A green photosensitive coloring composition, a color filter, a liquid crystal display device, and a solid-state imaging device.

Abstract

To provide a green photosensitive coloring composition capable of forming a color filter that is less prone to a reduction of brightness and a deterioration of dielectric loss tangent.SOLUTION: A green photosensitive coloring composition comprises (A) a colorant (comprising a phthalocyanine pigment), (B) a copper salt of a quinophthalone compound comprising a sulfo group, (C) an alkali-soluble resin, (D) a polymerizable compound, and (E) a photopolymerization initiator (comprising a compound of the formula illustrated below).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive coloring composition for use in a color filter or the like. [Background technology]

[0002] Generally, color filters are formed on the surface of a transparent substrate such as glass. They consist of fine stripe-shaped filter segments (pixels) consisting of red (R), green (G), and blue (B) filter layers, arranged parallel or crosswise, or fine filter segments arranged in a fixed array. The filter segments are as small as several microns to several hundred microns and are arranged in a regular array for each hue. In recent years, liquid crystal display devices equipped with such color filters have been required to have higher brightness and a wider color reproduction range. Therefore, color filters are also required to have increasingly higher light transmittance, higher color purity, and thinner films. Green filter segments, in particular, are important as a material that can provide color filters with high light transmittance and a wide color reproduction range.

[0003] In addition to a green pigment as a colorant, a yellow pigment is used as a colorant for adjusting the color (toning colorant) for the green filter segment, and examples of such pigments include CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 185, CI Pigment Yellow 231, and CI Pigment Yellow 233. Among these, quinophthalone pigments CI Pigment Yellow 138, CI Pigment Yellow 231, and CI Pigment Yellow 233 are often used because they provide high transmittance.

[0004] However, green filter segments using green pigments such as CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, and CI Pigment Green 63, zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, and JP 2004-70342 A, and phthalocyanine pigments described in JP 4893859 A, JP 2016-153481 A, and JP 2017-197685 A, etc., and quinophthalone yellow pigments have had problems such as a decrease in brightness due to continuous backlight irradiation, and a deterioration in dielectric dissipation factor that disrupts the alignment of liquid crystals and increases power consumption.

[0005] Therefore, as an effort to improve the decrease in brightness, Patent Document 1 discloses a colored resin composition containing, as colorants, a phthalocyanine colorant, a yellow colorant, and a metal compound that is a component different from the colorant. Furthermore, as an effort to improve the dielectric loss tangent, Patent Document 2 discloses a photosensitive colored resin composition for color filters that contains, as colorants, a phthalocyanine colorant, a yellow colorant, at least one anion selected from the group consisting of a specific azo compound and a mono-, di-, tri-, and tetra-anions of azo compounds having a tautomeric structure thereof, at least two metal ions, and a melamine derivative, and the dispersant is a polymer having a specific structural unit. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-186546 [Patent Document 2] Japanese Patent Application Publication No. 2018-010210 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the coloring composition of Patent Document 1 does not take into consideration the suppression of the dielectric loss tangent, and the coloring composition of Patent Document 2 does not take into consideration the suppression of the decrease in lightness. Therefore, the prior art could not simultaneously suppress the decrease in lightness and the dielectric loss tangent.

[0008] An object of the present invention is to provide a green photosensitive coloring composition that can form a thin, high-brightness color filter in which the decrease in lightness and the dielectric loss tangent are suppressed. [Means for solving the problem]

[0009] The present invention is a green photosensitive coloring composition comprising a colorant (A), a copper salt of a quinophthalone compound having a sulfo group (B), an alkali-soluble resin (C), a polymerizable compound (D), and a photopolymerization initiator (E), wherein the colorant (A) comprises a phthalocyanine pigment (A1), and the photopolymerization initiator (E) comprises a compound (E1) represented by the following general formula (1):

[0010] General formula (1) [ka]

[0011] In the general formula (1), X1, X3 and X6 each independently represent R 11 , OR 11 , C.O.R. 11 , S.R. 11 ,CONR 12 R 13 or CN, X2 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, X4 and X5 each independently represent R 11 , OR 11 , S.R. 11 , C.O.R. 11 ,CONR 12 R 13 , N.R. 12 COR11 ,OCOR 11 , COOR 11 , SCOR 11 , COSR 11 , COSR 11 , CSOR 11 , CN, a halogen atom or a hydroxyl group. 11 , R 12 and R 13 each independently represents a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, an optionally substituted arylalkyl group having 7 to 30 carbon atoms, or an optionally substituted heterocyclic group having 2 to 20 carbon atoms. a and b each independently represent an integer of 0 to 3. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a green photosensitive coloring composition capable of forming a color filter having a reduced dielectric loss tangent and excellent light resistance. Furthermore, it is possible to provide a color filter, a liquid crystal display device, and a solid-state imaging device. [Brief explanation of the drawings]

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

[0014] DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in detail below with reference to the preferred embodiments. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[0015] In this specification, unless otherwise specified, the terms "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" refer to "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. "CI" refers to the Color Index (CI; published by The Society of Dyers and Colourists). The monomer is an ethylenically unsaturated group-containing compound.

[0016] <Green photosensitive coloring composition> The present invention provides a green photosensitive coloring composition comprising a colorant (A), a copper salt of a quinophthalone compound having a sulfo group (B), an alkali-soluble resin (C), a polymerizable compound (D), and a photopolymerization initiator (E), In the green colored composition, the colorant (A) contains a phthalocyanine pigment (A1), and the photopolymerization initiator (E) contains a compound (E1) represented by the following general formula (1).

[0017] Generally, green filter segments using phthalocyanine pigment (A1) and quinophthalone pigment (A2) tend to exhibit a decrease in lightness and a deterioration in dielectric loss tangent due to continuous backlight irradiation. The decrease in lightness is believed to be caused by photoexcitation of the phthalocyanine pigment (A1) upon backlight irradiation, resulting in electron transfer from the quinophthalone pigment (A2), resulting in a new absorption peak derived from the anion radical of the phthalocyanine pigment (A1). The green photosensitive coloring composition of the present invention is believed to improve lightness by transferring electrons from the anion radical of the phthalocyanine pigment (A1) to the copper salt (B) of a quinophthalone compound having a sulfo group. Furthermore, while the dielectric loss tangent deteriorates due to pigment aggregation, the use of compound (E1) represented by the following general formula (1) promotes internal curing of the coating film, thereby suppressing pigment aggregation during post-baking and improving the dielectric loss tangent.

[0018] General formula (1) [ka]

[0019] [Colorant (A)] (Phthalocyanine pigment (A1)) The green photosensitive coloring composition contains a phthalocyanine pigment (A1) as a colorant (A).

[0020] Specific examples of the phthalocyanine pigment (A1) include compounds classified as pigments in the Color Index, such as CI Pigment Greens 7, 10, 36, 37, 58, 59, 62, and 63, zinc phthalocyanine pigments described in JP-A-2008-19383, JP-A-2007-320986, and JP-A-2004-70342, and aluminum phthalocyanines described in JP-A-4893859, JP-A-2016-57635, JP-A-2016-153481, and JP-A-2017-197685. Among these, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, and CI Pigment Green 63 are preferred from the viewpoint of initial brightness.

[0021] The phthalocyanine pigment (A1) can be used alone or in combination of two or more kinds.

[0022] The content of the phthalocyanine pigment (A1) is preferably from 20 to 90% by mass, more preferably from 30 to 80% by mass, based on 100% by mass of the colorant (A).

[0023] (Quinophthalone pigment (A2) represented by general formula (2)) The green photosensitive coloring composition preferably contains, as the colorant (A), a quinophthalone pigment (A2) represented by the following general formula (2).

[0024] General formula (2) [ka]

[0025] The quinophthalone pigment (A2) represented by general formula (2) preferably contains a quinophthalone pigment represented by the following general formula (3) from the viewpoint of coloring power and color reproducibility.

[0026] General formula (3) [ka] In general formula (3), R 29 ~R 43 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent.

