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

Abstract

To provide a photosensitive coloring composition which exhibits few pattern shape defects, suppresses water stains after development, and has excellent alkali developability and a high residual film ratio.SOLUTION: The photosensitive coloring composition contains a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D). The alkali-soluble resin (B) contains a non-photosensitive alkali-soluble resin (B1) having a glass transition temperature of 20°C or higher and an acid value of 20-100 mg KOH / g, and a photosensitive alkali-soluble resin (B2) having a glass transition temperature of 0°C or lower and an acid value of 20-100 mg KOH / g.SELECTED DRAWING: None

Description

Technical Field

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

Background Art

[0002] For a color filter used in an image display device or a solid-state imaging device, a photosensitive coloring composition is applied to a transparent substrate such as glass, and a step of removing a solvent from this coating film by drying, a step of irradiating and curing the coating film with radiation through a photomask having a desired pattern shape (hereinafter referred to as exposure), and then a step of washing and removing the unexposed portion of this coating film (hereinafter referred to as development). Thereafter, a first-color filter segment pattern is obtained by a heat treatment step (hereinafter referred to as post-bake) for sufficiently curing the cured film as necessary. Then, by performing the same operation as this, filter segment patterns of other colors are formed to complete the color filter.

[0003] In the above-described developing step, an alkaline developer is used as the developer to wash and remove the unexposed portion. At that time, there has been a problem that the exposed portion is chipped or peeled, and defects occur in the pattern shape. In addition, when the coating film is exposed to an alkaline developer, there has also been a problem that a phenomenon in which the coating film changes color (hereinafter referred to as water stain) occurs. Therefore, there is a demand for a photosensitive coloring composition in which defects in the pattern shape and water stain do not occur in the developing step. Furthermore, there has also been a problem that the film thickness of the coating film changes (hereinafter referred to as residual film rate) due to elution or vaporization of unreacted substances or the like during the developing step and the post-bake step.

[0004] In recent years, due to the miniaturization and high pixel density of image display devices, the area per pixel has a tendency to become smaller, and increasing the film thickness has been studied. However, when the film thickness is increased, there has been a problem that the remaining development of the unexposed portion (hereinafter referred to as alkali developability) increases.

[0005] Therefore, as an effort to improve water leakage, Patent Document 1 discloses a photosensitive coloring composition containing a fluorine-based surfactant with a specific structure. Also, as an effort to improve alkali developability, Patent Document 2 discloses a photosensitive coloring composition having characteristics in a curable polymer.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0007] However, conventional photosensitive coloring compositions could not satisfy all of the pattern shape, water leakage, alkali developability, and residual film ratio.

[0008] An object of the present invention is to provide a photosensitive coloring composition having few defects in the pattern shape, suppressing water leakage after development, excellent alkali developability, and a high residual film ratio.

Means for Solving the Problems

[0009] The present invention is a photosensitive coloring composition containing a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the alkali-soluble resin (B) contains a non-photosensitive alkali-soluble resin (B1) having a glass transition temperature of 20°C or higher and an acid value of 20 to 100 mgKOH / g, and a photosensitive alkali-soluble resin (B2) having a glass transition temperature of 0°C or lower and an acid value of 20 to 100 mgKOH / g.

Effects of the Invention

[0010] According to the present invention described above, it is possible to provide a photosensitive coloring composition having few pattern shape defects, suppressing water stains after development, excellent alkali developability, and a high residual film ratio. Further, the present invention can provide a color filter, an image display device, and a solid-state imaging device.

Embodiments for Carrying Out the Invention

[0011] Hereinafter, embodiments for carrying out the photosensitive coloring composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiments and can be implemented with modifications within a range capable of solving the problems.

[0012] In the present invention, “(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, unless otherwise specified. Further, “C.I.” means Color Index (C.I.; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond. Regarding the molecular weight of the compound in the present invention, for a low molecular compound whose molecular weight can be specified, it is the value calculated by calculation or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry). For a compound having a molecular weight distribution, it is the weight average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent.

[0013] <Photosensitive Coloring Composition> The present invention is a photosensitive coloring composition containing a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The photosensitive coloring composition is such that the alkali-soluble resin (B) contains a non-photosensitive alkali-soluble resin (B1) having a glass transition temperature of 20°C or higher and an acid value of 20 to 100 mgKOH / g, and a photosensitive alkali-soluble resin (B2) having a glass transition temperature of 0°C or lower and an acid value of 20 to 100 mgKOH / g.

[0014] [Colorant (A)] The photosensitive coloring composition of the present invention contains a colorant (A).

[0015] Examples of the colorant (A) include pigments and dyes. Among these, pigments are preferred because color filters require light resistance, heat resistance, and solvent resistance.

[0016] (Pigment) The pigment is not particularly limited, and examples thereof include compounds classified as pigments in the Color Index.

[0017] Red pigments include, for example, C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigments described in JP-A No. 2014-134712, the pigments described in Patent No. 6368844, and the like. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, C.I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigments described in JP-A No. 2014-134712, and the pigments described in Patent No. 6368844 are preferred, and C.I. Pigment Red 177, 254, 291, 295, 296, the pigments described in JP-A No. 2014-134712, and the pigments described in Patent No. 6368844 are particularly preferred.

[0018] Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 64, 71, 73, and the like.

[0019] Yellow pigments include, for example, C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and pigments described in JP-A-2012-226110. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, and the pigments described in JP-A-2012-226110 are preferred.

[0020] Green pigments include, for example, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc. Among these, C.I. Pigment Green 36, 58, 59, 62, 63 are preferred.

[0021] Blue pigments include, for example, C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.

[0022] Examples of the purple pigment include C.I. 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, 50, etc. Among these, C.I. Pigment Violet 19 and 23 are preferred.

[0023] Examples of the black pigment include C.I. Pigment Black 1, 6, 7, 12, 20, 31, etc.

[0024] Inorganic pigments can also be used as the colorant (A) in the photosensitive coloring composition of the present invention. Examples include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc.

[0025] (Dye) Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. Further, derivatives of these dyes or lake pigments obtained by lake formation of the dyes can also be used.

[0026] Acid dyes preferably have acidic groups such as sulfonic acid and carboxylic acid. Direct dyes preferably form salt-forming compounds with inorganic salts of acid dyes or with nitrogen-containing compounds such as quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds. Also preferred are salt-forming compounds that are salts of resin components having these functional groups and acid dyes. Further, the salt-forming compound can easily obtain a photosensitive coloring composition excellent in resistance (light resistance, solvent resistance) by sulfonamidation and modification into a sulfonic acid amide compound. In addition, salt-forming compounds of acid dyes and compounds having an onium base are also preferred because of their excellent resistance (light resistance, solvent resistance). Note that the compound having an onium base is preferably a resin having a cationic group.

[0027] Basic dyes can be used as they are, but salt-forming compounds formed by salification with organic acids, perchloric acid, or their metal salts are preferred. The salt-forming compounds of basic dyes are preferred because of their excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, among the salt-forming compounds of basic dyes, the anionic components that act as counterions are organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, anion compounds having a conjugate base of an organic acid having a halogenated hydrocarbon group, and salt-forming compounds formed by salifying with acid dyes. Note that the salt-forming compound has improved resistance when it contains a polymerizable unsaturated group in the molecule.

[0028] The chemical structure of the dye is derived from a dye selected from, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (such as oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (such as 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 their metal complex dyes.

[0029] Among these dye structures, from the viewpoint of color characteristics such as hue, color separation property, and color unevenness, a dye structure derived from a dye selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and a dye structure derived from a dye selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferable.

[0030] The colorant (A) can be used alone or in combination of two or more.

[0031] The content of the colorant (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass in 100% by mass of the non-volatile components of the photosensitive coloring composition.

[0032] (Micronization of Pigment) The pigment is preferably used after being micronized. The micronization method is not particularly limited, and for example, any of wet grinding, dry grinding, and solution precipitation methods can be used. Among these, salt milling treatment by the kneader method, which is a type of wet grinding, is preferable. The average primary particle diameter determined by TEM (transmission electron microscope) of the micronized pigment is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0033] The salt milling treatment is a treatment in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while heating using a kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, or a sand mill, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution can be obtained.

[0034] Examples of the water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from the perspective of cost. The amount of the water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment, from both the aspects of treatment efficiency and production efficiency.

[0035] The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (is miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, from the perspective of safety, a high-boiling solvent with a boiling point of 120°C or higher is preferred. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

[0036] A resin may be added to the salt milling treatment as needed. The type of the resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. Among these, it is preferably solid at room temperature, water-insoluble, and partially soluble in the above organic solvent. The amount of the resin added is preferably 2 to 200 parts by mass, per 100 parts by mass of the pigment.

[0037] [Alkali-soluble resin (B)] In the present invention, the alkali-soluble resin (B) includes a non-photosensitive alkali-soluble resin (B1) having a glass transition temperature of 20°C or higher and an acid value of 20 to 100 mgKOH / g, and a photosensitive alkali-soluble resin (B2) having a glass transition temperature of 0°C or lower and an acid value of 20 to 100 mgKOH / g.

[0038] The non-photosensitive alkali-soluble resin is likely to have defects in pattern shape due to insufficient photocuring, poor water bleeding, decomposition during post-baking, etc., and has a low remaining film rate, but has excellent alkali developability. On the other hand, the photosensitive alkali-soluble resin is excellent in terms of pattern shape defects, water bleeding, and remaining film rate, but due to the small number of alkali-soluble groups, its alkali developability deteriorates. Therefore, in the present invention, by combining alkali-soluble resins with different glass transition temperatures, namely a non-photosensitive alkali-soluble resin with a glass transition temperature of 20°C or higher and a photosensitive alkali-soluble resin with a glass transition temperature of 0°C or lower, it is possible to suppress pattern shape defects and water bleeding due to promoted photocuring, and further improve alkali developability. Also, by setting the acid value of both the non-photosensitive alkali-soluble resin and the photosensitive alkali-soluble resin to 20 to 100 mgKOH / g, it is presumed that decomposition during post-baking, etc. can be suppressed and the remaining film rate can be improved while suppressing pattern shape defects and water bleeding and maintaining alkali developability. In the present specification, examples of the alkali-soluble group include a carboxyl group, a phosphate group, a sulfonic acid group, a hydroxyl group, a phenolic hydroxyl group, etc. Among these, a carboxyl group is preferred.

[0039] (Non-photosensitive alkali-soluble resin (B1)) Examples of the resin type of the non-photosensitive alkali-soluble resin (B1) include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth)acrylic acid copolymer, or an isobutylene / (anhydrous) maleic acid copolymer, etc. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferred.

[0040] The non-photosensitive alkali-soluble resin (B1) is preferably contained in an amount of 5 to 70% by mass, more preferably 10 to 60% by mass, and even more preferably 20 to 50% by mass in 100% by mass of the alkali-soluble resin (B).

