Photosensitive coloring composition, color filter and image display device

Abstract

To provide a photosensitive coloring composition which is reduced in generation of wrinkles in curing, is excellent in development property and pattern formation property, and has high light-shielding property.SOLUTION: A photosensitive coloring composition contains a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D) and a thermosetting compound (E), wherein the coloring agent (A) contains a zinc halide phthalocyanine pigment (A1) having the number of halogen atoms in one molecule of 10-14 in average, the number of bromine atoms of 8-12 atoms in average and the number of chlorine atoms of 2-5 in average, and a metal azo pigment (A2) containing formula (1) or its tautomer, and a compound represented by formula (2).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 image display devices, solid-state imaging devices, and the like. [Background technology]

[0002] As a method for forming a color filter using a coloring composition, a method is known in which a coating film of a photosensitive coloring composition is formed on a substrate or on a substrate on which a light-shielding layer of a desired pattern has been formed in advance, and the coating film is irradiated with radiation (hereinafter referred to as "exposure") through a photomask having a predetermined pattern, developed to dissolve and remove the unexposed areas, and then post-baked to obtain pixels of each color. In recent years, liquid crystal display elements equipped with such color filters have been required to have higher brightness and an expanded color reproduction range, and therefore, color filters have also been required to have increasingly higher light transmittance and higher color purity in recent years.

[0003] Patent Document 1 discloses a photosensitive coloring composition containing a halogenated metal phthalocyanine pigment, a specific azo pigment, and a quinophthalone yellow pigment as a material that can provide a color filter with high light transmittance and a wide color reproduction range for the green pixels of a color filter. Patent Document 2 also discloses a photosensitive coloring resin composition for color filters that uses a specific zinc phthalocyanine pigment, a blue pigment, a specific azo pigment as a yellow pigment, and a dispersant having an amino group, thereby forming a colored layer with high brightness and excellent color reproduction while suppressing the occurrence of display defects. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2019-113612 [Patent Document 2] Japanese Patent Application Publication No. 2017-16132 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]

[0005] However, in order to improve the quality of color filters while reducing their thickness, it was necessary to increase the pigment concentration in the green pixels and to increase the brightness of the pixels, but there was a problem in that it was not possible to achieve both developability and heat resistance at the same time.

[0006] An object of the present invention is to provide a photosensitive coloring composition which has a thin film and high brightness, and yet has good developability and heat resistance. [Means for solving the problem]

[0007] The photosensitive coloring composition of the present invention is a photosensitive coloring composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and a thermosetting compound (E), The colorant (A) comprises a halogenated zinc phthalocyanine pigment (A1) having an average of 10 to 14 halogen atoms per molecule, of which the average is 8 to 12 bromine atoms and the average is 2 to 5 chlorine atoms, and a metal azo pigment (A2) containing a compound represented by formula (1) or a tautomer thereof and a compound represented by formula (2), A photosensitive coloring composition, wherein the alkali-soluble resin (B) comprises a photosensitive alkali-soluble resin (B1).

[0008] [ka] [In formula (1), R 1 and R 2 are each independently OH, NH2, or NHR 5 and R 3 and R 4 are each independently =O or =NR 5 and R 5 is a hydrogen atom or an alkyl group, and Me is Ni 2+ , Zn 2+ , Cu 2+, Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ , and Co 3+ 2 / 3 is a divalent or trivalent metal ion selected from the following series: In each case, based on 1 mole of the total compounds of formula (I), Zn 2+ and Ni 2+ The amount of metal ions from the system is 95 to 100 mol %, and Cu 2+ , Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ , and Co 3+ 2 / 3 The amount of metal ions selected from the system is 0 to 5 mol %, and the molar ratio of metal ions Zn to Ni in the total of the compounds of formula (1) is from (9:1) to (1:9). In formula (2), R 6 is a hydrogen atom or an alkyl group. [Effects of the Invention]

[0009] According to the present invention, it is possible to provide a photosensitive coloring composition which is thin and has high brightness while also having good developability and heat resistance, a color filter using the same, and a color filter and an image display device using the same. [Brief explanation of the drawings]

[0010] [Figure 1] FIG. 1 is a schematic cross-sectional view of a liquid crystal display device. DETAILED DESCRIPTION OF THE INVENTION

[0011] The terms used in this specification are defined below. Unless otherwise specified, when "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is written, it means "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. "CI" stands for Color Index (CI). Colorants include pigments and dyes. Polymerizable unsaturated groups are ethylenically unsaturated groups, and include vinyl groups, (meth)acryloyl groups, etc.

[0012] The photosensitive coloring composition of the present invention contains a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and a thermosetting compound (E). The photosensitive coloring composition is preferably used to form a green filter segment (also referred to as a green pixel).

[0013] <Colorant (A)> The colorant (A) used in the present invention contains a halogenated metal phthalocyanine pigment (A1) and a metal azo pigment (A2). These may be used in combination of two or more kinds. Furthermore, other pigments, dyes, etc. may be contained within a range that does not impair the effects of the present invention. Furthermore, the content of the colorant (A) is preferably 20 to 50% by mass based on the total amount of nonvolatile matter in the photosensitive coloring composition.

[0014] (Halogenated zinc phthalocyanine pigment (A1)) The halogenated zinc phthalocyanine pigment (A1) is a mixture of pigments having different numbers of halogen atoms, and is a halogenated zinc phthalocyanine having an average of 10 to 14 halogen atoms per molecule, of which an average of 8 to 12 bromine atoms and an average of 2 to 5 chlorine atoms. This allows for thin film formation and high brightness. The average number of halogen atoms per molecule is preferably 11 to 13, of which an average of 8 to 11 bromine atoms and an average of 2 to 3 chlorine atoms are preferred. The halogenated zinc phthalocyanine pigment is a pigment composition having a halogen distribution, and the average composition can be determined by X-ray fluorescence analysis.

[0015] The halogenated zinc phthalocyanine pigment (A1) has a specificity of producing a bluish hue, rather than the yellowish hue of conventional green pigments with a higher halogen number. Furthermore, by incorporating a halogenated zinc phthalocyanine pigment with high tinting power into a color filter, the film thickness of the green pixel can be reduced.

[0016] The halogenated zinc phthalocyanine pigment (A1) can be produced by a known production method such as a chlorosulfonic acid method, a halogenated phthalonitrile method, or a melting method.

[0017] The chlorosulfonic acid method involves dissolving zinc phthalocyanine in a sulfur oxide solvent such as chlorosulfonic acid, and then adding chlorine gas and bromine to the solution to halogenate it. The reaction is carried out at a temperature of 20 to 120°C for 3 to 20 hours.

[0018] The halogenated phthalonitrile method is, for example, a synthesis method using phthalic acid or phthalodinitrile in which some or all of the hydrogen atoms on the aromatic ring have been substituted with halogen atoms such as bromine or chlorine, and zinc metal or a metal salt as appropriate as starting materials. In this case, a catalyst such as ammonium molybdate may be used as necessary. The reaction is carried out at a temperature of 100 to 300°C for 7 to 35 hours.

[0019] The melting method includes, for example, a method in which zinc phthalocyanine is halogenated with a halogenating agent in a melt at about 10 to 170°C of one or a mixture of two or more compounds that serve as a solvent during halogenation, such as an aluminum halide such as aluminum chloride or aluminum bromide, a titanium halide such as titanium tetrachloride, an alkali metal halide or alkaline earth metal halide (hereinafter referred to as an alkali(earth) metal halide) such as sodium chloride or sodium bromide, or thionyl chloride.

[0020] The aluminum halide is preferably aluminum chloride. The amount of aluminum halide added in the melting method is usually 3 times or more by mole, and preferably 10 to 20 times by mole, based on the amount of zinc phthalocyanine.

[0021] When aluminum halide is used in combination with an alkaline (earth) metal halide, the melting temperature can be further lowered, which is advantageous in terms of operation. The alkaline (earth) metal halide is preferably sodium chloride. The amount of alkaline (earth) metal halide added is preferably 5 to 15 parts by mass per 10 parts by mass of aluminum halide, within the range that produces a molten salt.

[0022] Furthermore, the halogenating agent may also be chlorine gas, sulfuryl chloride, bromine, or the like.

[0023] The halogenation temperature is preferably 10 to 170° C., more preferably 30 to 140° C. Pressure can be applied to increase the halogenation reaction rate. The reaction time is preferably 5 to 100 hours, more preferably 30 to 45 hours.

