Photosensitive coloring composition, color filter, image display device, and solid-state imaging device

Abstract

To provide a photosensitive coloring composition having excellent developability, adhesion, pattern profile and solvent resistance.SOLUTION: A photosensitive coloring composition contains a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the polymerizable compound (C) includes two or more compounds selected from the group consisting of compounds represented by the general formulae (1)-(4), or the total content of the compounds represented by formulae (1)-(4) is 50 mass% or more in the polymerizable compound (C) 100 mass%.SELECTED DRAWING: None

Description

[Technical Field]

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

[0002] A color filter is formed by arranging two or more fine band-shaped filter segments of different hues on a transparent substrate such as a glass substrate, either parallel to each other (in stripes) or crossing each other, or by arranging two or more fine filter segments of different hues in order in both the vertical and horizontal directions. The filter segments have small dimensions of several microns to several hundred microns, and are arranged in a predetermined order for each hue.

[0003] Currently, color filter manufacturing methods include the steps of applying a photosensitive coloring composition to a transparent substrate such as glass and drying to remove the solvent from the coating, irradiating and curing the coating with ultraviolet light or the like through a photomask having the desired pattern (hereinafter referred to as exposure), washing and removing the unexposed areas of the coating (hereinafter referred to as development), and then, if necessary, performing a heat treatment (hereinafter referred to as post-baking) to sufficiently harden the cured film, thereby obtaining a filter segment pattern of a first color. Filter segment patterns of other colors are then formed by performing similar operations to complete a color filter.

[0004] In recent years, the trend toward smaller image display devices and solid-state imaging devices with higher pixel counts has led to a trend toward smaller pixel areas. This has led to demands for thinner films and higher-resolution patterns, thanks to increased concentrations of colorants contained in compositions forming color filters. However, increasing the concentration of colorants reduces the transmittance of ultraviolet light into the film, resulting in poorer curing and reduced adhesion to the substrate. This is particularly true when patterns are highly refined. Furthermore, increasing the amount of photopolymerization initiator to increase the curing degree results in problems such as patterns that are thicker than the desired line width and poorer in shape.

[0005] Furthermore, in order to increase the concentration of the colorant, it is necessary to reduce the amount of other components, which causes problems such as a decrease in the developability of the photosensitive coloring composition and a decrease in the solvent resistance of the coating film.

[0006] To address these problems, for example, Patent Document 1 discloses a curable composition for color filters that contains a binder resin having an acid group and an unsaturated double bond, in order to obtain a pattern with excellent resolution and adhesion. The acid group is bonded to the main chain via a linking group whose main skeleton has two or more atoms, and the unsaturated double bond is located in a side chain. Patent Document 2 discloses a photosensitive resin composition that contains an amine compound of a specific structure and an ultraviolet absorber having a maximum absorption wavelength (λmax) of 335 to 365 nm. Patent Document 3 discloses a curable composition that contains a multifunctional thiol compound having two or more thiol groups and an interactive group different from the thiol groups. Patent Document 4 discloses a photosensitive resin composition that contains a photopolymerization initiator of a specific structure and a photopolymerization initiator having a maximum absorption wavelength of 334 nm or longer in the wavelength range of 320 to 400 nm. Patent Document 5 also describes a polymerizable monomer M having three groups each having an ethylenically unsaturated group bond, in which the ratio of the mass of the photopolymerization initiator I to the mass of the polymerizable monomer M is 0.15 or less. 1 Photopolymerization initiator I has a molar absorption coefficient of 12,000 L mol at a wavelength of 365 nm. -1 ·cm -1 Photopolymerization initiator I 1A photosensitive composition comprising: [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2008-165059 [Patent Document 2] Japanese Patent Application Laid-Open No. 2016-143064 [Patent Document 3] International Publication No. 2017 / 221620 [Patent Document 4] International Publication No. 2018 / 052024 [Patent Document 5] International Publication No. 2017 / 164161 Summary of the Invention [Problem to be solved by the invention]

[0008] However, none of the compositions disclosed in Patent Documents 1 to 5 were satisfactory in all respects of developability, adhesion, pattern shape, and solvent resistance.

[0009] An object of the present invention is to provide a photosensitive coloring composition that is excellent in developability, adhesion, pattern shape, and solvent resistance. [Means for solving the problem]

[0010] The present invention provides a photosensitive coloring 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, wherein the polymerizable compound (C) contains two or more compounds selected from the group of compounds represented by the following general formulas (1) to (4).

[0011] General formula (1) [ka] (In general formula (1), R1 and R3 each independently represent a hydrogen atom or a methyl group, R2 and R4 each independently represent an alkylene group, and k and l each independently represent an integer of 1 to 20.) General formula (2) [ka] (In general formula (2), R5 and R7 each independently represent a hydrogen atom or a methyl group, R6 and R8 each independently represent an alkylene group, and m and n each independently represent an integer of 0 to 5. When m and n are 0, they represent a single bond.) General formula (3) [ka] (In general formula (3), R9, R 11 each independently represents a hydrogen atom or a methyl group, R 10 , R 12 each independently represents an alkylene group, and p and q each independently represent an integer of 1 to 10. General formula (4) [ka] (In general formula (4), R 13 , R 15 each independently represents a hydrogen atom or a methyl group, R 14 , R 16 each independently represents an alkylene group, and x and y each independently represent an integer of 0 to 10. When x and y are 0, they represent a single bond. [Effects of the Invention]

[0012] According to the present invention, a photosensitive coloring composition having excellent developability, adhesion, pattern shape, and solvent resistance can be provided. The present invention also provides a color filter, an image display device, and a solid-state imaging device. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, the embodiment 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 embodiment, and can be modified and carried out within a range that can solve the problem.

[0014] In this specification, 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. Furthermore, "CI" refers to the Color Index (CI; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond. Furthermore, the molecular weight of the compound in the present invention is a calculated value or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry) for low molecular weight compounds whose molecular weight can be specified, and is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent for compounds having a molecular weight distribution.

[0015] <Photosensitive coloring composition> The photosensitive coloring composition of the present invention is a photosensitive coloring composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The photosensitive coloring composition contains the polymerizable compound (C) containing two or more compounds selected from the group consisting of compounds represented by the following general formulas (1) to (4). General formula (1) [ka] (In general formula (1), R1 and R3 each independently represent a hydrogen atom or a methyl group, R2 and R4 each independently represent an alkylene group, and k and l each independently represent an integer of 1 to 20.) General formula (2) [ka] (In general formula (2), R5 and R7 each independently represent a hydrogen atom or a methyl group, R6 and R8 each independently represent an alkylene group, and m and n each independently represent an integer of 0 to 5. When m and n are 0, they represent a single bond.) General formula (3) [ka] (In general formula (3), R9, R 11 each independently represents a hydrogen atom or a methyl group, R 10 , R 12 each independently represents an alkylene group, and p and q each independently represent an integer of 1 to 10. General formula (4) [ka] (In general formula (4), R 13 , R 15 each independently represents a hydrogen atom or a methyl group, R 14 , R 16 each independently represents an alkylene group, and x and y each independently represent an integer of 0 to 10. When x and y are 0, they represent a single bond.

[0016] [Colorant (A)] The photosensitive coloring composition of the present invention contains a colorant (A).

[0017] The colorant (A) is not particularly limited and may be either a pigment or a dye, which may be used in combination. Since color filters are required to have light resistance, heat resistance, and solvent resistance, pigments are preferred.

