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

Abstract

To provide a photosensitive coloring composition that contains 50-90 mass% of a coloring agent with respect to 100 mass% of a non-volatile content in a coloring composition, and resolves a defect of which a residue is easily generated since a ratio of a component promoting development is lowered by the high coloring agent concentration and a defect of which stability of viscosity deteriorates due to high coloring agent concentration.SOLUTION: A photosensitive coloring composition contains a coloring agent, a resin, a polymerizable compound, a photopolymerization initiator and an organic solvent, contains 50-90 mass% of the coloring agent with respect to 100 mass% of a non-volatile content in the coloring composition, in which the organic solvent has the following structure, and 5-30 mass% of the organic solvent having a boiling point at 760 mmHg of 160°C or higher with respect to 100 mass% of the organic solvent. R1-O-(X-O)n-R2, in which R1 and R2 represent a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, and X represents an alkylene group having 2 or 3 carbon atoms; and n represents 2-4.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive coloring composition used in the production of color filters used in color liquid crystal displays, solid-state image pickup devices, etc., and to a color filter using the same. [Background technology]

[0002] Color filters that constitute color liquid crystal displays (LCDs), solid-state imaging devices, etc. are produced by applying a coating liquid (coloring composition) to a transparent substrate and drying it to form a coating film with a thickness of approximately 0.3 to 3 μm.

[0003] The most widely adopted method for producing color filters used in color liquid crystal displays and the like involves, for example, applying a pigment-dispersed photosensitive coloring composition to a substrate, drying to remove the solvent, exposing the dried coating to a desired pattern (irradiating with radiation), removing the unexposed areas by development, and optionally applying heat or other treatments to obtain each of the RGB color pixels. To produce each of the RGB color patterns, it is necessary to minimize residues in the unexposed areas removed by development. If residues remain in the unexposed areas removed by development, measures to remove the residues are required during color filter production, leading to reduced yields and increased production costs in color filter production. Examples of color filter coloring compositions that leave little residue include those containing a fluorine-containing surfactant obtained by reacting a hydroxyl-containing copolymer obtained by copolymerizing a radically polymerizable monomer having a poly(perfluoroalkylene ether) chain with a radically polymerizable monomer having a polyalkylene glycol chain with a compound having an isocyanate group and a radically polymerizable group (see, for example, Patent Document 1). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-250256 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention is characterized in that the coloring composition contains 50 to 90% by mass of colorant (A) relative to 100% by mass of the nonvolatile content in the coloring composition. The present invention was arrived at through extensive research aimed at solving the drawbacks of a high colorant concentration, which reduces the ratio of components that promote development, making residues more likely to be generated, and a high colorant concentration, which reduces viscosity stability. [Means for solving the problem]

[0006] That is, the present invention provides a photosensitive coloring composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and an organic solvent (S), wherein the colorant (A) is contained in an amount of 50 to 90% by mass relative to 100% by mass of the nonvolatile content of the coloring composition, and The photosensitive coloring composition is characterized in that the organic solvent (S) has a structure represented by the following formula (1) and contains an organic solvent (S1) having a boiling point of 160°C or higher at 760 mmHg in an amount of 5 to 30% by mass relative to 100% by mass of the organic solvent (S): R 1 -O-(XO)nR 2 Formula (1) (In formula (1), R 1 and R 2 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 1 and R 2 Either one of the above is a linear or branched alkyl group having 1 to 4 carbon atoms. X represents a linear or branched alkylene group having 2 or 3 carbon atoms. n represents an integer of 2 to 4. Multiple Xs may be the same or different.

[0007] The present invention also relates to the above photosensitive coloring composition, wherein the organic solvent (S1) has a boiling point at 760 mmHg of 200° C. or higher.

[0008] The present invention also relates to the above photosensitive coloring composition, wherein the organic solvent (S1) has a boiling point at 760 mmHg of 250° C. or higher.

[0009] The present invention also provides a color filter formed using the above photosensitive coloring composition.

[0010] The present invention also relates to a liquid crystal display device comprising the above color filter.

[0011] The present invention also relates to a solid-state imaging device comprising the above color filter. [Effects of the Invention]

[0012] According to the present invention, a photosensitive coloring composition that is easy to handle due to its good viscosity stability can be provided. Furthermore, by using the photosensitive coloring composition of the present invention, high-quality color filters, color liquid crystal displays, solid-state imaging devices, etc. that are suppressed in residue can be provided. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic cross-sectional view of a liquid crystal display device. DETAILED DESCRIPTION OF THE INVENTION

[0014] Each of the components of the photosensitive coloring composition of the present invention will be described below. In the present invention, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" refer to "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. Also, "CI" as used herein means Color Index (CI).

[0015] <Colorant (A)> In the photosensitive coloring composition of the present invention, the following pigments and dyes can be used as colorants either alone or in combination of two or more kinds in any ratio as required. The photosensitive coloring composition of the present invention is characterized by containing 50 to 90% by mass of the coloring agent (A) relative to 100% by mass of the nonvolatile content in the coloring composition, and having a high coloring agent concentration.

[0016] For example, red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 210, 212, 214, 216, 218, 219, 220, 221, 222, 223, 224, 226, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 249, 250, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 26 02, 206, 207, 208, 209, 210, 216, 220, 221, 224, 226, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 296. Examples of the pigment include, but are not limited to, azo pigments described in JP-A-2014-112527, azo pigments described in JP-A-2013-161026, and diketopyrrolopyrrole pigments described in JP-A-2011-523433.

[0017] Among these, CI Pigment Red 254 and CI Pigment Red 177 are preferred in terms of high transmittance.

[0018] Examples of orange pigments include, but are not limited to, CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, and 73. Among these, CI Pigment Orange 71 is preferred in terms of reproducing the color gamut of a color filter. Yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, and 73. , 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150 , 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231,233, and quinophthalone compounds described in JP-A-2012-226110, but are not particularly limited thereto. Among these, CI Pigment Yellow 138, 139, 150, 185 and the quinophthalone compounds described in JP-A-2012-226110 are preferred in terms of reproducing the color gamut of a color filter.

[0019] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, from the viewpoints of brightness and coloring strength, CI Pigment Green 7, 36, 58, 59, 62, and 63 are preferred. In addition, zinc phthalocyanine pigments described in JP-A Nos. 2008-19383, 2007-320986, and 2004-70342, and aluminum phthalocyanine pigments described in JP-A Nos. 2004-333817 and 2012-247588 can be used. Examples of blue pigments that can be used include CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, and 80. Examples of purple pigments that can be used include CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. Examples of black pigments that can be used include carbon black, aniline black, anthraquinone-based black pigments, and perylene-based black pigments, specifically CI Pigment Black 1, 6, 7, 12, 20, and 31. Metal lake pigments of rhodamine dyes such as CI Pigment Red 81, 81:1, 81:2, 81:3, 81:4, and 81:5 can also be used in combination.

[0020] Examples of inorganic pigments include metal oxide powders, metal sulfide powders, and metal powders such as silicon oxide, zirconia oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, titanium black, synthetic iron black, titanium oxide, and iron tetroxide.

[0021] As for the dye, for example, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Derivatives of these dyes or lake pigments obtained by laking dyes may also be used.

[0022] Furthermore, in the case of an acid dye having an acidic group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, it is preferable to use the acid dye as a salt-forming compound obtained by salt formation using an inorganic salt of the acid dye, a salt-forming compound of the acid dye with a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound, or a resin component having these functional groups, or to use the acid dye as a sulfonamide compound, which results in a coloring composition having excellent fastness, since the coloring composition has excellent resistance. Furthermore, a salt-forming compound of an acid dye with a compound having an onium salt group is also preferred because it has excellent fastness, and more preferably, the compound having an onium salt group is a resin having a cationic group in the side chain.

[0023] In the case of a basic dye, it can be used after being salted with an organic acid, perchloric acid, or a metal salt thereof. Among these, a salt-forming compound of a basic dye is preferred because of its excellent durability and compatibility with pigments, and it is more preferred to use a salt-forming compound obtained by salting a basic dye with a counter component acting as a counter ion, such as an organic sulfonic acid, an organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, a cyano-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye.

[0024] Furthermore, when the dye skeleton has a polymerizable unsaturated group, the dye can be made to have excellent durability, which is preferable.

[0025] 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, etc. Examples of the dye structure include dyes derived from dyes selected from the group consisting of oxonol-based dyes, merocyanine-based dyes, arylidene-based dyes, styryl-based dyes, cyanine-based dyes, squarylium-based dyes, and croconium-based dyes, quinophthalone-based dyes, phthalocyanine-based dyes, subphthalocyanine-based dyes, perinone-based dyes, indigo-based dyes, thioindigo-based dyes, quinoline-based dyes, nitro-based dyes, nitroso-based dyes, rhodamine-based dyes, and metal complex dyes thereof.

[0026] Among these dye structures, from the viewpoint of color properties such as hue, color separation, and color unevenness, dye structures derived from dyes selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and dye structures derived from dyes selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific dye compounds that can form the dye structure are described in "New Edition Dye Handbook" (edited by the Society of Organic Synthetic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyes and Colorists), "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986), etc.

[0027] In the present invention, the dye derivative (b) described below, which is added as needed, is classified as a colorant.