[0041] (Photosensitive alkali-soluble resin (B2)) The photosensitive alkali-soluble resin (B2) is an alkali-soluble resin having a polymerizable unsaturated group. Examples of the photosensitive alkali-soluble resin (B2) include resins prepared by adjusting the glass transition temperature of the above resin species to 0 °C or lower and further bonding a polymerizable unsaturated group. For example, resins synthesized by the following method (i) or (ii) are preferred. The resin (B2) is three-dimensionally crosslinked by curing with active energy rays, improving the crosslink density and chemical resistance.

[0042] [Method (i)] Method (i) is, for example, first, synthesizing a polymer of an epoxy group-containing monomer and other monomers. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the generated hydroxyl group to obtain a photosensitive alkali-soluble resin.

[0043] 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.

[0044] Other monomers include, for example, (meth)acrylates such as 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, phenoxydiethylene 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 p-cumylphenol, EO modified (meth)acrylate of nonylphenol, 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; Styrenes such as styrene or 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 acids such as vinyl acetate or vinyl propionate; N-substituted maleimides such as cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimide phenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine; Phosphate ester group-containing monomers such as 2-(meth)acryloyloxyethyl acid phosphate and compounds obtained by reacting a hydroxyl group-containing monomer described below with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid can be mentioned, and they can be used alone or in combination of two or more.

[0045] Examples of the monocarboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted products of (meth)acrylic acid, and they can be used alone or in combination of two or more.

[0046] Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and they can be used alone or in combination of two or more. Further, if necessary, a tricarboxylic acid dianhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic anhydride can be used to hydrolyze the remaining anhydride groups.

[0047] Also, as a method similar to method (i), for example, a polymer of a carboxyl group-containing monomer and other monomers is synthesized. Next, a method of adding an epoxy group-containing monomer to a part of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin can be mentioned.

[0048] [Method (ii)] Method (ii) includes, for example, synthesizing a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers. Next, a method of reacting the isocyanate group of an isocyanate group-containing monomer with the hydroxyl group of the polymer can be mentioned.

[0049] Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Also, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide, etc. to hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylate obtained by adding polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid, etc. can also be mentioned. These can be used alone or in combination of two or more. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferable in terms of being less likely to generate foreign substances in the film. Also, glycerol mono(meth)acrylate is preferable in terms of photosensitivity.

[0050] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis〔methacryloyloxy〕ethyl isocyanate, etc., and they can be used alone or in combination of two or more.

[0051] The monomer containing a monocarboxyl group and other monomers can use the monomers described above.

[0052] The alkali-soluble resins (B1) and (B2) can be synthesized by using the monomers described above alone or in combination of two or more.

[0053] The photosensitive alkali-soluble resin (B2) is preferably contained in an amount of 5 to 70% by mass in 100% by mass of the alkali-soluble resin (B).

[0054] The alkali-soluble resin (B) can contain thermosetting groups such as epoxy groups and oxetanyl groups.

[0055] From the viewpoint of developability, the weight-average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000. Also, the value of Mw / Mn is preferably 10 or less. An appropriate weight-average molecular weight (Mw) improves the adhesion to the substrate and the alkali developability.

[0056] The acid value of the alkali-soluble resin (B) is preferably 5 to 200 mgKOH / g, more preferably 10 to 150 mgKOH / g, and even more preferably 20 to 100 mgKOH / g. An appropriate acid value improves the adhesion to the substrate and the alkali developability.

[0057] The alkali-soluble resin (B) can contain resins other than the non-photosensitive alkali-soluble resin (B1) and the photosensitive alkali-soluble resin (B2).

[0058] The alkali-soluble resin (B) can be used alone or in combination of two or more.

[0059] The content of the alkali-soluble resin (B) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the colorant (A).

[0060] [Polymerizable compound (C)] The photosensitive coloring composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) is a compound that forms a film by polymerization.

[0061] The polymerizable compound (C) is a monomer (monomer), dimer, trimer, and oligomer containing a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, and the like. Examples of the polymerizable compound (C) include an acid group-containing (meth)acrylate (C1), a polymerizable compound (C2) having a caprolactone structure, a polymerizable compound (C3) having a urethane bond (excluding (C1-1)), and other polymerizable compounds (C4).

[0062] (Acid group-containing (meth)acrylate (C1)) From the viewpoint of alkali developability, the photosensitive coloring composition of the present invention preferably contains an acid group-containing (meth)acrylate (C1). Examples of the acid group of the acid group-containing (meth)acrylate (C1) include a sulfonic acid group, a carboxyl group, a phosphoric acid group, and the like. Among these, a carboxyl group is preferable.

[0063] The acid group-containing (meth)acrylate (C1) preferably contains an acid group-containing (meth)acrylate (C1-1) having a urethane bond represented by the following general formula (1).

[0064] General formula (1) (H2C=C(R 1 )COO) m -X-(OCOCH(R 1 )CH2S(R 2 )COOH) n In general formula (1), R 1 is a hydrogen atom or a methyl group, R 2 is a divalent hydrocarbon group having 1 to 12 carbon atoms, X is an organic group having a urethane bond with (m + n) valences and 3 to 60 carbon atoms, m is an integer of 2 to 18, and n is an integer of 1 to 3.

[0065] The acid group-containing (meth)acrylate (C1-1) having a urethane bond represented by the general formula (1) can be synthesized, for example, by first reacting a polyfunctional isocyanate compound with a hydroxyl group-containing (meth)acrylate, and then adding a mercapto compound having a carboxyl group to the product.

[0066] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, and the like.

[0067] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and carboxy (meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

[0068] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

[0069] From the viewpoint of suppressing development residues during alkali development, the content of the acid group-containing (meth)acrylate (C1-1) having a urethane bond represented by the general formula (1) is preferably 10 to 90% by mass, more preferably 25 to 80% by mass, based on 100% by mass of the polymerizable compound (C).

[0070] In the acid group-containing (meth)acrylate (C1), the acid group-containing (meth)acrylate (C1-2) having no urethane bond is, for example, an esterified product of a free hydroxyl group-containing poly(meth)acrylate of a polyhydric alcohol and (meth)acrylic acid and a dicarboxylic acid; an esterified product of a polyvalent carboxylic acid and a monohydroxyalkyl (meth)acrylate, and the like. Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like. Examples of the dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like. Examples of the polyvalent carboxylic acid include trimellitic acid, pyromellitic acid, and the like. Examples of the monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and the like.

[0071] Commercially available products of the acid group-containing (meth)acrylate (C1-2) having no urethane bond include Biscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520, M-521, etc. manufactured by Toagosei Co., Ltd.

[0072] From the viewpoints of alkali developability and pattern formability, the content of the acid group-containing (meth)acrylate (C1-2) having no urethane bond is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass in 100% by mass of the polymerizable compound (C).

[0073] (Polymerizable Compound (C2) Having a Caprolactone Structure) From the viewpoints of alkali developability and coating film resistance, the photosensitive coloring composition of the present invention preferably contains a polymerizable compound (C2) having a caprolactone structure.

[0074] When the polymerizable compound (C2) having a caprolactone structure is contained, the alkali developability and coating film resistance are further improved. The polymerizable compound (C2) having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, but it can be obtained by esterifying a polyhydric alcohol such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethol melamine, etc. with (meth)acrylic acid and ε-caprolactone. Among them, the compound represented by the following general formula (2) is preferable.

[0075] General formula (2)

Chemical formula

[0076] General formula (3)

Chemical formula

[0077] General formula (4)

Chemical formula

[0078] The polymerizable compound (C2) having a caprolactone structure is commercially available, for example, as the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. DPCA-20 (in the above general formulas (2) to (4), m = 1, the number of groups represented by the general formula (3) = 2, R 1 is a compound in which all are hydrogen atoms), DPCA-30 (in the above general formulas (2) to (4), m = 1, the number of groups represented by the general formula (3) = 3, R 1 is a compound in which all are hydrogen atoms), DPCA-60 (in the above general formulas (2) to (4), m = 1, the number of groups represented by the general formula (3) = 6, R 1 is a compound in which all are hydrogen atoms), DPCA-120 (in the above general formulas (2) to (4), m = 2, the number of groups represented by the general formula (3) = 6, R 1 is a compound in which all are hydrogen atoms), and the like can be mentioned.

[0079] From the viewpoint of suppressing water seepage, the polymerizable compound (C2) having a caprolactone structure is preferably a compound in which, in the above general formulas (2) to (4), m = 1, the number of groups represented by the general formula (3) = 2 to 6, and R 1 are all hydrogen atoms. More preferably, in the above general formulas (2) to (4), m = 1, the number of groups represented by the general formula (2) = 2 or 3, and R 1 are all hydrogen atoms.

[0080] From the viewpoint of suppressing water seepage, the content of the polymerizable compound (C2) having a caprolactone structure is preferably 5 to 85% by mass, more preferably 10 to 70% by mass, and particularly preferably 20 to 60% by mass in 100% by mass of the polymerizable compound (C).

[0081] (Polymerizable compound (C3) having a urethane bond) From the viewpoint of the coating film resistance, the photosensitive coloring composition of the present invention preferably contains, as the polymerizable compound (C), a polymerizable compound (C3) having a urethane bond (excluding (C1-1)).

[0082] The polymerizable compound (C3) having a urethane bond includes an aliphatic urethane (meth)acrylate (C3-1) and an alicyclic urethane (meth)acrylate (C3-2).

[0083] The aliphatic urethane (meth)acrylate (C3-1) is, for example, a compound obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate having an aliphatic structure, or a compound obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate having an aliphatic structure and then reacting with a (meth)acrylate having a hydroxyl group, and the like.

[0084] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth)acrylate, a hydroxyl group-containing polyol polyacrylate, and the like.

[0085] Examples of the polyfunctional isocyanate having an aliphatic structure include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylenediisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and the like. Further, their biuret bodies, isocyanate nurate bodies, trimethylolpropane adduct bodies, and the like are included.

[0086] The alicyclic urethane (meth)acrylate (C3-2) can be obtained, for example, by changing the polyfunctional isocyanate having an aliphatic structure used in the synthesis of the above-mentioned aliphatic urethane (meth)acrylate (C3-1) to a polyfunctional isocyanate having an alicyclic structure.

[0087] Examples of the polyfunctional isocyanate having the above alicyclic structure include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanatomethyl)cyclohexane, etc. Further, examples thereof include their burette bodies, isocyanate nurate bodies, trimethylolpropane adduct bodies, etc.

[0088] From the viewpoints of wrinkle suppression and pattern formability, the number of polymerizable unsaturated groups of the aliphatic urethane (meth)acrylate (C3-1) and the alicyclic urethane (meth)acrylate (C3-2) is preferably 4 to 15, and more preferably 6 to 12.

[0089] From the viewpoints of wrinkle suppression and pattern formability, the molecular weight of the aliphatic urethane (meth)acrylate (C3-1) and the alicyclic urethane (meth)acrylate (C3-2) is preferably 500 to 5,000, and more preferably 500 to 3,000.

