TW201912722A - Colored curable resin composition, color filter, and display device comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and an antioxidant - Google Patents

Abstract

With respect to a color filter and a display device formed of a conventional colored curable resin composition, the residual film ratio after post-baking is not necessarily sufficient to fulfill requirements as compared to before-post-baking. The present invention provides a colored curable resin composition which comprises a colorant, a resin, a polymerizable compound, a polymerization initiator, and an antioxidant, wherein the colorant comprises a triarylmethane color lake, and the antioxidant is an antioxidant having a heating mass reduction rate of 8.0% or less measured by a thermal analysis device and determined by the following formula: Heating quality reduction rate (%) = 100 - (mass after the temperature reaches 230 DEG C and maintained for 100 minutes/mass when the temperature reaches 230 DEG C) x 100. The colored curable resin composition preferably comprises a solvent and optionally comprises a leveling agent, and an adhesion enhancer.

Description

 Colored curable resin composition, color filter, and display device  

The present invention relates to a colored curable resin composition.

The color filter used for a solid-state imaging device such as a display device such as a liquid crystal display device, an electroluminescence display device, or a plasma display, or a CCD or a CMOS sensor is manufactured from a colored curable resin composition. As such a colored curable resin composition, a composition containing Sumilizer GP as an antioxidant is known (Patent Document 1).

Prior technical literature

Patent literature

Patent Document 1: Japanese Patent Laid-Open No. 2016-108288

In the color filter formed of the above-described colored curable resin composition, the residual film ratio after post-baking is not necessarily sufficient for the post-baking.

The gist of the present invention is as follows.

[1] A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and an antioxidant, the colorant comprising a triarylmethane lake, and an antioxidant for utilizing thermal analysis The antioxidant having a heating mass reduction rate of 8.0% or less as measured by the following formula.

Heating mass reduction rate (%) = 100 - (mass after 100 minutes after reaching 230 ° C / mass at 230 ° C) × 100

[2] The colored curable resin composition according to the above [1], wherein the triarylmethane lake is at least one selected from the group consisting of a compound represented by the formula (1) and a compound represented by the formula (2).

[In the formula (1), R ^41a to R ^44a each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent An aralkyl group of 7 to 30, in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by an unsubstituted amino group or a halogen atom, and the carbon in the saturated hydrocarbon group In the case of the number of 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not substituted by the oxygen atom at the same time, and the terminal methylene group is not substituted by the oxygen atom or -CO-. R ^41a and R ^42a may be bonded to form a ring together with the bonded nitrogen atoms, and R ^43a and R ^44a may be bonded to form a ring together with the bonded nitrogen atoms.

R ^47a to R ^54a each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and the methylene group constituting the alkyl group may be substituted with an oxygen atom or -CO-. R ^48a and R ^52a may be bonded to each other to form -NH-, -O-, -S- or -SO ₂ -.

The ring T ^1a represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent.

[Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, niobium and phosphorus with oxygen.

m represents an arbitrary natural number,

Further, in the case where a plurality of cations represented by the following formula are contained in one molecule, these may be the same structure or different structures.

[wherein, the rings T ^1a , R ^41a to R ^44a and R ^47a to R ^54a are respectively synonymous with the above. ]]

[In the formula (2), R ^41b to R ^44b each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent The 7 to 30 aralkyl group, the aromatic hydrocarbon group and the substituent which the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , and the hydrogen contained in the saturated hydrocarbon group The atom may be substituted with an unsubstituted amino group or a halogen atom, and in the case where the saturated hydrocarbon group has a carbon number of 2 to 20, the -CH ₂ - contained in the saturated hydrocarbon group may be replaced with -O- and At least one of -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not simultaneously substituted with -O-, and the terminal -CH ₂ - is not replaced with -O- or -CO-. R ^41b and R ^42b may be bonded and form a ring together with the bonded nitrogen atoms, and R ^43b and R ^44b may be bonded to form a ring together with the bonded nitrogen atoms.

R ^47b to R ^54b each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , or an alkyl group having 1 to 8 carbon atoms, constituting the alkane. The group -CH ₂ - may be replaced by at least one of -O- and -CO-, and R ^48b and R ^52b may be bonded to each other to form -NH-, -S- or -SO ₂ -. However, in the alkyl group, the adjacent -CH ₂ - is not simultaneously substituted by -O-, and the terminal -CH ₂ - is not substituted by -O- or -CO-.

The ring T ^1b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted amino group, or a carbon number 6 which may have a substituent 20 aromatic hydrocarbon groups. The substituent which the aromatic hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

M ^r+ represents a metal ion of r valence.

k represents the sum of the number of -SO ₃ ^{- and the} number of -SO ₂ -N ^- -SO ₂ -R ^{f of} R ^41b to R ^44b , R ^47b to R ^54b and ring T ^1b .

r represents an integer of 1 or more.

R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.

However, R ^41b to R ^44b , R ^47b to R ^54b and ring T ^1b have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . ]

[3] A color filter formed of the colored curable resin composition according to [1] or [2].

[4] A display device comprising the color filter according to [3].

According to the colored curable resin composition of the present invention, it is possible to form a color filter having a residual film ratio after post-baking that is higher than that before post-baking.

The colored curable resin composition of the present invention contains a coloring agent (hereinafter sometimes referred to as a coloring agent (A)), a resin (hereinafter sometimes referred to as a resin (B)), and a polymerizable compound (hereinafter sometimes referred to as a polymerizable property). The compound (C)), a polymerization initiator (hereinafter sometimes referred to as a polymerization initiator (D)), and an antioxidant.

The colorant contains a triarylmethane lake, and the antioxidant contains an antioxidant having a heating mass reduction rate of 8.0% or less under a predetermined condition (hereinafter sometimes referred to as an antioxidant (H)).

The colored curable resin composition of the present invention preferably further contains a solvent (hereinafter sometimes referred to as a solvent (E)).

The color-curable resin composition of the present invention may contain a leveling agent (hereinafter sometimes referred to as a leveling agent (F)).

The colored curable resin composition of the present invention may contain an adhesion promoter (hereinafter sometimes referred to as an adhesion promoter (G)).

In the present specification, the compounds exemplified for the respective components can be used singly or in combination of plural kinds unless otherwise specified.

<Colorant (A)>

The colorant (A) comprises a triarylmethane lake. The triarylmethane lake is an organic pigment which precipitates a triarylmethane dye soluble in water and an organic solvent by a precipitating agent to make it insoluble in water and an organic solvent.

The triarylmethane lake may be a compound containing a cation having a triarylmethane skeleton and an anion derived from a precipitating agent, or a compound containing an anion having a triarylmethane skeleton and a cation derived from a precipitating agent.

The triarylmethane lake is preferably at least one selected from the group consisting of a compound represented by the formula (1) and a compound represented by the formula (2).

The compound represented by the formula (1) (hereinafter also referred to as the compound (1)) will be described.

[In the formula (1), R ^41a to R ^44a each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent An aralkyl group of 7 to 30, in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted by an unsubstituted amino group or a halogen atom, and the carbon in the saturated hydrocarbon group In the case of the number of 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group is not substituted by the oxygen atom at the same time, and the terminal methylene group is not substituted by the oxygen atom or -CO-. R ^41a and R ^42a may be bonded to form a ring together with the bonded nitrogen atoms, and R ^43a and R ^44a may be bonded to form a ring together with the bonded nitrogen atoms.

R ^47a to R ^54a each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and the methylene group constituting the alkyl group may be substituted with an oxygen atom or -CO-. R ^48a and R ^52a may be bonded to each other to form -NH-, -O-, -S- or -SO ₂ -.

The ring T ^1a represents an aromatic heterocyclic ring having 3 to 10 carbon atoms which may have a substituent.

[Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, niobium and phosphorus with oxygen.

m represents an arbitrary natural number.

Further, in the case where a plurality of cations represented by the following formula are contained in one molecule, these may be the same structure or different structures.

[wherein, the rings T ^1a , R ^41a to R ^44a and R ^47a to R ^54a are respectively synonymous with the above. ]]

The aromatic heterocyclic ring of the ring T ^1a may be a single ring or a condensed ring.

Examples of the substituent which the aromatic heterocyclic ring of the ring T ^1a may have include a halogen atom, a cyano group, a C 1 to 20 alkyl group which may have a substituent, and a 6 to 20 carbon atom which may have a substituent. A hydrocarbon group, an amine group which may have a substituent, or the like. The ring T ^1a preferably has an amine group which may have a substituent such as an alkyl group having 1 to 10 carbon atoms.

Among them, the aromatic heterocyclic ring of the ring T ^1a is preferably an aromatic heterocyclic ring containing a nitrogen atom, and more preferably a five-membered aromatic heterocyclic ring containing a nitrogen atom.

Further, the ring T ^{1a is} particularly preferably a ring represented by the formula (Ab2-y1).

[In the formula (Ab2-y1), R ^56a represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent.

X2a represents an oxygen atom, -NR ^57a -, or a sulfur atom.

R ^57a represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ^45a and R ^46a independently of each other represent a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a group having 2 to 20 carbon atoms, and a methylene group contained in the alkyl group may be substituted with an oxygen atom. An aromatic hydrocarbon group which may have a substituent, an aralkyl group which may have a substituent, or a hydrogen atom. R ^45a and R ^46a may be bonded and form a ring together with the nitrogen atoms bonded thereto.

However, the adjacent methylene group is not substituted by an oxygen atom at the same time, and the methylene group at the terminal of the alkyl group is not substituted by the oxygen atom.

* indicates the bonding end with a carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^41a to R ^46a and R ^56a may be any of a straight chain, a branched chain, and a cyclic group. Examples of the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, a hexadecyl group, and a second group. A linear alkyl group such as a decyl group; a branched alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group or a 2-ethylhexyl group; and the like. The saturated hydrocarbon group is preferably from 1 to 10 carbon atoms, more preferably from 1 to 8 carbon atoms, still more preferably from 1 to 6 carbon atoms.

