Xanthene dye, colored curable resin composition, color filter, display device, solid-state imaging element, and method for producing xanthene dye

Abstract

To provide a xanthene dye and a colored curable resin composition that enable formation of a color filter with enhanced thermal resistance, and to provide a method for producing a xanthene dye enabling formation of a color filter with enhanced thermal resistance.SOLUTION: A xanthene dye has a specific crystal structure determined by powder X-ray diffraction with CuKα radiation, such as a dye expressed by formula (Ia1).SELECTED DRAWING: Figure 2

Description

[Technical Field]

[0001] The present invention relates to a xanthene dye, a colored curable resin composition containing the xanthene dye, a color filter formed from the colored curable resin composition, a display device and a solid-state imaging device each including the color filter, and a method for producing the xanthene dye. [Background technology]

[0002] As a xanthene dye contained in a colored curable resin composition used for forming a color filter, for example, a compound described in Patent Document 1 is known. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 2017-226814 Summary of the Invention [Problem to be solved by the invention]

[0004] When a xanthene dye is used as a colorant in a colored curable resin composition capable of forming color filters used in displays such as liquid crystal displays, electroluminescent displays, and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors, using a conventional xanthene dye such as the xanthene compound described in Patent Document 1 may result in the color filter formed having insufficient heat resistance. Therefore, an object of the present invention is to provide a xanthene dye and a colored curable resin composition capable of forming a color filter with improved heat resistance. Another object of the present invention is to provide a method for producing a xanthene dye capable of forming a color filter with improved heat resistance. [Means for solving the problem]

[0005] The gist of the present invention is as follows. [1] In the powder X-ray diffraction pattern using CuKα radiation at a diffraction angle (2θ±0.2°) of 2 to 40°, When the maximum intensity of the diffraction peaks in the range of 21.0 to 22.1° is taken as 1.0, the maximum intensity A1 of the diffraction peaks in the range of 5 to 20° is 1.3 or more, At least one diffraction peak exists in the range of 3 to 7 degrees. A xanthene dye represented by the following formula (I): [ka] [In formula (I), R 1 ~R 4 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, or -NR 11 - may be replaced by R 1 and R 2 may be bonded to each other to form a ring containing the nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring containing the nitrogen atom. R 5 -OH, -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , -CO2R 8 , -SO3R 8 , or -SO2NR 9 R 10 Represents. R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents 0 or 1. a represents 0 or 1. X represents a halogen atom. Z + teeth, + N(R12 )4, Na + , or K + represents the four R's 12 may be the same or different. R 8 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, -NH-, or -NR 8 - may be replaced by R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. R 11 and R 12 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. [2] In the powder X-ray diffraction pattern using CuKα radiation at a diffraction angle (2θ±0.2°) of 2 to 40°, The xanthene dye according to [1], wherein a diffraction peak with maximum intensity in the range of 2 to 22° exists in the range of 5 to 18°. [3] In the powder X-ray diffraction pattern using CuKα radiation at a diffraction angle (2θ±0.2°) of 2 to 40°, The xanthene dye according to [1] or [2], wherein, when the maximum intensity of the diffraction peak in the range of 21.0 to 22.1° is taken as 1.0, the maximum intensity A2 of the diffraction peak in the range of 13.5 to 15.2° is 0.3 or more, and the maximum intensity A3 of the diffraction peak in the range of 8 to 10° is 0.1 or more. [4] In the powder X-ray diffraction pattern using CuKα radiation at diffraction angles (2θ±0.2°) = 2 to 40°, When the maximum intensity of the diffraction peaks in the range of 3 to 7 degrees is taken as 1.0, the maximum intensity A4 of the diffraction peaks in the range of 13 to 20 degrees is 1.0 or less, The xanthene dye according to any one of [1] to [3], wherein a diffraction peak with maximum intensity in the range of 2 to 22° exists in the range of 14 to 18°. [5] In the powder X-ray diffraction pattern using CuKα radiation at diffraction angles (2θ±0.2°) = 2 to 40°, The xanthene dye according to any one of [1] to [4], which has one diffraction peak in the range of 3 to 7 degrees. [6] A colored curable resin composition comprising the xanthene dye according to any one of [1] to [5], a resin, a polymerizable compound, a polymerization initiator, and a solvent. [7] A color filter comprising the colored curable resin composition according to [6]. [8] A display device comprising the color filter according to [7]. [9] A solid-state imaging device comprising the color filter according to [7].

[10] A method for producing a xanthene dye represented by the following formula (I), comprising: a contacting step of stirring a xanthene dye represented by the following formula (I) in a solvent containing at least one selected from the group consisting of an alcohol having 3 to 6 carbon atoms, an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, an alkylene glycol monoalkyl ether, and an alkylene glycol monoalkyl ether acetate while maintaining the xanthene dye in a precipitated state; and a separation step of extracting the xanthene dye by solid-liquid separation: In the contacting step, the total content of the alcohol having 3 to 6 carbon atoms, the aromatic hydrocarbon solvent having 6 to 9 carbon atoms, the alkylene glycol monoalkyl ether, and the alkylene glycol monoalkyl ether acetate is 60 mass% or more of the total solvent. [ka] [In formula (I), R 1 ~R 4 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, or -NR 11 - may be replaced by R1 and R 2 may be bonded to each other to form a ring containing the nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring containing the nitrogen atom. R 5 -OH, -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , -CO2R 8 , -SO3R 8 , or -SO2NR 9 R 10 Represents. R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents 0 or 1. a represents 0 or 1. X represents a halogen atom. Z + teeth, + N(R 12 )4, Na + , or K + represents the four R's 12 may be the same or different. R 8 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, -NH-, or -NR 8 - may be replaced by R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. R 11 and R 12 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. [Effects of the Invention]

[0006] According to the present invention, it is possible to provide a xanthene dye and a colored curable resin composition capable of forming a color filter having good heat resistance. Furthermore, according to the present invention, a new method for producing a xanthene dye capable of forming a color filter having good heat resistance is provided. [Brief explanation of the drawings]

[0007] [Figure 1] FIG. 1 shows the powder X-ray diffraction pattern (spectrum) of the xanthene dye (Ia1) obtained in Synthesis Example 1, and an enlarged view of a part of the pattern. [Figure 2] FIG. 2 shows the powder X-ray diffraction pattern of the xanthene dye (Ia1-1) obtained in Example 1, and an enlarged view of a part of the pattern. [Figure 3] FIG. 3 shows the powder X-ray diffraction pattern of the xanthene dye (Ia1-2) obtained in Example 2, and an enlarged view of a part of the pattern. [Figure 4] FIG. 4 shows the powder X-ray diffraction pattern of the xanthene dye (Ia1-3) obtained in Example 3, and an enlarged view of a part of the pattern. [Figure 5] FIG. 5 shows the powder X-ray diffraction pattern of the xanthene dye (Ia1-4) obtained in Example 4, and an enlarged view of a part of the pattern. DETAILED DESCRIPTION OF THE INVENTION

[0008] <Xanthene dyes> The xanthene dye of the present invention has a predetermined chemical structure represented by the following formula (I) and also has a predetermined crystalline structure. A xanthene dye exhibiting the predetermined chemical structure and crystalline structure (hereinafter also referred to as xanthene dye (I)) can be used to form a color filter with good heat resistance. In a preferred embodiment, a color filter with good solvent resistance and / or light resistance in addition to heat resistance can be formed.

[0009] [ka] [In formula (I), R 1 ~R 4 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, or -NR 11 - may be replaced by R 1 and R 2 may be bonded to each other to form a ring containing the nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring containing the nitrogen atom. R 5 -OH, -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , -CO2R 8 , -SO3R 8 , or -SO2NR 9 R 10 Represents. R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents 0 or 1. a represents 0 or 1. X represents a halogen atom. Z + teeth, + N(R 12 )4, Na + , or K + represents the four R's 12 may be the same or different. R 8 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and -CH2- contained in the saturated hydrocarbon group is -O-, -CO-, -NH-, or -NR 8 - may be replaced by R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. R 11 and R 12 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

[0010] R 1 ~R 4 and R 8 ~R 12 Examples of saturated hydrocarbon groups having 1 to 20 carbon atoms represented by the formula (I) include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 15, more preferably 1 to 12, and even more preferably 1 to 10. R 1 ~R 4 -CH2- contained in the saturated hydrocarbon group having 1 to 20 carbon atoms represented by the formula: 11 - may be replaced.

[0011] R 1 ~R 4Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by the formula (I) include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2-ethylphenyl group, a 3-ethylphenyl group, a 4-ethylphenyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5-dimethylphenyl group, a 2,6-dimethylphenyl group, a 3,4-dimethylphenyl group, a 3,5-dimethylphenyl group, a 4-vinylphenyl group, an o-isopropylphenyl group, an m-isopropylphenyl group, a p-isopropylphenyl group, an o-tert-butylphenyl group, an m-tert-butylphenyl group, a p-tert-butylphenyl group, a 3,5-di(tert-butyl)phenyl group, a 3,5-di(tert-butyl)-4 Examples of such aromatic hydrocarbon groups include 1-methylphenyl, 4-butylphenyl, 4-pentylphenyl, 2,6-bis(1-methylethyl)phenyl, 2,4,6-tris(1-methylethyl)phenyl, 4-cyclohexylphenyl, 2,4,6-trimethylphenyl, 4-octylphenyl, 4-(1,1,3,3-tetramethylbutyl)phenyl, 1-naphthyl, 2-naphthyl, 6-methyl-2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, 5,6,7,8-tetrahydro-2-naphthyl, fluorenyl, phenanthryl, anthryl, 2-dodecylphenyl, 3-dodecylphenyl, 4-dodecylphenyl, perylenyl, chrysenyl, and pyrenyl groups. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 12, and even more preferably 6 to 10. The aromatic hydrocarbon group is preferably a dialkylphenyl group, more preferably a dimethylphenyl group or a diethylphenyl group, even more preferably a dimethylphenyl group, and even more preferably a 2,6-dimethylphenyl group.

