is preferably 100 to 300°C, and more preferably 150 to 250°C. The heating time is preferably 2 minutes to 1 hour, and more preferably 3 minutes to 30 minutes.

[0227] <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).

[0228] <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]

[0229] 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 "percentage by mass". Furthermore, in this invention, non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 280°C for 30 minutes.

[0230] Before presenting the examples, each measurement method will be explained.

[0231] The weight-average molecular weight (Mw), number-average molecular weight (Mn), and acid value (mgKOH / g) of the resin are as follows:

[0232] (Average molecular weight of alkali-soluble resin and dispersion resin) Alkali solubility and the number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the dispersed resin were measured by gel permeation chromatography (GPC) equipped with an RI 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. Average molecular weights are expressed on a polystyrene basis.

[0233] (Acid value of alkali-soluble resins and dispersion resins) 0.5 to 1 g of alkali-soluble resin and dispersion resin solution were 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 (mgKOH / 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 non-volatile content concentration of the resin solution.

[0234] (Amine value of dispersed resin) The amine value of the dispersion 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.

[0235] <Manufacturing of coloring agent (A)> (Finely milled red pigment (A-1)) 100 parts of C.I. Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60°C for 6 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating to about 80°C to make it into a slurry state, filtered and washed with water to remove sodium chloride and diethylene glycol, then dried at 80°C for a whole day and night, and pulverized to obtain a refined red pigment (A-1).

[0236] (Refined red pigment (A-2)) 100 parts of C.I. Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 60°C for 6 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating to about 80°C to make it into a slurry state, filtered and washed with water to remove sodium chloride and diethylene glycol, then dried at 80°C for a whole day and night, and pulverized to obtain a refined red pigment (A-2).

[0237] (Refined blue pigment (A-3)) 100 parts of C.I.Pigment Blue15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 50°C for 12 hours. This mixture was put into 3,000 parts of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 70°C to make it into a slurry state, filtered and washed repeatedly to remove salt and solvent, then dried at 80°C for 24 hours to obtain a refined blue pigment (A-3).

[0238] (Refined purple pigment (A-4)) 100 parts of C.I. Pigment Violet 23, 1,200 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 80°C for 6 hours. Next, this kneaded product was put into 8,000 parts of warm water, stirred for 2 hours while heating to 80°C to make it into a slurry state, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 85°C for 24 hours to obtain a micronized purple pigment (A-4).

[0239] (Micronized green pigment (A-5)) 100 parts of C.I. Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 70°C for 6 hours. This kneaded product was put into 3,000 parts of warm water, stirred for 1 hour while heating to 70°C to make it into a slurry state, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for a whole day and night to obtain a micronized green pigment (A-5).

[0240] (Micronized yellow pigment (A-6)) 100 parts of C.I. Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 80°C for 6 hours. This mixture was put into 2,000 parts of warm water, stirred for 1 hour while heating to 80°C to make it into a slurry state, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for a whole day and night to obtain a micronized yellow pigment (A-6).

[0241] <Manufacture of alkali-soluble resin (B)> (Alkali-soluble resin (B-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 dropwise addition was complete, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. 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. Propylene glycol monomethyl ether acetate (PGMAc) was then added to the previously synthesized resin solution to a non-volatile content of 20% by mass to prepare an alkali-soluble resin (B-1) solution. The weight-average molecular weight (Mw) was 26,000.

[0242] (Alkali-soluble resin (B-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 copolymer solution was stirred while injecting dry air for 1 hour after stopping the nitrogen gas supply, and then cooled to room temperature. A mixture of 6.5 parts 2-methacryloyloxyethyl isocyanate (Kalenz MOI, Showa Denko Co., Ltd.), 0.08 parts dibutyltin laurate, and 26 parts 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 an acrylic 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 to prepare an alkali-soluble resin (B-2) solution by reducing the non-volatile content to 20% by mass. The weight-average molecular weight (Mw) was 18,000.

[0243] (Alkali-soluble resin (B-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 to obtain an acrylic resin solution. 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 an acrylic 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 prepare an alkali-soluble resin (B-3) solution by reducing the non-volatile content to 20% by mass. The weight-average molecular weight (Mw) was 19,000.

[0244] (Alkali-soluble resin (B-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 an alkali-soluble resin (B-4) solution, with the non-volatile content reaching 20% ​​by mass. The weight-average molecular weight was 18,000.