The cyclic saturated hydrocarbon group represented by R ^41a to R ^46a and R ^56a may be a single ring or a polycyclic ring. Examples of the cyclic saturated hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and an adamantyl group. The cyclic saturated hydrocarbon group preferably has a carbon number of from 3 to 10, more preferably from 6 to 10 carbon atoms.

The saturated hydrocarbon group of R ^41a to R ^46a and R ^56a may be substituted by a halogen atom or an amine group which may be substituted. Examples of the substitutable amine group include an amine group; an alkylamino group such as a dimethylamino group or a diethylamino group. Further, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Further, when the halogen atom is a fluorine atom, it is preferably substituted with a halogen atom as in the case of forming a perfluoroalkyl unit such as a trifluoromethyl unit, a pentafluoroethyl unit or a heptafluoropropyl unit.

The alkyl group having 1 to 8 carbon atoms represented by R ^47a to R ^54a may, for example, be a group having 1 to 8 carbon atoms in the linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ^41a .

In addition, examples of the alkyl group having 1 to 10 carbon atoms represented by R ^57a include a group having 1 to 10 carbon atoms in the linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ^41a .

In the case where the carbon number of the saturated hydrocarbon group (preferably an alkyl group) represented by R ^41a to R ^46a is 2 or more, the methylene group contained in the saturated hydrocarbon group (preferably an alkyl group) may be an oxygen atom or -CO-substitution, preferably substituted by an oxygen atom. Further, an oxygen atom may be interposed between methylene groups constituting the saturated hydrocarbon group (preferably an alkyl group). The saturated hydrocarbon group (preferably an alkyl group) preferably has a carbon number of 2 to 10, more preferably 2 to 8. Further, when the methylene group is substituted by an oxygen atom or -CO-, the carbon number between the terminal and the oxygen atom or -CO-, or between the oxygen atom or -CO- and the oxygen atom or -CO- is, for example, 1 to 5 Preferably, it is 2 to 3, more preferably 2. However, the adjacent methylene group is not substituted by an oxygen atom at the same time, and the methylene group at the alkyl end is not substituted by an oxygen atom.

Further, the aromatic hydrocarbon group which may have a substituent represented by R ^41a to R ^46a and R ^56a is preferably a carbon number of 6 to 20, more preferably a carbon number of 6 to 15, and still more preferably a carbon number of 6 to 12. . Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a biphenylene group, and the like, and a phenyl group, a naphthyl group, a tolyl group, and the like are preferable. Xylyl group is particularly preferably a phenyl group or a tolyl group. In addition, the aromatic hydrocarbon group may have one or two or more substituents, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom; and a carbon number such as a methoxy group or an ethoxy group; Alkoxy group of 1 to 6; hydroxy group; amine sulfonyl group; alkylsulfonyl group having 1 to 6 carbon atoms such as methylsulfonyl group; alkane having 1 to 6 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group Oxycarbonyl group and the like.

The aralkyl group which may have a substituent represented by R ^41a to R ^46a may be an alkanediyl group having a carbon number of 1 to 5 such as a methylene group, an exoethyl group or a propyl group, as the above aromatic group. A group derived from a group described by a hydrocarbon group, and the like.

a ring formed by R ^41a and R ^42a bonded to the nitrogen atom bonded thereto, a ring in which R ^43a and R ^{44a are} bonded and formed together with the nitrogen atom to be bonded, and R ^45a and R The ring formed by ^46a and formed together with the nitrogen atom to be bonded thereto may, for example, be a nitrogen-containing non-aromatic four-membered ring to a seven-membered ring such as a pyrrolidine ring, a forklet ring, a piperidine ring or a piperazine ring. Preferably, a tetra- or seven-membered ring having only one nitrogen atom as a hetero atom such as a pyrrolidine ring or a piperidine ring is exemplified.

Wherein, as R ^41a to R ^44a and R ^56a , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent, more preferably each independently a saturated hydrocarbon group having 1 to 8 carbon atoms or The group represented. In the following formula, * represents a bonding end with a nitrogen atom.

R ^41a and R ^43a are each preferably independently a saturated hydrocarbon group having 1 to 10 carbon atoms, and R ^42a and R ^44a are each preferably independently an aromatic hydrocarbon group which may have a substituent, and R ^{56a is} preferably an aromatic group which may have a halogen atom. Hydrocarbyl group.

R ^41a and R ^43a are each independently a saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^42a and R ^44a are each preferably independently an aromatic hydrocarbon group, and R ^{56a is more} preferably an aromatic hydrocarbon group having a fluorine atom.

Further, R ^41a and R ^{43a are} more preferably each independently a methyl group or an ethyl group, and R ^42a and R ^{44a are} further more preferably each independently a phenyl group, and R ^{56a is} more preferably a phenyl group having a fluorine atom.

R ^45a to R ^46a are each preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, a group having an oxygen atom interposed between carbon atoms of an alkyl group having 2 to 20 carbon atoms, or an aromatic hydrocarbon group which may have a substituent. Or R ^45a is bonded to R ^46a and forms a ring together with the nitrogen atoms bonded thereto. A more preferable aspect is that R ^45a to R ^46a are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or a bond of R ^45a and R ^46a The junction forms a four-membered to seven-membered ring having only one nitrogen atom as a hetero atom. In the following formula, * represents a bonding end with a nitrogen atom.

Further, a group in which a methylene group having 1 to 8 carbon atoms represented by R ^47a to R ^54a and a methylene group having an alkyl group having 2 to 8 carbon atoms are substituted with an oxygen atom or -CO- can be exemplified from the above R A group having a carbon number of 8 or less selected from the groups corresponding to ^41a to ^R46a .

In terms of ease of synthesis, R ^47a to R ^{54a are} preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, more preferably each independently a hydrogen atom, a methyl group, a fluorine atom, or a chlorine atom. The atoms are further preferably each independently a hydrogen atom.

X2a is preferably a sulfur atom.

The cationic moiety of the formula (1), as shown in the following Table 1, may be cation 1 to cation 14 represented by the formula (1-1).

In Table 1, Ph1 to Ph9 mean a group represented by the following formula. Where * represents the bond end.

Among them, as the cationic moiety of the formula (1), preferred are a cation 1 to a cation 6, a cation 11 to a cation 14, and particularly preferably a cation 1, a cation 2, or a cation 12 to a cation 14, and most preferably a cation 12.

[Y] ^m- represents any m-valent anion containing at least one element selected from the group consisting of tungsten, molybdenum, niobium and phosphorus with oxygen.

The anion derived from a compound containing at least one element selected from the group consisting of tungsten, molybdenum, niobium and phosphorus and oxygen is preferably, for example, a heteropoly acid anion containing tungsten and a homopolyacid anion containing tungsten, more preferably phosphotungstic acid. An anion, a lanthanum tungstate anion, and a tungsten-like polyacid anion.

Examples of the heteropoly acid anion and the isopoly acid anion containing tungsten include Keggin-type phosphotungstic acid ion α-[PW ₁₂ O ₄₀ ] ^3- , Dawson-type phosphotungstic acid ion α-[P ₂ W ₁₈ O ₆₂ ^6- , β-[P ₂ W ₁₈ O ₆₂ ] ^6- , Keggin-type lanthanum tungstate ion α-[SiW ₁₂ O ₄₀ ] ^4- , β-[SiW ₁₂ O ₄₀ ] ^4- , γ-[SiW ₁₂ O ₄₀ ] ^4- , [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 ₄₂ ^- , and mixtures thereof.

m represents an arbitrary natural number, preferably from 1 to 20, more preferably from 2 to 14, still more preferably from 2 to 8, still more preferably from 3, 4 or 6.

The compound represented by the formula (1) includes the compounds shown in the following Tables 2 to 3.

Other compounds represented by the formula (1) preferably contain a cation 12 and [PW ₁₂ O ₄₀ ] ^3- .

The compound represented by the formula (1) can be produced by the method described in JP-A-2015-28121.

The tautomer and the salts thereof are also contained in the compound (1). Further, each component and functional group exemplified below can be used singly or in combination.

The triarylmethane lake is preferably a compound represented by the formula (2) (hereinafter sometimes referred to as a compound (2)).

[In the formula (2), R ^41b to R ^44b each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent The 7 to 30 aralkyl group, the aromatic hydrocarbon group and the substituent which the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , and the hydrogen contained in the saturated hydrocarbon group The atom may be substituted with an unsubstituted amino group or a halogen atom, and in the case where the saturated hydrocarbon group has a carbon number of 2 to 20, the -CH ₂ - contained in the saturated hydrocarbon group may be replaced with -O- and At least one of -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not simultaneously substituted with -O-, and the terminal -CH ₂ - is not replaced with -O- or -CO-. R ^41b and R ^42b may be bonded and form a ring together with the bonded nitrogen atoms, and R ^43b and R ^44b may be bonded to form a ring together with the bonded nitrogen atoms.

R ^47b to R ^54b each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f or an alkyl group having 1 to 8 carbon atoms, which constitutes the alkyl group. -CH ₂ - may be replaced by at least one of -O- and -CO-, and R ^48b and R ^52b may be bonded to each other to form -NH-, -S- or -SO ₂ -. However, in the alkyl group, the adjacent -CH ₂ - is not simultaneously substituted by -O-, and the terminal -CH ₂ - is not substituted by -O- or -CO-.

The ring T ^1b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted amino group, or a carbon number 6 which may have a substituent 20 aromatic hydrocarbon groups. The substituent which the aromatic hydrocarbon group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

M ^r+ represents a metal ion of r valence.

k represents the sum of the number of -SO ₃ ^{- and the} number of -SO ₂ -N ^- -SO ₂ -R ^{f of} R ^41b to R ^44b , R ^47b to R ^54b and ring T ^1b .

r represents an integer of 1 or more.

R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms.

