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

Abstract

To provide a photosensitive coloring composition having excellent developability, adhesion, and pattern profile.SOLUTION: A photosensitive coloring composition contains a colorant (A), a basic dispersant (B), a binder resin (C), a polymerizable monomer (D), and a photopolymerization initiator (E). The binder resin (C) includes a binder resin (C1) containing a polymerizable unsaturated group. The polymerizable monomer (D) includes a polymerizable monomer (D1) containing a fluorene skeleton and having a glass transition temperature of 200°C or lower.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a coloring composition and a photosensitive coloring composition used in the manufacture of a color filter for use in a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, electronic paper, and the like, and to a color filter having a filter segment formed using the same. [Background technology]

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

[0003] Currently, the manufacturing method of color filters includes a step of applying a photosensitive coloring composition to a transparent substrate such as glass, removing the solvent from the coating film by drying, a step of irradiating and curing the coating film with ultraviolet light or the like through a photomask having a desired pattern shape (hereinafter referred to as exposure), a step of cleaning and removing the unexposed parts of the coating film (hereinafter referred to as development), and then, if necessary, a step of heating the cured film to sufficiently cure (hereinafter referred to as post-baking) to obtain a filter segment pattern of a first color. Then, filter segment patterns of other colors are formed by carrying out the same operations as above to complete a color filter.

[0004] In recent years, the area per pixel has tended to become smaller due to the miniaturization and high pixel density of image display devices and solid-state imaging devices, and there has been a demand for increasing the concentration of the colorant contained in the composition forming the color filter to make it thinner and for the pattern to be highly fine. However, when the concentration of the colorant is increased, the transmittance of ultraviolet light into the inside of the film decreases, which causes a problem of poor curing degree and poor adhesion to the substrate. In particular, the adhesion decreases when the pattern is highly fine. In addition, when the amount of the photopolymerization initiator is increased to increase the curing degree, there is a problem of the pattern becoming thicker than the desired line width and the shape becoming poor.

[0005] In order to solve these problems, various methods have been investigated. Patent Document 1 discloses a photosensitive coloring composition containing a polyalkylene oxide or an alkylene oxide adduct of glycerin. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2007-058192 A Summary of the Invention [Problem to be solved by the invention]

[0007] An object of the present invention is to provide a photosensitive coloring composition which is excellent in developability, adhesion and pattern shape. [Means for solving the problem]

[0008] The present invention relates to a photosensitive coloring composition comprising a colorant (A), a basic dispersant (B), a binder resin (C), a polymerizable monomer (D), and a photopolymerization initiator (E), wherein the binder resin (C) comprises a binder resin (C1) containing a polymerizable unsaturated group, and the polymerizable monomer (D) comprises a polymerizable monomer (D1) containing a fluorene skeleton and having a glass transition temperature of 200° C. or lower.

[0009] The present invention also relates to the above photosensitive coloring composition, wherein the content of the polymerizable monomer (D1) is 50% by mass or more in 100% by mass of the polymerizable monomer (D).

[0010] The present invention also relates to the photosensitive coloring composition, wherein the content of the photopolymerization initiator (E) is 0.5 to 10 mass % based on the total mass of the binder resin (C1) containing a polymerizable unsaturated group and the polymerizable monomer (D).

[0011] The present invention also relates to the photosensitive coloring composition, wherein the binder resin (C1) containing a polymerizable unsaturated group contains at least two or more binder resins having different weight average molecular weights.

[0012] The present invention also relates to the photosensitive coloring composition, wherein the binder resin (C1) containing a polymerizable unsaturated group includes a binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight of 12,000 or less and a binder resin (C1-2) containing a polymerizable unsaturated group having a weight average molecular weight of 18,000 or more.

[0013] The present invention also relates to the photosensitive coloring composition, wherein the mass ratio of the binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight of 12,000 or less to the binder resin (C1-2) containing a polymerizable unsaturated group having a weight average molecular weight of 18,000 or more is 20:80 to 80:20.

[0014] The present invention also relates to the above photosensitive coloring composition, wherein the photopolymerization initiator (E) contains an oxime compound (E1).

[0015] The present invention also relates to the above photosensitive coloring composition, which further contains an acidic dispersant (F).

[0016] The present invention also relates to a color filter comprising a substrate and a filter segment formed from the above-mentioned photosensitive coloring composition.

[0017] The present invention also relates to an image display device comprising the above color filter.

[0018] The present invention also relates to a solid-state imaging device comprising the above color filter. Effect of the Invention

[0019] According to the present invention, a photosensitive coloring composition having excellent developability, adhesion, pattern shape, and solvent resistance can be provided. The present invention also provides a color filter, an image display device, and a solid-state imaging device. [Brief description of the drawings]

[0020] [Figure 1] FIG. 1 is a schematic cross-sectional view of a liquid crystal display device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Each of the components of the photosensitive coloring composition of the present invention will be described below. In this application, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" respectively mean "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide". In addition, "CI" as used herein means Color Index (CI).

[0022] <Colorant (A)> The photosensitive coloring composition of the present invention contains a colorant (A).

[0023] The colorant (A) is not particularly limited and may be either a pigment or a dye, which may be used in combination. Since color filters are required to have light resistance, heat resistance, and solvent resistance, pigments are preferred.

[0024] (Pigments) The pigment is not particularly limited, and examples thereof include compounds classified as pigments in the Color Index.

[0025] Specific examples of red pigments that can be used in the present invention include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57: 2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259 , 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in JP 2014-134712 A, and pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light fastness, and transmittance, CI Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6,368,844 are preferred, and CI Pigment Red 177,254,291,295,296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6,368,844 are particularly preferred.

[0026] Specific examples of orange pigments that can be used in the present invention include CI Pigment Orange 36, 38, 43, 64, 71, 73, and the like.

[0027] Specific examples of yellow pigments that can be used in the present invention include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 11 No. 9,120,123,126,127,128,129,138,139,147,150,151,152, 153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,192,193,194,196,198,199,213,214,231,233, and the like. Among these, CI Pigment Yellow 138, 139, 150, 185, 231, and 233, and the pigments described in JP-A-2012-226110 are preferred.

[0028] Specific examples of green pigments that can be used in the present invention include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, CI Pigment Green 36, 58, 59, 62, and 63 are preferred.