[0090] The aliphatic urethane (meth)acrylate (C3-1) and the alicyclic urethane (meth)acrylate (C3-2) can each be used alone or in combination of two or more.

[0091] (Polymerizable compound (C4) other than (C1) to (C3)) The photosensitive coloring composition of the present invention can contain a polymerizable compound (C4) other than (C1) to (C3) (hereinafter also referred to as other polymerizable compound (C4)).

[0092] Other polymerizable compounds (C4) 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, ethoxylated bisphenol A di(meth)acrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylate and other various acrylic acid esters and methacrylic acid esters, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, and the like. Among these, from the viewpoint of pattern formation, those having 5 or more polymerizable unsaturated groups are preferred.

[0093] Commercially available products of other polymerizable compounds (C4) include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330 manufactured by Nippon Kayaku Co., Ltd.; 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 manufactured by Toagosei Co., Ltd.; OGSOL EA-0200, EA-0300, GA-5060P, GA-2800 manufactured by Osaka Gas Chemical Co., Ltd.; Miramer HR6060, 6100, 6200 manufactured by Miwon Specialty Chemical Co., Ltd.; Viscote #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd.; NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd.; EBECRY 40, 130, 140, 145 manufactured by Daicel Ornex Co., Ltd., and the like.

[0094] The content of the polymerizable compound (C) is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, in 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0095] [Photoinitiator (D)] The photosensitive coloring composition of the present invention contains a photoinitiator (D). By containing the photoinitiator (D), a cured film can be formed by curing the photosensitive coloring composition by ultraviolet irradiation.

[0096] The photoinitiator (D) is not particularly limited as long as it is a compound capable of initiating the polymerization of the polymerizable compound (C) by light, and known photoinitiators can be used. For example, acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-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-based compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxyoxime); Acylphosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds, etc. can be mentioned. Among these, from the viewpoint of pattern formation, oxime compounds (D1) and acetophenone compounds (D2) are preferable, and oxime compounds (D1) are more preferable.

[0097] (Oxime compound (D1)) The oxime compound (D1) includes an oxime compound (D1-1) containing one oxime group in one molecule and an oxime compound (D1-2) containing two oxime groups in one molecule. Among these, from the viewpoints of pattern formation and residual film ratio, the oxime compound (D1-2) containing two oxime groups in one molecule is particularly preferable.

[0098] [Oxime compound (D1-1) containing one oxime group in one molecule] The oxime compound (D1-1) containing one oxime group in one molecule includes, for example, IRGACURE OXE-01, 02, 03, 04 manufactured by BASF, Adeka Arcles N-1919, NCI-730, 831, 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Qiangli New Materials Co., Ltd., OMNIRAD1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, DFI-020, 036, EOX-01, etc. manufactured by Daito Chemicals.

[0099] [Oxime compound (D1-2) containing two oxime groups in one molecule] The oxime-based compound (D1-2) containing two oxime groups in one molecule includes, for example, the compounds described in JP-A-2005-215378, JP-A-2011-105713, JP-T-2017-523465, etc., and the compounds represented by the following general formula (5). Among them, the compounds represented by the following general formula (5) are preferred.

[0100] General formula (5)

Chemical formula

[0101] In general formula (5), X1 and X2 each independently represent a carbonyl bond (-CO-) or a single bond. Among them, from the viewpoint of solubility in an organic solvent, it is preferable that at least one of X1 and X2 is a carbonyl bond (-CO-), and it is more preferable that X1 and X2 are carbonyl bonds (-CO-).

[0102] In general formula (5), R1 represents an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be any of a linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, etc. may be mentioned. Among these, an ethyl group, a propyl group, and an isopropyl group are preferable.

[0103] In the general formula (5), R2 and R3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic ring having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be any of a linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, etc. may be mentioned. Among these, a pentyl group, a hexyl group, a heptyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, and a cyclohexylmethyl group are preferable. Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, a morpholinyl group, etc. Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group, etc. Further, it may be an aryl group substituted with a halogen atom, an amino group, a nitro group, etc. Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, an α-methylbenzyl group, an α,α-dimethylbenzyl group, a phenylethyl group, etc. Further, it may be an arylalkyl group substituted with a halogen atom, an amino group, a nitro group, etc.

[0104] Among these, from the viewpoint of solubility in an organic solvent, at least one of R2 and R3 is preferably a linear alkyl group having 1 to 20 carbon atoms, and from the viewpoints of solubility in an organic solvent and suppression of water stain, it is more preferably a linear alkyl group having 1 to 20 carbon atoms and a cyclic alkyl group having 1 to 20 carbon atoms.

[0105] In the general formula (5), R4 and R5 each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be any of a linear, branched, cyclic, or a combination thereof alkyl group, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group, etc. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, etc. are included. Among these, from the viewpoint of reactivity, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferred. Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, a morpholinyl group, etc. Aryl groups having 6 to 30 carbon atoms include, for example, phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, etc., and may also be aryl groups substituted with a halogen atom, an amino group, a nitro group, etc. Among these, from the viewpoint of reactivity, a phenyl group is preferred. Arylalkyl groups having 7 to 30 carbon atoms include, for example, benzyl group, α-methylbenzyl, α,α-dimethylbenzyl group, phenylethyl group, etc., and may also be arylalkyl groups substituted with a halogen atom, an amino group, a nitro group, etc.

[0106] Among these, from the viewpoint of reactivity, R4 and R5 are preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or an ethyl group.

[0107] As a method for producing the compound represented by the general formula (5), for example, the method described in JP-T-2017-523465 can be used.

[0108] Hereinafter, specific examples of the oxime-based compound (D1-2) containing two oxime groups in one molecule are shown. Note that the present invention is not limited thereto.

[0109] [Chemical formula] [Chemical formula]

[0110] The photopolymerization initiator (D) can be used alone or in combination of two or more.

[0111] From the viewpoints of photocurability and pattern formability, the content of the photopolymerization initiator (D) is preferably 0.5 to 50 parts by mass, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 10 parts by mass with respect to 100 parts by mass of the colorant (A).

[0112] [Sensitizer (E)] From the viewpoint of pattern formation, the photosensitive coloring composition of the present invention preferably contains a sensitizer (E).

[0113] Examples of the sensitizer (E) include chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, polymethine dyes such as cyanine compounds, merocyanine compounds, oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyllin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organoruthenium complexes, or benzophenone compounds. Among these, from the viewpoint of pattern formation, thioxanthone compounds (E1) or benzophenone compounds (E2) are preferable, and benzophenone compounds (E2) are more preferable.

[0114] (Thioxanthone compounds (E1)) Examples of the thioxanthone compounds (E1) include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, etc. Among these, 2,4-diethylthioxanthone is preferable.

[0115] (Benzophenone compound (E2)) Examples of the benzophenone compound (E2) include 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 2-aminobenzophenone, etc. Among these, 4,4'-bis(diethylamino)benzophenone is preferable.

[0116] The sensitizer (E) can be used alone or in combination of two or more.

[0117] From the viewpoints of suppressing water stain and pattern formability, the content of the sensitizer (E) is preferably 150 to 400 parts by mass, more preferably 150 to 300 parts by mass, based on 100 parts by mass of the photopolymerization initiator (D).

[0118] [Dye derivative (F)] The photosensitive coloring composition of the present invention can contain a dye derivative (F).

[0119] The dye derivative (F) is not particularly limited, and examples include dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. The dye derivative (F) includes, for example, compounds having an acidic substituent such as a sulfo group, a carboxy group, a phosphoric acid group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group and a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group and a phthalimidalkyl group. Examples of the organic dye include diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, fluorene-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, polyazo, etc.

[0120] Specifically, as diketopyrrolopyrrole-based pigment derivatives, there are those described in JP-A No. 2001-220520, WO 2009 / 081930, WO 2011 / 052617, WO 2012 / 102399, JP-A No. 2017-156397; as phthalocyanine-based pigment derivatives, there are those described in JP-A No. 2007-226161, WO 2016 / 163351, JP-A No. 2017-165820, Patent No. 5753266; as anthraquinone-based pigment derivatives, there are those described in JP-A No. 63-264674, JP-A No. 09-272812, JP-A No. 10-245501, JP-A No. 10-265697, JP-A No. 2007-079094, WO 2009 / 025325; as quinacridone-based pigment derivatives, there are those described in JP-A No. 48-54128, JP-A No. 03-9961, JP-A No. 2000-273383; as dioxazine-based pigment derivatives, there are those described in JP-A No. 2011-162662; as thiazine indigo-based pigment derivatives, there are those described in JP-A No. 2007-314785; as triazine-based pigment derivatives, there are those described in JP-A No. 61-246261, JP-A No. 11-199796, JP-A No. 2003-165922, JP-A No. 2003-168208, JP-A No. 2004-217842, JP-A No. 2007-314681; as benzoisoindole-based pigment derivatives, there are those described in JP-A No. 2009-57478; as quinophthalone-based pigment derivatives, there are those described in JP-A No. 2003-167112, JP-A No. 2006-291194, JP-A No. 2008-31281, JP-A No. 2012-226110; as naphthol-based pigment derivatives, there are those described in JP-A No. 2012-208329, JP-A No. 2014-5439; as azo-based pigment derivatives, there are those described in JP-A No. 2001-172520, JP-A No. 2012-172092; as acidic substituents, there are those described in JP-A No. 2004-307854; as basic substituents, there are those described in JP-A No. 2002-201377, JP-A No. 2003-171594, JP-A No. 2005-181383, JP-A No. 2005-213404, etc. Known pigment derivatives are mentioned.In these documents, the dye derivatives may be described as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, etc. However, a compound having a substituent such as an acidic group, a basic group, or a neutral group in the above-described organic dye residue is synonymous with a dye derivative.

[0121] The dye derivative (F) can be used alone or in combination of two or more.

[0122] The content of the dye derivative (F) is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass, based on 100 parts by mass of the colorant (A).

[0123] [Dispersion resin (G)] The photosensitive composition of the present invention can contain a dispersion resin (G) as necessary. The dispersion resin (G) is preferably a resin having an adsorption group with high affinity for the colorant (A). The adsorption group preferably has at least one of a basic group and an acidic group. Note that an alkali-soluble resin (B) can also be used as the dispersion resin (G).

[0124] Examples of the basic group include groups containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring.

[0125] Examples of the acidic group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc. Among these, a carboxyl group and a phosphoric acid group are preferable from the viewpoints of adsorption to the pigment and developability.

[0126] Examples of the resin type of the dispersion resin (G) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyamino amidine salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, water-soluble resins and water-soluble polymer compounds such as polyvinyl alcohol and polyvinyl pyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, phosphate ester-based, and the like.

[0127] Examples of the structure of the dispersion resin (G) 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, a block structure or a comb structure is preferable.

[0128] Commercially available products of the dispersion resin (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 manufactured by BYK-Chemie Japan Co., Ltd.; or Anti-Terra-U203, 204; or BYK-P104, 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, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. manufactured by Lubrizol Japan Ltd.; EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF Japan Ltd.; Ajisuper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Inc.; and resins described in JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, etc.

