TWI707201B - Colored curable resin composition, color filter and display device - Google Patents

Abstract

The subject of the present invention is to provide a colored curable resin composition, a color filter and a display device excellent in heat resistance. The colored curable resin composition of the present invention comprises a xanthene compound (A-1), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), and is characterized in that the xanthene compound ( A-1) is a compound having a cation (AXa) and an anion (AXb), the cation (AXa) has a xanthene skeleton, and the anion (AXb) contains at least one element selected from tungsten, molybdenum, silicon and phosphorus and oxygen as An essential element, the above-mentioned xanthene skeleton is a xanthene skeleton having a substituted or unsubstituted sulfamsulfonyl group.

Description

Colored curable resin composition, color filter and display device

FIELD OF THE INVENTION The present invention relates to a colored curable resin composition containing a xanthene compound.

BACKGROUND OF THE INVENTION Xanthene compounds are used as coloring agents for color filters contained in various display devices such as liquid crystal display devices, solid-state imaging devices, and the like. For example, Patent Document 1 describes a compound represented by formula (A1).

現有技術文獻 專利文獻[Chemical formula 1]

Prior Art Document Patent Document

Patent Document 1: Japanese Patent Application Publication No. 2014-88558

Problems to be Solved by the Invention In the case of using the above-mentioned compounds known in the past, the heat resistance of the color filter obtained is not sufficiently satisfactory. Means to solve the problem

The present invention includes the following inventions. [1] A colored curable resin composition, which is a colored curable resin composition containing a xanthene compound (A-1), a resin (B), a polymerizable compound (C), and a polymerization initiator (D), wherein The above-mentioned xanthene compound (A-1) is a compound having a cation (AXa) and an anion (AXb). The cation (AXa) has a xanthene skeleton with a substituted or unsubstituted sulfamsulfonyl group, and the anion (AXb) contains At least one element of tungsten, molybdenum, silicon, and phosphorus and oxygen are essential elements, and the xanthene skeleton is a xanthene skeleton having a substituted or unsubstituted sulfamsulfonyl group. [2] The colored curable resin composition according to [1], wherein the cation (AXa) having a xanthene skeleton is a cation represented by formula (I).

[Chemical formula 2]

[In formula (I), R ^1a to R ^4a independently represent a hydrogen atom, an optionally substituted aromatic hydrocarbon group with 6 to 10 carbons, or an optionally substituted saturated hydrocarbon group with 1 to 20 carbons. The saturated The methylene group (-CH ₂ -) contained in the hydrocarbon group may be -O-, -CO-, -NR ^11a -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or- NHCO- substitution, R ^1a and R ^2a can form a ring containing a nitrogen atom together, and R ^3a and R ^4a can form a ring containing a nitrogen atom together. However, adjacent methylene groups will not be replaced with the same substituent at the same time, and the terminal methylene groups will not be replaced. R ^6a and R ^7a independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ma represents an integer from 1 to 5. R ^9a and R ^10a independently represent a hydrogen atom or a saturated hydrocarbon group with 1 to 20 carbon atoms which may have a substituent. The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO -, -NR ^11a -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement, R ^9a and R ^10a can be combined with each other to form a 3-10 element containing a nitrogen atom Cyclic heterocycle. However, adjacent methylene groups will not be replaced with the same substituent at the same time, and the terminal methylene groups will not be replaced. R ^11a represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. [3] The colored curable resin composition according to [1] or [2], wherein the anion (AXb) is an anion of a heteropolyacid or an isopolyacid containing tungsten as an essential element. [4] The colored curable resin composition according to any one of [1] to [3], wherein the anion (AXb) is an anion of phosphotungstic acid, an anion of silicotungstic acid, or a tungsten-based homopolyacid Any of the anions. [5] A color filter formed of the coloring curable resin composition according to any one of [1] to [4]. [6] A display device including the color filter described in [5]. Effect of invention

Since the colored curable resin composition of the present invention contains a specific xanthene compound, it can provide a color filter excellent in heat resistance.

BEST MODE FOR CARRYING OUT THE INVENTION The colored curable resin composition of the present invention contains a xanthene compound (A-1), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

<Colorant (A)> The xanthene compound (A-1) in the present invention has a cation (AXa) and an anion (AXb), the cation (AXa) has a xanthene skeleton, and the anion (AXb) contains tungsten, molybdenum, At least one element among silicon and phosphorus and oxygen are essential elements, and the xanthene skeleton has a substituted or unsubstituted sulfasulfonyl group. By having a cation (AXa) and an anion (AXb) having a xanthene skeleton, the heat resistance of the xanthene compound can be improved.

The cation (AXa) having a xanthene skeleton preferably has a substituted or unsubstituted sulfamethane group, and is more preferably a cation represented by formula (I).

[Chemical formula 3]

[In formula (I), R ^1a to R ^4a independently represent a hydrogen atom, an optionally substituted aromatic hydrocarbon group with 6 to 10 carbon atoms, or an optionally substituted saturated hydrocarbon group with 1 to 20 carbon atoms. The methylene group (-CH ₂ -) contained in the hydrocarbon group may be -O-, -CO-, -NR ^11a -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or- NHCO- substitution, R ^1a and R ^2a can form a ring containing a nitrogen atom together, and R ^3a and R ^4a can form a ring containing a nitrogen atom together. However, adjacent methylene groups will not be replaced with the same substituent at the same time, and the terminal methylene groups will not be replaced. R ^6a and R ^7a independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ma represents an integer from 1 to 5. R ^9a and R ^10a independently represent a hydrogen atom or a saturated hydrocarbon group with 1 to 20 carbon atoms which may have a substituent. The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO -, -NR ^11a -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement, R ^9a and R ^10a can be combined with each other to form a 3-10 element containing a nitrogen atom Cyclic heterocycle. However, adjacent methylene groups will not be replaced with the same substituent at the same time, and the terminal methylene groups will not be replaced. R ^11a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ]

In formula (I), when -SO ₃ ^- exists, its number is one.

Examples of saturated hydrocarbon groups having 1 to 20 carbon atoms in R ^1a to R ^4a and R ^9a to R ^11a include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, Nonyl, decyl, dodecyl, hexadecyl, eicosyl and other linear alkyl groups; isopropyl, isobutyl, isopentyl, neopentyl, 2-ethylhexyl and other branches Chain alkyl; cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl and other carbon 3-20 alicyclic saturated hydrocarbon groups. The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group can be -O-, -CO-, -NR ^11a -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- Or -NHCO- substitution. However, adjacent methylene groups will not be replaced with the same substituent at the same time, and the terminal methylene groups will not be replaced.

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is replaced by -O- include the following groups (* represents a bonding terminal).

[Chemical formula 4]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is replaced by -CO- include the following groups (* represents a bonding terminal).

[Chemical formula 5]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is replaced by -NR ^11a -include the following groups (* represents a bonding terminal).

[Chemical formula 6]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is replaced by -OCO- include the following groups (* represents a bonding terminal).

[Chemical formula 7]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is replaced by -COO- include the following groups (* represents a bonding terminal).

[Chemical formula 8]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is replaced by -OCONH- include the following groups (* represents a bonding terminal).

[Chemical formula 9]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is replaced by -NHCOO- include the following groups (* represents a bonding terminal).

[Chemical formula 10]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is replaced by -CONH- include the following groups (* represents a bonding terminal).

[Chemical formula 11]

Examples of the group in which the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group is replaced by -NHCO- include the following groups (* represents a bonding terminal).

