Colored curable resin composition, color filter, and display device

Abstract

To provide a colored curable resin composition that allows formation of a color filter exhibiting favorable pattern surface properties and superior heat resistance.SOLUTION: A colored curable resin composition comprising a colorant represented by formula (I), a resin containing a structural unit derived from a monomer having an ethylenically unsaturated bond and an epoxy group, a polymerizable compound, and a polymerization initiator.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a colored curable resin composition, a color filter, and a display device. [Background technology]

[0002] Color filters used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, as well as solid-state imaging devices such as CCD and CMOS sensors, are produced from colored resin compositions. Various colorants are used in such colored curable resin compositions, and for example, phthalocyanine having a catechol structure in an isoindoline skeleton is known as a colorant (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-125460 [Patent Document 2] Patent Publication No. 2021-56382 Summary of the Invention [Problem to be solved by the invention]

[0004] Phthalocyanines having a catechol structure in the isoindoline skeleton have various problems when used in color filters due to the catechol structure. For example, Patent Document 1 reveals that the heat resistance of phthalocyanines is poor, and Patent Document 2 reveals that the film surface becomes rough. Therefore, an object of the present invention is to provide a colored curable resin composition that forms a color filter having good pattern surface properties and excellent heat resistance. [Means for solving the problem]

[0005] The gist of the present invention is as follows. [1] A colorant, a resin, a polymerizable compound, and a polymerization initiator, The colorant comprises a compound represented by formula (I), the resin comprises a resin (B1) containing a structural unit derived from a monomer having an ethylenically unsaturated bond and an epoxy group, A colored curable resin composition characterized in that the content of the structural unit is 3 to 50 mol % of all structural units in the resin (B1). [ka] [In formula (I), A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 each independently represents a hydrogen atom or a halogen atom, A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 each independently represents a hydrogen atom, a halogen atom, or a group represented by the following formula (II), A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 At least one of the groups represents a group represented by the following formula (II): [ka] [In formula (II), X represents a divalent group, R represents a monovalent substituent, and n represents an integer of 0 to 5. [2]A 1 , A 4 , A 5 , A 8 , A 9 , A 12, A 13 , and A 16 The colored curable resin composition according to [1], wherein at least one of the following represents a halogen atom. [3] The colored curable resin composition according to [1] or [2], wherein the resin has an acid value of 90 mgKOH / g or more. [4] The colored curable resin composition according to any one of [1] to [3], wherein the content of the resin containing a structural unit derived from a monomer having an ethylenically unsaturated bond and an epoxy group is 50 mass% or more of the total resin. [5] The colored curable resin composition according to any one of [1] to [4], further comprising a solvent, the solvent being selected from the group consisting of ether solvents and ether ester solvents. [6] A color filter formed from the colored curable resin composition according to any one of [1] to [5]. [7] A display device comprising the color filter according to [6]. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a colored curable resin composition that forms a color filter having good pattern surface properties and excellent heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0007] The colored curable resin composition of the present invention contains a colorant (hereinafter may be referred to as colorant (A)), a resin (hereinafter may be referred to as resin (B)), a polymerizable compound (hereinafter may be referred to as polymerizable compound (C)), and a polymerization initiator (hereinafter may be referred to as polymerization initiator (D)). The colored curable resin composition of the present invention may further contain a solvent (hereinafter, may be referred to as solvent (E)). The colored curable resin composition of the present invention may further contain a polymerization initiation aid (hereinafter, may be referred to as polymerization initiation aid (D1)). The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, may be referred to as leveling agent (F)). In this specification, the compounds exemplified as each component can be used alone or in combination, unless otherwise specified.

[0008] <Colorant (A)> The colorant (A) contains a compound represented by formula (I) (also referred to as compound (I)). The compound represented by formula (I) may be one type or two or more types.

[0009] [ka] [In formula (I), A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 each independently represents a hydrogen atom or a halogen atom, A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 each independently represents a hydrogen atom, a halogen atom, or a group represented by the following formula (II), A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 At least one of the groups represents a group represented by the following formula (II):

[0010] [ka] [In formula (II), X represents a divalent group, R represents a monovalent substituent, and n represents an integer of 0 to 5.

[0011] In formula (I), A1 ~A 16 Examples of halogen atoms represented by the formula (I) include chlorine atoms, fluorine atoms, bromine atoms, and iodine atoms. 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 At least one of these preferably represents a halogen atom, more preferably a chlorine atom or a fluorine atom, and even more preferably a fluorine atom.

[0012] In formula (II), the divalent group represented by X is preferably -O-, -S-, or -NR- (wherein R represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms (preferably an aliphatic hydrocarbon group having 1 to 6 carbon atoms)), and more preferably -O-. Examples of the hydrocarbon group having 1 to 6 carbon atoms include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group.

[0013] In formula (II), R represents a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, -OR x , -COR x , -CO2R x , -CO2M (M represents an alkali metal atom), -OCOR x , -CON(R x )2, -OCON(R x )2, -N(R x )2, a cyano group, or a nitro group. R x preferably represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. * represents a bond. However, R or R x When there are multiple, they may be the same or different.

[0014] R and R xThe hydrocarbon group represented by the formula (I) may be saturated or unsaturated, may be linear, branched, or cyclic, and is preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group.

[0015] Examples of the aliphatic hydrocarbon group include linear alkyl groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl; isopropyl, (1-ethyl)propyl, isobutyl, sec-butyl, tert-butyl, (1-ethyl)butyl, (2-ethyl)butyl, (1-propyl)butyl, isopentyl, neopentyl, tert-pentyl, (2-methyl)pentyl, (1-ethyl)pentyl, (3-ethyl)pentyl, (1-propyl)pentyl, and (1-butyl)pentyl. branched alkyl groups such as an isohexyl group, an isohexyl group, a (2-methyl)hexyl group, a (5-methyl)hexyl group, a (2-ethyl)hexyl group, a (1-butyl)hexyl group, a (2-methyl)heptyl group, a (2-ethyl)heptyl group, a (3-ethyl)heptyl group, a (2-methyl)octyl group, and a (2-ethyl)octyl group; alkenyl groups such as a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), a (1-methyl)ethenyl group, a 2-butenyl group, a 3-butenyl group, a 1,3-butadienyl group, a (1-(2-propenyl))ethenyl group, a (1,2-dimethyl)propenyl group, and a 2-pentenyl group; and the like.

[0016] Examples of the alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; cycloalkenyl groups such as cyclohexenyl (e.g., cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, and cyclooctenyl; norbornyl, adamantyl, and bicyclo[2.2.2]octyl.

[0017] Examples of the aromatic hydrocarbon group include aryl groups such as phenyl, 1-naphthyl, and 2-naphthyl; alkylaryl groups such as o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4,6-trimethylphenyl, 2-methyl-6-ethylphenyl, 2,6-diethylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, 2-methyl-6-isopropylphenyl, 4-butylphenyl, o-tert-butylphenyl, m-tert-butylphenyl, and p-tert-butylphenyl; and alkenylaryl groups such as 4-vinylphenyl.

[0018] The hydrocarbon group having 1 to 20 carbon atoms may be a group comprising a combination of two or more of the chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups listed above, as long as the upper limit of the carbon number is 20. Examples of such groups include aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenylethyl; arylalkenyl groups such as phenylethenyl (phenylvinyl); arylalkynyl groups such as phenylethynyl; 1-methylcyclopropyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, and 3,4-dimethylcyclohexyl groups; Alicyclic hydrocarbon groups to which one or more alkyl groups or alicyclic hydrocarbon groups are bonded, such as a 3,5-dimethylcyclohexyl group, a 2,2-dimethylcyclohexyl group, a 3,3-dimethylcyclohexyl group, a 4,4-dimethylcyclohexyl group, a 2,4,6-trimethylcyclohexyl group, a 2,2,6,6-tetramethylcyclohexyl group, or a 3,3,5,5-tetramethylcyclohexyl group; and alkyl groups to which one or more alicyclic hydrocarbon groups are bonded, such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, or a cyclohexylethyl group.