[0027] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0028] Examples of the alkyl group which may have a substituent include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a stearyl group, and a 2-ethylhexyl group, as well as a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

[0029] Furthermore, examples of the alkoxyl group which may have a substituent include linear or branched alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentoxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group, as well as a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropyloxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

[0030] Examples of the aryl group which may have a substituent include aryl groups such as a phenyl group, a naphthyl group, and an anthranyl group, as well as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

[0031] R in general formula (3) 29 ~R 32 , and / or R 33 ~R 38 Adjacent groups can combine to form an aromatic ring which may have a substituent. The aromatic ring referred to here includes hydrocarbon aromatic rings and heteroaromatic rings. Examples of hydrocarbon aromatic rings include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of heteroaromatic rings include a pyridine ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

[0032] Examples of the quinophthalone pigment (A2) represented by general formula (2) include the following compounds: However, the quinophthalone pigment (A2) is not limited to these.

[0033] [ka] [ka] [ka] [ka]

[0034] [Method for producing quinophthalone pigment (A2) represented by general formula (2)] The quinophthalone pigment (A2) represented by general formula (2) can be synthesized, for example, by the methods described in JP-A-4-226163 and JP-A-2012-226110.

[0035] The quinophthalone pigment (A2) can be used alone or in combination of two or more kinds.

[0036] The content of the quinophthalone pigment (A2) is preferably from 10 to 80% by mass, and more preferably from 20 to 70% by mass, based on 100% by mass of the colorant (A).

[0037] (Other pigments (A3)) In the present invention, other pigments (A3) than the phthalocyanine pigment (A1) and the quinophthalone pigment (A2) can be contained to the extent that the problem can be solved.

[0038] Other pigments (A3) include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141 5,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,139,147,15 0,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,198,199,21 3,214,218,219,220,221, CI Pigment Blue 1, 1:2, 9,14,17,19,25,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,64,66,67,68,71,72,73,74,75,76,78,79, CIPigment 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, 203 6,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275 , 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, 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, 50, CI Pigment Orange 36, 38, 43, 64, 71, 73, etc. Among these, CI Pigment Red 177,254 and CI Pigment Blue 15:6 are preferred for adjusting brightness.

[0039] (dye) The colorant (A) can contain a dye.

[0040] Dyes include, for example, CI Solvent Green 1, 4, 5, 7, 34, 35, CI Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, CI Mordant Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, CI Acid Green Eloh 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 146, 148, 149, 150, 151, 152, 153, 154, 155, 156, 1 15,117,122,127,131,132,136,141,142,143,144,145,146,149,153,159,166,168,169,172,174,175,178,180,183,187,188,189,190,191,192,199, CI Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48 ,49,50,51,61,66,67,69,70,71,72,73,74,81,84,86,90,91,92,95,107,110,117,118,119,120,121,126,127,129,132,133,134,CI Basic Yellow 1,2,5,11,13,14,15,19,21,24,25,28,29,37,40,45,49,51,57,79,87,90,96,103,105,106,CISolvent Yellow 2, 7, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 1 86, 187, 188, 190, 191, 192, 194, 195, CI Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64, 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184:1, 202, 211, 229, 231, 232, 233, 241, 245, 246, 247, 248, 249, 250, 251, etc.

[0041] The content of the colorant (A) is preferably from 5 to 70 mass %, more preferably from 10 to 60 mass %, based on 100 mass % of the nonvolatile content of the colored composition.

[0042] (Micronization of organic pigments) In the present invention, the organic pigment is preferably micronized before use. The micronization method is not particularly limited, and for example, wet milling, dry milling, or solution precipitation can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the micronized pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0043] Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heat using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. Optimizing the conditions for salt milling a pigment can produce a pigment with an extremely fine primary particle size, a narrow distribution, and a sharp particle size distribution.

[0044] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from the standpoint of cost. From the standpoint of both treatment efficiency and production efficiency, the amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment.

[0045] The water-soluble organic solvent functions to moisten the pigment and water-soluble inorganic salt. It is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, a high-boiling solvent with a boiling point of 120°C or higher is preferred from a safety standpoint. Examples of water-soluble organic solvents that can be used include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

[0046] The resin used in the salt milling treatment may be changed as necessary. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, resins that are solid at room temperature and insoluble in water are preferred, and those that are partially soluble in the organic solvents are preferred. The amount of resin used is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[0047] [Copper salt of quinophthalone compound having a sulfo group (B)] The green photosensitive coloring composition can improve the decrease in brightness due to continuous irradiation with a backlight by using the copper salt (B) of a quinophthalone compound having a sulfo group.

[0048] Quinophthalone compounds are compounds having a structure represented by the following chemical formula (1): Specific examples include dyes such as CI Acid Yellow 3 and 5, and pigments and dyes such as CI Pigment Yellow 138, CI Solvent Yellow 33, 114, and 157, and CI Disperse Yellow 54, 64, and 67.

[0049] Chemical formula (1) [ka]

[0050] The quinophthalone compound having a sulfo group is a compound obtained by sulfonating a compound having a structure represented by the above chemical formula (1). Specific examples include the following compounds. However, the present invention is not limited to these.

[0051] [ka] [ka] [ka]

[0052] The copper salt (B) of the quinophthalone compound having a sulfo group can be obtained by counter-exchanging -SO3H of the above-mentioned exemplary compound with copper by a known method.

[0053] The content of the copper salt of a quinophthalone compound having a sulfo group (B) is preferably 1 to 40 parts by mass, more preferably 5 to 30 parts by mass, per 100 parts by mass of the phthalocyanine pigment (A1), from the viewpoint of suppressing a decrease in brightness.

[0054] [Alkali-soluble resin (C)] The green photosensitive coloring composition of the present invention contains an alkali-soluble resin (C).

[0055] The alkali-soluble resin (C) is a resin that dissolves in an alkali developer, and is preferably a resin that has a transmittance of 80% or more over the entire wavelength range of 400 to 700 nm when a 2 μm-thick coating is formed, with the transmittance preferably being 95% or more. The alkali-soluble resin (C) can be classified into a non-photosensitive alkali-soluble resin (C3) and a photosensitive alkali-soluble resin. Examples of the alkali-soluble group include a carboxyl group, a phosphate group, a sulfonic acid group, a hydroxyl group, and a phenolic hydroxyl group. Among these, a carboxyl group is preferred. The alkali-soluble resin (C) can also contain a thermosetting group such as an epoxy group or an oxetanyl group.

[0056] (Non-photosensitive alkali-soluble resin) Examples of non-photosensitive alkali-soluble resins include acrylic resins having acidic groups, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferred.

[0057] (photosensitive alkali-soluble resin) The photosensitive alkali-soluble resin has photosensitivity due to the presence of a polymerizable unsaturated group. Any known photosensitive alkali-soluble resin can be used as long as it is alkali-soluble and photosensitive. In this specification, resins synthesized by the following methods (i) and (ii) are preferred. When an alkali-soluble photosensitive resin is used, it undergoes three-dimensional crosslinking upon irradiation with light, increasing the crosslink density and improving the chemical resistance of the coating.

[0058] [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 an alkali-soluble photosensitive resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0059] 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.

[0060] 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.

[0061] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

[0062] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, and methoxypolypropylene glycol (meth)acrylate. or (meth)acrylates such as ethoxy polyethylene glycol (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol; 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.

[0063] 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)-2-propanol ... and N-substituted maleimides such as N-(4-phenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine.

[0064] Other examples include phosphate group-containing monomers such as 2-(meth)acryloyloxyethyl acid phosphate and compounds obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer described below with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0065] [Method (ii)] In the method (ii), for example, a polymer of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers is synthesized, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer to synthesize an alkali-soluble photosensitive resin.

[0066] 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.

[0067] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0068] The carboxyl group-containing monomer and other monomers that can be used are the monomers already explained.

[0069] The alkali-soluble resin (C) of the present invention preferably contains an alkali-soluble resin (C1) containing an alicyclic hydrocarbon-containing monomer unit (c1) from the viewpoint of reducing the dielectric loss tangent. The alicyclic hydrocarbon-containing monomer unit (c1) has a high glass transition temperature of the homopolymer, so the coating is less likely to flow at high temperatures. This is thought to suppress aggregation of pigments during post-baking, thereby reducing the dielectric loss tangent.