However, R ^41b to R ^44b , R ^47b to R ^54b and ring T ^1b have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . ]

The aromatic heterocyclic ring represented by the ring T ^1b may be a single ring or a condensed ring. The aromatic heterocyclic ring represented by the ring T ^1b preferably has a carbon number of from 3 to 10, more preferably from 3 to 8. Further, the aromatic heterocyclic ring is preferably a five-membered ring to a ten-membered ring, more preferably a five-membered ring to a nine-membered ring. Examples of the monocyclic aromatic heterocyclic ring include a five-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; and a five-membered nitrogen atom such as a furan ring or a thiophene ring. A ring of a ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring. Examples of the fused ring aromatic ring include a fused ring containing a nitrogen atom such as an anthracene ring, a benzimidazole ring, a benzothiazole ring or a quinoline ring, and a fused ring containing no nitrogen atom such as a benzofuran ring. .

Examples of the substituent which the aromatic heterocyclic ring of the ring T ^1b may have include a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an unsubstituted amino group, or may have The aromatic hydrocarbon group having 6 to 20 carbon atoms of the substituent, and the like, preferably a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsubstituted amino group, or a carbon group having 6 to 20 carbon atoms which may have a substituent A hydrocarbon group. The ring T ^1b preferably has an amine group which may have a substituent, and as the substituent which the amine group may have, a saturated hydrocarbon group having 1 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent An aralkyl group having 7 to 30 carbon atoms which may have a substituent.

Among them, the aromatic hetero ring as the ring T ^1b is preferably an aromatic hetero ring containing a nitrogen atom, and more preferably a five-membered ring aromatic ring containing a nitrogen atom.

The ring T ^{1b is} preferably a ring represented by the formula (t1).

[In the formula (t1), R ^56b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

X2b represents -O-, -N(R ^57b )- or -S-.

R ^57b represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R ^45b and R ^46b each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number 7 which may have a substituent In the case of the aralkyl group of 30, in the case where the carbon number of the saturated hydrocarbon group is 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be replaced with at least one of -O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not simultaneously substituted by -O-, and the terminal -CH ₂ - is not substituted by -O- or -CO-. R ^45b and R ^46b may be bonded and form a ring together with the nitrogen atoms bonded thereto.

* indicates the bonding end with a carbocation. ]

Further, the ring T ^{1b is} preferably also a ring represented by the formula (t2).

[In the formula (t2), the ring T ^3b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms having a nitrogen atom.

R ^58b represents a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

R ^59b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent .

K2 represents 0 or 1.

* indicates the bonding end with a carbocation. ]

The ring T ^{1b is} further preferably a ring represented by the formula (t2-1).

[In the formula (t2-1), R ^60b represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R ^61b represents a hydrogen atom, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

R ^59b is synonymous with the above.

* indicates the bonding end with a carbocation. ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^41b to R ^46b , R ^56b and R ^58b to R ^60b and the saturated hydrocarbon group having 1 to 20 carbon atoms which may be possessed by the amine group which may be substituted on the ring T ^1b may be Any of a linear chain, a branched chain, and a ring shape. Examples of the linear or branched saturated hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, a decyl group, a dodecyl group, and a decyl group. A linear alkyl group such as a hexaalkyl group or an eicosyl group; a branched alkyl group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group or a 2-ethylhexyl group; and the like. The saturated hydrocarbon group preferably has a carbon number of from 1 to 10, more preferably from 1 to 8, still more preferably from 1 to 6.

The cyclic saturated hydrocarbon group represented by R ^41b to R ^46b , R ^56b and R ^58b to R ^{60b and} the cyclic saturated hydrocarbon group which the amine group which the ring T ^1b may have may have a single ring or a polycyclic ring. Examples of the cyclic saturated hydrocarbon group include an alicyclic saturated hydrocarbon group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or an adamantyl group. The cyclic saturated hydrocarbon group preferably has a carbon number of from 3 to 10, more preferably from 6 to 10.

The saturated hydrocarbon group represented by R ^41b to R ^46b , R ^56b and R ^58b to R ^{60b and} the saturated hydrocarbon group which the amine group which the ring T ^1b may have may have an unsubstituted or halogen atom as a substituent. . The substituted amine group may, for example, be an alkylamine group such as a dimethylamino group or a diethylamino group. Further, examples of the halogen atom include fluorine, chlorine, bromine, and iodine. Further, when the halogen atom is a fluorine atom, the saturated hydrocarbon group having a fluorine atom as a substituent is preferably a perfluoroalkyl group such as a trifluoromethyl group, a perfluoroethyl group or a perfluoropropyl group.

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^47b to R ^54b include a group having 1 to 8 carbon atoms in the linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ^41b . .

In addition, examples of the alkyl group having 1 to 10 carbon atoms represented by R ^57b include a group having 1 to 10 carbon atoms in the linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ^41b .

In the case where the carbon number of the saturated hydrocarbon group represented by R ^41b to R ^46b is 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be replaced with at least one of -O- and -CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not simultaneously substituted by -O-, and the terminal -CH ₂ - is not substituted by -O- or -CO-. In this case, as the saturated hydrocarbon group, a linear or branched saturated hydrocarbon group (i.e., a linear or branched alkyl group) is preferred, and a linear saturated hydrocarbon group (i.e., a linear chain) is more preferred. Alkyl). The preferred carbon number of the saturated hydrocarbon group of at least one of -CH ₂ -substitutable -O- and -CO- is from 2 to 10, more preferably from 2 to 8. In addition, when -CH ₂ - is replaced by at least one of -O- and -CO-, the terminal is between -O- or -CO-, or -O- or -CO- and -O- or -CO- The carbon number between them is 1 or more, preferably 1 to 5, more preferably 2 to 3, still more preferably 2.

Further, the aromatic hydrocarbon group which may have a substituent represented by R ^41b to R ^46b , R ^56b and R ^58b to R ^{60b and} the aromatic hydrocarbon group which the ring T ^1b may have may have an aromatic hydrocarbon group (wherein the aromatic hydrocarbon group) The carbon number which may have a substituent) is preferably from 6 to 20, more preferably from 6 to 15, still more preferably from 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an anthracenyl group, a phenanthryl group, a biphenyl group, a biphenylene group, and the like, and a phenyl group, a naphthyl group, a tolyl group, and the like are preferable. Xylyl group is particularly preferably a phenyl group or a tolyl group. Further, the aromatic hydrocarbon group may have one or two or more substituents. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a hydroxyl group; an aminesulfonyl group; and a methyl group. Alkoxysulfonyl having 1 to 6 carbon atoms such as a sulfonyl group; an alkoxycarbonyl group having 1 to 6 carbon atoms such as a methoxycarbonyl group or an ethoxycarbonyl group; -SO ₃ ^- ; -SO ₂ -N ^- -SO _{2 -} R ^f or the like, preferably a halogen atom such as a fluorine atom, a chlorine atom, an iodine atom or a bromine atom; -SO ₃ ^- ; -SO ₂ -N ^- -SO ₂ -R ^f , more preferably a fluorine atom or -SO ₃ ^- . However, -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^{f are} preferably directly bonded to an aromatic hydrocarbon ring of an aromatic hydrocarbon group, that is, a hydrogen atom bonded to an aromatic hydrocarbon ring.

Specific examples of the aromatic hydrocarbon group which may have a substituent include, for example, a group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

The aralkyl group which may have a substituent represented by R ^41b to R ^46b and R ^{59b and} the aralkyl group which the amine group which the ring T ^1b may have (wherein the aralkyl group may have a substituent) may be A group obtained by bonding an alkanediyl group having a carbon number of 1 to 10 (preferably having a carbon number of 1 to 5) such as a methylene group, an exoethyl group or a propyl group to a group described as the above aromatic hydrocarbon group is exemplified. Wait. The aralkyl group preferably has a carbon number of 7 to 30, more preferably 7 to 20, still more preferably 7 to 17 carbon atoms.

a ring in which R ^41b is bonded to R ^42b and formed together with the nitrogen atoms bonded thereto, a ring in which R ^43b is bonded to R ^44b and formed together with the nitrogen atoms bonded ^thereto , and R ^45b and R A ring formed by bonding ^46b and forming a nitrogen atom bonded thereto may, for example, be a nitrogen-containing non-aromatic four-membered ring to a seven-membered ring such as a pyrrolidine ring, a forklet ring, a piperidine ring or a piperazine ring. Preferably, a tetra- or seven-membered ring having only one nitrogen atom as a hetero atom such as a pyrrolidine ring or a piperidine ring is exemplified.

R ^{58b is} preferably a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

Wherein, as R ^41b to R ^44b , R ^56b , R ^58b to R ^60b , a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group which may have a substituent is preferable, and more preferably each independently has a carbon number of 1 to 8. a saturated hydrocarbon group or a group represented by the following formula, R ^41b and R ^{43b are} further more preferably each independently a saturated hydrocarbon group having 1 to 20 carbon atoms, and R ^42b and R ^{44b are} further more preferably each independently an aromatic hydrocarbon group which may have a substituent. Further, R ^{56b is} more preferably an aromatic hydrocarbon group which may have a substituent.

Further, R ^56b and R ^58b to R ^{60b are} more preferably a group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

R ^45b to R ^{46b are} preferably each independently obtained by a saturated hydrocarbon group having 1 to 20 carbon atoms, a -CH ₂ - constituting an alkyl group having 2 to 20 carbon atoms, and at least one of -O- and -CO-. a group, or an aromatic hydrocarbon group which may have a substituent, or R ^45b is bonded to R ^46b and forms a ring together with the nitrogen atom to which it is bonded. More preferably, R ^45b to R ^46b are each independently a saturated hydrocarbon group having 1 to 8 carbon atoms, an alkoxyalkyl group, or a group represented by the following formula, or R ^45b is bonded to R ^46b to form only one nitrogen atom as The four-membered to seven-membered ring of the hetero atom is further preferably a saturated hydrocarbon group independently having a carbon number of 1 to 8, an alkoxyalkyl group, or a group represented by the following formula. In the following formula, * represents a bonding end with a nitrogen atom.

Among them, R ^{45b is} preferably a saturated hydrocarbon group having 1 to 4 carbon atoms, and R ^{46b is} preferably an ortho-tolyl group.