[0024] The melting method is preferable because the content ratio of halogenated zinc phthalocyanine having a specific halogen atom composition in the halogenated zinc phthalocyanine to be produced can be arbitrarily controlled by adjusting the ratio of chloride, bromide and iodide in the molten salt or by changing the amount of chlorine gas, bromine or iodine introduced or the reaction time.

[0025] The metal phthalocyanine suitable as a raw material for the halogenated zinc phthalocyanine pigment (A1) is zinc phthalocyanine. The preferred synthesis method is a melting method, which involves less decomposition of the raw material during the reaction, provides a higher yield, and allows synthesis using inexpensive equipment without using a strong acid.

[0026] Furthermore, by optimizing the raw material charging method, catalyst type and amount used, reaction temperature and reaction time, it is possible to obtain a halogenated zinc phthalocyanine having a halogen atom composition different from that of existing halogenated zinc phthalocyanines.

[0027] After the synthesis of the halogenated zinc phthalocyanine, the resulting mixture is poured into water or an acidic aqueous solution such as hydrochloric acid, whereby the produced halogenated zinc phthalocyanine precipitates. The halogenated zinc phthalocyanine may be used as is, but it is preferable to subsequently filter it, wash it with water or aqueous sodium hydrogen sulfate, aqueous sodium hydrogen carbonate, or aqueous sodium hydroxide, and, if necessary, wash it with an organic solvent such as acetone, toluene, methyl alcohol, ethyl alcohol, or dimethylformamide, and then use it for post-treatment such as drying.

[0028] The halogenated zinc phthalocyanine is dry-ground in a grinder such as an attritor, a ball mill, a vibration mill or a vibration ball mill, as required, and then pulverized by a solvent salt milling method, a solvent boiling method or the like, to obtain a pigment that is excellent in dispersibility and coloring power and develops a green color with high brightness.

[0029] The method for micronizing the halogenated zinc phthalocyanine is not particularly limited. For example, the halogenated zinc phthalocyanine before micronization may be dispersed in a dispersion medium and micronized at the same time. However, it is preferable to employ a solvent salt milling treatment, in which crystal growth can be more easily suppressed and pigment particles having a large specific surface area can be obtained, compared to a solvent treatment in which a halogenated metal phthalocyanine is heated and stirred in a large amount of organic solvent.

[0030] (Metallic azo pigment (A2)) The metal azo pigment (A2) includes a metal azo pigment (A2) containing a compound represented by formula (1) or a tautomer thereof, and formula (2).

[0031] [ka] [In formula (1), R 1 and R 2 are each independently OH, NH2, or NHR 5 and R 3 and R 4 are each independently =O or =NR 5 and R 5 is a hydrogen atom or an alkyl group, and Me is Ni 2+ , Zn 2+ , Cu 2+ , Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ , and Co 3+ 2 / 3 is a divalent or trivalent metal ion selected from the following series: In each case, based on 1 mole of the total compounds of formula (I), Zn 2+ and Ni 2+ The amount of metal ions from the system is 95 to 100 mol %, and Cu 2+ , Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ , and Co 3+ 2 / 3 The amount of metal ions selected from the system is 0 to 5 mol %, and the molar ratio of metal ions Zn to Ni in the total of the compounds of formula (1) is from (9:1) to (1:9). In formula (2), R 6 is a hydrogen atom or an alkyl group.

[0032] More preferably, in formula (1), R 1 and R 2 is OH and R 3 and R 4 is =O.

[0033] Preferably, in formula (2), R 6 is hydrogen or C1-C4 alkyl optionally mono- or polysubstituted with OH. More preferably, in formula (2), R 6 is hydrogen.

[0034] Based on 1 mole of all metal ions present in the metallic azo pigment, Ni 2+ and Zn 2+ The combined amount of metal ions is generally 95-100 mol %, and Cu 2+ , Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ , and Co 3+ 2 / 3 The amount of metal ions selected from the system is 0 to 5 mol%; Ni 2+ and Zn 2+ The combined amount of is preferably 98 to 100 mol %, Cu 2+ , Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ , and Co 3+ 2 / 3 The amount of metal ions selected from the system is 0 to 2 mol%; Ni 2+ and Zn 2+ The combined amount of Cu is more preferably 99.9 to 100 mol %, 2+ , Al 3+ 2 / 3 , Fe 2+ , Fe 3+ 2 / 3 , Co 2+ , and Co 3+ 2 / 3 The amount of metal ions selected from the above system is 0 to 0.1 mol %.

[0035] Generally, Ni in metallic azo pigments 2+ Against Zn 2+ The molar ratio of is 1:1 to 9:1, preferably 2:1 to 4:1, and more preferably 2.3:1 to 3:1.

[0036] <Other colorants (A3)> The colorant (A) may contain other colorants (A3) in addition to the halogenated zinc phthalocyanine pigment (A1) and the metal azo pigment (A2). Examples of pigments and dyes as the other colorants (A3) are listed below.

[0037] (yellow pigment) Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, and 123. , 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the pigments described in JP-A-2012-226110. Preferred are CI Pigment Yellows 138, 139, 150, 185, 231, and 233, and the pigments described in JP-A-2012-226110.

[0038] (red pigment) Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179 , 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigments described in JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light fastness, and transmittance of the filter segment, preferred are CI Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, and 296, the pigments described in JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844, and more preferred are CI Pigment Red 177, 254, 291, 295, and 296, the pigments described in JP 2014-134712 A, and the pigments described in Japanese Patent No. 6368844.

[0039] (blue pigment) Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, from the viewpoints of heat resistance, light fastness, and transmittance of the filter segment, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and CI Pigment Blue 15:6 is more preferred.

[0040] (purple pigment) Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, from the viewpoints of heat resistance, light fastness, and transmittance of the filter segment, CI Pigment Violet 19 or 23 is preferred, and CI Pigment Violet 23 is more preferred.

[0041] (green pigment) Examples of green pigments include CI Pigment Green 7, 36, 58, 62, and 63.

[0042] (inorganic pigments) Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, and synthetic iron black.

[0043] As the other colorant (A3), CI Pigment Green 7, 36, 58, 62, 63, CI Pigment Yellow 138, 139, 150, 185, 231, 233 are preferred, and CI Pigment Green 58, 62, 63, CI Pigment Yellow 138, 139, 150, 231, 233 are more preferred.

[0044] <Pigment miniaturization> It is preferable that the organic pigment be mixed with other raw materials after undergoing a micronization treatment. Examples of methods for the micronization treatment include wet grinding, dry grinding, and solution precipitation. Among these, salt milling using a kneader, which is a type of wet grinding, is preferred. The average primary particle size of the organic pigment after micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. A moderate particle size improves dispersibility and the contrast ratio of the coating. The average primary particle size is the average value of approximately 20 particles randomly selected from an enlarged image taken with a TEM (transmission electron microscope). When the particle has both a vertical axis length and a horizontal axis length, the vertical axis length is used.

[0045] 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, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or a planetary mixer, followed by washing with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is utilized to crush the pigment during salt milling. Optimizing the conditions for salt milling a pigment can produce a pigment with a very fine primary particle size, a narrow distribution, and a sharp particle size distribution.

[0046] Examples of water-soluble inorganic salts include sodium chloride, barium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the viewpoint of cost. From the viewpoint of both treatment efficiency and production efficiency, the amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment.

[0047] The water-soluble organic solvent moistens the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (is miscible with) water but does not substantially dissolve the water-soluble inorganic salt. A high-boiling point solvent with a boiling point of 120°C or higher is preferred as the water-soluble organic solvent is less likely to volatilize due to the temperature increase during salt milling. Examples of water-soluble organic solvents include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, per 100 parts by mass of the pigment.

[0048] Resins can be added during salt milling. Examples of resins include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in water-soluble organic solvents. The amount of resin used is preferably 5 to 200 parts by mass per 100 parts by mass of the pigment.

[0049] <dye> Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Also included are dye derivatives and lake pigments obtained by lake-forming dyes.

[0050] The acid dye preferably has an acidic group such as a sulfonic acid or carboxylic acid. The direct dye preferably forms an inorganic salt of the acid dye, or a salt-forming compound between the acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound. Also preferred are salt-forming compounds that are salts of the acid dye and a resin component having these functional groups. Furthermore, the salt-forming compound can be sulfonamidated to modify it into a sulfonic acid amide compound, which makes it easy to obtain a photosensitive coloring composition with excellent resistance (light resistance, solvent resistance). In addition, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferred because it has excellent resistance (light resistance, solvent resistance). The compound having an onium salt group is preferably a resin having a cationic group.