[0012] R 1 ~R 4 Examples of the substituent that may be possessed by the saturated hydrocarbon group having 1 to 20 carbon atoms or the aromatic hydrocarbon group having 6 to 20 carbon atoms represented by the formula (I) include a halogen atom, —OH, —OR 8 , -SO3 - , -SO3H, -SO3 - Z +, -CO2H, -CO2 - Z + , -CO2R 8 , -SR 8 , -SO2R 8 , -SO3R 8 , -SO2NR 9 R 10 (R 8 , Z + , R 9 , R 10 (The meaning of -SO3 is the same as above.) - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , and -SO2NR 9 R 10 At least one selected from the group consisting of -SO3 - Z + , -CO2H, -CO2 - Z + , and -SO2NR 9 R 10 At least one selected from the group consisting of -CO2H and -CO2 - Z + More preferably, at least one selected from the group consisting of:

[0013] R 1 ~R 4 The saturated hydrocarbon group having 1 to 20 carbon atoms represented by the formula: - Z + As a substituent, the saturated hydrocarbon group preferably has a hydrogen atom bonded to the terminal carbon atom (primary carbon atom) of -CO2H or -CO2 - Z + It is more preferred that it is substituted with -CO2H, and even more preferred that it is substituted with -CO2H.

[0014] R 1 and R 2 may combine with the nitrogen atom to form a ring containing the nitrogen atom, and R 3 and R4 may combine with the nitrogen atom to form a ring containing a nitrogen atom. Examples of the ring containing a nitrogen atom include the following.

[0015] [ka]

[0016] -OR 8 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group, and an icosyloxy group.

[0017] -CO2R 8 Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

[0018] -SR 8 Examples of the sulfanyl group include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.

[0019] -SO2R 8 Examples of the sulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

[0020] -SO3R 8 Examples of the sulfonyl group include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

[0021] -SO2NR 9 R 10 For example, sulfamoyl group; N-Methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N-(1-ethylpropyl)sulfamoyl group, N-(1,1-dimethylpropyl)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-1-substituted sulfamoyl groups such as a sulfamoyl group, an N-(3-methylbutyl)sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, an N-(1,3-dimethylbutyl)sulfamoyl group, an N-(3,3-dimethylbutyl)sulfamoyl group, an N-heptylsulfamoyl group, an N-(1-methylhexyl)sulfamoyl group, an N-(1,4-dimethylpentyl)sulfamoyl group, an N-octylsulfamoyl group, an N-(2-ethylhexyl)sulfamoyl group, an N-(1,5-dimethyl)hexylsulfamoyl group, and an N-(1,1,2,2-tetramethylbutyl)sulfamoyl group; N,N-disubstituted sulfamoyl groups such as N,N-dimethylsulfamoyl group, N,N-ethylmethylsulfamoyl group, N,N-diethylsulfamoyl group, N,N-propylmethylsulfamoyl group, N,N-isopropylmethylsulfamoyl group, N,N-tert-butylmethylsulfamoyl group, N,N-butylethylsulfamoyl group, N,N-bis(1-methylpropyl)sulfamoyl group, and N,N-heptylmethylsulfamoyl group.

[0022] R 9 and R 10 Examples of the substituent that the saturated hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) may have include -OH and a halogen atom, and -CH2- contained in the saturated hydrocarbon group can be -O-, -CO-, -NH-, or -NR 8 - may be replaced.

[0023] R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring together with the nitrogen atom. Examples of such heterocyclic rings include the following.

[0024] [ka]

[0025] R 5 As for -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , and -SO2NR 9 R 10 At least one selected from the group consisting of -SO3 - , -SO3 - Z + , -CO2H, -CO2 - Z + , and -SO2NR 9 R 10 More preferably, at least one selected from the group consisting of -SO3 - , -SO3 - Z + , and -SO2NR 9 R 10 More preferably, at least one selected from the group consisting of -SO3 - is even more preferred.

[0026] R 6 and R 7 Examples of the alkyl group having 1 to 6 carbon atoms and represented by the formula (R) include the linear alkyl groups and branched alkyl groups listed above, which have 1 to 6 carbon atoms. 6 , R 7 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and particularly preferably a hydrogen atom.

[0027] R 11 and R12 Examples of the aralkyl group having 7 to 10 carbon atoms represented by the following formula include a benzyl group, a phenylethyl group, and a phenylbutyl group.

[0028] Z + teeth, + N(R 12 )4, Na + , or K + and preferably + N(R 12 )4. + N(R 12 )4 is the four R 12 At least two of these groups are preferably saturated hydrocarbon groups having 5 to 20 carbon atoms.

[0029] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom, a chlorine atom, or a bromine atom is preferred.

[0030] m is 0 or 1, and more preferably 1. a is 0 or 1, and more preferably 0.

[0031] The xanthene dye (I) preferably has a chemical structure represented by the following formula (Ia).

[0032] [ka] [In formula (Ia), R 11 and R 14 each independently represents an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms, or an alkylsulfonyl group having 1 to 4 carbon atoms, R 12 and R 13 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent, R 11 and R 12 may combine with the nitrogen atom to form a ring containing the nitrogen atom, and R 13and R 14 may be combined with the nitrogen atom to form a ring containing the nitrogen atom. p and q each independently represent an integer of 0 to 5, and when p is an integer of 2 or more, a plurality of R 11 may be the same or different, and when q is 2 or more, a plurality of R 14 may be the same or different.]

[0033] R 11 and R 14 Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.

[0034] R 11 and R 14 Examples of the alkylsulfanyl group having 1 to 4 carbon atoms represented by the formula (I) include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.

[0035] R 11 and R 14 Examples of the alkylsulfonyl group having 1 to 4 carbon atoms represented by the formula (I) include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.

[0036] R 11 and R 14 are each independently preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group.

[0037] p and q are each independently preferably an integer of 0 to 4, more preferably an integer of 1 to 4, further preferably 1 or 2, and even more preferably 2. When p and q are 2, two R 11 or two R's 14 is R 11 or R 14is preferably bonded at the ortho position relative to the bond of the phenyl group to which it is bonded.

[0038] R 12 and R 13 Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; and branched alkyl groups such as an isopropyl group, an isobutyl group, an isopentyl group, and a neopentyl group.

[0039] R 12 and R 13 As the alkyl group, a linear alkyl group having 1 to 6 carbon atoms is preferred, and a linear alkyl group having 2 to 4 carbon atoms is more preferred.

[0040] R 12 and R 13 Examples of the substituent that the alkyl group having 1 to 6 carbon atoms represented by the formula (I) may have include a halogen atom, —OH, —OR 8 , -SO3 - , -SO3H, -SO3 - Z + , -CO2H, -CO2 - Z + , -CO2R 8 , -SR 8 , -SO2R 8 , -SO3R 8 , -SO2NR 9 R 10 (R 8 , Z + , R 9 , R 10 (The meanings are the same as above.) Among these substituents, -CO2H, -CO2 - Z + , and -CO2R 8 At least one selected from the group consisting of -CO2H and -CO2R is preferred. 8 More preferred is at least one selected from the group consisting of:

[0041] R 11 and R 12may combine with the nitrogen atom to form a ring containing the nitrogen atom, and R 13 and R 14 may combine with the nitrogen atom to form a ring containing a nitrogen atom. Examples of the ring containing a nitrogen atom include the following.

[0042] [ka]

[0043] In formula (Ia), R 11 and R 14 are each independently preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and even more preferably a methyl group; R 12 and R 13 are, independently of each other, -CO2H or -CO2R 8 is preferably an alkyl group having 1 to 6 carbon atoms and having as a substituent -CO2H or -CO2R 8 as a substituent, more preferably a linear alkyl group having 2 to 4 carbon atoms and having —COH as a substituent, and still more preferably a linear alkyl group having 2 to 4 carbon atoms and having —COH as a substituent, p and q are each independently preferably 1 or 2, more preferably 2; -SO3 bonded to phenyl group - is preferably bonded at the ortho position relative to the bond of the phenyl group.

[0044] As the chemical structure represented by formula (Ia), the chemical structure represented by the following formula (Ia1) is particularly preferred.

[0045] [ka]

[0046] The crystal structure of the xanthene dye is identified by powder X-ray diffraction. Specifically, the xanthene dye (I) of the present invention has a crystal structure in which, when the maximum intensity of the diffraction peaks in the range of 21.0 to 22.1° is taken as 1.0, the maximum intensity A1 of the diffraction peaks in the range of 5 to 20° is 1.3 or more, and at least one diffraction peak exists in the range of 3 to 7°, in a diffraction pattern at a diffraction angle (2θ±0.2°) of 2 to 40° obtained by powder X-ray diffraction using CuKα radiation. A xanthene dye (I) having this crystal structure can form a color filter having good heat resistance. Furthermore, according to a preferred embodiment of the xanthene dye (I) of the present invention, a color filter having good light resistance and / or solvent resistance in addition to heat resistance can be formed. In the present invention, the color filter having good heat resistance, light resistance, or solvent resistance is said to be excellent in terms of the color difference (ΔE * The diffraction peak in the present invention preferably exhibits a diffraction peak with a half-width of 3.0° or less, and more preferably exhibits a diffraction peak with a half-width of 2.0° or less.

[0047] In the powder X-ray diffraction analysis of the present invention, CuKα rays (1.5418 Å) from the anticathode are used as the X-ray source.

[0048] From the viewpoint of heat resistance and / or solvent resistance, the maximum strength A1 is preferably 1.4 or more, more preferably 1.5 or more, even more preferably 1.6 or more, even more preferably 1.7 or more, and even more preferably 2.0 or more, and is preferably 5.0 or less, more preferably 4.0 or less, even more preferably 3.5 or less, and even more preferably 3.2 or less.

[0049] The number of diffraction peaks present in the range of 3 to 7° in the powder X-ray diffraction pattern may be one or more, but from the viewpoint of solvent resistance, it is preferably three or less, more preferably two or less, and even more preferably one.

[0050] In the diffraction pattern of the powder X-ray diffraction, the diffraction peak with the maximum intensity in the range of 2 to 22° is preferably in the range of 5 to 18° from the viewpoint of heat resistance, preferably in the range of 14 to 18° from the viewpoint of light resistance, and preferably in the range of 5 to 15° from the viewpoint of solvent resistance.

[0051] In the powder X-ray diffraction pattern, when the maximum intensity of the diffraction peaks in the range of 21.0 to 22.1° is taken as 1.0, it is preferable from the viewpoint of heat resistance that the maximum intensity A2 of the diffraction peaks in the range of 13.5 to 15.2° is 0.3 or more, and the maximum intensity A3 of the diffraction peaks in the range of 8 to 10° is 0.1 or more. The maximum strength A2 is more preferably 0.4 or more, further preferably 0.5 or more, and is preferably 4.0 or less, more preferably 3.5 or less, further preferably 3.0 or less. The maximum strength A3 is more preferably 0.15 or more, and even more preferably 0.20 or more, and is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.5 or less.

[0052] In the diffraction pattern of the powder X-ray diffraction, when the maximum intensity of the diffraction peaks in the range of 3 to 7° is set to 1.0, it is preferable from the viewpoint of heat resistance that the maximum intensity A4 of the diffraction peaks in the range of 13 to 20° is 2.0 or less. The maximum intensity A4 is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.3 or more, and from the viewpoint of light resistance, it is more preferably 1.5 or less, more preferably 1.0 or less, and even more preferably 0.9 or less.