[0018] (pigment) The pigment is not particularly limited, and examples thereof include compounds classified as pigments in the Color Index.

[0019] Specific examples of red pigments that can be used in the present invention include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57: 2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177, 178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259 , 260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280,281,282,283,284,285,286,287,291,295,296, pigments described in JP 2014-134712 A, and pigments described in Japanese Patent No. 6368844 A can be mentioned. Among these, from the viewpoints of heat resistance, light fastness, and transmittance, CI Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 are preferred, and CI Pigment Red 177,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6368844 are particularly preferred.

[0020] Specific examples of orange pigments that can be used in the present invention include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0021] Specific examples of yellow pigments that can be used in the present invention include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 16 Nos. 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 the like. Among these, CI Pigment Yellows 138, 139, 150, 185, 231, and 233, and the pigments described in JP-A-2012-226110 are preferred.

[0022] 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. Of these, CI Pigment Green 36, 58, 59, 62, and 63 are preferred.

[0023] Specific examples of blue pigments that can be used in the present invention include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

[0024] Specific examples of purple pigments that can be used in the present invention include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 and 23 are preferred.

[0025] Specific examples of black pigments that can be used in the present invention include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0026] The photosensitive coloring composition of the present invention can also use inorganic pigments as the colorant (A), such as titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, and synthetic iron black.

[0027] (dye) The dye is not particularly limited, and examples thereof include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Furthermore, the dye may be in the form of a derivative thereof or a lake pigment obtained by laking a dye.

[0028] Furthermore, in the case of an acid dye having an acidic group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, it is preferable to use the acid dye as a salt-forming compound obtained by salt formation using an inorganic salt of the acid dye, a salt-forming compound of the acid dye with a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound, or a resin component having these functional groups, or to use the acid dye as a sulfonamide compound, which results in a coloring composition having excellent fastness, since the coloring composition has excellent resistance. Furthermore, a salt-forming compound of an acid dye with a compound having an onium salt group is also preferred because it has excellent fastness, and more preferably, the compound having an onium salt group is a resin having a cationic group in the side chain.

[0029] In the case of a basic dye, it can be used after being salted with an organic acid, perchloric acid, or a metal salt thereof. Among these, a salt-forming compound of a basic dye is preferred because of its excellent durability and compatibility with pigments, and it is more preferred to use a salt-forming compound obtained by salting a basic dye with a counter component acting as a counter ion, such as an organic sulfonic acid, an organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye.

[0030] Furthermore, when the dye skeleton has a polymerizable unsaturated group, the dye can be made to have excellent durability, which is preferable.

[0031] Examples of the chemical structure of the dye include azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene 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, and the like. Examples of the dye structure include, but are not limited to, dyes derived from dyes selected from tin dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0032] Among these dye structures, from the viewpoint of color properties such as hue, color separation, and color unevenness, dye structures derived from dyes selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and dye structures derived from dyes selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific dye compounds that can form the dye structure are described in "New Edition Dye Handbook" (edited by the Society of Organic Synthetic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyes and Colorists), "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986), etc.

[0033] The colorant (A) can be used alone or in combination of two or more kinds.

[0034] The content of the colorant (A) is preferably from 5 to 70 mass %, more preferably from 10 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0035] (Fine pigment particle size) The pigment is preferably micronized before use. The micronization method is not particularly limited, and for example, wet milling, dry milling, or solution precipitation can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the micronized pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0036] Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heat using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. Optimizing the conditions for salt milling a pigment can produce a pigment with an extremely fine primary particle size, a narrow distribution, and a sharp particle size distribution.

[0037] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from the standpoint of cost. From the standpoint of both treatment efficiency and production efficiency, 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 the pigment.

[0038] The water-soluble organic solvent functions to moisten the pigment and water-soluble inorganic salt. It is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, a high-boiling solvent with a boiling point of 120°C or higher is preferred for safety reasons. Examples of water-soluble organic solvents that can be used include 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, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

[0039] A resin may be added to the salt milling treatment as needed. By adding a resin, the pigment is coated with the resin, improving stability, light resistance, and the like. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, resins that are solid at room temperature and insoluble in water are preferred, and those that are partially soluble in the organic solvents mentioned above are also preferred. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[0040] [Alkali-soluble resin (B)] The photosensitive composition of the present invention contains an alkali-soluble resin (B).

[0041] The alkali-soluble resin (B) is not particularly limited, and known resins can be used.

[0042] The alkali-soluble resin (B) can be classified into a non-photosensitive alkali-soluble resin (B1) and a photosensitive alkali-soluble resin (B2). Among these, a photosensitive alkali-soluble resin (B2) is preferably included from the viewpoints of adhesion, pattern shape, and solvent resistance. Furthermore, the alkali-soluble resin (B) preferably contains an alkali-soluble group from the viewpoint of developability. Examples of the alkali-soluble group include a carboxyl group, a phosphate group, a sulfonic acid group, a hydroxyl group, and a phenolic hydroxyl group. Among these, a carboxyl group is preferred. The alkali-soluble resin (B) may contain a thermosetting group such as an epoxy group or an oxetanyl group.

[0043] (Non-photosensitive alkali-soluble resin (B1)) Examples of the non-photosensitive alkali-soluble resin (B1) include an acrylic resin having an acidic group, an α-olefin / maleic acid (anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth)acrylic acid copolymer, or an isobutylene / maleic acid (anhydride) copolymer, etc. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferred.

[0044] (Photosensitive alkali-soluble resin (B2)) The photosensitive alkali-soluble resin (B2) is an alkali-soluble resin having a polymerizable unsaturated group. The photosensitive alkali-soluble resin (B2) is preferably a resin synthesized by, for example, the following method (i) or (ii).

[0045] [Method (i)] In the method (i), for example, a polymer of an epoxy group-containing monomer and other monomers is first synthesized, and then a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain the photosensitive alkali-soluble resin (B2).

[0046] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0047] 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 styrenes 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 fatty acid vinyl compounds such as vinyl acetate or vinyl propionate; Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichloroethylene) N-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; Examples include phosphate group-containing monomers such as 2-(meth)acryloyloxyethyl acid phosphate and compounds obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer described below with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid, and these can be used alone or in combination of two or more types.

[0048] Examples of the monocarboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position, and these can be used alone or in combination of two or more types.

[0049] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these can be used alone or in combination of two or more. If necessary, the remaining anhydride groups can also be hydrolyzed using a tricarboxylic acid dianhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic anhydride.

[0050] In addition, as a method similar to method (i), for example, a polymer of a carboxyl group-containing monomer and other monomers is synthesized, and then an epoxy group-containing monomer is added to some of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin (B2).

[0051] [Method (ii)] In the method (ii), for example, a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers is synthesized, and then the hydroxyl group of the polymer is reacted with the isocyanate group of an isocyanate group-containing monomer.

[0052] Examples of hydroxyl group-containing monomers include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to a hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by addition polymerization of poly(γ-valerolactone), poly(ε-caprolactone), and / or poly(12-hydroxystearic acid). These can be used alone or in combination. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred in terms of their resistance to foreign matter formation in the coating. Furthermore, glycerol mono(meth)acrylate is preferred in terms of photosensitivity.

[0053] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate, and these can be used alone or in combination of two or more.