[0070] [Alicyclic hydrocarbon-containing monomer unit (c1)] Examples of the monomer forming the alicyclic hydrocarbon-containing monomer unit (c1) include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, from the viewpoint of reducing the dielectric loss tangent, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0071] The content of the alicyclic hydrocarbon-containing monomer unit (c1) is preferably 1 to 60 mol %, more preferably 1 to 40 mol %, of all the constituent units of the alkali-soluble resin (C1), from the viewpoints of suppressing water stains and pattern shape.

[0072] From the viewpoint of reducing the dielectric loss tangent, the alkali-soluble resin (C) of the present invention is preferably an alkali-soluble resin (C1) containing the alicyclic hydrocarbon-containing monomer unit (c1), and more preferably a resin (C2) containing an aromatic ring-containing monomer unit (c2) having a homopolymer glass transition temperature of 80° C. or higher. It is presumed that the high glass transition temperature of the alicyclic hydrocarbon-containing monomer unit (c1) and the inclusion of the aromatic ring-containing monomer unit (c2) having a high homopolymer glass transition temperature suppress the fluidity of the coating film during post-baking and prevent pigment aggregation due to the steric hindrance of the aromatic ring, thereby reducing the dielectric loss tangent.

[0073] [Aromatic ring-containing monomer unit (c2) having a homopolymer glass transition temperature of 80°C or higher] Examples of the monomer that forms the aromatic ring-containing monomer unit (c2) having a homopolymer glass transition temperature of 80° C. or higher include styrene and styrenes such as α-methylstyrene.

[0074] The content of aromatic ring-containing monomer units (c2) having a homopolymer glass transition temperature of 80°C or higher is preferably 1 to 60 mol%, more preferably 1 to 40 mol%, of all structural units of the alkali-soluble resin (C2), from the viewpoint of reducing the dielectric loss tangent.

[0075] The alkali-soluble resin (C1) and the alkali-soluble resin (C2) may contain the monomer units already described above in addition to the alicyclic hydrocarbon-containing monomer unit (c1) and the aromatic ring-containing monomer unit (c2) having a homopolymer glass transition temperature of 80°C or higher.

[0076] The alkali-soluble resin (C) can be used alone or in combination of two or more kinds.

[0077] From the viewpoint of developability, the weight average molecular weight (Mw) of the alkali-soluble resin (C) is 2,000 to 40,000, preferably 3,000 to 300,000, and more preferably 4,000 to 20,000. The Mw / Mn value is preferably 10 or less. An appropriate weight average molecular weight (Mw) improves adhesion to the substrate and solubility in alkaline development.

[0078] The acid value of the alkali-soluble resin (C) is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 90 to 170 mgKOH / g. A suitable acid value improves adhesion to substrates and solubility in alkaline development.

[0079] The content of the alkali-soluble resin (C) is preferably from 20 to 400 parts by mass, more preferably from 50 to 250 parts by mass, relative to 100 parts by mass of the colorant (A).

[0080] [Polymerizable compound (D)] The polymerizable compound (D) is a monomer or oligomer containing a polymerizable unsaturated group. The polymerizable compound (D) contributes to the formation of a film of the green photosensitive coloring composition by polymerization. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. Examples of the polymerizable compound (D) include an acid group-containing monomer (D1), a urethane bond-containing monomer, and other monomers. The number of polymerizable unsaturated groups in the polymerizable compound (D) is preferably 2 or more. (Acid group-containing monomer (D1)) Examples of the acid group of the acid group-containing monomer (D1) include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc. When the acid group-containing monomer (D1) is used to form a pattern by photolithography, development residues can be suppressed.

[0081] Examples of the acid group-containing monomer (D1) 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.

[0082] Commercially available products of the acid group-containing monomer (D1) include Viscoat #2500P manufactured by Osaka Organic Chemical Industry Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520, and M-521 manufactured by Toagosei Co., Ltd.

[0083] (Urethane bond-containing monomer (D2)) Examples of the urethane bond-containing monomer (D2) include a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the resulting alcohol with a (meth)acrylate having a hydroxyl group.

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

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

[0086] Commercially available urethane bond-containing monomers (D2) include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., UA-160TM and 1100H manufactured by Shin-Nakamura Chemical Co., Ltd., and UV-4108F and UV-4117F manufactured by Osaka Organic Chemical Industry Ltd.

[0087] (Other monomers) 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.

[0088] Other commercially available monomers include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, and M-310 manufactured by Toagosei Co., Ltd. Examples include M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, and M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, and #405 manufactured by Osaka Organic Chemical Co., Ltd., and NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.

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

[0090] The content of the polymerizable compound (D) is preferably from 1 to 60 mass %, more preferably from 2 to 50 mass %, based on 100 mass % of the nonvolatile content of the green photosensitive coloring composition.

[0091] [Photopolymerization initiator (E)] (Compound (E1) represented by general formula (1)) The green photosensitive coloring composition contains a compound (E1) represented by general formula (1) as a photopolymerization initiator (E). This promotes deep curing of the coating upon photocuring, thereby reducing the dielectric tangent and improving display defects caused by liquid crystal blending disorders.

[0092] General formula (1) [ka]

[0093] [In the general formula (1), X1, X3, and X6 each independently represent R 11 , OR 11, C.O.R. 11 , S.R. 11 ,CONR 12 R 13 or CN, X2 represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, X4 and X5 each independently represent R 11 , OR 11 , S.R. 11 , C.O.R. 11 ,CONR 12 R 13 , N.R. 12 COR 11 ,OCOR 11 , COOR 11 , SCOR 11 , COSR 11 , COSR 11 , CSOR 11 , CN, a halogen atom or a hydroxyl group. 11 , R 12 and R 13 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group having 6 to 30 carbon atoms which may have a substituent, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. a and b each independently represent an integer of 0 to 3.

[0094] X 1From the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition, alkyl groups having 10 or less carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-amyl group, an isoamyl group, a t-amyl group, an n-hexyl group, and a 2-ethylhexyl group; cyclic alkyl groups having 10 or less carbon atoms, such as a cyclopentyl group and a cyclohexyl group, which may have a side chain; and carbon chains having 10 or less carbon atoms and one ether bond, such as a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2-(1-methoxypropyl) group, and a 2-(1-ethoxypropyl) group, are preferred.

[0095] X 3 From the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition, is preferably hydrogen, or an alkyl group having 6 or less carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-amyl group, an isoamyl group, a t-amyl group, or an n-hexyl group; a cyclic alkyl group having 6 or less carbon atoms such as a cyclopentyl group or a cyclohexyl group; or a carbon chain having 6 or less carbon atoms and one ether bond such as a methoxymethyl group, an ethoxymethyl group, an ethoxyethyl group, a 2-(1-methoxypropyl) group, or a 2-(1-ethoxypropyl) group.

[0096] X 6 From the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition, preferred are alkyl groups having 6 or less carbon atoms, such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, and n-hexyl group; cyclic alkyl groups having 6 or less carbon atoms, such as a cyclopentyl group and a cyclohexyl group; and carbon chains having 6 or less carbon atoms and one ether bond, such as a methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group, and 2-(1-ethoxypropyl) group.

[0097] X 2From the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition, alkyl groups having 6 or less carbon atoms such as methyl groups, ethyl groups, n-propyl groups, isopropyl groups, n-butyl groups, isobutyl groups, t-butyl groups, n-amyl groups, isoamyl groups, t-amyl groups, and n-hexyl groups, cyclic alkyl groups having 6 or less carbon atoms such as cyclopentyl groups and cyclohexyl groups, and carbon chains having 6 or less carbon atoms and one ether bond such as methoxymethyl groups, ethoxymethyl groups, ethoxyethyl groups, 2-(1-methoxypropyl) groups, and 2-(1-ethoxypropyl) groups are preferred.

[0098] X 4 and X 5 From the viewpoints of ease of synthesis, sensitivity, solubility, and storage stability when contained in a photosensitive coloring composition, is preferably hydrogen or an alkyl group having 6 or less carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-amyl group, an isoamyl group, a t-amyl group, or an n-hexyl group.