[0129] The dispersion resin (G) can be used alone or in combination of two or more.

[0130] From the viewpoint of dispersion stability, the content of the dispersion resin (G) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the colorant (A).

[0131] [Thermosetting compound (H)] The photosensitive coloring composition of the present invention can contain a thermosetting compound (H). Thereby, the thermosetting compound (H) reacts in the heating step, and the crosslinking density increases, so the heat resistance is improved.

[0132] The thermosetting compound (H) may be a low molecular compound or a high molecular compound such as a resin. Examples of the thermosetting compound (H) include an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Among these, an epoxy compound and an oxetane compound are preferable.

[0133] (Epoxy compound (H1)) The epoxy compound (H1) includes, for example, polycondensates of bisphenols (such as bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (such as phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (such as formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polymers of phenols and various diene compounds (such as dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (such as benzenedimethanol, α,α,α’,α’-benzenedimethanol, biphenyldimethanol, α,α,α’,α’-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (such as α,α’-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like.

[0134] Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, 191P manufactured by Yuka Shell Epoxy Co., Ltd., TECHMORE VG3101L manufactured by Mitsui Chemicals, Inc., EPPN-201, 501H, 502H manufactured by Nippon Kayaku Co., Ltd., EOCN-102S, 103S, 104S, 1020 manufactured by Japan Epoxy Resins Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154, 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, etc. manufactured by Nissan Chemical Industries, Ltd.

[0135] From the viewpoint of the heat resistance of the cured film, the content of the epoxy compound (H1) is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass with respect to 100 parts by mass of the colorant (A).

[0136] (Oxetane compound (H2)) The oxetane compound (H2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or higher oxetane compounds.

[0137] Examples of the monofunctional oxetane compound 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, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, and the like.

[0138] Commercially available products include, for example, OXE-10, 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., OXT-101, 212 manufactured by Toagosei Co., Ltd., and the like.

[0139] The bifunctional oxetane compounds include, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl)ether, and the like.

[0140] Commercially available products include, for example, OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0141] Oxetane compounds having three or more functional groups include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, oxetane-modified phenol novolak resins described in Japanese Patent No. 3783462, etc.), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0142] The content of the oxetane compound (H2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0143] The melamine compound is a compound having a melamine ring structure. Melamine compounds are preferably methylol-type or ether-type compounds, and more preferably melamine compounds having an average of 5.0 or more methylol groups and / or ether groups per melamine ring. Appropriate numbers of methylol groups and ether groups make it easy to obtain heat resistance without excess or deficiency.

[0144] Commercially available products include, for example, 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, MX-410 manufactured by Sanwa Chemical Co., Ltd., Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 manufactured by Nippon Cytec Industries, Inc., and the like.

[0145] Among these, Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, 350 manufactured by Nippon Cytec Industries, Inc., which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are preferable in terms of increasing the crosslink density.

[0146] The thermosetting compound (H) can be used alone or in combination of two or more.

[0147] [Hardening agent (hardening accelerator)] In order to assist the curing of the thermosetting compound (H), a curing agent (curing accelerator) can be used in combination with the photosensitive coloring composition of the present invention. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like. Examples of the curing agent include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (for example, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (for example, dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.), and the like.

[0148] The curing agent can be used alone or in combination of two or more.

[0149] The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (H).

[0150] [Thiol-based chain transfer agent (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 the photopolymerization initiator (D), during radical polymerization after light irradiation, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated, and the photosensitivity of the photosensitive coloring composition is improved.

[0151] The thiol-based chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol-based chain transfer agent has four or more SH groups. When the number of functional groups increases, it becomes easier to photocure from the surface to the deepest part of the film.

[0152] Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, etc. are mentioned.

[0153] The thiol-based chain transfer agent (I) can be used alone or in combination of two or more kinds.

[0154] The content of the thiol-based chain transfer agent (I) is preferably 1 to 10% by mass, more preferably 2 to 8% by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, the photosensitivity is improved and wrinkles are less likely to occur on the pattern surface.

[0155] [Polymerization inhibitor (J)] The photosensitive coloring composition of the present invention can contain a polymerization inhibitor (J).

[0156] The polymerization inhibitor (J) is, for example, alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol, etc.; alkylresorcinol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, etc.; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, etc.; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, etc.; phosphine oxide compounds such as trioctylphosphine oxide, triphenylphosphine oxide, etc.; phosphite compounds such as triphenylphosphite, trisnonylphenylphosphite, etc.; pyrogallol, phloroglucin, etc.

[0157] The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition.

[0158] [Ultraviolet absorber (K)] The photosensitive coloring composition of the present invention can contain an ultraviolet absorber (K).

[0159] The ultraviolet absorber (K) is an organic compound having an ultraviolet absorption 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.

[0160] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and straight-chain alkyl ester, 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, the reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 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, 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, 2-ethylhexyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0161] Commercially available products include, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan, Adeka LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA, KEMISORB 71, 73, 74, 79, 279 manufactured by Chemipro Kasei, RUVA-93 manufactured by Otsuka Chemical, etc.

[0162] Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 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, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, etc.

[0163] Commercially available products include, for example, KEMISORB 102 manufactured by Chemipro Kasei, TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan, Adeka LA-46, LA-F70 of ADEKA, CYASORB UV-1164 manufactured by Sankyo Chemical, etc.

[0164] Benzophenone compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3 water temperature, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like.

[0165] Commercially available products include, for example, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Cipro Kasei Co., Ltd., Adeka Stab 1413 manufactured by ADEKA Corporation, UV-12 manufactured by Sankyo Chemical Co., Ltd., and the like.

[0166] Salicylic acid ester compounds include, for example, phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

[0167] The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass in a total of 100% by mass of the photopolymerization initiator (D) and the ultraviolet absorber (K).

[0168] [Antioxidant (L)] The photosensitive coloring composition of the present invention can contain an antioxidant (L). The antioxidant (L) prevents yellowing due to oxidation of the photopolymerization initiator (D) and the thermosetting compound (I) contained in the photosensitive coloring composition during the heat curing process or the heat process during ITO annealing. In particular, when the concentration of the colorant (A) in the photosensitive coloring composition is high, the content of the polymerizable compound (C) relatively decreases. Therefore, when dealing with an increase in the amount of the photopolymerization initiator (D) or the addition of the thermosetting compound (I), the cured film is likely to turn yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented.

[0169] The antioxidant (L) includes, for example, 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.

[0170] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0171] Hindered phenol antioxidants include, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), 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, 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), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc. can be mentioned.

[0172] Commercially available products include, for example, Adeka Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA, Keminox 101, 179, 76, 9425 manufactured by Chemipro, Irganox 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan, Cyanox CY-1790, CY-2777 manufactured by Sankyo Chemical, and the like.

[0173] Hindered amine antioxidants include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-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]], ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N’-4,7-tetrakis〔4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl〕-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decanedioate, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyrpiperidyl)[[3,5-bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate methyl 1,2,2,6,6-pentamethyl-4-pyrpiperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N’-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,Examples include 6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0174] Commercially available products include, for example, AdekaStab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP manufactured by ADEKA Corporation; KAMISTAB 29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd.; Tinuvin 111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan Ltd.; and Siasorb-UV-3346, UV-3529, UV-3853 manufactured by Sankyo Chemical Co., Ltd., etc.

[0175] Phosphorus-based antioxidants include, for example, bis(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl) 2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyldiphosphonite, tris(tridecyl) phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, phenyldi(tridecyl) phosphite, diphenylisooctyl phosphite, diphenyltridecyl phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 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-methylenebis(4,6-di-t-butylphenyl) phosphite, 1,3-bis(diphenoxyphosphoniloxy) benzene, ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite, etc.

[0176] Commercially available products include, for example, Adeka Stub PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA Corporation, IRGAFOS 168 manufactured by BASF Japan Ltd., Hostanox P-EPQ manufactured by Clariant Chemicals, etc.

[0177] Sulfur-based antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diyl bis[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, 2,4-bis[(laurylthio)methyl]-o-cresol, etc.

[0178] Commercially available products include, for example, Adeka Stub AO-412S, AO-503 manufactured by ADEKA Corporation, Keminox PLS manufactured by Chemipro Kasei Co., Ltd., etc.

[0179] The antioxidant (L) can be used alone or in combination of two or more.

[0180] The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass in 100% by mass of the non-volatile components of the photosensitive coloring composition. When contained in an appropriate amount, the transmittance, spectral characteristics, and sensitivity are improved.

[0181] [Leveling agent (M)] The photosensitive coloring composition of the present invention can contain a leveling agent (M). Thereby, the wettability and drying property with respect to the substrate during coating are further improved. Examples of the leveling agent (M) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, etc.

[0182] Examples of the silicone-based surfactant include linear polymers composed of siloxane bonds and modified siloxane polymers having organic groups introduced into the side chains or terminals.

[0183] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK-Chemie GmbH; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning Co., Ltd.; X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0184] Fluorine-based surfactants include, for example, surfactants or leveling agents having a fluorocarbon chain.

[0185] Commercially available products include, for example, Surfynol S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM, R-41, RS-72-K, DS-21 manufactured by DIC Corporation; FC-4430, 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; Phthalgen 602A manufactured by Neos Corporation.

[0186] Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrylated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, 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 sorbitol tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanolamide, alkylimidazoline, and the like.

[0187] Commercially available products include, for example, Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodol 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), Amite 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA's Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical's (meth)acrylic acid-based (co)polymers Polyflow - No.75, No.90, No.95, etc.

[0188] Examples of cationic surfactants include alkylamine salts, and alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0189] Commercially available products include, for example, Kao's Acetamine 24, Kotamine 24P, 60W, 86P Conc, etc.

[0190] Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate esters, and the like.

[0191] Commercially available products include, for example, Ftaigent 100, 150 manufactured by Neos Co., Ltd., ADEKA Hope YES-25 manufactured by ADEKA Corporation, ADEKA Cole TS-230E, PS-440E, EC-8600, etc.

[0192] Amphoteric surfactants include, for example, alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkyl dimethylaminoacetic acid betaine, and alkylamine oxides such as lauryl dimethylamine oxide.

[0193] Commercially available products include Anhtol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N, etc. manufactured by Kao Corporation.

[0194] The leveling agent (M) can be used alone or in combination of two or more.

[0195] The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. Within this range, the balance between the coatability and adhesion of the photosensitive coloring composition is further improved.

[0196] [Storage stabilizer (N)] The photosensitive coloring composition of the present invention can contain a storage stabilizer (N). Thereby, the viscosity of the photosensitive coloring composition over time is stabilized. Examples of the storage stabilizer (N) include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphites, etc.

[0197] The content of the storage stabilizer (N) is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant (A).