[0054] The monocarboxyl group-containing monomer and other monomers may be the same as those mentioned above.

[0055] The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably from 2,000 to 40,000, more preferably from 3,000 to 300,000, and particularly preferably from 5,000 to 25,000.The value of Mw / Mn is preferably 10 or less.

[0056] The acid value of the alkali-soluble resin (B) is preferably from 50 to 200 mgKOH / g, more preferably from 70 to 180 mgKOH / g.

[0057] The alkali-soluble resin (B) can be used alone or in combination of two or more. From the viewpoints of developability, adhesion, pattern shape, and solvent resistance, it is preferable to use two or more photosensitive alkali-soluble resins (B2) having different weight-average molecular weights (Mw). Among these, it is preferable to use a photosensitive alkali-soluble resin (B2) having a weight-average molecular weight (Mw) of 12,000 or less in combination with a photosensitive alkali-soluble resin (B2) having a weight-average molecular weight (Mw) of 18,000 or more in combination, and it is more preferable to use a photosensitive alkali-soluble resin (B2) having a weight-average molecular weight (Mw) of 5,000 to 10,000 in combination with a photosensitive alkali-soluble resin (B2) having a weight-average molecular weight (Mw) of 20,000 to 25,000 in combination.

[0058] The mass ratio of the photosensitive alkali-soluble resin (B2) having a weight-average molecular weight (Mw) of 12,000 or less to the photosensitive alkali-soluble resin (B2) having a weight-average molecular weight (Mw) of 18,000 or more is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, from the viewpoints of developability, adhesion, pattern shape, and solvent resistance.

[0059] The content of the alkali-soluble resin (B) is preferably from 20 to 400 parts by mass, more preferably from 30 to 250 parts by mass, relative to 100 parts by mass of the colorant (A).

[0060] [Polymerizable compound (C)] The photosensitive coloring composition of the present invention contains, as the polymerizable compound (C), two or more compounds selected from the group consisting of compounds represented by the following general formulas (1) to (4).

[0061] General formula (1) [ka] (In general formula (1), R1 and R3 each independently represent a hydrogen atom or a methyl group, R2 and R4 each independently represent an alkylene group, and k and l each independently represent an integer of 1 to 20.) General formula (2) [ka] (In general formula (2), R5 and R7 each independently represent a hydrogen atom or a methyl group, R6 and R8 each independently represent an alkylene group, and m and n each independently represent an integer of 0 to 5. When m and n are 0, they represent a single bond.) General formula (3) [ka] (In general formula (3), R9, R 11 each independently represents a hydrogen atom or a methyl group, R 10 , R 12 each independently represents an alkylene group, and p and q each independently represent an integer of 1 to 10. General formula (4) [ka] (In general formula (4), R 13 , R 15 each independently represents a hydrogen atom or a methyl group, R 14 , R 16each independently represents an alkylene group, and x and y each independently represent an integer of 0 to 10. When x and y are 0, they represent a single bond.

[0062] When the polymerizable compound (C) contains two or more compounds selected from the group consisting of compounds represented by general formulas (1) to (4), the developability, adhesion, pattern shape, and solvent resistance are improved. Although the detailed mechanism is unclear, it is believed that the compounds represented by general formulas (1) to (4) have multiple aromatic rings in each molecule, which allows molecules to stack tightly together through π-π interactions, improving film adhesion. Furthermore, because they have a bulky structure, the uniform distribution of polymerizable unsaturated groups throughout the film is thought to enhance curability and improve adhesion. Furthermore, because compounds with different structures are polymerized, the polymer has a random structure, and because there are two polymerizable unsaturated groups, it has an appropriate cross-linking density. As a result, the coating film is easy to develop and has a structure that softens moderately when exposed to heat. This is thought to cause thermal sagging of the pattern during post-baking, resulting in a good cross-sectional pattern shape.

[0063] (Compound represented by general formula (1)) Specific examples of the compound represented by general formula (1) include the following compounds.

[0064] [ka]

[0065] Among these, compounds of chemical formula (1-2) and chemical formula (1-3) are preferred from the viewpoints of adhesion and pattern shape.

[0066] (Compound represented by general formula (2)) Specific examples of the compound represented by general formula (2) include the following compounds.

[0067] [ka]

[0068] Among these, the compound of chemical formula (2-1) is preferred from the viewpoints of adhesion and pattern shape.

[0069] (Compound represented by general formula (3)) Specific examples of the compound represented by general formula (3) include the following compounds.

[0070] [ka]

[0071] Among these, the compounds of the chemical formula (3-1) and the chemical formula (3-2) are preferred from the viewpoints of adhesion and pattern shape.

[0072] (Compound represented by general formula (4)) Specific examples of the compound represented by general formula (4) include the following compounds.

[0073] [ka]

[0074] Among these, the compound of chemical formula (4-1) is preferred from the viewpoints of adhesion and pattern shape.

[0075] From the viewpoints of adhesion and pattern shape, the total content of the compounds represented by general formulas (1) to (4) is preferably 50% by mass or more, more preferably 70% by mass or more, and particularly preferably 90% by mass or more, based on 100% by mass of the polymerizable compound (C).

[0076] From the viewpoints of adhesion and pattern shape, the polymerizable compound (C) preferably contains at least a compound represented by general formula (1) or a compound represented by general formula (3), and more preferably contains at least a compound represented by general formula (1) and a compound represented by general formula (3).

[0077] From the viewpoints of adhesion and pattern shape, the total content of the compound represented by general formula (1) and the compound represented by general formula (3) is preferably 10% by mass or more, and more preferably 20% by mass or more, of the total content of the compounds represented by general formulas (1) to (4) (100% by mass). In this calculation, any one or more of the compounds represented by general formulas (1) to (4) may be 0% by mass.

[0078] (Compounds other than compounds represented by general formulas (1) to (4)) The polymerizable compound (C) can contain polymerizable compounds other than the compounds represented by the general formulae (1) to (4) (hereinafter also referred to as other polymerizable compounds).

[0079] Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, Examples of suitable acrylic acid esters include acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylate, and various acrylic acid esters and methacrylic acid esters such as urethane (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.

[0080] Other commercially available polymerizable compounds include, for example, KAYARAD manufactured by Nippon Kayaku Co., Ltd. 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, Aronix M-303, M-305, M-306, M-309, M-310, 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, Viscoat #2500P, UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Co., Ltd., NK Ester A-DOG, A-DCP, A-9300, UA-160TM, U-15HA, 1100H manufactured by Shin-Nakamura Chemical Co., Ltd., AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., and EBECRLY220, 1290, 4513, 5129 manufactured by Daicel-Allnex Corporation.

[0081] Among these, from the viewpoint of developability, it is preferable to contain a compound having an acid group, such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group.

[0082] Examples of the compound having an acid group include an esterification product of a dicarboxylic acid and a free hydroxyl group-containing poly(meth)acrylate of a polyhydric alcohol and (meth)acrylic acid; an esterification product of a polycarboxylic acid and a (meth)acrylate having a hydroxyl group; and a compound obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate and then adding a mercapto compound having a carboxyl group to the product. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol. Examples of the dicarboxylic acid include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like. Examples of the polycarboxylic acid include trimellitic acid and pyromellitic acid. Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate. Examples of the polyfunctional isocyanate include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, and 2,6-diisocyanate. Examples of the isocyanate-benzyl chloride include bis(isocyanatemethyl)benzene, butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, and bis(isocyanatemethyl)cyclohexane. Also included are their biuret derivatives, isocyanate nurate derivatives, and trimethylolpropane adducts. Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0083] Examples of commercially available compounds having an acid group include Viscoat #2500P manufactured by Osaka Organic Chemicals, and Aronix M-5300, M-5400, M-5700, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd.