In addition, examples of the alkyl group having 1 to 8 carbon atoms represented by R ^47b to R ^54b include a carbon number of 1 to 8 in a linear or branched saturated hydrocarbon group exemplified as the saturated hydrocarbon group represented by R ^41b . Group. Further, the group -CH ₂ - which constitutes the alkyl group having 2 to 8 carbon atoms represented by R ^47b to R ^54b is substituted with at least one of -O- and -CO- (however, the alkyl group) In the above, the adjacent -CH ₂ - is not substituted by -O- at the same time, and the terminal -CH ₂ - is not substituted by -O- or -CO-), and the carbon represented by the above R ^41b to R ^46b is exemplified. The group having 2 to 20 alkyl groups of -CH ₂ - is substituted with at least one of -O- and -CO-, and the group having 8 or less carbon atoms.

R ^47b to R ^54b are each preferably independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms, more preferably each independently a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom, and further preferably each independently A hydrogen atom.

Further, as R ^57b , a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferable.

As R ^61b , a hydrogen atom is preferred.

X2b is preferably -S-.

Examples of the r-valent metal ion represented by Mr ⁺ include alkali metal ions such as lithium ions, sodium ions, and potassium ions; alkaline earth metal ions such as barium ions, magnesium ions, calcium ions, barium ions, and barium ions; titanium ions, Transition metal ions such as zirconium ions, chromium ions, manganese ions, iron ions, cobalt ions, nickel ions, and copper ions; typical metal ions such as zinc ions, cadmium ions, aluminum ions, indium ions, tin ions, lead ions, and cesium ions . r is preferably 1 or more, more preferably 2 or more, and is preferably 5 or less, more preferably 4 or less, still more preferably 3 or less.

The Mn ^{+ is more} preferably an alkaline earth metal ion, a typical metal ion or the like, and more preferably an alkaline earth metal ion or a zinc ion, and still more preferably an alkaline earth metal ion.

In the formula (2), the number of Mr ⁺ is a ratio of -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^f of the ratios R ^41b to R ^44b , R ^47b to R ^54b and the ring T ^1b . The sum of the numbers (k) is one less than the number. Therefore, the valence of the compound (I) is 0, that is, it becomes an electrically neutral compound.

Examples of the fluoroalkyl group having 1 to 12 carbon atoms represented by R ^f include a monofluoromethyl group, a difluoromethyl group, a perfluoromethyl group, a monofluoroethyl group, a difluoroethyl group, a trifluoroethyl group, and a tetrafluoroethyl group. Fluoroethyl, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, tetrafluoropropyl, pentafluoropropyl, hexafluoropropyl, perfluoropropyl, monofluorobutyl, di Fluoryl butyl, trifluorobutyl, tetrafluorobutyl, pentafluorobutyl, hexafluorobutyl, heptafluorobutyl, octafluorobutyl, perfluorobutyl, and the like. Among them, as the fluoroalkyl group represented by R ^f , a perfluoroalkyl group is preferred. Further, the fluoroalkyl group represented by R ^f preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, still more preferably 1 to 3 carbon atoms.

In the formula (2), R ^41b to R ^44b , R ^47b to R ^54b and ring T ^1b have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , preferably at least one -SO ₃ ^- . The sum (k) of -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^{f of} R ^41b to R ^44b , R ^47b to R ^54b and ring T ^1b is 1 or more, preferably 1 Up to 7, more preferably 2 to 7, further more preferably 2 to 4, still more preferably 2 or 3, particularly preferably 2.

-SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f preferably satisfies at least one condition selected from the following (Ia) to (Id), and more preferably satisfies at least one selected from (Ia) and (Ib) condition.

(Ia) Any one of the above-mentioned R ^47b to R ^54b which is (Ib) bonded to an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms represented by R ^41b to R ^44b ( Ic) bonded to any of the optionally substituted aralkyl groups having 7 to 30 carbon atoms represented by R ^41b to R ^44b (Id) bonded to a hydrogen atom of an aromatic heterocyclic ring represented by T ^1b Any one of substituted aromatic hydrocarbon groups having 6 to 20 carbon atoms

Wherein, in the case where -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^{f is} bonded to the aromatic hydrocarbon group or the aralkyl group, -SO ₃ ^- or -SO ₂ -N ^- -SO is preferred ₂ -R ^{f is} directly bonded to an aromatic hydrocarbon ring of an aromatic hydrocarbon group or an aralkyl group. That is, it is preferred that -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^{f is} substituted for a hydrogen atom bonded to an aromatic hydrocarbon ring.

Is preferably -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f representing R ^41b to R ^44b may be a substituent having a carbon number of 6 to 20 aromatic hydrocarbon group, or R ^41b to R ^44b represents the The aromatic hydrocarbon ring (for example, a benzene ring) in the aralkyl group having 7 to 30 carbon atoms which may have a substituent may be bonded to the para position with respect to the bonding position with the nitrogen atom.

In the case where the compound (2) contains a plurality of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , a plurality of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f may be used. Bonded to the same aromatic hydrocarbon ring, but preferably bonded to a different aromatic hydrocarbon ring.

The compound (2) preferably does not have an ethylenically unsaturated bond.

The compound (2) is preferably a compound represented by the following formula (2-1) (hereinafter sometimes referred to as "compound (2-1)")

[In the formula (2-1), R ^81b to R ^90b each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, a halogen atom, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .

K1 represents the sum of the number of -SO ₃ ^{- and the} number of -SO ₂ -N ^- -SO ₂ -R ^{f of} R ^41b , R ^43b , R ^47b to R ^54b , R ^81b to R ^90b and ring T ^1b .

R ^41b , R ^43b , R ^47b to R ^54b , T ^1b , M ^r+ , r, R ^{f are} synonymous with the above.

Wherein R ^41b , R ^43b , R ^47b to R ^54b , R ^81b to R ^90b and ring T ^1b have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f . ]

The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ^81b to R ^90b is the same as the group exemplified as the saturated hydrocarbon group represented by R ^41b . R ^81b to R ^{90b are} preferably a hydrogen atom, a saturated hydrocarbon group having 1 to 8 carbon atoms, -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , more preferably a hydrogen atom, -SO ₃ ^- Or -SO ₂ -N ^- -SO ₂ -R ^f , further more preferably a hydrogen atom or -SO ₃ ^- .

-SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f preferably satisfies at least one condition selected from (Ie) to (Ig), more preferably at least one selected from (If) and (Ig) A condition that further better satisfies the condition of (If).

(Ie) is contained as any one of R ^47b to R ^54b (If) as any of R ^81b to R ^90b and is contained (Ig) bonded to a hydrogen atom of an aromatic heterocyclic ring represented by T ^1b Substituted aromatic hydrocarbon group having 6 to 20 carbon atoms

-SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f further satisfies the condition of (If').

(If') is contained in any one of R ^86b and R ^89b , in the formula (2-1), R ^41b , R ^43b , R ^47b to R ^54b , R ^81b to R ^90b and ring T ^1b - The sum (k1) of the number of SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^f is preferably from 1 to 7, more preferably from 1 to 4, still more preferably from 1 or 2.

As the compound (2), as shown in Tables 4 to 7, a compound represented by the formula (I-I-1) to the formula (I-I-270) and the like can be given.

In Tables 4 to 7, Me represents a methyl group, Et represents an ethyl group, Pr represents a n-propyl group, Bt represents an n-butyl group, and Ph1 to Ph19 mean a group represented by the formula (Ph1) to the formula (Ph19), respectively. Where * is the bond end.

The compound (2), as shown in Tables 8 to 9, may also be a compound represented by the formula (I-II-1) to the formula (I-II-135). However, in the formula (I-II-1) to the formula (I-II-135), the hydrogen atom may be substituted by -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -CF ₃ , and represents R ^41b The aromatic hydrocarbon ring (benzene ring) of Ph8' to Ph12', Ph20 to Ph22 to R ^46b or R ^56b may be bonded with -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -CF ₃ , R ^h , The sum of the number of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -CF ₃ of R ^41b to R ^46b and R ^56b is 2.

In Tables 8 to 9, Me represents a methyl group, Et represents an ethyl group, Pr represents a n-propyl group, Bt represents an n-butyl group, and Ph8' to Ph12' and Ph20 to 22 respectively mean a formula (Ph8') to a formula (Ph12). '), a group represented by the formula (Ph20) to the formula (Ph22). Where * is the bond end.

As the compound (2), preferred are the formula (II-1) to the formula (II-135), the formula (II-136), the formula (II-270), and the formula (I-II-1) to (I- The compound represented by II-135), more preferably from the formula (II-1) to the formula (II-21), the formula (II-40) to the formula (II-42), the formula (II-55) to the formula (II) -57), formula (II-70) to formula (II-72), formula (II-85) to formula (II-87), formula (II-100) to formula (II-102), formula (II- 112) to formula (II-117), formula (I-II-1) to formula (I-II-21), formula (I-II-40) to formula (I-II-42), formula (I- II-55) to formula (I-II-57), formula (I-II-70) to formula (I-II-72), formula (I-II-85) to formula (I-II-87), a compound represented by the formula (I-II-100) to the formula (I-II-117), particularly preferably from the formula (II-7) to the formula (II-21), the formula (II-112) to the formula (II- 117), a compound represented by the formula (I-II-7) to the formula (I-II-21) and the formula (I-II-103) to the formula (I-II-117).

Further, in the case of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , in the above compound, from the formula (Ph8') to the formula (Ph12'), the formula (Ph20) to the formula The bonding terminal of the group represented by (Ph22) preferably has a hydrogen atom substituted in any of the para, ortho or meta positions, and more preferably a hydrogen atom at the para position.

The compound (2) having -SO ₃ ^- can be sulfonated, for example, by a compound represented by the formula (IC) (hereinafter sometimes referred to as a compound (IC)), and further mixed with a halide containing a r-valent metal ion. It is produced by the reaction of chloride, acetate, phosphate, sulfate, citrate or cyanide.

[In the formula (IC), R ^1b to R ^4b each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number which may have a substituent The aralkyl group of 7 to 30, in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an unsubstituted amino group or a halogen atom, and the saturated hydrocarbon group is contained -CH ₂ - may be replaced by at least one of -O- and -CO-. R ^1b and R ^2b may be bonded and form a ring together with the bonded nitrogen atoms, and R ^3b and R ^4b may be bonded and form a ring together with the bonded nitrogen atoms.