[0028] <Pigment miniaturization> When a pigment is used as the colorant (A), it is preferable to make it finely divided. The method for micronizing the pigment used in the photosensitive coloring composition of the present invention is not particularly limited, and for example, wet milling, dry milling, or solution precipitation can all be used. As exemplified in the present invention, micronization can be achieved by salt milling using a kneader, which is a type of wet milling. The average primary particle diameter of the pigment as determined by TEM (transmission electron microscope) is preferably in the range of 10 to 80 nm. If the particle diameter is smaller than 10 nm, it becomes difficult to disperse it in an organic solvent, and if the particle diameter is larger than 80 nm, a sufficient contrast ratio may not be obtained. For these reasons, the average primary particle diameter is more preferably in the range of 15 to 70 nm.

[0029] Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heating using a batch or continuous mixer such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or planetary mixer, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. Optimizing the conditions for salt milling a pigment can produce a pigment with an extremely fine primary particle size, a narrow distribution, and a sharp particle size distribution.

[0030] Examples of water-soluble inorganic salts that can be used include sodium chloride, barium chloride, potassium chloride, and sodium sulfate, but sodium chloride (table salt) is preferred from the standpoint of cost. From the standpoints of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, and most preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment.

[0031] The water-soluble organic solvent functions to moisten the pigment and water-soluble inorganic salt. It is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, a high-boiling solvent with a boiling point of 120°C or higher is preferred from a safety standpoint. Examples of water-soluble organic solvents that can be used include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of 5 to 1,000 parts by weight, and most preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

[0032] When the pigment is subjected to salt milling, a resin may be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvents. The amount of resin used is preferably in the range of 5 to 200 parts by mass per 100 parts by mass of the pigment.

[0033] <Resin (B)> The resin (B) in the present invention includes a resin-type dispersant (B1) and a binder resin (B2) described later. Since the photosensitive coloring composition of the present invention has a high colorant concentration in the nonvolatile matter, the resin (B) must not be able to maintain sufficient dispersion stability, and a dye derivative (b) is added as needed.

[0034] The content of the resin (B) in the photosensitive coloring composition of the present invention is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, based on the total mass of the colorant (A) (100 parts by mass).

[0035] <Resin-type dispersant (B1)> In the photosensitive coloring composition of the present invention, a resin-type dispersant (B1) can be used to effectively disperse the colorant.The resin-type dispersant may be any dispersant that has a colorant affinity site that has the property of adsorbing to the 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.Specific examples of the resin-type dispersant include urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof. Examples of suitable dispersants include oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imine) with a polyester having a free carboxyl group, and salts thereof; water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone; polyester-based compounds, modified polyacrylate-based compounds, ethylene oxide / propylene oxide adducts, and phosphate ester-based compounds; 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 in the side chains containing tertiary amino groups, quaternary ammonium salt groups, nitrogen-containing heterocycles, etc. These can be used alone or in combination of two or more.

[0036] 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, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, and 2160 manufactured by BYK Japan. 155, 2163, 2164 or Anti-Terra-U, 203, 204 or BYK-P104, P104S, 220S, LPN6919, LPN21116, LPN21324 or Lactimon, Lactimon-WS or Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 2165 ... 1000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajispa-PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0037] <Dye derivative (b)> As the dye derivative used as needed in the present invention, known dye derivatives having an acidic group, a basic group, a neutral group, or the like in the organic dye residue can be used. Examples include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and their amine salts; compounds having a sulfonamide group or a basic substituent such as a tertiary amino group at the terminal; and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Since the resin-type dispersant used in combination has an acidic group, dye derivatives having a basic group are preferred. Examples of organic dyes of the organic dye residue include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0038] Specifically, diketopyrrolopyrrole dye derivatives are disclosed in JP 2001-220520 A, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, and JP 2017-156397 A, phthalocyanine dye derivatives are disclosed in JP 2007-226161 A, WO2016 / 163351 pamphlet, JP 2017-165820 A, and Japanese Patent No. 5753266 A, and anthraquinone dye derivatives are disclosed in JP-A No. 63-264674, JP-A No. 09-272812, JP-A No. 10-245501, JP-A No. 10-265697, JP-A No. 2007-079094, WO2009 / 025325 pamphlet; quinacridone dye derivatives are disclosed in JP-A No. 48-54128, JP-A No. 03-9961, and JP-A No. 2000-273383; dioxazine dye derivatives are disclosed in JP-A No. 2011-162662; and thiazine indigo dye derivatives are disclosed in JP-A No. 2007-314785. As triazine dye derivatives, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, as benzisoindole dye derivatives, JP-A-2009-57478, as quinophthalone dye derivatives, JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-2 Examples of naphthol dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439; examples of azo dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092; examples of acidic substituents include those described in JP-A-2004-307854; and examples of basic substituents include those known in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, etc.In these documents, the dye derivative is sometimes referred to as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

[0039] These dye derivatives can be used alone or in combination of two or more.

[0040] The dye derivative is preferably added in an amount of 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of the pigment.

[0041] By adding a dye derivative to a pigment and carrying out a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling, the dye derivative is adsorbed onto the pigment surface, and the primary particles of the pigment can be made finer than when the dye derivative is not added.

[0042] Adding a dye derivative to a pigment and conducting a dispersion process such as wet dispersion using a two-roll or three-roll roller or beads allows the dye derivative to adsorb to the pigment surface, making the pigment surface polar and promoting the adsorption of the resin-type dispersant. This improves compatibility with the pigment, dye derivative, resin-type dispersant, solvent, and other additives, resulting in improved dispersion stability and viscosity stability over time when the resulting colored composition or colored curable composition is formed. Furthermore, improved compatibility results in excellent coating film stability over time when the colored curable composition is applied to a glass substrate or the like, improving the stability and characteristic dependence of pattern shape and linewidth sensitivity on the waiting time from application to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay). Furthermore, adsorption and coating of the pigment surface with the dye derivative and resin-type dispersant suppresses pigment aggregation and crystal precipitation due to sublimation when the coating is baked. Furthermore, development time variability and development residue are also suppressed.

[0043] <Binder resin (B2)> The photosensitive coloring composition of the present invention contains a binder resin (B2). The binder resin (B2) preferably has a transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm. Binder resins can be classified according to their main curing method, such as thermoplastic resins, thermosetting resins, and active energy ray-curable resins having ethylenically unsaturated double bonds. The active energy ray-curable resin may be a thermoplastic resin or one that also has a thermosetting function, and is preferably an alkali-soluble resin from the viewpoint of developability. The composition may also contain a thermoplastic resin that is not active energy ray-curable, and this is also preferably alkali-soluble. These may be used alone or in combination of two or more.

[0044] <Thermoplastic resin> Examples of thermoplastic resins that can be used as binder resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. The thermoplastic resin is preferably alkali-soluble, and examples thereof include resins having acidic groups such as carboxyl groups and sulfonic groups. Specific examples of the resin include acrylic resins having acidic groups, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, at least one resin selected from acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers, particularly alkali-soluble resins having acidic groups and / or hydroxyl groups, are preferably used because of their high developability, heat resistance, and transparency.

[0045] <Alkali-soluble resin> The photosensitive coloring composition of the present invention preferably contains an alkali-soluble resin as the binder resin (B) from the viewpoints of developability, heat resistance, and transparency. The alkali-soluble resin has an acid group and / or a hydroxyl group and is used to impart development solubility in the alkaline development step during color filter production. As the alkali-soluble resin, an alkali-soluble resin (B2-1) having no ethylenically unsaturated double bond or an alkali-soluble resin (B2-2) having an ethylenically unsaturated double bond that improves the photosensitivity of the composition is used alone or in combination.

[0046] The alkali-soluble resin in the present invention is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more over the entire wavelength range of 400 to 700 nm in the visible light region.

[0047] In order to impart alkali-developing solubility, the weight-average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The ratio (Mw / Mn) of the weight-average molecular weight to the number-average molecular weight (Mn) is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, adhesion to the substrate decreases, making it difficult to retain an exposed pattern. If it exceeds 40,000, alkali-developing solubility decreases, residues are generated, and the linearity of the pattern deteriorates. The acid value of the alkali-soluble resin in the present invention is preferably 50 to 200 (KOH mg / g) to impart alkali-developing solubility, more preferably 70 to 180, and more preferably 90 to 170. If the acid value is less than 50, alkali-developing solubility decreases, residues are generated, and the linearity of the pattern deteriorates. If the acid value exceeds 200, adhesion to the substrate decreases, making it difficult to retain the exposed pattern.

[0048] <Alkali-soluble resin (B2-1) having no ethylenically unsaturated double bond> The photosensitive coloring composition of the present invention can contain an alkali-soluble resin (B2-1) that does not have an ethylenically unsaturated double bond in order to adjust the curing degree of the coating film.By synthesizing at least one kind of carboxyl group-containing ethylenically unsaturated monomer and one or more kinds of other ethylenically unsaturated monomers, and not adding an ethylenically unsaturated bond to the side chain, an alkali-soluble resin that does not have an ethylenically unsaturated double bond can be obtained.

[0049] <Alkali-soluble resin having an ethylenically unsaturated double bond (B2-2)> The alkali-soluble resin contained in the photosensitive coloring composition of the present invention preferably has an ethylenically unsaturated double bond. In particular, by using a resin into which an ethylenically unsaturated double bond has been introduced by the following method (i) or (ii), the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film, thereby increasing the crosslink density and improving chemical resistance.

[0050] [Method (i)] Method (i) includes, for example, a method in which a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added to the side-chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers, and the resulting hydroxyl group is then reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0051] Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

[0052] Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position, and these may be used alone or in combination of two or more.