[0051] Although basic dyes can be used as they are, salt-forming compounds that form salts with organic acids, perchloric acid, or metal salts thereof are preferred. Salt-forming compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in the salt-forming compounds of basic dyes, the anion component that acts as a counter ion is preferably an organic sulfonic acid, 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 with a halogenated hydrocarbon group, or a salt-forming compound formed with an acid dye. Furthermore, the resistance of salt-forming compounds is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

[0052] Examples 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, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc. Among these, from the viewpoint of color properties such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific structures of dyes 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.

[0053] <Dye derivatives> The photosensitive coloring composition can contain a dye derivative. When the dye derivative is adsorbed onto the surface of the organic pigment, the surface of the organic pigment becomes polar, which increases affinity with the dispersant, thereby further improving the dispersibility of the organic pigment. The dye derivative is a known dye derivative having an acidic group, a basic group, a neutral group, or the like in the organic dye residue. Examples of the dye derivative 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. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0054] Specifically, diketopyrrolopyrrole dye derivatives are disclosed in JP 2001-220520 A, WO2009 / 081930 A, WO2011 / 052617 A, WO2012 / 102399 A, and JP 2017-156397 A; phthalocyanine dye derivatives are disclosed in JP 2007-226161 A, WO2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A; and anthraquinone dye derivatives are disclosed in JP-A Nos. 63-264674, 09-272812, 10-245501, 10-265697, 2007-079094, and WO2009 / 025325. Quinacridone dye derivatives are disclosed in JP-A Nos. 48-54128, 03-9961, and 2000-273383. Dioxazine dye derivatives are disclosed in JP-A No. 2011-162662. Thiazine indigo dye derivatives are disclosed in JP-A No. 2007-3147. 85, triazine dye derivatives are disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, benzisoindole dye derivatives are disclosed in JP-A-2009-57478, quinophthalone dye derivatives are disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2009-314681, Examples of the naphthol dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439, examples of the azo dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092, examples of the acidic substituents include those described in JP-A-2004-307854, and examples of the basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404. 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.

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

[0056] The amount of the dye derivative used is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the pigment.

[0057] By adding a dye derivative to a pigment and carrying out a micronization 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.

[0058] 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, etc., 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), as well as linewidth sensitivity stability. 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.

[0059] <Resin-type dispersant> The photosensitive coloring composition of the present invention may contain a resin-type dispersant. The resin-type dispersant has a colorant affinity moiety that adsorbs to the colorant (A) and a relaxation moiety that has high affinity with components other than the colorant and causes steric repulsion between dispersed particles. Examples of resin-type dispersants 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; amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters. 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 that include tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc.

[0060] The content of the resin-type dispersant is preferably about 3 to 200% by mass relative to the colorant (A), and from the viewpoint of film-forming properties, more preferably about 5 to 100% by mass.

[0061] <Alkali-soluble resin (B)> The alkali-soluble resin (B) is a resin having an acidic group and being soluble in a developer. The alkali-soluble resin (B) is a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a 2 μm-thick coating is formed, and is preferably selected from photosensitive alkali-soluble resins and alkali-soluble resins. The transmittance is preferably 95% or more. Photosensitive means having a polymerizable unsaturated group.

[0062] The alkali-soluble resin (B) is preferably a thermoplastic resin having an acidic group. Examples of the acidic group include a carboxyl group and a sulfonic group. Examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / maleic acid (anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth)acrylic acid copolymer, or an isobutylene / maleic acid (anhydride) copolymer. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferred in terms of developability, heat resistance, and transparency, and an acrylic resin having an acidic group is more preferred.

[0063] The alkali-soluble resin (B) includes a photosensitive alkali-soluble resin (B1).

[0064] <Photosensitive alkali-soluble resin (B1)> The photosensitive alkali-soluble resin (B1) can be synthesized, for example, by the following methods (i) and (ii): Three-dimensional crosslinking occurs upon irradiation with light, increasing the crosslink density, thereby improving the developability and heat resistance of the coating film.

[0065] [Method (i)] In method (i), for example, a polymer of an epoxy group-containing monomer and other monomers is first synthesized. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain a photosensitive alkali-soluble resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0066] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0067] Examples of the monocarboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

[0068] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

[0069] Examples of other monomers 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.

[0070] Also, 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-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples of the ethylene oxide (EO)-modified (meth)acrylate include N-substituted maleimides such as N-isopropyl acrylate, ...

[0071] A method similar to method (i) is, for example, a method in which a polymerizable unsaturated group and a carboxyl group are introduced by addition reaction of an epoxy group-containing monomer with part of the side chain carboxyl groups of a copolymer obtained by copolymerizing a monocarboxyl group-containing monomer with another monomer.

[0072] [Method (ii)] In the method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer, and then the hydroxyl group of the polymer is reacted with the isocyanate group of an isocyanate group-containing monomer to synthesize a photosensitive alkali-soluble resin.

[0073] Examples of hydroxyl group-containing monomers include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to a hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by addition polymerization of poly(γ-valerolactone), poly(ε-caprolactone), and / or poly(12-hydroxystearic acid). Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, with glycerol mono(meth)acrylate being more preferred.

[0074] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0075] Monomers that can be used other than the above-mentioned monomers include the other monomers exemplified in the above method (i) as well as phosphate ester group-containing monomers.

[0076] The phosphate group-containing monomer is, for example, a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0077] Other examples of the photosensitive alkali-soluble resin (B1) include the polymer (A) described in JP-A No. 2004-300204.

[0078] In the present invention, the photosensitive alkali-soluble resin (B1) is preferably a resin synthesized by the method (i) in terms of developability and heat resistance.

[0079] <Non-photosensitive alkali-soluble resin> The photosensitive coloring composition can contain a non-photosensitive alkali-soluble resin that does not have a polymerizable unsaturated bond. This allows the degree of curing of the coating to be adjusted. Examples of the non-photosensitive alkali-soluble resin include resins obtained by removing the polymerizable unsaturated group from the photosensitive alkali-soluble resin (B1).

[0080] The weight-average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 38,000, and even more preferably 4,000 to 35,000. A suitable Mw improves adhesion to the substrate and reduces the generation of residues due to alkaline development. The value of Mw / Mn (number-average molecular weight) is preferably 10 or less.

[0081] The acid value of the alkali-soluble resin (B) is preferably 50 to 200 (mgKOH / g), more preferably 60 to 180, and even more preferably 70 to 170. Having an appropriate acid value makes it possible to highly achieve both alkali developability and a good pattern shape of pixels after development.

[0082] The alkali-soluble resin (B) can be used alone or in combination of two or more kinds.

[0083] The content of the alkali-soluble resin (B) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, per 100 parts by mass of the colorant (A). When an appropriate amount is contained, a coating can be easily formed and good color characteristics can be easily obtained.

[0084] <Polymerizable compound (C)> The polymerizable compound (C) is a monomer or oligomer containing a polymerizable unsaturated group. Examples of the polymerizable compound (C) include an acid group-containing monomer, a urethane bond-containing monomer, and other monomers.

[0085] Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

[0086] Examples of the acid group-containing monomer include esters of dicarboxylic acids and free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid; and esters of polycarboxylic acids and monohydroxyalkyl (meth)acrylates. 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 free carboxyl group-containing oligoesters of tricarboxylic acids, such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), 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, with monohydroxy monoacrylates or monohydroxy monomethacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0087] (urethane bond-containing monomer) Examples of the urethane bond-containing monomer 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.

[0088] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylate, and various acrylic acid esters and methacrylic acid esters such as urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0089] The polymerizable compound (C) can be used alone or in combination of two or more kinds.

[0090] The blending amount of the polymerizable compound (C) is preferably 0.5 to 50 mass %, more preferably 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When blended in an appropriate amount, the curability and developability are further improved. <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-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 2-(dimethylamino)-2-[(4- acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t- benzophenone compounds such as butylperoxycarbonyl)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( 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 diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds. Among these, oxime ester compounds are preferred.

[0091] (Oxime ester compounds) When oxime ester compounds absorb ultraviolet light, the NO bond of the oxime undergoes cleavage, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, allowing for pattern formation with a small amount of exposure.