[0198] [Adhesion improver (O)] The photosensitive coloring composition of the present invention can contain an adhesion improver (O). Thereby, the adhesion between the cured film and the substrate is improved. Also, it becomes easier to form a pattern with a narrow width by the photolithography method.

[0199] The adhesion promoter (O) includes, for example, silane coupling agents. Examples of silane coupling agents 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; aminosilanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and the hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptans such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatopropyltriethoxysilane.

[0200] The adhesion promoter (O) can be used alone or in combination of two or more.

[0201] The content of the adhesion promoter (O) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the colorant (A).

[0202] [Organic solvent (P)] The photosensitive composition of the present invention can contain an organic solvent (P).

[0203] The organic solvent (P) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-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-butyrolactone, 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,Dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters and the like. Among these, from the viewpoints of the dispersibility of the pigment and the solubility of the alkali-soluble resin, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferable.,

[0204] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0205] [Method for producing photosensitive coloring composition] The photosensitive coloring composition of the present invention can be produced, for example, by adding a colorant (A), an alkali-soluble resin (B) and / or a dispersion resin (G), a dye derivative (F), an organic solvent (P), etc., and performing a dispersion treatment to produce a dispersion. Then, a polymerizable compound (C), a photopolymerization initiator (D), etc. are blended and mixed with the dispersion. The timing of blending each material is arbitrary. Also, the dispersion step can be performed multiple times.

[0206] Examples of the disperser for performing 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, or an attritor.

[0207] The average dispersed particle diameter (secondary particle diameter) of the pigment in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. A photosensitive coloring composition having high dispersion stability is easily obtained when it has an appropriate particle diameter.

[0208] Examples of the measurement method of the average dispersed particle diameter (secondary particle diameter) include using Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd. that employs the dynamic light scattering method (FFT power spectrum method), setting the particle permeability to the absorption mode, the particle shape to non-spherical, and the D50 particle diameter as the average diameter. As the dilution solvent for measurement, the organic solvents used for dispersion are each used, and it is preferable to measure the sample immediately after sample preparation for the sample treated with ultrasonic waves because less variation in results is likely to be obtained.

[0209] It is preferable to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust from the photosensitive coloring composition by means such as centrifugation, filtration using a sintered filter or a membrane filter. 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.

[0210] <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 filter segments preferably have a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of the colorant (A) to be used. Further, the color filter can have a magenta filter segment, a cyan filter segment, a yellow filter segment, etc. instead of or in addition to the color filter segments. The substrates include a transparent substrate and a reflective substrate. The transparent substrate includes, for example, a glass substrate. The reflective substrate includes, for example, a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0211] [Method for manufacturing a color filter] The method for manufacturing a color filter is not particularly limited. For example, it can be manufactured by performing the following steps: (1) a step of applying a photosensitive coloring composition on a substrate to form a film; (2) a step of exposing the film in a pattern through a mask; (3) a step of developing the unexposed portion with an alkali to form a patterned cured film; and (4) a step of heat-treating (post-baking) the pattern.

[0212] Hereinafter, the method for manufacturing a color filter will be described in detail. (Step (1)) In the step (1) of forming a film, the photosensitive coloring composition is applied on the substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and dried (pre-baked) at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, hot plate, etc. as necessary. 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. Further, a primer layer may be provided on the substrate as necessary to improve adhesion to an upper layer, prevent diffusion of substances, and planarize the substrate surface. The film thickness of the layer is preferably applied so as to be 0.05 to 10.0 μm after drying, and more preferably applied so as to be 0.3 to 5 μm.

[0213] (Step (2)) In the exposure step, the film obtained in step (1) is exposed to a specific pattern through a mask using an exposure apparatus such as a stepper. Thereby, a cured film is obtained. Examples of the radiation used for exposure include ultraviolet rays such as g-line, h-line, and i-line.

[0214] (Step (3)) The cured film obtained in step (2) is subjected to an alkali development process, where the layer of the composition in the unexposed portion is eluted into an aqueous alkali solution, leaving only the cured portion to obtain 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 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. Using at an appropriate pH suppresses pattern roughness and peeling, and improves the residual film rate after development.

[0215] Examples of the development method include the dip method, spray method, paddle method, etc. The development temperature is preferably 15 to 40°C. After alkali development, it is preferably washed with pure water.

[0216] (Step (4)) The heat treatment (post-bake) sufficiently cures the patterned cured film obtained in step (3) by heating. The post-bake heating temperature is preferably 100 to 300°C, more preferably 150 to 250°C. Also, the heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

[0217] <Image display device> The image display device of the present invention includes the color filter of the present invention. The form used in the image display device only needs to function as an image display device and is not particularly limited. For example, the configurations described in "Next-generation Liquid Crystal Display Technology" (written by Tatsuo Uchida, published by Kogyo Chosa Kai, 1994) can be mentioned. For the definition of the image display device and details of each image display device, refer to, for example, "Electronic Display Devices (by Akio Sasaki, published by Kogyo Chosa Kai, Ltd. in 1990)", "Display Devices (by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989)", etc.

[0218] <Solid-state imaging device> The solid-state imaging device of the present invention includes the color filter of the present invention. The form used for the solid-state imaging device is not particularly limited. For example, on a substrate, it has a plurality of photodiodes constituting the light-receiving area of the solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon, etc., has a light-shielding film with only the light-receiving part of the photodiode opened on the photodiode and the transfer electrodes, and has a device protection film made of silicon nitride, etc., formed to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode on the light-shielding film, and has a color filter on the device protection film. Further, it may have a configuration having condensing means (such as a microlens, etc. The same applies hereinafter) on the device protection film and below the color filter (closer to the substrate side), or a configuration having condensing means on the color filter. Also, the color filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partition walls. In this case, the partition walls are preferably of a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (such as mobile phones, smartphones, etc.), but also for in-vehicle cameras and surveillance cameras.

Example

[0219] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited thereto. Note that "parts" means "parts by mass" and "%" means "% by mass". Also, in the present invention, the non-volatile content or non-volatile content concentration refers to the mass residue after standing in an oven at 280°C for 30 minutes.

[0220] Before presenting the examples, each measurement method will be described.

[0221] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and glass transition temperature of the resin are as follows.

[0222] (Average molecular weight of alkali-soluble resin and dispersed resin) The number average molecular weight (Mn) and weight average molecular weight (Mw) of the alkali-soluble and dispersed resins were measured by gel permeation chromatography (GPC) equipped with an RI detector. As the apparatus, HLC-8220GPC (manufactured by Tosoh Corporation) was used. Two separation columns were connected in series, and for both packing materials, "TSK-GEL SUPER HZM-N" was connected in a pair and used. The oven temperature was 40 °C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 mass% of the above eluent and 20 microliters were injected. The average molecular weight is a polystyrene conversion value.

[0223] (Acid value of alkali-soluble resin and dispersed resin) To 0.5 - 1 g of the alkali-soluble resin and dispersed resin solution, 80 ml of acetone and 10 ml of water were added and stirred to dissolve uniformly. Using a 0.1 mol / L KOH aqueous solution as the titrant, titration was performed using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH / g) was measured. Then, from the acid value of the resin solution and the non-volatile content concentration of the resin solution, the acid value per non-volatile content of the resin was calculated.

[0224] (Amine value of dispersed resin) The amine value of the dispersed resin is the value obtained by converting the total measured amine value (mgKOH / g) to non-volatile content in accordance with the method of ASTM D 2074.

[0225] (Glass transition temperature) The glass transition temperature of the alkali-soluble resin is the value measured by differential scanning calorimetry ("DSC-1" manufactured by Mettler Toledo).

[0226] <Manufacture of Colorant (A)> (Fine Red Pigment (A-1)) 100 parts of C.I. Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 60°C for 6 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating to about 80°C to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, then dried at 80°C for 24 hours and pulverized to obtain the fine red pigment (A-1).

[0227] (Fine Red Pigment (A-2)) 100 parts of C.I. Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 60°C for 6 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating to about 80°C to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, then dried at 80°C for 24 hours and pulverized to obtain the fine red pigment (A-2).

[0228] (Fine Blue Pigment (A-3)) 100 parts of C.I. Pigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 50°C for 12 hours. This mixture was put into 3,000 parts of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and the solvent, then dried at 80°C for 24 hours to obtain the fine blue pigment (A-3).

[0229] (Fine Violet Pigment (A-4)) 100 parts of C.I. Pigment Violet 23, 1,200 parts of sodium chloride, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. Next, this kneaded product was put into 8,000 parts of warm water, stirred for 2 hours while heating to 80°C to make it into a slurry state, and filtration and washing were repeated to remove sodium chloride and diethylene glycol, and then dried at 85°C for 24 hours to obtain a micronized purple pigment (A-4).

[0230] (Dye (A-5)) The dye (A-5), which is a salt-forming compound composed of C.I. Acid Red 52 and a resin 1 having a cationic group in the side chain, was produced by the following procedure. 67.3 parts of methyl ethyl ketone was charged into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were made uniform and then charged into a dropping funnel, attached to the four-neck separable flask, and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more based on the non-volatile content and the weight average molecular weight (Mw) was 6,830, and it was cooled to 50°C. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added here, reacted at 50°C for 2 hours, then heated to 80°C over 1 hour, and further reacted for 2 hours. In this way, a resin 1 having a cationic group in the side chain having an ammonium group of 47% by mass of the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g. Next, 30 parts of Resin 1 having a cationic group in the side chain in terms of non-volatile content was added to 2,000 parts of water, and after sufficient stirring and mixing, it was heated to 60°C. On the other hand, an aqueous solution was prepared by dissolving 10 parts of C.I. Acid Red 52 in 90 parts of water and was gradually added dropwise to the resin solution prepared above. After the addition, it was stirred at 60°C for 120 minutes to allow sufficient reaction. As the confirmation of the end point of the reaction, the reaction solution was dropped onto filter paper, and when there was no bleeding, it was judged that the end point was reached and a salt-forming compound was obtained. After allowing it to cool to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried in a dryer to remove moisture and dried to obtain 32 parts of Dye (A-5), which is a salt-forming compound of C.I. Acid Red 52 and Resin 1 having a cationic group in the side chain. At this time, the content of the component derived from C.I. Acid Red 52 in Dye (A-5) was 25% by mass.

[0231] (Fine Green Pigment (A-6)) 100 parts of C.I. Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 6 hours. This kneaded product was put into 3,000 parts of warm water, stirred for 1 hour while heating to 70°C to make it slurry-like, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol, and then dried at 80°C for one day and night to obtain a fine green pigment (A-5).

[0232] (Fine Yellow Pigment (A-7)) 100 parts of C.I. Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. This mixture was put into 2,000 parts of warm water, stirred for 1 hour while heating to 80°C to make it slurry-like, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol, and then dried at 80°C for one day and night to obtain a fine yellow pigment (A-6).

[0233] (Fine Yellow Pigment (A-8)) 100 parts of C.I. Pigment Yellow 138, 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80 °C for 6 hours. This mixture was poured into 2,000 parts of warm water, stirred for 1 hour while heating to 80 °C to form a slurry, and the filtration and washing with water were repeated to remove salt and solvent. Then, it was dried at 80 °C for a whole day and night to obtain 95 parts of a micronized yellow pigment (A-7).