[0084] From the viewpoints of developability, adhesion, and pattern shape, the content of other polymerizable compounds is preferably less than 10% by mass relative to 100% by mass of the polymerizable compound (C).

[0085] The content of the polymerizable compound (C) is preferably from 1 to 60 mass %, more preferably from 5 to 55 mass %, particularly preferably from 10 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0086] [Photopolymerization initiator (D)] The photosensitive coloring composition of the present invention contains a photopolymerization initiator (D). By containing the photopolymerization initiator (D), the photosensitive coloring composition can be cured by ultraviolet irradiation to form a cured film.

[0087] The photopolymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating 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-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the compound include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.

[0088] Commercially available products include acetophenone compounds such as Omnirad 907, 369, and 379EG manufactured by IGM Resins; acylphosphine compounds such as Omnirad 819 and TPO manufactured by IGM Resins; oxime compounds such as IRGACURE OXE-01, 02, 03, and 04 manufactured by BASF Japan Ltd.; N-1919, 730, 831, and 930 manufactured by ADEKA Corporation; TRONLY TR-PBG-301, 304, 305, 309, 345, 346, 358, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd.; Omnirad 1312, 1314, and 1316 manufactured by IGM Resins; SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation; and DFI-020, 306, and EOX-01 manufactured by Daito Chemiks Co., Ltd. Further examples include oxime compounds described in JP 2005-215378 A, JP 2011-105713 A, JP 2017-523465 A, JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, WO 2015 / 036910, and the like.

[0089] Among these, oxime compounds are preferred from the viewpoints of reactivity and pattern formability.

[0090] The photopolymerization initiator (D) can be used alone or in combination of two or more kinds.

[0091] From the viewpoints of adhesion and pattern shape, the content of the photopolymerization initiator (D) is preferably 0.5 to 10 parts by mass, and more preferably 1 to 5 parts by mass, per 100 parts by mass of the total content of the photosensitive alkali-soluble resin (B2) and the polymerizable compound (C).

[0092] [Dye derivative (E)] The photosensitive coloring composition of the present invention can contain a dye derivative (E) as needed. When the dye derivative (E) is adsorbed to the surface of the colorant (A), the surface of the colorant (A) becomes polar, which increases affinity with other components, thereby improving dispersibility. When calculating the content of the colorant (A) when the dye derivative (E) is contained, the dye derivative (E) is calculated as part of the colorant (A).

[0093] Examples of the dye derivative (E) include dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. Examples of the dye derivative (E) include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0094] Specifically, diketopyrrolopyrrole dye derivatives are disclosed in JP 2001-220520 A, WO 2009 / 081930 A, WO 2011 / 052617 A, WO 2012 / 102399 A, and JP 2017-156397 A, phthalocyanine dye derivatives are disclosed in JP 2007-226161 A, WO 2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A, and anthraquinone dye derivatives are disclosed in JP 63-26 A 4674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009 / 025325; quinacridone dye derivatives are disclosed in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; dioxazine dye derivatives are disclosed in JP-A-2011-162662; thiazine indigo dye derivatives are disclosed in JP-A-2007-314785; Azine dye derivatives are disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681; benzisoindole dye derivatives are disclosed in JP-A-2009-57478; quinophthalone dye derivatives are disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-2 Examples of known dye derivatives include those described in JP-A-26110, naphthol dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439, azo dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092, acidic substituents include those described in JP-A-2004-307854, and basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, etc. In these documents, the dye derivative is sometimes referred to as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

[0095] The dye derivative (E) can be used alone or in combination of two or more kinds.

[0096] The content of the dye derivative (E) is preferably from 1 to 20 parts by mass, more preferably from 2 to 10 parts by mass, relative to 100 parts by mass of the total of the colorant (A) and the dye derivative (E).

[0097] [Dispersion resin (F)] The photosensitive coloring composition of the present invention can contain a dispersing resin (F).

[0098] The dispersion resin (F) is not particularly limited, and any known resin can be used as long as it has dispersibility. Among them, it is preferable that the dispersion resin (F) has an adsorption group with high affinity for the colorant, and it is more preferable that the adsorption group has at least one of a basic group and an acidic group. When an alkali-soluble dispersion resin (F) is included, the alkali-soluble dispersion resin (F) is counted as the alkali-soluble resin (B) when calculating the content of the alkali-soluble resin (B).

[0099] Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle.

[0100] Examples of the acidic group include a carboxyl group, a phosphate group, a sulfonic acid group, etc. Among these, the carboxyl group and the phosphate group are preferred from the viewpoint of adsorption onto the pigment and developability.

[0101] Examples of resin types for the dispersion resin (F) 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 phosphate salts, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof, 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 alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0102] Examples of the structure of the dispersing resin (F) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of dispersion stability, the block structure, the graft structure, and the comb structure are preferred.

[0103] Commercially available dispersion resins (F) 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, and 2164 manufactured by BYK Japan, as well as Anti-Terra-U203 and 204, and BYK-P104 and P104S. , 220S, or Lactimon, Lactimon-WS, or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36 600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 455 manufactured by BASF Japan 0, 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., Inc., and resins described in JP-A Nos. 2008-029901, 2009-155406, 2010-185934, 2011-157416, etc.

[0104] The dispersing resin (F) can be used alone or in combination of two or more kinds.

[0105] From the viewpoint of dispersion stability, the content of the dispersing resin (F) is preferably from 3 to 200 parts by mass, more preferably from 5 to 100 parts by mass, relative to 100 parts by mass of the colorant (A).

[0106] [Sensitizer (G)] The photosensitive coloring composition of the present invention can contain a sensitizer (G).

[0107] Examples of the sensitizer (G) include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyra. Examples of suitable ruthenium compounds include ruthenium ether derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxy esters, acyl oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4′-diethylisophthalophenone, 3,3′ or 4,4′-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4′-bis(diethylamino)benzophenone.

[0108] Among the sensitizers (G), thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. Specific examples of preferred compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole.

[0109] The sensitizer (G) can be used alone or in combination of two or more kinds.

[0110] The content of the sensitizer (G) is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the photopolymerization initiator (D). When an appropriate amount is contained, photocurability and developability are improved.

[0111] [Thermosetting compound (H)] The photosensitive coloring composition of the present invention can contain a thermosetting compound (H), which reacts in the heating step to increase the crosslink density and improve the heat resistance.

[0112] The thermosetting compound (H) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (H) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0113] (Epoxy compound (H1)) Examples of the epoxy compound (H1) include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), polycondensates of 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.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.), and polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.). Examples of suitable epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins.

[0114] Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celloxide 2021, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, Ltd., and the like.

[0115] The content of the epoxy compound (H1) is preferably from 0.5 to 50 mass %, more preferably from 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0116] (Oxetane Compound (H2)) The oxetane compound (H2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0117] Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0118] Examples of commercially available products include OXE-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101,212 manufactured by Toagosei Co., Ltd.