[0092] Examples of the oxime ester compound include oxime ester photopolymerization initiators described in JP-A Nos. 2007-210991, 2009-179619, 2010-037223, 2010-215575, and 2011-020998.

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

[0094] The content of the photopolymerization initiator (D) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, relative to 100 parts by mass of the colorant (A). When an appropriate amount is added, photocurability and developability are further improved.

[0095] <Sensitizer> The photosensitive coloring composition can 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, tetrapyrazinoporphyrazine ...ine derivatives, fluorine derivatives, fluorine derivatives, fluorine derivatives, fluorine derivatives, fluorine derivatives, fluorine derivatives, fluorine derivatives, fluorine derivatives, fluorine derivatives, fluorine derivatives, Examples of the suitable phthalocyanine derivatives include 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, Michler's ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0096] Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred, 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, 3,6-dibenzoyl-N-ethylcarbazole, and the like are more preferred.

[0097] The sensitizers can be used alone or in combination of two or more.

[0098] The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, the curability and developability are further improved.

[0099] <Thermosetting compound (E)> The photosensitive coloring composition can contain a thermosetting compound. When the thermosetting compound is contained, it reacts with the filter segment during baking to increase the crosslink density of the coating film, thereby improving heat resistance and suppressing pigment aggregation. In addition, the contrast ratio is also improved.

[0100] The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0101] (epoxy compounds) Examples of 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, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbenzene), and polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbenzene). Examples of suitable epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins.

[0102] 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) Examples of such an anti-oxidant include: TTA3150 (manufactured by Kusumoto Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, and 721 (all trade names manufactured by Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, and TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.), and the like. These include, but are not limited to:

[0103] The epoxy equivalent of the epoxy compound is preferably 100 to 400 (g / eq: molecular weight per epoxy group = molecular weight ÷ number of epoxy groups). If the epoxy equivalent is 100 g / eq or more, the crosslink density of the film does not become too high and shrinkage during curing is small, resulting in good film flatness. If the epoxy equivalent is 400 g / eq or less, sufficient curing properties are obtained, resulting in significant improvements in adhesion and solvent resistance.

[0104] The amount of the epoxy compound is preferably 0.1 to 15.0% by mass based on the weight of the nonvolatile content of the photosensitive coloring composition for color filters. If it is less than 0.1% by mass, the heat resistance effect will be reduced, and if it is more than 15.0% by mass, the developability of the photosensitive coloring composition may be deteriorated.

[0105] The oxetane compound is a compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0106] Examples of monofunctional oxetane compounds include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane. Commercially available products 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.

[0107] Examples of the bifunctional oxetane compound include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane, 3-methyl ... -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. Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

[0108] Examples of oxetane groups with three 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, and caprolactone-modified dipentaerythritol. Examples of such a polymer include dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing an oxetane group (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30.

[0109] The content of the oxetane compound is preferably 0.1 to 15.0% by mass of the nonvolatile content of the photosensitive coloring composition. When the oxetane compound is contained in an appropriate amount, both heat resistance and developability can be highly achieved.

[0110] The thermosetting compound (E) can be used alone or in combination of two or more kinds.

[0111] <Thiol-based chain transfer agents> The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, a thiyl radical that is resistant to polymerization inhibition by oxygen is generated during radical polymerization after light irradiation, thereby improving the sensitivity of the photosensitive coloring composition.

[0112] The thiol chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent has four or more SH groups. As the number of functional groups increases, the coating becomes more easily photocured from the surface to the deepest part.

[0113] Examples of polyfunctional thiols include hexanedithiol and decanedithiol. , 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and the like are mentioned, and preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate.

[0114] The 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 10 mass %, more preferably 0.1 to 5 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

[0116] <Polymerization inhibitor> The photosensitive coloring composition may contain a polymerization inhibitor, which can suppress photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a pattern with a desired shape.

[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; alkylresorcinol compounds such as ethylresorcinol, 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.

[0118] The polymerization inhibitors can be used alone or in combination of two or more.

[0119] The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition, in which the effect of the polymerization inhibitor is enhanced, resulting in improved tapered linearity, wrinkles in the coating film, pattern resolution, etc.

[0120] <UV absorber> The photosensitive coloring composition may contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds. The ultraviolet absorber may be an oligomer or a polymer.

[0121] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-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- 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.

[0122] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)glycidic acid ester. Examples of such compounds include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0123] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-oxide, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0124] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0125] The ultraviolet absorbers can be used alone or in combination of two or more kinds.

[0126] 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. When an appropriate amount is contained, the resolution after development is further improved.

[0127] The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

[0128] <Antioxidants> The photosensitive coloring composition can contain an antioxidant. The antioxidant prevents the coating film formed from the photosensitive coloring composition from yellowing due to oxidation during thermal curing or ITO annealing, and can suppress a decrease in the transmittance of the coating. In particular, when the colorant concentration of the photosensitive coloring composition is high, the content of the photopolymerizable compound (D) is relatively reduced, and if the amount of photopolymerization initiator is increased or a thermosetting compound is added to address this, the coating is likely to yellow. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented and a decrease in the transmittance of the coating can be suppressed.

[0129] Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Note that, in this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

[0130] Among these, from the viewpoint of achieving both transmittance and sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0131] The antioxidants can be used alone or in combination of two or more.

[0132] The content of the antioxidant is preferably 0.5 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the photosensitive coloring composition, which further improves the transmittance, spectral characteristics, and sensitivity.

[0133] <Leveling agent> The photosensitive coloring composition can contain a leveling agent. This improves the wettability of the composition to the transparent substrate during film formation and the drying properties of the film. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

[0134] The surfactants can be used alone or in combination of two or more.

[0135] The content of the surfactant is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, of the nonvolatile content of the photosensitive coloring composition. Within this range, the balance between the coatability, pattern adhesion, and transmittance of the photosensitive coloring composition is further improved.

[0136] <Storage stabilizer> The photosensitive coloring composition can contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer 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.

[0137] The content of the storage stabilizer is preferably 0.1 to 10 mass % relative to 100 mass parts of the colorant (A).

[0138] <Adhesion improver> The photosensitive coloring composition may contain an adhesion improver. This improves the adhesion between the coating and the substrate. It also makes it easier to form narrow patterns using photolithography. Examples of adhesion improvers include silane coupling agents.

[0139] Examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-( aminosilanes such as N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl compounds such as p-styryltrimethoxysilane; ureido compounds such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

[0140] The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the colorant (A). When an appropriate amount is contained, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the coating is further improved, and the resolution of the pattern is also further improved.

[0141] <Method for producing photosensitive composition> The photosensitive coloring composition is prepared by dispersing a colorant (A), a resin-type dispersant, a solvent, and the like to produce a colorant dispersion. The colorant dispersion, resin-type dispersant, alkali-soluble resin (B), polymerizable compound (C), and photopolymerization initiator (D) are then mixed to produce a photosensitive coloring composition. The colorant (A) can be more finely dispersed by using a dispersing aid such as a dye derivative during the dispersion process. For the colorant dispersion, a pigment dispersant can be prepared for each pigment. Alternatively, two or more pigments can be mixed to produce a pigment dispersant. It goes without saying that the timing of blending each material is optional.

[0142] The dispersion treatment can be carried out using, for example, 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.

[0143] The photosensitive coloring composition is preferably prepared as a so-called resist material. The resist material may be a solvent development type or an alkali development type, with the alkali development type being preferred.

[0144] <Solvent> The photosensitive coloring composition can contain a solvent. This makes it easy to adjust the viscosity of the photosensitive coloring composition, making it easy to form a coating with a smooth surface. The solvent can be appropriately selected depending on the purpose of use, and an appropriate amount can be contained.

[0145] Examples of the solvent include ester solvents (solvents that contain -COO- in the molecule but do not contain -O-), ether solvents (solvents that contain -O- in the molecule but do not contain -COO-), 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.

[0146] Among the above solvents, from the viewpoint of coatability and drying property, it is preferable to use an organic solvent having a boiling point at 1 atm of 120° C. or more and 180° C. or less. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0147] <Removal of large particles> In this specification, it is preferable to remove the contained coarse particles at the stage of the colorant dispersion or after preparing the photosensitive coloring composition, which makes it easier to form a fine pattern since foreign matter can be removed from the coating. The removal of coarse particles is preferably carried out by centrifuging the photosensitive coloring composition at a gravitational acceleration of 3,000 to 25,000 G, or filtering through a sintered filter or membrane filter to remove coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, and more preferably coarse particles of 0.5 μm or larger, and mixed dust. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or larger. More preferably, particles of 0.3 μm or smaller are preferred.