[0053] From the viewpoint of heat resistance and light resistance, it is particularly preferable that the xanthene dye (I) has a 2θmax (2 to 22°) in the range of 12 to 18° (preferably in the range of 14 to 18°) and a maximum intensity A4 of 1.5 or less (preferably 1.0 or less).

[0054] In terms of heat resistance, light resistance, and solvent resistance, the xanthene dye (I) preferably has a 2θmax (2 to 22°) in the range of 12 to 18° (preferably in the range of 14 to 18°), one or more diffraction peaks in the range of 3 to 7° (preferably one), a maximum intensity A1 of 1.5 or more (preferably 2.0 or more), a maximum intensity A2 of 0.3 or more (preferably 0.5 or more), a maximum intensity A3 of 0.1 or more (preferably 0.20 or more), and a maximum intensity A4 of 1.5 or less (preferably 1.0 or less).

[0055] When the maximum intensity of the diffraction peaks present in the diffraction angle range (2θ±0.2°) of 2 to 40° in the powder X-ray diffraction is taken as 1.0, the xanthene dye (I) preferably has four or more diffraction peaks, more preferably six or more diffraction peaks, and more preferably 25 or less diffraction peaks, whose relative intensity is 0.01 or more but less than 1.0.

[0056] Examples of the xanthene dye (I) include those having peaks at the following diffraction angles (2θ±0.2°) in the powder X-ray diffraction pattern. Example (i): 6.3°, 7.8°, 8.2°, 10.6°, 12.2°, 14.6°, 14.7°, 15.4°, 15.7°, 16.6°, 17.5°, 18.0°, 18.7°, 19.7°, 20.5°, 21.6°, 22.0°, 23.7°, 24.5°, 25.3°, 27.8°, 28.4° Example (ii): 6.0°, 8.1°, 9.9°, 10.3°, 11.0°, 14.8°, 15.4°, 16.5°, 17.9°, 19.6°, 21.1°, 21.7°, 22.8°, 23.2°, 23.9°, 24.5°, 26.2°, 28.8° Example (iii): 3.5°, 5.5°, 9.2°, 11.1°, 13.0°, 13.9°, 14.3°, 16.4°, 17.8°, 18.3°, 19.6°, 20.5°, 22.5°, 23.0°, 23.7°, 24.5°, 25.1°, 26.4°, 28.2° Example (iv): 6.6°, 6.9°, 7.4°, 9.6°, 10.5°, 11.1°, 12.1°, 12.3°, 13.2°, 13.9°, 14.3°, 14.9°, 15.4°, 15.9°, 17.0°, 17.4°, 18.6°, 19.2°, 19.7°, 20.1°, 20.9°, 21.9°, 22.4°, 24.3°, 25.4°, 26.6°, 27.4°, 27.9°, 28.5°, 28.9°, 30.0°

[0057] The xanthene dye (I) having a predetermined chemical structure and crystal structure can be produced, for example, by treating a xanthene dye having a predetermined chemical structure with a specific solvent to give it a predetermined crystal structure.

[0058] The xanthene dye having a predetermined chemical structure (the chemical structure represented by formula (I)) may be a commercially available xanthene dye, or may be synthesized using a commercially available xanthene dye as a starting material, for example, by referring to the description in JP-A-2017-226814.

[0059] The solvent treatment method includes a contacting step of a xanthene dye having a chemical structure represented by formula (I) in a solvent containing at least one selected from the group consisting of an alcohol having 3 to 6 carbon atoms, an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, an alkylene glycol monoalkyl ether, and an alkylene glycol monoalkyl ether acetate, while maintaining the xanthene dye in a precipitated state, and a separation step of extracting the xanthene dye by solid-liquid separation. The contacting step is characterized in that the total content of the alcohol having 3 to 6 carbon atoms, the aromatic hydrocarbon solvent having 6 to 9 carbon atoms, the alkylene glycol monoalkyl ether, and the alkylene glycol monoalkyl ether acetate is 60 mass% or more of the total solvent. The xanthene dye used in the contacting step may have the chemical structure represented by formula (I), and may be a single dye consisting of one xanthene dye or a mixed dye containing two or more xanthene dyes. Furthermore, the xanthene dye used in the contacting step is preferably amorphous. As shown in FIG. 1, for example, amorphous is one that does not have a clear diffraction peak in X-ray measurement (particularly, a diffraction peak with a half-value width of 3.0° or less).

[0060] A xanthene dye (I) having a predetermined crystal structure (i.e., a predetermined diffraction pattern) can be obtained by contacting a xanthene dye having a specific chemical structure (particularly, a xanthene dye having a specific chemical structure and an amorphous structure) with a solvent of a specific composition while maintaining the dye in a precipitated state. Furthermore, by changing the type and / or content of the solvent used in the contacting step within the above range, it is possible to produce and select different crystal structures within a predetermined range.

[0061] The alcohol having 3 to 6 carbon atoms in the contacting step is a solvent having 3 to 6 carbon atoms and containing one or more -OH groups in the molecule but not -O-. The alcohol having 3 to 6 carbon atoms may contain -CO- and / or -COO- in the molecule. The number of -OH groups that the alcohol having 3 to 6 carbon atoms has is preferably 1 to 3, more preferably 1 or 2, and even more preferably 1. Examples of alcohols having 3 to 6 carbon atoms include alcohols that contain -OH but do not contain -CO- or -COO-, such as 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-methyl-1-butanol, 2-methyl-1-butanol, 2-methyl-2-butanol, 2,2-dimethyl-1-propanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 3-methyl-2-pentanol, and cyclohexanol; alcohols that contain -OH and -CO- but do not contain -COO-, such as 4-hydroxy-2-butanone and diacetone alcohol; and alcohols that contain -OH and -COO-, such as ethyl lactate. The alcohol having 3 to 6 carbon atoms is preferably a secondary or tertiary alcohol. In the contacting step, when an alcohol having 3 to 6 carbon atoms is used without using an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, an alkylene glycol monoalkyl ether, or an alkylene glycol monoalkyl ether acetate, the alcohol having 3 to 6 carbon atoms is preferably an alcohol that contains -OH but does not contain -CO- or -COO-, more preferably a secondary or tertiary alcohol that contains -OH but does not contain -CO- or -COO-, such as 2-propanol, 2-butanol, 2-methyl-2-propanol, 2-pentanol, 3-methyl-1-butanol, 2-methyl-2-butanol, 2-hexanol, or 2-methyl-2-pentanol, even more preferably a secondary alcohol that contains -OH but does not contain -CO- or -COO-, such as 2-propanol, 2-butanol, 2-pentanol, 3-methyl-1-butanol, or 2-hexanol, and even more preferably 2-propanol, 2-butanol, 2-pentanol, or 2-hexanol. In the contacting step, when an alcohol having 3 to 6 carbon atoms and at least one selected from the group consisting of an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, an alkylene glycol monoalkyl ether, and an alkylene glycol monoalkyl ether acetate are used, the alcohol having 3 to 6 carbon atoms is preferably an alcohol containing -OH and -CO- but not containing -COO-, or an alcohol containing -OH and -COO-, more preferably an alcohol containing -OH and -CO- but not containing -COO-, and even more preferably diacetone alcohol.

[0062] Examples of aromatic hydrocarbon solvents having 6 to 9 carbon atoms in the contacting step include benzene, toluene, xylene, and mesitylene, with solvents having 6 to 8 carbon atoms being preferred, benzene, toluene, and xylene being more preferred, and xylene being even more preferred.

[0063] The alkylene glycol monoalkyl ether in the contacting step is a solvent containing -O- and -OH groups in the molecule. Examples of alkylene glycol monoalkyl ethers include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether. Of these, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, and propylene glycol monobutyl ether are preferred, propylene glycol monomethyl ether and propylene glycol monoethyl ether are more preferred, and propylene glycol monomethyl ether is even more preferred.

[0064] The alkylene glycol monoalkyl ether acetate in the contacting step is preferably a solvent containing -O- and -COO- in the molecule and not containing -OH. Examples of alkylene glycol monoalkyl ether acetates include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate. Of these, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, and propylene glycol monobutyl ether acetate are preferred, with propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate being more preferred, and propylene glycol monomethyl ether acetate being even more preferred.

[0065] In the contact step, it is preferable to use a combination of alkylene glycol monoalkyl ether and alkylene glycol monoalkyl ether acetate, and the content ratio thereof (alkylene glycol monoalkyl ether: alkylene glycol monoalkyl ether acetate) is preferably 10:1 to 1:10, more preferably 7:1 to 1:9.

[0066] In all solvents used in the contacting step, the total content of the alcohol having 3 to 6 carbon atoms, the aromatic hydrocarbon solvent having 6 to 9 carbon atoms, the alkylene glycol monoalkyl ether, and the alkylene glycol monoalkyl ether acetate is 60% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass. By performing the contacting step using specific solvents in specific proportions, the crystal structure of the xanthene dye can be made to have a desired structure.

[0067] In order to obtain a xanthene dye capable of forming a color filter having excellent solvent resistance in addition to heat resistance, the content of the aromatic hydrocarbon solvent having 6 to 9 carbon atoms and / or alkylene glycol monoalkyl ether is preferably 40 mass% or more, more preferably 50 mass% or more, and even more preferably 60 mass% or more of the total solvent.

[0068] In order to obtain a xanthene dye capable of forming a color filter having good light resistance in addition to heat resistance, the content of the alcohol having 3 to 6 carbon atoms, the aromatic hydrocarbon solvent having 6 to 9 carbon atoms, and / or the alkylene glycol monoalkyl ether acetate is preferably 50 mass% or more, more preferably 60 mass% or more, even more preferably 70 mass% or more, and even more preferably 80 mass% or more of the total solvent.

[0069] In order to obtain a xanthene dye capable of forming a color filter having good heat resistance, light resistance, and solvent resistance, it is preferable to use an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, and the content of the aromatic hydrocarbon solvent in the total solvent is more preferably 60 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, and even more preferably 90 mass% or more.

[0070] The amount of solvent used in the contacting step may be determined appropriately depending on the type of xanthene dye and solvent used so that the mixture of xanthene dye and solvent maintains a precipitated state. From the viewpoint of yield, the amount is preferably 0.1 to 150 times by mass of the xanthene dye, more preferably 0.5 to 100 times by mass, even more preferably 1 to 100 times by mass, even more preferably 50 to 100 times by mass, even more preferably 30 to 100 times by mass, even more preferably 20 to 100 times by mass. The xanthene dye used in the contacting step is preferably not only a dried product but also a residue containing the xanthene dye obtained by solid-liquid separation from the reaction mixture. In the latter case, the residue may contain the solvent used in the reaction or the solvent used for washing. The amount of solvent used in the contacting step is calculated to include the solvent used in the reaction or the solvent used for washing contained in the residue.