R ^7b to R ^14b each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group or an alkyl group having 1 to 8 carbon atoms, and -CH ₂ - constituting the alkyl group may be substituted with at least one of -O- and -CO-. By. R ^8b and R ^12b may be bonded to each other to form -NH-, -S-, or -SO ₂ -.

The ring T ^10b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

M ¹ represents Cl ^- , a phosphate ion, a perchlorate ion, BF ₄ ^- or PF ₆ ^- . ]

The compound (2) having -SO ₂ -N ^- -SO ₂ -R ^f is permeable to a compound (2) having a -SO ₃ ^- group and having no -SO ₂ -N ^- -SO ₂ -R ^f The compound reaction represented by (IB) is further produced by reacting a halide (preferably chloride), an acetate, a phosphate, a sulfate, a citrate or a cyanide containing a r-valent metal ion.

[In the formula (IB), R ^f is synonymous with the above. ]

As a method of sulfonation, various conventional methods can be mentioned, for example, the method described in Journal of Organic Chemistry, (1994), Vol. 59, No. 11, pp. 3232 to 3236.

The compound (1) and the compound (2) are dispersed by a dispersant to obtain a dispersion in which the compound (1) and the compound (2) are uniformly dispersed in a solution.

Examples of the dispersing agent include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These dispersing agents may be used singly or in combination of two or more. As a dispersing agent, KP (made by Shin-Etsu Chemical Co., Ltd.), flowlen (made by Kyoei Chemical Co., Ltd.), solsperse (made by Zeneca Co., Ltd.), EFKA ( Ciba (manufactured by CIBA), ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), and the like. As the other dispersing agent, a resin (B) (preferably, resin [K1]) described later can be used.

When a dispersing agent is used, the amount thereof to be used is preferably 1% by mass or more and 100% by mass or less, and more preferably 5% by mass or more and 50% by mass or less based on the total amount of the coloring agent. When the amount of the dispersant used is within the above range, a dispersion liquid in a uniformly dispersed state tends to be obtained.

The colorant (A) may contain one or both of the dye (A1) and the pigment (A2).

The dye (A1) is not particularly limited, and a conventional dye can be used, and examples thereof include a solvent dye, an acid dye, a direct dye, and a mordant dye. As the dye, for example, a compound classified as a substance having a color tone other than a pigment in a color index (published by The Society of Dyers and Colourists), and a dyeing note (dyeing dyeing) can be cited. A conventional dye described in the company. Further, according to the chemical structure, an azo dye, a cyanine dye, a triphenylmethane dye, a xanthene dye, a phthalocyanine dye, an anthraquinone dye, a naphthoquinone dye, a quinone imine dye, A methine dye, a methine azo dye, a squarylium dye, an acridine dye, a styryl dye, a coumarin dye, a quinoline dye, and a nitro dye. Among these dyes, organic solvent-soluble dyes are preferred.

Specifically, CI solvent yellow 4 (hereinafter, the description of CI solvent yellow is omitted, only the serial number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 117, 162, 163, 167, 189; CI solvent red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227 , 230, 245, 247; CI Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86; 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, 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 green 1, 3, 4, 5, 7, 28, 29, 32 CI solvent dyes such as 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, 16 9, 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, 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 Oranges 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, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; CI Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1 335, 340; 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 CI acid dyes such as 65, 80, 104, 105, 106, 109; 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, 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 Green 25 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and other CI direct dye; CI disperse yellow 51, 54, 76; CI disperse violet 26, 27; CI Disperse Blue 1, 1, 56, 60, 60, etc. CI Disperse Dyes; CI Basic Red 1, 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 alkaline violet 2; CI alkaline red 9; CI Basic green 1 and other CI basic dyes; CI active yellow 2, 76, 116; CI active orange 16; CI active 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, 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 purple 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 mord green 1, CI mordant dyes such as 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, and 53; CI reduction green 1 and other CI vat dyes.

These dyes can be appropriately selected depending on the spectral spectrum of the desired color filter.

The pigment (A2) is not particularly limited, and a conventional pigment can be used. For example, a pigment classified as a pigment in an excellent index (published by the British Dyestuff and Colorist Society) can be cited.

Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, and 125. Yellow pigments such as 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; 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 , red pigments such as 224, 242, 254, 255, 264, 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 19, 23, 29, Purple pigments such as 32, 36, 38; CI pigment green 7, 36, 58 and other green pigments; CI pigment brown 23, 25 and other brown pigments; CI pigment black 1, 7 and other black pigments.

As the pigment, preferred are blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments, Jia is CI Pigment Blue 15:3, 15:6 and CI Pigment Violet 23, and further preferably CI Pigment Blue 15:6. By including the above pigment, the optimization of the transmission spectrum is easy, and the light resistance and chemical resistance of the color filter become good.

For the pigment, if necessary, the following treatment can be carried out: rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, graft treatment of a pigment surface with a polymer compound or the like, and use of sulfuric acid particles. A micronization treatment such as a chemical method, or a washing treatment using an organic solvent or water to remove impurities, a treatment for removing ionic impurities by an ion exchange method, or the like.

The pigment preferably has a uniform particle size. By performing a dispersion treatment by containing a pigment dispersant, a pigment dispersion liquid in which a pigment is uniformly dispersed in a solution can be obtained.

Examples of the pigment dispersant include surfactants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used singly or in combination of two or more. The pigment dispersant is represented by a trade name, and KP (manufactured by Shin-Etsu Chemical Co., Ltd.), flowlen (manufactured by Kyoei Chemical Co., Ltd.), solsperse (manufactured by Jielikang Co., Ltd.), and EFKA (Ciba) Made by the company), ajisper (manufactured by Ajinomoto Precision Technology Co., Ltd.), Disperbyk (manufactured by BYK Chemical Co., Ltd.), etc.

In the case of using a pigment dispersant, the amount of the pigment (A2) is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less based on the total amount of the pigment (A2). the following. When the amount of the pigment dispersant used is in the above range, the pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

In the coloring agent (A), the content ratio of the dye (A1) and the pigment (A2) is usually from 1:99 to 99:1, preferably from 5:95 to 95:5, more preferably 10: on a mass basis. 90 to 90:10.

Here, the "total amount of solid content" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid components and the content of each component with respect to the solid components can be measured by a known analytical method such as liquid chromatography or gas chromatography.

With respect to the content of the compound (1) or the compound (2), in the total amount of the colorant (A), it is preferably from 1 to 100% by mass, more preferably from 20 to 100% by mass, still more preferably from 40 to 100% by mass.

The content of the compound (1) or the compound (2) is preferably from 1 to 80% by mass, more preferably from 2 to 70% by mass, still more preferably from 3 to 60% by mass in the dispersion.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, still more preferably from 10 to 50% by mass, based on the total amount of the solid component. When the content of the coloring agent (A) is within the above range, the color density when the color filter is formed is sufficient, and the resin (B) and the polymerizable compound (C) can be contained in the composition. A pattern having sufficient mechanical strength is formed. Here, the "total amount of solid content" in the present specification means an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. The total amount of the solid components and the content of each component with respect to the solid components can be measured by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, and is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

Resin [K1]: having a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (a) (hereinafter sometimes referred to as "(a)") and a ring having a carbon number of 2 to 4. a copolymer of a structural unit of an ether structure and an ethylenically unsaturated bond (b) (hereinafter sometimes referred to as "(b)"); a resin [K2]: having a structural unit derived from (a), from ( The structural unit of b) and the copolymerization of the structural unit derived from the monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as "(c)") Resin [K3]: a copolymer having a structural unit derived from (a) and a structural unit derived from (c); a resin [K4] having a structure obtained by adding (b) a structural unit derived from (a) a structural unit and a copolymer of the structural unit derived from (c); a resin [K5]: a copolymer having a structural unit obtained by adding (a) the structural unit derived from (b) and a structural unit derived from (c) Resin [K6]: a copolymer having a structural unit obtained by adding (a) a structural unit derived from (b) and further adding a carboxylic anhydride, and a structural unit derived from (c).

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid, fumaric acid, and citrine Acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6 - unsaturated dicarboxylic acids such as tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexene dicarboxylic acid; methyl-5-norbornene-2,3-dicarboxylate 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]g 2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6 a carboxyl group-containing bicyclic unsaturated compound such as ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinyl Phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5 , 6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and other unsaturated Carboxylic anhydrides; succinic acid mono [2-(methyl) propylene methoxyethyl] ester, phthalic acid mono [2-(methyl) propylene methoxyethyl] ester, etc. An acid unsaturated mono[(meth)acryloxyalkylalkyl]ester; an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule, such as α-(hydroxymethyl)acrylic acid.

Among these compounds, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable from the viewpoints of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

(b) means, for example, 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 oxindole 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)acryloxy group.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions "(meth)acrylonitrile" and "(meth)acrylate" have the same meaning.

(b), for example, a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxonium group and an ethylenically unsaturated bond may be mentioned. The monomer (b2) (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)")).

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

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and 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(glycidoxymethyl)styrene, 2, 4-bis(glycidoxymethyl)styrene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3, 4-tris(glycidoxymethyl)styrene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidoxymethyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

(b1-2), vinyl cyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE 2000; manufactured by Daicel Co., Ltd.), (methyl) 3,4-epoxycyclohexylmethyl acrylate (for example, CYCLOMER A400; manufactured by Daicel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, CYCLOMER M100; Daicel Co., Ltd. Manufactured by the company, a compound represented by the formula (I), a compound represented by the formula (II), and the like.

[In the formulae (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a and X ^b represents a single ^{bond, * - R c -, *} - R c -O -, * - R c -S- or * -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* indicates the bond end with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, and a tertiary butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted by a hydroxyl 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, and a 1-hydroxy group. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ^a and R ^{b are} preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. - Diyl, hexane-1,6-diyl and the like.

Preferred examples of X ^a and X ^b include a single bond, a methylene group, an exoethyl group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O-, and more preferably a single bond, * -CH ₂ CH ₂ -O- (* indicates the bonding end with O).