[0053] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. These may be used alone or in combination of two or more. If necessary, for example, to increase the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. Furthermore, using tetrahydrophthalic anhydride or maleic anhydride, which have ethylenically unsaturated double bonds, as the polybasic acid anhydride can further increase the number of ethylenically unsaturated double bonds.

[0054] As a method similar to method (i), for example, there is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0055] [Method (ii)] Method (ii) is a method in which an ethylenically unsaturated monomer having a hydroxyl group is used and copolymerized with another monomer of an unsaturated monobasic acid having a carboxyl group or another monomer, and the side chain hydroxyl group of the copolymer is reacted with an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group.

[0056] As the ethylenically unsaturated monomer having a hydroxyl group, 2-hydroxyethyl (meth)acrylate is acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3 Examples of suitable hydroxyalkyl methacrylates include hydroxyalkyl methacrylates such as 4- or 5-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. These may be used alone or in combination of two or more. Polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone), and / or poly(12-hydroxystearic acid) may also be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred. Furthermore, from the viewpoint of sensitivity, it is preferable to use a compound having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

[0057] Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate, but are not limited to these, and two or more types can also be used in combination.

[0058] Examples of monomers constituting the alkali-soluble resin include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; Alternatively, examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0059] Alternatively, 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-triphenyl)maleimide, N-substituted maleimides such as N-(4-chlorophenyl)maleimide, 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 the compound represented by the following general formula (12) include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0060] General formula (12) [ka]

[0061] (In general formula (12), R6 is a hydrogen atom or a methyl group, R7 is an alkylene group having 2 or 3 carbon atoms, R8 is an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, and n is an integer of 1 to 15.)

[0062] Carboxyl group-containing ethylenically unsaturated monomers can also be used, such as acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

[0063] Hydroxyl-containing ethylenically unsaturated monomers can also be used. Examples of hydroxyl-containing ethylenically unsaturated monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and / or (poly)12-hydroxystearic acid.

[0064] Alternatively, a phosphate group-containing ethylenically unsaturated monomer can be used. Examples of the phosphate group-containing ethylenically unsaturated monomer include monomers that can be obtained by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0065] <Thermosetting compound (E)> In the present invention, a thermosetting compound (E) can be further contained in combination with the thermoplastic resin as a binder resin. When a color filter is produced using the coloring composition for color filters of the present invention, the thermosetting compound reacts during baking of the filter segments to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segments, suppressing pigment aggregation during baking of the filter segments, and improving the contrast ratio.

[0066] The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of thermosetting compounds include, but are not limited to, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Epoxy compounds and oxetane compounds are preferably used in the coloring composition for color filters of the present invention.

[0067] (epoxy compounds) The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of such epoxy compounds include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropyl ether, methyl methyl ether, methyl ethyl ... Examples of epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins, but are not limited to these, so long as they are commonly used epoxy compounds. These may be used alone or in combination of two or more.

[0068] Commercially available products include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (all trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (all trade names; manufactured by Japan Epoxy Resins Co., Ltd.), TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade names; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; manufactured by Japan Epoxy Resins Co., Ltd.), and JER 157S65, 157S70 (trade names; manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (all trade names; manufactured by Japan Epoxy Resins Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all trade names; manufactured by Nippon Kayaku Co., Ltd.), Celloxide 2021, EHPE- 3150 (all trade names; 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 (all trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), and the like. These include, but are not limited to, the following.

[0069] The amount of the epoxy compound blended is preferably 0.5 to 20 parts by mass, and more preferably 1.0 to 10 parts by mass, per 100 parts by mass of the colorant. If the amount is less than 0.5 parts by mass, the effect of improving the contrast ratio and heat resistance is small, and if the amount is more than 20 parts by mass, problems may occur when forming filter segments by photolithography.

[0070] (Oxetane compounds) It is preferable to add an oxetane compound to the photosensitive coloring composition of the present invention. As the oxetane compound, any known compound having an oxetane group can be used without any particular limitation. Examples of the oxetane compound include those in which the oxetane group is monofunctional, those in which the oxetane group is bifunctional, and those in which the oxetane group is bifunctional or more.

[0071] Examples of those having a monofunctional oxetane group 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. Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

[0072] Examples of compounds having a bifunctional oxetane group 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, and di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane. 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl bisphenol A 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. Specific examples include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

[0073] Examples of oxetane groups having two or more functional groups 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, caprolactone-modified dipentaerythritol hexa Examples of such polymers include (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (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 aforementioned OXE-30. Such polymers can be obtained using known polymerization methods.

[0074] The content of the oxetane compound used in the photosensitive coloring composition of the present invention is usually 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, relative to 100 parts by mass of the colorant. When the content of the oxetane compound is within the above range, an excellent coating film having good resistance to water stains and high chemical resistance can be obtained, which is preferable.

[0075] (melamine compounds) The melamine compound in the present invention refers to a compound having a melamine ring structure. The melamine compound may be a low molecular weight compound or a high molecular weight compound such as a resin. In the present invention, melamine compounds of the methylol type or ether type, in which the number of methylol groups and / or ether groups per melamine ring is 5.0 or more on average, are preferred. If the number of methylol groups and / or ether groups per melamine ring is less than 5.0 on average, there are few reaction sites, and the crosslinked structure during curing is not sufficiently dense, which may reduce the effects of suppressing a decrease in contrast ratio due to a heat treatment step and improving NMP resistance.

[0076] 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.), but are not limited thereto.

[0077] Among these, Nikalac 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.) are preferred because they have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, and can provide a dense crosslinked structure.

[0078] (hardening agent) The coloring composition for color filters of the present invention may contain a curing agent (curing accelerator) or the like, if necessary, to aid in the curing of the thermosetting compound. Effective curing agents include, but are not limited to, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Any curing agent may be used as long as it can react with the thermosetting compound. Examples of curing agents include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-methyl-4-methylimidazole, etc.), and the like. Examples of compounds that can be used include 1-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, phosphorus compounds (e.g., triphenylphosphine, etc.), and S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc.). These compounds may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermosetting compound.

[0079] <Organic solvent (S)> The photosensitive coloring composition of the present invention contains a solvent to facilitate the formation of a colored film by coating the composition on a substrate such as glass so that the dry film thickness is 0.2 to 5 μm. The solvent is selected in consideration of the good coatability of the coloring composition, the solubility of each component of the coloring composition, and safety.

[0080] The photosensitive coloring composition of the present invention is characterized by containing 5 to 30 mass % of an organic solvent (S1) having a structure of the following formula (1) and a boiling point of 160°C or higher at 760 mmHg, relative to 100 mass % of the organic solvent (S). R 1 -O-(XO)nR 2 Formula (1) (In formula (1), R 1 and R 2 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 1 and R 2 Either one of the groups is a linear or branched alkyl group having 1 to 4 carbon atoms. X represents a linear or branched alkylene group having 2 or 3 carbon atoms. n represents an integer of 2 to 4. Multiple Xs may be the same or different.

[0081] Examples of the organic solvent (S1) include diethylene glycol dimethyl ether (boiling point 162°C), diethylene glycol diethyl ether (boiling point 188°C), diethylene glycol dibutyl ether (boiling point 255°C), diethylene glycol ethyl methyl ether (boiling point 176°C), diethylene glycol butyl methyl ether (boiling point 212°C), triethylene glycol dimethyl ether (boiling point 216°C), triethylene glycol methyl ether (boiling point 249°C), tripropylene glycol methyl ether (boiling point 241°C), and tetraethylene glycol dimethyl ether (boiling point 276°C). The boiling point of the organic solvent (S1) at 760 mmHg is more preferably 200°C or higher, and most preferably 250°C or higher.

[0082] The organic solvent (S) used in the present invention can be used in combination with other organic solvents that are commonly used in the relevant field, as long as the effects of the present invention are not impaired. These solvents are used alone or in combination as appropriate, taking into consideration properties such as boiling point, SP value, evaporation rate, and viscosity, and in accordance with application conditions (speed, drying conditions, etc.).

[0083] Examples of organic solvents that can be used in combination with the organic solvent (S1) in the present invention include ester solvents (solvents that contain -COO- in the molecule but do not contain -O-), ether solvents other than those of formula (1) (solvents that contain -O- in the molecule but do not contain -COO-, although -OH may be contained in the molecule), ether ester solvents (solvents that contain -COO- and -O- in the molecule), ketone solvents (solvents that contain -CO- in the molecule but do not contain -COO-), alcohol solvents (solvents that contain -OH in the molecule but do not contain -O-, -CO-, or -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0084] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0085] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, phenetole, and methylanisole.

[0086] Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxy ...propyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, Examples of the methyl ether acetate include butyl ether acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and dipropylene glycol diacetate.

[0087] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0088] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin.

[0089] Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, and the like.

[0090] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These organic solvents may be used alone or in combination of two or more.

[0091] <Polymerizable compound (C)> The photosensitive coloring composition of the present invention contains a polymerizable compound (C). The polymerizable compound (C) includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin.

[0092] Examples of monomers and oligomers that harden when exposed to ultraviolet light or heat to produce a transparent resin 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, 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, and the like. (meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylate, urethane acrylate, and other various acrylic and methacrylic acid esters; Examples include, but are not limited to, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0093] 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 usable acrylic resins include acrylic resins 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 Chemicals, and NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.

[0094] (Polymerizable compound having an acid group) The polymerizable compound (C) in the present invention may contain a polymerizable compound having an acid group, such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group.