[0119] Examples of the bifunctional oxetane compound 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, ethyleneglycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenylbis(3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether, and the like.

[0120] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0121] Examples of trifunctional or higher oxetane compounds 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 dipentaerythritol. Examples of such polymers include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing an oxetane group (for example, 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 above-mentioned OXE-30.

[0122] The content of the oxetane compound (H2) is preferably from 0.5 to 50 mass %, more preferably from 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0123] The melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol or ether type compound, and more preferably a melamine compound having an average of 5.0 or more methylol groups and / or ether groups per melamine ring. Having an appropriate number of methylol groups or ether groups makes it easier to obtain just the right amount of heat resistance.

[0124] Examples of commercially available products include Nikalac 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 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries Co., Ltd.

[0125] Among these, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, and MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, and 350 manufactured by Nippon Cytec Industries Co., Ltd., which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are preferred in terms of increasing crosslink density.

[0126] The thermosetting compound (H) can be used alone or in combination of two or more kinds.

[0127] [Curing agent (curing accelerator)] The photosensitive coloring composition of the present invention can be used in combination with a curing agent (curing accelerator) to aid in the curing of the thermosetting compound (H). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent 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 derivative bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Examples of suitable amines include 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine, etc.), and 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.).

[0128] The curing agents can be used alone or in combination of two or more.

[0129] The content of the curing agent is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting compound (H).

[0130] [Thiol-based chain transfer agents (I)] The photosensitive coloring composition of the present invention can contain a thiol-based chain transfer agent (I). When the thiol-based chain transfer agent (I) is used in combination with a photopolymerization initiator (D), a thiyl radical that is resistant to polymerization inhibition by oxygen is generated during radical polymerization after light irradiation, thereby improving the photosensitivity of the photosensitive coloring composition.

[0131] The thiol chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). The thiol chain transfer agent more preferably 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.

[0132] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples of the thiopropionate include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0133] The thiol chain transfer agent (I) can be used alone or in combination of two or more kinds.

[0134] The content of the thiol chain transfer agent (I) is preferably 1 to 10 mass %, more preferably 2 to 8 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, photosensitivity is improved and wrinkles are less likely to occur on the pattern surface.

[0135] [Polymerization inhibitor (J)] The photosensitive coloring composition of the present invention may contain a polymerization inhibitor (J).

[0136] Examples of the polymerization inhibitor (J) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol; alkylresorcinol compounds such as 4-n-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 tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucinol.

[0137] The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0138] [Ultraviolet absorber (K)] The photosensitive coloring composition of the present invention may contain an ultraviolet absorber (K).

[0139] The ultraviolet absorber (K) is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0140] Examples of benzotriazole compounds include 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-methylethoxybenzotriazole. Mixture of methyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and straight chain alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl) 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, Examples of suitable hydroxybenzotriazoles 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-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0141] Examples of commercially available products include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Japan Ltd., ADK STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA Corporation, KEMISORB71, 73, 74, 79, and 279 manufactured by Chemipro Chemical Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

[0142] Examples of triazine compounds include 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-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0143] Examples of commercially available products include KEMISORB102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF Japan, ADK STAB LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

[0144] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-oxide, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-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.

[0145] Examples of commercially available products include KEMISORB10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB101 and 107 manufactured by Shipro Chemicals, Adekastab 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

[0146] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0147] The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator (D) and the ultraviolet absorber (K).

[0148] [Antioxidant (L)] The photosensitive coloring composition of the present invention can contain an antioxidant (L). The antioxidant (L) prevents the photopolymerization initiator (D) and thermosetting compound (H) contained in the photosensitive coloring composition from yellowing due to oxidation during the thermal process of thermal curing or ITO annealing. In particular, when the concentration of colorant (A) in the photosensitive coloring composition is high, the content of polymerizable compound (C) is relatively reduced, and if the amount of photopolymerization initiator (D) is increased or the thermosetting compound (H) is added to address this issue, the cured film is likely to yellow. Therefore, the inclusion of an antioxidant prevents yellowing of the cured film due to oxidation during the heating process.

[0149] Examples of the antioxidant (L) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

[0150] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0151] Examples of hindered phenol antioxidants include 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), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl 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-hydroxy-hydrocinnamamide), 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-hexanediol bis[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-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), and 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol.

[0152] Examples of commercially available products include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA Corporation, KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd., and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0153] Examples of the hindered amine antioxidant include 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-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl tetramethyl-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-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bi N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,6,6-tetramethyl-4-piperidyl ...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.

[0154] Examples of commercially available products include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION, KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals, Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan, and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical.

[0155] Examples of phosphorus-based antioxidants include 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 to C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidene Diphenyl alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol 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 ethyl bis(2,4-di-t-butyl-6-methylphenyl)phosphite.

[0156] Examples of commercially available products include Adeka Stab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA Corporation, IRGAFOS168 manufactured by BASF Japan, and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0157] 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.

[0158] Examples of commercially available products include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0159] The antioxidant (L) can be used alone or in combination of two or more kinds.

[0160] The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

[0161] [Leveling agent (M)] The photosensitive coloring composition of the present invention can contain a leveling agent (M). This improves the wettability and drying properties of the composition to the substrate during application. Examples of the leveling agent (M) include silicon-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0162] Examples of silicone surfactants include linear polymers formed from siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0163] 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, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002 and 211 manufactured by Dow Corning Toray Co., Ltd. 0, 2122, 2123, 2191, 5609, and X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0164] Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

[0165] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Futergent 602A manufactured by Neos Corporation.

[0166] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. 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, alkyl imidazoline, and the like.

[0167] Commercially available products include, for example, 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, and L manufactured by Kao Corporation. 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, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0168] Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0169] Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, manufactured by Kao Corporation.

[0170] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0171] Examples of commercially available products include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0172] 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.

[0173] Commercially available products include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0174] The leveling agent (M) can be used alone or in combination of two or more kinds.

[0175] The content of the leveling agent (M) is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition. Within this range, the balance between the coatability and adhesion of the photosensitive coloring composition is further improved.

[0176] [Storage stabilizer (N)] The photosensitive coloring composition of the present invention can contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive coloring composition over time. Examples of the storage stabilizer (N) include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

[0177] The content of the storage stabilizer (N) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the colorant (A).

[0178] [Adhesion improver (O)] The photosensitive coloring composition of the present invention may contain an adhesion improver (O), which improves the adhesion between the cured film and the substrate and also makes it easier to form narrow patterns by photolithography.

[0179] Examples of the adhesion improver (O) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl) silane coupling agents such as aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl compounds such as p-styryltrimethoxysilane; ureido compounds such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

[0180] The adhesion improver (O) can be used alone or in combination of two or more kinds.

[0181] The content of the adhesion improver (O) is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, relative to 100 parts by mass of the colorant (A).

[0182] [Organic solvent (P)] The photosensitive composition of the present invention may contain an organic solvent (P).

[0183] Examples of the organic solvent (P) include 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-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyro 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 of the alkyl esters 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, and dibasic acid esters. Among these, from the viewpoints 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.

[0184] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0185] [Method for producing photosensitive coloring composition] The photosensitive coloring composition of the present invention can be produced by, for example, adding a colorant (A), a dye derivative (E), a dispersing resin (F), an organic solvent (P), and the like and dispersing the mixture. The dispersion can then be mixed with an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). The timing of mixing each material can be arbitrary. The dispersion process can also be performed multiple times.