[0019] R and R x When the hydrocarbon group represented by the formula (I) is a saturated chain aliphatic hydrocarbon group, the saturated chain aliphatic hydrocarbon group is preferably a linear alkyl group or a branched alkyl group, and has preferably 1 to 10 carbon atoms, more preferably 1 to 8, even more preferably 1 to 6, and even more preferably 1 to 4 carbon atoms. R and R xWhen the hydrocarbon group represented by the formula (I) is an unsaturated chain aliphatic hydrocarbon group, the unsaturated chain aliphatic hydrocarbon group is preferably an alkenyl group or an alkynyl group, and preferably has 2 to 10 carbon atoms, more preferably 2 to 8, even more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. R and R x When the hydrocarbon group represented by the formula (I) is an alicyclic hydrocarbon group, it preferably has 3 to 10 carbon atoms, more preferably 3 to 8 carbon atoms, and even more preferably 3 to 6 carbon atoms. R and R x When the hydrocarbon group represented by the formula (I) is an aromatic hydrocarbon group, it preferably has 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms, and even more preferably 6 to 8 carbon atoms. The group formed by combining two or more groups selected from the group consisting of chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups preferably has 7 to 18 carbon atoms, and more preferably 7 to 15 carbon atoms.

[0020] R and R x The hydrocarbon group represented by the formula (I) may have a substituent, and examples of the substituent include a halogen atom, a nitro group, a cyano group, -OR x , -CO2R x , -CO2M, -CON(R x )2, -NR x COR x , -SR x , -SO2R x , -SO2N(R x )2, -SO3R x , -SO3M, and -N(R x )2 etc. x and M are the same as above, and R x Alternatively, when there are multiple M's, they may be the same or different.

[0021] Examples of the halogen atom represented by R and the halogen atom used as a substituent on the hydrocarbon group having 1 to 20 carbon atoms include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom and a chlorine atom being preferred.

[0022] -OR represented by Rx and -OR used as a substituent of the hydrocarbon group having 1 to 20 carbon atoms. x is preferably a hydrogen atom or an oxy group having an aliphatic hydrocarbon group bonded thereto, more preferably a hydroxy group; a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, or a pentyloxy group, and even more preferably a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, or a butoxy group.

[0023] -COR represented by R x is preferably a hydrogen atom or a carbonyl group having an aliphatic hydrocarbon group bonded thereto, more preferably a formyl group; an acetyl group, a propanoyl group, a butanoyl group, or a 2,2-dimethylpropanoyl group, still more preferably an acetyl group, a propanoyl group, or a butanoyl group.

[0024] -CO2R represented by R x and -COR, which is used as a substituent of the hydrocarbon group having 1 to 20 carbon atoms. x is preferably a hydrogen atom or an oxycarbonyl group having an aliphatic hydrocarbon group bonded thereto, more preferably a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a butoxycarbonyl group, or a pentyloxycarbonyl group, and even more preferably a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl group.

[0025] -OCOR represented by R x is preferably a hydrogen atom or a carbonyloxy group having an aliphatic hydrocarbon group bonded thereto, more preferably a formyloxy group; an acetoxy group, a propanoyloxy group, a butanoyloxy group, a 2,2-dimethylpropanoyloxy group, or a pentanoyloxy group, still more preferably an acetoxy group, a propanoyloxy group, or a butanoyloxy group.

[0026] R represents -CON(R x )2, and -CON(Rx )2 is preferably a hydrogen atom or a carbamoyl group having an aliphatic hydrocarbon group bonded thereto, more preferably a carbamoyl group; an N-1-substituted carbamoyl group such as an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, an N-isopropylcarbamoyl group, an N-butylcarbamoyl group, an N-isobutylcarbamoyl group, an N-sec-butylcarbamoyl group, an N-tert-butylcarbamoyl group, or an N-pentylcarbamoyl group; an N,N-dimethylcarbamoyl group, an N,N-ethylcarbamoyl group, or an N-methylcarbamoyl group; and N-disubstituted carbamoyl groups such as N-disubstituted methylcarbamoyl group, N,N-diethylcarbamoyl group, N,N-propylmethylcarbamoyl group, N,N-dipropylcarbamoyl group, N,N-isopropylmethylcarbamoyl group, N,N-diisopropylcarbamoyl group, N,N-tert-butylmethylcarbamoyl group, N,N-diisobutylcarbamoyl group, N,N-disec-butylcarbamoyl group, N,N-di-tert-butylcarbamoyl group, and N,N-butylmethylcarbamoyl group.

[0027] -OCON(R x )2 includes, for example, the aforementioned -CON(R x ) A group in which —O— is bonded to the bond of 2.

[0028] R represents -N(R x )2, and —N(R x)2 is preferably an amino group having a hydrogen atom or an aliphatic hydrocarbon group bonded thereto, more preferably an amino group; an N-1-substituted amino group such as an N-methylamino group, an N-ethylamino group, an N-propylamino group, an N-isopropylamino group, an N-butylamino group, an N-isobutylamino group, an N-sec-butylamino group, an N-tert-butylamino group, or an N-pentylamino group; or an N-2-substituted amino group such as an N,N-dimethylamino group, an N,N-ethylmethylamino group, an N,N-diethylamino group, an N,N-propylmethylamino group, an N,N-dipropylamino group, an N,N-isopropylmethylamino group, an N,N-diisopropylamino group, an N,N-tert-butylmethylamino group, an N,N-diisobutylamino group, an N,N-disec-butylamino group, an N,N-ditert-butylamino group, an N,N-butylmethylamino group, an N,N-dibutylamino group, or an N,N-dipentylamino group.

[0029] -SR used as a substituent of the hydrocarbon group having 1 to 20 carbon atoms x Examples of the sulfanyl group include a sulfanyl group, a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.

[0030] -SO2R used as a substituent of the hydrocarbon group having 1 to 20 carbon atoms x Examples of the sulfonyl group include a sulfonyl group, a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

[0031] -SO3R used as a substituent of the hydrocarbon group having 1 to 20 carbon atoms x Examples of the sulfonyl group include a sulfonyl group, a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

[0032] -SO2N(R x)2 includes, for example, a sulfamoyl group; an N-methylsulfamoyl group, an N-ethylsulfamoyl group, an N-propylsulfamoyl group, an N-isopropylsulfamoyl group, an N-butylsulfamoyl group, an N-isobutylsulfamoyl group, an N-sec-butylsulfamoyl group, an N-tert-butylsulfamoyl group, an N-pentylsulfamoyl group, an N-(1-ethylpropyl)sulfamoyl group, an N-(1,1-dimethyl N-(propyl)sulfamoyl group, N-(1,2-dimethylpropyl)sulfamoyl group, N-(2,2-dimethylpropyl)sulfamoyl group, N-(1-methylbutyl)sulfamoyl group, N-(2-methylbutyl)sulfamoyl group, N-(3-methylbutyl)sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexylsulfamoyl group, N-(1,3-dimethylbutyl)sulfamoyl group, N-(3,3-dimethyl N-1-substituted sulfamoyl groups such as N-(butyl)sulfamoyl group, N-heptylsulfamoyl group, N-(1-methylhexyl)sulfamoyl group, N-(1,4-dimethylpentyl)sulfamoyl group, N-octylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group, N-(1,5-dimethyl)hexylsulfamoyl group, and N-(1,1,2,2-tetramethylbutyl)sulfamoyl group; N,N-dimethylsulfamoyl groups N,N-disubstituted sulfamoyl groups such as an N,N-ethylmethylsulfamoyl group, an N,N-diethylsulfamoyl group, an N,N-propylmethylsulfamoyl group, an N,N-isopropylmethylsulfamoyl group, an N,N-tert-butylmethylsulfamoyl group, an N,N-butylethylsulfamoyl group, an N,N-bis(1-methylpropyl)sulfamoyl group, and an N,N-heptylmethylsulfamoyl group.

[0033] M represents an alkali metal atom, and specific examples thereof include a lithium atom, a sodium atom, and a potassium atom, with a sodium atom and a potassium atom being preferred.

[0034] R is -CO2R x a hydrocarbon group having 1 to 20 carbon atoms and having as a substituent -CO2R xis preferred, an oxycarbonyl group having a hydrogen atom or an aliphatic hydrocarbon group bonded thereto is more preferred, a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a butoxycarbonyl group, or a pentyloxycarbonyl group is even more preferred, a methoxycarbonyl group, an ethoxycarbonyl group, or a propoxycarbonyl group is even more preferred, and an ethoxycarbonyl group is particularly preferred.