[Chemical formula 12]

The saturated hydrocarbon group in R ^1a to R ^4a may have a substituent, and examples of the substituent include an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. Examples of the aromatic hydrocarbon groups having 6 to 10 carbon atoms that the saturated hydrocarbon groups of R ^1a to R ^4a may have include the same groups as those exemplified as the aromatic hydrocarbon groups having 6 to 10 carbon atoms in R ^1a to R ^4a . group. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. The saturated hydrocarbon group in R ^9a and R ^10a may have a substituent, and examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, or a hydroxyl group.

Examples of the ring formed by R ^1a and R ^2a together and the ring formed by R ^3a and R ^4a together include the following rings. In the formula, * represents the bonding end.

[Chemical formula 13]

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^1a to R ^4a include phenyl, tolyl, xylyl, mesityl, propylphenyl, and butylphenyl. The aromatic hydrocarbon group having 6 to 10 carbon atoms may have a substituent. Examples of the aromatic hydrocarbon group may have a substituent group include a halogen ^{atom, -R 8a, -OH, -OR 8a} , -SO 3 -, -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO ₂ R ^8a , -SR ^8a , -SO ₂ R ^8a , -SO ₃ R ^8a and -SO ₂ NR ^12a R ^13a . Among these, as a substituent group, preferably _{^{-R 8a, -SO 3 -, -SO}} 3 H, -SO 3 - Z + and -SO ₂ NR ^12a R ^13a, and more preferably -R ^8a, -SO ₃ ^- Z ⁺ and -SO ₂ NR ^12a R ^13a . As -R ^{8a in} this case, a saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 5 carbon atoms is still more preferable. In addition, as -SO ₃ ^- Z ^{+ in} this case, -SO ₃ ^- N ⁺ (R ^11a ) ₄ is preferable. Z ⁺ represents ⁺ N (R ^11a ) ₄ , Na ⁺ or K ⁺ , and the four R ^11a may be the same or different. R ^8a represents a saturated hydrocarbon group having 1 to 20 carbon atoms which may be substituted by a halogen atom. R ^12a and R ^13a independently represent a hydrogen atom or a saturated hydrocarbon group with 1 to 20 carbon atoms that may have a substituent, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO -, -NR ^11a -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement, R ^12a and R ^13a can be combined with each other to form 3~10 elements containing nitrogen atoms Cyclic heterocycle. However, adjacent methylene groups will not be replaced with the same substituent at the same time, and the terminal methylene groups will not be replaced.

Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^8a , R ^12a and R ^13a include the same groups as the saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^1a to R ^4a . The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^12a and R ^13a may have a substituent, and examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, or a hydroxyl group.

Examples of -OR ^8a include methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and di Alkoxy groups such as decaalkoxy and the like.

Examples of -CO ₂ R ⁸ include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl, and eicosyloxycarbonyl.

Examples of -SR ^8a include methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, decylsulfanyl, and eicosylsulfanyl. Base etc. Examples of -SO ₂ R ^8a include alkyl sulfonyl groups such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl, and eicosylsulfonyl. Sulfonyl and so on. Examples of -SO ₃ R ^8a include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosane Alkoxysulfonyl such as oxysulfonyl and the like.

Examples of -SO ₂ NR ^12a R ^13a include: sulfasulfonyl; N-methylsulfasulfonyl, N-ethylsulfasulfonyl, N-propylsulfasulfonyl, and N-isopropyl Sulfonyl, N-Butyl Sulfonyl, N-Isobutyl Sulfonyl, N-sec-Butyl Sulfonyl, N-tert-Butyl Sulfonyl, N-Pentylamine Sulfonyl, N-(1-ethylpropyl)sulfamoyl, N-(1,1-dimethylpropyl)sulfamoyl, N-(1,2-dimethylpropyl) Sulfamoyl, N-(2,2-Dimethylpropyl)sulfasulfonyl, N-(1-methylbutyl)sulfasulfonyl, N-(2-methylbutyl)sulfasulfon Acetyl, N-(3-methylbutyl)sulfasulfonyl, N-cyclopentylsulfasulfonyl, N-hexylsulfasulfonyl, N-(1,3-dimethylbutyl)amine Sulfonyl, N-(3,3-dimethylbutyl)sulfasulfonyl, N-heptylsulfasulfonyl, N-(1-methylhexyl)sulfasulfonyl, N-(1, 4-Dimethylpentyl)sulfasulfonyl, N-octylsulfasulfonyl, N-(2-ethylhexyl)sulfasulfonyl, N-(1,5-dimethylhexyl)sulfonyl N-1 substituted sulfasulfonyl groups such as sulfamate and N-(1,1,2,2-tetramethylbutyl)sulfasulfonyl; N,N-dimethylsulfasulfonyl, N,N- Ethyl methylsulfamate, N,N-diethylsulfamate, N,N-propyl methylsulfamate, N,N-isopropyl methylsulfamate, N, N-tert-Butylmethylsulfasulfonyl, N,N-butylethylsulfasulfonyl, N,N-bis(1-methylpropyl)sulfasulfonyl and N,N-heptylmethylamine Sulfonyl and other N, N-2 substituted sulfamyl and so on.

ma is preferably 1 to 4, more preferably 1 or 2.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^6a and R ^7a include alkyl groups having 1 to 6 carbon atoms among the alkyl groups listed above.

R ^12a and R ^13a may represent a 3- to 10-membered nitrogen-containing heterocyclic ring together with the nitrogen atom. Examples of the heterocyclic ring include the following heterocyclic rings. In the formula, * represents the bonding end.

[Chemical formula 14]

Examples of the aralkyl group having 7 to 10 carbon atoms in R ^11a include benzyl, phenylethyl, and phenylbutyl.

Z ⁺ is preferably ⁺ N(R ^11a ) ₄ , Na ⁺ or K ⁺ , and more preferably ⁺ N(R ^11a ) ₄ . As the above-mentioned ⁺ N(R ^11a ) ₄ , it is preferable that at least two of the four R ^11a are monovalent saturated hydrocarbon groups having 5 to 20 carbons. In addition, the total carbon number of the four R ^11a is preferably 20 to 80, and more preferably 20 to 60.

As -SO ₂ NR ^9a R ^10a , the same groups as those exemplified as -SO ₂ NR ^12a R ^{13a can} be mentioned. In addition, as a 3- to 10-membered heterocyclic ring containing a nitrogen atom formed by R ^9a and R ^10a which can be combined with each other, a 3- to 10-membered nitrogen-containing heterocycle that can be formed with a nitrogen atom together with R ^12a and R ^13a can be mentioned. Ring the same ring.

Among them, as R ^1a and R ^4a , a saturated hydrocarbon group having 1 to 20 carbons which may have a substituent and an aromatic hydrocarbon group having 6 to 10 carbons which may have a substituent are preferable, and a carbon 6 to 10 which may have a substituent is more preferable. 10 aromatic hydrocarbon groups. The carbon number of the saturated hydrocarbon in R ^1a and R ^4a is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and preferably does not have a substituent. In addition, the substituent of the aforementioned aromatic hydrocarbon group is preferably -R ^8a . As R ^2a and R ^3a , a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent is preferable. The carbon number of the saturated hydrocarbon group in R ^2a and R ^3a is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and preferably does not have a substituent. As R ^6a and R ^7a , a hydrogen atom is preferable. The carbon number of the saturated hydrocarbon group in R ^8a is preferably 1-10, more preferably 1-5, and still more preferably 1-3. As R ^9a , R ^10a , R ^12a and R ^13a , a hydrogen atom and a saturated hydrocarbon group having 1 to 12 carbon atoms are preferable. In addition, it is preferable that at least one of R ^9a and R ^10a is a saturated hydrocarbon group, and it is more preferable that both of R ^9a and R ^10a are saturated hydrocarbon groups. In addition, it is preferable that at least one of R ^12a and R ^13a is a saturated hydrocarbon group, and it is more preferable that both of R ^12a and R ^13a are saturated hydrocarbon groups. As -SO ₂ NR ^9a R ^10a and -SO ₂ NR ^12a R ^13a , N-1 substituted sulfasulfonyl and N-2 substituted sulfasulfonyl are preferable. As R ^11a , a saturated hydrocarbon group having 1 to 20 carbon atoms is preferable.