[0245] (Alkali-soluble resin (B-5) solution) In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 150 parts of PGMAc were introduced. After changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100°C. Then, 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 reaction was carried out at 120°C for 3.5 hours to obtain a photosensitive transparent resin solution with an acid value of 80 mg KOH / g. After cooling to room temperature, approximately 2 parts of the photosensitive transparent 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 photosensitive transparent resin solution to prepare an alkali-soluble resin (B-5) solution by reducing the non-volatile content to 20% by mass. The mass-average molecular weight (Mw) was 12,000.

[0246] (Alkali-soluble resin (B-6) solution) Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 150 parts of PGMAc were introduced. After changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 °C. Then, a solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture 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 was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued at 100 °C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)] of glycidyl methacrylate, 0.9 part of tris(dimethylaminomethyl)phenol, and 0.145 part of hydroquinone were charged into the flask, and the reaction was continued at 110 °C for 6 hours to obtain a photosensitive transparent resin solution with an acid value of 79 mgKOH / g. After cooling to room temperature, about 2 parts of the photosensitive transparent resin solution were sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized photosensitive transparent resin solution so that the nonvolatile content became 20% by mass to prepare an alkali-soluble resin (B-6) solution. The mass average molecular weight (Mw) was 13,000.

[0247] <Production of Acid Group-Containing Aromatic Urethane (Meth)acrylate (C1)> (Acid Group-Containing Aromatic Urethane Acrylate (C1-1) Solution) Into a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 400 parts of 2-hydroxy-3-acryloyloxypropyl methacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged. The temperature was raised to 70 °C, and a mixture of 162 parts of toluene diisocyanate and 162 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the reaction was carried out at a temperature of 50 to 70 °C for 8 hours, and by IR at 2180 cm ー1The disappearance of the absorption of the isocyanate was confirmed. Next, 85 parts of mercaptoacetic acid and 0.4 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 solution of acid-containing aromatic urethane acrylate (C1-1) with an average polymerizable unsaturated group count of 3.

[0248] (Solution of acid-containing aromatic urethane acrylate (C1-2)) In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 400 parts pentaerythritol triacrylate, 100 parts PGMAc, and 0.5 parts N,N-dimethylbenzylamine were charged. The temperature was raised to 70°C, and a mixture of 116 parts toluene diisocyanate and 116 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). ー1 The disappearance of the absorption of the isocyanate was confirmed. Next, 66 parts of mercaptoacetic acid and 0.4 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 an acid group-containing aromatic urethane acrylate (C1-2) solution with an average polymerizable unsaturated group count of 5.

[0249] (Solution of acid-containing aromatic urethane acrylate (C1-3)) 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). ー1 The 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 an acid group-containing aromatic urethane acrylate (C1-3) solution with an average polymerizable unsaturated group count of 9.

[0250] <Manufacturing of Aliphatic Urethane (Meth)acrylate (C3)> (Aliphatic urethane acrylate (C3-1) solution) In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 400 parts pentaerythritol triacrylate, 100 parts PGMAc, and 0.5 parts N,N-dimethylbenzylamine were charged. The temperature was raised to 70°C, and a mixture of 112 parts hexamethylene diisocyanate and 112 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). ー1 The disappearance of the absorption of the isocyanate was confirmed. The non-volatile content was adjusted to 50% by mass to obtain a polymerizable aliphatic urethane acrylate (C3-1) solution with 6 polymerizable unsaturated groups.

[0251] (Aliphatic urethane acrylate (C3-2) solution) 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 64 parts hexamethylene diisocyanate and 64 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). ー1 The disappearance of the absorption of the isocyanate was confirmed. The non-volatile content was adjusted to 50% by mass to obtain a polymerizable aliphatic urethane acrylate (C3-2) solution with 10 unsaturated groups.

[0252] (Aliphatic urethane acrylate (C3-3) solution) 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 64 parts hexamethylene diisocyanate and 64 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). ー1The disappearance of the absorption of isocyanate was confirmed. Subsequently, 35 parts of mercaptoacetic acid and 0.4 part of 4-methoxyphenol were charged, and the reaction was carried out at a temperature of 50 to 60 °C for 6 hours. It was adjusted so that the nonvolatile content became 50% by mass, and an acid group-containing aliphatic urethane acrylate (C3-3) solution having an average number of polymerizable unsaturated groups of 9 was obtained.