[0099] Examples of the heterocyclic group having 2 to 20 carbon atoms include 3- to 7-membered heterocyclic rings, such as pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, and morpholinyl, and other 5- to 7-membered heterocyclic rings.

[0100] Examples of the compound (E1) represented by the general formula (1) include the following compounds.

[0101] [ka] [ka] [ka]

[0102] (Alkylphenone compounds (E2)) The photopolymerization initiator (E) preferably further contains an alkylphenone compound (E2). The use of the alkylphenone compound (E2) allows for more efficient absorption of light on the short wavelength side around 300 nm during photocuring, accelerating the curing of the coating. This is thought to reduce the dielectric tangent, improving display defects caused by liquid crystal blending disorders.

[0103] Examples of the alkylphenone compound (E2) 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, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and compounds represented by general formula (4).

[0104] General formula (4) [ka] (In general formula (4), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent.)

[0105] R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylmethyl group, etc. Of these, from the viewpoints of suppressing water stains and pattern shape, a linear alkyl group having 3 to 8 carbon atoms is preferred, and a linear alkyl group having 4 to 6 carbon atoms is more preferred.

[0106] R3 represents a hydrogen atom or any monovalent substituent. Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; optionally substituted benzoyl groups; and optionally substituted thenoyl groups. Substituents that the benzoyl group or thenoyl group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred.

[0107] Examples of methods for producing the compound represented by general formula (4) include those described in JP-T-2019-507108 and JP-T-2019-528331.

[0108] Specific examples of the compound represented by formula (4) are shown below, but the present invention is not limited to these.

[0109] [ka]

[0110] Commercially available alkylphenone compounds (E2) include "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), and "Omnirad 379EG" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone) (all manufactured by IGM Resins).

[0111] The content of the photopolymerization initiator (E) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, based on 100 parts by mass of the colorant (A) from the viewpoints of photocurability and developability.

[0112] The photopolymerization initiator (E) preferably has a mass ratio of the compound (E1) represented by general formula (1) to the alkylphenone-based compound (E2) of E1:E2 = 10:90 to 90:10, more preferably 20:80 to 80:20. The compound (E1) represented by general formula (1) utilizes its long-wavelength emission line around 400 nm, while the alkylphenone-based compound (E2) utilizes its short-wavelength emission line around 300 nm, enhancing photocuring. This is thought to further reduce the dielectric loss tangent of the coating formed from the green photosensitive coloring composition after photocuring, thereby reducing the likelihood of display defects due to liquid crystal blending irregularities.

[0113] From the viewpoint of reducing the dielectric loss tangent, the total content of the compounds (E1) represented by general formula (1) is preferably 10 to 90 mass %, and more preferably 20 to 80 mass %, in 100 mass % of the photopolymerization initiator (C).

[0114] The total content of the compound (E1) represented by general formula (1) and the alkylphenone compound (E2) is preferably 50 to 80% by mass, more preferably 80 to 100% by mass, based on 100% by mass of the photopolymerization initiator (E), from the viewpoint of reducing the dielectric loss tangent, with the upper limit of the total amount being 100% by mass.

[0115] The photopolymerization initiator (E) can be used alone or in combination of two or more kinds.

[0116] (Other photopolymerization initiators (E3)) The photosensitive composition of the present invention can contain a photopolymerization initiator (E3) other than the compound (E1) represented by general formula (1) and the alkylphenone compound (E2) (hereinafter also referred to as other photopolymerization initiator (E3)).

[0117] The photopolymerization initiator (E3) is not particularly limited as long as it is a compound that can initiate polymerization of the polymerizable compound (D) by light, and known photopolymerization initiators can be used. For example, triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the compound include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.

[0118] The other photopolymerization initiators (C3) can be used alone or in combination of two or more.

[0119] [Dispersion resin (F)] The green photosensitive coloring composition may contain a dispersing resin (F) as needed. The dispersing resin (F) is preferably a resin having an adsorptive group that has a high affinity for the pigment, and the adsorptive group is preferably one or more of a cationic group and an anionic group.

[0120] Examples of the cationic group-containing resin include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium salt group, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle.

[0121] Examples of the anionic group-containing resin include a carboxyl group, a phosphate group, a sulfonic acid group, etc. Among these, a carboxyl group and a phosphate group are preferred from the viewpoint of adsorption to the pigment.

[0122] Examples of resin types for the dispersion resin (F) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphate salts, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups, and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0123] Examples of the structure of the dispersing resin (F) include a random structure, a block structure, a graft structure, a comb structure, and a star structure. Among these, the block structure or the comb structure is preferred from the viewpoint of dispersion stability.

[0124] Commercially available dispersion resins (F) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, and 2164 manufactured by BYK Japan, and Anti-Terra-U203 and 204, and BYK-P104 and P104S. 220S, Lactimon, Lactimon-WS, Bykumen, etc., and SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 3660 manufactured by Lubrizol Japan 0, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550 manufactured by BASF Japan , 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Aji Super PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd., and resins described in JP 2008-029901 A, JP 2009-155406 A, JP 2010-185934 A, JP 2011-157416 A, etc.

[0125] The dispersing resin (F) can be used alone or in combination of two or more kinds.

[0126] From the viewpoint of dispersion stability, the content of the dispersing resin (F) is preferably from 3 to 200 parts by mass, more preferably from 5 to 100 parts by mass, relative to 100 parts by mass of the colorant (A).

[0127] [Dispersing agent (G)] The green photosensitive coloring composition may contain a dispersing aid (G) as needed.

[0128] The dispersing aid (G) is not particularly limited, and examples thereof include compounds having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. Specific examples of the dispersing aid (G) include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.

[0129] Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone-based pigments, perylene-based pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline-based pigments, isoindolinone pigments, naphthol pigments, threne pigments, metal complex-based pigments, and azo-based pigments such as azo, disazo, and polyazo.

[0130] The dispersing aid (G)) can be used alone or in combination of two or more kinds.

[0131] The content of the dispersing aid (G) is preferably from 1 to 15 parts by mass, more preferably from 2 to 10 parts by mass, relative to 100 parts by mass of the colorant (A).

[0132] [Leveling agent (H)] The photosensitive coloring composition of the present invention can contain a leveling agent (H). This improves the wettability and drying properties of the composition to the substrate during application. Examples of the leveling agent (M) include silicon-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0133] Examples of silicone surfactants include linear polymers formed from siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0134] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002 and 211 manufactured by Dow Corning Toray Co., Ltd. 0, 2122, 2123, 2191, 5609, and X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0135] Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

[0136] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Futergent 602A manufactured by Neos Corporation.

[0137] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, and the like.

[0138] Commercially available products include, for example, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, and L manufactured by Kao Corporation. S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW- L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0139] Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0140] Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, manufactured by Kao Corporation.

[0141] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0142] Examples of commercially available products include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0143] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine; and alkylamine oxides such as lauryldimethylamine oxide.

[0144] Commercially available products include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

[0145] The leveling agent (H) can be used alone or in combination of two or more kinds.

[0146] The content of the leveling agent (H) is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition. Within this range, the balance between the coatability and adhesion of the photosensitive coloring composition is further improved.

[0147] [Sensitizer (I)] The green photosensitive coloring composition can contain a sensitizer (I).

[0148] Examples of the sensitizer (I) include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine. derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acyl oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0149] Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. Specific preferred compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole.

[0150] The sensitizer (I) can be used alone or in combination of two or more kinds.

[0151] The content of the sensitizer (I) is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator (E). When an appropriate amount is contained, photocurability and developability are improved.

[0152] [Thermosetting compound (J)] The green photosensitive coloring composition can contain a thermosetting compound (J), which reacts in the heating step after film formation to increase the crosslink density, thereby improving heat resistance.

[0153] The thermosetting compound (J) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (J) 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.

[0154] (Epoxy compound (J1)) Examples of the epoxy compound (J1) include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.). , divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates 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, glycidyl ester epoxy resins, etc.

[0155] Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P (all trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004 and 1256 (all trade names; manufactured by Japan Epoxy Resins Co., Ltd.), TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H and 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 name; manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, 154 (all trade names; manufactured by Japan Epoxy Resins Co., Ltd.), EOCN-102S, 103S, 104S, 1020 (all trade names; manufactured by Nippon Kayaku Co., Ltd.), Celloxide 2021, EHPE-3150 (all trade names; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 (all trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, H, S (manufactured by Nissan Chemical Industries, Ltd.), and the like.