As the cation (AXa) having a xanthene skeleton, a cation having a xanthene skeleton represented by formula (I-1) is preferable. The cation represented by formula (I-1) may be its tautomer.

[Chemical formula 15]

[In formula (I-1), R ^1b to R ^4b independently represent a saturated hydrocarbon group with 1 to 20 carbon atoms that may have a substituent, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be -O-, -CO-, -NR ^11b -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement, R ^1b and R ^2b can form a nitrogen atom Ring, R ^3b and R ^4b may together form a ring containing a nitrogen atom. However, adjacent methylene groups will not be replaced with the same substituent at the same time, and the terminal methylene groups will not be replaced. R ^6b and R ^7b independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. mb represents an integer from 0 to 5. When mb is 2 or more, the plurality of -SO ₂ NR ^9b R ^10b may be the same or different. R ^9b and R ^10b independently represent a hydrogen atom or a saturated hydrocarbon group with 1 to 20 carbon atoms that may have a substituent. The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO -, -NR ^11b -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement, R ^9b and R ^10b can be combined with each other to form a 3~10 element containing a nitrogen atom Cyclic heterocycle. However, adjacent methylene groups will not be replaced with the same substituent at the same time, and the terminal methylene groups will not be replaced. R ^11b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ]

Preferred forms of R ^1b to R ^11b and mb are selected from the above-mentioned preferred forms of R ^1a to R ^11a and ma, within a range that does not exceed the concept of R ^1b to R ^11b and mb.

In addition, as the cation (AXa) having a xanthene skeleton, a cation having a xanthene skeleton represented by formula (I-2) is preferable. The cation represented by formula (I-2) may be its tautomer.

[Chemical formula 16]

[In formula (I-2), R ^1c and R ^4c independently represent an alkyl group with 1 to 4 carbons, an alkylsulfanyl group with 1 to 4 carbons, or an alkylsulfonyl group with 1 to 4 carbons . p and q represent an integer from 0 to 5 independently of each other. When p is 2 or more, the plurality of R ^1c may be the same or different, and when q is 2 or more, the plurality of R ^4c may be the same or different. R ^2c and R ^3c independently represent a hydrogen atom, an optionally substituted monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be -O- , -CO-, -NR ^11c -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement. However, adjacent methylene groups will not be replaced with the same substituent at the same time, and the terminal methylene groups will not be replaced. R ^1c and R ^2c can together form a ring containing a nitrogen atom, and R ^3c and R ^4c can together form a ring containing a nitrogen atom. R ^6c and R ^7c independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. mc represents an integer from 0 to 5. When mc is 2 or more, the plurality of -SO ₂ NR ^9c R ^10c may be the same or different. R ^9c and R ^10c independently represent a hydrogen atom or a saturated hydrocarbon group with 1 to 20 carbon atoms that may have a substituent. The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO -, -NR ^11c -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO-Replacement, R ^9c and R ^10c can be combined with each other to form 3~10 elements containing nitrogen atoms Cyclic heterocycle. However, adjacent methylene groups will not be replaced with the same substituent at the same time, and the terminal methylene groups will not be replaced. R ^11c represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbons, or an aralkyl group having 7 to 10 carbons. ]

Preferred forms of R ^1c to R ^4c , R ^6c to R ^7c , R ^9c to R ^11c and mc are selected from the preferred forms of substituents that the aromatic hydrocarbon groups represented by R ^1a to R ^11a , ma and R ^1a may have, respectively , Choose within the range not exceeding the concepts of R ^1c ~R ^4c , R ^6c ~R ^7c , R ^9c ~R ^11c and mc.

Examples of the cation (AXa) include a cation represented by the following formula (AXa-I). It should be noted that in Table 1, R ⁴⁰ represented by R ^2A , R ^3A , R ^10A represents a monovalent saturated hydrocarbon group having 1 to 20 carbons, preferably represents a branched chain alkyl group having 6 to 12 carbons, and more preferably Represents 2-ethylhexyl.

[Chemical formula 17]

【Table 1】

In Table 1, Me represents a methyl group, Et represents an ethyl group, Pr represents an n-propyl group, and iPr represents an isopropyl group. Ph1~Ph10 means groups represented by the following formula, Hc1~Hc4 are the cases where R ^1A and R ^2A , R ^3A and R ^4A together form a ring containing a nitrogen atom, corresponding to the respective ring of Hc1~Hc4 Descriptive expression.

[Chemical formula 18]

[Chemical formula 19]

Among them, cations (AXa) are preferably cations (AXa-1) to (AXa-4), (AXa-27) to (AXa-30).

The above-mentioned cation (AXa) can be produced, for example, by sulfaminating the compound represented by formula (II).

[式（II）中，R^1a ~R^4a 、R^6a ~R^7a 和ma與上述同義。][Chemical formula 20]

[In formula (II), R ^1a to R ^4a , R ^6a to R ^7a and ma have the same meaning as above. ]

The anion (AXb) used in combination with the cation (AXa) having a xanthene skeleton contains at least one element selected from tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements, and preferably contains tungsten and oxygen as essential elements. From the viewpoint of heat resistance, these anions are preferable. As the anion (AXb), heteropolyacid or homopolyacid anions containing tungsten as an essential element are preferable, and anions of phosphotungstic acid, silicotungstic acid, and tungsten homopolyacid are more preferable.

Examples of the heteropoly acid and isopoly acid anion containing tungsten as an essential element include Keggin type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- and Dawson type phosphotungstic acid ion α-[P ₂ W ₁₈ O ₆₂ ] ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type tungstic acid ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , and as other examples, [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α-[SiW ₉ O ₃₄ ] ^10- , γ-[SiW ₁₀ O ₃₆ ] ^8- , α-[SiW ₁₁ O ₃₉ ] ^8- , β-[ SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and their mixtures.

In addition, an anion composed of at least one element selected from silicon and phosphorus and oxygen is also preferable. Examples of such anions composed of at least one element selected from silicon and phosphorus and oxygen include SiO ₃ ^2- and PO ₄ ^3- .

Phosphotungstic acid as the anion (AXb), preferably phosphotungstic acid ion Keggin type, Dawson type phosphotungstic acid ion; Keggin-type anion Silicotungstic acid Silicotungstic acid ion, [W ₁₀ O _32] ^4-, etc. with tungsten Polyacid anion. Among them, phosphotungstic acid anions and tungsten-based homopolyacid anions are particularly preferred.

As the anion (AXb), heteropolyacid and homopolyacid anions containing tungsten as an essential element are more preferable, phosphotungstic acid anions, silicotungstic acid anions, and tungsten homopolyacid anions are more preferable, and [ PW ₁₂ O ₄₀ ] ^3- , [P ₂ W ₁₈ O ₆₂ ] ^6- , [SiW ₁₂ O ₄₀ ] ^4- and [W ₁₀ O ₃₂ ] ^4- , particularly preferably [PW ₁₂ O ₄₀ ] ^3- and [P ₂ W ₁₈ O ₆₂ ] ^6- . From the viewpoint of heat resistance, an anion of a heteropoly acid or homopoly acid containing tungsten as an essential element can be used.