[0095] Examples of polymerizable compounds having an acid group include esters of dicarboxylic acids with free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid; 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, and dipentaerythritol pentamethacrylate with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and propane-1,2,3-tricarboxylic acid (tricarballylic acid). Examples of the free carboxyl group-containing oligoesters include those of 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.

[0096] As commercially available products thereof, Viscoat #2500P manufactured by Osaka Organic Industries, and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd., and the like can be suitably used.

[0097] (Polymerizable compound having a urethane bond) The polymerizable compound (C) in the present invention may contain a polymerizable compound containing at least one ethylenically unsaturated bond and one urethane bond. Examples thereof 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 then reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[0098] 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.

[0099] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0100] Suitable commercially available products include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., UA-160™ manufactured by Shin-Nakamura Chemical Co., Ltd., and UV-4108F and UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd.

[0101] The above polymerizable compounds (C) can be used alone or in combination of two or more kinds in any ratio as required.

[0102] The blending amount of the polymerizable compound (C) is preferably 1 to 50 parts by mass, based on the total nonvolatile content of the photosensitive coloring composition (100 parts by mass), and more preferably 2 to 40 parts by mass from the viewpoint of photocurability and developability.

[0103] <Photopolymerization initiator (D)> Examples of the photopolymerization initiator (D) include 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)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-benzyl- Acetophenone compounds such as 2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butyl)benzoate benzophenone compounds such as (peroxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; 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, triazine-based compounds such as 2-(4-methoxy-naphth-1-yl)-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, and 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples of suitable compounds include oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.

[0104] Commercially available products include, for example, acetophenone compounds such as "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), and "Omnirad 379" (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one), all manufactured by IGM Resins BV; and phosphine compounds such as "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) and "Omnirad TPO" (2,4,6-trimethylbenzoyldiphenylphosphine oxide), all manufactured by BASF.

[0105] The photopolymerization initiator (D) can be used alone or in combination of two or more kinds.

[0106] <Sensitizer (F)> Furthermore, the photosensitive coloring composition of the present invention may contain a sensitizer. Examples of sensitizers include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, polymethine dyes such as benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine 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, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0107] Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 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 are used.

[0108] These sensitizers can be used alone or in combination of two or more in any ratio as required. Commercially available products include "KAYACURE DETX-S" (2,4-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP" (4,4'-bis(diethylamino)benzophenone, manufactured by Chemark Chemical Co., Ltd.).

[0109] More specifically, examples of sensitizers include, but are not limited to, those described in "Dye Handbook" edited by Makoto Okawara et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Makoto Okawara et al. (CMC, 1981), "Special Function Materials" edited by Chuzaburo Ikemori et al., and "Special Function Materials" (CMC, 1986). In addition, sensitizers that absorb light in the ultraviolet to near-infrared region may also be contained.

[0110] When a sensitizer is used, the content thereof is preferably 3 to 60 parts by mass relative to 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and more preferably 5 to 50 parts by mass from the viewpoints of photocurability and developability.

[0111] <Thiol-based chain transfer agents (G)> The photosensitive coloring composition of the present invention preferably contains a thiol-based chain transfer agent as a chain transfer agent. By using thiol together with a photopolymerization initiator, it acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates thiyl radicals that are not easily inhibited by oxygen in polymerization, so that the obtained coloring composition has high sensitivity.

[0112] Also preferred are polyfunctional aliphatic thiols having two or more SH groups bonded to aliphatic groups such as methylene or ethylene groups. Polyfunctional aliphatic thiols having four or more SH groups are more preferred. Increasing the number of functional groups improves polymerization initiation function, allowing curing from the surface of the pattern to near the substrate.

[0113] 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, ... Examples of the thiopropionate include tris(2-hydroxyethyl)trimercaptopropionic acid, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0114] These thiol chain transfer agents can be used alone or in combination of two or more.

[0115] The content of the thiol chain transfer agent is preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass, relative to 100 parts by mass of the colorant. Within this range, the effect of the chain transfer agent is enhanced, and sensitivity, tapered shape, wrinkles, film shrinkage rate, etc. are improved.

[0116] <Polymerization inhibitor (H)> The photosensitive coloring composition of the present invention may contain a polymerization inhibitor to prevent photosensitivity due to diffracted light from the mask during exposure. By adding the polymerization inhibitor, the effect of preventing curing from progressing beyond the desired pattern due to chain polymerization caused by photosensitivity can be obtained.

[0117] Examples of the polymerization inhibitor 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-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n-butyl Examples of suitable polymerization inhibitors include alkylresorcinol compounds such as 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol, alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-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 phloroglucin. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass per 100 parts by mass of the nonvolatile content of the coloring composition excluding the solvent. Within this range, the effect of the polymerization inhibitor becomes greater, and the linearity of the taper, wrinkles in the coating film, pattern resolution, etc. become better.

[0118] <Ultraviolet absorber (I)> The photosensitive coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention 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.

[0119] The content of the ultraviolet absorber is preferably 5 to 70% by mass, based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. If the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small and the resolution cannot be ensured. If the content is more than the above, the sensitivity may decrease, causing problems such as pixel peeling and hole diameters larger than designed values.

[0120] In this case, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

[0121] The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass relative to 100% by mass of the nonvolatile content of the photosensitive coloring composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above range, adhesion may be weakened, causing pixel peeling, while if it is more than the above range, the sensitivity may be too high, resulting in poor resolution.

[0122] In this case, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

[0123] Benzotriazole organic compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 branched and linear alkyl ester mixture, 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- Examples include 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. Other oligomer and polymer compounds having a benzotriazole structure can also be used.

[0124] More specific examples include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF 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.

[0125] Triazine organic compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of suitable compounds include the product 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. Other compounds, such as oligomers and polymers, having a triazine structure can also be used.

[0126] More specific examples include KEMISORB 102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF, Adekastab LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

[0127] Examples of benzophenone-based organic compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-oxide, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomeric and polymeric compounds having a benzophenone structure can also be used.

[0128] More specifically, examples thereof include KEMISORB 10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB 101 and 107 manufactured by Shipro Chemicals, Adekastab 1413 manufactured by ADEKA Corporation, and UV-12 manufactured by Sun Chemical.

[0129] Examples of salicylate organic compounds include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. Oligomeric and polymeric compounds having a salicylate structure can also be used.

[0130] <Antioxidant (J)> The photosensitive coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator or thermosetting compound contained in the photosensitive coloring composition from oxidizing and yellowing during the thermal process of thermal curing or ITO annealing, thereby increasing the transmittance of the coating film. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film crosslinking component decreases, so measures such as using a highly sensitive crosslinking component or increasing the amount of photopolymerization initiator are taken, resulting in a phenomenon in which yellowing during the thermal process becomes more severe. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0131] The "antioxidant" in the present invention may be any compound having a radical scavenging function or a peroxide decomposing function, and specific examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds, and known antioxidants can be used. Furthermore, the antioxidant used in the present invention is preferably one that does not contain a halogen atom.

[0132] Among these antioxidants, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, preferred ones include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

[0133] Hindered phenolic antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5 -methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di- t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4, 6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, Examples include 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), and 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol. Other examples include oligomeric and polymeric compounds with a hindered phenol structure.

[0134] More specific examples 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; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Corporation; and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0135] Hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl Methyl-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-pi Ester of peridineethanol 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 N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,6,6-tetramethyl-4-piperidyl ...Examples include 6-hexamethylenediamine and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide. Other examples include oligomeric and polymeric compounds having a hindered amine structure.

[0136] More specific examples 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 Kasei Co., Ltd.; Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, and 5100 manufactured by BASF Corporation; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

[0137] 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 diphosphonate, tris(tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylide Diphenyl alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butanetriphosphite, 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, ethyl bis(2,4-ditert-butyl-6-methylphenyl)phosphite, etc. Oligomeric and polymeric compounds having a phosphite structure can also be used.

[0138] More specifically, examples thereof include ADK STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Corporation, and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0139] 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, 2,4-bis[(laurylthio)methyl]-o-cresol, etc. Oligomeric and polymeric compounds having a thioether structure can also be used.

[0140] More specifically, examples include ADK STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0141] These antioxidants can be used alone or in combination of two or more kinds in any ratio as required.

[0142] Furthermore, when the antioxidant is added in an amount of 0.05 to 5.0 parts by mass relative to 100 parts by mass of the colorant, the transmittance, spectral characteristics, and sensitivity may be improved.

[0143] <Leveling Agent (K)> It is preferable to add a leveling agent to the photosensitive coloring composition of the present invention in order to improve the coating properties of the composition on a transparent substrate and the drying properties of the colored coating. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

[0144] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0145] More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345 / 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK-Chemie, and FZ-7002 and 2110 manufactured by Toray Dow Corning Co., Ltd. , 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.

[0146] The fluorosurfactant may be a surfactant or leveling agent having a fluorocarbon chain.

[0147] More specific examples include Surflon S-242, S-243, S-420, S-611, S-651, and S-386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and FC-4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Ftergent 602A manufactured by Neos Corporation.

[0148] Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. , sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, and the like.

[0149] More specifically, Kao Corporation's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, and LS-107. -110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, 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-L1 06, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amit 102, 10 5, 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 Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0150] Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0151] More specifically, examples include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, all manufactured by Kao Corporation.

[0152] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters.

[0153] More specifically, examples thereof include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0154] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0155] More specifically, examples include Amphitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

[0156] When the photosensitive coloring composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total nonvolatile content of the composition of the present invention. Within this range, the balance between the coatability of the coloring composition, the pattern adhesion, and the transmittance is good. The photosensitive coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, the total amount thereof is preferably within the above range.