The compound represented by the formula (I) may, for example, be a compound represented by any one of the formula (I-1) to the formula (I-15). Wherein, it is preferably from the formula (I-1), the formula (I-3), the formula (I-5), the formula (I-7), the formula (I-9), or the formula (I-11) to the formula The compound represented by the formula (I-15) is more preferably a compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15).

The compound represented by the formula (II) includes a compound represented by any one of the formula (II-1) to the formula (II-15). Wherein, it is preferably from the formula (II-1), the formula (II-3), the formula (II-5), the formula (II-7), the formula (II-9), or the formula (II-11) to the formula The compound represented by (II-15) is more preferably a compound represented by the formula (II-1), the formula (II-7), the formula (II-9), or the formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. In the case where the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio [compound represented by the formula (I): compound represented by the formula (II)] is calculated on a molar basis. Preferably, it is from 5:95 to 95:5, more preferably from 20:80 to 80:20.

As (b2), a monomer having an oxonium group and a (meth)acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methylpropenyloxymethyloxanium, 3-methyl-3-propenyloxymethyloxime, and 3-ethyl-3-methyl. Acryloxymethyloxanium, 3-ethyl-3-propenyloxymethyloxanium, 3-methyl-3-methylpropenyloxyethyloxanium, 3-methyl-3 - propylene methoxyethyl oxime, 3-ethyl-3-methylpropenyloxyethyl oxonium, 3-ethyl-3-propenyloxyethyl oxonium, and the like.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, VISCOAT V #150, manufactured by Osaka Organic Chemical Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(b), it is preferable that (b) is further improved in reliability such as heat resistance and chemical resistance of the obtained color filter. Further, in terms of excellent storage stability of the colored curable resin composition, (b1-2) is more preferable.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, n-butyl (meth)acrylate, and (meth)acrylic acid III. Butyl methacrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylate ring Amyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth) In the technical field, it is called "dicyclopentanyl (meth)acrylate" as a conventional name. In addition, it may be called "tricyclodecyl (meth)acrylate) or tricyclo(meth)acrylate [5.2. 1.0 ^2,6 ]nonene-8-yl ester (in the technical field, as a conventional name, it is called "dicyclopentenyl (meth) acrylate)), (cyclo) pentyloxyethyl (meth) acrylate, ( Isobornyl methyl methacrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate (meth) acrylate such as benzyl (meth) acrylate (hydroxy)-containing (meth) acrylates such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; diethyl maleate, diethyl fumarate, and Ikon Dicarboxylic acid diester such as diethyl acid; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]g 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-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-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-tris-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(tertiarybutoxycarbonyl)bicyclo[2.2.1] a bicyclic unsaturated compound such as 2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenylmaleimide, N-cyclohexyl horse醯iimine, N-benzylmaleimide, N-succinimide-3-maleimide benzoate, N-succinimide-4-maleimide Butyrate, N-succinimide-6-maleimide caproate, N-succinimide-3-maleimide propionate, N-(9-acridinyl) Dicarbonylimine derivatives such as maleimide; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene , acrylonitrile, methacrylonitrile, vinyl chloride, dichloroethylene, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl Base-1,3-butadiene and the like.

Among these compounds, styrene, vinyl toluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzyl group are preferred from the viewpoints of copolymerization reactivity and heat resistance. Maleimide, bicyclo [2.2.1] hept-2-ene, and the like.

In the resin [K1], the ratio of the structural unit derived from each monomer in all the structural units constituting the resin [K1] is preferably:

Structural unit from (a): 2 to 60 mol%

The structural unit from (b): 40 to 98 mol%, more preferably:

Structural unit from (a): 10 to 50 mol%

Structural unit from (b): 50 to 90 mol%.

When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that the storage stability of the colored curable resin composition, the developability when a colored pattern is formed, and the obtained color filter are obtained. Excellent solvent resistance.

The resin [K1] can be referred to, for example, the method described in the "Experimental Method for Polymer Synthesis" (Dazu Takashi, Press-Technology Co., Ltd., 1st Edition, 1st Printing, March 1, 1972). And the cited documents described in this document are manufactured.

Specifically, a method of charging a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like into a reaction vessel, for example, replacing oxygen with nitrogen to form an oxygen-removing atmosphere, and heating while stirring And insulation. In addition, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and those generally used in the field can be used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), and an organic Peroxide (benzaldehyde peroxide, etc.). The solvent (E) of the colored curable resin composition of the present invention may be a solvent to be described later, and the like.

Incidentally, as the obtained copolymer, the solution after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) product taken out by a method such as reprecipitation may be used. In particular, in the polymerization, the solvent contained in the colored curable resin composition of the present invention can be used as a solvent, and the solution after the reaction 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 the present invention can be simplified.

In the resin [K2], the ratio of the structural unit derived from each monomer is preferably: in all the structural units constituting the resin [K2]:

Structural unit from (a): 2 to 45 mol%

Structural unit from (b): 2 to 95 mol%

The structural unit from (c): 1 to 65 mol%, more preferably:

Structural unit from (a): 5 to 40 mol%

Structural unit from (b): 5 to 80 mol%

Structural unit from (c): 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is within the above range, there is a tendency that the storage stability of the colored curable resin composition is excellent in developability when forming a colored pattern; and the obtained color filter Excellent in solvent resistance, heat resistance and mechanical strength.

The resin [K2] can be produced, for example, in the same manner as the method described in the production method of the resin [K1].

In the resin [K3], among all the structural units constituting the resin [K3], the ratio of the structural unit derived from each monomer is preferably:

Structural unit from (a): 2 to 60 mol%

The structural unit from (c): 40 to 98 mol%, more preferably:

Structural unit from (a): 10 to 50 mol%

Structural unit from (c): 50 to 90 mol%.

The resin [K3] can be produced, for example, in the same manner as the method described in the production method of the resin [K1].

The resin [K4] can be produced by obtaining a copolymer of (a) and (c), adding (b) a cyclic ether having 2 to 4 carbon atoms, and (a) a carboxylic acid and/or a carboxylic anhydride. .

First, the copolymers (a) and (c) can be produced in the same manner as the method described in the production method of the resin [K1]. In this case, the ratio of the structural unit derived from each monomer is preferably the same ratio as the ratio enumerated in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms which is contained in (b) is reacted with a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer.

After the copolymer of (a) and (c) is produced, the atmosphere in the flask is replaced with nitrogen by air, and a catalyst for reacting (b), a carboxylic acid or a carboxylic anhydride with a cyclic ether (for example, tris(dimethylamino) A resin [K4] can be produced by charging a reaction medium (for example, hydroquinone or the like) and a polymerization inhibitor (for example, hydroquinone) into the flask, for example, at 60 to 130 ° C for 1 to 10 hours.

With respect to the amount of use of (b), it is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, per 100 moles (a). When it is in this range, the storage stability of the colored curable resin composition and the developability at the time of pattern formation are improved, and the solvent resistance, heat resistance, mechanical strength, and photosensitivity of the obtained pattern are obtained. The balance of sex has become good. Since the cyclic ether has high reactivity and the unreacted (b) does not easily remain, the (b) used for the resin [K4] is preferably (b1), more preferably (b1-1).

The amount of use of the above-mentioned reaction catalyst is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).

The reaction conditions such as the feeding method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment, the amount of heat generation by polymerization, and the like. Further, similarly to the polymerization conditions, the feeding method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generation by polymerization, and the like.

In the first step of the resin [K5], a copolymer of (b) and (c) was obtained in the same manner as in the above-described method for producing the resin [K1]. Similarly to the above, the obtained copolymer may be used as it is, or a concentrated or diluted solution may be used, or a solid (powder) product taken out by a method such as reprecipitation may be used.

With respect to the ratio of the structural units derived from (b) and (c), the total number of moles relative to all the structural units constituting the above copolymer is preferably each:

Structural unit from (b): 5 to 95 mol%

The structural unit from (c): 5 to 95 mol%, more preferably:

Structural unit from (b): 10 to 90 mol%

Structural unit from (c): 10 to 90 mol%.

Further, under the same conditions as in the method for producing the resin [K4], the reaction is carried out by reacting the carboxylic acid or carboxylic anhydride having (a) with the cyclic ether derived from (b) of the copolymer of (b) and (c). Thus, the resin [K5] can be obtained.

The amount of (a) used for the reaction with the above copolymer is preferably from 5 to 80 moles per 100 moles (b). Since the cyclic ether has high reactivity and the unreacted (b) does not easily remain, the (b) used for the resin [K5] is preferably (b1), more preferably (b1-1).

The resin [K6] is a resin obtained by further reacting a carboxylic anhydride with a resin [K5]. The carboxylic acid anhydride is reacted with a hydroxyl group produced by reacting a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydroortylene. Dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. . The amount of the carboxylic anhydride used is 1 mol, preferably 0.5 to 1 mol, relative to the amount used in (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxytricycloacrylate [5.2.1.0 ^2.6]. Resin such as oxime ester/(meth)acrylic copolymer [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, acrylic acid 3 , 4-epoxytricyclo[5.2.1.0 ^2.6 ]decyl ester/(meth)acrylic acid/N-cyclohexylmaleimide/2-hydroxyethyl (meth)acrylate copolymer, 3-methyl- Resin such as 3-(meth)acryloxymethoxymethyloxindole/(meth)acrylic acid/styrene copolymer [K2]; benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/ a resin such as a (meth)acrylic copolymer [K3]; a resin obtained by adding a glycidyl (meth)acrylate and a benzyl (meth)acrylate/(meth)acrylic acid copolymer, and (meth) Glycidyl acrylate and tricyclodecyl (meth) acrylate / styrene / (A a resin obtained by addition of an acrylic copolymer, and a glycidyl (meth)acrylate and a tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer are added thereto. a resin such as a resin [K4]; a resin obtained by reacting a copolymer of (meth)acrylic acid with tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, and (meth)acrylic acid ( Resin such as resin obtained by reacting a copolymer of tricyclodecyl methacrylate/styrene/glycidyl (meth)acrylate [K5]; (meth)acrylic acid and tricyclodecyl (meth)acrylate A resin such as a resin obtained by a reaction of a copolymer of glycidyl (meth)acrylate and a resin obtained by a reaction with tetrahydrophthalic anhydride, etc. [K6].