As the compound (AI), three arbitrary cations among the above-mentioned cations (AXa-1) to (AXa-52), preferably cations (AXa-1) to (AXa-4) and (AXa-27) can be cited ~(AXa-30) any combination of 3 cations and anion α-[PW ₁₂ O ₄₀ ] ^3- , any 6 cations of the above cations (AXa-1)~(AXa-52), preferably cations (AXa-1)~(AXa-4) and (AXa-27)~(AXa-30) any combination of 6 cations and anions α-[P ₂ W ₁₈ O ₆₂ ] ^6- , the above cations (AXa -1) Any 4 cations from ~(AXa-52), preferably any 4 cations and anions from cation (AXa-1)~(AXa-4) and (AXa-27)~(AXa-30) α-[SiW ₁₂ O ₄₀ ] ^4- and [W ₁₀ O ₃₂ ] ^4- combination, etc.

Specifically, it is preferably a compound (Xa) composed of the following cation (AXa) and anion (AXb).

【Table 2】

The xanthene compound (A-1) can be produced, for example, by mixing the compound represented by the formula (III) and the alkali metal salt of the anion (Axb) described above in a solvent. Examples of alkali metals include lithium, sodium, and potassium.

[Chemical formula 21]

[In formula (III), R ^1a to R ^4a , R ^6a to R ^7a , R ^9a to R ^10a and ma have the same meaning as above. ]

Examples of solvents include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, Ethanol, isopropanol, acetone, tetrahydrofuran, dioxane, water and chloroform. The compound represented by formula (III) can be produced by a known method.

In the present invention, a colored dispersion containing the xanthene compound (A-1) and a solvent can be prepared, and the obtained colored dispersion can be used for coloring the curable resin composition. As the solvent used in the colored dispersion liquid, the same solvent as the solvent (E) described later can be used. In addition, it is preferable to further use a pigment dispersant in the colored dispersion liquid, and if necessary, part or all (preferably a part) of the resin (B) used in the colored curable resin composition may be contained in advance.

As the colorant (A), the xanthene compound (A-1) described above may be contained alone, but for the purpose of toning, that is, to adjust the spectral characteristics, it may further contain other dyes (A1) and pigments (P).

Examples of the dye (A1) include dyes such as oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, and sulfonamide derivatives of acid dyes. Examples include color index ( Compounds classified as dyes published by The Society of Dyers and Colourists, and well-known dyes described in the dyeing notes (Sei Dyesha). In addition, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, naphthoquinone dyes, quinonimine dyes, methine dyes, azomethine dyes, Squaraine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Among these, organic solvent-soluble dyes are preferably used.

Specifically, CI Solvent Yellow 4 (hereinafter the description of CI Solvent Yellow is omitted, and only the serial number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162 can be cited; CI solvent red 45, 49, 125, 130, 218; CI solvent orange 2, 7, 11, 15, 26, 56; CI solvent blue 4, 5, 37, 67, 70, 90; CI solvent green 1, 4, 5, 7, 34, 35 and other CI solvent dyes, 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, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 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, 169, 173; CI Acid Violet 6B, 7, 9, 17, 19, 30, 102; CI Acid Blue 1, 7, 9 , 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120 , 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335; CI Acid Green 1, 3 , 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and other CI acid dyes, CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 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 purple 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; CI direct blue 1, 2, 6, 8, 15, 22, 25, 41, 57, 71, 76, 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 green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dyes, CI disperse yellow 54, 76 and other CI dispersion Dyes, CI Basic Red 1, 10; CI Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68; CI basic dyes such as CI Basic Green 1, CI Reactive Yellow 2, 76, 116; CI Reactive Orange 16; CI Reactive Red 36 and other CI Reactive Dyes, CI Mordant Yellow 5, 8, 10, 16, 20 , 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; CI mordant red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 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, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58; CI Mordant Blue 1, 2, 3 , 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61, 74, 77, 83, 84 ; CI mordant dyes such as CI mordant green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, and CI vat dyes such as CI vat green 1. Among them, cyan dyes, violet dyes, and red dyes are preferred. These dyes may be used alone or in combination of two or more kinds.

The pigment (P) is not particularly limited, and known pigments can be used. For example, pigments classified as pigments in the color index (published by The Society of Dyers and Colourists) can be used. Examples of pigments include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, Orange pigments such as 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216 , 224, 242, 254, 255, 264, 265 and other red pigments; CI pigment blue 15, 15: 3, 15: 4, 15: 6, 60 and other cyan pigments; CI pigment violet 1, 19, 23, 29, 32 , 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58, 59 and other green pigments.

For pigments, if necessary, rosin treatment, surface treatment using pigment derivatives introduced with acidic or basic groups, etc., grafting treatment to the surface of the pigment using polymer compounds, etc., and micronization with sulfuric acid A micronization treatment such as a method or the like, a washing treatment using an organic solvent, water, etc., for removing impurities, a removal treatment such as an ion exchange method for ionic impurities, and the like. It is preferable that the particle diameters of the pigments are individually uniform.

Regarding the pigment, by containing the pigment dispersant and performing the dispersion treatment, it is possible to obtain a pigment dispersion in a state where the pigment dispersant is uniformly dispersed in the solution. Regarding the pigment, the dispersion treatment may be performed individually, or a plurality of types may be mixed and subjected to the dispersion treatment.

Examples of the above-mentioned pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other pigment dispersants. These pigment dispersants can be used individually or in combination of 2 or more types. As a pigment dispersant, it is expressed by a trade name, and includes KP (manufactured by Shin-Etsu Chemical Co., Ltd.), FLORENE (manufactured by Kyoeisha Chemical Co., Ltd.), Ceruspas (manufactured by Zebeka Co., Ltd.), and EFKA (manufactured by BASF Co., Ltd.) ), Ajispa (manufactured by Ajinomoto Fyntec Co., Ltd.), Disperbyk (manufactured by BYK Chemie), etc.

The content of the xanthene compound (A-1) is usually 1% by mass or more and 100% by mass or less, and preferably 10% by mass or more and 100% by mass or less relative to the total amount of the coloring agent (A). In addition, it may be 30% by mass or more, preferably 50% by mass or more, more preferably 70% by mass or more. When the dye (A1) is included, the content of the dye (A1) relative to the total amount of the colorant (A) is preferably 0.5% by mass or more and 90% by mass or less, more preferably 40% by mass or more and 80% by mass the following. When the pigment (P) is included, relative to the total amount of the colorant (A), the content of the pigment (P) is preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 70% by mass Hereinafter, it is more preferably 1% by mass or more and 50% by mass or less.

The content of the colorant (A) relative to the total solid content is preferably 0.1% by mass or more and 70% by mass or less, more preferably 0.5% by mass or more and 60% by mass or less, and still more preferably 1% by mass or more and 50% by mass. Less than mass%. If the content of the colorant (A) is within the above-mentioned range, the desired spectral and color density can be obtained. In addition, the "total amount of solid content" in this specification means the total amount of the components after removing the solvent (E) from the coloring curable resin composition of this invention. The total amount of solid content and the content of each component relative to it can be measured by a known analysis means such as liquid chromatography or gas chromatography, for example.

<Resin (B)> The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, preferably having a structural unit derived from at least one monomer (a) selected from unsaturated carboxylic acid and unsaturated carboxylic anhydride polymer. The resin (B) preferably has a structural unit derived from the above-mentioned monomer (a), a monomer (b) derived from a cyclic ether structure having a carbon number of 2 to 4 and an ethylenically unsaturated bond, and a monomer (b) that can be combined with the monomer ( a) A copolymer of a structural unit of at least one of the copolymerized monomers (c). The reaction sequence is not limited, and monomer (a) and at least one of monomers (b) and (c) can be simultaneously copolymerized. In addition, when using all of the monomers (a) to (c), the monomer (c) may be reacted after the monomer (a) and the monomer (b) are copolymerized, or the monomer (a) ) After copolymerizing with monomer (c), the monomer (b) is reacted. In addition, the monomer (a), the monomer (b), and the copolymer of the monomer (c) may be reacted to further react the carboxylic anhydride.

Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid; maleic acid, fumaric acid, citraconic acid, medium Conic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydro Unsaturated dicarboxylic acids such as phthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; 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-carboxymethylbicyclo[2.2.1]hept-2-ene, 5 -Bicyclic unsaturated compounds containing carboxyl groups such as carboxyethylbicyclo[2.2.1]hept-2-ene; carboxylic anhydrides such as anhydrides of the above-mentioned unsaturated dicarboxylic acids other than fumaric acid and mesaconic acid. Examples include succinic acid mono[2-(meth)acryloyloxyethyl] ester, phthalic acid mono[2-(meth)acryloyloxyethyl] ester, etc. Unsaturated mono[(meth)acryloyloxyalkyl] esters; α-(hydroxymeth)acrylic acid, unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the viewpoint of copolymerization reactivity and the solubility of the obtained resin in an aqueous alkali solution.

(B) Refers to the polymerization of a cyclic ether structure with 2 to 4 carbon atoms (for example, at least one selected from an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond Sexual compounds. (B) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group is preferred.

Examples of (b) include monomers (b1) having oxirane groups and ethylenically unsaturated bonds (hereinafter sometimes referred to as "(b1)"), oxetanyl groups and ethylenically unsaturated bonds. The bond monomer (b2) (hereinafter may be referred to as “(b2)”), the monomer (b3) having a tetrahydrofuran group and an ethylenically unsaturated bond (hereinafter may be referred to as “(b3)”), and the like.

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter may be referred to as "(b1-1)") , A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

As (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specific examples of (b1-1) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, and glycidyl Vinyl ether, vinyl benzyl glycidyl ether, α-methyl vinyl benzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyl) Glyceryloxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidyl) Glyceryloxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5 -Tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, etc.

Examples of (b1-2) include vinylcyclohexene monoxide and 1,2-epoxy-4-vinylcyclohexane (for example, Cerocoide (registered trademark) 2000; manufactured by Daicel Co., Ltd.) , 3,4-epoxycyclohexyl methyl (meth)acrylate (for example, Seikromam (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexyl methyl (meth)acrylate (For example, Seikromam (registered trademark) M100; manufactured by Daicel Co., Ltd.), a compound represented by formula (BI), a compound represented by formula (BII), and the like.

[Chemical formula 22]

[In formula (BI) and formula (BII), R ^a and R ^b independently represent 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 by a hydroxyl group. X ^a and X ^b each independently represents a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-. R ^c represents an alkylene group having 1 to 6 carbon atoms. * Indicates the bonding end with O. ]

As the compound represented by the formula (BI), a compound represented by any one of the formula (BI-1) to the formula (BI-15), etc. can be cited, preferably, the formula (BI-1), Compounds represented by formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) or formula (BI-11) ~ formula (BI-15), more preferably, The compounds represented by formula (BI-1), formula (BI-7), formula (BI-9), or formula (BI-15) are listed.

[Chemical formula 23]

[Chemical formula 24]

The compound represented by the formula (BII) includes a compound represented by any one of the formula (BII-1) to the formula (BII-15), etc. Preferably, the compound represented by the formula (BII-1), Compounds represented by formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) and formula (BII-11) to formula (BII-15), more preferably, can The compounds represented by formula (BII-1), formula (BII-7), formula (BII-9), and formula (BII-15) are listed.

[Chemical formula 25]

[Chemical formula 26]

The compound represented by formula (BI) and the compound represented by formula (BII) may each be used alone, or the compound represented by formula (BI) and the compound represented by formula (BII) may be used in combination. When they are used in combination, the content ratio of the compound represented by the formula (BI) and the compound represented by the formula (BII) on a molar basis is preferably 5:95 to 95:5, more preferably 10:90 to 90 : 10, more preferably 20:80 to 80:20.

As said (b2), the monomer which has an oxetanyl group and a (meth)acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane Cyclobutane, 3-methyl-3-(meth)acryloyloxyethyloxetane and 3-ethyl-3-(meth)acryloyloxyethyloxetane, etc. .

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, and tert-butyl (meth)acrylate. Ester, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate , (Meth)acrylic acid tricyclo[5.2.1.0 ^2,6 ]decane-8-yl ester (in this technical field, as a common name, called "(meth)acrylate dicyclopentyl ester". In addition, there are When called "(meth)acrylate tricyclodecyl ester".), (meth)acrylate tricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester, (meth)acrylate tricyclo[5.2. 1.0 ^2,6 ]decene-8-yl ester (in this technical field, it is called "dicyclopentenyl (meth)acrylate" as a common name.), tricyclic (meth)acrylate [5.2.1.0 ^{2 ,6} ] Decene-9-yl ester, biscyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, (Meth) acrylates such as propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate And (meth)acrylates containing hydroxyl groups such as 2-hydroxypropyl (meth)acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; bicyclic [2.2.1]Hept-2-ene, 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'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methyl Oxybicyclo[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-Bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(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-cyclohexoxycarbonylbicyclo[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 and 5,6-bis(cyclohexoxycarbonyl)bicyclo[2.2.1]hept- Bicyclic unsaturated compounds such as 2-ene; N- Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N- Succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide Dicarbonyl imine derivatives such as amine propionate and N-(9-acridinyl) maleimide; styrene, α-methylstyrene, vinyl toluene and p-methoxystyrene, etc. Vinyl aromatic compounds; vinyl-containing nitriles such as (meth)acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl-containing amides such as (meth)acrylamide; vinyl acetate, etc. Esters; Dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene, etc. Among these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, and N-benzylmaleimide are preferred. Amine and bicyclo[2.2.1]hept-2-ene, etc.

The polymerization initiator, solvent, etc. are not particularly limited, and those commonly used in this field can be used. For example, as the polymerization initiator, azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic peroxides The oxide (benzyl peroxide, etc.) can be a solvent as long as each monomer is dissolved, and the solvent (E) described later as the solvent (E) of the colored curable resin composition of the present invention can be mentioned.

It should be noted that the obtained copolymer may be directly used as a solution after the reaction, or a concentrated or diluted solution may be used, or a product obtained as a solid by a method such as reprecipitation may be used. In particular, as a solvent during the polymerization, by using the solvent contained in the colored curable resin composition of the present invention, the reacted solution can be directly used in the preparation of the colored curable resin composition of the present invention. The manufacturing process of the colored curable resin composition of this invention can be simplified. In addition, a reaction catalyst of a carboxylic acid or a carboxylic anhydride and a cyclic ether (for example, tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (for example, hydroquinone, etc.), etc. can be used as necessary. Examples of carboxylic acid anhydrides include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. . The amount of carboxylic anhydride used is preferably 0.5 to 1 mol relative to 1 mol of the amount of (a) used.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, and 3,4-epoxy tricyclic (meth)acrylate [ 5.2.1.0 ^2.6 ] Resins such as decyl ester/(meth)acrylic acid copolymer; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate Ester/styrene/(meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ] decyl ester/(meth)acrylic acid/N-cyclohexylmaleimide Copolymer, (meth)acrylic acid 3,4-epoxy tricyclo[5.2.1.0 ^2.6 ]decyl ester/(meth)acrylic acid/vinyltoluene copolymer, 3-methyl-3-(meth)acrylic acid Resins such as oxymethyl oxetane/(meth)acrylic acid/styrene copolymer; benzyl(meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, Resins such as benzyl (meth)acrylate/tricyclodecyl(meth)acrylate/(meth)acrylic acid copolymer; make glycidyl (meth)acrylate and benzyl (meth)acrylate/(meth) Resin made by addition of acrylic copolymer, resin made by addition of glycidyl (meth)acrylate and tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, made of (A Base) glycidyl acrylate and tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer resins and other resins; make (meth)acrylic acid and (form) (Base) Tricyclodecyl acrylate/glycidyl (meth)acrylate copolymer reaction resin, made of (meth)acrylic acid and tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate Resins such as resins formed by the reaction of ester copolymers; resins formed by reacting (meth)acrylic acid and tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate copolymers are further reacted with tetrahydro Resins such as resins formed by the reaction of phthalic anhydride.