[0157] <Storage stabilizer (L)> The coloring composition of the present invention can contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the colorant (100% by mass).

[0158] <Adhesion improver (M)> The photosensitive coloring composition of the present invention can contain an adhesion improver such as a silane coupling agent to improve adhesion to the substrate. The improved adhesion due to the adhesion improver improves the reproducibility of fine lines and improves resolution.

[0159] Examples of the adhesion improver include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and N-2-(aminoethyl)-3 Examples of suitable silane coupling agents include aminosilanes such as 2-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryl compounds such as p-styryltrimethoxysilane, ureido compounds such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the colorant in the coloring composition. Within this range, the effect is enhanced, and a good balance of adhesion, resolution, and sensitivity is achieved, which is more preferable.

[0160] <Method for producing photosensitive coloring composition> The photosensitive coloring composition of the present invention can be produced by finely dispersing a pigment in a dispersant, a binder resin and / or a solvent, preferably together with a dispersing aid (a dye derivative or a surfactant), using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, two or more pigments may be dispersed simultaneously in a colorant carrier, or they may be dispersed separately in pigment carriers and then mixed.

[0161] In addition, the photosensitive coloring composition can be prepared as a solvent-developable or alkali-developable coloring composition. The solvent-developable or alkali-developable coloring composition can be prepared by mixing the coloring composition with a polymerizable compound and / or a photopolymerization initiator, and, if necessary, a solvent, other dispersing aids, additives, etc. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

[0162] <Removal of large particles> The photosensitive coloring composition of the present invention 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 contaminated dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more, and more preferably 0.3 μm or less.

[0163] <Color filter> Next, the color filter of the present invention will be described. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment.

[0164] <Color filter manufacturing method> The color filter can be manufactured by a printing method or a photolithography method. Formation of filter segments by printing methods allows for patterning by simply repeating the printing and drying of a coloring composition prepared as a printing ink, making it a cost-effective and mass-producible method for producing color filters. Furthermore, advances in printing technology have made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to use a composition that prevents the ink from drying or solidifying on the printing plate or blanket. Controlling the ink's fluidity on the printing press is also important, and the ink viscosity can be adjusted using dispersants and extender pigments.

[0165] When forming filter segments by photolithography, the colored composition prepared as the solvent-developable or alkali-developable colored resist material is applied to a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating to a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern, which is placed in contact with or out of contact with the film. The uncured portions are then removed by immersion in a solvent or alkali developer or sprayed with a developer, etc., to form the desired pattern. The same process is then repeated for other colors to produce a color filter. Furthermore, heating can be applied as needed to promote polymerization of the colored resist material. Photolithography allows for the production of color filters with higher precision than the printing method.

[0166] For development, an aqueous solution of sodium carbonate, sodium hydroxide, or the like is used as an alkaline developer, and organic alkalis such as dimethylbenzylamine, triethanolamine, etc. may also be used. An antifoaming agent or a surfactant may also be added to the developer. In order to increase the exposure sensitivity, after the colored resist is applied and dried, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, may be applied and dried to form a film that prevents polymerization inhibition by oxygen, and then exposure may be performed.

[0167] The color filter of the present invention can be produced by the above-mentioned method, as well as by an electrodeposition method, a transfer method, an inkjet method, or the like, and the coloring composition of the present invention can be used for any of these methods. The electrodeposition method is a method of producing a color filter by using a transparent conductive film formed on a substrate and electrodepositing each color filter segment onto the transparent conductive film by electrophoresis of colloidal particles. The transfer method is a method in which filter segments are formed in advance on the surface of a peelable transfer base sheet, and then the filter segments are transferred to a desired substrate.

[0168] A black matrix can be formed on a transparent or reflective substrate before forming each color filter segment. Examples of black matrices that can be used include, but are not limited to, chromium or chromium / chromium oxide multilayer films, inorganic films such as titanium nitride, and resin films with a dispersed light-blocking agent. Thin film transistors (TFTs) can also be formed on the transparent or reflective substrate beforehand, followed by the formation of each color filter segment. An overcoat film, a transparent conductive film, or the like can be formed on the color filter of the present invention as needed.

[0169] A color liquid crystal display device is manufactured by laminating the color filter of the present invention to an opposing substrate using a sealant, injecting liquid crystal through an injection port provided in the seal, sealing the injection port, and laminating a polarizing film or a retardation film to the outside of the substrate as needed. This color liquid crystal display device can be used in liquid crystal display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convencive bend (OCB).

[0170] The color filter of the present invention can be used in the manufacture of solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, and the like, in addition to color liquid crystal displays.

[0171] <Liquid crystal display device> A liquid crystal display device equipped with the color filter of the present invention will be described. The liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFLs) and white LEDs. In the present invention, it is preferable to use a white LED because it broadens the red reproduction range. Figure 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the color filter of the present invention. The device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged at a distance from each other, with a liquid crystal LC sealed between them.

[0172] The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), or OCB (Optically Compensated Birefringence). 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. A polarizer 15 is formed on the outer surface of the transparent substrate 11.

[0173] 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 that make up the color filter 22 are separated by a black matrix (not shown).

[0174] A transparent protective film (not shown) is formed as needed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0175] 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.

[0176] The white LED light source includes a blue LED with a fluorescent filter formed on the surface, and a blue LED with a fluorescent material contained in the resin package, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity becomes maximum, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity becomes maximum, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity becomes maximum, and the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less. Therefore, a white LED light source (LED1) having spectral characteristics in which the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum in the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity in the range of 530 nm to 580 nm, and a ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferred.

[0177] Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0178] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

[0179] <Solid-state imaging element> The solid-state imaging device of the present invention includes the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration including the color filter for the solid-state imaging device of the present invention and functions as a solid-state imaging device, but examples thereof include the following configurations. The solid-state imaging device has a substrate on which are disposed a plurality of photodiodes constituting the light receiving area of the solid-state imaging element (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) and transfer electrodes made of polysilicon or the like; a light-shielding film made of tungsten or the like with only the light-receiving portion of the photodiodes exposed on the photodiodes and the transfer electrodes; 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 photodiodes; and a color filter segment for the solid-state imaging element of the present invention on the device protection film. Furthermore, the device may have a configuration in which a focusing means (e.g., a microlens, etc.; the same applies below) is provided on the device protection layer and below the color filter segments (on the side closer to the substrate), or a configuration in which a focusing means is provided on the color filter segments. The organic CMOS sensor is composed of a thin-film panchromatic organic photoelectric conversion film as the photoelectric conversion layer and a CMOS signal readout substrate, and has a two-layer hybrid structure in which the organic material captures light and converts it into an electrical signal, while the inorganic material extracts the electrical signal externally, and in principle, can achieve a 100% aperture ratio for incident light.The organic photoelectric conversion film is a structure-free continuous film that can be laid on the CMOS signal readout substrate, so it does not require expensive microfabrication processes and is suitable for miniaturizing filter segments. The arrangement of the color filter segments is not particularly limited, and any known method can be used. [Example]

[0180] The present invention will be described below with reference to examples. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively. It should be noted that Examples 3, 4, 11, and 12 are reference examples.

[0181] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), amine value (mgKOH / g), and ammonium salt value (mgKOH / g) for resins such as binder resins, resin-type dispersants, and resins that form dye salts are as follows:

[0182] <Non-volatile content, non-volatile content concentration> In the present invention, the nonvolatile content refers to the mass remaining after leaving the mixture to stand in an oven at 180°C for 20 minutes.

[0183] <Weight average molecular weight (Mw), number average molecular weight (Mn)> The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (Tosoh Corporation). Two separation columns were connected in series, and both columns were packed with "TSK-GEL SUPER HZM-N" packing. Measurements were performed at an oven temperature of 40°C, a THF solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters was injected. All molecular weights are expressed in terms of polystyrene.

[0184] <Acid value (mgKOH / g)> 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of resin solution, and the mixture was stirred to dissolve uniformly. The resin solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo) with a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mg KOH / g) of the resin solution was measured. The acid value per unit of nonvolatile content of the resin was then calculated from the acid value of the resin solution and the concentration of nonvolatile content of the resin solution.

[0185] <Ammonium salt value (mgKOH / g)> The ammonium salt value is determined by titration with 0.1N silver nitrate solution using 5% potassium chromate solution as an indicator, and then converted into the potassium hydroxide equivalent, and indicates the ammonium salt value of the non-volatile content.

[0186] <Fine particle size of colorant (A)> (Colorant (A-1)) 100 parts of CI Pigment Red 254 (BASF's "Irgaphor Red B-CF"), 10 parts of dye derivative (b-1), 1000 parts of ground salt, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 8 hours at 70° C. This mixture was poured into 2000 parts of warm water, heated to about 80° C. and stirred in a high-speed mixer for about 1 hour to form a slurry, which was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain colorant (A-1).

[0187] (Colorant (A-2)) 500 parts of CI Pigment Red 177 (BASF "Cromophtal Red A2B"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 8 hours at 120° C. Next, this kneaded mixture was poured into 5 liters of warm water and stirred for 1 hour while heating to 70° C. to form a slurry. After repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, the mixture was dried at 80° C. for one day to obtain colorant (A-2).