[0186] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0187] The average dispersed particle size (secondary particle size) of the colorant (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the colorant (A) has an appropriate particle size, it is easy to obtain a photosensitive coloring composition with high dispersion stability.

[0188] The average dispersed particle size (secondary particle size) is measured using, for example, Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and the D50 particle size set to the average size. The dilution solvent used for measurement is the same organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to provide results with little variation.

[0189] The photosensitive coloring composition is preferably subjected to centrifugation, filtration using a sintered filter or a membrane filter, etc., to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and dust particles mixed in. The photosensitive coloring composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0190] <Color filter> The color filter of the present invention includes 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. The color filter can also have magenta, cyan, and yellow filter segments instead of or in addition to the color filter segments. The substrate may be a transparent substrate or a reflective substrate. The transparent substrate may be, for example, a glass substrate. The reflective substrate may be, for example, a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0191] [Color filter manufacturing method] The method for producing a color filter is not particularly limited, and the color filter can be produced, for example, by carrying out the following steps: step (1) of applying a photosensitive coloring composition onto a substrate to form a layer of the composition; step (2) of exposing the layer to light in a pattern through a mask; step (3) of developing the unexposed portions with an alkali to form a patterned cured film; and step (4) of heat-treating (post-baking) the pattern.

[0192] The method for producing a color filter will be described in detail below. (Process (1)) In the step (1) of forming a composition layer, the photosensitive coloring composition is applied onto a substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and then dried (pre-baked) at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, a hot plate, or the like, as needed. Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have an imaging element such as a CCD or a CMOS formed on its surface. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with upper layers, prevent diffusion of substances, and flatten the substrate surface. The coating is preferably carried out so that the layer has a thickness of 0.05 to 10.0 μm after drying, and more preferably 0.3 to 5 μm.

[0193] (Process (2)) In the exposure step, the layer obtained in step (1) is exposed to light in a specific pattern through a mask using an exposure device such as a stepper, thereby obtaining a cured film. Examples of radiation used for exposure include ultraviolet rays such as g-rays, h-rays, and i-rays.

[0194] (Step (3)) The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the composition layer in the unexposed areas is dissolved in an alkaline aqueous solution, leaving only the cured areas, thereby obtaining a patterned cured film. Examples of the developer 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, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the developer is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses pattern roughening and peeling, and improves the remaining film rate after development.

[0195] Examples of the developing method include a dipping method, a spraying method, a puddling method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0196] (Step (4)) The heat treatment (post-baking) is performed by heating the patterned cured film obtained in step (3) to sufficiently cure it. The heating temperature for post-baking is preferably 100 to 300° C., more preferably 150 to 250° C. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

[0197] <Image display device> The image display device of the present invention comprises the color filter of the present invention. The configuration used for 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) can be mentioned. The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Nobuaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0198] <Solid-state imaging element> The solid-state imaging device of the present invention comprises the color filter of the present invention. The solid-state imaging device may be formed in any suitable form, including, for example, a substrate having a plurality of photodiodes constituting the light-receiving area of ​​the solid-state imaging device (e.g., a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like; a light-shielding film formed on the photodiodes and transfer electrodes, with only the light-receiving portions of the photodiodes exposed; a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes; and a color filter on the device protection film. Furthermore, the device protection film may have a light-focusing means (e.g., a microlens, etc.; the same applies hereinafter) on the device protection film below the color filter (closer to the substrate), or a light-focusing means on the color filter. The color filter may have a structure in which a cured film forming each color pixel is embedded in spaces partitioned by partition walls, for example, in a grid pattern. In this case, the partition walls preferably have a low refractive index relative to the color pixels. An imaging device including a solid-state imaging element of the present invention can be used for digital cameras, electronic devices with imaging functions (such as mobile phones and smartphones), as well as in-vehicle cameras and surveillance cameras. [Example]

[0199] 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" means "parts by mass" and "%" means "% by mass."

[0200] Before describing the examples, each measurement method will be explained. The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are as follows:

[0201] (Average molecular weight of alkali-soluble resin and dispersing resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the alkali-soluble resin and dispersion resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was a Tosoh HLC-8220GPC. Two separation columns were connected in series, and both columns were packed with TSK-GEL SUPER HZM-N. Measurements were performed at an oven temperature of 40°C, a 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 was injected. The molecular weight is expressed in terms of polystyrene.

[0202] (Acid value of alkali-soluble resin and dispersion resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of alkali-soluble resin and dispersed resin solution, and the mixture was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant to measure the acid value (mg KOH / g). The acid value per unit of nonvolatile content of the resin was then calculated from the acid value of the resin solution and the concentration of nonvolatile content of the resin solution.

[0203] (Amine value of dispersion resin) The amine value of the dispersing resin is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into nonvolatile content.

[0204] <Production of Colorant (A)> (Finely divided green pigment (A-1)) 100 parts of CI Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70° C. This kneaded mixture was poured into 3,000 parts of warm water and stirred for 1 hour while heating to 70° C. to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80° C. to obtain a finely divided green pigment (A-1).

[0205] (Finely divided yellow pigment (A-2)) 100 parts of CI Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 80° C. This mixture was poured into 2,000 parts of warm water and stirred for 1 hour while heating to 80° C. to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80° C. to obtain a finely divided yellow pigment (A-2).

[0206] <Production of alkali-soluble resin (B)> (Non-photosensitive alkali-soluble resin (B1-1) solution) A separable four-neck flask was fitted with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 196 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and purged with nitrogen. Then, a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd.'s "Aronix M110"), and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the addition was complete, the reaction was continued for another 2 hours to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate (PGMAc) was added to obtain a non-photosensitive alkali-soluble resin (B1-1) solution with a weight-average molecular weight (Mw) of 20,000.

[0207] (Photosensitive alkali-soluble resin (B2-1) solution) A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 333 parts of PGMAc, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and then a solution 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 a tricyclodecane-skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 5.0 parts of azobisisobutyronitrile added to a mixture of 164 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued at 100°C for an additional 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 parts (0.5 mol, 100 mol% relative to the glycidyl groups of the glycidyl methacrylate used in this reaction) of methacrylic acid, 0.9 parts of tris(dimethylaminomethyl)phenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110°C for 6 hours and terminated when the nonvolatile acid value reached 1 mgKOH / g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the reaction was continued at 120°C for 3.5 hours to obtain a resin solution with an acid value of 80 mgKOH / g. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to obtain a photosensitive alkali-soluble resin (B2-1) solution with a weight-average molecular weight (Mw) of 9,000.

[0208] (Photosensitive alkali-soluble resin (B2-2) solution) A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 182 parts of PGMAc, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and a solution of 3.0 parts of azobisisobutyronitrile added to a mixture 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 a tricyclodecane-based monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 136 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for a further 5 hours at 100°C. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol (50 mol% relative to the carboxyl groups of the methacrylic acid used in this reaction)], 0.9 parts of tris(dimethylaminomethyl)phenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued for 6 hours at 110 °C to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content. PGMAc was added to obtain a photosensitive alkali-soluble resin (B2-2) solution with a nonvolatile content of 20% by weight. The weight-average molecular weight (Mw) was 14,960.