[0035] n is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, even more preferably 1 or 2, and even more preferably 1.

[0036] When the group represented by formula (II) has R, R may be bonded at any of the ortho, meta, or para positions relative to the group represented by "*-X-" in formula (II), preferably at the meta or para position, and more preferably at the para position. If R is bonded at the ortho position relative to the group represented by "*-X-" in formula (II), the surface roughness of the colored pattern tends to worsen.

[0037] A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 Among these, it is preferred that one or more are groups represented by formula (II), more preferred that two or more are groups represented by formula (II), even more preferred that four or more are groups represented by formula (II), and even more preferred that six or more are groups represented by formula (II), and A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 is particularly preferably a group represented by formula (II). Among them, A 2, A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 is a group represented by formula (II), and R in formula (II) is -COR x a hydrocarbon group having 1 to 20 carbon atoms and having as a substituent -CO2R x and R in formula (II) is preferably bonded to the meta or para position relative to the group represented by "*-X-". In addition, in the group represented by formula (II), R is -CO2R x and it is preferable that R does not contain a group bonded to the para-position or ortho-position relative to the group represented by "*-X-".

[0038] A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 Among these, it is preferable that one or more are halogen atoms, more preferable that two or more are halogen atoms, even more preferable that four or more are halogen atoms, and even more preferable that six or more are halogen atoms. 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 is particularly preferably a halogen atom.

[0039] As a method for producing compound (I), a known method can be adopted, and for example, it can be appropriately produced by the method described in WO 2020 / 171060.

[0040] The content of compound (I) in the total amount of colorant (A) is preferably 5 to 40 mass%, more preferably 7 to 35 mass%, even more preferably 9 to 30 mass%, still more preferably 11 to 25 mass%, and even more preferably 13 to 20 mass%. When the content of compound (I) in colorant (A) is within the above range, it becomes easier to obtain the desired spectrum, and reliability such as heat resistance, solvent resistance, and light resistance tends to be improved.

[0041] The content of compound (I) in the colored curable resin composition is preferably 0.1 to 25 mass%, more preferably 1 to 20 mass%, even more preferably 2 to 18 mass%, still more preferably 3 to 16 mass%, and even more preferably 5 to 14 mass%, of the total amount of solids. When the content of compound (I) in the colored curable resin composition is within the above range, it becomes easier to obtain the desired spectrum, and reliability such as heat resistance, solvent resistance, and light resistance tends to be improved.

[0042] The colorant (A) may further contain a colorant (hereinafter, sometimes referred to as colorant (A1)) different from the compound (I). The colorant (A1) may be either a dye or a pigment, or may contain both.

[0043] Examples of dyes include compounds classified as compounds having a hue other than pigments in the Color Index (published by The Society of Dyers and Colourists) and known dyes described in Dyeing Notes (Shikisensha).

[0044] Examples of dyes include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, thiazole dyes, oxazine dyes, quinophthalone dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, and phthalocyanine dyes, etc. Among these, azo dyes, xanthene dyes, and phthalocyanine dyes other than compound (1) are preferred.

[0045] Specific examples of dyes include CI Solvent Yellow 4 (hereinafter, the term CI Solvent Yellow will be omitted and only the numbers will be listed. The same applies to the others), 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, and 189; CI Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI solvent dyes such as CI Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35; CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 177, 178, 180, 181, 182, 183, 184, 185, 186, 187, 188, 189, 190, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 219, 220, 221, 222, 223, 224, 225, 226, 227, 228, 229, 230, 231, 232, 233, 234, 235, 23 82, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, ​​383, 388, 394, 401, 412, 417, 418, 422, 426; CI Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123 , 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340; CI Acid dyes such as CI Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109; CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166 6, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; CI Direct Dyes, such as CI Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82; CI Disperse Yellow 51, 54, 76; CI Disperse Violet 26, 27; CI Disperse dyes such as CI Disperse Blue 1, 14, 56, 60, etc. CI Basic Red 1, 9, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; CI Basic Violet 2; CI Basic dyes, such as CI Basic Green 1; CI Reactive Yellow 2, 76, 116; CI Reactive Orange 16; CI Reactive dyes, such as CI Reactive Red 36; CI Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; CI Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; CI Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; CI Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; CI Mordant dyes, such as CI Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53; Examples include CI Vat dyes such as CI Vat Green 1; These dyes may be one type of dye or a plurality of dyes for each color, or dyes of each color may be combined.

[0046] Examples of pigments include those classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0047] Examples of pigments classified as pigments include yellow pigments such as CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231, 235, and 236; Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73; Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 272, 273, 291, 297; Blue pigments such as CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60; Violet pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 37, 38; Green pigments such as CI Pigment Green 7, 36, 58, 59, 62, 63, 64, 65, 66, 67; Brown pigments such as CI Pigment Brown 23 and 25; Black pigments such as CI Pigment Black 1, 7, 31, and 32; One or more of these pigments may be used for each color, or pigments of each color may be combined.

[0048] The pigment may be subjected, as necessary, to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group has been introduced, a grafting treatment onto the pigment surface using a polymer compound or the like, an atomization treatment using a sulfuric acid atomization method or the like, a washing treatment using an organic solvent or water to remove impurities, a treatment to remove ionic impurities using an ion exchange method or the like, etc. It is preferable that the particle size of the pigment is approximately uniform.

[0049] The colorant (A1) preferably contains a yellow pigment and a green pigment. The yellow pigment is preferably CI Pigment Yellow 137, 138, 139, 150, 185, more preferably CI Pigment Yellow 138, 150, 185. The green pigment is preferably CI Pigment Green 7, 36, 58, 59, more preferably CI Pigment Green 58.

[0050] The content of the yellow pigment is preferably 10 to 50 mass %, more preferably 15 to 45 mass %, and even more preferably 20 to 40 mass %, of the total amount of the colorant (A). The content of the green pigment in the total amount of the colorant (A) is preferably 10 to 70 mass %, more preferably 15 to 65 mass %, even more preferably 20 to 60 mass %, and still more preferably 25 to 55 mass %.

[0051] The content of the colorant (A) in the colored resin composition is preferably 0.5 to 85 mass%, more preferably 1 to 80 mass%, even more preferably 5 to 75 mass%, still more preferably 10 to 70 mass%, and even more preferably 15 to 65 mass%, based on the total amount of solids. When the content of the colorant (A) is within the above range, it becomes easier to obtain the desired spectrum and color density. In this specification, the term "total amount of solids" refers to the total amount of components in the composition of the present invention excluding the solvent. The total amount of solids and the content of each component relative to the total amount of solids can be measured by known analytical means such as liquid chromatography or gas chromatography.

[0052] <Resin (B)> Resin (B) includes resin (B1) containing a structural unit derived from a monomer having an ethylenically unsaturated bond and an epoxy group. Here, the epoxy group is an ether structure in which an oxygen atom is cyclically bonded to two carbon atoms in the same molecule, and is represented by the general formula: O[-CR z1 R z2 -(CR z3 R z4 ) z -CR z5 R z6 -*] (R z1 ~R z6 Each independently represents a monovalent substituent. z represents an integer such as 0, 1, or 2, and when z is 0, it represents oxirane, when z is 1, it represents oxetane, and when z is 2, it represents oxolane (tetrahydrofuran). * represents a bond to O. Examples of the monovalent substituent include a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, and a hydrocarbon group having 1 to 6 carbon atoms.

[0053] Resin (B) is preferably an alkali-soluble resin. Examples of resin (B1) include the following resins [K1] to [K2], and it is preferably at least one selected from resins [K1] to [K2].

[0054] Resin [K1]: a copolymer having structural units derived from at least one monomer (a) (hereinafter, sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and structural units derived from a monomer (b) (hereinafter, sometimes referred to as "(b)") having an ethylenically unsaturated bond and an epoxy group; Resin [K2]: a copolymer having structural units derived from (a), structural units derived from (b), and structural units derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, sometimes referred to as "(c)");

[0055] Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; bicyclounsaturated compounds containing a carboxy group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; Unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid; and the like. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an alkaline aqueous solution.