[0071] The atmosphere in the reactor during stirring in the contact step is not particularly limited and may include air, nitrogen, other inert gases, etc., but from the viewpoint of production safety, it is preferable to carry out the step under a nitrogen atmosphere.

[0072] The mixture of the xanthene dye and the solvent is stirred to bring the xanthene dye and the solvent into contact with each other. Stirring may be carried out using a known stirrer, and the stirring conditions may be appropriately set depending on the xanthene dye and the solvent used, but the following stirring temperature, stirring time, stirring speed, etc. are preferred.

[0073] The stirring temperature (contact temperature) may be any temperature at which the xanthene dye can be maintained in a precipitated state in the solvent, and is preferably 0 to 200°C, more preferably 10 to 150°C. The upper limit of the temperature is preferably equal to or lower than the boiling point of the solvent used at 1 atm. For example, when the solvent used is primarily composed of an alcohol having 3 to 6 carbon atoms, an alkylene glycol monoalkyl ether, or an alkylene glycol monoalkyl ether acetate (i.e., the solvent with the highest content among all solvents), the stirring temperature is preferably 0 to 100°C, more preferably 0 to 80°C, and even more preferably 0 to 60°C. When the solvent used is primarily composed of an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, the stirring temperature is preferably 50 to 200°C, more preferably 70 to 180°C, and even more preferably 90 to 170°C. Here, the stirring temperature refers to the internal temperature of the reaction system, not the temperature of the vessel during stirring. The term "precipitated state" means a state in which a solid xanthene dye that is not dissolved in the solvent is present in the mixture of the xanthene dye and the solvent, and a part of the xanthene dye may be dissolved in the solvent.

[0074] The stirring time (contact time) is preferably 10 minutes or more, more preferably 30 minutes or more, even more preferably 1 hour or more, still more preferably 2 hours or more, and is preferably 60 hours or less, more preferably 48 hours or less, even more preferably 36 hours or less, and still more preferably 30 hours or less.

[0075] The stirring speed (number of rotations) is preferably 50 to 300 rpm, more preferably 100 to 200 rpm, and even more preferably 150 to 180 rpm.

[0076] By carrying out the contact step under the above conditions, the xanthene dye can have a specific crystal structure. In particular, preferred conditions for the contact step for producing the xanthene dye (I) having the diffraction peaks of Examples (i) to (iv) above are as follows: Example (i): 180 to 220 parts by weight (preferably 190 to 210 parts by weight) of diacetone alcohol, 380 to 420 parts by weight (preferably 390 to 410 parts by weight) of propylene glycol monomethyl ether, and 45 to 85 parts by weight (preferably 55 to 75 parts by weight) of propylene glycol monomethyl ether acetate are used as solvents in the contacting step, the stirring temperature is 20 to 30°C, and the stirring time is 12 hours or more and less than 30 hours. The ratio of diacetone alcohol, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate used (diacetone alcohol:propylene glycol monomethyl ether:propylene glycol monomethyl ether acetate) is 2.5 to 3.5:5.5 to 6.5:0.5 to 1.5, preferably 2.8 to 3.2:5.8 to 6.2:8.8 to 1.2. Example (ii): 800 to 1,100 parts by mass of xylene (preferably 820 to 1,000 parts by mass, more preferably 840 to 900 parts by mass) per 100 parts by mass of the xanthene colorant is used as a solvent in the contact step, the stirring temperature is 110 to 130°C, and the stirring time is 2 hours or more and less than 12 hours. Example (iii): 610 to 745 parts by mass (preferably 630 to 725 parts by mass, more preferably 650 to 700 parts by mass) of 2-propanol is used as a solvent in the contact step relative to 100 parts by mass of the xanthene colorant, the stirring temperature is 20 to 30°C, and the stirring time is 2 hours or more and less than 12 hours. Example (iv): 700 to 860 parts by mass (preferably 730 to 830 parts by mass, more preferably 750 to 810 parts by mass) of propylene glycol monomethyl ether acetate, 85 to 110 parts by mass (preferably 90 to 100 parts by mass) of diacetone alcohol, and 80 to 105 parts by mass (preferably 85 to 100 parts by mass) of propylene glycol monomethyl ether are used as solvents in the contact step relative to 100 parts by mass of the xanthene colorant, the stirring temperature is 20 to 30°C (preferably 22 to 27°C), and the stirring time is 2 hours or more but less than 12 hours. The ratio of propylene glycol monomethyl ether acetate, diacetone alcohol, and propylene glycol monomethyl ether used (propylene glycol monomethyl ether acetate:diacetone alcohol:propylene glycol monomethyl ether) is 7.5-8.5:0.5-1.5:0.5-1.5, preferably 7.8-8.3:0.8-1.3:0.7-1.2.

[0077] The xanthene dye contacted with the solvent by stirring is separated from the solvent by solid-liquid separation and extracted as a solid. That is, in the separation step provided after the contacting step, the xanthene dye (I) having a predetermined chemical structure and crystalline structure can be extracted by solid-liquid separation.

[0078] The solid-liquid separation in the separation step is preferably carried out by natural filtration, vacuum filtration, pressure filtration, centrifugal filtration, centrifugation, or the like. The xanthene colorant (I) from which the solvent has been removed by solid-liquid separation may be further subjected to treatments such as washing, recrystallization, drying, etc. Examples of the drying method include natural drying, heat drying, vacuum drying, and a combination thereof.

[0079] <Colored curable resin composition> The xanthene dye (I) having a predetermined chemical structure and crystal structure may be contained in the following colored curable resin composition. The colored curable resin composition of the present invention contains the xanthene dye (I), a resin (hereinafter also referred to as resin (B)), a polymerizable compound (hereinafter also referred to as polymerizable compound (C)), a polymerization initiator (hereinafter also referred to as polymerization initiator (D)), and a solvent (hereinafter also referred to as solvent (E)). The xanthene dye (I) can be used as a colorant (hereinafter also referred to as colorant (A)). The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter also referred to as leveling agent (F)). In this specification, the compounds exemplified as components can be used alone or in combination unless otherwise specified.

[0080] <Colorant (A)> The colorant (A) contains a xanthene dye (I) having a predetermined chemical structure and crystalline structure. When the colorant (A) contains the xanthene dye (I), a colored curable resin composition containing the colorant can form a color filter having good heat resistance, and preferably a color filter having good light resistance and / or solvent resistance in addition to heat resistance.

[0081] <Xanthene dyes (I)> The xanthene dye (I) is as described above, and the preferred embodiments thereof are also the same.

[0082] The content of the xanthene dye (I) in the total amount of the colorant (A) is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 60% by mass or more, even more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0083] <Colorant (A1)> In addition to the xanthene colorant (I), the colorant (A) may contain a colorant (hereinafter also referred to as colorant (A1)) different from the xanthene colorant (I). The colorant (A1) may be either a dye (hereinafter also referred to as dye (A1-1)) or a pigment (hereinafter also referred to as pigment (A1-2)). The colorant (A1) may contain one or both of the dye (A1-1) and the pigment (A1-2).

[0084] The dye (A1-1) is not particularly limited, and known dyes can be used as long as they do not contain the xanthene dye (I). Examples include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified as non-pigment dyes with hues in the Color Index (published by The Society of Dyes and Colourists) and known dyes listed in Dyeing Notes (Shikisensha). Based on their chemical structure, dye (A1-1) can include azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes (excluding xanthene dye (I)), phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, perylene dyes, quinophthalone dyes, isoindoline dyes, and nitro dyes. Of these, organic solvent-soluble dyes are preferred as dye (A1-1).

[0085] Specific examples of the dye (A1-1) include: CI Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 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, 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, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 1 23, 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, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324, 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, 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, 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, 77, 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 Red 9; 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; CI Vat Green 1; CI Vat dyes such as and other dyes with Color Index (CI) numbers such as:

[0086] These dyes may be appropriately selected in accordance with the desired spectral spectrum of the color filter.

[0087] The pigment (A1-2) is not particularly limited, and any known pigment can be used as long as it does not contain the xanthene colorant (I), and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists).

[0088] Specific examples of the pigment (A1-2) include: Yellow pigments such as CI Pigment Yellow 1, 3, 10, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 81, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231; Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 62, 64, 65, 71, 72, 73; Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 190, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, 291, 295, 296; 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, 38; Green pigments such as CI Pigment Green 7, 36, 58, 59, 62, 63; Brown pigments such as CI Pigment Brown 23 and 25; Black pigments such as CI Pigment Black 1 and 7 Examples of pigments with Color Index (CI) numbers such as:

[0089] These pigments may be appropriately selected in accordance with the desired spectral spectrum of the color filter.

[0090] 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 graft treatment onto the pigment surface using a polymer compound or the like, a microparticle treatment using a sulfuric acid microparticle 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, or the like.

[0091] The pigment preferably has a uniform particle size. By adding a dispersant and carrying out a dispersion treatment, it is possible to obtain a pigment dispersion in which the pigment is uniformly dispersed in the solution.

[0092] Examples of the dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These dispersants may be used alone or in combination of two or more. Examples of the dispersant include, by trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flourene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Corporation), EFKA (manufactured by CIBA), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), and Disperbyk (manufactured by BYK-Chemie). When a dispersant is used, the amount used is preferably from 1 to 150% by mass, more preferably from 5 to 100% by mass, and even more preferably from 20 to 80% by mass, relative to the total amount of pigment. When the amount of dispersant used is within the above range, a pigment dispersion in a uniformly dispersed state tends to be obtained.

[0093] The content of colorant (A) is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 50% by mass or less, even more preferably 1.0% by mass or more and 40% by mass or less, still more preferably 2.0% by mass or more and 30% by mass or less, and even more preferably 4.0% by mass or more and 20% by mass or less, based on the total amount of solids. When the content of colorant (A) is within the above range, the color density when made into a color filter is sufficient, and since the resin (B) and the polymerizable compound (C) can be contained in the composition in the required amounts, a colored coating film (colored pattern) with sufficient mechanical strength can be formed.

[0094] Here, the "total amount of solids" in this specification refers to the amount obtained by excluding the content of the solvent from the total amount of the colored curable resin composition. 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.

[0095] <Resin (B)> Resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of resin (B) include the following resins [K1] to [K6], and it is preferably at least one selected from the group consisting of resins [K1] to [K6].