[0029] Specific examples of blue pigments that can be used in the present invention include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

[0030] Specific examples of purple pigments that can be used in the present invention include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 and 23 are preferred.

[0031] Specific examples of black pigments that can be used in the present invention include CI Pigment Black 1, 6, 7, 12, 20, 31, and the like.

[0032] The photosensitive coloring composition of the present invention can also use inorganic pigments as the colorant (A). Examples include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

[0033] (dye) The dye is not particularly limited, and examples thereof include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Furthermore, the dye may be in the form of a derivative of these dyes or a lake pigment obtained by making the dye into a lake.

[0034] Furthermore, in the case of an acid dye having an acidic group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, it is preferable to use a salt-forming compound obtained by salting using an inorganic salt of the acid dye, a salt-forming compound obtained by salting the acid dye with a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound, or a resin component having these functional groups, or to use the acid dye as a sulfonamide compound, which has excellent resistance, thereby making it possible to obtain a coloring composition having excellent fastness. Further, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferred because it has excellent fastness, and more preferably, the compound having an onium salt group is a resin having a cationic group in the side chain.

[0035] In the case of the basic dye, it can be used after being salted with an organic acid, perchloric acid or a metal salt thereof. Among them, a salt-forming compound of a basic dye is preferred because of its excellent resistance and compatibility with pigments, and it is more preferred to use a salt-forming compound obtained by salting a basic dye with a counter component acting as a counter ion, such as an organic sulfonic acid, an organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye.

[0036] Furthermore, when the dye skeleton has a polymerizable unsaturated group, the dye can be made to have excellent durability, which is preferable.

[0037] Examples of the chemical structure of the dye include azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, polymer dyes, etc. Examples of dye structures that may be used include, but are not limited to, dyes derived from dyes selected from tin dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, and croconium dyes), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0038] Among these dye structures, from the viewpoint of color properties such as hue, color separation, and color unevenness, dye structures derived from dyes selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and dye structures derived from dyes selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific dye compounds that can form the dye structure are described in "New Edition Dyes Handbook" (edited by the Society of Organic Synthesis Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Dyes Handbook" (edited by Okawara et al.; Kodansha, 1986), and the like.

[0039] The colorant (A) can be used alone or in combination of two or more kinds.

[0040] The content of the colorant (A) is preferably from 5 to 70 mass %, and more preferably from 10 to 60 mass %, in 100 mass % of the nonvolatile content of the photosensitive color composition.

[0041] (Micronization of pigments) The pigment is preferably used in a finely divided state. The method of finely dividing is not particularly limited, and for example, any of wet grinding, dry grinding, and solution precipitation can be used. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferred. The average primary particle size of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

[0042] Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or other kneading machine, 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 during salt milling by utilizing the high hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0043] Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate, etc., and sodium chloride (table salt) is preferred from the viewpoint of cost. The amount of the water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

[0044] The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, dissolves (mixes) in water, and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporate, a high boiling point solvent with a boiling point of 120°C or more is preferable from the viewpoint of safety. 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, relative to 100 parts by mass of the pigment.

[0045] In the salt milling treatment, a resin may be added as necessary. By adding a resin, the pigment is coated with the resin, and the stability, light resistance, etc. are improved. The type of the resin is not particularly limited, and examples thereof include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature and insoluble in water, and is partially soluble in the organic solvent. The amount of the resin added is preferably 2 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0046] <Basic dispersant (B)>

[0047] A known basic dispersant (B) can be used in the photosensitive coloring composition of the present invention. The basic dispersant (B) may be any dispersant that has a colorant affinity site that has the property of adsorbing to an added colorant and a site that is compatible with the colorant carrier, and that functions to adsorb to the added colorant and stabilize the dispersion in the colorant carrier. Specifically, urethane-based dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylates, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modifications thereof. Examples of the dispersants that can be used include oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups and their salts, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters, and these can be used alone or in combination of two or more. Examples of polymer dispersants having a basic functional group include nitrogen atom-containing graft copolymers, and nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in the side chains.

[0048] Commercially available resin-type dispersants include 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, and 200 manufactured by BYK Chemical Japan Co., Ltd. 000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, Lactimon, Lactimon-WS or Bykumen, etc., Nippon Lubrizol SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36 600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. BASF EFKA-46, 47, 48, 452, 4008, 4060, 4406, 4408, 450, 451, 453, 4540, 4800, 5070, 7500, 7554, 1101, 120, 150, 1502, Efka PU 4009, 4010, 4015, 4020, 4046, 4047, 4050, 4055, 4061, 4063, 4080, Efka PA 4400, 4401, 4402, 4403, 4414, 4450, Efka PX 4300, 4310, 4320, 4330, 4340, 4350, 4700, 4701, 4731, 4732, Efka FA4610, 4665, 4666, Dispex Ultra PA 4501, 4503, 4550, 4560, 4580, 4590, and Ajispa-PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0049] In the photosensitive coloring composition of the present invention, a resin type dispersant having a carboxyl group can be suitably used. The shape of the resin type dispersant having a carboxyl group includes a straight-chain resin type dispersant and a comb-shaped resin type dispersant.

[0050] The basic dispersant (B) is preferably used in an amount of about 3 to 200% by mass based on the total amount of the colorant, and from the viewpoint of developability, more preferably about 3 to 100% by mass.

[0051] <Binder resin (C)> The binder resin (C) can be classified into a binder resin (C1) containing a polymerizable unsaturated group and a binder resin (C2) not containing a polymerizable unsaturated group. Among them, it is preferable to include a photosensitive binder resin (C1) from the viewpoint of adhesion, pattern shape, and solvent resistance. And, it is preferable that the binder resin (C) has an alkali-soluble group from the viewpoint of developability. Examples of the alkali-soluble group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, and a phenolic hydroxyl group, and among these, a carboxyl group is preferable. The binder resin (C) may also contain a thermosetting group such as an epoxy group or an oxetanyl group.

[0052] (Binder resin (C1) containing a polymerizable unsaturated group) Examples of the binder resin (C1) containing a polymerizable unsaturated group include an acrylic resin having an acidic group, an α-olefin / maleic acid (anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth)acrylic acid copolymer, or an isobutylene / maleic acid (anhydride) copolymer, etc. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferred.