Among them, as the resin (B), a resin [K1] and a resin [K2] are preferable, and a resin [K2] is particularly preferable.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, still more preferably from 5,000 to 30,000. When the molecular weight is within the above range, the hardness of the color filter is increased, the residual film ratio is high, the solubility of the unexposed portion to the developer is good, and the resolution of the colored pattern tends to be improved.

The degree of dispersion [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH/g (mg-KOH/g), more preferably 60 to 150 mg-KOH/g, even more preferably 70 to 70 in terms of solid content. 135 mg-KOH/g. Here, the acid value is a value measured by neutralizing the amount (mg) of potassium hydroxide required for 1 gram of the resin (B), and can be obtained, for example, by titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid component. When 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 ratio tend to increase.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated by the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. (Meth) acrylate compound.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dinoxin. Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentenol octa (meth) acrylate, tripentanisitol hepta (meth) acrylate, Tetrakis pentaerythritol deca (meth) acrylate, tetrapentaerythritol 九 (meth) acrylate, tris(2-(methyl) propylene methoxyethyl) isocyanurate, ethylene glycol Modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa(meth) acrylate, propylene glycol modified neopentyltetrakis tetra(meth) acrylate, Propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified neopentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol hexa(methyl) ) Acrylate and the like.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

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

The content of the polymerizable compound (C) is preferably from 7 to 65 mass%, more preferably from 13 to 60 mass%, still more preferably from 17 to 55 mass%, based on the total amount of the solid component. When the content of the polymerizable compound (C) is within the above range, there is a tendency that the residual film ratio at the time of formation of the colored pattern and the chemical resistance of the color filter are improved.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, an acid, or the like by the action of light or heat, and starts polymerization. A conventional polymerization initiator can be used. Examples of the polymerization initiator which generates the living radicals include an alkylphenone compound, a triazine compound, a mercaptophosphine oxide compound, an O-mercaptopurine compound, and a biimidazole compound.

The above O-indenyl ruthenium compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * indicates the key end.

Examples of the above O-indenyl ruthenium compound include N-benzylideneoxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine and N-benzoic acid.醯oxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylhydrothiophenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-carbazole- 3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4- Dioxolylmethyloxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl- 6-(2-Methylbenzimidyl)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl -6-(2-Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as IRGACURE OXE01, OXE02 (above, BASF) and N-1919 (made by ADEKA) can be used. Wherein, the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylhydrothiophenyl)butan-1-one-2-imine, N-benzidine Oxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine, and N-benzylideneoxy-1-(4-phenylhydrothiophenyl) At least one of 3-cyclopentylpropan-1-one-2-imine, more preferably N-benzylideneoxy-1-(4-phenylhydrothiophenyl)octane-1- Keto-2-imine. If such an O-fluorenyl ruthenium compound is used, it tends to obtain a high-density color filter.

The above alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

The compound having a partial structure represented by the formula (d2) includes, for example, 2-methyl-2-morpholin-1-(4-methylhydrothiophenyl)propan-1-one, 2 -Dimethylamino-1-(4-morpholinylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylbenzene) Methyl]-1-[4-(4-]folinyl)phenyl]butan-1-one and the like. Commercial products such as IRGACURE 369, 907, and 379 (manufactured by BASF Corporation) can be used.

The compound having a partial structure represented by the formula (d3) includes, for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4 -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 a ketone oligomer, α,α-diethoxyacetophenone, benzyldimethylketal, and the like.

In terms of photosensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

The triazine compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine or 2,4-bis (three) Chloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-mallowyl-1,3,5-tri Pyrazine, 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, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three And so on.

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide. A commercially available product such as IRGACURE (registered trademark) 819 (manufactured by BASF Corporation) can be used.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis (2,3). -Dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (for example, see JP-A-6-75372, JP-A-6-75373, etc.) 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5 , 5'-tetrakis(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to Japanese Patent Publication No. Sho 48-38403 An imidazole compound in which a 4,4', 5,5'-position phenyl group is substituted with an alkoxycarbonyl group (for example, see Japanese Patent Laid-Open No. Hei 7-10913, etc., for example, JP-A-62-174204, etc.) )Wait.

Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Compounds; benzophenone, methyl o-benzhydrylbenzoate, 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3' , 4,4'-tetrakis (tertiary butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone and other benzophenone compounds; 9,10-phenanthrenequinone, 2- An anthraquinone compound such as ethyl hydrazine or camphor quinone; 10-butyl-2-chloroacridone, diphenylethylenedione, methyl phenylglyoxylate, a titanocene compound, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) to be described later.

Examples of the acid generator include 4-hydroxyphenyldimethylhydrazine p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, and 4-ethyloxyphenyl dimethyl carbonate.鋶p-toluenesulfonate, 4-acetoxyphenylmethylbenzylphosphonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodide An anthracene salt such as p-toluenesulfonate or diphenyliodonium hexafluoroantimonate, a nitrobenzyl tosylate or a benzoin tosylate.

As the polymerization initiator (D), it is preferred to include an polymerization starting from at least one selected from the group consisting of an alkylphenone compound, a triazine compound, a mercaptophosphine oxide compound, an O-mercaptophosphonium compound, and a biimidazole compound. The agent is more preferably a polymerization initiator containing an O-fluorenyl hydrazine compound.

The content of the polymerization initiator (D) is preferably from 0.1 to 30 parts by mass, more preferably from 1 to 20 parts by mass, per 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). . When the content of the polymerization initiator (D) is within the above range, the photosensitivity is high and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<Polymerization starter (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer for promoting polymerization of a polymerizable compound which starts polymerization using a polymerization initiator. In the case where the polymerization initiation aid (D1) is contained, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include an amine compound, an alkoxy fluorene compound, a thioxanthone compound, and a carboxylic acid compound.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethyl Isoamyl benzoate benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine; 4'-bis(dimethylamino)benzophenone (commonly known as miconesone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylamino)benzophenone or the like, among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can be used.

Examples of the alkoxyfluorene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl. -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

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

Examples of the carboxylic acid compound include phenyl thioacetic acid, methylphenyl thioacetic acid, ethyl phenyl thioacetic acid, methyl ethyl phenyl thioacetic acid, and dimethyl phenyl. Hydrogenthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine , phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

In the case of using the polymerization initiator (D1), the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Up to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, the coloring pattern can be further formed with high sensitivity, and the productivity of the color filter tends to increase.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent which is generally used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and a solvent containing no -O-), an ether solvent (a solvent containing -O- in the molecule, a solvent containing no -COO-), an ether ester solvent (in the case of a solvent containing -COO- and -O- in the molecule), a ketone solvent (a solvent containing -CO- in the molecule, a solvent not containing -COO-), an alcohol solvent (containing OH in the molecule, not containing -O-, - A solvent of CO- and -COO-), an aromatic hydrocarbon solvent, a guanamine solvent, dimethyl hydrazine, or the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, ethyl acetate methyl acetate, ethyl acetate ethyl acetate, cyclohexyl Alcohol acetate, γ-butyrolactone and the like.

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, and diethyl ether. 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 Alcohol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether, and methyl anisole.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethyl 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, and diethyl Glycol monobutyl ether acetate and the like.

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

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, and 1,3,5-trimethylbenzene.

Examples of the guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

Among the above-mentioned solvents, an organic solvent having a boiling point of 120 ° C or more and 180 ° C or less at 1 atm is preferred from the viewpoints of coatability and drying properties. As the solvent, preferred is propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl. Ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide, more preferably propylene glycol monomethyl ether acetate, propylene glycol Monomethyl ether, ethyl lactate, and ethyl 3-ethoxypropionate.

The content of the solvent (E) is preferably from 70 to 95% by mass, more preferably from 75 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total content of the solid content of the colored curable resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of application is good, and the color density is not insufficient when the color filter is formed. Therefore, the display characteristics tend to be good.

<Leveling agent (F)>

Examples of the leveling agent (F) include an organic lanthanoid surfactant, a fluorine-based surfactant, and an organic lanthanoid surfactant having a fluorine atom. These may have a polymerizable group in the side chain.

Examples of the organic oxime-based surfactant include surfactants having a decane bond in the molecule. 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 Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (made by Momentive Advanced Materials Japan Co., Ltd.).

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, FLUORAD (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.); MEGAFAC (registered trademark) F142D, F171, F172, F173, F177, F183, F554, R30, RS-718-K ( Manufactured by DIC Co., Ltd.; EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Corporation); SURFLON (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) ; and E5844 (made by Daikin Fine Chemical Research Institute Co., Ltd.).

The organic ruthenium-based surfactant having a fluorine atom may, for example, be a surfactant having a decane bond or a fluorocarbon chain in the molecule. Specifically, MEGAFAC (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) may be mentioned.

The content of the leveling agent (F) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less based on the total amount of the colored curable resin composition. Further, it is more preferably 0.01% by mass or more and 0.05% by mass or less. In addition, the content of the above-mentioned dispersing agent is not contained in this content. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Antioxidant (H)>

The antioxidant (H) is an antioxidant which is measured by a thermal analyzer and has a heating mass reduction rate of 8.0% or less represented by the following formula.

Heating mass reduction rate (%) = 100 - (mass after 100 minutes after reaching 230 ° C / mass at 230 ° C) × 100

As the thermal analysis device, for example, a differential thermal thermal mass synchronous measuring device can be cited.

The heating mass reduction rate of the antioxidant (H) is 8.0% or less, preferably 7.0% or less, more preferably 6.0% or less, still more preferably 5.0% or less.

The lower limit of the heating mass reduction rate of the antioxidant (H) is not limited, and is preferably close to 0%, and may be, for example, 0.01%, 0.1% or 1%.

As the antioxidant (H), a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, or the like can be used.

Among them, a phenol-based antioxidant and a phosphorus-based antioxidant are preferably used, and a phenol-based antioxidant is more preferably used.