[0096] Resin [K1]: a copolymer having structural units derived from at least one monomer (a) (hereinafter also 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 also referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond; 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 also referred to as "(c)"); 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) has been added and a structural unit derived from (c), the copolymer including a structural unit derived from (a) to which (b) has not been added; Resin [K4']: a copolymer having a structural unit derived from (a) and a structural unit derived from (c), wherein the structural unit is derived from (a) and not from (b); Resin [K5]: a copolymer having a structural unit derived from (b) to which (a) has been added and a structural unit derived from (c) (which may contain, but preferably does not contain, a structural unit derived from (b) to which (a) has not been added); Resin [K6]: A copolymer having a structural unit obtained by adding the (a) to a structural unit derived from the (b) and further adding a carboxylic acid anhydride, and a structural unit derived from the (c).

[0097] 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 the solubility of the resulting resin in a developer (particularly an alkaline aqueous solution).

[0098] 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.

[0099] Specifically, (b) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0100] Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter also referred to as "(b3)").

[0101] Examples of (b1) include a monomer (b1-1) (hereinafter also referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon has been epoxidized, and a monomer (b1-2) (hereinafter also referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon has been epoxidized.

[0102] As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferred. Examples of (b1-1) 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, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl Examples thereof include 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, and 2,4,6-tris(glycidyloxymethyl)styrene.

[0103] Examples of (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., CELLOXIDE (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER (registered trademark) M100; manufactured by Daicel Corporation), compounds represented by formula (BI), and compounds represented by formula (BII).

[0104] [ka] [In formula (BI) and formula (BII), R e and R f represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X e and X f is a single bond, *-R g -, *-R g -O-, *-R g -S- or *-R g represents -NH-. R g represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.]

[0105] R e and R f Examples of the alkyl group having 1 to 4 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Examples of alkyl groups in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group. R e and R f Preferred examples of the alkyl group include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferred examples include a hydrogen atom and a methyl group.

[0106] Examples of the alkanediyl group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group. X e and X f Preferred examples of the alkyl group include a single bond, a methylene group, an ethylene group, *-CH2-O-, and *-CH2CH2-O-, and more preferred examples include a single bond and *-CH2CH2-O- (* represents a bond to O).

[0107] Examples of the compound represented by formula (BI) include compounds represented by any one of formulas (BI-1) to (BI-15). Among these, compounds represented by formula (BI-1), (BI-3), (BII-5), (BI-7), (BI-9), or (BI-11) to (BI-15) are preferred, and compounds represented by formula (BI-1), (BI-7), (BI-9), or (BI-15) are more preferred.

[0108] [ka]

[0109] Examples of the compound represented by formula (BII) include compounds represented by any of formulas (BII-1) to (BII-15). Among these, compounds represented by formula (BII-1), (BII-3), (BII-5), (BII-7), (BII-9), or (BII-11) to (BII-15) are preferred, and compounds represented by formula (BII-1), (BII-7), (BII-9), or (BII-15) are more preferred.

[0110] [ka]

[0111] The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, the content ratio thereof [compound represented by formula (BI) : compound represented by formula (BII)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

[0112] 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.

[0113] 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.

[0114] As (b), (b1) is preferred in that it can further increase the reliability of the heat resistance, chemical resistance, etc. of the obtained color filter. Furthermore, (b1-2) is more preferred in that it provides excellent storage stability of the colored curable resin composition.

[0115] 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.

[0116] 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 decan-8-yl (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 decene-8-yl (meth)acrylate (commonly referred to as "dicyclopentenyl (meth)acrylate" in the technical field), dicyclopentanyloxyethyl (meth)acrylate, etc.; (meth)acrylic acid esters having an aromatic ring, such as phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, and phenoxybenzyl (meth)acrylate; 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.

[0117] Among these unsaturated carboxylic acid esters, from the viewpoint of copolymerization reactivity and heat resistance, C such as methyl methacrylate and 2-ethylhexyl acrylate 1-10 Alkyl (meth)acrylate; Tricyclo[5.2.1.0 2,6 ] (meth)acrylic acid esters having a cyclic saturated hydrocarbon group, such as decan-8-yl (meth)acrylate; Tricyclo[5.2.1.0 2,6 ](meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, such as decene-8-yl(meth)acrylate; (meth)acrylic acid esters having an aromatic ring, such as benzyl (meth)acrylate and phenoxybenzyl (meth)acrylate; Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate are preferred; Hydroxy group-containing (meth)acrylic acid esters are more preferred, and 2-hydroxyethyl (meth)acrylate is even more preferred.

[0118] 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.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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 are preferred, dicarbonyl imide derivatives are more preferred, and N-cyclohexylmaleimide is even more preferred.

[0123] 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) constituting 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 oxiranyl 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.

[0124] 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 oxiranyl 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.

[0125] The structural unit obtained by adding (a) to a structural unit derived from (b) and then further adding a carboxylic acid anhydride is a structural unit in which (a) is added to a structural unit derived from (b) constituting the main chain of the copolymer, and the carboxylic acid anhydride is attached to the resulting hydroxyl group by half-esterification. This structural unit has a pendant carboxy group derived from the carboxylic acid anhydride and 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 oxiranyl 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. Examples of carboxylic acid anhydrides include saturated aliphatic polycarboxylic acid anhydrides such as malonic anhydride, succinic anhydride, glutaric anhydride, and adipic anhydride; unsaturated aliphatic polycarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, and itaconic anhydride; aromatic polycarboxylic acid anhydrides such as 3-vinylphthalic anhydride and 4-vinylphthalic anhydride; and alicyclic polycarboxylic acid anhydrides such as 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.

[0126] In the resin [K1], 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 (b): 40 to 98 mol% Preferably, Structural units derived from (a): 10 to 50 mol% Structural units derived from (b): 50 to 90 mol% It is more preferable that: When the ratio of the structural units of the resin [K1] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and solvent resistance of the resulting color filter.

[0127] 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.

[0128] 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 the atmosphere is deoxygenated, 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.). Solvents that dissolve each monomer can be used, and examples of the solvent (E) for the colored curable resin composition of the present invention include the solvents described below.

[0129] The resulting copolymer may be used as a solution after the reaction as is, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation. In particular, by using the solvent contained in the colored curable resin composition of the present invention as the solvent during the polymerization, the solution after the reaction can be used as is for preparing the colored curable resin composition of the present invention, thereby simplifying the production process for the colored curable resin composition of the present invention.

[0130] In the resin [K2], the ratio of the structural units derived from each of these is as follows: Structural units derived from (a): 1 to 70 mol% Structural units derived from (b): 1 to 60 mol% Structural units derived from (c): 20 to 95 mol% Preferably, Structural units derived from (a): 3 to 50 mol% Structural units derived from (b): 3 to 40 mol% Structural units derived from (c): 30 to 90 mol% It is more preferable that Structural units derived from (a): 5 to 40 mol% Structural units derived from (b): 5 to 30 mol% Structural units derived from (c): 40 to 80 mol% It is more preferable that: When the ratio of the structural units of the resin [K2] is within the above range, the colored curable resin composition tends to have excellent storage stability, developability when forming a colored pattern, and the obtained color filter tends to have excellent solvent resistance, heat resistance, and mechanical strength.

[0131] In the resin [K2], (a) is preferably an unsaturated monocarboxylic acid such as (meth)acrylic acid. As (b), a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond is preferred, and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized is more preferred. As (c), (meth)acrylic acid esters having a cyclic unsaturated aliphatic hydrocarbon group, (meth)acrylic acid esters having an aromatic ring, dicarbonyl imide derivatives, and hydroxyl group-containing (meth)acrylic acid esters are preferred, and dicarbonyl imide derivatives and hydroxyl group-containing (meth)acrylic acid esters are more preferred.

[0132] Resin [K2] can be produced, for example, in the same manner as described above for producing resin [K1].

[0133] 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% Preferably, Structural units derived from (a): 10 to 50 mol% Structural units derived from (c): 50 to 90 mol% It is more preferable that Structural units derived from (a): 35 to 45 mol% Structural units derived from (c): 55 to 65 mol% It is more preferable that:

[0134] Resin [K3] can be produced, for example, in the same manner as described above for producing resin [K1].

[0135] 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)): 1 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% Preferably, Structural units derived from (a) (without addition of (b)): 5 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 Structural units derived from (a) (without addition of (b)): 10 to 40 mol% Structural units in which (b) is added to structural units derived from (a): 10 to 25 mol% Structural units derived from (c): 40 to 75 mol% It is more preferable that:

[0136] Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and then adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic acid anhydride contained in (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]. Next, a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (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].

[0137] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). This range tends to improve the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance of the solvent resistance, heat resistance, mechanical strength, and sensitivity of the resulting pattern. Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K4], and (b1-1) is even more preferred. 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.

[0138] In the resin [K4'], the ratio of the structural units derived from each of these is as follows, among all the structural units constituting the resin [K4']: Structural units obtained by adding (b) to structural units derived from (a): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% Preferably, Structural units obtained by adding (b) to structural units derived from (a): 15 to 90 mol% Structural units derived from (c): 10 to 85 mol% It is more preferable that Structural units obtained by adding (b) to structural units derived from (a): 20 to 80 mol% Structural units derived from (c): 20 to 80 mol% It is even more preferable that:

[0139] Resin [K4'] may be produced by referring to the production method of resin [K4] described above, and the amount of (b) used is preferably 100 mol or more per 100 mol of (a).

[0140] In the resin [K5], the ratio of structural units derived from each of these is as follows among all structural units constituting the resin [K5]: Structural units derived from (b) (without (a) added): 0 to 30 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% Preferably, Structural units derived from (b) (without (a) added): 0 to 10 mol% Structural units obtained by adding (a) to structural units derived from (b): 15 to 90 mol% Structural units derived from (c): 10 to 85 mol% It is more preferable that Structural units derived from (b) (without (a) added): 0 to 5 mol% Structural units in which (a) is added to structural units derived from (b): 20 to 80 mol% Structural units derived from (c): 20 to 80 mol% It is even more preferable that:

[0141] 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% Preferably, Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:

[0142] Furthermore, under the same conditions as in the production method of resin [K4] or resin [K4'], resin [K5] can be obtained by reacting a cyclic ether derived from (b) contained in a copolymer of (b) and (c) with a 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). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K5], and (b1-1) is more preferred.