[0056] In this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

[0057] Examples of (b) include a monomer having an oxiranyl group and an ethylenically unsaturated bond (preferably a monomer having an oxiranyl group and a (meth)acryloyl group, more preferably a monomer having an oxiranyl group and a (meth)acryloyloxy group) (b1) (hereinafter also referred to as "(b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (preferably a monomer having an oxetanyl group and a (meth)acryloyl group, more preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group) (b2) (hereinafter also referred to as "(b2)"), and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (b3) (hereinafter also referred to as "(b3)"). (b1) is preferably a monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized, or a monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon has been epoxidized.

[0058] Examples of the monomer (b1-1) having an epoxidized structure of a linear or branched aliphatic unsaturated hydrocarbon include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, and α-methyl-p-vinylbenzyl glycidyl ether. diethyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, and the like.

[0059] Examples of the monomer (b1-2) having an epoxidized alicyclic unsaturated hydrocarbon structure include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), 3,4-epoxytricyclo[5.2.1.0] 2,6 ]decyl (meth)acrylate, and the like.

[0060] As the (b2) having an oxetanyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and a (meth)acryloyloxy group is more preferred. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, and 3-ethyl-3-acryloyloxyethyloxetane.

[0061] As the (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond, a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferred. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0062] Examples of (c) include (meth)acrylic acid ester monomers, unsaturated carboxylic acid esters such as unsaturated dicarboxylic acid esters, and vinyl monomers having an unsaturated aliphatic hydrocarbon ring, an unsaturated heterocyclic ring, or an aromatic ring. Examples of the (meth)acrylic acid ester monomer include (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group, such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, and cyclopentyl (meth)acrylate; (meth)acrylic acid esters having a linear or branched aliphatic unsaturated hydrocarbon group, such as allyl (meth)acrylate and propargyl (meth)acrylate; Cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, such as decyl (meth)acrylate (commonly referred to in the technical field as "dicyclopentanyl (meth)acrylate" and also referred to as "tricyclodecyl (meth)acrylate"), isobornyl (meth)acrylate, and adamantyl (meth)acrylate; Tricyclo[5.2.1.0 2,6 (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, such as ]decenyl (meth)acrylate (commonly referred to as "dicyclopentenyl (meth)acrylate" in the technical field), and dicyclopentanyloxyethyl (meth)acrylate; (meth)acrylic acid esters having an aromatic ring, such as phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, and phenoxybenzyl (meth)acrylate; Examples thereof include hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate. Examples of the unsaturated dicarboxylic acid ester include dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate.

[0063] Among these unsaturated carboxylic acid esters, C esters such as methyl methacrylate and 2-ethylhexyl acrylate are preferred. 1-10 Alkyl (meth)acrylate; Tricyclo[5.2.1.0 2,6 ](meth)acrylic acid esters having a cyclic saturated hydrocarbon group, such as decyl (meth)acrylate; Tricyclo[5.2.1.0 2,6 ](meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, such as decenyl (meth)acrylate; Preferred are (meth)acrylic acid esters having an aromatic ring, such as benzyl (meth)acrylate and phenoxybenzyl (meth)acrylate.

[0064] Examples of vinyl monomers having an unsaturated aliphatic hydrocarbon ring include bicyclo[2.2.1]hept-2-ene (also called 2-norbornene), 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxy diethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6 -Dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1] ]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene, and other bicyclounsaturated compounds. Examples of vinyl monomers having an unsaturated heterocycle include dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide. Examples of vinyl monomers having an aromatic ring include styrene-based monomers such as styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene. Other vinyl monomers include nitrile group-containing monomers such as acrylonitrile and methacrylonitrile; Halogen atom-containing monomers such as vinyl chloride and vinylidene chloride; Examples include acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. Among these vinyl monomers, from the viewpoints of copolymerization reactivity and heat resistance, styrene-based monomers such as styrene and vinyltoluene, dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide, and bicyclounsaturated compounds such as bicyclo[2.2.1]hept-2-ene (also called 2-norbornene) are preferred.

[0065] The content of structural units derived from the monomer (b) having an ethylenically unsaturated bond and an epoxy group is 3 to 50 mol %, preferably 3 to 45 mol %, more preferably 4 to 40 mol %, even more preferably 5 to 35 mol %, and particularly preferably 6 to 30 mol %, of all structural units in the resin (B1). Within this content range, the surface properties of the color filter tend to be good, and heat resistance tends to be improved. The content of structural units derived from the monomer (b) having an ethylenically unsaturated bond and an epoxy group may be 1 to 80 mol %, or 2 to 50 mol %, of all structural units in the resin (B1).

[0066] The content of the structural units derived from the monomer (a) in all structural units of the resin (B1) is preferably from 10 to 60 mol %, more preferably from 20 to 40 mol %.

[0067] The content of the structural units derived from the monomer (c) in all structural units of the resin (B1) is preferably from 10 to 60 mol %, more preferably from 20 to 40 mol %.

[0068] Resin [K1] can be produced, for example, by the method described in the literature "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and by reference to the references described in said literature.

[0069] Specifically, a method can be exemplified in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and a deoxygenated atmosphere is created, for example, by replacing oxygen with nitrogen, followed by heating and keeping the temperature while stirring. The polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.), and the solvent can be any solvent that dissolves each monomer, such as the solvent (E) described below.

[0070] The obtained copolymer may be used as a solution after the reaction as it is, or may be used as a concentrated or diluted solution, or may be used as a solid (powder) extracted by a method such as reprecipitation. In particular, by using the solvent contained in the colored resin composition as a solvent during this polymerization, the solution after the reaction can be used as it is for preparing the colored resin composition, which simplifies the production process of the colored resin composition.

[0071] Resin [K2] can be produced, for example, in the same manner as described above for producing resin [K1].

[0072] Specific examples of the resin (B1) include 3,4-epoxycyclohexylmethyl(meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2.6 ] Decyl acrylate / (meth)acrylic acid copolymer and other resins [K1]; Glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide / tricyclo[5.2.1.0 2,6 ]decene-8-yl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate / (meth)acrylic acid / benzyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] decyl acrylate / (meth)acrylic acid / phenoxybenzyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer, and other resins [K2].

[0073] The polystyrene-equivalent weight average molecular weight of the resin (B1) is preferably 3,000 to 100,000, more preferably 4,000 to 50,000, and even more preferably 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film rate is high, and the solubility of the unexposed areas in the developer is good, which tends to improve the resolution of the colored pattern.

[0074] The polydispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B1) is preferably 1.1-6, more preferably 1.2-4.

[0075] The acid value of the resin (B1) is preferably 90 mg-KOH / g or more, more preferably 90 to 170 mg-KOH / g, even more preferably 90 to 150 mg-KOH / g, and even more preferably 90 to 135 mg-KOH / g, calculated as solid content. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B1), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0076] The content of the resin (B1) containing a structural unit derived from a monomer having an ethylenically unsaturated bond and an epoxy group in the entire resin (B) is preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass.

[0077] Resin (B) may contain other resins (B2) as long as it contains resin (B1) containing structural units derived from a monomer having an ethylenically unsaturated bond and an epoxy group. Examples of other resins (B2) include resins [K3] to [K6] below. Resins [K3] to [K6] are preferably resins in which the content of structural units derived from a monomer having an ethylenically unsaturated bond and an epoxy group is less than 3 mol %.

[0078] Resin [K3]: a copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]: a copolymer having a structural unit derived from (a) to which (b) is added, and a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit derived from (b) by addition of (a) and a structural unit derived from (c); Resin [K6]: A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride.

[0079] The structural unit obtained by adding (b) to a structural unit derived from (a) refers to a unit formed by adding (b) to a structural unit derived from (a) that constitutes the main chain of the copolymer, and has a pendant unsaturated group derived from (b). In this structural unit, (a) may be any of the above-mentioned examples, and (b) may also be any of the above-mentioned examples. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred. As (b), a monomer (b1) having an epoxy group and an ethylenically unsaturated bond is preferred, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferred.

[0080] The structural unit obtained by adding (a) to a structural unit derived from (b) refers to a unit formed by adding (a) to a structural unit derived from (b) constituting the main chain of the copolymer, and has a pendant unsaturated group derived from (a). In this structural unit, (b) may be any of the above-mentioned examples, and (a) may also be any of the above-mentioned examples. As (b), a monomer (b1) having an epoxy group and an ethylenically unsaturated bond is preferred, and a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized is more preferred. As (a), an unsaturated monocarboxylic acid such as (meth)acrylic acid is preferred.