[0209] (Photosensitive alkali-soluble resin (B2-3) solution) A separable four-neck flask was fitted with a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirrer. 207 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and purged with nitrogen. A mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd., Aronix M110), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 0.99 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the addition was complete, the reaction was continued for another 3 hours to obtain a resin solution. The resulting resin solution was then stirred while stopping the nitrogen gas flow and injecting dry air for 1 hour. After cooling to room temperature, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenzu MOI, Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70°C over 3 hours. After the addition was completed, the reaction was continued for another hour to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to obtain a photosensitive alkali-soluble resin (B2-3) solution. The weight-average molecular weight (Mw) was 22,050.

[0210] <Production of other polymerizable compounds> (Compounds with acid groups) A five-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the IR reading was 2180 cm. -1 The disappearance of the isocyanate absorption was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were added and reacted for 6 hours at a temperature of 50 to 60°C. The nonvolatile content was adjusted to 50% by mass, and a urethane acrylate solution (C-10) having an average of 9 polymerizable unsaturated groups and an acid group was obtained.

[0211] <Production of Dispersion Resin (F)> (Dispersion resin (F-1) solution) A reaction vessel equipped with a gas inlet tube, thermostat, condenser, and stirrer was charged with 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts i-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts PGMAc, and the atmosphere was purged with nitrogen gas. The reaction vessel was heated to 50°C with stirring, and 12 parts 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts 2,2'-azobisisobutyronitrile and 90 parts PGMAc was added while the reaction was continued for 7 hours. Measurement of the nonvolatile content confirmed that 95% reaction had occurred. 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 continued for 7 hours at 100°C. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. PGMAc was added to dilute the solution so that the non-volatile content was 30%, yielding a dispersion resin (F-1) solution with an acid value of 70 mgKOH / g and a weight-average molecular weight of 8,500.

[0212] (Dispersion resin (F-2) solution) A 500 mL round-bottom, four-neck separable flask equipped with a condenser, a dropping funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer was charged with 250 parts by weight of tetrahydrofuran (THF) and 5.81 parts by weight of the initiator dimethylketene methyltrimethylsilyl acetal via the dropping funnel, and the atmosphere was thoroughly purged with nitrogen. 0.5 parts by weight of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was added using a syringe, and solvent-compatible blocking monomers (19.7 parts by weight of 2-hydroxyethyl methacrylate, 7.5 parts by weight of 2-ethylhexyl methacrylate, 12.9 parts by weight of n-butyl methacrylate, 10.7 parts by weight of benzyl methacrylate, and 30.9 parts by weight of methyl methacrylate) were added dropwise over 60 minutes using the dropping funnel. The temperature of the reaction flask was maintained below 40 °C by cooling in an ice bath. After 1 hour, 18.3 parts by weight of dimethylaminopropyl methacrylamide, a monomer for the colorant adsorption functional block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by weight of methanol was added to terminate the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, filtered, and purified by vacuum drying. Next, 15.0 parts by mass of the obtained block copolymer were dissolved in 35 parts by mass of PGMAc in a 100 mL round-bottom flask, and 1.1 parts by mass of phenylphosphinic acid (0.5 molar equivalents relative to dimethylaminopropylmethacrylamide), a salt-forming component, was added. The mixture was stirred at a reaction temperature of 30°C for 20 hours, and PGMAc was added to adjust the content, yielding a dispersion resin (F-2) solution with a non-volatile content of 30%.

[0213] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, then dispersed in an Eiger mill (Eiger Japan, "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The organic solvent (P-1) was PGMAc. Finely divided green pigment (A-1): 10.5 parts Finely divided yellow pigment (A-2): 4.5 parts Dispersion resin (F-1) solution: 11.0 parts Dispersion resin (F-2) solution: 11.0 parts Organic solvent (P-1): 63.0 parts

[0214] <Production of Photosensitive Coloring Composition> [Example 1] (Photosensitive coloring composition 1) The following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition 1. Dispersion 1: 50.0 parts Photosensitive alkali-soluble resin (B2-1) solution: 11.5 parts Photosensitive alkali-soluble resin (B2-3) solution: 8.5 parts Polymerizable compound (C-1): 2.5 parts Polymerizable compound (C-4): 0.5 part Photopolymerization initiator (D-1): 0.15 parts Leveling agent (M): 1.0 part Organic solvent (P): 25.85 parts

[0215] [Examples 2 to 32, Comparative Examples 1 to 9] (Photosensitive compositions 2-41) Photosensitive coloring compositions 2 to 41 were prepared in the same manner as in Example 1, except that the photosensitive coloring composition 1 of Example 1 was changed to the raw materials and amounts shown in Tables 1-1 to 1-4.

[0216] [Table 1-1]

[0217] [Table 1-2]

[0218] [Table 1-3]

[0219] [Table 1-4]

[0220] The raw materials listed in Tables 1-1 to 1-4 are as follows:

[0221] [Polymerizable compound (C)] (Compound represented by general formula (1)) C-1: NK Ester ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd., a compound represented by chemical formula (1-2)) C-2: NK Ester A-BEP-4 (manufactured by Shin-Nakamura Chemical Co., Ltd., a compound represented by chemical formula (1-3)) C-3: NK Ester A-BEP-10 (manufactured by Shin-Nakamura Chemical Co., Ltd., a compound represented by chemical formula (1-4)) (Compound represented by general formula (2)) C-4: Epoxy Ester 3000A (manufactured by Kyoeisha Chemical Co., Ltd., a compound represented by chemical formula (2-1)) C-5: Epoxy ester 3002A(N) (manufactured by Kyoeisha Chemical Co., Ltd., a compound represented by chemical formula (2-3)) (Compound represented by general formula (3)) C-6: OGSOL EA-0200 (Osaka Gas Chemicals Co., Ltd., compound represented by chemical formula (3-1)) C-7: OGSOL EA-0300 (Osaka Gas Chemicals Co., Ltd., compound represented by chemical formula (3-2)) (Compound represented by general formula (4)) C-8: OGSOL GA-5060P (Osaka Gas Chemicals, compound represented by chemical formula (4-1)) C-9: OGSOL GA-2800 (Osaka Gas Chemicals, compound represented by chemical formula (4-2)) (Other polymerizable compounds) C-10: The above-mentioned urethane acrylate solution having an average of 9 polymerizable unsaturated groups and an acid group. C-11: NK Ester A-DCP (Shin-Nakamura Chemical Co., Ltd., tricyclodecane dimethanol diacrylate) C-12: Aronix M-350 (manufactured by Toagosei Co., Ltd., trimethylolpropane ethylene oxide modified triacrylate) C-13: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

[0222] [Photopolymerization initiator (D)] (oxime compounds) D-1: ADEKA Cruise NCI-831 (ADEKA Corporation) D-2: Irgacure OXE-04 (BASF) (Acetophenone compounds) ·D-3: Omnirad907 (manufactured by IGM Resins)

[0223] [Leveling agent (M)] One part each of BYK-330 (manufactured by BYK-Chemie) and Megafac F-551 (manufactured by DIC Corporation) was mixed and dissolved in 98 parts of PGMAc to form a mixed solution, which was used as a leveling agent (M).

[0224] [Organic solvent (P)] 80 parts of propylene glycol monomethyl ether acetate, 10 parts of cyclohexanone, and 10 parts of ethyl 3-ethoxypropionate were mixed to prepare an organic solvent (P).