[0143] In the resin [K6], the ratio of structural units derived from each of these is as follows: Structural units derived from (b) (without (a) added): 0 to 30 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% Preferably, Structural units derived from (b) (without (a) added): 0 to 10 mol% Structural units in which (a) is added to structural units derived from (b) (no carboxylic acid anhydride is added); 40 to 80 mol% Structural units 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 (a) added): 0 to 5 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 more preferable that:

[0144] 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% Preferably, Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:

[0145] Furthermore, under the same conditions as in the production of Resin [K4] or Resin [K4'], the cyclic ether derived from (b) contained in the copolymer of (b) and (c) is 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).

[0146] The hydroxy 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 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, relative to 1 mol of (a) used (in other words, 1 mol of hydroxy groups generated by the use of (a)).

[0147] Specific examples of the resin (B) 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]; Resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer [K3]; Resins such as a resin in which glycidyl (meth)acrylate is added to some of the carboxylic acid groups of a benzyl (meth)acrylate / (meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to some of the carboxylic acid groups of a tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to some of the carboxylic acid groups of a tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, a resin in which glycidyl (meth)acrylate is added to some of the carboxylic acid groups of a norbornene / vinyltoluene / (meth)acrylic acid copolymer, and a resin in which glycidyl (meth)acrylate is added to some of the carboxylic acid groups of a norbornene / styrene / (meth)acrylic acid copolymer [K4]; Resins such as a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / (meth)acrylic acid with glycidyl (meth)acrylate, and a resin obtained by reacting a copolymer of tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid with glycidyl (meth)acrylate [K4']; Resins such as resins obtained by reacting tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymers with (meth)acrylic acid, and resins obtained by reacting tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate copolymers with (meth)acrylic acid [K5]; Resins obtained by reacting a copolymer of tricyclodecyl (meth)acrylate and glycidyl (meth)acrylate with (meth)acrylic acid and then reacting the resulting resin with tetrahydrophthalic anhydride; resins obtained by reacting a copolymer of 2-ethylhexyl (meth)acrylate and tricyclodecyl (meth)acrylate and glycidyl (meth)acrylate with (meth)acrylic acid and then reacting the resulting resin with succinic anhydride; resins obtained by reacting a copolymer of 2-ethylhexyl (meth)acrylate and tricyclodecyl (meth)acrylate and glycidyl (meth)acrylate with (meth)acrylic acid and then reacting some of the hydroxyl groups with succinic anhydride; resins obtained by reacting a copolymer of methyl (meth)acrylate and 2-ethylhexyl (meth)acrylate and tricyclodecyl (meth)acrylate and glycidyl (meth)acrylate with (meth)acrylic acid and then reacting the resulting resin with succinic anhydride [K6]; and the like.

[0148] The resins [K1] to [K6] may be one type or a combination of two or more types. Among them, the resin (B) is preferably at least one type selected from the group consisting of the resin [K1] and the resin [K2], and particularly preferably contains the resin [K1].

[0149] The polystyrene-equivalent weight average molecular weight of resin (B) is preferably 3,000 to 100,000, more preferably 5,000 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, the solubility of the unexposed areas in the developer is good, and the resolution of the colored pattern tends to be improved.

[0150] The polydispersity of the resin (B) [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.1-6, and more preferably 1.2-4.

[0151] The acid value of the resin (B) is preferably 20 to 170 mg-KOH / g, more preferably 25 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 (B), and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0152] The content of resin (B) is preferably 5% by mass or more and 65% by mass or less, more preferably 10% by mass or more and 60% by mass or less, and even more preferably 15% by mass or more and 55% by mass or less, based on the total amount of solids in 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.

[0153] <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.

[0154] Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, N-vinylpyrrolidone, and the above-mentioned monomers (a), (b), and (c).

[0155] Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.

[0156] 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, and it is more preferable to include at least one selected from the group consisting of trimethylolpropane triacrylate and dipentaerythritol polyacrylate.

[0157] The weight average molecular weight of the polymerizable compound (C) is preferably 50 or more and 4,000 or less, more preferably 70 or more and 3,500 or less, even more preferably 100 or more and 3,000 or less, still more preferably 150 or more and 2,900 or less, and particularly preferably 250 or more and 1,500 or less.

[0158] The content of the polymerizable compound (C) may be, for example, 5% by mass or more and 65% by mass or less, preferably 10% by mass or more and 60% by mass or less, more preferably 15% by mass or more and 55% by mass or less, and even more preferably 20% by mass or more and 50% by mass or less, relative to 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 improved.

[0159] <Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound that can generate active radicals, acids, etc. by the action of light or heat and initiate polymerization, and known polymerization initiators can be used. Examples of the polymerization initiator (D) that generates active radicals include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds.

[0160] The O-acyloxime compound is a compound having a partial structure represented by formula (d-1): In the formula, * represents a bond.

[0161] [ka]

[0162] 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-dimethylphenyl)-2-methylbenzoyl]ethan-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethylphenyl) ...

[0033] N-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-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, and the like. Commercially available products such as Irgacure OXE01 (N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine), Irgacure OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine) (all manufactured by BASF), N-1919 (manufactured by ADEKA), and TR-PBG327 (N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine) (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) may also be used.Among them, the O-acyloxime compounds include N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine, and N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine. Preferably, at least one selected from the group consisting of N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine is used. These O-acyloxime compounds tend to produce color filters with high brightness.

[0163] The alkylphenone compound is a compound having a partial structure represented by formula (d-2) or a partial structure represented by formula (d-3). In these partial structures, the benzene ring may have a substituent. In the formula, * represents a bond.

[0164] [ka]

[0165] Examples of compounds having a partial structure represented by formula (d-2) 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.

[0166] Examples of compounds having a partial structure represented by formula (d-3) 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 (d-2).

[0167] 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.

[0168] 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.

[0169] 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'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, Examples of suitable biimidazole compounds include 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 No. 48-38403 and JP-A No. 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 No. 7-10913). Among these, compounds represented by the following formula and mixtures thereof are preferred:

[0170] [ka]

[0171] 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.

[0172] Examples of the polymerization initiator (D) 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.

[0173] The polymerization initiator (D) preferably contains at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds, and biimidazole compounds, more preferably contains an O-acyloxime compound and / or a biimidazole compound, and even more preferably contains an O-acyloxime compound.

[0174] 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 tends to be increased and exposure time tends to be shortened, thereby improving productivity of the color filter.

[0175] <Polymerization initiator aid (D1)> The polymerization initiation aid (D1) is a compound or sensitizer used to promote the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator (D). When the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).

[0176] Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0177] 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, 4,4'-bis(ethylmethylamino)benzophenone, etc., and preferably 4,4'-bis(diethylamino)benzophenone. In addition, commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used as the amine compound.

[0178] 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.

[0179] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0180] 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.

[0181] 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 all resins (B) and polymerizable compounds (C) contained in the colored curable resin composition. When the amount of the polymerization initiation aid (D1) is within this range, colored patterns can be formed with even higher sensitivity, and the productivity of color filters tends to improve.

[0182] <Solvent (E)> The solvent (E) is not particularly limited, and any solvent commonly used in the relevant field can be used. Examples of the solvent (E) 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, dimethyl sulfoxide, etc. Two or more of these solvents may be used in combination.

[0183] 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.

[0184] 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.

[0185] 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, and 2-ethoxy-2-methylpropionate. Examples of the methyl ether acetate include ethyl acrylate, 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, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

[0186] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone (also known as diacetone alcohol), acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0187] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0188] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0189] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0190] The solvent (E) is preferably a solvent containing at least one selected from ester solvents, ether solvents, ether ester solvents, and ketone solvents, more preferably a solvent containing at least one selected from ester solvents, ether ester solvents, and ketone solvents. In particular, a solvent containing at least one selected from propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, and diacetone alcohol is preferred, and a solvent containing propylene glycol monomethyl ether acetate and / or ethyl lactate is more preferred.

[0191] The content of the solvent (E) relative to the total amount of the colored curable resin composition is usually 99.99% by mass or less, preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 97% by mass or less, even more preferably 60% by mass or more and 95% by mass or less, and even more preferably 70% by mass or more and 93% by mass or less. In other words, the total amount of solids in the colored curable resin composition is usually 0.01% by mass or more, preferably 1% by mass or more and 60% by mass or less, more preferably 3% by mass or more and 50% by mass or less, even more preferably 5% by mass or more and 40% by mass or less, and even more preferably 7% by mass or more and 30% by mass or less. When the content of the solvent (E) is within the above range, flatness during application is good, and when a color filter is formed, the color density is not insufficient, so the display characteristics tend to be good.

[0192] <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.

[0193] 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).

[0194] Examples of fluorine-based surfactants 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), and E5844 (manufactured by Daikin Fine Chemical Research Institute, Ltd.).

[0195] Examples of silicone surfactants having fluorine atoms 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).

[0196] When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.0005% by mass or more and 1% by mass or less, more preferably 0.001% by mass or more and 0.5% by mass or less, and even more preferably 0.005% by mass or more and 0.3% by mass or less, relative to the total amount of the colored curable resin composition. Note that this content does not include the content of the dispersant. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

[0197] <Other ingredients> The colored curable resin composition may contain additives known in the technical field, such as fillers, other polymer compounds, adhesion promoters, quenchers, antioxidants, light stabilizers, and chain transfer agents, as needed.

[0198] <Method for producing colored curable resin composition> The colored curable resin composition can be prepared, for example, by mixing the xanthene dye (I), resin (B), polymerizable compound (C), polymerization initiator (D), and solvent (E), as well as the dye (A1-1), pigment (A1-2), leveling agent (F), and other components that are used as needed. Mixing can be carried out using known or conventional equipment and conditions.

[0199] The colorant (A) may be mixed with part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle size is approximately 0.2 μm or less to obtain a dispersion (colorant-containing liquid). It is preferable to use the colorant (A) as a dispersion. In this case, the dispersant and part or all of the resin (B) may be blended as needed. The remaining components are preferably mixed with the dispersion thus obtained to obtain a predetermined concentration to prepare the desired colored curable resin composition. When using a bead mill, 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. When a dye is contained as the colorant (A), the dye may be dissolved in advance in part or all of the solvent (E) to prepare a solution. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.

[0200] <Color filter manufacturing method> A color filter can be formed from the colored curable resin composition of the present invention. Methods for producing a colored pattern of a color filter include photolithography, inkjet printing, and printing. Among these, photolithography is preferred. The photolithography method involves applying the colored curable resin composition to a substrate, drying the composition to form a colored composition layer, and then exposing and developing the colored composition layer through a photomask. In the photolithography method, a colored coating film, which is a cured product of the colored composition layer, can be formed by not using a photomask during exposure and / or not developing the layer. The colored pattern or colored coating film thus formed is the color filter of the present invention.