[0053] (Binder resin (C1) containing a polymerizable unsaturated group) The binder resin (C1) containing a polymerizable unsaturated group is a binder resin having a polymerizable unsaturated group. The binder resin (C1) containing a polymerizable unsaturated group is preferably a resin synthesized by the following method (i) or (ii).

[0054] [Method (i)] In the method (i), for example, a polymer of an epoxy group-containing monomer and other monomers is first synthesized, and then a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain a binder resin (C1) containing a polymerizable unsaturated group.

[0055] 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.

[0056] Examples of other monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxy (meth)acrylates such as diethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, ethoxy polyethylene glycol (meth)acrylate, ethylene oxide (EO) modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO modified (meth)acrylate of phenol, EO or propylene oxide (PO) modified (meth)acrylate of paracumylphenol, EO modified (meth)acrylate of nonylphenol, PO modified (meth)acrylate of nonylphenol, etc.; (Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Styrene or styrenes such as alpha-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl acetate or vinyl propionate or other vinyl fatty acids; Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichloro N-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; Examples of such monomers include phosphate group-containing monomers such as 2-(meth)acryloyloxyethyl acid phosphate and compounds in which the hydroxyl group of a hydroxyl group-containing monomer described below is reacted with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid. These monomers can be used alone or in combination of two or more.

[0057] Examples of monocarboxyl group-containing monomers include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position. These can be used alone or in combination of two or more kinds.

[0058] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. If necessary, the remaining anhydride groups may be hydrolyzed using a tricarboxylic dianhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic anhydride.

[0059] As a method similar to the method (i), for example, a polymer of a carboxyl group-containing monomer and other monomers is synthesized, and then an epoxy group-containing monomer is added to a part of the carboxyl groups of the polymer to obtain a binder resin (C1) containing a polymerizable unsaturated group.

[0060] [Method (ii)] In the method (ii), for example, a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers is synthesized, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer.

[0061] Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexane dimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to a hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylate obtained by addition of polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. These can be used alone or in combination of two or more. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred in terms of the difficulty of generating foreign matter in the coating. Glycerol mono(meth)acrylate is also preferred in terms of photosensitivity.

[0062] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate, and these can be used alone or in combination of two or more kinds.

[0063] As the monocarboxyl group-containing monomer and other monomers, the above-mentioned monomers can be used.

[0064] The weight average molecular weight (Mw) of the binder resin (C) is preferably from 2,000 to 40,000, more preferably from 3,000 to 300,000, and particularly preferably from 5,000 to 25,000. The value of Mw / Mn is preferably 10 or less.

[0065] The acid value of the binder resin (C) is preferably from 40 to 200 mgKOH / g, more preferably from 50 to 180 mgKOH / g.

[0066] The binder resin (C) can be used alone or in combination of two or more kinds, and from the viewpoints of developability, adhesion, pattern shape, and solvent resistance, it is preferable to include a binder resin (C1) containing two or more kinds of polymerizable unsaturated groups having different weight average molecular weights (Mw). Among them, it is preferable to use a binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight (Mw) of 12,000 or less in combination with a binder resin (C1-2) containing a polymerizable unsaturated group having a weight average molecular weight (Mw) of 18,000 or more, and it is more preferable to use a photosensitive binder resin (C1-1) having a weight average molecular weight (Mw) of 5,000 to 10,000 in combination with a photosensitive binder resin (C1-2) having a weight average molecular weight (Mw) of 20,000 to 25,000 in combination.

[0067] The mass ratio of the binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight (Mw) of 12,000 or less to the binder resin (C1-2) containing a polymerizable unsaturated group having a weight average molecular weight (Mw) of 18,000 or more is preferably 20:80 to 80:20, and more preferably 30:70 to 70:30, from the viewpoints of developability, adhesion, pattern shape, and solvent resistance.

[0068] The content of the binder resin (C) is preferably from 20 to 400 parts by mass, and more preferably from 30 to 250 parts by mass, based on 100 parts by mass of the colorant (A).

[0069] <Polymerizable monomer (D)> The photosensitive coloring composition of the present invention is characterized in that it contains a polymerizable monomer (D1) that contains a fluorene skeleton and has a glass transition temperature (Tg) of 200° C. or less as the polymerizable monomer (D). The polymerizable monomer (D) is a monomer (also called a monomer) and an oligomer that contain a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.

[0070] Commercially available polymerizable monomers (D1) that contain a fluorene skeleton and have a glass transition temperature of 200° C. or lower include OGSOL EA-0300 and GA-2800 manufactured by Osaka Gas Chemicals Co., Ltd.

[0071] The measurement can be performed by preparing a cured film by reacting a polymerizable monomer (D1) containing a fluorene skeleton and having a glass transition temperature of 200° C. or less with a photopolymerization initiator, and subjecting the cured film to differential scanning calorimetry. Specifically, the measurement was performed by the method described in Example 2 of JP 2009-173646 A.

[0072] The polymerizable monomer (D1) containing a fluorene skeleton and having a glass transition temperature of 200° C. or lower is preferably a compound represented by the following general formulas (1) to (2).

[0073] General formula (1) [ka]

[0074] (In general formula (1), R1 and R3 each independently represent a hydrogen atom or a methyl group, R2 and R4 each independently represent an alkylene group, and m and n each independently represent an integer of 1 to 10.)

[0075] General formula (2) [ka]

[0076] (In general formula (2), R5 and R7 each independently represent a hydrogen atom or a methyl group, R6 and R8 each independently represent an alkylene group, and x and y each independently represent an integer of 1 to 10.)

[0077] Examples of the polymerizable monomer (D) in the present invention include monomers and oligomers that are cured by ultraviolet light, heat, or the like to form a transparent resin. Examples of the polymerizable monomer (D) in the present invention include 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, and the like. Polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropane Examples of the acrylic acid esters and methacrylic acid esters include, but are not limited to, butyl ether 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 urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0078] Commercially available products of these include 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, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, and M-32 manufactured by Toagosei Co., Ltd. Suitable examples of the polymerizable compound that can be used include, for example, M-1, 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, and M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, and #405 manufactured by Osaka Organic Chemical Co., Ltd., and NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.