[0234] <Production of Alkali-Soluble Resin (B)> (Alkali-Soluble Resin (B1-1) Solution) Into a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 10 parts of methacrylic acid, 90 parts of methyl methacrylate, 50 parts of ethyl acrylate, 50 parts of i-butyl methacrylate, and 50 parts of propylene glycol monomethyl ether acetate were charged and purged with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 °C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90 °C, and a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate was added while reacting for 7 hours. It was confirmed by non-volatile content measurement that 95% of the reaction had occurred. 19 parts of pyromellitic dianhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100 °C for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. Propylene glycol monomethyl ether acetate was added for dilution so that the non-volatile content became 30% by non-volatile content measurement, and an alkali-soluble resin (B1-1) solution with an acid value of 70 mgKOH / g, a glass transition temperature of 35 °C, and a weight average molecular weight of 8,500 was obtained.

[0235] (Alkali-Soluble Resin (B1-2) Solution) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic dianhydride, 23.5 parts of cyclohexanone, and 0.01 part of mono-n-butyltin(IV) oxide were charged respectively, and the vessel was purged with nitrogen gas. The inside of the reaction vessel was heated to 100 °C and reacted for 7 hours. After confirming by acid value measurement that 97% or more of the acid anhydride was half-esterified, the temperature inside the system was cooled to 70 °C, and 70 parts of methyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 10 parts of methacrylic acid were charged. A solution prepared by dissolving 0.1 part of 2,2'-azobisisobutyronitrile in 26.2 parts of cyclohexanone was added, and the reaction was carried out for 10 hours. The reaction was terminated after confirming by non-volatile content measurement that the polymerization had proceeded by 95%. After the reaction was completed, the non-volatile content was adjusted to 30% with propylene glycol monomethyl ether acetate, and an alkali-soluble resin (B1-2) solution with an acid value of 99 mgKOH / g, a glass transition temperature of 60 °C, and a weight-average molecular weight of 9500 was obtained.

[0236] (Alkali-soluble resin (B1-3) solution) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 12 parts of 3-mercapto-1,2-propanediol, 25 parts of pyromellitic dianhydride, 66 parts of cyclohexanone, and 0.06 part of monobutyltin oxide as a catalyst were added, and the reaction was carried out at 100 °C for 7 hours. After confirming by acid value measurement that 98% or more of the acid anhydride was half-esterified, 80 parts of n-butyl acrylate, 20 parts of 2-hydroxypropyl methacrylate, 60 parts of (3-ethyloxetan-3-yl)methyl methacrylate, and 40 parts of t-butyl methacrylate were charged and purged with nitrogen gas. The inside of the reaction vessel was heated to 80 °C, and 200 parts of a cyclohexanone solution in which 0.5 part of 2,2'-azobisisobutyronitrile was dissolved was added, and the reaction was carried out for 10 hours. The reaction was terminated after confirming by non-volatile content measurement that 95% of the reaction had occurred. The non-volatile content was adjusted to 30% with propylene glycol monomethyl ether acetate, and an alkali-soluble resin (B1-3) solution with an acid value of 59 mgKOH / g, a glass transition temperature of 50 °C, and a weight-average molecular weight of 5000 was obtained.

[0237] (Alkali-soluble resin (B1-4) solution) 196 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer, and the temperature was raised to 80 °C. After purging the inside of the reaction vessel with nitrogen, a mixture of 20.4 parts of benzyl methacrylate, 18.8 parts of n-butyl methacrylate, 3.6 parts of methacrylic acid, 11.4 parts of 2-hydroxyethyl methacrylate, 45.7 parts of p-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2’-azobisisobutyronitrile was added dropwise over 2 hours through the dropping tube. After completion of the addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was used to adjust the nonvolatile content of the previously synthesized resin solution to 30%, and an alkali-soluble resin (B1-4) solution with an acid value of 24 mgKOH / g, a glass transition temperature of 55 °C, and a weight average molecular weight of 30,000 was obtained.

[0238] (Alkali-soluble resin (B1-5) solution) 196 parts of propylene glycol monomethyl ether acetate were charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer, and the temperature was raised to 80 °C. After purging the inside of the reaction vessel with nitrogen, a mixture of 15.2 parts of benzyl methacrylate, 20.5 parts of n-butyl methacrylate, 7.4 parts of methacrylic acid, 16.1 parts of 2-hydroxyethyl methacrylate, 40.8 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2’-azobisisobutyronitrile was added dropwise through the dropping tube over 2 hours. After completion of the addition, the reaction was continued for another 3 hours to obtain a solution of the acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content. The nonvolatile content of the previously synthesized resin solution was adjusted to 30% with propylene glycol monomethyl ether acetate so that the nonvolatile content became 30%. A solution of an alkali-soluble resin (B1-5) having an acid value of 48 mgKOH / g, a glass transition temperature of 23 °C, and a weight average molecular weight of 10,000 was obtained.

[0239] (Alkali-soluble resin (B2-1) solution) Charge 370 parts of cyclohexanone into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device. Heat the temperature to 80 °C, replace the air in the flask with nitrogen, and then drop a mixture of 0.4 part of styrene, 20.7 parts of 2-ethylhexyl acrylate, 38.6 parts of glycidyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile from the dropping tube over 2 hours. After the dropping, react at 100 °C for 3 hours, then add a solution of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone, and continue the reaction at 100 °C for 1 hour. Next, replace the air in the container with air, add 0.5 part of tris(dimethylamino)phenol and 0.1 part of hydroquinone to 19.6 parts of acrylic acid (100% of the glycidyl group) into the above container, continue the reaction at 120 °C for 6 hours, and end the reaction when the non-volatile acid value reaches 0.5 to obtain a solution of an acrylic resin. Further, continue to add 20.7 parts of tetrahydrophthalic anhydride (50% of the generated hydroxyl groups) and 0.5 part of triethylamine, and react at 120 °C for 3.5 hours to obtain a solution of an acrylic resin. After cooling to room temperature, sample about 2 parts of the resin solution, heat and dry it at 180 °C for 20 minutes to measure the non-volatile content, and adjust the non-volatile content of the previously synthesized resin solution to 30% with propylene glycol monomethyl ether acetate to obtain a solution of an alkali-soluble resin (B2-1) with an acid value of 76 mgKOH / g, a glass transition temperature of -30 °C, and a weight average molecular weight of 10,000.

[0240] (Alkali-soluble resin (B2-2) solution) 370 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, and the temperature was raised to 80 °C. After purging the inside of the flask with nitrogen, a mixture of 0.4 part of styrene, 9.6 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 44.1 parts of glycidyl methacrylate, and 2.0 parts of 2,2’-azobisisobutyronitrile was added dropwise from the dropping tube over 2 hours. After the addition, the reaction was further carried out at 100 °C for 3 hours. Then, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100 °C for 1 hour. Next, the inside of the container was replaced with air, 0.5 part of tris(dimethylamino)phenol and 0.1 part of hydroquinone were added to 22.3 parts of acrylic acid (100% of glycidyl groups) in the above container, and the reaction was continued at 120 °C for 6 hours until the nonvolatile acid value reached 0.5, and then the reaction was terminated to obtain a solution of an acrylic resin. Subsequently, 23.6 parts of tetrahydrophthalic anhydride (50% of the generated hydroxyl groups) and 0.5 part of triethylamine were added and reacted at 120 °C for 3.5 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was used to adjust the nonvolatile content of the previously synthesized resin solution to 30%, and an alkali-soluble resin (B2-1) solution with an acid value of 87 mgKOH / g, a glass transition temperature of -5 °C, and a weight average molecular weight of 10,000 was obtained.

[0241] (Alkali-soluble resin (B2-3) solution) Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 182 parts of propylene glycol monomethyl ether acetate were introduced. After changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100 °C. Then, a solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 40 parts of benzyl methacrylate, 29.3 parts of methacrylic acid, 6.6 parts of a monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 136 parts of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued at 100 °C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, 24.2 parts of glycidyl methacrylate [(50% relative to the carboxyl group of methacrylic acid used in this reaction)], 0.9 part of tris(dimethylaminomethyl)phenol, and 0.145 part of hydroquinone were charged into the flask, and the reaction was continued at 110 °C for 6 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled, heated and dried at 180 °C for 20 minutes to measure the nonvolatile content, and the resin solution synthesized previously was adjusted with propylene glycol monomethyl ether acetate so that the nonvolatile content became 30%, thereby obtaining a solution of an alkali-soluble resin (B2-3) having an acid value of 95 mgKOH / g, a glass transition temperature of -8 °C, and a weight average molecular weight of 10,000.

[0242] (Alkali-soluble resin (B2-4) solution) Into a separable four-necked flask equipped with a thermometer, a condenser tube, a nitrogen gas inlet tube, a dropping tube, and a stirring device as a reaction vessel, 207 parts of cyclohexanone was charged, and the temperature was raised to 80 °C. After replacing the inside of the reaction vessel with nitrogen, a mixture of 4.2 parts of methacrylic acid, 33.0 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 20.3 parts of benzyl methacrylate, 25.2 parts of glycerin monomethacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was dropped from the dropping tube over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, nitrogen gas was stopped and dry air was injected for 1 hour while stirring, and then after cooling to room temperature, a mixture of 17.3 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK), 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was dropped at 70 °C over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content became 30% to prepare an alkali-soluble resin (B2-4). The acid value was 23 mgKOH / g, the glass transition temperature was -3 °C, and the weight average molecular weight was 5000.

[0243] (Alkali-soluble resin (B3-1) solution) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were charged, and after replacing with nitrogen gas, it was heated and stirred at 120 °C for 4 hours. After confirming by nonvolatile content measurement that 98% had reacted, 73.3 parts of pyromellitic dianhydride was added and reacted at 120 °C for 2 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. An alkali-soluble resin (B3-1) solution with a nonvolatile content of 30% was obtained by adjusting the nonvolatile content with propylene glycol monomethyl ether acetate. The acid value was 49 mgKOH / g, the glass transition temperature was -30 °C, and the weight average molecular weight was 4000.

[0244] (Alkali-soluble resin (B3-2) solution) 196 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube and a stirrer, and the temperature was raised to 80 °C. After purging the inside of the reaction vessel with nitrogen, a mixture of 26.5 parts of benzyl methacrylate, 24.4 parts of n-butyl methacrylate, 14.9 parts of 2-hydroxyethyl methacrylate, 16.1 parts of methacrylic acid, 18.1 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2’-azobisisobutyronitrile was added dropwise over 2 hours through the dropping tube. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of the acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the nonvolatile content became 30% to prepare an alkali-soluble resin (B3-2) solution. The acid value was 105 mgKOH / g, the glass transition temperature was 40 °C, and the weight average molecular weight was 26,000.