[0156] From the viewpoint of heat resistance of the coating film, the content of the epoxy compound (J1) is preferably from 0.5 to 300 parts by mass, more preferably from 1.0 to 50 parts by mass, per 100 parts by mass of the colorant (A).

[0157] (Oxetane Compound (J2)) The oxetane compound (J2) is a known compound having an oxetane group, and examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0158] 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-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101,212 manufactured by Toagosei Co., Ltd.

[0159] Examples of the bifunctional oxetane compound include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyloxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethyleneglycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenylbis(3-ethyl- 3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether, and the like. Commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0160] Examples of trifunctional or higher oxetane compounds include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, and caprolactone-modified dipentaerythritol. Examples of such polymers include erythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing an oxetane group (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30.

[0161] The content of the oxetane compound (J2) is preferably from 0.5 to 50 mass %, more preferably from 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the colored composition.

[0162] The melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol or ether type compound, and more preferably a melamine compound having an average of 5.0 or more methylol groups and / or ether groups per melamine ring. Having an appropriate number of methylol groups or ether groups makes it easy to obtain just the right amount of heat resistance.

[0163] Examples of commercially available products include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 (manufactured by Nippon Cytec Industries Co., Ltd.).

[0164] Among these, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, and MX-45 (manufactured by Sanwa Chemical Co., Ltd.) and Cymel 232, 235, 236, 238, 300, 301, 303, and 350 (manufactured by Nippon Cytec Industries Co., Ltd.), which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are preferred in terms of increasing crosslink density.

[0165] The thermosetting compound (J) can be used alone or in combination of two or more kinds.

[0166] [Curing agent (curing accelerator)] The green photosensitive resin composition can be used in combination with a curing agent (curing accelerator) to aid in the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Examples of suitable amines include 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine, etc.), and S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc.).

[0167] The curing agents can be used alone or in combination of two or more.

[0168] The content of the curing agent is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting compound (J).

[0169] [Thiol-based chain transfer agent (K)] The green photosensitive coloring composition can contain a thiol-based chain transfer agent (K). When the thiol-based chain transfer agent (K) is used in combination with the photopolymerization initiator (E), it generates a thiyl radical that is resistant to polymerization inhibition by oxygen during radical polymerization after light irradiation, thereby improving the photosensitivity of the green photosensitive coloring composition.

[0170] The thiol chain transfer agent (K) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). The thiol chain transfer agent (K) more preferably 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.

[0171] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples of the thiopropionate include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0172] The thiol chain transfer agent (K) can be used alone or in combination of two or more kinds.

[0173] The content of the thiol chain transfer agent (K) is preferably 0.1 to 10 mass %, more preferably 0.5 to 5 mass %, based on 100 mass % of the nonvolatile content of the colored composition. When an appropriate amount is contained, photosensitivity is improved and wrinkles are less likely to occur on the coating surface.

[0174] [Polymerization inhibitor (L)] The green photosensitive coloring composition may contain a polymerization inhibitor (L). Examples of the polymerization inhibitor (L) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol; Examples of the alkyl resorcinol compound include alkylresorcinol compounds such as ethylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucin.

[0175] The content of the polymerization inhibitor (L) is preferably 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the colored composition.

[0176] [Ultraviolet absorber (M)] The green photosensitive coloring composition may contain an ultraviolet absorber (M). The ultraviolet absorber (M) is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0177] 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 side chain 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 octyl-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.

[0178] Commercially available products include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Japan Ltd., ADK STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA Corporation, KEMISORB71, 73, 74, 79, and 279 manufactured by Chemipro Chemical Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

[0179] 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.

[0180] Commercially available products include KEMISORB 102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF Japan, Adekastab LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

[0181] 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.

[0182] Commercially available products include KEMISORB 10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB 101 and 107 manufactured by Shipro Chemicals, Adekastab 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

[0183] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0184] The content of the ultraviolet absorber (M) is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber.

[0185] [Antioxidant (N)] The green photosensitive coloring composition may contain an antioxidant (N). The antioxidant (N) prevents the photopolymerization initiator and thermosetting compound contained in the coloring composition from yellowing due to oxidation during the thermal process of thermal curing or ITO annealing, thereby suppressing a decrease in the transmittance of the coating. In particular, when the pigment concentration of the photosensitive composition is high, the content of the photopolymerizable compound decreases relatively, 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.

[0186] Examples of the antioxidant (N) 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.

[0187] Among these, from the viewpoint of achieving both transmittance and sensitivity of the coating, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0188] Examples of hindered phenol antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di- t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4, 6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, 2 , 2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc.

[0189] Commercially available products include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA Corporation; KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd.; and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0190] Examples of the hindered amine antioxidant include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl Tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1 -Ester of piperidineethanol with 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5- Bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonate methyl 1,2,2,6,6-pentamethyl-4-pyridyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,Examples include 6-hexamethylenediamine and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide.

[0191] Commercially available products include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA Corporation; KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals; Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, and 5100 manufactured by BASF Japan Ltd.; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Company.

[0192] Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12 to C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidene Diphenyl alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-di-t-butyl-6-methylphenyl)phosphite.

[0193] Commercially available products include ADK STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA Corporation, IRGAFOS168 manufactured by BASF Japan, and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0194] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0195] Commercially available products include ADK STAB AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0196] The antioxidant (N) can be used alone or in combination of two or more kinds.

[0197] The content of the antioxidant (N) is preferably 0.5 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the colored composition. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

[0198] [Storage stabilizer (O)] The green photosensitive coloring composition may contain a storage stabilizer (O). This stabilizes the viscosity of the coloring composition over time. Examples of the storage stabilizer (O) 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.

[0199] The content of the storage stabilizer (O) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the colorant (A).

[0200] [Adhesion improver (P)] The green photosensitive coloring composition may contain an adhesion promoter (P), which improves the adhesion between the coating and the substrate and also makes it easier to form narrow patterns by photolithography.

[0201] Examples of the adhesion improver (P) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl) silane coupling agents such as aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl compounds such as p-styryltrimethoxysilane; ureido compounds such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

[0202] The adhesion improver (P) can be used alone or in combination of two or more kinds.

[0203] The content of the adhesion improver (P) is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, relative to 100 parts by mass of the colorant (A). [Organic solvent (R)] The green photosensitive coloring composition may contain an organic solvent (R).

[0204] Examples of the organic solvent (R) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy- 3-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyro Lactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,Examples of the alkyl esters include dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. Among these, from the viewpoints of pigment dispersibility and alkali-soluble resin solubility, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0205] The organic solvent (R) can be used alone or in combination of two or more kinds.

[0206] <Method for producing green photosensitive coloring composition> The green photosensitive coloring composition is produced by dispersing a colorant (A), a copper salt of a quinophthalone compound having a sulfo group (B), an alkali-soluble resin (C), and optionally a dispersing resin (F), an organic solvent (R), etc., to produce a dispersion. The dispersion may be prepared by simultaneously adding two or more colorants and dispersing them, or by mixing colorants that have been separately dispersed. The dispersion is then mixed with a leveling agent (H), and optionally a polymerizable compound (D) and a photopolymerization initiator (E). The timing of mixing each material is optional. The dispersion step can also be repeated multiple times.

[0207] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0208] The average dispersed particle size (secondary particle size) of the colorant (A) in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the colorant (A) has an appropriate particle size, it is easy to obtain a colored composition with high dispersion stability.

[0209] The average dispersed particle size (secondary particle size) is measured using, for example, Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and the D50 particle size set to the average size. The dilution solvent used for measurement is the same organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to provide results with little variation.

[0210] The green photosensitive coloring composition is preferably subjected to centrifugation, filtration using a sintered filter or a membrane filter, etc. to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and dust particles mixed in. The green photosensitive coloring composition preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0211] <Color filter> The color filter of the present invention includes a substrate and a filter segment formed from a green photosensitive coloring composition, the filter segment being a green filter segment. The filter segments preferably have red, green, and blue filter segments by appropriately selecting the type of colorant (A) used. Furthermore, the color filter may have magenta, cyan, and yellow filter segments instead of the filter segments. A reflective substrate may 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.