The weight average molecular weight in terms of polystyrene of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. If the molecular weight is within the above-mentioned range, the hardness of the coating film will increase, the residual film rate will also be high, the solubility of the unexposed part in the developing solution will be good, and the resolution of the colored pattern will tend to increase. The degree of dispersion [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value in terms of solid content of the resin (B) is preferably 50 to 170 mg-KOH/g, more preferably 50 to 150 mg-KOH/g, and still more preferably 50 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and it can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) relative to the total solid content is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. If the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the residual film rate tend to increase.

<Polymerizable compound (C)> The polymerizable compound (C) is a compound that can be polymerized by living radicals and/or acid generated by the polymerization initiator (D), and examples thereof include polymerizable ethylenic unsaturated bonds Among the compounds of, preferably (meth)acrylate compounds are mentioned.

Examples of polymerizable compounds having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylate. Ester, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and the above (a), (b) and (c).

As the polymerizable compound having two ethylenically unsaturated bonds, for example, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate Base) acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

Among them, 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 tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Esters, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, pentaerythritol deca(meth)acrylate, pentaerythritol non(meth)acrylate Ester, tris(2-(meth)acryloyloxyethyl) isocyanurate, glycol modified pentaerythritol tetra(meth)acrylate, glycol modified dipentaerythritol hexa(meth)acrylic acid Ester, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate and caprolactone modified dipentaerythritol hexa(meth) (Base) acrylate etc., preferably, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are mentioned.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2900 or less, and more preferably 250 or more and 1500 or less.

The content of the polymerizable compound (C) relative to the total solid content is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass. In addition, the content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] on a mass basis is preferably 20:80 to 80:20, more preferably 35:65 ~80:20. If the content of the polymerizable compound (C) is within the above-mentioned range, the residual film rate during the formation of the colored pattern and the chemical resistance of the color filter tend to improve.

<Polymerization initiator (D)> The polymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating polymerization by generating living radicals, acids, etc. by the action of light and heat, and known polymerization initiators can be used . Examples of the polymerization initiator (D) include O-acyl oxime compounds, alkyl phenyl ketone compounds, biimidazole compounds, triazine compounds, and acyl phosphine oxide compounds.

The above-mentioned O-acetoxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents the bonding end.

[Chemical formula 27]

Examples of the O-acetoxime compound include N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyl Acetyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzyloxy-1-(4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzyl)-9H-oxazole- 3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4- Dioxolylmethoxy)benzyl}-9H-oxazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6- (2-Methylbenzyl)-9H-oxazol-3-yl]-3-cyclopentylpropane-1-imine and N-benzyloxy-1-[9-ethyl-6 -(2-Methylbenzyl)-9H-oxazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) can be used. Among them, the O-acyl oxime compound is preferably selected from N-benzyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzyl oxime Oxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-benzyloxy-1-(4-phenylsulfanylphenyl)- At least one of 3-cyclopentylpropane-1-one-2-imine, more preferably N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1- Keto-2-imine. In addition, in 100 parts by mass of the polymerization initiator, the content of the O-acetoxime compound is preferably 5 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 70 parts by mass or more, and still more preferably 80 parts by mass or more It is preferably 100 parts by mass or less.

The above-mentioned alkyl phenyl ketone compound is, for example, a compound having a partial structure represented by formula (d2) or a partial structure represented by formula (d3). In these partial structures, the benzene ring may have a substituent.

[Chemical formula 28]

As the compound having a partial structure represented by the formula (d2), for example, 2-methyl-2-morpholino-1-(4-methylsulfanylphenyl)propan-1-one, 2- Dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one and 2-(dimethylamino)-2-[(4-methylphenyl) Methyl]-1-[4-(4-morpholinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (the above are made by BASF) can be used. As a compound having a partial structure represented by the formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4 -(2-Hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 -Oligomers of ketones, α,α-diethoxy acetophenone and benzyl dimethyl ketal, etc. From the viewpoint of sensitivity, the alkyl phenyl ketone compound is preferably a compound having a partial structure represented by formula (d2).

As the biimidazole compound, for example, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-di Chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, refer to Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2'- Bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra (Alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2' -Bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. 48-38403 and Japanese Patent Application Publication No. 62- No. 174204, etc.) and imidazole compounds in which the phenyl group at the 4, 4', 5, and 5'-positions is substituted with an alkoxycarbonyl group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913 etc.). Among them, the compounds represented by the following formulas and their mixtures are preferred.

[Chemical formula 29]

As the triazine compound, for example, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl) Chloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-tri Oxazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6- [2-(5-Methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl) ) Vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl] -1,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-tri Azine etc.

As said acyl phosphine oxide compound, 2,4,6-trimethylbenzyl diphenyl phosphine oxide etc. are mentioned.

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether can be cited ; Benzophenone, o-benzyl methyl benzoate, 4-phenyl benzophenone, 4-benzyl-4'-methyl diphenyl sulfide, 3,3',4 ,4'-Tetra(tert-butylperoxycarbonyl)benzophenone and 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2-ethyl Quinone compounds such as anthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate and titanocene compounds. These are preferably used in combination with the polymerization initiator (D1) described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from an alkyl phenyl ketone compound, a triazine compound, an phosphine oxide compound, an O-oxime compound, and a biimidazole compound, and is more preferably A polymerization initiator containing an O-oxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, and more preferably 1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).

<Polymerization initiation adjuvant (D1)> The polymerization initiation adjuvant (D1) is a compound or a sensitizer for accelerating the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D). As the polymerization initiation auxiliary (D1), amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acid compounds, and the like can be cited.

Examples of the above-mentioned amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as Michler’s ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-bis(ethylmethyl) (Diamino)benzophenone and the like, preferably 4,4'-bis(diethylamino)benzophenone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) can be used.

Examples of the above-mentioned alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl- 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene, etc.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1 -Chloro-4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, and dimethylphenyl Sulfuryl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine , Phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid, etc.

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

<Solvent (E)> The solvent (E) is not particularly limited, and solvents generally used in this field can be used. For example, ester solvents (solvents containing -COO- and no -O- in the molecule), ether solvents (solvents containing -O- and no -COO- in the molecule), ether ester solvents Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- and no -COO- in the molecule), alcohol solvents (containing OH in the molecule, no -O-, -CO -And -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfide, etc.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclic Hexanol acetate and γ-butyrolactone, etc.

Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and 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, phenylethyl ether and methyl anisole, etc.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, 2-methoxypropyl propionate, 2-ethoxy methyl propionate, 2-ethoxy ethyl propionate, 2-methoxy-2-methyl propionate, 2- Ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol Monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, Diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate, etc.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone, etc.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin. Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, 1,3,5-trimethylbenzene, and the like. Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, and the like.

These solvents may be used alone or in combination of two or more kinds. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether are preferred. Alcohol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone, etc., more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, Ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and N-methylpyrrolidone.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass relative to the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. If the content of the solvent (E) is within the above-mentioned range, the flatness at the time of application becomes good, and the color density is not insufficient when the color filter is formed, so there is a tendency for the display characteristics to become good.