[0225] <Evaluation of Photosensitive Coloring Composition> The resulting photosensitive coloring compositions 1 to 41 were evaluated for developability, adhesion, pattern shape, and solvent resistance by the following methods. The evaluation results are shown in Table 2.

[0226] [Developability evaluation] The obtained photosensitive coloring compositions 1 to 41 were applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness was 2.0 μm, and then dried on a hot plate at 70°C for 1 minute. Then, an ultra-high pressure mercury lamp was used to apply the coating with an illuminance of 30 mW / cm. 2 , 50 mJ / cm 2The substrate was exposed to ultraviolet light through a photomask with a 100 μm wide stripe pattern. After cooling to room temperature, the substrate was spray-developed using organic alkaline developer NMD-3 (Tokyo Ohka Kogyo Co., Ltd.) at 23°C for two development times (40 seconds and 70 seconds). The substrate was then washed with ion-exchanged water and air-dried, forming a striped pattern on the substrate. The pattern was observed under an optical microscope and evaluated for development residues and chipping in unexposed areas. The evaluation criteria were as follows, with a score of 3 or higher being practical. 5: After a development time of 70 seconds, there was no development residue in the unexposed areas and no pattern defects. 4: After a development time of 70 seconds, a slight development residue or slight pattern defects occurred in the unexposed area. 3: At a development time of 70 seconds, development residue or pattern defects occurred in the unexposed areas. 2: At a development time of 40 seconds, a large amount of development residue or a large amount of pattern defects occurred in the unexposed areas. 1: Pattern defects occurred at a development time of 40 seconds.

[0227] [Adhesion evaluation] The obtained photosensitive coloring compositions 1 to 41 were applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the film thickness after drying would be 2.0 μm, and then dried on a hot plate at 70°C for 1 minute. Then, after cooling the substrate to room temperature, a high-pressure mercury lamp was used to apply the coloring compositions to a photomask with a stripe pattern at 5 μm intervals at an illuminance of 30 mW / cm. 2 , 50 mJ / cm 2 The substrate was then spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 30 minutes to obtain a substrate for evaluation. The spray development was carried out for the shortest time possible to form a pattern without leaving any residual development residue on the coating of each photosensitive coloring composition, and this was defined as the appropriate development time. Of the patterns on the evaluation substrate, fine line patterns with widths of 5 to 25 μm were observed under an optical microscope to confirm the minimum line width of the remaining fine line patterns. The evaluation criteria are as follows, with 3 or higher being practical. 5: Fine lines of 10 μm or less remain. 4: Fine lines of 15 μm or less remain. 3: Fine lines of 20 μm or less remain. 2: Fine lines of 25 μm or less remain. 1: No fine lines remain.

[0228] [Pattern shape evaluation (1): Linearity] The substrate prepared for the adhesion evaluation was evaluated by measuring the maximum and minimum line widths of the stripe pattern at 10 locations using a Nikon ECLIPSE LV100POL Model optical microscope and calculating the average. The evaluation criteria are as follows, with 3 or higher being practical. 5: The difference between the maximum and minimum line widths is less than 0.5 μm 4: The difference between the maximum and minimum line widths is 0.5 μm or more and less than 1.0 μm 3: The difference between the maximum and minimum line widths is 1.0 μm or more and less than 1.5 μm 2: The difference between the maximum and minimum line widths is 1.5 μm or more and less than 2.0 μm 1: The difference between the maximum and minimum line widths is 2.0 μm or more

[0229] [Pattern shape evaluation (2): Cross-sectional shape] The pattern shape of the substrate prepared for adhesion evaluation was confirmed using a scanning electron microscope (Hitachi High-Tech's "S-3000H"). Evaluation was performed by capturing an SEM image 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. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: Taper angle is between 30 degrees and 50 degrees 4: Taper angle between 50 degrees and 60 degrees 3: Taper angle less than 30 degrees or between 60 degrees and 70 degrees 2: Taper angle between 70 degrees and 90 degrees 1: Taper angle of 90 degrees or more

[0230] [Solvent resistance] The substrate prepared for the adhesion evaluation was immersed in N-methylpyrrolidone at room temperature for 30 minutes, then washed with ion-exchanged water and air-dried, and the 100 μm wide stripe pattern was observed using an optical microscope. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: No change in appearance or color. 4: Slight wrinkling occurs, but there is no change in color. 3: Some wrinkles or other imperfections occur, but there is no change in color. 2: Wrinkles appear all over the surface and the color fades slightly. 1: Peeling and fading occur.

[0231] [Table 2]

Claims

1. A photosensitive coloring composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The polymerizable compound (C) contains two or more compounds selected from the group consisting of compounds represented by the following general formulas (1) to (4): the alkali-soluble resin (B) contains a photosensitive alkali-soluble resin (B2), the photosensitive alkali-soluble resin (B2) is an alkali-soluble resin having a polymerizable unsaturated group, The photosensitive alkali-soluble resin (B2) is A resin obtained by adding a monocarboxyl group-containing monomer to the epoxy group of a polymer of an epoxy group-containing monomer and another monomer, and then reacting the resulting hydroxyl group with a polybasic acid anhydride. A resin in which an epoxy group-containing monomer is added to a part of the carboxyl groups of a polymer of a carboxyl group-containing monomer and another monomer; and a resin obtained by reacting an isocyanate group of an isocyanate group-containing monomer with a hydroxyl group of a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers, Photosensitive coloring composition. General formula (1) 【Chemistry 1】 (In general formula (1), R １ , R ３ each independently represents a hydrogen atom or a methyl group, R ２ , R ４ each independently represents an alkylene group, and k and l each independently represent an integer of 1 to 20. General formula (2) 【Chemistry 2】 (In general formula (2), R ５ , R ７ each independently represents a hydrogen atom or a methyl group, R ６ , R ８ each independently represents an alkylene group, and m and n each independently represent an integer of 0 to 5. When m and n are 0, they represent a single bond. General formula (3) 【Transformation 3】 (In general formula (3), R ９ , R １１ each independently represents a hydrogen atom or a methyl group, R １０ , R １２ each independently represents an alkylene group, and p and q each independently represent an integer of 1 to 10. General formula (4) 【Chemistry 4】 (In general formula (4), R １３ , R １５ each independently represents a hydrogen atom or a methyl group, R １４ , R １６ each independently represents an alkylene group, and x and y each independently represent an integer of 0 to 10. When x and y are 0, they represent a single bond.

2. The total content of the compounds represented by the general formulas (1) to (4) is 50 mass% or more in 100 mass% of the polymerizable compound (C). The photosensitive coloring composition according to claim 1.

3. The photosensitive coloring composition according to claim 1 or 2, wherein the polymerizable compound (C) comprises a compound represented by the general formula (1) or a compound represented by the general formula (3).

4. The total content of the compound represented by the general formula (1) and the compound represented by the general formula (3) is 10 mass% or more in 100 mass% of the total content of two or more compounds selected from the group consisting of compounds represented by the general formulas (1) to (4). The photosensitive coloring composition according to any one of claims 1 to 3.

5. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the polymerizable compound (C) further contains a compound having an acid group.

6. The photosensitive coloring composition according to any one of claims 1 to 5, wherein the photopolymerization initiator (D) comprises an oxime compound.

7. A color filter comprising a substrate and filter segments formed using the photosensitive coloring composition according to any one of claims 1 to 6.

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

9. A solid-state imaging device comprising the color filter according to claim 7 .

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