[0212] [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.

[0213] 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. Among these, the photolithography method is preferred in terms of being able to produce a highly accurate color filter. In the photolithography method, for example, a photosensitive coloring composition containing a colorant of a certain color tone is applied to a transparent substrate to form a coating film with a dry film thickness of approximately 0.2 to 5 μm. The resulting coating film (hereinafter referred to as the first coating film) is exposed (irradiated with light) through a mask having a predetermined pattern. The coating film is then developed by immersing it in a solvent or alkaline developer or by spraying the developer onto the film using a spray or the like, 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 film (oxygen barrier film) can be formed on the first coating film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first coating film 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.

[0214] 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.

[0215] 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.

[0216] <Liquid crystal display device> The liquid crystal display device of the present invention comprises the color filter of the present invention. In a liquid crystal display device, the color filter after the filter segments are formed is bonded to an opposing substrate using a sealant, and liquid crystal is injected through an injection port provided in the seal portion, and the injection port is then sealed. If necessary, a polarizing film or a retardation film can be bonded to the outside of the substrate to produce a liquid crystal display device.

[0217] The liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFLs) and white LEDs. In the present invention, it is preferable to use a white LED because it broadens the red reproduction range. Figure 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the color filter of the present invention. The device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged at a distance from each other, with a liquid crystal LC sealed between them.

[0218] The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (En-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.

[0219] 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).

[0220] 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.

[0221] 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.

[0222] The white LED light source includes a blue LED with a fluorescent filter formed on the surface, and a blue LED with a fluorescent material contained in a resin package, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity becomes maximum, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity becomes maximum, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity becomes maximum, and the ratio (E4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less. Therefore, a white LED light source (LED1) having spectral characteristics in which the ratio (E5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum in the range of 430 nm to 485 nm, a second peak wavelength (λ2) of the emission intensity in the range of 530 nm to 580 nm, and a ratio (E2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferred.

[0223] Examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0224] Examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries), NSSW304D (manufactured by Nichia Chemical Industries), and the like.

[0225] <Solid-state imaging element> The solid-state imaging device of the present invention includes the color filter of the present invention. The configuration of the solid-state imaging device is not limited as long as it functions as a solid-state imaging device. For example, the following configurations can be mentioned.

[0226] The present invention is configured to have a substrate on which are disposed a plurality of photodiodes constituting the light receiving area of a solid-state imaging element (such as a CCD sensor, a CMOS sensor, or an organic CMOS sensor) and transfer electrodes made of polysilicon or the like, a light-shielding film made of tungsten or the like with only the light-receiving portion of the photodiodes being opened on the photodiodes and the transfer electrodes, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portion of the photodiodes, and the color filter of the present invention on the device protection film. Furthermore, the device may have a light-collecting means (for example, a microlens, etc.; the same applies below) on the device protection layer and below the color filter (on the side closer to the substrate), or may have a light-collecting means on the color filter. The organic CMOS sensor is composed of a thin-film panchromatic organic photoelectric conversion film as the photoelectric conversion layer and a CMOS signal readout substrate, and has a two-layer hybrid structure in which the organic material captures light and converts it into an electrical signal, while the inorganic material extracts the electrical signal externally, making it possible in principle to achieve a 100% aperture ratio for incident light.The organic photoelectric conversion film is a structure-free continuous film that can be laid on the CMOS signal readout substrate, eliminating the need for expensive microfabrication processes and making it suitable for miniaturizing filter segments. [Example]

[0227] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass."

[0228] Before describing the examples, each measurement method will be explained.

[0229] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are as follows:

[0230] (Average molecular weight of alkali-soluble resin and dispersing resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the alkali-soluble resin and dispersion resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (Tosoh Corporation). Two separation columns were connected in series, and both columns were packed with "TSK-GEL SUPER HZM-N" packing. Measurements were performed at an oven temperature of 40°C, a tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters was injected. The molecular weight is expressed in terms of polystyrene.

[0231] (Acid value of alkali-soluble resin and dispersion resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of alkali-soluble resin and dispersed resin solution, and the mixture was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant to measure the acid value (mg KOH / g). The acid value per unit of nonvolatile content of the resin was then calculated from the acid value of the resin solution and the concentration of nonvolatile content of the resin solution.

[0232] (Amine value of dispersion resin) The amine value of the dispersing resin is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into solid content.

[0233] <Production example of fine phthalocyanine pigment (A1)> (Fine Phthalocyanine Pigments (A1-1 to A1-3)) According to the examples of JP 2017-111398 A, finely divided phthalocyanine pigments (A1-1 to A1-3) represented by the following chemical formulas (43) to (45) were obtained. The structures are shown below.

[0234] (Fine Phthalocyanine Pigment (A1-1) Chemical formula (43) [ka]

[0235] [ka]

[0236] (Fine Phthalocyanine Pigment (A1-4) 100 parts of CI Pigment Green 58 ("FASTGEN GREEN A110" manufactured by DIC Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70° C. This kneaded mixture was poured into 3000 parts of warm water and stirred for 1 hour while heating to 70° C. to form a slurry. The slurry was filtered and washed with water repeatedly to remove the sodium chloride and diethylene glycol, and then dried overnight at 80° C. to obtain 97 parts of a finely divided phthalocyanine pigment (A1-4).

[0237] (Fine Phthalocyanine Pigment (A1-5)) 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 finely divided phthalocyanine pigment (A1-5). X-ray fluorescence analysis of the resulting finely divided phthalocyanine pigment (A1-6) 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. This was a halogenated zinc phthalocyanine pigment.

[0238] (Fine Phthalocyanine Pigment (A1-6)) 200 parts of 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) 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 repeatedly filtering and washing with water to remove the sodium chloride and diethylene glycol, the mixture was dried overnight at 85° C. to obtain 190 parts of a finely divided phthalocyanine pigment (A1-6).

[0239] <Production of finely divided quinophthalone pigment (A2)> (Finely divided quinophthalone pigment (A2-1)) 100 parts of CI Pigment Yellow 138 (BASF Japan Ltd., "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 Seisakusho) and kneaded for 6 hours at 80° C. This mixture was added to 2,000 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 95 parts of a finely divided quinophthalone pigment (A2-1).

[0240] (Finely divided quinophthalone pigment (A2-2)) 100 parts of the quinophthalone compound of the following chemical formula (46), 1200 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 60° C. Next, this kneaded mixture was poured into warm water and stirred for 1 hour while heating to about 70° C. to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80° C. to obtain 97 parts of a micronized quinophthalone pigment (A2-2).

[0241] Chemical formula (46) [ka]

[0242] (Finely divided quinophthalone pigment (A2-3)) A finely divided quinophthalone pigment (A2-3) represented by the following chemical formula (47), the structure of which is shown below, was obtained according to the method for producing a yellow colorant described in Japanese Patent No. 6432076.

[0243] Chemical formula (47) [ka]

[0244] <Production of Metal Salt of Quinophthalone Compound Having a Sulfo Group (B)> (Copper salt of quinophthalone compound having a sulfo group (B1-1)) Thirty parts of CI Pigment Yellow 138 (BASF Japan "Paliotol Yellow K0960-HD"), a quinophthalone compound, were dissolved in 300 parts of 101% sulfuric acid and stirred at 70°C for 8 hours to carry out a sulfonation reaction. The reaction was terminated by measuring the spectroscopic spectrum of the sulfuric acid solution, and the point at which no further change in the spectrum was observed was determined. Next, this reaction solution was poured into 3,000 parts of ice water, and the precipitate was filtered, washed with water, and dried at 80°C to obtain quinophthalone compound (b-1) having a sulfo group, represented by the following chemical formula (48).

[0245] Chemical formula (48) [ka]

[0246] Next, 10 g of the quinophthalone compound (b-1) having a sulfo group was added to 500 parts of water and redispersed by stirring at 25°C for 2 hours. 4.8 parts of copper (II) sulfate pentahydrate was then gradually added to this solution, and the mixture was allowed to react at 60°C for 2 hours. The reaction product was filtered, washed with water, and dried at 80°C to obtain the copper salt (B1-1) of the quinophthalone compound having a sulfo group represented by the following chemical formula (49).