[0079] (Polymerizable compound having an acid group) The polymerizable monomer (D) in the present invention may contain a polymerizable compound having an acid group. By using a polymerizable compound having an acid group, when the photosensitive coloring composition of the present invention is subjected to alkaline development, the solubility of the formed coating film in an alkaline developer can be increased, and the development speed can be improved and the residue can be reduced. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

[0080] Examples of polymerizable compounds having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl(meth)acrylates, etc. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid, etc.; propane-1,2,3-tricarboxylic acid (tricarballylic acid). Examples of the free carboxyl group-containing oligoesters include tricarboxylic acids such as butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, but the effects of the present invention are not limited to these.

[0081] As commercially available products thereof, Viscoat #2500P manufactured by Osaka Organic Coatings Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd., and the like can be suitably used.

[0082] (Polymerizable compound having urethane bond) The polymerizable monomer (D) in the present invention may contain a polymerizable compound containing at least one ethylenically unsaturated bond and at least one urethane bond. By containing a polymerizable compound having a urethane bond, it is possible to suppress precipitation of the coloring material when the formed coating film is heated, and to improve the solvent resistance and adhesion to the substrate.

[0083] Examples of the polymerizable compound having a urethane bond include a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[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, and a hydroxyl group-containing polyol polyacrylate.

[0085] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

[0086] As commercially available products thereof, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd., UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like can be suitably used.

[0087] The above polymerizable monomer (D) may be used alone or in combination with the polymerizable monomer (D1) in any desired ratio, if necessary.

[0088] The blending amount of the polymerizable monomer (D) is preferably 1 to 50 parts by mass based on the total solid content of the photosensitive coloring composition (100 parts by mass). The ratio of the polymerizable monomer (D1) to the polymerizable monomer (D) is preferably 50:50 to 80:20, more preferably 80:20 to 90:10, and most preferably 90:10 to 100:0.

[0089] [Photopolymerization initiator (E)] The photosensitive coloring composition of the present invention contains a photopolymerization initiator (E). By containing the photopolymerization initiator (E), the photosensitive coloring composition can be cured by ultraviolet irradiation to form a cured film.

[0090] The photopolymerization initiator (E) is not particularly limited as long as it is a compound capable of initiating the polymerization of the polymerizable monomer (C) by light, and known photopolymerization initiators can be used. For example, acetophenone compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the compound include quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds.

[0091] Commercially available products include Omnirad 907, 369, and 379EG manufactured by IGM Resins as acetophenone-based compounds, and Omnirad 819 and TPO manufactured by IGM Resins as acylphosphine-based compounds. Examples of the oxime compound (E1) include IRGACURE OXE-01, 02, 03, and 04 manufactured by BASF Japan Ltd., N-1919, 730, 831, and 930 manufactured by ADEKA Corporation, TRONLY TR-PBG-301, 304, 305, 309, 345, 346, 358, 3054, and 3057 manufactured by Changzhou Strong New Materials Co., Ltd., OMNIRAD1312, 1314, and 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, and 07 manufactured by Samyang Corporation, and DFI-020, 036, and EOX-01 manufactured by Daito Chemistry Co., Ltd. Further examples include the oxime compounds (E1) described in JP2005-215378A, JP2011-105713A, JP2017-523465A, JP2007-210991A, JP2009-179619A, JP2010-037223A, JP2010-215575A, JP2011-020998A, WO2015 / 036910, and the like.

[0092] Among these, the oxime compound (E1) is preferred from the viewpoints of reactivity and pattern formability.

[0093] The photopolymerization initiator (E) can be used alone or in combination of two or more kinds.

[0094] From the viewpoints of adhesion and pattern shape, the content of the photopolymerization initiator (E) is preferably 0.5 to 10 mass %, more preferably 1 to 5 mass %, and most preferably 1 to 3 mass %, based on the total mass of the binder resin (C1) containing a polymerizable unsaturated group and the polymerizable monomer (D).

[0095] [Acidic dispersant (F)] The photosensitive coloring composition of the present invention preferably contains an acidic dispersant (F) having an acidic group such as a carboxyl group. [Comb-shaped resin-type dispersant having carboxyl groups (F1)] The comb-shaped resin-type dispersant (F1) having a carboxyl group can be produced by known methods such as those described in WO2008 / 007776, JP2008-029901A, and JP2009-155406A. For example, the resin-type dispersant is a reaction product between the hydroxyl group of a polymer having a hydroxyl group and the acid anhydride group of a tetracarboxylic dianhydride, or the resin-type dispersant is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between the hydroxyl group of a compound having a hydroxyl group and the acid anhydride group of a tetracarboxylic dianhydride.

[0096] The acidic dispersant (F) is preferably used in an amount of about 3 to 200% by mass based on the total amount of the colorant, and from the viewpoint of film-forming properties, more preferably about 3 to 100% by mass.

[0097] [Sensitizer (G)] The photosensitive coloring composition of the present invention can contain a sensitizer (G).

[0098] Examples of the sensitizer (G) include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyra, and the like. Examples of the compound include aryl ether derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxy esters, acyl oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0099] Among the sensitizers (G), thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred.Specific examples of preferred compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole.

[0100] The sensitizer (G) can be used alone or in combination of two or more kinds.

[0101] The content of the sensitizer (G) is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator (E). When an appropriate amount is contained, photocurability and developability are improved.

[0102] [Thermosetting compound (H)] The photosensitive coloring composition of the present invention can contain a thermosetting compound (H). This allows the thermosetting compound (H) to react in the heating step, increasing the crosslink density and improving the heat resistance.

[0103] The thermosetting compound (H) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (H) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0104] (Epoxy compound (H1)) Examples of the epoxy compound (H1) include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.), and polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.). Examples of such epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, and glycidyl ester epoxy resins.

[0105] Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celloxide 2021, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, Ltd., and the like.

[0106] The content of the epoxy compound (H1) is preferably from 0.5 to 50 mass %, and more preferably from 1 to 40 mass %, in 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0107] (Oxetane Compound (H2)) The oxetane compound (H2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher oxetane compounds.

[0108] Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0109] Examples of commercially available products include OXE-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101,212 manufactured by Toagosei Co., Ltd.