[0201] The film thickness of the color filter (cured film) is not particularly limited and can be adjusted appropriately depending on the purpose, application, etc., and is, for example, 30 μm or less, preferably 20 μm or less, more preferably 6 μm or less, even more preferably 4.5 μm or less, and is preferably 0.1 μm or more, more preferably 0.2 μm or more, even more preferably 0.3 μm or more.

[0202] 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 (hexamethyldisilazane) may be used.

[0203] The formation of each color pixel by photolithography can be carried out using known or conventional equipment and conditions. For example, it can be produced as follows.

[0204] First, a colored curable resin composition is applied to a substrate, and then heated and dried (prebaked) and / or dried under reduced pressure to remove volatile components such as solvents and dry the composition to obtain a smooth colored composition layer. Examples of application methods include spin coating, slit coating, and slit and spin coating. The temperature for heat drying is preferably 30°C or higher and 120°C or lower, and more preferably 50°C or higher and 110°C or lower. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When drying under reduced pressure is performed, it is preferably performed under a pressure of 50 Pa or more and 150 Pa or less at a temperature range of 20° C. or more and 25° C. The film thickness of the coloring composition layer is not particularly limited and may be appropriately selected depending on the film thickness of the intended color filter.

[0205] Next, the colored composition layer is exposed through a photomask to form a desired colored pattern. The pattern on the photomask is not particularly limited, and a pattern appropriate for the intended use is used. In addition, it is preferable to use an exposure device such as a mask aligner or a stepper, since this allows uniform irradiation of parallel light rays over the entire exposure surface and allows accurate alignment between the photomask and the substrate on which the colored composition layer is formed. When a colored coating film is formed, exposure can be performed without using a photomask. The light source used for exposure is preferably a light source that emits light with a wavelength of 250 nm or more and 450 nm or less. For example, light less than 350 nm may be cut using a filter that cuts this wavelength range, or light around 436 nm, 408 nm, and 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.

[0206] A colored pattern is formed on the substrate by contacting the exposed colored composition layer with a developer and developing it. The unexposed portions of the colored 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% by mass or more and 10% by mass or less, more preferably 0.03% by mass or more and 5% by mass or less. 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, the substrate is preferably washed with water.

[0207] Furthermore, the obtained colored pattern or colored coating film is preferably post-baked. The post-baking temperature is preferably 80° C. or higher and 250° C. or lower, more preferably 90° C. or higher and 245° C. or lower. The post-baking time is preferably 1 minute or higher and 120 minutes or lower, more preferably 2 minutes or higher and 40 minutes or lower.

[0208] The colored pattern and colored coating film thus obtained are useful as a color filter.

[0209] <Display device> The color filter is useful as a color filter for use in display devices (for example, liquid crystal display devices, organic EL devices, etc.), electronic paper, solid-state imaging devices, etc. [Example]

[0210] 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, and can of course be practiced with appropriate modifications within the scope of the above and below-described aims, all of which are included within the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0211] The structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 model, MASS; Agilent LC / MSD6130 model).

[0212] The crystal structure of the xanthene dye was identified by powder X-ray measurement under the following conditions: Equipment: RINT2000, manufactured by Rigaku Corporation X-ray: Cu-Kα ray Device control: centralized method Measurement angle: 2~40° Voltage: 40kV Current: 40mA

[0213] (Synthesis Example 1) <Synthesis of xanthene dye (Ia1)> A xanthene dye represented by the following formula (Ia1) (also referred to as xanthene dye (Ia1)) was synthesized according to the description in paragraphs 0190 to 0194 of JP 2017-226814 A. The powder X-ray diffraction pattern (spectrum) of the xanthene dye (Ia1) is shown in Figure 1. Because the xanthene dye (Ia1) has an amorphous structure, no clear diffraction peaks were observed.

[0214] [ka]

[0215] Identification of the xanthene pigment (Ia1) (Mass spectrometry) Ionization mode = ESI + : m / z=[M+H] + 747.5 Exact Mass: 746.3

[0216] Example 1 <Synthesis of xanthene dye (Ia1-1)> Under a nitrogen atmosphere, 60.0 parts of the xanthene dye (Ia1) obtained in Synthesis Example 1, 120 parts of diacetone alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.), 240 parts of propylene glycol monomethyl ether (manufactured by Tokyo Chemical Industry Co., Ltd.), and 40 parts of propylene glycol monomethyl ether acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at room temperature for 24 hours, followed by filtration and drying to obtain 26.5 parts of the xanthene dye (Ia1-1) as a deep purple solid (yield 44%). The powder X-ray diffraction pattern of the xanthene dye (Ia1-1) is shown in FIG. 2, and the powder X-ray diffraction parameters are shown in Table 1.

[0217] Example 2 <Synthesis of xanthene dyes (Ia1-2)> Under a nitrogen atmosphere, 30.0 parts of the xanthene dye (Ia1) obtained in Synthesis Example 1 and 258 parts of xylene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed and heated to an internal temperature of 120°C. After stirring at the same temperature for 4 hours, the mixture was cooled to room temperature and filtered. After drying under reduced pressure, 29.4 parts of the xanthene dye (Ia1-2) were obtained as a deep purple solid (yield 98%). The powder X-ray diffraction pattern of the xanthene dye (Ia1-2) is shown in FIG. 3, and the powder X-ray diffraction parameters are shown in Table 1.

[0218] Example 3 <Synthesis of xanthene dyes (Ia1-3)> Under a nitrogen atmosphere, 43.0 parts of the xanthene dye (Ia1) obtained in Synthesis Example 1 and 291 parts of 2-propanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed and stirred at room temperature for 4 hours. The mixture was then filtered and dried under reduced pressure to obtain 28.2 parts of the xanthene dye (Ia1-3) as a deep purple solid (yield 94%). The powder X-ray diffraction pattern of the xanthene dye (Ia1-3) is shown in FIG. 4, and the powder X-ray diffraction parameters are shown in Table 1.

[0219] Example 4 <Synthesis of xanthene dyes (Ia1-4)> Under a nitrogen atmosphere, 30.0 parts of the xanthene dye (Ia1) obtained in Synthesis Example 1, 233 parts of propylene glycol monomethyl ether acetate (Tokyo Chemical Industry Co., Ltd.), 28.2 parts of diacetone alcohol (Tokyo Chemical Industry Co., Ltd.), and 27.6 parts of propylene glycol monomethyl ether (Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at room temperature for 4 hours. The mixture was then filtered and dried under reduced pressure to obtain 28.2 parts of the xanthene dye (Ia1-4) compound as a deep purple solid (yield 94%). The powder X-ray diffraction patterns of the xanthene dyes (Ia1-4) are shown in FIG. 5, and the powder X-ray diffraction parameters are shown in Table 1.

[0220] [Table 1]

[0221] In Table 1, A1 to A4 represent the following values ​​in the diffraction pattern of each xanthene dye at diffraction angles (2θ±0.2°) of 2 to 40° in powder X-ray diffraction using CuKα radiation. A1: The maximum intensity of the diffraction peaks in the range of 5 to 20° when the maximum intensity of the diffraction peaks in the range of 21.0 to 22.1° is taken as 1.0 A2: The maximum intensity of the diffraction peaks in the range of 13.5 to 15.2° when the maximum intensity of the diffraction peaks in the range of 21.0 to 22.1° is taken as 1.0 A3: The maximum intensity of the diffraction peaks in the range of 8 to 10° when the maximum intensity of the diffraction peaks in the range of 21.0 to 22.1° is taken as 1.0 A4: The maximum intensity of the diffraction peaks in the range of 13 to 20° when the maximum intensity of the diffraction peaks in the range of 3 to 7° is taken as 1.0 Furthermore, "2θmax (2 to 22°)" represents the diffraction angle at which the diffraction peak with the maximum intensity exists in the range of 2 to 22°, and "number of peaks (3 to 7°)" represents the number of diffraction peaks existing in the range of 3 to 7°.

[0222] (Resin synthesis example 1) A flask equipped with a reflux condenser, a dropping funnel, and a stirrer was filled with nitrogen to replace the atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added and heated to 85°C with stirring. Next, 38 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 A mixed solution of 25 parts of a mixture of decan-9-yl acrylate (content ratio 1:1 by molar ratio), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a mixed solution of 5 parts of 2,2-azobisisobutyronitrile dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was maintained at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (Resin B-1) solution with a solids content of 25.6%. The resulting copolymer (Resin B-1) had a weight-average molecular weight Mw of 8000, a polydispersity of 2.1, and an acid value calculated as solids of 111 mg-KOH / g. Resin B-1 has the following structural units:

[0223] [ka]

[0224] (Resin synthesis example 2) A suitable amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to replace the atmosphere with nitrogen, and 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80°C with stirring. Next, 38 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 2,6A mixed solution of 289 parts of a mixture of decan-9-yl acrylate (content ratio 1:1 by molar ratio) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a mixed solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was maintained at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (Resin B-2) solution with a solids content of 35.1% and a viscosity of 125 mPas measured with a Brookfield viscometer (23°C). The resulting copolymer (Resin B-2) had a weight-average molecular weight Mw of 9200, a polydispersity of 2.08, and an acid value converted to solids of 77 mg-KOH / g. Resin B-2 has the following structural units:

[0225] [ka]

[0226] The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC (gel permeation chromatography) under the following conditions. Device: HLC-8120GPC (Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40℃ Solvent: Tetrahydrofuran Flow rate: 1.0mL / min Test liquid solid content concentration: 0.001~0.01% by mass Injection volume: 50μL Detector: RI Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (Manufactured by Tosoh Corporation) The ratio of the weight average molecular weight and the number average molecular weight (Mw / Mn) calculated in terms of polystyrene obtained above was taken as the dispersity.

[0227] (Examples 5 to 8 and Comparative Example 1) <Preparation of colorant-containing liquid (P-1)> 50.0 parts of the xanthene dye (Ia1-1) obtained in Example 1, 35.0 parts of a dispersant (DISPER BYK-2001 manufactured by BYK) (solid content equivalent), 40.0 parts of resin B-1 (solid content equivalent), and 875 parts of propylene glycol monomethyl ether acetate were mixed, and 300 parts of 0.05 mm zirconia beads were added and the mixture was shaken. The zirconia beads were removed by filtration, yielding a colorant-containing liquid (P-1) in which the xanthene dye (Ia1-1) was dispersed.