[0188] (Colorant (A-3)) 100 parts of CI Pigment Red 242 (Novopalm Scarlet 4RF manufactured by Clariant), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 10 hours at 60° C. Next, this mixture was poured into 3 liters of warm water, and while heated to about 80° C., it was stirred in a high-speed mixer for about 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and solvent, and then dried at 80° C. for one day and night to obtain colorant (A-3).

[0189] (Colorant (A-4)) 100 parts of CI Pigment Red 269 ("Toner Magenta F8B" manufactured by Clariant), 800 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 5 hours at 70° C. This mixture was added to 4,000 parts of warm water, and stirred for about 1 hour with a high-speed mixer while heating to about 80° C. to form a slurry. The slurry was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain colorant (A-4).

[0190] (Colorant (A-5)) 100 parts of CI Pigment Green 58 (DIC Corporation "FASTGEN GREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 6 hours at 70° C. This kneaded mixture was poured into 3000 parts of warm water and stirred for 1 hour while heating to 70° C. to form a slurry. The mixture was filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80° C. to obtain 97 parts of colorant (A-5).

[0191] (Colorant (A-6)) 500 parts of CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyocolor Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded for 4 hours at 120° C. Next, this kneaded mixture was poured into 5 liters of warm water and stirred for 1 hour while heating to 70° C. to form a slurry, which was then repeatedly filtered and washed with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80° C. to obtain 490 parts of colorant (A-6).

[0192] (Colorant (A-7)) 500 parts of CI Pigment Green 7 ("Lionol Green YS-07" manufactured by Toyocolor Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded for 4 hours at 120° C. Next, this kneaded mixture was poured into 5 liters of warm water and stirred for 1 hour while heating to 70° C. to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80° C. to obtain 490 parts of colorant (A-7).

[0193] (Colorant (A-8)) 100 parts of CI Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyocolor Co., Ltd.), 1000 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 50°C. This mixture was poured into 3000 parts of warm water, and stirred for about 1 hour in a high-speed mixer while heated to about 70°C to form a slurry. The slurry was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80°C for 24 hours to obtain colorant (A-8).

[0194] (Colorant (A-9)) 100 parts of CI Pigment Yellow 138 (BAS-F "Paliothol Yellow K0961HD"), 800 parts of ground salt, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 4 hours at 70°C. This mixture was added to 3,000 parts of warm water, and stirred for about 1 hour in a high-speed mixer while heated to about 80°C to form a slurry. The slurry was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80°C for 24 hours to obtain colorant (A-9).

[0195] (Colorant (A-10)) 100 parts of CI Pigment Yellow 139 ("Irgaphor Yellow 2R-CF" manufactured by BAS-F), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 10 hours at 60° C. Next, this mixture was poured into 3 liters of warm water, and while heated to about 80° C., it was stirred in a high-speed mixer for about 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and solvent, and then dried at 80° C. for one day and night to obtain colorant (A-10).

[0196] (Colorant (A-11)) 100 parts of CI Pigment Yellow 150 (Yellow Pigment E4GN manufactured by Lanxess), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 10 hours at 60° C. Next, this mixture was poured into 3 liters of warm water, and while heated to about 80° C., it was stirred in a high-speed mixer for about 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and solvent, and then dried at 80° C. for one day and night to obtain colorant (A-11).

[0197] (Colorant (A-12)) 500 parts of CI Pigment Yellow 185 (BASF "Paliotol Yellow D1155"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 8 hours at 120° C. Next, this kneaded mixture was poured into 5 liters of warm water and stirred for 1 hour while heating to 70° C. to form a slurry. After repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, the mixture was dried at 80° C. for one day to obtain colorant (A-12).

[0198] (Colorant (A-13)) 300 parts of a dioxazine-based purple pigment, PV23 ("Lionogen Violet RL" manufactured by Toyocolor Co., Ltd.), were added to 3,000 parts of 96% sulfuric acid, stirred for 1 hour, and then poured into 5°C water. After stirring for 1 hour, the mixture was filtered, washed with warm water until the washings were neutral, and then dried at 70°C. 120 parts of the acid-pasted pigment, 5 parts of the dye derivative (b-2), 1,500 parts of ground salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 20 hours. This mixture was then poured into 5,000 parts of warm water, heated to approximately 70°C, and stirred in a high-speed mixer for approximately 1 hour to form a slurry. The mixture was then filtered and washed repeatedly to remove the salt and solvent, and then dried at 80°C for 24 hours to obtain the finely divided pigment (A-13).

[0199] (Dye solution (a-1~3)) (Resin 1 having cationic groups on the side chains) A four-neck separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized and then placed in a dropping funnel. The four-neck separable flask was attached and added dropwise over 2 hours. Two hours after the completion of the dropwise addition, the polymerization yield was confirmed to be 98% or higher based on the nonvolatile content, and the weight-average molecular weight (Mw) was confirmed to be 6,830. The mixture was then cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was allowed to react at 50°C for 2 hours, then heated to 80°C over 1 hour and allowed to react for another 2 hours. In this way, Resin 1, which had a resin component of 47% by mass and a cationic group in the side chain having an ammonium group, was obtained. The ammonium salt value of the resulting resin was 34 mgKOH / g.

[0200] (dye 1) 30 parts of Resin 1 with a cationic group in the side chain (based on nonvolatile content) was added to 2,000 parts of water, thoroughly stirred, and then heated to 60°C. Separately, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52 in 90 parts of water. This solution was added dropwise to the resin solution. After the addition, the mixture was stirred at 60°C for 120 minutes to allow the reaction to proceed. The reaction endpoint was confirmed by dropping the reaction solution onto filter paper. The point at which no bleeding occurred was considered the end point, and the salt-forming compound was determined to have been obtained. After allowing the mixture to cool to room temperature while stirring, it was subjected to suction filtration. After washing with water, the salt-forming compound remaining on the filter paper was removed and dried in a dryer to obtain a colorant (Dye 1), a salt-forming compound of CI Acid Red 52 and Resin 1 with a cationic group in the side chain. The content of the active colorant component derived from CI Acid Red 52 in Colorant (Dye 1) was 25% by mass.

[0201] (dye 2) A colorant (dye 2), which is a salt-forming compound of CI Acid Red 289 and Resin 1 having a cationic group on the side chain, was obtained in the same manner as in the production of colorant (dye 1), except that CI Acid Red 52 was changed to CI Acid Red 289. At this time, the content of the active colorant component derived from CI Acid Red 289 in colorant (dye 2) was 27% by mass.

[0202] (dye 3) In a 1 L stainless steel reaction vessel equipped with a reflux condenser, 5.0 parts of CI Basic Violet 10 (BV10: Taoka Chemical Co., Ltd.: Rhodamine B) and 1.6 parts of hydroxyethyl methacrylate (HEMA) were dissolved in 40 ml of dichloromethane under a nitrogen atmosphere, and 2.2 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.25 parts of dimethylaminopyridine were added and stirred at room temperature for 24 hours. The resulting dichloromethane solution was washed with water, dried under reduced pressure, and then purified using a silica gel column to obtain a colorant (dye 3).

[0203] (Preparation of dye solution (a-1)) The following mixture was stirred and mixed to become uniform, and then filtered through a filter with a pore size of 5.0 μm to prepare a colored composition (dye solution (a-1)). Colorant (dye 1) 12.5 parts Propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PGMAc) 87.5 parts

[0204] (Preparation of dye solutions (a-2) and (a-3)) In the same manner as for the dye solution (a-1), dye solutions (a-2) and (a-3) were prepared using colorants (dye 2 and dye 3), respectively.

[0205] (Dye derivative (b)) The structures of the dye derivatives (b-1 to b-4) used are shown in Table 1.

[0206] [Table 1]

[0207] (Preparation of Resin-Type Dispersant (B1-1) Solution) A reaction vessel equipped with a gas inlet tube, a thermometer, 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 propylene glycol monomethyl ether acetate, and the inside atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 50°C with stirring, 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 in 90 parts of propylene glycol monomethyl ether acetate was added, while the reaction was continued for 7 hours. Measurement of the nonvolatile content confirmed that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 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 for 7 hours at 100 ° C. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated, and propylene glycol monomethyl ether acetate was added to dilute the solution so that the nonvolatile content was 20% by measuring the nonvolatile content, yielding a resin-type dispersant (B1-1) solution with an acid value of 70 mg KOH / g and a weight average molecular weight of 8500.

[0208] (Preparation of Resin-Type Dispersant (B1-2) Solution) A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of Karenz MOI-BM (Showa Denko), 20 parts of ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate, Ube Industries), and 100 parts of propylene glycol monomethyl ether acetate, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 80 °C, and a solution of 14 parts of 2-mercapto-2-methyl-1,3-propanediol and 0.1 parts of 2,2'-azobisisobutyronitrile was added and reacted for 10 hours. Measurement of the nonvolatile content confirmed that 95% had reacted. Next, 39 parts of BPAF (9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride) (manufactured by JFE Chemical Corporation), 106 parts of C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N (hydroxyl value 112 mg KOH / g, manufactured by Kuraray Co., Ltd.)), 33 parts of trimellitic anhydride, 392 parts of cyclohexanone, and 0.40 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 acid value measurement. The nonvolatile content was adjusted to 20% with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant (B1-2) solution with an acid value of 94 mg KOH / g and a weight-average molecular weight of 25,000.