[0110] Examples of the bifunctional oxetane compound include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyl oxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethyleneglycol bis(3-ethyl-3-oxetanylmethyl)ether, 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.

[0111] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and 221 manufactured by Toagosei.

[0112] Examples of the trifunctional or higher oxetane compounds include pentaerythritol tris(3-ethyl-3-oxetanylmethyl)ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl)ether, and caprolactone-modified dipentaerythritol. Examples of such polymers include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing an oxetane group (e.g., the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30.

[0113] The content of the oxetane compound (H2) is preferably from 0.5 to 50 mass %, and more preferably from 1 to 40 mass %, in 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0114] The melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol type or ether type compound, and more preferably a melamine compound having an average of 5.0 or more methylol groups and / or ether groups per melamine ring. If the compound has an appropriate number of methylol groups or ether groups, it is easy to obtain just the right amount of heat resistance.

[0115] Examples of commercially available products include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries Co., Ltd.

[0116] Among these, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, and MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, and 350 manufactured by Nippon Cytec Industries Co., Ltd., which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are preferred in terms of increasing the crosslink density.

[0117] The thermosetting compound (H) can be used alone or in combination of two or more kinds.

[0118] [Hardening agent (curing accelerator)] The photosensitive coloring composition of the present invention can be used in combination with a curing agent (curing accelerator) to aid in the curing of the thermosetting compound (H). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., 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 (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

[0119] The curing agents can be used alone or in combination of two or more kinds.

[0120] The content of the curing agent is preferably 0.01 to 15 parts by mass based on 100 parts by mass of the thermosetting compound (H).

[0121] [Thiol-based chain transfer agents (I)] The photosensitive coloring composition of the present invention can contain a thiol chain transfer agent (I). When the thiol chain transfer agent (I) is used in combination with a photopolymerization initiator (E), a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, improving the photosensitivity of the photosensitive coloring composition.

[0122] The thiol chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent has four or more SH groups. As the number of functional groups increases, the film becomes easier to photocure from the surface to the deepest part.

[0123] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples of the thiopropionate include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and the like. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

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

[0125] The content of the thiol chain transfer agent (I) is preferably 0.1 to 10 mass%, more preferably 0.5 to 8 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the photosensitivity is improved and wrinkles are less likely to occur on the pattern surface.

[0126] [Polymerization inhibitor (J)] The photosensitive coloring composition of the present invention may contain a polymerization inhibitor (J).

[0127] Examples of the polymerization inhibitor (J) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, 2-n alkyl resorcinol compounds such as 1-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucinone.

[0128] The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0129] [Ultraviolet absorber (K)] The photosensitive coloring composition of the present invention may contain an ultraviolet absorber (K).

[0130] The ultraviolet absorber (K) is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0131] 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, 5% 2-methoxy-1-methylethene, Mixture of methyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and straight chain alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl) -5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 reaction products, 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, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0132] Examples of commercially available products include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Japan Ltd., ADK STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA CORPORATION, KEMISORB71, 73, 74, 79, and 279 manufactured by Chemipro Chemical Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

[0133] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the compound include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0134] Examples of commercially available products include KEMISORB102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF Japan, Adeka STAB LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

[0135] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3-water, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0136] Examples of commercially available products include KEMISORB10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB101 and 107 manufactured by Shipro Chemicals, Adeka STAB 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

[0137] Examples of the salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0138] The content of the ultraviolet absorber (K) is preferably from 5 to 70% by mass in 100% by mass of the total of the photopolymerization initiator (E) and the ultraviolet absorber (K).

[0139] [Antioxidants (L)] The photosensitive coloring composition of the present invention can contain an antioxidant (L). The antioxidant (L) prevents the photopolymerization initiator (E) and the thermosetting compound (H) contained in the photosensitive coloring composition from yellowing due to oxidation during the thermal process of thermal curing or ITO annealing. In particular, when the concentration of the colorant (A) in the photosensitive coloring composition is high, the content of the polymerizable compound (C) is relatively reduced, so that the cured film is likely to yellow if the amount of the photopolymerization initiator (E) is increased or the thermosetting compound (H) is added. Therefore, by including an antioxidant, the yellowing of the cured film due to oxidation during the heating process is prevented.

[0140] Examples of the antioxidant (L) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

[0141] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0142] Examples of the hindered phenol antioxidant include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]Undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di -t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4 ,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylene bisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, Examples of such phenols include 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), and 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol.

[0143] Examples of commercially available products include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA CORPORATION, KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd., and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0144] Examples of the hindered amine antioxidant include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, 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, and 1,2,2,6,6-pentamethyl-4-piperidyl tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1- Ester of piperidineethanol with 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bi 1,2,2,6,6-pentamethyl-4-pyridyl 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)-1,6-Hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0145] Examples of commercially available products include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION, KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals Co., Ltd., Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan Ltd., and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

[0146] Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl)phosphite, diphenyl isodecyl phosphite, tris(isodecyl)phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonite, tris(tridecyl)phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl)phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylide diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples of such phosphite include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-di-t-butyl-6-methylphenyl)phosphite.

[0147] Examples of commercially available products include Adeka STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Japan Ltd., and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0148] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0149] Examples of commercially available products include Adeka STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0150] The antioxidants (L) can be used alone or in combination of two or more.

[0151] The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

[0152] [Leveling agent (M)] The photosensitive coloring composition of the present invention can contain a leveling agent (M). This improves the wettability and drying property of the composition when applied to a substrate. Examples of the leveling agent (M) include silicon-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0153] Examples of silicone surfactants include linear polymers formed from siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or ends.

[0154] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002 and 211 manufactured by Dow Corning Toray Co., Ltd. 0, 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341.

[0155] The fluorosurfactant may be, for example, a surfactant or a leveling agent having a fluorocarbon chain.

[0156] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd., Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation, FC-4430 and 4432 manufactured by Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A manufactured by Neos Corporation.

[0157] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, alkyl alkanolamides, alkyl imidazolines, and the like.

[0158] Commercially available products include, for example, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, and L manufactured by Kao Corporation. S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, LATEMURU PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW- L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Ami-to 102, Examples of such polymers include 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyfluor No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0159] Examples of the cationic surfactant include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0160] Commercially available products include, for example, Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate manufactured by Kao Corporation.