[0148] <Color filter> In this specification, a color filter comprises a base material (also referred to as a transparent substrate) and filter segments formed from a photosensitive coloring composition. The color filter can have red filter segments, green filter segments, and blue filter segments by appropriately selecting the type of colorant (A) used. It can also have magenta filter segments, cyan filter segments, and yellow filter segments. A reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface. A transparent electrode such as an ITO film can also be formed on the substrate.

[0149] <Color filter manufacturing method> It is preferable to form a color filter by first forming a black matrix on a substrate and then forming filter segments. Alternatively, thin film transistors (TFTs) can be formed on the substrate before forming the black matrix. Examples of the black matrix include a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light-blocking agent is dispersed.

[0150] The filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, etc. In this specification, the most preferred method is the photolithography method.

[0151] In the photolithography method, for example, a photosensitive coloring composition containing a colorant of a certain color tone is applied to a transparent substrate so that the dry film thickness is approximately 0.2 to 5 μm to form a coating. The resulting coating (hereinafter referred to as the first coating) is exposed (irradiated with light) through a mask having a predetermined pattern. The coating is then developed by immersing in a solvent or alkaline developer or by spraying the developer onto the substrate, and the uncured portions are removed to obtain the desired pattern. This process can be similarly performed using photosensitive coloring compositions containing colorants of other colors to produce color filters having filter segments of each color. Furthermore, a second coating (oxygen barrier film) can be formed on the first coating before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first coating from coming into contact with oxygen, thereby further improving exposure sensitivity. Furthermore, the color filter can be heated to cure any uncured photopolymerizable compound in the filter segments.

[0152] Examples of the coating device include a spray coater, a spin coater, a slit coater, and a roll coater. A drying step can be carried out during coating. Examples of the drying device include a hot air oven and an infrared heater.

[0153] The developer may be an alkaline developer, such as an inorganic alkali such as sodium carbonate or sodium hydroxide, or an organic alkali such as dimethylbenzylamine or triethanolamine. The developer may also contain an antifoaming agent or a surfactant.

[0154] 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).

[0155] The color filters herein can be used in applications other than liquid crystal displays, such as solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, and head-mounted displays.

[0156] <Image display device> An image display device equipped with the color filter of the present invention will be described. The image 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 white LEDs because they broaden the red reproduction range. Figure 1 is a schematic cross-sectional view of an image 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.

[0157] 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.

[0158] 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).

[0159] 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.

[0160] 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.

[0161] The white LED light source may have a fluorescent filter formed on the surface of a blue LED or a blue LED resin package containing a fluorescent material, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity is maximized, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity is maximized, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity is maximized, 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, Preferred are white LED light sources (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, and white LED light sources (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.

[0162] Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0163] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries), NSSW304D (manufactured by Nichia Chemical Industries), and the like. [Example]

[0164] The present invention will be described below with reference to examples. In the examples, "parts" means "parts by mass" and "%" means "% by mass."

[0165] Before describing the examples, the methods for measuring and calculating the average molecular weight of a resin and the acid value of a resin will be described.

[0166] (average molecular weight of resin) The number-average molecular weight (Mn) and mass-average molecular weight (Mw) of the resin were measured using gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (Tosoh Corporation), with two separation columns connected in series. Both columns were packed with "TSK-GEL SUPER HZM-N" packing materials. 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 wt% of the above eluent, and 20 microliters was injected. All molecular weights are expressed in terms of polystyrene.

[0167] (resin acid value) 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 Co., Ltd.) 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.

[0168] <Method for producing halogenated zinc phthalocyanine pigment (A1)> (Production of halogenated zinc phthalocyanine pigment (A1-1)) A 300 mL flask was charged with 91 parts sulfuryl chloride, 109 parts aluminum chloride, 15 parts sodium chloride, 30 parts zinc phthalocyanine, and 74 parts bromine. The mixture was heated to 130°C over 40 hours, then poured into water and filtered to obtain a green crude pigment. 20 parts of the resulting green crude pigment, 140 parts pulverized sodium chloride, 32 parts diethylene glycol, and 1.8 parts xylene were charged into a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was poured into 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain halogenated zinc phthalocyanine pigment (A1-1). X-ray fluorescence analysis using a Rigaku ZSX100E revealed that the obtained halogenated zinc phthalocyanine pigment (A1-1) contained an average of 13.97 halogen atoms per molecule, of which the average number of bromine atoms was 11.46 and the average number of chlorine atoms was 2.51.

[0169] (Production of halogenated zinc phthalocyanine pigment (A1-2)) A 300 mL flask was charged with 91 parts sulfuryl chloride, 109 parts aluminum chloride, 15 parts sodium chloride, 30 parts zinc phthalocyanine, and 59 parts bromine. The mixture was heated to 130°C over 40 hours, then poured into water and filtered to obtain a crude green pigment. 20 parts of the resulting crude green pigment, 140 parts pulverized sodium chloride, 32 parts diethylene glycol, and 1.8 parts xylene were charged into a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was poured into 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a halogenated zinc phthalocyanine pigment (A1-2). X-ray fluorescence analysis of the resulting halogenated zinc phthalocyanine pigment (A1-2) revealed that it contained an average of 12.71 halogen atoms per molecule, including an average of 10.22 bromine atoms and 2.49 chlorine atoms.

[0170] (Production of halogenated zinc phthalocyanine pigment (A1-3)) A 300 mL flask was charged with 91 parts sulfuryl chloride, 109 parts aluminum chloride, 15 parts sodium chloride, 30 parts zinc phthalocyanine, and 44 parts bromine. The mixture was heated to 130°C over 40 hours, then poured into water and filtered to obtain a crude green pigment. 20 parts of the resulting crude green pigment, 140 parts pulverized sodium chloride, 32 parts diethylene glycol, and 1.8 parts xylene were charged into a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was poured into 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a halogenated zinc phthalocyanine pigment (A1-3). X-ray fluorescence analysis of the resulting halogenated zinc phthalocyanine pigment (A1-3) revealed that it contained an average of 11.98 halogen atoms per molecule, including an average of 9.00 bromine atoms and 2.98 chlorine atoms.

[0171] (Production of halogenated zinc phthalocyanine pigment (A1-4)) A 300 mL flask was charged with 109 parts sulfuryl chloride, 131 parts aluminum chloride, 18 parts sodium chloride, 30 parts zinc phthalocyanine, and 52 parts bromine. The mixture was heated to 130°C over 40 hours, then poured into water and filtered to obtain a crude green pigment. 20 parts of the resulting crude green pigment, 140 parts pulverized sodium chloride, 32 parts diethylene glycol, and 1.8 parts xylene were charged into a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was poured into 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain halogenated zinc phthalocyanine pigment (A1-4). X-ray fluorescence analysis of the resulting halogenated zinc phthalocyanine pigment (A1-4) revealed that it contained an average of 12.70 halogen atoms per molecule, including an average of 8.54 bromine atoms and 4.16 chlorine atoms.

[0172] <Production of Metallic Azo Pigment (A2)> (Yellow colorant (Y-1)) The azobarbituric acid precursor was prepared according to the synthesis method described in JP 2017-171915 A. (Instruction 1) 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were introduced into 1100 parts of distilled water at 85° C. The pH was then adjusted to about pH 5 with aqueous potassium hydroxide solution and stirring was continued for 90 minutes. Azobarbituric acid (0.3 moles) prepared in accordance with Instruction 1 was then mixed with 1500 parts of distilled water at 82°C. 10 parts of 30% hydrochloric acid were then added dropwise to adjust the pH to 2-2.5. 79.4 parts of melamine (0.63 moles) were then added. 0.3 moles of approximately 25% nickel chloride solution was then added dropwise. After 3 hours at 82°C, the pH was adjusted to approximately 5.5 using aqueous potassium hydroxide. This was followed by dilution with approximately 100 parts of distilled water at 90°C. 21 parts of 30% hydrochloric acid were then added dropwise, and the temperature was maintained at 90°C for 12 hours. The pH was then adjusted to approximately 5 using aqueous potassium hydroxide. The pigment was then isolated on a suction filter, washed, dried in a vacuum drying cabinet at 80°C, and ground in a standard laboratory mill for 2 minutes to obtain a yellow colorant (Y-1), which is an adduct of nickel azobarbituric acid and melamine.