<Leveling agent (F)> As the leveling agent (F), organosilicon surfactants, fluorine surfactants, organosilicon surfactants having fluorine atoms, and the like can be cited. These may have a polymerizable group in the side chain. Examples of the organosilicon-based surfactant include surfactants having siloxane bonds in the molecule, and the like. Specifically, TORAY SILICONE DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by MOM ティティブ・パフォーマテズンジズパンズ)

Examples of the above-mentioned fluorine-based surfactants include surfactants having a fluorocarbon chain in the molecule, and the like. Specifically, Flourrad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megofack (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K (Manufactured by DIC Co., Ltd.), Eftup (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Marmel Electronic Chemicals Co., Ltd.), SFron (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) ) And E5844 ((manufactured by Diinkin Fumikalu Research Institute)) and so on.

Examples of the aforementioned organosilicon surfactants having fluorine atoms include surfactants having siloxane bonds and fluorocarbon chains in the molecule. Specifically, Megofack (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Co., Ltd.) and the like can be cited.

When the leveling agent (F) is contained, the content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, and more preferably 0.002% by mass relative to the total amount of the colored curable resin composition % Or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.07% by mass or less. If the content of the leveling agent (F) is within the above-mentioned range, the flatness of the color filter can be improved.

<Other components> The colored curable resin composition of the present invention may contain fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., as required, which are known in the technical field additive.

<Method for producing colored curable resin composition> The colored curable resin composition of the present invention can be obtained by, for example, mixing the colorant (A), the resin (B), the polymerizable compound (C), the polymerization initiator (D), And it is prepared by mixing solvent (E), leveling agent (F), polymerization initiator (D1), and other components used as needed. When the coloring agent (A) other than the xanthene compound (A-1) contains the pigment (P), the pigment (P) is preferably mixed with a part or all of the solvent (E) in advance and dispersed by a bead mill or the like until the pigment The average particle size of the product is about 0.2 μm or less. In this case, part or all of the above-mentioned pigment dispersant and resin (B) can be blended as necessary. It is preferable to filter the mixed colored curable resin composition using a filter with a pore diameter of about 0.01 to 10 μm.

<The manufacturing method of a color filter> As a method of manufacturing a colored pattern from the coloring curable resin composition of this invention, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, photolithography is preferred. The photolithography method is a method of applying the above-mentioned colored curable resin composition to a substrate, drying to form a colored composition layer, and exposing the colored composition layer through a photomask to develop it. In the photolithography method, by not using a photomask and/or not developing during exposure, it is possible to form a colored coating film that is a cured product of the colored composition layer. The colored pattern and colored coating film formed in this way can be used as the color filter of the present invention. The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose, use, etc., and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, glass plates, resin plates, silicon, and products in which aluminum, silver, and silver/copper/palladium alloy thin films are formed on a substrate of the above materials can be used. Additional color filter layers, resin layers, transistors, circuits, etc. can be formed on these substrates.

The formation of pixels of each color by photolithography can be performed under known or customary equipment and conditions. For example, it can be produced as follows. First, the colored curable resin composition is applied on a substrate, and dried by heating (pre-baking) and/or under reduced pressure to remove volatile components such as the solvent and drying to obtain a smooth colored composition layer. As the coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. can be cited.

Next, the coloring composition layer is exposed to light via a photomask for forming the target coloring pattern. Since it is possible to uniformly irradiate the entire exposure surface with parallel light and perform accurate alignment of the photomask and the substrate on which the coloring composition layer is formed, it is preferable to use exposure devices such as a mask aligner and a stepper.

The coloring composition layer after exposure is brought into contact with a developing solution for development, thereby forming a coloring pattern on the substrate. By development, the unexposed part of the coloring composition layer is dissolved and removed in the developer. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide are preferred. The development method may be any of the rotary immersion method, dipping method, and spray method. Furthermore, the substrate can be inclined at an arbitrary angle during development. It is preferable to wash with water after development. Preferably, the obtained colored pattern is further post-baked. The resulting colored pattern can be constructed as a color filter.

The coloring curable resin composition of the present invention can produce a color filter having particularly excellent heat resistance. This color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements. Example

The following examples are given to illustrate the present invention more specifically, but the present invention is not limited by the following examples at all, and of course it can be implemented with appropriate changes within the scope of the main content described above and below. They all include In the technical scope of the present invention. It should be noted that in the following, unless otherwise specified, "parts" means "parts by mass", and "%" means "% by mass".

(Synthesis example 1) Into a flask equipped with a cooling tube and a stirring device, 10 parts of the compound represented by the formula (AXa-1), 300 parts of chloroform, and 5.7 parts of N,N-dimethylformamide were put into the flask, and maintained under stirring Below 20°C, 12.6 parts of sulfite chloride was added dropwise, and the reaction was maintained for 5 hours. Then, while maintaining the temperature below 20°C under stirring, a mixed solution of 6.7 parts of N-ethylmethylamine and 11.5 parts of triethylamine was added dropwise. Then, it was stirred at the same temperature for 5 hours for reaction. Next, after distilling off the solvent of the obtained reaction mixture with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixed solution of 375 parts of ion-exchanged water while stirring to precipitate crystals. The precipitated crystals were separated by filtration, sufficiently washed with ion-exchanged water, and dried under reduced pressure at 60° C. to obtain 10.7 parts of the compound represented by the formula (AXa-1a).

[Chemical formula 30]

Identification (mass analysis) of the compound represented by the formula (AXa-1a) Ionization mode=ESI+: m/Z=701.9[M-Cl] ⁺ exact mass: 736.4

400 parts of methanol was added to 7.3 parts of the compound represented by formula (AXa-1a), and it stirred at 20-30 degreeC for 1 hour, and obtained the solution. 400 parts of ion-exchange water was added to this solution, and it stirred for 2 hours, and obtained the solution (AXa-1aKA). On the other hand, 28.8 parts of ion-exchange water was added to 9.6 parts of phospho-12 tungstic acid 3 hydrogen, and the mixture was stirred at 20°C to 30°C for 1 hour. Next, 28.8 parts of methanol was added and stirred for 2 hours to obtain a solution (AXa- 1aKB). Add the solution (AXa-1aKB) to the solution (AXa-1aKA) and stir at 20°C~30°C for 12 hours. The generated precipitate was collected by filtration, washed twice with 200 parts of ion-exchanged water, and then washed twice with 200 parts of methanol. The filtered crystals were dried at 60°C for 24 hours to obtain 10.2 parts of the compound represented by the formula (AXa-1A).

[Chemical formula 31]

(Synthesis Example 2) In Synthesis Example 1, except that 2-ethylhexylamine was used instead of N-ethylmethylamine, it was synthesized in the same manner as Synthesis Example 1, and 10.2 parts of the compound represented by the formula (AXa-2A) was obtained.

[Chemical formula 32]

(Synthesis example 3) In a flask equipped with a reflux cooler, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed into a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was charged and heated to 85 while stirring. ℃. Next, in the flask, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and Acrylic acid 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decane-9-yl ester mixture (content ratio expressed in molar ratio, 50:50) (trade name "E-DCPA", Co., Ltd. Made by Daicel) A solution of 171 parts dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, 26 parts of polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl by dripping into the flask for about 5 hours using another drip pump. A solution in 120 parts of ether acetate. After the dripping of the polymerization initiator was completed, it was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer and resin (B-1) with a solid content of 43.5%. The weight average molecular weight of the obtained resin (B-1) was 8000, the degree of dispersion was 1.98, and the acid value in terms of solid content was 53 mg-KOH/g.

[Chemical formula 33]

(Synthesis example 4) In a flask equipped with a reflux cooler, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed into a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was charged, and heated to 80 parts while stirring. ℃. Next, in the flask, 38 parts of acrylic acid and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8 and 9-yl ester of acrylic acid were dropped into the flask for about 5 hours using a dropping pump. A solution in which 289 parts of the mixture (the content ratio is represented by a molar ratio of 50:50) (trade name "E-DCPA", manufactured by Daicel Co., Ltd.) was dissolved in 125 parts of propylene glycol monomethyl ether acetate. On the other hand, 33 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl ether by dripping into the flask for about 6 hours using another drip pump. A solution in 235 parts of acetate. After the dripping of the polymerization initiator was completed, it was kept at the same temperature for about 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) with a solid content of 35.1%. The weight average molecular weight of the obtained resin (B-2) was 9,200, the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g.