[0161] Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0162] Examples of commercially available products include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adeka Col TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0163] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethyl amino acetate betaine; and alkyl amine oxides such as lauryl dimethyl amine oxide.

[0164] Commercially available products include Anhythol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0165] The leveling agents (M) can be used alone or in combination of two or more kinds.

[0166] 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, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. By being within this range, the balance between the coatability and adhesion of the photosensitive coloring composition is further improved.

[0167] [Storage stabilizer (N)] The photosensitive coloring composition of the present invention can contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive coloring composition over time. Examples of the storage stabilizer (N) include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butyl pyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphites.

[0168] The content of the storage stabilizer (N) is preferably 0.1 to 10 parts by mass based on 100 parts by mass of the colorant (A).

[0169] [Adhesion improver (O)] The photosensitive coloring composition of the present invention can contain an adhesion improver (O). This improves the adhesion between the cured film and the substrate. In addition, it becomes easier to form a narrow pattern by photolithography.

[0170] Examples of the adhesion improver (O) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyl trimethoxysilane and vinyl triethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxysilane, 3-methacryloxypropyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, 3-methacryloxypropyl triethoxysilane, and 3-acryloxypropyl trimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, and 3-glycidoxypropyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl) silane coupling agents such as aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

[0171] The adhesion improver (O) can be used alone or in combination of two or more kinds.

[0172] The content of the adhesion improver (O) is preferably from 0.01 to 10 parts by mass, and more preferably from 0.05 to 5 parts by mass, based on 100 parts by mass of the colorant (A).

[0173] [Organic solvent (P)] The photosensitive composition of the present invention can contain an organic solvent (P).

[0174] The organic solvent (P) may be, 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, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy- 3-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyro lactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,Examples of the dipropylene glycol methyl ether acetate include dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. Among these, from the viewpoints of pigment dispersibility and alkali-soluble resin solubility, preferred are glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

[0175] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0176] [Method of producing photosensitive coloring composition] The photosensitive coloring composition of the present invention is produced by, for example, adding a colorant (A), a binder resin (B), a polymerizable compound (C), a photopolymerization initiator (E), a dispersion resin (F), an organic solvent (P), and the like, and carrying out a dispersion treatment. Then, the dispersion is mixed with the polymerizable compound (C) and the photopolymerization initiator (D), and the composition can be produced. The timing of mixing each material is arbitrary. The dispersion process can also be carried out multiple times.

[0177] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0178] The average dispersed particle size (secondary particle size) of the colorant (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the colorant (A) has an appropriate particle size, a photosensitive coloring composition having high dispersion stability is easily obtained.

[0179] The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso Microtrack UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and D50 particle size set to average size. The dilution solvent used for measurement is the organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasonic waves immediately after sample preparation, as this tends to provide results with less variation.

[0180] The photosensitive coloring composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. 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.

[0181] <Color filters> The color filter of the present invention includes a substrate and a filter segment formed from the photosensitive coloring composition of the present invention. The color filter segment preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant (A) used. The color filter may have a magenta filter segment, a cyan filter segment, and a yellow filter segment instead of or in addition to the color filter segments. The substrate may be a transparent substrate or a reflective substrate. The transparent substrate may be, for example, a glass substrate. The reflective substrate may be, for example, a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0182] [Color filter manufacturing method] The method for producing a color filter is not particularly limited, and the color filter can be produced by carrying out, for example, a step (1) of applying a photosensitive coloring composition onto a substrate to form a layer of the composition, a step (2) of exposing the layer to light in a pattern through a mask, a step (3) of developing the unexposed parts with an alkali to form a patterned cured film, and a step (4) of heat-treating (post-baking) the pattern.

[0183] The method for producing a color filter will now be described in detail. (Process (1)) In the step (1) of forming a composition layer, the photosensitive coloring composition is applied onto a substrate by, for example, spin coating, roll coating, slit coating, casting coating, inkjet coating, or the like, and dried (prebaked) at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, a hot plate, or the like as necessary. Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have an image sensor such as a CCD or a CMOS formed on the surface. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with an upper layer, prevent diffusion of substances, and flatten the substrate surface. The coating is preferably carried out so that the layer has a thickness of 0.05 to 10.0 μm after drying, and more preferably 0.3 to 5 μm.

[0184] (Process (2)) In the exposure step, the layer obtained in step (1) is exposed to light in a specific pattern through a mask using an exposure device such as a stepper, thereby obtaining a cured film. Examples of radiation used for exposure include ultraviolet rays such as g-rays, h-rays, and i-rays.

[0185] (Step (3)) The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the composition layer in the unexposed areas is dissolved in an aqueous alkali solution, leaving only the cured areas to obtain a patterned cured film. Examples of the developing solution include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the developer is preferably from 0.001 to 10% by mass, and more preferably from 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses roughening and peeling of the pattern and improves the remaining film rate after development.

[0186] Examples of the developing method include a dipping method, a spraying method, a paddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0187] (Step (4)) In the heat treatment (post-baking), the patterned cured film obtained in step (3) is sufficiently cured by heating. The heating temperature in the post-baking is preferably 100 to 300° C., and more preferably 150 to 250° C. The heating time is preferably about 2 minutes to 1 hour, and more preferably about 3 minutes to 30 minutes.

[0188] <Image display device> The image display device of the present invention comprises the color filter of the present invention. The form of the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) can be mentioned. The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Yoshiaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0189] Fig. 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with a color filter of the present invention. The device 10 shown in Fig. 1 includes a pair of transparent substrates 11 and 21 arranged to face each other with a space therebetween, with liquid crystal LC sealed between them.

[0190] A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0191] On the other hand, a color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0192] A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of the transparent protective film. An alignment layer 24 is provided to cover the transparent electrode layer 23.