[0173] (Metallic azo pigment (A2-1)) Metallic azo pigment (A2-1) was obtained in the same manner as in the preparation of yellow colorant (Y-1), except that "0.3 moles of 25% strength nickel chloride solution" in the preparation example for yellow colorant (Y-1) was replaced with "a mixed solution of 0.225 moles of 25% nickel chloride and 0.075 moles of 25% strength zinc chloride." Note that metallic azo pigment (A2-1) is a hybrid compound containing the components 25 mole % Zn and 75 mole % nickel as a melamine adduct of zinc / nickel azobarbituric acid.

[0174] (Metallic azo pigment (A2-2)) Metallic azo pigment (A2-2) was obtained in the same manner as in the production example of yellow colorant (Y-1), except that the "0.3 moles of 25% nickel chloride solution" in the production example of yellow colorant (Y-1) was replaced with "a mixed solution of 0.150 moles of 25% nickel chloride and 0.150 moles of 25% zinc chloride." Note that metallic azo pigment (A2-2) is a hybrid compound containing a melamine adduct of zinc / nickel azobarbituric acid, 50 mole % Zn, and 50 mole % nickel.

[0175] (Metallic azo pigment (A2-3)) Metallic azo pigment (A2-3) was obtained in the same manner as in the production example of yellow colorant (Y-1), except that the "0.3 moles of 25% nickel chloride solution" in the production example of yellow colorant (Y-1) was replaced with "a mixed solution of 0.075 moles of 25% nickel chloride and 0.225 moles of 25% zinc chloride." The metallic azo pigment (A2-3) is a hybrid compound containing a melamine adduct of zinc / nickel azobarbituric acid, 75 mole % Zn, and 25 mole % nickel.

[0176] (Fine-graining treatment of metal azo pigment (A2-1)) 100 parts of the metal azo pigment (A2-1), 10 parts of the dye derivative (d-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 70° C. This mixture was poured into 2000 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 mixture was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain a micronized metal azo pigment (A2-1).

[0177] Pigment derivative (d-1) [ka]

[0178] (Fine-graining treatment of metallic azo pigment (A2-2)) A micronized metal azo pigment (A2-2) was obtained in the same manner as in the micronization treatment of the metal azo pigment (A2-2), except that the metal azo pigment (A2-1) was changed to the metal azo pigment (A2-2).

[0179] (Fine grain processing of metal azo pigment (A2-3)) A micronized metal azo pigment (A2-3) was obtained in the same manner as in the micronization treatment of the metal azo pigment (A2-2), except that the metal azo pigment (A2-1) was changed to the metal azo pigment (A2-3).

[0180] (Production of other halogenated zinc phthalocyanine pigments (A3)) (Production of other halogenated zinc phthalocyanine pigments (A3-1)) A 300 mL flask was charged with 91 parts sulfuryl chloride, 72 parts aluminum chloride, 15 parts sodium chloride, 30 parts zinc phthalocyanine, and 29 parts bromine. The mixture was heated to 130°C over 40 hours, then poured into water and filtered to obtain a crude green pigment. 20 parts of the resulting crude green pigment, 140 parts pulverized sodium chloride, 32 parts diethylene glycol, and 1.8 parts xylene were charged into a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was poured into 2000 parts of water at 80°C and stirred for 1 hour. The mixture was then filtered, washed with hot water, dried, and pulverized to obtain a halogenated zinc phthalocyanine pigment (A3-1). X-ray fluorescence analysis of the resulting halogenated zinc phthalocyanine pigment (A3-1) revealed that it contained an average of 8.88 halogen atoms per molecule, including an average of 6.90 bromine atoms and 1.98 chlorine atoms.

[0181] (Production of other halogenated zinc phthalocyanine pigments (A3-2)) Commercially available CI Pigment Green 58 (FASTOGEN Green A110 manufactured by DIC Corporation) was used as is. X-ray fluorescence analysis revealed that the pigment was a halogenated zinc phthalocyanine pigment with an average of 15.46 halogen atoms per molecule, including an average of 14.75 bromine atoms and 0.71 chlorine atoms.

[0182] (Finely divided copper phthalocyanine pigment (A3-3)) 200 parts of the phthalocyanine green pigment CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyocolor Co., Ltd.), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80° C. Next, this kneaded mixture was poured into 8 liters of warm water and stirred for 2 hours while heating to 80° C. to form a slurry. After repeated filtration and washing with water to remove the sodium chloride and diethylene glycol, the slurry was dried overnight at 85° C. to obtain 190 parts of a finely divided copper phthalocyanine pigment (A3-3).

[0183] (Fine Yellow Pigment (A3-4)) 100 parts of a metal complex yellow pigment (CI Pigment Yellow 150, manufactured by Lanxess AG, "Yellow Pigment E4GN"), 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 with a high-speed mixer for about 1 hour to form a slurry. The slurry was 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 a finely divided yellow pigment (A3-4).

[0184] (Fine Yellow Pigment (A3-5)) 100 parts of CI Pigment Yellow 138 (PY138) (BASF Japan "Paliotol Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) and kneaded for 6 hours at 80°C. This mixture was added to 2000 parts of warm water and stirred for 1 hour while heating to 80°C to form a slurry. The slurry was filtered and washed repeatedly with water to remove the salt and solvent, and then dried overnight at 80°C to obtain a finely divided yellow pigment (A3-5).

[0185] (Production of resin-type dispersant solution 1) A reaction vessel equipped with a gas inlet tube, thermostat, condenser, and stirrer was charged with 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts i-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts propylene glycol monomethyl ether acetate (PGMAc), and the atmosphere was purged with nitrogen gas. The reaction vessel was heated to 50°C with stirring, and 12 parts 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts 2,2'-azobisisobutyronitrile and 90 parts PGMAc was added while the reaction was continued for 7 hours. Measurement of the nonvolatile content confirmed that 95% reaction had occurred. Next, 19 parts pyromellitic anhydride, 50 parts PGMAc, 50 parts cyclohexanone, and 0.4 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was continued at 100°C for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and PGMAc was added to adjust the non-volatile content to 30%. Resin-type dispersant solution 1 with an acid value of 70 mgKOH / g and a weight-average molecular weight of 8,500 was obtained.

[0186] <Production example of alkali-soluble resin (B) liquid> <Production example of alkali-soluble resin (B1: photosensitive resin)> (Preparation of alkali-soluble resin (B1-1) solution) A separable four-necked flask was fitted with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 207 parts of PGMAc 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 solution. Next, the nitrogen gas flow was stopped and the entire copolymer solution was stirred while injecting dry air for 1 hour. After cooling to room temperature, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenzu MOI, Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of PGMAc 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. PGMAc was added to the previously synthesized resin solution to achieve a nonvolatile content of 20%, producing an alkali-soluble resin (B1-1). The mass-average molecular weight (Mw) was 18,000.

[0187] (Preparation of alkali-soluble resin (B1-2) solution) A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 333 parts of PGMAc, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and then a solution obtained by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of a tricyclodecane-skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 164 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for a further 5 hours at 100°C. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 parts of methacrylic acid (0.5 mol, 100 mol% relative to the glycidyl groups of the glycidyl methacrylate used in this reaction), 0.9 parts of tris(dimethylaminomethyl)phenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110 ° C for 6 hours, and the reaction was terminated when the nonvolatile acid value reached 1 mg KOH / g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the reaction was continued at 120 ° C for 3.5 hours to obtain a resin solution with an acid value of 80 mg KOH / g. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried at 180 ° C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution so that the nonvolatile content reached 20% by mass, and an alkali-soluble resin (B1-2) solution was prepared. The mass average molecular weight (Mw) was 12,000.

[0188] (Preparation of alkali-soluble resin (B1-3) solution) A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 182 parts of PGMAc, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and a solution of 3.6 parts of azobisisobutyronitrile added to a mixture of 70.5 parts (0.40 mol) of benzyl methacrylate, 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of a tricyclodecane-skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and 136 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for a further 5 hours at 100°C. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol (50 mol% relative to the carboxyl groups of the methacrylic acid used in this reaction)], 0.9 parts of tris(dimethylaminomethyl)phenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110 °C for 6 hours, yielding a resin solution with an acid value of 79 mg KOH / g. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried at 180 °C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution to obtain an alkali-soluble resin (B2-3) solution with a nonvolatile content of 20% by weight. The mass-average molecular weight (Mw) was 13,000.