[0228] <Preparation of colorant-containing liquids (P-2) to (P-4)> Colorant-containing liquids (P-2) to (P-4) were obtained in the same manner as in the preparation of colorant-containing liquid (P-1), except that the xanthene dye (Ia1-1) used in the preparation of colorant-containing liquid (P-1) was changed to the xanthene dye shown below. Colorant-containing liquid (P-2): Xanthene dye (Ia1-2) obtained in Example 2 Colorant-containing liquid (P-3): Xanthene dye (Ia1-3) obtained in Example 3 Colorant-containing liquid (P-4): Xanthene dye (Ia1-4) obtained in Example 4

[0229] <Preparation of colorant-containing liquid (P-5)> 58.2 parts of the xanthene dye (Ia1) obtained in Synthesis Example 1, 847 parts of diacetone alcohol, and 94.2 parts of propylene glycol monomethyl ether acetate were mixed and shaken to obtain a colorant-containing liquid (P-5). Note that, because the xanthene dye (Ia1) obtained in Synthesis Example 1 has an amorphous structure, the viscosity of the dispersed solution increased significantly, resulting in poor stability. Using this solution, it was not possible to stably produce a color filter. For this reason, the xanthene dye (Ia1) was dissolved in a solvent to form a colorant-containing liquid.

[0230] <Preparation of Colored Curable Resin Composition> A colored curable resin composition was obtained by mixing the colorant-containing liquid (P), resin (B), polymerizable compound (C), polymerization initiator (D), solvent (E), and leveling agent (F) components to obtain the composition shown in Table 2 below.

[0231] [Table 2]

[0232] In Table 2, each component represents the following compound. Resin (B-2): Resin B-2 (solid content equivalent) Polymerizable compound (C-1): dipentaerythritol polyacrylate (trade name "A-9570", manufactured by Shin-Nakamura Chemical Co., Ltd.) Polymerization initiator (D-1): N-acetyloxy-1-(4-phenylsulfanylphenyl)-3-cyclohexylpropan-1-one-2-imine (trade name "PBG-327"; O-acyloxime compound, manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) Solvent (E-1): Propylene glycol monomethyl ether acetate Leveling agent (F-1): Polyether-modified silicone oil (product name "Toray Silicone SH8400", manufactured by Toray Dow Corning Co., Ltd.)

[0233] <Preparation of colored coating film> A colored curable resin composition was applied by spin coating onto a 5 cm square glass substrate (Eagle XG; manufactured by Corning Incorporated) so that the film thickness after post-baking would be 2 μm, and then pre-baked at 100° C. for 3 minutes to form a colored composition layer. After cooling, the colored composition layer formed on the substrate was exposed to 80 mJ / cm 2 in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). 2 After the light irradiation, the film was post-baked in an oven at 230°C for 30 minutes to obtain a colored coating film. The film thickness of the obtained colored coating film was measured using a DEKTAK3 (manufactured by ULVAC, Inc.).

[0234] <Heat resistance evaluation> The resulting colored coating film was heated in an oven at 230°C for 120 minutes. The xy chromaticity coordinates (x, y) and stimulus value Y of the colored coating film before and after heating were measured from spectral data measured with a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the color difference ΔE was calculated from the measured values ​​using the method described in JIS Z 8730:2009 (7. Calculation method of color difference). * ab was calculated. △E * The smaller the ab, the smaller the color change. The results are shown in Tables 3 to 5.

[0235] <Lightfastness evaluation> An ultraviolet cut filter (COLORED OPTICAL GLASS L38, manufactured by Hoya Co., Ltd.; cuts light of 380 nm or less) was placed on the obtained colored coating film, and the upper surface of the filter was irradiated with xenon lamp light for 48 hours using a lightfastness tester (SUNTEST CPS+, manufactured by Toyo Seiki Co., Ltd.). The colored coating film before and after light irradiation was measured from spectral data measured with a colorimeter (OSP-SP-200, manufactured by Olympus Co., Ltd.) to measure the xy chromaticity coordinates (x, y) and stimulus value Y. The color difference ΔE was calculated from the measured values ​​using the method described in JIS Z 8730:2009 (7. Calculation method for color difference). * ab was calculated. △E * The smaller the ab, the smaller the color change. The results are shown in Tables 4 and 5.

[0236] <Solvent resistance evaluation> The resulting colored coating film was immersed for 40 minutes in a large excess of N-methyl-2-pyrrolidone maintained at a constant temperature of 23°C, and then thoroughly washed with water. Before and after immersion, the colored coating film was measured for xy chromaticity coordinates (x, y) and stimulus value Y from spectral data measured with a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the color difference ΔE was calculated from the measured values ​​using the method described in JIS Z 8730:2009 (7. Calculation method for color difference). * ab was calculated. △E * The smaller the ab, the smaller the color change. * If ab was 7.0 or more, it was evaluated as "×", if it was 3.0 or more and less than 7.0, it was evaluated as "△", and if it was less than 3.0, it was evaluated as "○". The results are shown in Tables 3 and 4.

[0237] [Table 3]

[0238] [Table 4]

[0239] [Table 5]

[0240] The results of Examples 5 to 8 and Comparative Example 1 showed that even xanthene dyes with the same chemical structure could form color filters with excellent heat resistance by having the specified crystal structure of the present invention. It was also possible to preferably improve light resistance and / or solvent resistance. Specifically, in the diffraction pattern of the xanthene dye at diffraction angles (2θ±0.2°) of 2 to 40°, a color filter with excellent light resistance could be formed when 2θmax (2 to 22°) was within the range of 14 to 18° and the A4 value was 1.0 or less. Furthermore, a color filter with excellent solvent resistance could be formed when the number of diffraction peaks present in the range of 3 to 7° was one. In particular, if the xanthene dye has a crystalline structure in which, in the diffraction pattern at a diffraction angle (2θ±0.2°) of 2 to 40°, 2θmax (2 to 22°) is in the range of 14 to 18°, the number of diffraction peaks present in the range of 3 to 7° is one or more, the value of A1 is 2.0 or more, the value of A2 is 0.3 or more, the value of A3 is 0.1 or more, and the value of A4 is 1.0 or less, it was possible to form a color filter with excellent heat resistance, light resistance, and solvent resistance.

Claims

1. In the diffraction pattern at a diffraction angle (2θ±0.2°) of 2 to 40° in powder X-ray diffraction using CuKα radiation, When the maximum intensity of the diffraction peaks in the range of 21.0 to 22.1° is set to 1.0, the maximum intensity A of the diffraction peaks in the range of 5 to 20° is 1 is 1.3 or more, At least one diffraction peak exists in the range of 3 to 7 degrees. A xanthene dye represented by the following formula (I): 【Chemical 1】 [In formula (I), R 1 ~R 4 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and —CH 2 - represents -O-, -CO-, or -NR 11 - may be replaced by R 1 and R 2 may be bonded to each other to form a ring containing a nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring containing the nitrogen atom. R 5 is -OH, -SO 3 - , -SO 3 H, -SO 3 - Z + , -CO 2 H, -CO 2 - Z + , -CO 2 R 8 , -SO 3 R 8 , or -SO 2 NR 9 R 10 Represents. R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents 0 or 1. a represents 0 or 1. X represents a halogen atom. Z + teeth, + N (R 12 ) 4 , Na + , or K + represents the four R 12 may be the same or different. R 8 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH 2 - represents -O-, -CO-, -NH-, or -NR 8 - may be replaced by R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. R 11 and R 12 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

2. In the diffraction pattern at a diffraction angle (2θ±0.2°) of 2 to 40° in powder X-ray diffraction using CuKα radiation, 2. The xanthene dye according to claim 1, wherein a diffraction peak with maximum intensity in the range of 2 to 22 degrees is present in the range of 5 to 18 degrees.

3. In the diffraction pattern at a diffraction angle (2θ±0.2°) of 2 to 40° in powder X-ray diffraction using CuKα radiation, When the maximum intensity of the diffraction peaks in the range of 21.0 to 22.1° is taken as 1.0, the maximum intensity A of the diffraction peaks in the range of 13.5 to 15.2° is 2 is 0.3 or more, and the maximum intensity A of the diffraction peak existing in the range of 8 to 10 degrees 3 The xanthene dye according to claim 1 , wherein

4. In the diffraction pattern at a diffraction angle (2θ±0.2°) of 2 to 40° in powder X-ray diffraction using CuKα radiation, When the maximum intensity of the diffraction peaks in the range of 3 to 7 degrees is taken as 1.0, the maximum intensity A of the diffraction peaks in the range of 13 to 20 degrees is 4 is 1.0 or less, 2. The xanthene dye according to claim 1, wherein a diffraction peak with maximum intensity in the range of 2 to 22 degrees is present in the range of 14 to 18 degrees.

5. In the diffraction pattern at a diffraction angle (2θ±0.2°) of 2 to 40° in powder X-ray diffraction using CuKα radiation, 2. The xanthene dye according to claim 1, which has one diffraction peak in the range of 3 to 7 degrees.

6. A colored curable resin composition comprising the xanthene dye according to any one of claims 1 to 5, a resin, a polymerizable compound, a polymerization initiator, and a solvent.

7. A color filter comprising the colored curable resin composition according to claim 6.

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

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

10. The method includes a contacting step of stirring a xanthene colorant represented by the following formula (I) in a solvent containing at least one selected from the group consisting of an alcohol having 3 to 6 carbon atoms, an aromatic hydrocarbon solvent having 6 to 9 carbon atoms, an alkylene glycol monoalkyl ether, and an alkylene glycol monoalkyl ether acetate while maintaining the xanthene colorant in a precipitated state, and a separation step of isolating the xanthene colorant by solid-liquid separation: In the contacting step, the total content of the alcohol having 3 to 6 carbon atoms, the aromatic hydrocarbon solvent having 6 to 9 carbon atoms, the alkylene glycol monoalkyl ether, and the alkylene glycol monoalkyl ether acetate is 60 mass% or more of the total solvents. 【Chemistry 2】 [In formula (I), R 1 ~R 4 are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and —CH 2 - represents -O-, -CO-, or -NR 11 - may be replaced by R 1 and R 2 may be bonded to each other to form a ring containing a nitrogen atom, R 3 and R 4 may be bonded to each other to form a ring containing the nitrogen atom. R 5 is -OH, -SO 3 - , -SO 3 H, -SO 3 - Z + , -CO 2 H, -CO 2 - Z + , -CO 2 R 8 , -SO 3 R 8 , or -SO 2 NR 9 R 10 Represents. R 6 and R 7 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. m represents 0 or 1. a represents 0 or 1. X represents a halogen atom. Z + teeth, + N (R 12 ) 4 , Na + , or K + represents the four R 12 may be the same or different. R 8 represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom. R 9 and R 10 each independently represents a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and —CH 2 - represents -O-, -CO-, -NH-, or -NR 8 - may be replaced by R 9 and R 10 may be bonded to each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom. R 11 and R 12 each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

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