[0209] (Preparation of Resin-Type Dispersant (B1-3) Solution) A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 108 parts of 3-mercapto-1,2-propanediol, 174 parts of pyromellitic dianhydride, 650 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of monobutyltin oxide as a catalyst. After purging with nitrogen gas, the mixture was reacted at 120°C for 5 hours (first step). Acid value measurement confirmed that 95% or more of the acid anhydride groups had been half-esterified. Next, 160 parts of the compound obtained in the first step (based on nonvolatile content), 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl methacrylate, 50 parts of methacrylic acid, and 663 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel, which was heated to 80°C. 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added, and the reaction was continued for 12 hours (second step). Measurement of the nonvolatile content confirmed that 95% had reacted. Finally, 500 parts of a 50% propylene glycol monomethyl ether acetate solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and IR analysis revealed a peak at 2270 cm based on the isocyanate group. -1 The reaction was continued until the disappearance of the peak was confirmed (third step). After the disappearance of the peak was confirmed, the reaction solution was cooled and the nonvolatile content was adjusted with propylene glycol monomethyl ether acetate to obtain a resin-type dispersant (B1-3) solution with a nonvolatile content of 20%. The acid value of the resulting dispersant was 68, the unsaturated double bond equivalent was 1593, and the weight-average molecular weight was 13000.

[0210] <Production of binder resin (B2-1-M: non-photosensitive resin) mixed solution> (Preparation of binder resin (B2-1-1) liquid) A separable four-necked flask was fitted with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 196 parts of propylene glycol monomethyl ether acetate was charged into the reaction vessel, which was then heated to 80°C. The atmosphere inside the reaction vessel was replaced with nitrogen, and a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd.'s "Aronix M110"), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the resin solution synthesized earlier to make the nonvolatile content 20%, and a binder resin (B2-1-1) liquid was prepared. The mass average molecular weight (Mw) was 26,000.

[0211] (Preparation of binder resin (B2-1-2) liquid) A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube was filled with a nitrogen atmosphere, and 210 parts of propylene glycol monomethyl ether acetate was added and heated to 100°C with stirring. Next, a solution prepared by dissolving 106 parts of benzyl methacrylate, 22 parts of acrylic acid, and 22 parts of dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) in 215 parts of propylene glycol monomethyl ether acetate and further dissolving 3.6 parts of 2,2'-azobisisobutyronitrile was added dropwise to the flask, and stirring was continued at 100°C for 5 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 20%, thereby preparing a binder resin (B2-1-2) solution with a mass average molecular weight (Mw) of 10,000.

[0212] (Preparation of binder resin (B2-1-M) liquid) Equal amounts of binder resin (B2-1-1) liquid and binder resin (B2-1-2) liquid were mixed and stirred to prepare a binder resin (B2-1-M) mixed liquid.

[0213] <Preparation of Coloring Composition> (Production of Coloring Composition) [Manufacturing Example 1] The mixture below was stirred and mixed until uniform, and then dispersed for 3 hours in an Eiger mill (Eiger Japan Co., Ltd., "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (X-1) with a non-volatile content of 33% by mass. Pigment (A-1) 30.0 parts Dispersant (B1-1: 20% non-volatile liquid) 10.0 parts Binder resin (B2-1-M: 20% non-volatile liquid) 5.0 parts Solvent (SM) 55.0 parts The solvent (SM) is a mixture of the following (S-4) to (S-9) in the parts by mass shown below. (S-4) PGMAc (boiling point 146℃) 20 parts (S-5) Cyclohexanone (boiling point 155°C) 20 parts (S-6) Ethyl 3-ethoxypropionate (boiling point 169°C) 20 parts (S-7) Propylene glycol monomethyl ether (boiling point 121°C) 20 parts (S-8) Cyclohexanol acetate (boiling point 172°C) 10 parts (S-9) Dipropylene glycol methyl ether acetate (boiling point 188°C) 10 parts

[0214] [Manufacturing Examples 2 to 26] (Production of Coloring Compositions (X-2 to 26)) Colored compositions (X-2 to 26) were prepared in the same manner as for colored composition (X-1), except that the compositions were changed as shown in Table 2.

[0215] [Table 2]

[0216] [Example 1] The mixture of the following composition was stirred and mixed until uniform, and then filtered through a 1 μm filter. A photosensitive coloring composition (Y-1) was obtained. (Photosensitive coloring composition (Y-1)) The following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1). Coloring composition solution (X-1: non-volatile content 33%): 65.0 parts Resin solution (B1-1: non-volatile content 20%): 10.0 parts Polymerizable compound (C): 3.0 parts Photopolymerization initiator (D): 0.4 parts Thermosetting compound solution (E-1): 0.5 part Thermosetting compound solution (E-2): 0.5 part Sensitizer (F): 0.1 parts Thiol chain transfer agent (G): 0.4 parts Polymerization inhibitor (H): 0.05 parts Ultraviolet absorber (I): 0.1 part Antioxidant (J): 0.1 part Leveling agent (K: non-volatile content 3%): 1.0 part Storage stabilizer (L): 0.1 parts Adhesion improver (M): 0.1 part Solvent (S-1): 15.0 parts Solvent (SM): 3.65 parts

[0217] [Examples 2 to 48, Comparative Examples 1 to 4] (Photosensitive coloring composition (Y-2~52)) Except for changing the composition and blending amount (mass parts) shown in Table 3, the same as in the case of photosensitive coloring composition (Y-1), the mixture was stirred and mixed until it was homogeneous, and then filtered through a 1 μm filter to obtain photosensitive coloring composition (Y-2 to 52).

[0218] [Table 3]

[0219] Details of the photosensitive coloring composition (Y-1) and the components used in Table 3 are as follows. <Production of binder resin (B2-2-M) mixed liquid> (Preparation of binder resin (B2-2-1) liquid) A separable four-neck flask was fitted with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 207 parts of propylene glycol monomethyl ether acetate was charged into the reaction vessel, which was then heated to 80°C and purged with nitrogen. Then, a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd., Aronix M110), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas flow was stopped and the resulting copolymer solution was stirred with dry air for 1 hour. After cooling to room temperature, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karens MOI, Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70°C over 3 hours. After the addition was completed, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution to achieve a nonvolatile content of 20% to prepare binder resin (B2-2-1). The mass-average molecular weight (Mw) was 18,000.

[0220] (Preparation of binder resin (B2-2-2) liquid) 333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube. The atmosphere in the flask was then changed from air to nitrogen, and the temperature was then raised to 100°C. After that, a solution of 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g (0.10 mol) of a tricyclodecane-based monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 164 g of propylene glycol monomethyl ether acetate to which 3.6 g of azobisisobutyronitrile had been added was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for a further 5 hours at 100°C. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 g (0.5 mol, (100 mol% relative to the glycidyl groups of the glycidyl methacrylate used in this reaction) of methacrylic acid, 0.9 g of tris(dimethylaminomethyl)phenol, and 0.145 g of hydroquinone were added to the flask. The reaction was continued for 6 hours at 110 ° C., and the reaction was terminated when the nonvolatile acid value reached 1 mg KOH / g. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added, and the reaction was continued for 3.5 hours at 120 ° C., resulting in a photosensitive transparent resin solution with an acid value of 80 mg KOH / g. After cooling to room temperature, approximately 2 g of the photosensitive transparent resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized photosensitive transparent resin solution to adjust the nonvolatile content to 20% by mass, thereby preparing a binder resin (B2-2-2). The mass-average molecular weight (Mw) was 12,000.

[0221] (Adjustment of binder resin (B2-2-3) liquid) A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 182 g of propylene glycol monomethyl ether acetate, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and then a solution of 3.6 g of azobisisobutyronitrile added to a mixture of 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of a tricyclodecane-based monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 136 g of propylene glycol monomethyl ether acetate was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for a further 5 hours at 100°C. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate (0.25 mol, 50 mol% relative to the carboxyl groups of the methacrylic acid used in this reaction), 0.9 g of tris(dimethylaminomethyl)phenol, and 0.145 g of hydroquinone were added to the flask. The reaction was continued at 110 °C for 6 hours, resulting in a photosensitive transparent resin solution with an acid value of 79 mg KOH / g. After cooling to room temperature, approximately 2 g of the photosensitive transparent resin solution was sampled and dried at 180 °C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized photosensitive transparent resin solution to achieve a nonvolatile content of 20% by weight, thereby preparing a binder resin (B2-2-3). The mass-average molecular weight (Mw) was 13,000.

[0222] (Preparation of binder resin (B2-2-4) liquid) A separable flask equipped with a condenser was prepared as a reaction vessel. On the other hand, a monomer dropping vessel containing 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 40 parts of propylene glycol monomethyl ether acetate was prepared with thorough stirring. A chain transfer agent dropping vessel containing 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate was prepared with thorough stirring. A reactor was charged with 395 parts of propylene glycol monomethyl ether acetate and purged with nitrogen. The reactor was then heated in an oil bath with stirring to 90°C. After the reactor temperature stabilized at 90°C, dropwise addition was initiated from the monomer dropper and chain transfer agent dropper. The dropper was maintained at 90°C for 135 minutes. Sixty minutes after the dropper was completed, the temperature was raised to 110°C. After maintaining the temperature at 110°C for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling with a 5 / 95 (volume ratio) oxygen / nitrogen mixed gas began. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged to the reactor, and the reaction was continued at 110°C for 12 hours. After that, 150 parts of propylene glycol monomethyl ether acetate was added and the mixture was cooled to room temperature. Approximately 2 g of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. Further addition of propylene glycol monomethyl ether acetate to the resin solution synthesized earlier to achieve a nonvolatile content of 20% by mass produced binder resin (B2-2-4). The resin had a mass average molecular weight (Mw) of 18,000 and an acid value per nonvolatile content of 2 mgKOH / g.