[0081] In the resin [K3], the ratio of the structural units derived from each of these is as follows: Structural units derived from (a): 2 to 60 mol% Structural units derived from (c): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (c): 50 to 90 mol% It is more preferable that:

[0082] Resin [K3] can be produced, for example, in the same manner as described above for producing resin [K1].

[0083] In the resin [K4], the ratio of the structural units derived from each of these is as follows: Structural units derived from (a) (without addition of (b)): 0 to 60 mol% Structural units in which (b) is added to structural units derived from (a): 1 to 50 mol% Structural units derived from (c): 30 to 90 mol% It is preferred that Structural units derived from (a) (without addition of (b)): 1 to 50 mol% Structural units in which (b) is added to structural units derived from (a): 5 to 40 mol% Structural units derived from (c): 35 to 80 mol% It is more preferable that:

[0084] The structural unit derived from (a) (without the addition of (b)) is preferably a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid. The structural unit obtained by adding (b) to a structural unit derived from (a) is preferably a structural unit obtained by adding a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized to a structural unit derived from an unsaturated monocarboxylic acid such as (meth)acrylic acid. The structural unit derived from (c) is preferably one or more selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group, (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, bicyclounsaturated compounds, and styrene-based monomers.

[0085] Resin [K4] can be produced by obtaining a copolymer of (a) and (c) and then adding the epoxy group of (b) to the carboxylic acid and / or carboxylic acid anhydride of (a). First, a copolymer of (a) and (c) is produced in the same manner as described for the production of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that described for resin [K3].

[0086] Next, a portion of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with the epoxy group possessed by (b). Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b), a reaction catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the reaction is carried out, for example, at 60 to 130°C for 1 to 10 hours, thereby producing the resin [K4]. The amount of (b) used is preferably 5 to 100 mol, more preferably 10 to 80 mol, and even more preferably 10 to 75 mol, relative to 100 mol of (a). By setting it within this range, the storage stability of the colored resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of (a), (b), and (c).The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of (a), (b), and (c). The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc. As with the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.

[0087] In resin [K5], the ratio of structural units derived from each of these is as follows among all structural units constituting resin [K5]: Structural units derived from (b) (without addition of (a)): 0 to 2.9 mol% Structural units in which (a) is added to structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b) (without addition of (a)): 0 to 2.9 mol% Structural units in which (a) is added to structural units derived from (b): 15 to 90 mol% Structural units derived from (c): 10 to 85 mol% It is more preferable that:

[0088] The structural unit derived from (b) (without (a) added) is preferably a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized. The structural unit in which (a) has been added to a structural unit derived from (b) is preferably a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid has been added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized. The structural unit derived from (c) is preferably one or more selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, more preferably two or more selected from these.

[0089] Resin [K5] is obtained in the first step by the same method as in the production of resin [K1] described above, to obtain a copolymer of (b) and (c). As in the above, the obtained copolymer may be used as a solution after the reaction as is, a concentrated or diluted solution, or a solid (powder) obtained by a method such as reprecipitation. The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are as follows: Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:

[0090] Furthermore, under the same conditions as in the manufacturing method of resin [K4], resin [K5] can be obtained by reacting the epoxy group derived from (b) in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a). The amount of (a) used to react with the copolymer is preferably 5 to 100 moles per 100 moles of (b). As (b) used in resin [K5], (b1) is preferred, and (b1-1) is more preferred, because the reactivity of the epoxy group is high and unreacted (b) is unlikely to remain.

[0091] In the resin [K6], the ratio of structural units derived from each of these is as follows: Structural units derived from (b) (without addition of (a)): 0 to 2.9 mol% Structural units in which (a) is added to structural units derived from (b) (no carboxylic acid anhydride is added); 20 to 85 mol% Structural units obtained by adding (a) to structural units derived from (b) and then adding a carboxylic acid anhydride thereto: 2 to 40 mol% Structural units derived from (c): 10 to 60 mol% It is preferred that Structural units derived from (b) (without addition of (a)): 0 to 2.9 mol% Structural units in which (a) is added to structural units derived from (b) (no carboxylic acid anhydride is added); 40 to 80 mol% a structural unit obtained by adding (a) to a structural unit derived from (b) and then adding a carboxylic acid anhydride thereto; 3 to 30 mol% Structural units derived from (c): 15 to 50 mol% It is more preferable that Structural units derived from (b) (without addition of (a)): 0 to 2.9 mol% Structural units in which (a) is added to structural units derived from (b) (no carboxylic acid anhydride is added); 50 to 70 mol% Structural units obtained by adding (a) to structural units derived from (b) and then adding a carboxylic acid anhydride thereto: 5 to 20 mol% Structural units derived from (c): 20 to 40 mol% It is even more preferable that:

[0092] As the structural unit derived from (b) (without (a) added), a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized is preferred. As the structural unit in which (a) has been added to a structural unit derived from (b) (without carboxylic acid anhydride added), a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid has been added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized is preferred. As the structural unit in which (a) has been added to a structural unit derived from (b) and a carboxylic acid anhydride has further been added, a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid has been added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized is preferred, a structural unit in which an unsaturated monocarboxylic acid such as (meth)acrylic acid has been added to a structural unit derived from a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized, and a saturated aliphatic polycarboxylic acid anhydride such as succinic acid has further been added. The structural unit derived from (c) is preferably one or more types selected from (meth)acrylic acid esters having a linear or branched aliphatic saturated hydrocarbon group and (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, and more preferably two or more types.

[0093] Resin [K6] is obtained in the first step by the same method as in the production of resin [K1] described above, to obtain a copolymer of (b) and (c). As in the above, the obtained copolymer may be used as a solution after the reaction as is, a concentrated or diluted solution, or a solid (powder) obtained by a method such as reprecipitation. The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are as follows: Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% It is preferred that Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:

[0094] Furthermore, under the same conditions as in the production of resin [K4], the epoxy groups derived from (b) in the copolymer of (b) and (c) are reacted with the carboxylic acid or carboxylic anhydride contained in (a). The amount of (a) used is preferably 80 to 100 moles per 100 moles of (b).

[0095] The hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic acid anhydride contained in (a) is reacted with the carboxylic acid anhydride. The amount of the carboxylic acid anhydride used is preferably 0.05 to 1 mol, more preferably 0.10 to 0.8 mol, and even more preferably 0.13 to 0.7 mol, per 1 mol of the amount of (a) used (in other words, per 1 mol of the hydroxyl group generated by the use of (a)).

[0096] Examples of carboxylic acid anhydrides include succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

[0097] Specific examples of the other resin (B2) include: Resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer [K3]; A resin in which glycidyl (meth)acrylate is added to benzyl (meth)acrylate / (meth)acrylic acid copolymer, tricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate / styrene / (meth)acrylic acid copolymer with glycidyl (meth)acrylate added, tricyclo[5.2.1.0 2,6]Resins such as a resin obtained by adding glycidyl (meth)acrylate to a decan-8-yl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, a resin obtained by adding glycidyl (meth)acrylate to a norbornene / vinyl toluene / (meth)acrylic acid copolymer, and a resin obtained by adding glycidyl (meth)acrylate to a norbornene / styrene / (meth)acrylic acid copolymer [K4]; Tricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate / glycidyl (meth)acrylate copolymer is reacted with (meth)acrylic acid, tricyclo[5.2.1.0 2,6 ]Resins such as resins obtained by reacting a copolymer of decan-8-yl (meth)acrylate / styrene / glycidyl (meth)acrylate with (meth)acrylic acid [K5]; Tricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate / glycidyl (meth)acrylate copolymer is reacted with (meth)acrylic acid to form a resin, which is then reacted with tetrahydrophthalic anhydride, 2-ethylhexyl (meth)acrylate / tricyclo[5.2.1.0 2,6 ]Decan-8-yl (meth)acrylate / glycidyl (meth)acrylate copolymer is reacted with (meth)acrylic acid, and the resulting resin is further reacted with succinic anhydride, methyl (meth)acrylate / 2-ethylhexyl (meth)acrylate / tricyclo[5.2.1.0 2,6 ] Resins such as resins obtained by reacting a copolymer of decan-8-yl (meth)acrylate / glycidyl (meth)acrylate with (meth)acrylic acid and then reacting the resulting resin with succinic anhydride [K6]; and the like.