[0193] In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0194] <Solid-state imaging element> The solid-state imaging device of the present invention comprises the color filter of the present invention. The form used for the solid-state imaging element is not particularly limited, but may be, for example, a structure in which a substrate has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) and a transfer electrode made of polysilicon or the like, a light shielding film having an opening only for the light receiving portion of the photodiode on the photodiode and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light shielding film so as to cover the entire light shielding film and the light receiving portion of the photodiode, and a color filter on the device protection film. Furthermore, a structure in which a light collecting means (e.g., a microlens, etc., the same below) is provided on the device protection film and below the color filter (the side closer to the substrate), a structure in which a light collecting means is provided on the color filter, etc. may also be used. In addition, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned, for example, in a lattice shape, by partition walls. In this case, the partition walls preferably have a low refractive index with respect to each color pixel. An imaging device including a solid-state imaging element of the present invention can be used not only in digital cameras and electronic devices having an imaging function (such as mobile phones and smartphones), but also in vehicle-mounted cameras and surveillance cameras. EXAMPLES

[0195] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these. In addition, "parts" means "parts by mass" and "%" means "% by mass".

[0196] Before describing the examples, each measurement method will be described. The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are as follows.

[0197] (Average molecular weight of binder resin and dispersing resin) The number average molecular weight (Mn) and weight average molecular weight (Mw) of the binder resin and the dispersion resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

[0198] (Acid value of binder resin and dispersing resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of binder resin and dispersed resin solution, and the mixture was stirred to dissolve uniformly. The mixture was titrated with an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) using a 0.1 mol / L KOH aqueous solution as the titrant to measure the acid value (mgKOH / g). The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution.

[0199] (Amine value of dispersion resin) The amine value of the dispersing resin is the total amine value (mgKOH / g) measured according to the method of ASTM D 2074 and converted into non-volatile content.

[0200] <Production of Colorant (A)> (Finely divided green pigment (A-1)) 100 parts of CI Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70° C. This kneaded mixture was poured into 3,000 parts of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain a finely divided green pigment (A-1).

[0201] (Finely divided yellow pigment (A-2)) 100 parts of CI Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 80° C. This mixture was poured into 2,000 parts of warm water and stirred for 1 hour while heating to 80° C. to form a slurry, which was then filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried overnight at 80° C. to obtain a finely divided yellow pigment (A-2).

[0202] <Production of Basic Dispersant (B)> (Basic dispersant (B-1) solution) In a 500 mL round-bottomed 4-neck separable flask equipped with a cooling tube, a dropping funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts by mass of dimethylketene methyl trimethylsilyl acetal as an initiator were added through the dropping funnel, and sufficient nitrogen replacement was performed. 0.5 parts by mass of a 1 mol / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe, and 19.7 parts by mass of 2-hydroxyethyl methacrylate, 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate as solvent-philic blocking monomers were dropped using the dropping funnel over 60 minutes. The temperature was kept below 40°C by cooling the reaction flask in an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, a monomer for colorant adsorption functional blocks, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The resulting block copolymer THF solution was reprecipitated in hexane, filtered, and purified by vacuum drying. Next, 15.0 parts by mass of the obtained block copolymer were dissolved in 35 parts by mass of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc) in a 100 mL round-bottom flask, and 1.1 parts by mass of phenylphosphinic acid (0.5 molar equivalent relative to dimethylaminopropyl methacrylamide), which is a salt-forming component, was added. The mixture was stirred at a reaction temperature of 30°C for 20 hours, and PGMAc was added to adjust the content, thereby obtaining a basic dispersant (B-1) solution with a non-volatile content of 30%.

[0203] <Production of binder resin (C)> The binder resins (C1-1-1) to (C1-1-4), (C1-3), (C1-2-1) to (C1-2-4), and (C2-1) to (C2-2) were synthesized by changing the ingredients and composition ratios as shown in Tables 1 and 2, and PGMAc was added to adjust the non-volatile content to 20%.

[0204] The synthesis and production methods were carried out in accordance with the description in JP 2020-060631 A.

[0205] [Table 1]

[0206] [Table 2]

[0207] The terms shown in Tables 1-2 are as follows: GMA+AA: Polymerizable unsaturated group-containing monomer obtained by reacting epoxy groups of glycidyl methacrylate with acrylic acid GMA+AA+TPHA: A polymerizable unsaturated group-containing monomer modified with fatty acid anhydride obtained by esterification of the hydroxyl group of GMA+AA with tetrahydrophthalic anhydride. GMA+MAA: Polymerizable unsaturated group-containing monomer obtained by reacting the epoxy group of glycidyl methacrylate with methacrylic acid

[0208] <Production of Acidic Dispersant (F)> (Acidic dispersant (F-1) solution) A reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile and 90 parts of PGMAc was added and reacted for 7 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts 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. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the solution was diluted with PGMAc to make the non-volatile content 30%, to obtain an acidic dispersant (F-1) solution with an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500.

[0209] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, then dispersed in an Eiger mill (Eiger Japan "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The organic solvent (P-1) was PGMAc. Finely divided green pigment (A-1): 9.7 parts Finely divided yellow pigment (A-2): 4.4 parts Basic dispersant (B-1) solution: 19.5 parts Organic solvent (P-1): 66.4 parts

[0210] The blending types and amounts were changed so as to achieve the composition ratios shown in Table 3, and dispersions 1 to 5 were obtained.

[0211] [Table 3]

[0212] <Production of Photosensitive Coloring Composition> [Example 1] (Photosensitive coloring composition 1) The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition 1. Dispersion 1: 56.5 parts Polymerizable unsaturated group-containing binder resin (C1-1-3) solution: 11.5 parts Polymerizable unsaturated group-containing binder resin (C1-2-2) solution: 8.5 parts Polymerizable compound (D1-1): 2.5 parts Photopolymerization initiator (E1-1): 0.15 parts Leveling agent (M): 1.0 part Organic solvent (P): 19.85 parts

[0213] The types and amounts of ingredients were changed so as to achieve the composition ratios shown in Tables 4 to 9, and photosensitive coloring compositions 1 to 38 were obtained. It should be noted that Examples 18, 21, 24, and 25 are reference examples.