[0223] (Preparation of binder resin (B2-2-M) mixed solution) Equal amounts of four types of binder resin liquids (B2-2-1) to (B2-2-4) were mixed and stirred to prepare a binder resin (B2-2-M) mixed liquid.

[0224] <Polymerizable compound (C)> (C-1) Trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)] (C-2) Dipentaerythritol penta- and hexaacrylate [Aronix M402 (manufactured by Toagosei Co., Ltd.)] (C-3) Polybasic acidic acrylic oligomer [Aronix M520 (manufactured by Toagosei Co., Ltd.)] (C-4) Caprolactone-modified dipentaerythritol hexaacrylate [KAYARAD DPCA-30 (manufactured by Nippon Kayaku)]

[0225] (C-5) Multifunctional urethane acrylate Pentaerythritol triacrylate (432 g) and hexamethylene diisocyanate (84 g) were charged into a 1-liter five-necked reaction vessel and reacted at 60°C for 8 hours to obtain a product containing a multifunctional urethane acrylate (C-5) having a (meth)acryloyl group. The proportion of the multifunctional urethane acrylate (C-5) in the product was 70 mass%, with the remainder being made up of other photopolymerizable monomers. IR analysis confirmed that no isocyanate groups were present in the reaction product.

[0226] (C-6) Difunctional bisphenol A (meth)acrylate [ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] (C-7) Ethoxylated isocyanuric acid triacrylate [A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] (C-8) Ethylene oxide 12 mole modified dipentaerythritol hexaacrylate [KAYARAD DPEA-12 (manufactured by Nippon Kayaku)] The above (C-1) to (C-8) were mixed in equal amounts to obtain a polymerizable compound (C).

[0227] <Photopolymerization initiator (D)> (D-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Omnirad 907 (IGM Resins)] (D-2) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Omnirad 379EG (manufactured by IGM Resins)] (D-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Omnirad TPO (manufactured by IGM Resins)] (D-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [Biimidazole (Kurokane Chemicals)] (D-5) p-Dimethylaminoacetophenone [DMA (manufactured by Daikifine)] (D-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime) [Irgacure OXE02 (BASF Japan)] (D-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [Omnirad 2959 (IGM Resins)] (D-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Omnirad 819 (IGM Resins)] The above (D-1) to (D-8) were mixed in equal amounts to prepare a photopolymerization initiator (D).

[0228] <Thermosetting compound (E)> ·Thermosetting compound (E-1) (E-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel)] (E-1-2) Glycidyl etherified epoxy compounds of sorbitol [Denacol EX611 (manufactured by Nagase ChemteX Corporation)] (E-1-3) Triglycidyl isocyanurate Equal amounts of (E-1-1) to (E-1-3) were mixed together to prepare a thermosetting compound (E-1). ·Thermosetting compound (E-2): 3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

[0229] <Sensitizer (F)> (F-1) 2,4-diethylthioxanthone [Kayacure DETX-S (Nippon Kayaku)] (F-2) 4,4'-bis(diethylamino)benzophenone [CHEMARK DEABP (Chemark Chemical)] Equal amounts of (F-1) and (F-2) were mixed together to form sensitizer (F).

[0230] <Thiol-based chain transfer agents (G)> (G-1) Trimethylolethane tris(3-mercaptobutyrate) [TEMB (Showa Denko)] (G-2) Trimethylolpropane tris(3-mercaptobutyrate) [TPMB (Showa Denko)] (G-3) Pentaerythritol tetrakis(3-mercaptopropionate) [PEMP (Sakai Chemical Industry Co., Ltd.)] (G-4) Trimethylolpropane tris(3-mercaptopropionate) [TMMP (Sakai Chemical Industry Co., Ltd.)] (G-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)] The above (G-1) to (G-5) were mixed in equal amounts to prepare a thiol-based chain transfer agent (G).

[0231] <Polymerization inhibitor (H)> (H-1) 3-Methylcatechol (H-2) Methylhydroquinone (H-3) tert-Butylhydroquinone The above (H-1) to (H-3) were mixed in equal amounts to prepare a polymerization inhibitor (H).

[0232] <Ultraviolet absorber (I)> (I-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine [TINUVIN 400 (BASF Japan)] (I-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN 900 (BASF Japan)] Equal amounts of (I-1) and (I-2) were mixed together to prepare an ultraviolet absorber (I).

[0233] <Antioxidant (J)> (J-1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (J-2) Dioctadecyl 3,3'-thiodipropanoate (J-3) Tris[2,4-di-(t)-butylphenyl]phosphine (J-4) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (J-5) p-Octylphenyl salicylate The above (J-1) to (J-5) were mixed in equal amounts to prepare an antioxidant (J).

[0234] <Leveling Agent (K)> 1 copy of BYK-330 manufactured by BYK Chemical Co., Ltd. One copy of DIC's "Megafac F-551" and A mixed solution of 1 part of Kao Corporation's "Emulgen 103" dissolved in 97 parts of PGMAc.

[0235] <Storage stabilizer (L)> (L-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.) (L-2) Triphenylphosphine ("TPP" manufactured by Hokko Chemical Industry Co., Ltd.) The above (L-1) and (L-2) were mixed in equal amounts to prepare a storage stabilizer (L).

[0236] <Adhesion improver (M)> (M-1) "KBM-5103 (Shin-Etsu Chemical Co., Ltd.)" (M-2) 3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (Shin-Etsu Chemical Co., Ltd.)] (M-3) 3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (Shin-Etsu Chemical Co., Ltd.)] (M-4) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (Shin-Etsu Chemical Co., Ltd.)] (M-5) 3-mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (Shin-Etsu Chemical Co., Ltd.)] The above (M-1) to (M-5) were mixed in equal amounts to prepare an adhesion improver (M).

[0237] <Solvent (S)> (S-1) Tetraethylene glycol dimethyl ether (boiling point 276°C) (S-2) Triethylene glycol dimethyl ether (boiling point 216°C) (S-3) Tripropylene glycol methyl ether (boiling point 241°C) The solvent (SM) is a mixture of the following (S-4) to (S-9) in the parts by mass shown below. (S-4) PGMAc (boiling point 146℃) 20 parts (S-5) Cyclohexanone (boiling point 155°C) 20 parts (S-6) Ethyl 3-ethoxypropionate (boiling point 169°C) 20 parts (S-7) Propylene glycol monomethyl ether (boiling point 121°C) 20 parts (S-8) Cyclohexanol acetate (boiling point 172°C) 10 parts (S-9) Dipropylene glycol methyl ether acetate (boiling point 188°C) 10 parts

[0238] <Evaluation of Photosensitive Coloring Composition> The obtained photosensitive coloring compositions (Y-1 to 52) were evaluated by the following methods. The results are shown in Table 4. Each test was carried out according to the following method. The test results are shown in Table 4. The meaning of the evaluation rank is as follows: ◎: Excellent 〇: Good △: Practical ×: Not suitable for practical use

[0239] <Formation of filter segments> A black matrix was patterned on a 100 mm x 100 mm, 0.7 mm thick glass substrate, and the obtained photosensitive coloring composition was applied to the substrate using a spin coater and dried at 90°C for 90 seconds to remove the solvent, obtaining a coating film with a film thickness of 2.4 μm. Next, the coating film was irradiated with 100 mJ / cm using an ultra-high pressure mercury lamp through a photomask having a predetermined pattern. 2 The coated film was irradiated with ultraviolet light of 1000 W at 1000 W, and then spray-developed with an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate to remove the uncured portions and form the desired pattern. The resulting coating film was then heat-treated in an oven at 230°C for 20 minutes to form filter segments. The coating film thickness was measured using a Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.).

[0240] <Development residue> The resulting filter segments were checked for the presence or absence of development residues using a microscope (Olympus Optical Co., Ltd., "BX-51") The remaining area of residues in a square pixel with a 50 μm × 50 μm hollow was calculated and evaluated as follows: ◎: Not remaining ○: 100 μm 2 less than △: 100 μm 2 More than 500μm 2 less than ×:500μm 2 End

[0241] (Storage stability) The storage stability of the obtained photosensitive coloring composition was evaluated by the following method. The initial viscosity of the photosensitive coloring composition on the day after preparation and the viscosity over time after aging at 40°C for 1 week were measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. From the values of the initial viscosity and the viscosity over time, the viscosity change rate over time was calculated using the following formula, and the storage stability was evaluated in two stages. [Change in viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| x 100 ◎: Change rate less than 3% ○: Change rate is 3% or more but less than 5% △: Change rate is 5% or more but less than 10% ×: Change rate 10% or more

[0242] [Table 4] [Explanation of symbols]

[0243] 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 resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and an organic solvent (S), wherein the colorant (A) is contained in an amount of 50 to 90% by mass relative to 100% by mass of nonvolatile matter in the coloring composition, and The organic solvent (S1) is contained in an amount of 6.5 to 30% by mass relative to 100% by mass of the organic solvent (S), A photosensitive coloring composition characterized in that the organic solvent (S1) is tetraethylene glycol dimethyl ether.

2. A method for manufacturing a color filter, which comprises forming a pattern of the photosensitive coloring composition described in claim 1 on a transparent substrate by photolithography, and then heating the pattern.

3. A method for manufacturing a liquid crystal display device, which comprises placing a color filter obtained as in claim 2 on a light source.

4. A method for manufacturing a solid-state imaging device, comprising placing a color filter obtained as in claim 2 on a device protective film.

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