[0189] (Preparation of alkali-soluble resin (B1-4) solution) 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 PGMAc was prepared with thorough stirring. A chain transfer agent dropping vessel containing 8 parts of n-dodecanethiol and 32 parts of PGMAc was prepared with thorough stirring. A reactor was charged with 395 parts of PGMAc 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 dropwise addition took 135 minutes, maintaining the temperature at 90°C. Sixty minutes after the dropwise addition was completed, the temperature was raised to 110°C. After maintaining the temperature at 110°C for three 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 PGMAc was added and the mixture was cooled to room temperature. Approximately 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was then added to the previously synthesized resin solution to obtain an alkali-soluble resin (B1-4). The resin had a mass-average molecular weight (Mw) of 18,000 and an acid value of 2 mgKOH / g per nonvolatile content.

[0190] (Preparation of alkali-soluble resin (B1-M) solution) Equal amounts of the four alkali-soluble resin solutions (B1-1) to (B1-4) were mixed and stirred to prepare alkali-soluble resin solution (B1-M).

[0191] <Production of alkali-soluble resin (B2: non-photosensitive resin)> (Preparation of alkali-soluble resin (B2-1) solution) A separable four-necked flask equipped with a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer was charged with 196 parts of PGMAc and heated to 80°C. The atmosphere inside the reaction vessel was replaced with nitrogen, and then a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd., "Aronix M110"), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the addition was completed, the reaction was continued for another 3 hours to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution to achieve a nonvolatile content of 20% to prepare an alkali-soluble resin (B2-1). The mass average molecular weight (Mw) was 26,000.

[0192] (Preparation of alkali-soluble resin (B2-2) solution) A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube was placed under a nitrogen atmosphere, and 210 parts of PGMAc was added. The temperature was raised to 100 °C while stirring. Next, 106 parts of benzyl methacrylate, 22 parts of acrylic acid, and 22 parts of dicyclopentanyl methacrylate (Hitachi Chemical Co., Ltd. FA-513M) were dissolved in 215 parts of PGMAc. 3.6 parts of 2,2'-azobisisobutyronitrile was dissolved in the solution, which was then added dropwise to the flask and stirred at 100 °C for 5 hours to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180 °C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20%, and an alkali-soluble resin (B2-2) solution with a mass average molecular weight (Mw) of 10,000 was obtained.

[0193] (Preparation of alkali-soluble resin (B2-M) solution) Equal amounts of alkali-soluble resin (B2-1) solution and alkali-soluble resin (B2-2) solution were mixed and stirred to prepare alkali-soluble resin (B2-M) solution.

[0194] <Method for producing pigment dispersion> (Pigment Dispersion (P-1)) The following mixture was stirred and mixed until uniform, and then dispersed for 5 hours in an Eiger mill (Eiger Japan, "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to prepare a yellow pigment dispersion (PG-1). Halide zinc phthalocyanine pigment (A1-1): 14.0 parts Resin-type dispersant solution 1 (non-volatile content 30%): 20.0 parts PGMAC: 66.0 copies

[0195] (Pigment Dispersion (P-2~12) The following pigment dispersions (P-2 to P-12) were prepared in the same manner as pigment dispersion (P-1), except that the types and blending amounts (parts by mass) of the finely divided pigment, dye derivative, resin-type dispersant solution, and solvent were changed to those shown in Table 1.

[0196] [Table 1]

[0197] <Method for producing photosensitive coloring composition for color filter> [Example 1] (Photosensitive green composition (GR-1)) The following mixture was stirred and mixed to become uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition for color filters (GR-1). Pigment dispersion (P-1: halogenated zinc phthalocyanine pigment): 27.00 parts Pigment dispersion (P-5: metal azo pigment): 11.57 parts Alkali-soluble resin solution (B1-1): 30.64 parts Photopolymerizable compound (CM): 2.70 parts Photopolymerization initiator (DM): 0.31 parts Thermosetting compound (E-1): 0.05 part Sensitizer (F): 0.14 parts Thiol chain transfer agent (G): 0.18 parts Polymerization inhibitor (H): 0.01 parts Ultraviolet absorber (I): 0.18 parts Antioxidant (J): 0.18 parts Leveling agent (K: non-volatile content 3%): 0.30 parts Storage stabilizer (L): 0.09 parts Adhesion improver (M): 0.18 parts Solvent (N): 26.47 parts

[0198] [Examples 2 to 29, Comparative Examples 1 to 5] (Photosensitive coloring composition (GR-2~34) Hereinafter, photosensitive coloring compositions for color filters (GR-2 to GR-34) were prepared in the same manner as the photosensitive green composition (GR-1), except that the pigment dispersion, alkali-soluble resin solution, photopolymerizable compound, photopolymerization initiator, and thermosetting compound were changed to the types and amounts (parts by mass) shown in Table 2.

[0199] [Table 2-1]

[0200] [Table 2-2] The symbols are as follows:

[0201] <Polymerizable compound (CM)> (C-1) Trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei)] (C-2) Dipentaerythritol penta- and hexaacrylate (E-2) [Aronix M402 (manufactured by Toagosei)] (C-3) (Polybasic acid-modified acrylic oligomer) [Aronix M510 (manufactured by Toagosei)] (C-4) Polybasic acidic acrylic oligomer [Aronix M520 (manufactured by Toagosei)] (C-5) (Tricyclodecane dimethanol diacrylate) [A-DCP (manufactured by Shin Nakamura Chemical Co., Ltd.)]

[0202] (C-6) Photopolymerizable compound (C-6) A separable four-neck flask equipped with a thermometer, condenser, air inlet, dropping tube, and stirrer was charged with 400 parts of dipentaerythritol pentaacrylate, 400 parts of PGMAC, 1.0 parts of N,N-dimethylbenzylamine, and 1.0 parts of 4-methoxyphenol. The temperature was raised to 70°C, and a mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAC was added dropwise over 1 hour. After the addition, the reaction was continued for an additional 7 hours, and IR analysis confirmed the absence of isocyanate groups in the reaction product. After cooling to room temperature, 35.1 parts of mercaptopropionic acid and 35.1 parts of PGMAC were added and the reaction was continued for 6 hours at 50-60°C to obtain photopolymerizable compound (C-6). The above (C-1) to (C-6) were mixed in equal amounts to prepare a photopolymerizable monomer (CM).

[0203] <Photopolymerization initiator (DM)> (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) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime) [Irgacure OXE02 (BASF Japan)] (D-4) ADEKA "ADEKA Arcles NCI-831E" (D-5) BASF Japan "Irgacure OXE04" (D-6) 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime [Irgacure OXE01 (BASF Japan)] (D-7) Nikko Chemtech "TR-PBG-305" The above (D-1) to (D-7) were mixed in equal amounts to prepare a photopolymerization initiator (DM).

[0204] <Thermosetting compound (E)> Epoxy compounds (E1) (E1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel)] (E1-2) Glycidyl etherified epoxy compounds of sorbitol [Denacol EX611 (Nagase ChemteX Corporation)] (E1-3) N,N,N',N'-Tetraglycidyldiaminodiphenylmethane epoxy resin [jER604 (Mitsubishi Chemical Corporation)] (E1-4) Triglycidyl isocyanurate [TEPIC-S (Nissan Chemical Industries)] The epoxy equivalent weights of each are shown in Table 3.

[0205] [Table 3]

[0206] Oxetane compounds (E2): (E2-1) 3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei)]

[0207] <Sensitizer (F)> (F-1) 2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku)] (F-2) 4,4'-bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)] Equal amounts of (F-1) and (F-2) were mixed together to form sensitizer (F).

[0208] <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).

[0209] <Polymerization inhibitor (H)> (H-1) 3-Methylcatechol (H-2) Methylhydroquinone (H-3) t-Butylhydroquinone The above (H-1) to (H-3) were mixed in equal amounts to prepare a polymerization inhibitor (H).

[0210] <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 [TINUVIN400 (BASF Japan)] (I-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (BASF Japan)] The above (I-1) and (I-2) were mixed in equal amounts to prepare an ultraviolet absorber (I).

[0211] <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).

[0212] <Leveling Agent (K)> 1 copy of BYK-330 manufactured by BYK-Chemie, 1 copy of DIC "Megafac F-551" 1 copy of Kao Corporation's "Emulgen 103" A mixed solution of 97 parts of PGMAc.