[0214] [Polymerizable compound (C)] (D1, a compound represented by general formula (1) having a Tg of 200° C. or less) D1-1: OGSOL EA-0300 (Osaka Gas Chemicals, Tg 17℃) D1-2: OGSOL GA-2800 (Osaka Gas Chemicals, Tg7℃) (D2, a compound not represented by general formula (1) or with a Tg of more than 200°C) D2-1: Aronix M-402 (manufactured by Toagosei Co., Ltd., trimethylolpropane ethylene oxide modified triacrylate) D2-2: OGSOL EA-0200 (Osaka Gas Chemicals, Tg211℃)

[0215] [Photopolymerization initiator (E)] (Oxime compounds) E1-1: ADEKA Cruise NCI-831 (ADEKA) E1-2: Irgacure OXE04 (BASF Japan) (Acetophenone compounds) E2: Irgacure 907 (BASF Japan)

[0216] [Leveling agent (M)] A mixed solution in which one part each of BYK-330 (manufactured by BYK-Chemie) and Megafac F-551 (manufactured by DIC) was mixed and dissolved in 98 parts of PGMAc was used as a leveling agent (M).

[0217] [Organic solvent (P)] 80 parts of PGMAc, 10 parts of cyclohexanone, and 10 parts of ethyl 3-ethoxypropionate were mixed to prepare an organic solvent (P).

[0218] [Table 4]

[0219] [Table 5]

[0220] [Table 6]

[0221] [Table 7]

[0222] [Table 8]

[0223] [Table 9]

[0224] <Evaluation of Photosensitive Coloring Composition> The developability, adhesion, and pattern shape of the photosensitive coloring compositions 1 to 38 were evaluated by the following methods. The evaluation results are shown in Table 10.

[0225] [Table 10]

[0226] [Developability] The obtained photosensitive coloring compositions 1 to 38 were applied to a glass substrate (Corning Eagle 2000) having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm using a spin coater so that the dry film thickness was 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. Then, an ultra-high pressure mercury lamp was used to apply the coating with an illumination intensity of 30 mW / cm. 2 , 50mJ / cm 2 The substrate was exposed to ultraviolet light through a photomask with a 100 μm wide stripe pattern. After cooling the substrate to room temperature, it was spray-developed using an organic alkaline developer NMD-3 (Tokyo Ohka Kogyo Co., Ltd.) at 23°C for two development times (40 seconds and 70 seconds), washed with ion-exchanged water, and air-dried to form a striped pattern on the substrate. The pattern was observed under an optical microscope to evaluate the presence or absence of development residues and chipping in unexposed areas. The evaluation criteria are as follows, with 3 or more being practical. 5: When the development time was 70 seconds, there was no development residue in the unexposed areas and no pattern loss. 4: After a development time of 70 seconds, a slight development residue was observed in the unexposed area or a slight pattern defect was observed. 3: When the development time was 70 seconds, development residue occurred or pattern defects occurred in the unexposed areas. 2: When the development time was 40 seconds, a large amount of development residue was generated in the unexposed area or a large amount of pattern loss was generated. 1: Pattern loss occurred when the development time was 40 seconds.

[0227] [Adhesion] The obtained photosensitive coloring compositions 1 to 38 were applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the film thickness after drying would be 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp was used to illuminate the substrate through a photomask with a stripe pattern with 5 μm width intervals at an illumination intensity of 30 mW / cm. 2 , 50mJ / cm 2 Then, the substrate was spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 30 minutes to obtain a substrate for evaluation. The spray development was carried out for the shortest time possible for a pattern to be formed without residual development for each coating of the photosensitive coloring composition, and this was determined as the appropriate development time. Among the patterns on the evaluation substrate, fine line patterns with widths of 5 to 25 μm were observed with an optical microscope to confirm the minimum line width of the remaining fine line patterns. The evaluation criteria are as follows, with 3 or more being practical. 5: Fine lines of 10 μm or less remain. 4: Fine lines of 15 μm or less remain. 3: Fine lines of 20 μm or less remain. 2: Fine lines of 25 μm or less remain. 1: No fine lines remain.

[0228] [Pattern shape (cross-sectional shape evaluation)] The pattern shape of the substrate prepared for the adhesion evaluation was confirmed using a scanning electron microscope (Hitachi High-Tech's "S-3000H"). The cross-sectional shape was evaluated by capturing an SEM image of the cross section of a 100 μm wide stripe pattern and measuring the taper angle between the substrate and the edge of the pattern cross section. The evaluation criteria are as follows, with 3 or higher being considered practical. 5: Taper angle is between 30 degrees and 50 degrees 4: Taper angle is 50 degrees or more and less than 60 degrees 3: Taper angle less than 30 degrees or between 60 degrees and 70 degrees 2: Taper angle is between 70 degrees and 90 degrees 1: Taper angle 90 degrees or more [Explanation of symbols]

[0229] 10 LCD display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color Filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing Plate 30 Backlight unit 31 White LED light source LC Liquid Crystal

Claims

1. A photosensitive coloring composition comprising a colorant (A), a basic dispersant (B), a binder resin (C), a polymerizable monomer (D), and a photopolymerization initiator (E), The photosensitive coloring composition, wherein the binder resin (C) comprises a binder resin (C1) containing a polymerizable unsaturated group, the polymerizable monomer (D) comprises a polymerizable monomer (D1) containing a fluorene skeleton and having a glass transition temperature of 200° C. or lower, and the binder resin (C1) containing a polymerizable unsaturated group comprises a binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight of 12,000 or lower and a binder resin (C1-2) containing a polymerizable unsaturated group having a weight average molecular weight of 18,000 or more and 25,000 or less.

2. The photosensitive coloring composition according to claim 1, wherein the content of the polymerizable monomer (D1) is 50% by mass or more in 100% by mass of the polymerizable monomer (D).

3. The content of the photopolymerization initiator (E) is 0.5 to 10 mass% with respect to the total mass of the binder resin (C1) containing a polymerizable unsaturated group and the polymerizable monomer (D). The photosensitive coloring composition according to claim 1 or 2.

4. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the weight ratio of the binder resin (C1-1) containing a polymerizable unsaturated group having a weight average molecular weight of 12,000 or less and the binder resin (C1-2) containing a polymerizable unsaturated group having a weight average molecular weight of 18,000 or more and 25,000 or less is 20:80 to 80:

20.

5. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the photopolymerization initiator (E) comprises an oxime compound (E1).

6. The photosensitive coloring composition according to any one of claims 1 to 5, further comprising an acidic dispersant (F).

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

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

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

Images