[0253] <Production of alicyclic urethane (meth)acrylate (C4)> (Alicyclic urethane acrylate (C4-1) solution) Into a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged, and the temperature was raised to 70 °C. A mixture of 84 parts of isophorone diisocyanate and 84 parts of PGMAc was dropped from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70 °C for 8 hours, and the disappearance of the absorption of isocyanate at 2180 cm ー1 was confirmed by IR. It was adjusted so that the nonvolatile content became 50% by mass, and an alicyclic urethane acrylate (C4-1) solution having a polymerizable unsaturated group number of 10 was obtained.

[0254] <Production of other polymerizable compounds (C5)> (Aromatic urethane acrylate (C5-1) solution) Into a five-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged, and the temperature was raised to 70 °C. A mixture of 66 parts of toluene diisocyanate and 100 parts of PGMAc was dropped from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70 °C for 8 hours, and the disappearance of the absorption of isocyanate at 2180 cm ー1 was confirmed by IR. PGMAc was added so that the nonvolatile content became 50% by mass, and an aromatic urethane acrylate (C5-1) solution having a polymerizable unsaturated group number of 10 was obtained.

[0255] <Production of dispersion resin (G)> (Dispersion resin (G-1) solution) 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 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%, yielding a dispersion resin (G-1) solution with an acid value of 70 mgKOH / g and a weight-average molecular weight of 8,500.

[0256] (Dispersion resin (G-2) solution) 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% of the mixture 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 the reaction was carried out by IR until the disappearance of the 2270 cm-1 peak based on the isocyanate group was confirmed (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 (G-2) solution with a non-volatile content of 30%. The acid value of the obtained dispersion resin (G-2) was 68 mgKOH / g, the unsaturated double bond equivalent was 1,593, and the weight-average molecular weight was 13,000.

[0257] (Dispersion resin (G-3) 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. PGMAc was added to dilute the solution so that the non-volatile content was 30%, obtaining a dispersed resin (G-3) solution with an amine value of 57 mgKOH / g per non-volatile content and a number-average molecular weight of 4,500 (Mn).

[0258] <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. Finely milled red pigment (A-1): 14.0 parts Pigment derivative (F-1): 1.0 part Dispersion resin (G-1) solution: 10.0 parts Dispersion resin (G-2) solution: 10.0 parts Organic solvent (P-1): 65.0 parts

[0259] Dye derivative (F-1): See below structure [ka]

[0260] Dispersions 2-6 were prepared in the same manner as dispersion 1, except that the raw materials and quantities listed in Table 1 were changed.

[0261] [Table 1]

[0262] Dye derivative (F-2) in Table 1: Structure shown below [ka]

[0263] <Manufacturing of photosensitive colored compositions> [Example 1] (Photosensitive coloring composition 1) The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain photosensitive colored composition 1. Dispersion 1: 17.0 parts Dispersion 2: 15.0 parts Dispersion 6: 0.3 parts Alkali-soluble resin (B) solution: 15.0 parts Acid group-containing urethane acrylate (C1-1) solution: 3.0 parts Lactone-modified (meth)acrylate (C2-1): 1.5 parts Other polymerizable compounds (C5-2): 2.7 parts Photopolymerization initiator (D1-2-1): 0.15 parts Epoxy compound (H1): 0.4 parts Polymerization inhibitor (J): 0.01 part Leveling agent (M): 1.0 part Organic solvent (P): 43.94 parts

[0264] [Examples 2-40, Comparative Examples 1-4] (Photosensitive coloring composition 2-44) Photosensitive colored compositions 2 to 44 were prepared in the same manner as in Example 1, except that the raw materials and quantities of photosensitive colored composition 1 in Example 1 were changed to those listed in Tables 2-1 to 2-4.

[0265] [Table 2-1]

[0266] [Table 2-2]

[0267] [Table 2-3]

[0268] [Table 2-4]

[0269] The ingredients listed in Tables 2-1 to 2-4 are as follows:

[0270] [Alkali-soluble resin (B) solution] Alkali-soluble resin solutions (B-1) to (B-6) were mixed in equal amounts to obtain alkali-soluble resin solution (B).

[0271] [Polymerizable compound (C)] (Lactone-modified (meth)acrylate (C2)) C2-1: KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) C2-2: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.) C2-3: KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.) (Other polymerizable compounds (C5)) C5-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) C5-3: Arronix M-521 (manufactured by Toagosei Co., Ltd.)