[Chemical formula 34]

The measurement of the weight average molecular weight (MW) and number average molecular weight (Mn) in terms of polystyrene of the resin was carried out under the following conditions by the GPC method. Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.) Column: TSK-GELG2000HXL Column temperature: 40°C Solvent: THF Flow rate: 1.0 mL/min Solid content concentration of the test liquid: 0.001 to 0.01 mass% Injection volume: 50 μL detector : RI standard material for calibration: TSK STANDARD POLYSTYRENE (manufactured by Dongcao (strain) and conversion of the above-mentioned molecular weight), F-40, F-4, F-288, A-2500, and A-500 The ratio of the number average molecular weight (Mw/Mn) is taken as the degree of dispersion.

[Preparation of colored curable resin composition] Examples 1, 2, and Comparative Example 1 The components shown in the following table were mixed to obtain a colored curable resin composition.

【table 3】

In the table, each component is as follows. Dye (A-1): Compound represented by formula (AXa-1A) Dye (A-2): Compound represented by formula (AXa-2A) Dye (A-3): Rhodamine B (Tokyo Chemical Industry Co., Ltd. Co., Ltd.) Resin (B): Resin (B-1) (in terms of solid content) Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Nippon Kayaku Co., Ltd.) Polymerization initiation Agent (D): N-benzyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF ; O-Acetyl oxime compound) Solvent (E-1): Propylene glycol monomethyl ether acetate solvent (E-2): Propylene glycol monomethyl ether solvent (E-3): Ethyl lactate solvent (E-4 ): Dimethylformamide leveling agent (F): Megofack (registered trademark) F554 (manufactured by DIC Co., Ltd.)

[Pattern formation] After applying the colored photosensitive composition to a 2-inch square glass substrate (Icer XG; manufactured by Corning Incorporated) by a spin coating method, it was pre-baked at 100° C. for 3 minutes to obtain a composition layer. After cooling, the gap between the glass substrate on which the composition layer was formed and the quartz glass photomask was 100 μm, and the exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to expose at 150 mJ/cm ² in an air atmosphere. The amount of light (365nm reference) is irradiated. As the photomask, a photomask formed with a pattern of 100 μm lines and gaps was used. After light irradiation, the above-mentioned coating film was immersed and developed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23°C for 80 seconds. After washing with water, it was carried out in an oven at 220°C for 20 seconds. Bake in minutes and get the pattern.

[Evaluation of heat resistance] In the formation of the above-mentioned pattern, a coating film was obtained in the same manner as described above except that the photomask was not passed through the light irradiation. The chromaticity of the obtained coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). Next, after heating the same coating film at 230°C for 20 minutes, the chromaticity was measured again using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS), and the color difference (ΔEab*) of the coating film before and after heating was determined. ). The color difference (ΔEab*) of the coating films formed from the colored curable resin compositions of Examples 1 and 2 were 4.5 and 3.8, respectively. In addition, the color difference (ΔEab*) of the coating film formed from the coloring curable resin composition of Comparative Example 1 was 80.1. From this, it can be seen that the coating film and pattern formed from the colored curable resin composition of the present invention have excellent heat resistance.

Comparative Example 2 (Preparation of Dispersion Liquid) Weighed 10.0 parts of Pigment Red 81, dispersant DISPERBYK-LPN6919 (Propylene Glycol Monomethyl Ether Acetate Solution with 38% Solid Content) 10.5 parts, as a dispersion resin (Resin B- 2) After 5.7 parts of propylene glycol monomethyl ether acetate solution (35% solid content) and 163.7 parts of propylene glycol monomethyl ether acetate, 300 parts of 0.4μm zirconia beads are filled, and a paint conditioner ( LAU Corporation) shaken for 3 hours to prepare a dispersion.

(Preparation of colored curable resin composition) The above dispersion: 15 parts; alkali-soluble resin (B): Resin (B-1) (solid content) 1.0 parts; polymerizable compound (C): dipentaerythritol hexaacrylate Ester (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) octyl octyl group (2-phenylmethyl thioalkyl) (D) 2-phenyl-methyl thiol group; polymerization initiator (D) 2.0 parts -1-Ketone-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-amino oxime compound) 0.3 copies; solvent (E): propylene glycol monomethyl ether acetate 18 copies Leveling agent (H): Polyether modified silicone oil (solid content conversion) (TORAY SILICONE SH8400; manufactured by Toray Dow Corning Co., Ltd.), mixed with 9 copies.

The heat resistance was evaluated by the same method as in Examples 1 and 2 and Comparative Example 1. As a result, the color difference (ΔEab*) was 17.7. Industrial availability

If the colored curable resin composition of the present invention is used, a color filter having good heat resistance can be provided. This color filter can be used as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

(no)

Claims (6)

A colored curable resin composition, which is a colored curable resin composition comprising xanthene compound (A-1), resin (B), polymerizable compound (C), and polymerization initiator (D), xanthene The xanthene compound (A-1) is a compound having a cation (AXa) and an anion (AXb). The cation (AXa) has a xanthene skeleton with a substituted or unsubstituted sulfamsulfonyl group, and the anion (AXb) contains tungsten At least one element among, molybdenum, silicon and phosphorus and oxygen are essential elements. Such as the colored curable resin composition of claim 1, wherein the cation (AXa) having a xanthene skeleton is a cation represented by formula (I):

In the formula (I), R ^1a to R ^4a independently represent a hydrogen atom, an optionally substituted aromatic hydrocarbon group with 6 to 10 carbons, or an optionally substituted saturated hydrocarbon group with 1 to 20 carbons, the saturated hydrocarbon group The methylene group (-CH ₂ -) contained in can be -O-, -CO-, -NR ^11a -, -OCO-, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO -Replacement, R ^1a and R ^2a can form a ring containing a nitrogen atom together, and R ^3a and R ^4a can form a ring containing a nitrogen atom together. However, adjacent methylene groups will not be replaced with the same substituent at the same time. , The methylene group at the end will not be replaced, R ^6a and R ^7a independently represent a hydrogen atom or an alkyl group with 1 to 6 carbon atoms, ma represents an integer of 1 to 5, and R ^9a and R ^10a represent independently of each other A hydrogen atom or a saturated hydrocarbon group with 1 to 20 carbon atoms that may have a substituent. The methylene group (-CH ₂ -) contained in the saturated hydrocarbon group may be replaced by -O-, -CO-, -NR ^11a -, -OCO -, -COO-, -OCONH-, -NHCOO-, -CONH- or -NHCO- replacement, R ^9a and R ^10a can be combined with each other to form a 3- to 10-membered heterocyclic ring containing a nitrogen atom, but adjacent The methylene group will not be replaced with the same substituent at the same time, and the methylene group at the terminal will not be replaced. R ^11a represents a hydrogen atom, a monovalent saturated hydrocarbon group with 1 to 20 carbons, or 7 to 10 carbons.的arylalkyl. The coloring curable resin composition of claim 1, wherein the anion (AXb) is an anion of a heteropolyacid or a homopolyacid containing tungsten as an essential element. The coloring curable resin composition of claim 1, wherein the anion (AXb) is any one of phosphotungstic acid anion, silicotungstic acid anion, or tungsten-based homopolyacid anion. A color filter formed of the coloring curable resin composition according to any one of claims 1 to 4. A display device including the color filter of claim 5.