[0098] The acid value of the other resin (B2) is preferably 10 to 170 mg-KOH / g, more preferably 20 to 150 mg-KOH / g, and even more preferably 30 to 135 mg-KOH / g, calculated as solid content. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B2), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0099] The content of resin (B) (preferably resin (B1)) is preferably 7 to 50 mass %, more preferably 9 to 45 mass %, even more preferably 11 to 40 mass %, and still more preferably 13 to 35 mass % of the total solid content of the colored curable resin composition. When the content of resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film rate of the colored pattern tend to be improved. The content of the compound (I) relative to 100 parts by mass of the resin (B) is preferably 1 to 50 parts by mass, more preferably 5 to 45 parts by mass, and even more preferably 10 to 40 parts by mass.

[0100] <Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by active radicals and / or acids generated from the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylic acid ester compounds.

[0101] Among these, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol poly(meth)acrylate (e.g., pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate), dipentaerythritol poly(meth)acrylate (e.g., dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate), tripentaerythritol poly(meth)acrylate (e.g., tri(meth)acrylate ... pentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate), tetrapentaerythritol poly(meth)acrylates (e.g., tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate), tris(2-(meth)acryloyloxyethyl)isocyanurate, alkoxylated pentaerythritol poly(meth)acrylates (e.g., ethoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate), alkoxylated dipentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate), alkoxylated dipentaerythritol poly(meth)acrylates (e.g., ethoxylated dipentaerythritol penta(meth)acrylate, ethoxylated dipentaerythritol hexa(meth)acrylate, propoxylated dipentaerythritol penta(meth)acrylate, propoxylated dipentaerythritol caprolactone-modified pentaerythritol poly(meth)acrylates (for example, caprolactone-modified pentaerythritol tri(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate), caprolactone-modified dipentaerythritol poly(meth)acrylates (for example, caprolactone-modified dipentaerythritol penta(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate), and the like. Among these, it is preferable to include at least one selected from the group consisting of trimethylolpropane tri(meth)acrylate and dipentaerythritol poly(meth)acrylate, it is more preferable to include at least one selected from the group consisting of trimethylolpropane triacrylate and dipentaerythritol polyacrylate, and it is even more preferable to include at least one selected from the group consisting of dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0102] The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 250 or more and 1,500 or less.

[0103] The content of the polymerizable compound (C) is preferably 7 to 65 mass%, more preferably 13 to 60 mass%, and even more preferably 17 to 55 mass%, of the total amount of solids in the colored curable resin composition. When the content of the polymerizable compound (C) is within the above range, the residual film rate during colored pattern formation and the chemical resistance of the color filter tend to be further improved.

[0104] <Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that generates active radicals, acids, etc. by the action of light or heat and can initiate polymerization, and known polymerization initiators can be used.

[0105] Examples of polymerization initiators that generate active radicals include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds.

[0106] The O-acyloxime compound is a compound having a partial structure represented by formula (d1): Hereinafter, * represents a bond.

[0107] [ka]

[0108] Examples of the O-acyloxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethan-1-imine, N- Examples thereof include acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, and 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one. Commercially available products such as Irgacure OXE01, OXE02, and OXE03 (all manufactured by BASF), N-1919, NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA), PBG-314, PBG-317, PBG-326, PBG-327, and PBG-329 (all manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) may also be used.Among them, O-acyloxime compounds include N-acetyloxy-1-[4-(2-hydroxyethyloxy)phenylsulfanylphenyl]propan-1-one-2-imine, N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one. At least one selected from the group consisting of 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine is preferred, and at least one selected from the group consisting of 2-[(acetyloxy)imino]-3-cyclohexyl-1-[4-(phenylsulfanyl)phenyl]propan-1-one, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine is more preferred. These O-acyloxime compounds tend to produce color filters with high brightness.

[0109] The alkylphenone compound is preferably a compound having a partial structure represented by formula (d2) or (d3), in which the benzene ring may have a substituent.

[0110] [ka]

[0111] Examples of compounds having a partial structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one, etc. Commercially available products such as Irgacure 369, 907, and 379 (all manufactured by BASF) may also be used.

[0112] Examples of compounds having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one, α,α-diethoxyacetophenone, and benzyl dimethyl ketal. In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by formula (d2).

[0113] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[ 2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, and the like.

[0114] Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, etc. Commercially available products such as Irgacure (registered trademark) 819 (manufactured by BASF) may also be used.

[0115] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372 and JP-A-6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, ... 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913).

[0116] Further examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, and 2,4,6-trimethylbenzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with the polymerization initiator aid (D1) (especially amines) described below.

[0117] Examples of the polymerization initiator that generates an acid include onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, and diphenyliodonium hexafluoroantimonate; nitrobenzyl tosylates; and benzoin tosylates.

[0118] The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound, and more preferably a polymerization initiator containing an O-acyloxime compound.

[0119] The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, sensitivity is increased and exposure time tends to be shortened, thereby improving productivity of the color filter.

[0120] <Polymerization initiator aid (D1)> The polymerization initiation aid (D1) is a compound or sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0121] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone, among which 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

[0122] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

[0123] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0124] Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0125] When these polymerization initiation aids (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the amount of the polymerization initiation aid (D1) is within this range, a colored pattern can be formed with even higher sensitivity, and the productivity of the color filter tends to improve.

[0126] <Solvent (E)> The colored curable resin composition of the present invention may further contain a solvent. The solvent (E) is not particularly limited, and a solvent commonly used in the relevant field can be used. Examples include ester solvents (solvents containing -COO- in the molecule but not -O-), ether solvents (solvents containing -O- in the molecule but not -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not -COO-), alcohol solvents (solvents containing -OH in the molecule but not -O-, -CO-, or -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0127] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0128] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.

[0129] Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, methyl 2-ethoxy ... Examples of the alkyl ether acetate include ethyl 2-methoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0130] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0131] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0132] Aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0133] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0134] Among the above solvents, from the viewpoints of coatability and drying property, organic solvents having a boiling point at 1 atm of 120° C. or more and 180° C. or less are preferred. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone, ethyl lactate, and ethyl 3-ethoxypropionate are more preferred. The solvent is preferably selected from the group consisting of ether solvents and ether ester solvents, more preferably an ether ester solvent.

[0135] The content of the solvent (E) is preferably 70 to 95 mass%, more preferably 75 to 92 mass%, based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30 mass%, more preferably 8 to 25 mass%. When the content of the solvent (E) is within the above range, the flatness during coating is good, and the color density is not insufficient when a color filter is formed, so that the display characteristics and sensitivity tend to be good.

[0136] <Leveling Agent (F)> Examples of the leveling agent (F) include silicone surfactants, fluorine surfactants, and silicone surfactants containing fluorine atoms, which may have a polymerizable group in the side chain.

[0137] Examples of silicone surfactants include surfactants having a siloxane bond in the molecule, such as Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (trade names: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), and TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan, LLC).

[0138] Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule, such as Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, and RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by AGC Corporation (formerly Asahi Glass Co., Ltd.)), and E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.).

[0139] Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, such as Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

[0140] The content of the leveling agent (F) is preferably 0.001 to 0.2 mass%, more preferably 0.002 to 0.1 mass%, and even more preferably 0.005 to 0.05 mass%, of the total amount of the colored curable resin composition. Note that this content does not include the content of the dispersant described below. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0141] <Other ingredients> The colored curable resin composition may contain additives known in the technical field, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, as needed.

[0142] <Method for producing colored curable resin composition> The colored curable resin composition can be prepared, for example, by mixing the compound (I) as the colorant (A), the resin (B), the polymerizable compound (C), and the polymerization initiator (D), as well as the colorant (A1), the solvent (E), the leveling agent (F), the polymerization initiation aid (D1), and other components that are used as needed. The mixing can be carried out using known or conventional equipment and conditions.