[0272] [Photopolymerization initiator (D)] (Oxime compound (D1)) [Oxime compounds containing one oxime group per molecule (D1-1)] D1-1-1: Irgacure OXE-02 (manufactured by BASF) [Oxime compounds containing two oxime groups in one molecule (D2-1)] D2-1-1: Compound represented by the above chemical formula (5) D2-1-2: Compound represented by the above chemical formula (6) (Acetophenone compound (D2)) D2-1: Irgacure 907 (BASF) D2-2: Irgacure 369 (BASF)

[0273] [Sensitizer (E)] (Thioxanthone compound (E1)) E1-1: 2,4-Diethylthioxanthone (Benzophenone compounds (E2)) E2-1: 4,4'-Bis(diethylamino)benzophenone

[0274] [Thermosetting compound (H)] (Epoxy compound (H1)) H1-1: EHPE-3150 (manufactured by Daicel Corporation) H1-2: Denacol EX611 (manufactured by Nagase ChemteX Corporation) H1-3: Triglycidyl isocyanurate Equal amounts of (H1-1) to (H1-3) were mixed to obtain the thermosetting compound (H).

[0275] [Polymerization inhibitor (J)] J-1: 4-methylcatechol J-2: Methylhydroquinone J-3: t-Butylhydroquinone Equal amounts of (J-1) to (J-3) were mixed to form polymerization inhibitor (J).

[0276] [Leveling agent (M)] A solution prepared by dissolving 2 parts of M-1:BYK-330 (manufactured by Bic Chemie) in 98 parts of PGMAc was used as the leveling agent (M).

[0277] [Organic solvent (P)] P-1: Propylene glycol monomethyl ether acetate 30 parts P-2: Cyclohexanone 30 parts P-3: 3-Ethoxypropionate 10 parts 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).

[0278] <Evaluation of photosensitive colored compositions> The obtained photosensitive colored compositions 1 to 44 (Examples 1 to 40, Comparative Examples 1 to 4) were evaluated for water staining, pattern formation (adhesion, shape, residual film rate), and surface wrinkles using the methods described below. The evaluation results are shown in Table 3.

[0279] [Water stain evaluation] The obtained photosensitive colored composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) to a dry film thickness of 3.0 μm, and dried on a hot plate at 70°C for 1 minute. Then, illuminating it with a high-pressure mercury lamp at an intensity of 30 mW / cm² through a mask having a 100 μm wide stripe pattern was performed. 2 40 mJ / cm² 2 The samples were exposed to ultraviolet light under the specified conditions. Subsequently, they were developed by immersion in an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C for 40 seconds, and then washed with pure water. The resulting patterns were observed using a Nikon ECLIPSE LV100POL Model optical microscope, and the degree of discoloration was evaluated. A score of 3 or higher was considered practical. 5: There were no water stains. 4. Water stains accounted for less than 10% of the total area. 3. Water stains accounted for 10% to less than 20% of the total area. 2: Water stains accounted for 20% to less than 30% of the total area. 1: Water stains covered more than 30% of the surface.

[0280] <Fabrication of substrates for pattern formation evaluation> The obtained photosensitive colored composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 3.0 μm, and dried on a hot plate at 70°C for 1 minute. After cooling the substrate to room temperature, illuminating it at 30 mW / cm² was performed using a high-pressure mercury lamp through photomasks with 100 μm wide (200 μm pitch) and 10 μm wide (20 μm pitch) stripe patterns. 2 40 mJ / cm² 2 The substrate was exposed to light. Subsequently, this substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C. After that, it was washed with deionized water, air-dried, and heated in a clean oven at 230°C for 30 minutes to obtain a substrate for pattern formation evaluation. Spray development was performed for the shortest possible time that allowed for pattern formation without any development residue for each photosensitive coloring composition.

[0281] [Pattern formation evaluation (1): Adhesion] Fine line patterns with a width of 6 to 25 μm on substrates prepared using the above method were observed with an optical microscope to confirm the minimum line width of the remaining fine line patterns. A value of 3 or higher is considered practical. 5: Fine lines smaller than 10 μm remain. 4: Fine lines smaller than 15 μm remain. 3: Fine lines smaller than 20 μm remain. 2: Fine lines smaller than 25 μm remain. 1: No thin lines remain.