[0247] Chemical formula (49) [ka]

[0248] (Copper salt of quinophthalone compound having a sulfo group (B1-2)) A quinophthalone compound (b-2) having a sulfo group represented by the following chemical formula (50) was obtained by a production method similar to that for the quinophthalone compound (QL-c-1) described in the examples of JP 2015-172732 A.

[0249] Chemical formula (50) [ka]

[0250] Next, 10 g of the quinophthalone compound (b-2) having a sulfo group was added to 500 parts of water and redispersed by stirring at 25°C for 2 hours. 5.5 parts of copper (II) sulfate pentahydrate was then gradually added to this solution, and the mixture was allowed to react at 60°C for 2 hours. The reaction product was filtered, washed with water, and dried at 80°C to obtain the copper salt (B1-2) of the quinophthalone compound having a sulfo group represented by the following chemical formula (51).

[0251] Chemical formula (51) [ka]

[0252] <Production of alkali-soluble resin (C)>

[0253] (Preparation of Alkali-Soluble Resin Solution (C1)) A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube was charged with 182 parts of propylene glycol monomethyl ether acetate, and the atmosphere in the flask was changed from air to nitrogen. After heating to 100 ° C, a solution of 70.5 parts of benzyl methacrylate, 43.0 parts of methacrylic acid, 22.0 parts of tricyclodecane-based monomethacrylate (Hitachi Chemical Co., Ltd. FA-513M) and 3.6 parts of azobisisobutyronitrile was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was stirred for 5 hours at 100 ° C. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate, 0.9 parts of tris(dimethylaminomethyl)phenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued for 6 hours at 110 ° C., and then the reaction was terminated. 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. The previously synthesized resin solution was adjusted to a nonvolatile content of 20% with propylene glycol monomethyl ether acetate to obtain an alkali-soluble resin solution (C1) with a weight average molecular weight (Mw) of 13,000.

[0254] (Preparation of Alkali-Soluble Resin Solution (C2)) 100 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a separable four-neck flask thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer, and the vessel was heated to 120°C while injecting nitrogen gas into it. At the same temperature, a mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 17.0 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added. The reaction was continued for 5 hours at 120°C, and the reaction was terminated when the acid value of the solid content reached 0.8, yielding a resin solution with a weight-average molecular weight of approximately 12,000. Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours, and propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 20% to prepare a resin solution (C2).

[0255] (Preparation of Alkali-Soluble Resin Solution (C3)) A separable four-neck flask was fitted with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 207 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80 ° C. and purged with nitrogen. Then, a mixture of 4.2 parts of methacrylic acid, 33.0 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 20.3 parts of benzyl methacrylate, 25.2 parts of glycerin monomethacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas flow was stopped and dry air was injected into the resulting copolymer solution for 1 hour while stirring. After cooling to room temperature, a mixture of 17.3 parts of 2-methacryloyloxyethyl isocyanate (Karens MOI, Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70°C over 3 hours. After the addition was completed, the reaction was continued for another hour to obtain 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. Cyclohexanone was added to the previously synthesized resin solution to achieve a nonvolatile content of 20% to prepare alkali-soluble resin (C3). The weight-average molecular weight (Mw) was 5000.

[0256] (Dispersed resin (G) solution) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of propylene glycol monomethyl ether acetate were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block (Block B). After 4 hours of polymerization, a sample was taken from the polymerization solution and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Next, 61 parts of propylene glycol monomethyl ether acetate and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as the second block (A block) monomer were added to the reactor, and the reaction was continued with stirring at 110 °C under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, a sample of the polymerization solution was measured for nonvolatile content. The conversion rate of the second block (A block) was confirmed to be 98% or higher based on the nonvolatile content. The reaction solution was then cooled to room temperature to terminate the polymerization. The solution was diluted with propylene glycol monomethyl ether acetate to a nonvolatile content of 30%, yielding a dispersion resin (G) solution with an amine value of 57 mg KOH / g and a number-average molecular weight (Mn) of 4,500.

[0257] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, then dispersed in an Eiger mill (Eiger Japan, Mini Model M-250 MKII) using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The organic solvent (R-1) was PGMAc. Finely divided phthalocyanine pigment (A1-1): 10.0 parts Dispersion resin (G) solution: 17.0 parts Alkali-soluble resin (C2) solution: 10.0 parts Organic solvent (R): 63.0 parts

[0258] (Dispersion 2~13) Dispersions 2 to 13 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 1 were changed.

[0259] [Table 1]

[0260] <Production of Coloring Composition> [Example 1] (Coloring composition 1) The following raw materials were mixed by stirring until uniform, and then filtered through a filter with a pore size of 1.0 μm to obtain colored composition 1. Dispersion P1: 37.3 parts Dispersion P8: 16.9 parts Dispersion P12: 9.3 parts Alkali-soluble resin (C2): 4.7 parts Polymerizable compound (D1): 0.8 parts Compound (E1) represented by general formula (1): 0.2 parts Photopolymerization initiator (E2-1): 0.1 parts Leveling agent (H): 1.0 part Sensitizer (I): 0.1 parts Thermosetting compound (J): 0.1 part Thiol chain transfer agent (K): 0.2 parts Polymerization inhibitor (L): 0.1 parts UV absorber (M): 0.1 parts Antioxidant (N): 0.1 parts Storage stabilizer (O): 0.1 parts Organic solvent (R): 29.0 parts

[0261] [Examples 2 to 24, Comparative Examples 1 and 2] (Coloring composition 2-24) Colored compositions 2 to 24 were prepared in the same manner as colored composition 1 in Example 1, except that the raw materials and amounts shown in Table 2 were changed.

[0262] [Table 2-1]

[0263] [Table 2-2]

[0264] [Table 2-3]

[0265] The ingredients listed in Table 2-1 are as follows:

[0266] [Polymerizable compound (D)] (D1): Aronix M309 (manufactured by Toagosei Co., Ltd.) (D2): Aronix M402 (manufactured by Toagosei) (D3): Aronix M520 (manufactured by Toagosei) (D4): KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.) The above (D-1) to (D-4) were mixed in equal amounts to obtain a polymerizable compound (D).

[0267] [Photopolymerization initiator (E)] (E1): A compound represented by chemical formula (32) (E2-1): Omnirad 369 (manufactured by IGM Resins) (E2-2): Omnirad 379EG (manufactured by IGM Resins) (E2-3): Omnirad 907 (manufactured by IGM Resins) (E2-4): A compound represented by the above chemical formula (40) (E3) IRGACURE OXE01 (BASF Japan)

[0268] [Leveling Agent (H)] Two parts of BYK-330 (manufactured by BYK-Chemie) were dissolved in 98 parts of PGMAc.

[0269] [Sensitizer (I)] (I1): Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) (I1):CHEMARK DEABP (manufactured by Chemark Chemical) The above (I1) and (I2) were mixed in equal amounts to form sensitizer (I).

[0270] [Thermosetting compound (J)] (Epoxy compound (J1)) J1-1: EHPE-3150 (Daicel) J1-2: Denacol EX611 (Nagase ChemteX Corporation) J1-3: Triglycidyl isocyanurate Equal amounts of (J1-1) to (J1-3) were mixed together to obtain epoxy compound (J1).

[0271] [Thiol-based chain transfer agent (K)] (K1): Trimethylolethane tris(3-mercaptobutyrate) (K2): Trimethylolpropane tris(3-mercaptobutyrate) (K3): Pentaerythritol tetrakis(3-mercaptopropionate) (K4): Trimethylolpropane tris(3-mercaptopropionate) (K5): Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate The above (K1) to (K5) were mixed in equal amounts to prepare a thiol-based chain transfer agent (K).

[0272] [Polymerization inhibitor (L)] (L1): 4-methylcatechol (L2): Methylhydroquinone (L3): t-butylhydroquinone The above (L1) to (L3) were mixed in equal amounts to prepare a polymerization inhibitor (L).