[0213] <Storage stabilizer (L)> (L-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol (Honshu Chemical Industry Co., Ltd. "BHT") (L-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.) The above (L-1) and (L-2) were mixed in equal amounts to prepare a storage stabilizer (L).

[0214] <Adhesion improver (M)> (M-1) 3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (Shin-Etsu Chemical Co., Ltd.)] (M-2) 3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (Shin-Etsu Chemical Co., Ltd.)] (M-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (Shin-Etsu Chemical Co., Ltd.)] (M-4) 3-Mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (Shin-Etsu Chemical Co., Ltd.)] Equal amounts of (M-1) to (M-4) were mixed together to prepare a silane coupling agent (M).

[0215] <Solvent (N)> (N-1) PGMAc 30 copies (N-2) Cyclohexanone 30 parts (N-3) Ethyl 3-ethoxypropionate 10 parts (N-4) Propylene glycol monomethyl ether 10 parts (N-5) Cyclohexanol acetate 10 parts (N-6) Dipropylene glycol methyl ether acetate 10 parts The above (N-1) to (N-6) were mixed in the above-mentioned parts by mass to form a solvent (N).

[0216] <Evaluation of Photosensitive Coloring Composition for Color Filter> The photosensitive coloring compositions obtained in the examples and comparative examples were evaluated for developability, film thickness, brightness, and heat resistance by the following methods. The results are shown in Tables 4 and 5.

[0217] <Developability> The obtained photosensitive coloring composition was applied to a glass substrate of 100 mm length x 100 mm width x 0.7 mm thickness using a spin coater at a rotation speed that resulted in a film thickness of 2.0 μm after drying, and the coating was dried at 90 ° C for 90 seconds to remove the solvent, obtaining a coated substrate. Next, the substrate was spray-developed with an alkaline developer consisting of a 0.2 mass % aqueous solution of sodium carbonate, and the time until the coating film was completely dissolved was taken as the development dissolution time, which was evaluated according to the following criteria. ⊚: The development dissolution time was less than 20 seconds, and the developability was extremely good. ◯: The development dissolution time was 20 seconds or more and less than 40 seconds, and the development property was good. △: The development dissolution time was 40 seconds or more and less than 60 seconds, and the developability was practical. ×: The development dissolution time was 60 seconds or more, and the developability was not practical.

[0218] <Formation of filter segments> A black matrix was patterned on a glass substrate measuring 100 mm long x 100 mm wide and 0.7 mm thick. The resulting photosensitive coloring composition was then applied to the glass substrate using a spin coater at a rotation speed such that, after baking, y in the XYZ color system was 0.586 when a C light source was used as a backlight, and the composition was dried at 90°C for 90 seconds to remove the solvent, yielding a coated substrate. The coating was then irradiated with 100 mJ / cm 2 using an ultra-high pressure mercury lamp through a mask having a pattern of 400 μm long x 400 μm wide. 2 The coated substrate was then irradiated with ultraviolet light of 1000 kJ / cm². The uncured portions were then removed by spray development using an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate, forming the desired pattern. The coated substrate was then heated in an oven at 230°C for 20 minutes to form filter segments. The transmission spectrum was measured using a microspectrophotometer (OSP-SP100 manufactured by Olympus Optical Co., Ltd.), and y was calculated.

[0219] <Film thickness> The film thickness of the patterned portion of the obtained filter segment, 400 μm long×400 μm wide, was measured using Dektak 3030 (manufactured by Nippon Shinku Gijutsu Co., Ltd.). The evaluation criteria are as follows: ◎: Less than 2.0 μm, extremely good film thickness. ◯: 2.0 μm or more and less than 2.4 μm, good film thickness. △: 2.4 μm or more and less than 3.0 μm, a practical film thickness. ×: 3.0 μm or more, impractical film thickness.

[0220] <lightness> The transmission spectrum of the pattern portion of the obtained filter segment, measuring 400 μm in length and 400 μm in width, was measured using a microspectrophotometer (OSP-SP100 manufactured by Olympus Optical Co., Ltd.), and the Y value (brightness) in the XYZ color system was calculated when a C light source was used as the backlight. The evaluation criteria are as follows: ◎: 50.0 pts or more, extremely good brightness. Good: 49.5 pts or more and less than 50.0 pts, good brightness. △: 49.0 pts or more and less than 49.5 pts, practical brightness. ×: Less than 49.0 pts, unusable brightness

[0221] <Heat resistance> The chromaticity ([L*(1), a*(1), b*(1)]) of the resulting filter segment pattern, measured under Illuminant C, was measured using a microspectrophotometer (Olympus Optical Co., Ltd., "OSP-SP100"). The sample was then heated at 230°C for 40 minutes to evaluate heat resistance. The chromaticity ([L*(2), a*(2), b*(2)]) of the 400 μm x 400 μm pattern was then measured under Illuminant C, and the color difference ΔE*a*b* was calculated using the following formula: ΔE*a*b* = {(L*(2)-L*(1)) 2 +(b*(2)-b*(1)) 2 +(a*(2)-a*(1)) 2} 0.5 The evaluation criteria are as follows: ◎: ΔE*a*b* is less than 1.0, and the heat resistance is extremely good. ○: ΔE*a*b* is 1.0 or more and less than 3.0, and the heat resistance is good. △: ΔE*a*b* is 3.0 or more and less than 5.0, and the heat resistance is sufficient for practical use. ×: ΔE*a*b* is 5.0 or more, and the heat resistance is not practical.

[0222] [Table 4]

[0223] The photosensitive coloring compositions of the present invention (Examples 1 to 29) were thin and had high brightness, and were good in developability and heat resistance. On the other hand, Comparative Examples 1 and 3 had poor brightness, Comparative Example 2 had poor film thickness, Comparative Example 4 had poor developability, and Comparative Example 5 had poor heat resistance. [Explanation of symbols]

[0224] 10 Image 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), an alkali-soluble resin (B), a polymerizable compound (C), a photopolymerization initiator (D), and a thermosetting compound (E), The colorant (A) comprises a halogenated zinc phthalocyanine pigment (A1) having an average of 10 to 14 halogen atoms per molecule, of which the average is 8 to 12 bromine atoms and the average is 2 to 5 chlorine atoms, and a metal azo pigment (A2) containing a compound represented by formula (1) or a tautomer thereof and a compound represented by formula (2), the alkali-soluble resin (B) contains a photosensitive alkali-soluble resin (B1); the thermosetting compound (E) comprises at least one selected from the group consisting of a 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol, a glycidyl etherified epoxy compound of sorbitol, an N,N,N',N'-tetraglycidyldiaminodiphenylmethane epoxy resin, and triglycidyl isocyanurate; A photosensitive coloring composition, wherein the content of the thermosetting compound (E) is 0.1 to 15.0 mass% in 100 mass% of the total nonvolatile content of the photosensitive coloring composition. 【Chemistry 1】 [In formula (1), R １ and R ２ are independently OH, NH ２ , or NHR ５ and R ３ and R ４ are each independently ═O or ═NR ５ and R ５ is a hydrogen atom or an alkyl group, and Me is Ni ２＋ , Zn ２＋ , Cu ２＋ , Al ３＋ ２／３ , Fe ２＋ , Fe ３＋ ２／３ , Co ２＋ , and Co ３＋ ２／３ is a divalent or trivalent metal ion selected from the following series: In each case, based on 1 mole of the total compounds of formula (I), Zn ２＋ and Ni ２＋ The amount of metal ions from the system is 95 to 100 mol %, and Cu ２＋ , Al ３＋ ２／３ , Fe ２＋ , Fe ３＋ ２／３ , Co ２＋ , and Co ３＋ ２／３ is 0 to 5 mol %, and the molar ratio of Zn to Ni metal ions in the total compound of formula (1) is from (9:1) to (1:9). In formula (2), R ６ is a hydrogen atom or an alkyl group.

2. The photosensitive coloring composition according to claim 1, wherein the content of the colorant (A) is 20 to 50 mass% in 100 mass% of the total nonvolatile content of the photosensitive coloring composition.

3. A color filter comprising a substrate and filter segments formed from the photosensitive coloring composition according to claim 1 or 2.

4. An image display device comprising the color filter according to claim 3 .

5. A solid-state imaging device comprising the color filter according to claim 3.

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