[0143] The colored curable resin composition may be prepared using a dispersion composition prepared in advance. In this case, the dispersion composition prepared in advance may contain a colorant (A1) (particularly a pigment) in addition to the compound (I). Alternatively, a dispersion composition containing a colorant (A1) (particularly a pigment) and a dispersant without containing the compound (I) may be prepared in advance. The dispersion composition prepared in advance may further contain part or all of the solvent (E) and part or all of the resin (B) in the colored curable resin composition. When the dispersion composition contains the solvent (E), it can be used as a dispersion liquid in which the compound (I) and / or the pigment are uniformly dispersed in the solution by performing a dispersion treatment such as mixing. The target colored curable resin composition can be easily prepared by mixing the remaining components with such a dispersion liquid to a predetermined concentration. The compound (I) and the pigment may be dispersed individually or in a mixture of multiple types.

[0144] Examples of dispersants include surfactants, which may be cationic, anionic, nonionic, or amphoteric. Specific examples include polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. Examples of dispersants by trade name include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLORENE (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Corporation), EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark), and BYK (registered trademark) (manufactured by BYK-Chemie).

[0145] The content of compound (I) and / or pigment (particularly the content of compound (I)) in the dispersion composition (dispersion) is preferably 1 to 90 mass %, more preferably 3 to 80 mass %, even more preferably 5 to 70 mass %, and even more preferably 10 to 60 mass %, of the total amount of solids. When the content of compound (I) and / or pigment (particularly the content of compound (I)) is within the above range, a dispersion composition (dispersion) in a uniformly dispersed state tends to be obtained.

[0146] The content of the solvent (E) is preferably 40 to 99 mass%, more preferably 50 to 95 mass%, and even more preferably 55 to 93 mass%, based on the total amount of the dispersion composition (dispersion). In other words, the solid content of the dispersion composition (dispersion) is preferably 1 to 60 mass%, more preferably 5 to 50 mass%, and even more preferably 7 to 45 mass%. When the content of the solvent (E) is within the above range, a dispersion composition (dispersion) in a uniformly dispersed state tends to be obtained.

[0147] The content of the dispersant is preferably 1 to 150 parts by mass, more preferably 10 to 100 parts by mass, and even more preferably 20 to 90 parts by mass, relative to 100 parts by mass of the total of Compound (I) and pigment in the dispersion composition (dispersion). When the content of the dispersant is within the above range, a dispersion composition (dispersion) in a uniformly dispersed state tends to be obtained.

[0148] Compound (I) and the pigment may be used in a state where they are dispersed in a dispersion liquid using a bead mill or the like until the average particle size becomes about 0.2 μm or less. When a bead mill is used, the diameter of the beads is preferably 0.05 mm or more and 0.5 mm or less, and the material of the beads may be glass, ceramic, metal, or the like.

[0149] When the colorant (A) contains a dye, the dye may be dissolved in advance in a part or all of the solvent (E) in the colored curable resin composition to prepare a solution, which is then preferably filtered through a filter having a pore size of about 0.01 to 1 μm.

[0150] <Color filter manufacturing method> Methods for producing a colored pattern of a color filter from a colored curable resin composition include photolithography, inkjet printing, and printing. Among these, photolithography is preferred. The photolithography is a method in which the colored curable resin composition is applied to a substrate, dried to form a composition layer, and then exposed to light through a photomask and developed. In the photolithography, a colored coating film, which is a cured product of the composition layer, can be formed by not using a photomask during exposure and / or not developing.

[0151] The film thickness of the color filter (cured film) is not particularly limited and can be adjusted appropriately depending on the purpose, use, etc., and is, for example, 30 μm or less, preferably 20 μm or less, more preferably 10 μm or less, even more preferably 6 μm or less, still more preferably 3 μm or less, even more preferably 1.5 μm or less, and preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0152] The substrate may be a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, or silica-coated soda lime glass; a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate; silicon; or a substrate having a thin film of aluminum, silver, or a silver / copper / palladium alloy formed thereon. A separate color filter layer, a resin layer, a transistor, a circuit, or the like may be formed on these substrates. Alternatively, a silicon substrate treated with HMDS may be used.

[0153] Formation of colored coating films and colored patterns by photolithography can be carried out using known or conventional equipment and conditions. For example, they can be produced as follows. First, a colored resin composition is applied to a substrate, and then the composition is dried by heating and drying (pre-baking) and / or drying under reduced pressure to remove volatile components such as solvents and obtain a smooth composition layer. Examples of coating methods include spin coating, slit coating, and slit and spin coating. When drying by heating, the temperature is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When drying under reduced pressure, the temperature is preferably 20 to 25°C under a pressure of 50 to 150 Pa. The film thickness of the composition layer is not particularly limited and may be appropriately selected depending on the film thickness of the desired color filter.

[0154] Next, the composition layer is exposed through a photomask to form a desired color pattern. The pattern on the photomask is not particularly limited, and a pattern appropriate for the intended application is used. The light source used for exposure is preferably a light source that emits light with a wavelength of 250 to 450 nm. For example, light less than 250 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, or 365 nm may be selectively extracted using a bandpass filter that extracts these wavelength ranges. Specific examples include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps. It is preferable to use a reduction projection exposure device or proximity exposure device such as a mask aligner or stepper, as this allows for uniform irradiation of the entire exposure surface with parallel light and allows for accurate alignment of the photomask and substrate.

[0155] A colored pattern is formed on the substrate by bringing the exposed composition layer into contact with a developer and developing it. The unexposed portions of the composition layer are dissolved and removed by development. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may also contain a surfactant. The development method may be any of a puddle method, a dipping method, a spray method, or the like. Furthermore, the substrate may be tilted at any angle during development. After development, it is preferable to wash with water.

[0156] Furthermore, it is preferable to post-bake the obtained colored pattern or colored coating film. The post-bake temperature is preferably 80 to 250° C., more preferably 100 to 245° C. The post-bake time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes.

[0157] The colored patterns and colored coating films thus obtained are useful as color filters, and can be suitably used as color filters for displays (e.g., liquid crystal displays, organic EL devices, etc.), electronic paper, solid-state imaging devices, etc. [Example]

[0158] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples. In the examples, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".

[0159] (Colorant Synthesis Example 1) A compound represented by the following formula (X) was produced according to the description of Synthesis Example 1 of WO 2020 / 171060.

[0160] [ka]

[0161] (Colorant Synthesis Example 2) A compound represented by the following formula (Y) was produced according to the description in Example 1 of JP-A-2014-125460.

[0162] [ka]

[0163] (Resin synthesis example 1) <Preparation of Resin (B-1)> 276.8 parts of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred and heated to 120°C while purging with nitrogen. Next, a monomer mixture consisting of 92.4 parts of 2-ethylhexyl acrylate, 184.9 parts of glycidyl methacrylate, and 12.3 parts of dicyclopentanyl methacrylate, to which 35.3 parts of t-butylperoxy-2-ethylhexanoate (polymerization initiator) had been added, was added dropwise from the dropping funnel to the flask over 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes at 120°C to carry out the copolymerization reaction, producing an addition copolymer. The flask was then purged with air, and 93.7 parts of acrylic acid, 1.5 parts of triphenylphosphine (catalyst), and 0.8 parts of methoquinone (polymerization inhibitor) were added to the addition copolymer solution. The reaction was continued at 110°C for 10 hours. The epoxy groups derived from glycidyl methacrylate reacted with the acrylic acid, cleaving the epoxy groups and simultaneously introducing polymerizable unsaturated bonds into the polymer side chains. Next, 24.2 parts of succinic anhydride were added to the reaction system, and the reaction was continued at 110°C for 1 hour. The hydroxyl groups generated by the cleavage of the epoxy groups reacted with the succinic anhydride, introducing carboxyl groups into the side chains, yielding a polymer. Finally, 383.3 parts of propylene glycol monomethyl ether acetate was added to the reaction solution, yielding a polymer (Resin (B-1)) solution with a polymer solids content of 40%. The weight-average molecular weight Mw of the resulting copolymer (Polymer; Resin (B-1)) was 6.3 x 10 3 The acid value calculated as solid content was 34 mg-KOH / g. Resin (B-1) has the following structural units.