[0282] [Pattern formation evaluation (2): Cross-sectional shape] The pattern shape of the substrate prepared using the above method for pattern formation evaluation was confirmed using a scanning electron microscope (Hitachi High-Tech Corporation's "S-3000H"). The evaluation involved acquiring SEM images of the cross-section of a 100 μm wide stripe pattern and measuring the taper angle between the substrate and the edge of the pattern cross-section to assess the cross-sectional shape. A score of 3 or higher is considered practical. 5: Taper angle of 30 degrees or more and less than 50 degrees 4: Taper angle 50 degrees or more and less than 60 degrees 3: Taper angle less than 30 degrees or 60 degrees or more but less than 70 degrees 2: Taper angle 70 degrees or more and less than 90 degrees 1: Taper angle of 90 degrees or more

[0283] [Pattern formation evaluation (3): Residual film rate] During the preparation of the substrate for evaluating pattern formation, spray development was performed, followed by washing with deionized water and air drying. The film thickness of the coating was then measured. This film thickness was defined as the post-development film thickness. Subsequently, the substrate was heated in a clean oven at 230°C for 30 minutes, and the film thickness was measured again at the same location where the post-development film thickness was measured. This film thickness was defined as the post-bake film thickness. The residual film percentage was calculated from the two film thicknesses using the following formula. A percentage of 3 or higher is considered practical. The film thickness was measured using a Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.). Formula: Residual film percentage (%) = Film thickness after baking ÷ Film thickness after development × 100 5: Remaining film rate 85% or more 4: Residual film rate 80% or more but less than 85% 3: Residual film rate 75% or more but less than 80% 2: Residual film rate 70% or more but less than 75% 1: Residual film rate less than 70%

[0284] [Surface wrinkle evaluation] The pattern surface of the above pattern-forming evaluation substrate was observed using an optical microscope (Olympus Optical Co., Ltd. "BX-51", magnification: 200x). A score of 3 or higher is considered practical. 5: No wrinkles are observed on the surface of the pattern. 4: Very slight wrinkles are observed on the surface of the pattern. 3: Slight wrinkles are observed on the surface of the pattern. 2: Wrinkles are observed on the surface of the pattern. 1: Severe wrinkles are observed on the surface of the pattern.

[0285] [Table 3]

Claims

1. Coloring agent (A), alkali-soluble resin (B) (however, acid group-containing aromatic urethane (meth) A compound comprising a polymerizable compound (C) and a photopolymerization initiator (D), excluding acrylate (C1), A photosensitive colored composition for a light filter, The polymerizable compound (C) is an acid group-containing aromatic urethane (meth)acrylate (C1), and also includes lactone-modified (meth)acrylate (C2), Acid group-containing aromatic urethane (meth)acrylate (C1) is a (meth)acrylate having a hydroxyl group. Urethane bonds formed by the reaction of acrylate with polyfunctional isoanates having an aromatic ring structure. It is a polymerizable compound having a compound, The number of polymerizable unsaturated groups in acid group-containing aromatic urethane (meth)acrylate (C1) is 3 to 1. Five photosensitive colored compositions for color filters.

2. The acid group-containing aromatic urethane (meth)acrylate (C1) and the lactone-modified (meth The total content of acrylate (C2) is 20% by mass of the polymerizable compound (C) A photosensitive colored composition for color filters according to claim 1, wherein the amount is % by mass or more.

3. The polymerizable compound (C) is further aliphatic urethane (meth)acrylate (C3), and At least one selected from the group consisting of cyclamate urethane (meth)acrylate (C4) A photosensitive colored composition for color filters according to claim 1 or 2, comprising the above.

4. The acid group-containing aromatic urethane (meth)acrylate (C1) and the aliphatic urethane ( A compound of meth)acrylate (C3) and the alicyclic urethane (meth)acrylate (C4) The color filter according to claim 3, wherein the ratio of mass to weight is 90:10 to 50:

50. Photosensitive coloring composition for use.

5. The photopolymerization initiator (D) comprises an oxime compound (D1), any one of claims 1 to 4. A photosensitive colored composition for color filters as described in item 1.

6. The oxime compound (D1) contains two oxime groups in one molecule. A photosensitive colored composition for color filters according to claim 5, comprising a compound (D1-2).

7. Furthermore, a color filter sensitizer according to any one of claims 1 to 6, comprising a sensitizer (E). Photosensitive coloring composition.

8. A substrate and the photosensitive colored composition for color filters according to any one of claims 1 to 7. A color filter having a filter segment formed using [a specific material / method].

9. An image display device having the color filter described in claim 8.

10. A solid-state image sensor having the color filter described in claim 8.

Images