[0273] [Ultraviolet absorber (M)] (M1): TINUVIN400 (BASF Japan) (M2): TINUVIN900 (BASF Japan) The above (M1) and (M2) were mixed in equal amounts to prepare an ultraviolet absorber (M).

[0274] [Antioxidant (N)] (N1): Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (N2): Dioctadecyl 3,3'-thiodipropanoate (N3): Tris[2,4-di-(t)-butylphenyl]phosphine (N4): Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (N5): p-Octylphenyl salicylate The above (N-1) to (N-5) were mixed in equal amounts to prepare an antioxidant (N).

[0275] [Storage stabilizer (O)] (O1): 2,6-bis(1,1-dimethylethyl)-4-methylphenol (O2): Triphenylphosphine The above (O1) and (O2) were mixed in equal amounts to prepare a storage stabilizer (O).

[0276] [Organic solvent (R)] (R1): 30 parts of propylene glycol monomethyl ether acetate (R2): 30 parts cyclohexanone (R3): 10 parts of ethyl 3-ethoxypropionate (R4): Propylene glycol monomethyl ether 10 parts (R5): Cyclohexanol acetate 10 parts (R6): Dipropylene glycol methyl ether acetate 10 parts The above (R1) to (R6) were mixed in the above-mentioned parts by mass to form an organic solvent (R).

[0277] <Evaluation of Coloring Composition> Each test was carried out by the following method. The evaluation results are shown in Table 2.

[0278] [Dielectric loss tangent evaluation] The obtained coloring composition was applied to a glass substrate on which a transparent conductive film (ITO film) had been formed using a spin coater, and the coating on the electrode part was wiped off with a solvent. After that, an integrated light intensity of 50 mJ / cm was applied. 2 Then, the substrate was subjected to a heat treatment at 230°C for 40 minutes, and after cooling, an Au vapor deposition agent was applied to an area of 3.464 × 10 -4 m -2 The electrode part was then fabricated, and a dielectric loss tangent evaluation substrate was fabricated. The luminance of the surface irradiated from the opposite side of the coated surface of this measurement substrate was 1000 cd / m 2 The coating surface was irradiated with light under the conditions of and the dielectric loss tangent at a frequency of 20 Hz was measured using an impedance analyzer ("1260" manufactured by Solartron). The evaluation criteria are as follows: 5: Less than 0.065 4: 0.065 or more, less than 0.075 3: 0.080 or more and less than 0.090 2: 0.090 or more and less than 0.100 1:0.100 or more

[0279] [Lightness rating] The obtained colored composition was applied to a glass substrate using a spin coater so that the chromaticity value of the coating after heat treatment was y = 0.65 with Illuminant C, and dried at 70 °C for 20 minutes. Then, an ultra-high pressure mercury lamp was used to irradiate the coating with an ultraviolet ray intensity of 50 mJ / cm. 2 The resist was then exposed to ultraviolet light at 40°C, spray-developed with a sodium carbonate aqueous solution at 23°C, washed with ion-exchanged water, air-dried, and heat-treated in an oven at 230°C for 40 minutes to form a colored composition layer on the glass substrate. Next, an overcoat agent was applied onto the colored composition layer using a spin coater, and the organic solvent was removed using a vacuum dryer. Thereafter, the resultant was baked on a hot plate at 90°C for 2 minutes, and then heat-treated at 230°C for 60 minutes to obtain a substrate for brightness evaluation. The initial brightness of the obtained substrate for brightness evaluation in the XYZ color system was measured using LVmicroZ (manufactured by Lambda Vision). The evaluation criteria for initial brightness are as follows: 5:55.0pts or above, extremely good brightness. 4: 54.0pts or more and less than 55.0pts, good brightness. 3: Practical brightness: 53.0pts or more and less than 54.0pts. 2: 52.0pts or more and less than 53.0pts, brightness that is not practical Less than 1:52.0pts, unusable brightness

[0280] After that, the LED lighting was irradiated for 200 hours, and the brightness was measured again. The brightness change rate was calculated using the following formula. A value of 3 or more is practical. Brightness change rate = |Brightness after 200 hours - initial brightness| / initial brightness x 100 The evaluation criteria are as follows: 5: Less than 3% 4: 3% or more, less than 5% 3: 5% or more, less than 10% 2: 10% or more, less than 15% 1:15% or more

[0281] [Film thickness evaluation] The obtained photosensitive coloring composition was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the chromaticity value of the coating after heat treatment was y = 0.65 with Illuminant C, and then dried on a hot plate at 70 °C for 1 minute. Next, an ultra-high pressure mercury lamp was used to apply ultraviolet light with an integrated dose of 50 mJ / cm. 2The film was exposed to ultraviolet light through a stripe pattern photomask and spray-developed with a 23°C aqueous sodium carbonate solution. Spray development was carried out for the shortest time possible for forming a pattern without leaving any residual development residue on the coating of each photosensitive coloring composition. The film was then washed with ion-exchanged water and air-dried. After that, it was heat-treated in an oven at 230°C for 40 minutes to form a coloring composition layer on the glass substrate, and the film thickness of the pattern portion measuring 400 μm long x 400 μm wide was measured using a Dektak 3030 (manufactured by Japan Vacuum Engineering Co., Ltd.). The evaluation criteria are as follows: 5: Less than 2.0 μm, very good film thickness. 4: Good film thickness, 2.0 μm or more and less than 2.2 μm. 3: A practical film thickness of 2.2 μm or more and less than 2.5 μm. 2: A thickness of 2.5 μm or more and less than 3.0 μm, which is not practical. 1: 3.0 μm or more, impractical film thickness.

[0282] [Table 3] [Explanation of symbols]

[0283] 10 LCD display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color Filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing Plate 30 Backlight unit 31 White LED light source LC liquid crystal

Claims

1. A green photosensitive coloring composition comprising a colorant (A), a copper salt of a quinophthalone compound having a sulfo group (B), an alkali-soluble resin (C), a polymerizable compound (D), and a photopolymerization initiator (E), The colorant (A) contains a phthalocyanine pigment (A1) containing at least one selected from the group consisting of C.I. Pigment Green 58, C.I. Pigment Green 59, C.I. Pigment Green 62, and C.I. Pigment Green 63, and a quinophthalone pigment (A2) represented by the following general formula (2): the alkali-soluble resin (C) comprises an alkali-soluble resin (C1) containing an alicyclic hydrocarbon-containing monomer unit (c1), and the alkali-soluble resin (C1) containing the alicyclic hydrocarbon-containing monomer unit (c1) is a resin (C2) further containing an aromatic ring-containing monomer unit (c2) having a homopolymer glass transition temperature of 80°C or higher; the photopolymerization initiator (E) contains at least one compound (E1) represented by any one of chemical formulas (32) to (39) and an alkylphenone compound (E2), and the mass ratio of E1 to E2 is E1:E2=80:20 to 20:80; A film formed from the green photosensitive coloring composition has a dielectric loss tangent value of less than 0.090 under the following conditions: Green photosensitive coloring composition. <Conditions> The obtained coloring composition was spin-coated onto a glass substrate on which a transparent conductive film (ITO film) had been formed. After wiping off the coating on the electrode with a solvent, the coating was applied with an integrated light dose of 50 mJ / cm 2 After UV exposure, a coated substrate was obtained. Then, the substrate was heat-treated at 230° C. for 40 minutes, and then cooled. A gold deposition agent was applied to the obtained colored composition film to an area of 3.464×10 −4 m −2 . The electrode was then formed on the substrate for dielectric loss tangent evaluation. A light was irradiated from the opposite surface under the condition that the luminance of the irradiated surface was 1000 cd / m 2 . The coating surface was measured using an impedance analyzer (Solartron "1260" model). The dielectric loss tangent was measured at several tens of Hz. 【Chemical 1】 【change】 General formula (2) 【Chemistry 2】 (In general formula (2), R 1 to R 13 each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent. Adjacent groups of R 1 to R 4 and / or R 5 to R 8 may combine to form an aromatic ring which may have a substituent.)

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

3. A liquid crystal display device comprising the color filter according to claim 2.

4. A solid-state imaging device comprising the color filter according to claim 2 .

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