[0164] [ka]

[0165] (Resin synthesis example 2) <Preparation of Resin (B-2)> A flask equipped with a reflux condenser, a dropping funnel, and a stirrer was purged with nitrogen in an appropriate amount, and 371 parts of propylene glycol monomethyl ether acetate was added, followed by heating to 85°C with stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0] 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 A mixture of 225 parts of a mixture of decan-9-yl acrylate (trade name "E-DCPA," manufactured by Daicel Corporation), 81 parts of vinyltoluene (isomer mixture), and 80 parts of 1-methoxy-2-propyl acetate was added dropwise over 4 hours. Meanwhile, a solution of 30 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the initiator solution was added dropwise, the mixture was held at the same temperature for 4 hours, then cooled to room temperature. The viscosity measured by Brookfield viscometer (23°C) was 246 mPa·s. The solids content of the resin (B-2) solution was 37.5%, and the acid value calculated as solids was 115 mg-KOH / g. The weight-average molecular weight (Mw) of the resulting copolymer was 10,600, and the molecular weight distribution (Mw / Mn) was 2.01. Resin (B-2) has the following structural units:

[0166] [ka]

[0167] (Resin synthesis example 3) <Preparation of Resin (B-3)> Into a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 547 parts of propylene glycol monomethyl ether acetate was added, and the mixture was stirred while replacing the atmosphere with nitrogen and heated to 120°C. Next, a monomer mixture of 272 parts of benzyl methacrylate and 73.8 parts of methacrylic acid, to which 4.2 parts of t-butylperoxy-2-ethylhexanoate had been added, was added dropwise from the dropping funnel to the flask over 2 hours. After the dropwise addition, the mixture was stirred for an additional 30 minutes to carry out the copolymerization reaction, yielding a polymer. Propylene glycol monomethyl ether acetate was added to the reaction solution to a polymer solids concentration of 35%, yielding a polymer solution (Resin (B-3)).

[0168] (Dispersion Preparation Example 1) <Preparation of Dispersion Liquid (A-1)> 15.0 parts of CI Pigment Green 58, 3.0 parts of a dispersant (BYK BYKLPN-6919), 3.8 parts of resin (B-1) (solid content equivalent), and 78.2 parts of propylene glycol monomethyl ether acetate were mixed, to which 300 parts of 0.4 mm zirconia beads were added, followed by shaking for 1 hour using a paint conditioner (LAU). The zirconia beads were then removed by filtration to obtain dispersion (A-1).

[0169] (Dispersion Preparation Example 2) <Preparation of Dispersion Liquid (A-2)> 10.0 parts of CI Pigment Yellow 185, 4.0 parts of a dispersant (BYK BYKLPN-6919), 3.0 parts of resin (B-1) (solid content equivalent), and 83.0 parts of propylene glycol monomethyl ether acetate were mixed, to which 300 parts of 0.4 mm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (LAU). The zirconia beads were then removed by filtration to obtain dispersion (A-2).

[0170] (Dispersion Preparation Example 3) <Preparation of Dispersion Liquid (A-3)> 15.0 parts of CI Pigment Yellow 138, 3.0 parts of a dispersant (BYK BYKLPN-6919), 6.0 parts of resin (B-1) (solid content equivalent), and 76.0 parts of propylene glycol monomethyl ether acetate were mixed, to which 300 parts of 0.4 mm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (LAU). The zirconia beads were then removed by filtration to obtain dispersion (A-3).

[0171] [Example 1, Comparative Example 1, Comparative Example 2] (Preparation of Colored Curable Resin Composition) The components shown in Table 1 were mixed to obtain each colored curable resin composition.

[0172] [Table 1]

[0173] <Colorant (A)> Compound (X): The compound represented by formula (X) prepared in Colorant Synthesis Example 1 Compound (Y): Compound represented by formula (Y) prepared in Colorant Synthesis Example 2 Dispersion (A-1): Dispersion (A-1) prepared in Dispersion Preparation Example 1 Dispersion (A-2): Dispersion (A-2) prepared in Dispersion Preparation Example 2 Dispersion (A-3): Dispersion (A-3) prepared in Dispersion Preparation Example 3 <Resin (B)> Resin (B-1): Resin (B-1) prepared in Resin Synthesis Example 1 (solid content equivalent) Resin (B-2): Resin (B-2) prepared in Resin Synthesis Example 2 (solid content equivalent) <Polymerizable compound (C)> Polymerizable compound (C-1): Ethylene oxide-modified dipentaerythritol hexaacrylate (A-DPH12E, manufactured by Shin-Nakamura Chemical Co., Ltd., solid content equivalent) <Polymerization initiator (D)> Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.: trade name "PBG-327") <Leveling Agent (E)> Leveling agent (E-1): Polyether-modified silicone oil (Toray Silicone SH8400 manufactured by Toray Dow Corning Co., Ltd., solid content equivalent) <Solvent (F)> Solvent (F-1): Propylene glycol monomethyl ether acetate

[0174] (Production of colored patterns) A colored curable resin composition was applied by spin coating onto a 5 cm square glass substrate (Eagle 2000; Corning Incorporated) so that the film thickness after post-baking would be 0.8 μm, and then pre-baked at 90°C for 2 minutes to obtain a colored composition layer. After cooling, the coating was exposed to 60 mJ / cm 2 in an air atmosphere using an exposure machine (TME-150RSK; Topcon Corporation). 2 The colored composition layer was irradiated with light at an exposure dose (365 nm standard) of 1000 kJ / cm2. The colored composition layer after light irradiation was immersed and developed in an aqueous developer containing tetramethylammonium hydroxide at 23°C for 30 seconds, washed with water, and then post-baked at 230°C for 5 minutes to obtain a colored pattern (color filter).

[0175] (Evaluation of surface roughness of colored patterns) The colored film formed on the glass substrate having the colored pattern obtained above was observed from above at 10x magnification using a laser microscope (OLS-4100, manufactured by OLYMPUS Corporation), and an image of 1024 pixels wide and 1024 pixels high was obtained. The obtained image was converted to grayscale, and the brightness distribution of each pixel was output as a histogram. The histogram of each image was approximated with a Gaussian function, and the half-width was evaluated as surface roughness. The larger the surface roughness value, the greater the variation in sensitivity of each pixel when mounted on an image sensor. It was found that Example 1 was better than Comparative Example 1, which was 6.0, and Comparative Example 2, which was 12.8.

[0176] [Table 2]

[0177] Example 1 The colored curable resin composition obtained in Example 1 was evaluated for heat resistance.

[0178] (Heat resistance evaluation) The colored pattern on the glass substrate was measured for spectroscopy using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). After heating in an oven at 260°C for 10 minutes, the same spot was measured for spectroscopy to evaluate the change in the spectrum. Using the characteristic function of the C illuminant, the color difference △E is calculated using the method described in JIS Z 8730:2009 (7. Calculation method of color difference). * ab was calculated and the results are shown in Table 3. △E * The smaller ab is, the smaller the color change is.

[0179] [Table 3]

Claims

1. The composition includes a colorant, a resin, a polymerizable compound, and a polymerization initiator, The colorant comprises a compound represented by formula (I): the resin comprises a resin (B1) containing a structural unit derived from a monomer having an ethylenically unsaturated bond and an epoxy group, The colored curable resin composition is characterized in that the content of the structural unit is 3 to 50 mol % based on all structural units of the resin (B1). 【Chemical 1】 [In formula (I), A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 each independently represents a hydrogen atom or a halogen atom, A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 each independently represents a hydrogen atom, a halogen atom, or a group represented by the following formula (II), A 2 , A 3 , A 6 , A 7 , A 10 , A 11 , A 14 , and A 15 At least one of the groups represents a group represented by the following formula (II): 【Chemistry 2】 [In formula (II), X represents a divalent group, R represents a monovalent substituent, and n represents an integer of 0 to 5.

2. A 1 , A 4 , A 5 , A 8 , A 9 , A 12 , A 13 , and A 16 The colored curable resin composition according to claim 1, wherein at least one of the following represents a halogen atom.

3. 3. The colored curable resin composition according to claim 1, wherein the resin has an acid value of 90 mg KOH / g or more.

4. 3. The colored curable resin composition according to claim 1, wherein the content of the resin containing a structural unit derived from a monomer having an ethylenically unsaturated bond and an epoxy group is 50% by mass or more of the total resin.

5. 3. The colored curable resin composition according to claim 1, further comprising a solvent selected from the group consisting of ether solvents and ether ester solvents.

6. A color filter formed from the colored curable resin composition according to claim 1 or 2.

7. A display device comprising the color filter according to claim 6.

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