[0245] (Alkali-soluble resin (B3-3) solution) 196 parts of cyclohexanone were charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer, and the temperature was raised to 80 °C. After purging the inside of the reaction vessel with nitrogen, a mixture of 19.8 parts of benzyl methacrylate, 18.3 parts of n-butyl methacrylate, 11.1 parts of 2-hydroxyethyl methacrylate, 2.4 parts of methacrylic acid, 48.4 parts of para-cumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours from the dropping tube. After completion of the dropwise addition, the reaction was continued for an additional 3 hours to obtain a solution of the acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the nonvolatile content became 30% to prepare an alkali-soluble resin (B3-2) solution. The acid value was 16 mgKOH / g, the glass transition temperature was 25 °C, and the weight average molecular weight was 26,000.

[0246] (Alkali-soluble resin (B4-1) solution) 370 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 °C, and after replacing the inside of the flask with nitrogen, a mixture of 5.9 parts of benzyl methacrylate, 31.2 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), 29.9 parts of glycidyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the reaction was further carried out at 100 °C for 3 hours, then a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 100 °C for 1 hour. Next, the inside of the container was replaced with air, 0.5 part of tris(dimethylamino)phenol and 0.1 part of hydroquinone were added to 15.2 parts of acrylic acid (100% of the glycidyl group) into the above container, and the reaction was continued at 120 °C for 6 hours until the non-volatile acid value reached 0.5, and the reaction was terminated to obtain a solution of an acrylic resin. Further, 16.0 parts of tetrahydrophthalic anhydride (50% of the generated hydroxyl groups) and 0.5 part of triethylamine were added and reacted at 120 °C for 3.5 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 °C for 20 minutes to measure the non-volatile content, and the non-volatile content of the previously synthesized resin solution was adjusted to 30% with propylene glycol monomethyl ether acetate so that the non-volatile content was 30%, and an alkali-soluble resin (B4-1) solution having an acid value of 59 mgKOH / g, a glass transition temperature of 8 °C, and a weight average molecular weight of 15000 was obtained.

[0247] (Alkali-soluble resin (B4-2) solution) Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 182 parts of propylene glycol monomethyl ether acetate were introduced. After changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 °C. Then, a solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 34.2 parts of methacrylic acid, 37.5 parts of a monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 136 parts of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued at 100 °C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, 28.3 parts of glycidyl methacrylate [(50% based on the carboxyl group of methacrylic acid used in this reaction), 0.9 part of tris(dimethylaminomethyl)phenol, and 0.145 part of hydroquinone were added to the flask, and the reaction was continued at 110 °C for 6 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled, heated and dried at 180 °C for 20 minutes to measure the nonvolatile content, and the resin solution synthesized previously was adjusted with propylene glycol monomethyl ether acetate so that the nonvolatile content became 30%, thereby obtaining a solution of an alkali-soluble resin (B4-2) having an acid value of 112 mgKOH / g, a glass transition temperature of 40 °C, and a weight average molecular weight of 25,000.

[0248] (Alkali-soluble resin (B4-3) solution) In a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping funnel, and a stirrer, 207 parts of cyclohexanone was charged, and the temperature was raised to 80 °C. After purging the inside of the reaction vessel with nitrogen, a mixture of 1.6 parts of methacrylic acid, 31.4 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 18.0 parts of benzyl methacrylate, 28.3 parts of glycerin monomethacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise through the dropping funnel over 2 hours. After completion of the addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, nitrogen gas was stopped, and while stirring, dry air was injected for 1 hour, and then cooled to room temperature. Then, a mixture of 13.7 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 °C over 3 hours. After completion of the addition, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content became 30% to prepare an alkali-soluble resin (B4-3). The acid value was 11 mgKOH / g, the glass transition temperature was 50 °C, and the weight average molecular weight was 30,000.

[0249] The acid values and glass transition temperatures of the alkali-soluble resins (B1-1) to (B4-3) are summarized in Table 1.

[0250] [Table 1]

[0251] <Production of Acid Group-containing (Meth)acrylate (C1)>

[0252] (Solution of Acid Group-containing (Meth)acrylate (C1-1) Having a Urethane Bond) Into a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of propylene glycol monomethyl ether acetate, and 0.5 part of N,N-dimethylbenzylamine were charged, and the temperature was raised to 70 °C. A mixture of 66 parts of toluene diisocyanate and 66 parts of propylene glycol monomethyl ether acetate was added dropwise from the dropping tube over 2 hours. After the addition, the reaction was carried out at a temperature of 50 to 70 °C for 8 hours, and the disappearance of the absorption of isocyanate at 2180 cm -1 was confirmed by IR. Next, 35 parts of mercaptoacetic acid and 0.6 part of 4-methoxyphenol were charged, and the reaction was carried out at a temperature of 50 to 60 °C for 6 hours. It was adjusted so that the nonvolatile content became 50% by mass, and an acrylate (C1-1) solution containing an acid group having a urethane bond with an average polymerizable unsaturated group number of 9 was obtained.

[0253] <Production of polymerizable compound (C3) having a urethane bond>

[0254] (Aliphatic urethane (meth)acrylate (C3-1) solution) Into a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of propylene glycol monomethyl ether acetate, and 0.5 part of N,N-dimethylbenzylamine were charged, and the temperature was raised to 70 °C. A mixture of 64 parts of hexamethylene diisocyanate and 64 parts of propylene glycol monomethyl ether acetate was added dropwise from the dropping tube over 2 hours. After the addition, the reaction was carried out at a temperature of 50 to 70 °C for 8 hours, and the disappearance of the absorption of isocyanate at 2180 cm -1 was confirmed by IR. It was adjusted so that the nonvolatile content became 50% by mass, and an aliphatic urethane acrylate (C3-1) solution having a polymerizable unsaturated group number of 10 was obtained.

[0255] (Cycloaliphatic urethane (meth)acrylate (C3-2) solution) Into a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of propylene glycol monomethyl ether acetate, and 0.5 part of N,N-dimethylbenzylamine were charged, and the temperature was raised to 70 °C. A mixture of 84 parts of isophorone diisocyanate and 84 parts of propylene glycol monomethyl ether acetate was added dropwise from the dropping tube over 2 hours. After the addition, the reaction was carried out at a temperature of 50 to 70 °C for 8 hours, and the disappearance of the absorption of isocyanate at 2180 cm -1 was confirmed by IR. It was adjusted so that the nonvolatile content became 50% by mass to obtain an alicyclic urethane acrylate (C3-2) solution having 10 polymerizable unsaturated groups.

[0256] <Production of Dispersion Resin (G)>

[0257] (Dispersion Resin (G) Solution) Into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50 °C for 1 hour while flowing nitrogen to replace the system with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of propylene glycol monomethyl ether acetate were charged, and the temperature was raised to 110 °C under a nitrogen stream to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for nonvolatile content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of nonvolatile content. Next, 61 parts of propylene glycol monomethyl ether acetate and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Fanacryl FA-711MM) as the second block (A block) monomer were charged into this reactor, and the mixture was stirred while maintaining the temperature at 110°C under a nitrogen atmosphere to continue the reaction. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled for non-volatile content measurement. It was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. Propylene glycol monomethyl ether acetate was added for dilution so that the non-volatile content was 30% in the non-volatile content measurement, and a dispersion resin (G) solution with an amine value of 57 mgKOH / g per non-volatile content and a number average molecular weight of 4,500 (Mn) was obtained.

[0258] <Production of Dispersion> (Dispersion 1) After stirring and mixing the following raw materials uniformly, they were dispersed using zirconia beads with a diameter of 0.5 mm for 3 hours in an Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 1.0 μm to prepare Dispersion 1. The organic solvent (P-1) is propylene glycol monomethyl ether acetate. Fine red pigment (A-1): 14.0 parts Dye derivative (F-1): 2.0 parts Alkali-soluble resin (B3-1) solution: 3.0 parts Alkali-soluble resin (B3-2) solution: 3.0 parts Alkali-soluble resin (B4-1) solution: 3.0 parts Alkali-soluble resin (B4-2) solution: 3.0 parts Alkali-soluble resin (B4-3) solution: 3.0 parts Dispersion resin (G-1) solution: 5.0 parts Organic solvent (P-1): 64.0 parts

[0259] Dye derivative (F-1): The following structure [Chemistry]

[0260] Dispersions 2 to 8 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts described in Table 2 were changed.

[0261] [Table 2]

[0262] Dye derivative (F-2) in Table 2: The following structure [Chemistry]

[0263] [Production of Photosensitive Coloring Composition] [Example 1] (Photosensitive Coloring Composition 1) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain Photosensitive Coloring Composition 1. Dispersion 1: 17.0 parts Dispersion 2: 17.0 parts Dispersion 6: 0.5 part Alkali-soluble resin (B1-1) solution: 9.0 parts Alkali-soluble resin (B2-1) solution: 10.5 parts Acid group-containing (meth)acrylate having a urethane bond (C1-1): 6.0 parts Polymerizable compound (C2) having a caprolactone structure: 2.0 parts Other polymerizable compound (C4): 2.0 parts Photopolymerization initiator (D1-2-1): 1.0 part Thioxanthone-based compound (E1): 0.1 part Epoxy compound (H1): 0.1 part Thiol-based chain transfer agent (I): 0.1 part Polymerization inhibitor (J): 0.1 part Antioxidant (L): 0.1 part Leveling agent (M): 1.0 part Organic solvent (P): 33.5 parts

[0264] [Examples 2 to 40, Comparative Examples 1 to 4] (Photosensitive coloring compositions 2 to 44) The photosensitive coloring compositions 2 to 44 were prepared in the same manner as in Example 1, except that the raw materials and amounts described in Tables 3-1 to 3-4 were changed for the photosensitive coloring composition 1 of Example 1. Note that Examples 21 and 22 in this specification are reference examples.

[0265]

Table 3-1

[0266]

Table 3-2

[0267]

Table 3-3

[0268]

Table 3-4

[0269] Regarding each of the raw materials described in Tables 3-1 to 3-4, it is as follows.

[0270] [Polymerizable compound (C)] (Acid group-containing (meth)acrylate (C1)) C1-2: Aronix M-520 (manufactured by Toagosei Co., Ltd.) (Polymerizable compound (C2) having a caprolactone structure) C2-1: KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) (In general formulas (2) to (4), m = 1, the number of groups represented by general formula (3) = 2, R 1 are all hydrogen atoms) C2-2: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.) (In the general formulas (2) to (4), m = 1, the number of groups represented by the general formula (3) = 3, and all R1 are hydrogen atoms) C2-3: KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.) (In the general formulas (2) to (4), m = 1, the number of groups represented by the general formula (3) = 6, R 1 are all hydrogen atoms) As described above, (C2-1) to (C2-3) were each mixed in the same amount to obtain a polymerizable compound (C2) having a caprolactone structure. (Other polymerizable compound (C4)) C4-1: Aronix M402 (manufactured by Toagosei Co., Ltd.) C4-2: Aronix M309 (manufactured by Toagosei Co., Ltd.) C4-3: ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) C4-4: A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.) As described above, (C4-1) to (C4-4) were each mixed in the same amount to obtain other polymerizable compound (C4).

[0271] [Photoinitiator (D)] (Oxime-based compound (D1)) [Oxime-based compound (D1-1) containing one oxime group in one molecule] D1-1-1: Adeka Arcles NCI-730 (manufactured by ADEKA Corporation) [Oxime-based compound (D2-1) containing two oxime groups in one molecule] D2-1-1: The compound represented by the above chemical formula (6) D2-1-2: The compound represented by the above chemical formula (7) (Acetophenone-based compound (D2)) D2-1: Omnirad 907 (manufactured by IGM Resins) D2-2: Omnirad 379EG (manufactured by IGM Resins)

[0272] [Sensitizer (E)] (Thioxanthone-based compound (E1)) E1-1: 2,4-diethylthioxanthone (Benzophenone compound (E2)) E2-1: 4,4'-Bis(diethylamino)benzophenone

[0273] [Thermosetting compound (H)] (Epoxy compound (H1)) H1-1: EHPE-3150 (manufactured by Daicel Corporation) H1-2: Denacol EX611 (manufactured by Nagase ChemteX Corporation) H1-3: Triglycidyl isocyanurate The above (H1-1) to (H1-3) were each mixed in the same amount to obtain the epoxy compound (H1).

[0274] [Thiol chain transfer agent (I)] I-1: Trimethylolethane tris(3-mercaptobutyrate) I-2: Trimethylolpropane tris(3-mercaptobutyrate) I-3: Pentaerythritol tetrakis(3-mercaptopropionate) I-4: Trimethylolpropane tris(3-mercaptopropionate) I-5: Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate The above (I-1) to (I-5) were each mixed in the same amount to obtain the thiol chain transfer agent (I).

[0275] [Polymerization inhibitor (J)] J-1: 4-Methylcatechol J-2: Methylhydroquinone J-3: t-Butylhydroquinone The above (J-1) to (J-3) were each mixed in the same amount to obtain the polymerization inhibitor (J).

[0276] [Antioxidant (L)] L-1: Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate L-2: Dioctadecyl 3,3'-thiodipropionate L-3: Tris[2,4-di-(t)-butylphenyl]phosphine L-4: Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate L-5: p-Octylphenyl salicylate The above (L-1) to (L-5) were each mixed in the same amount to obtain the antioxidant (L).

[0277] [Leveling agent (M)] 1 part of BYK-330 (manufactured by BYK-Chemie), 0.5 part of Megafac F-563 (manufactured by DIC), 0.5 part of Emulgen A-60 (manufactured by Kao Corporation), The solution obtained by dissolving the above in 98 parts of PGMAc was used as the leveling agent (M).

[0278] [Organic solvent (P)] P-1: Propylene glycol monomethyl ether acetate 30 parts P-2: Cyclohexanone 30 parts P-3: Ethyl 3-ethoxypropionate 10 parts P-4: Propylene glycol monomethyl ether 10 parts P-5: Cyclohexanol acetate 10 parts P-6: Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were each mixed in the above parts by mass to obtain the organic solvent (P).

[0279] [Evaluation of the photosensitive coloring composition] For the obtained photosensitive coloring compositions 1 to 44 (Examples 1 to 40, Comparative Examples 1 to 4), evaluations of the pattern shape, water stain, alkali developability, and residual film ratio were carried out by the following methods. The evaluation results are shown in Table 4.

[0280] [Pattern shape evaluation] The obtained photosensitive coloring composition was applied by spin coating onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm in length × 100 mm in width and 0.7 mm in thickness so that the film thickness after drying was 3.0 μm, and then dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, it was exposed through a photomask with a stripe pattern of 100 μm width (pitch 200 μm) at an illuminance of 30 mW / cm 2 ², 40 mJ / cm 2 ². Thereafter, this substrate was spray developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C, then washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 30 minutes to obtain a substrate for pattern formability evaluation. The spray development was performed at the shortest time capable of forming a pattern without any remaining development for the film of each photosensitive coloring composition. The obtained pattern was evaluated by counting the number of defects such as streaks at the edge of the pattern using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon Corporation. A value of 3 or more is considered practical. 5: No defects such as streaks can be confirmed at all. 4: Defects such as streaks were confirmed at one or more locations to less than 10 locations. 3: Defects such as streaks were confirmed at 10 or more locations to less than 20 locations. 2: Defects such as streaks were confirmed at 20 or more locations. 1: Part of the 100-μm-wide pattern fine line remains.

[0281] <Water stain evaluation> Regarding the obtained photosensitive coloring composition, it was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm in length × 100 mm in width and 0.7 mm so that the film thickness after drying was 3.0 μm, and then dried on a hot plate at 70°C for 1 minute. Next, using a high-pressure mercury lamp through a photomask with a stripe pattern of 100 μm width (pitch 200 μm) at an illuminance of 30 mW / cm 2 ², 40 mJ / cm 2Ultraviolet exposure was performed under the following conditions. Subsequently, it was developed by immersing it in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23°C for 40 seconds, and then washed with pure water. The obtained pattern was observed for the surface of the pattern using a Nikon ECLIPSE LV100POL Model optical microscope, and the degree of the discolored part was evaluated. A value of 3 or more was considered practical. 5: There was no water stain. 4: The water stain was less than 10% of the whole. 3: The water stain was 10% or more and less than 20% of the whole. 2: The water stain was 20% or more and less than 30% of the whole. 1: The water stain was 30% or more of the whole.

[0282] <Alkali developability evaluation> [Preparation of carbon black dispersion] 100 parts of carbon black (No. 47 manufactured by Mitsubishi Chemical Corporation, average primary particle diameter 23 nm, specific surface area 132 m2 / g, oil absorption 64 cm3 / 100 g), 4 parts of the dye derivative (F-3) shown in the following chemical formula, 14 parts of an alkali-soluble resin (B1-1) solution, and 6 parts of an alkali-soluble resin (B2-1) solution were mixed and diluted with cyclohexanone so that the nonvolatile content became 20%. The obtained mixture was dispersed for 2 hours using a paint shaker with glass beads having a diameter of 0.8 mm to prepare a carbon black dispersion A. The viscosity of the obtained carbon black dispersion A was 8.70 mPa·s at 25°C.

[0283] Dye derivative (F-3): The following structure

Chemical formula

[0284] Carbon black dispersion A was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a size of 100 mm in length × 100 mm in width and a thickness of 0.7 mm, and dried under reduced pressure to form a coating film with a thickness of 1 μm. After the entire surface of this coating film was exposed with a high-pressure mercury lamp at 50 mJ / cm2, it was spray-developed for 60 seconds using a 0.05% potassium hydroxide aqueous solution maintained at 25°C, then thoroughly washed with ion-exchanged water, dried with clean air, and the obtained substrate was post-baked at 230°C for 30 minutes to prepare an evaluation substrate (hereinafter referred to as BM substrate). Thereafter, the photosensitive coloring composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) or BM substrate with a size of 100 mm in length × 100 mm in width and a thickness of 0.7 mm, and dried under reduced pressure to form a coating film with a thickness of 2 microns. After the entire surface of this coating film was exposed with a high-pressure mercury lamp at 50 mJ / cm2 using a photomask with a stripe pattern having a line width of 100 μm (pitch 200 μm), it was spray-developed for 60 seconds using a 0.05% potassium hydroxide aqueous solution maintained at 25°C, then thoroughly washed with ion-exchanged water, and dried with clean air to obtain an evaluation coating film. This evaluation is to evaluate the development residues on the BM coating film when continuously forming each color filter segment. On a glass substrate or BM substrate with a size of 100 mm in length × 100 mm in width and a thickness of 0.7 mm from which the coating film was removed by development, the presence or absence of residues was observed using a Nikon ECLIPSE LV100POL Model optical microscope, and the degree of development residues was evaluated. A value of 3 or more is considered practical. 5: No residues were confirmed on the glass substrate and BM substrate 4: No residues were confirmed on the glass substrate, but one or more to less than 10 locations were confirmed on the BM substrate 3: No residues were confirmed on the glass substrate, but 10 or more to less than 20 locations were confirmed on the BM substrate 2: One or more to less than 10 residues were present on the glass substrate, and 20 or more were confirmed on the BM substrate 1: 10 or more residues were present on the glass substrate, and 20 or more were confirmed on the BM substrate.

[0285] <Residual film rate evaluation> The obtained photosensitive coloring composition was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm in length × 100 mm in width and 0.7 mm in thickness by the spin coating method so that the film thickness after drying was 3.0 μm, and then dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, it was exposed through a photomask with a stripe pattern of 100 μm width (pitch 200 μm) at an illuminance of 30 mW / cm 2 , 40 mJ / cm 2 . Then, this substrate was spray-developed using an aqueous developer containing 0.12% by mass of a nonionic surfactant and 0.04% by mass of potassium hydroxide at 23°C. The spray development was carried out at the shortest time capable of forming a pattern without any remaining development for the coating film of each photosensitive coloring composition. Then, it was washed with ion-exchanged water and air-dried, and the film thickness of the coating film was measured. This film thickness was taken as the film thickness after development. Then, it was heated in a clean oven at 230°C for 30 minutes, and the film thickness at the same location where the film thickness after development was measured was measured. This film thickness was taken as the film thickness after baking. The remaining film ratio was calculated from the two film thicknesses using the following formula. A value of 3 or more was considered practical. The film thickness measurement was carried out using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.). Formula: Remaining film ratio (%) = Film thickness after baking ÷ Film thickness after development × 100 5: Remaining film ratio 85% or more 4: Remaining film ratio 80% or more and less than 85% 3: Remaining film ratio 75% or more and less than 80% 2: Remaining film ratio 70% or more and less than 75% 1: Remaining film ratio less than 70%

[0286]

Table 4

Claims

1. A photosensitive coloring composition comprising a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the alkali-soluble resin (B) comprises a non-photosensitive alkali-soluble resin (B1) having a glass transition temperature of 20°C or higher and an acid value of 20 to 100 mgKOH / g, and a photosensitive alkali-soluble resin (B2) having a glass transition temperature of 0°C or lower and an acid value of 20 to 100 mgKOH / g, The photosensitive coloring composition containing 5 to 60% by mass of the non-photosensitive alkali-soluble resin (B1) in 100% by mass of the alkali-soluble resin (B).

2. The photosensitive coloring composition according to claim 1, wherein the photopolymerization initiator (D) comprises an oxime-based compound (D1).

3. The photosensitive coloring composition according to claim 2, wherein the oxime-based compound (D1) comprises an oxime-based compound (D1-2) containing two oxime groups in one molecule.

4. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the polymerizable compound (C) comprises an acid group-containing (meth)acrylate (C1).

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

6. An image display device having the color filter according to claim 5.

7. A solid-state imaging device having the color filter according to claim 5.

Images