The phenolic antioxidant is an antioxidant having a phenolic hydroxyl group in the molecule, and preferably does not have a phosphorus atom. An antioxidant which generates a phenolic hydroxyl group by heating is also contained in the phenolic antioxidant.

As the phenolic antioxidant, for example, as a partial structure, a methyl group or a tertiary butyl group is preferably bonded at one or two positions ortho to the hydroxy group bonded to the phenyl group.

The antioxidant (H) has a molecular weight of preferably 100 or more, more preferably 300 or more, still more preferably 500 or more, still more preferably 700 or more and 3,000 or less. Two or more antioxidants can be used.

In addition, as the phenolic antioxidant, the hydroxyl equivalent (hereinafter referred to as OH equivalent) represented by the following formula is preferably 150 or more and 700 or less, more preferably 250 or more and 400 or less.

OH equivalent = molecular weight / number of hydroxyl groups in a molecule

In the case of an antioxidant that generates a phenolic hydroxyl group by heating, it is calculated by a structure in which a hydroxyl group is formed.

As the phenolic antioxidant, ADEKA STAB AO-20 (1,3,5-tris(3,5-di-tri-butyl-4-hydroxybenzyl) 1,3,5-triazine-2 is exemplified. , 4,6(1H,3H,5H)-trione, manufactured by Adico Co., Ltd.), ADEKA STAB AO-60 (neopentitol tetrakis[3-(3,5-di-tertiary butyl-) 4-hydroxyphenyl)propionate], manufactured by Adico Co., Ltd., GPA-5001 (manufactured by Adico Co., Ltd.), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), and the like.

Examples of the phosphorus-based antioxidant include triphenyl phosphite (ADEKA STAB TPP, manufactured by AIDCO Co., Ltd.).

In the present invention, an antioxidant which satisfies at least the above-described heating mass reduction rate among the conventional antioxidants can be used.

The content of the antioxidant (H) is preferably 0.001% by mass or more and 1% by mass or less, more preferably 0.002% by mass or more and 0.5% by mass or less, based on the total amount of the colored curable resin composition. More preferably, it is 0.01 mass% or more and 0.3 mass% or less.

<Other ingredients>

The colored curable resin composition of the present invention may contain a filler conventionally known in the art, such as a filler, another polymer compound, an adhesion promoter (G), a light stabilizer, and a chain transfer agent, as needed.

Examples of the adhesion promoter (G) include vinyltrimethoxydecane, vinyltriethoxydecane, vinyltris(2-methoxyethoxy)decane, and 3-glycidoxypropyl group. Trimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-glycidoxypropylmethyldiethoxylate Baseline, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropene醯oxypropyltrimethoxydecane, 3-hydrothiopropyltrimethoxydecane, 3-isocyanatepropyltriethoxydecane, N-2-(aminoethyl)-3-aminopropyl Methyldimethoxydecane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxydecane, N-2-(aminoethyl)-3-aminopropyl Trimethoxy decane, N-2-(aminoethyl)-3-aminopropylmethyldiethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethyl Oxydecane, N-phenyl-3-aminopropyltrimethoxydecane, and N-phenyl-3-aminopropyltriethoxydecane .

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention can pass, for example, a coloring agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), an antioxidant (H), and a solvent used as needed. (E), a leveling agent (F), a polymerization starting aid (D1), and other components are prepared by mixing.

<Method of Manufacturing Color Filter>

A method of producing a colored pattern by the colored curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. In the photolithography method, the colored curable resin composition is applied onto a substrate, dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and/or no development at the time of exposure. The colored pattern or colored coating film thus formed is the color filter of the present invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted depending on the purpose, use, and the like, 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, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda-lime glass coated with cerium oxide can be used; polycarbonate, polymethyl methacrylate, polyterephthalic acid a resin plate such as ethylene glycol ester; ruthenium; a product of aluminum, silver, silver/copper/palladium alloy film or the like formed on the substrate. Additional color filter layers, resin layers, transistors, circuits, and the like can be formed on the substrates.

The formation of the respective color pixels by photolithography can be carried out under conventional or conventional devices and conditions. For example, it can be produced as follows.

First, the colored curable resin composition is applied onto a substrate, dried by heating (prebaking), and/or dried under reduced pressure to remove volatile components such as a solvent and dried to obtain a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit coating method, a slit, and a spin coating method.

The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, as the heating time, it is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably carried out at a temperature of from 20 to 25 ° C under a pressure of from 50 to 150 Pa.

The film thickness of the colored composition layer is not particularly limited, and can be appropriately selected depending on the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the mask is not particularly limited, and a pattern matching the intended use can be used.

As the light source for exposure, a light source that generates light of a wavelength of 250 to 450 nm is preferable. For example, a wavelength range can be cut off using a filter that cuts light of less than 350 nm, or a band pass filter that takes out light near 436 nm, near 408 nm, and around 365 nm can be used. The wavelength ranges are selectively taken out. Specifically, a mercury lamp, a light-emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

Since the parallel light can be uniformly irradiated to the entire exposed surface, and the mask and the substrate on which the colored composition layer is formed are properly aligned, an exposure apparatus such as a mask aligner and a stepper is preferably used.

The colored composition layer after exposure is developed in contact with the developer to form a colored pattern on the substrate. Through the development, the unexposed portion of the colored composition layer is dissolved in the developer to be removed. As the developer, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of these basic compounds is preferably from 0.01 to 10% by mass, more preferably from 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The development method may be any of a paddle method, a dipping method, and a spray method. Further, the substrate can be tilted at an arbitrary angle during development.

It is preferred to carry out water washing after development.

Further, it is preferred to post-bake the obtained colored pattern. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

According to the colored curable resin composition of the present invention, a color filter having particularly excellent residual film ratio can be produced. The color filter can be used as a color filter for a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.) and a solid-state image sensor.

<Example>

The invention is described in more detail below by way of examples, but the invention is not limited by these examples. In the examples, the % and the parts indicating the content or the amount used are based on mass unless otherwise specified.

Hereinafter, the structure of the compound was confirmed by mass analysis (LC; Agilent Model 1200, MASS; Agilent LC/MSD type).

[Synthesis Example 1]

The compound represented by the formula (a1) is synthesized according to the method described in JP-A-2015-38201.

[Synthesis Example 2]

The following reaction was carried out under a nitrogen atmosphere. After 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N,N-dimethylformamide were placed in a flask equipped with a condenser and a stirring device, the mixed solution was ice-cooled. After 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little for 30 minutes under ice cooling, the mixture was stirred for 1 hour while warming to room temperature. 10.4 parts of 4,4'-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little to the reaction mixture, and stirred at room temperature for 24 hours. The reaction mixture was added to 200 parts of ice water little by little, and then allowed to stand at room temperature for 15 hours, and water was removed by decantation to obtain a viscous solid as a residue. After 60 parts of methanol was added to the viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was separated by filtration and purified by column chromatography. The purified pale yellow solid was dried under reduced pressure at 60 ° C to give 9.8 part of the compound of formula (C-I-2). The yield was 53%.

The following reaction was carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, 50 parts of the compound represented by the formula (C-1-2) and 188 parts of N,N-dimethylformamide were placed, and the mixture was stirred for 30 minutes while cooling with an ice bath. 40 parts of potassium butyrate (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in the flask, and the mixture was further stirred for 1 hour while cooling with an ice bath. In a state where the reaction liquid was ice-cooled, 55.6 parts of iodoethane (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped. The reaction solution was heated to 35 ° C using an oil bath, stirred for 5 hours, and then allowed to cool to room temperature. In a separate flask equipped with a stirring apparatus, 1000 parts of a 10% aqueous sodium chloride solution was placed, and the above reaction liquid was added dropwise with stirring. After stirring for 30 minutes, it was filtered to give a solid. The obtained solid was washed three times with 500 parts of ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 53.0 parts of a compound represented by formula (BP-2). The yield was 93.5%.

The following reaction was carried out under a nitrogen atmosphere. After 26.4 parts of potassium thiocyanate and 156 parts of acetonitrile were placed in a flask equipped with a condenser and a stirring device, the mixture was stirred at room temperature for 30 minutes. 40.0 parts of 2,6-difluorobenzhydryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into the flask over 30 minutes, and the mixture was stirred at room temperature for 1 hour. 30.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped into the flask over 30 minutes, and the mixture was stirred at room temperature for 1 hour. An aqueous solution obtained by dissolving 79.2 parts of sodium monochloroacetate in 120 parts of ion-exchanged water was placed in the flask, and 60.4 parts of a 30% aqueous sodium hydroxide solution was added thereto, followed by stirring at room temperature for 18 hours. After further adding 600 parts of ion-exchanged water to the above flask, the mixture was stirred for 1 hour, and a precipitated yellow-white solid was collected by filtration. The obtained yellowish white solid was washed with 120 parts of acetonitrile and then washed with 560 parts of ion-exchanged water. In a flask equipped with a stirring device, a yellow-white solid after washing, 156 parts of ion-exchanged water, 35.0 parts of 99% acetic acid (manufactured by Wako Pure Chemical Industries, Ltd.), and 156 parts of toluene were placed, and the mixture was stirred at room temperature for 2 hours. After 80.8 parts of a 30% aqueous sodium hydroxide solution was added dropwise thereto over 10 minutes, the mixture was stirred for 5 minutes, and the aqueous layer was removed by a liquid separation operation. To the obtained organic layer, 156 parts of ion-exchanged water was added, and after liquid separation washing, 156 parts of ion-exchanged water and 0.1 part of 35% hydrochloric acid were added, and liquid separation washing was performed. The obtained organic layer was concentrated with an evaporator, and dried under reduced pressure at 35 ° C to obtain a compound represented by formula (B-I-2) as a white solid. The yield was 43.4 parts and the yield was 58.0%.

The following reaction was carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, 13.2 parts of a compound represented by the formula (BI-2), 19.0 parts of a compound represented by the formula (BP-2), and 38 parts of toluene were charged, followed by addition of phosphorus oxychloride. 9.2 parts were stirred at 100 ° C for 7 hours. Next, after cooling the reaction mixture to room temperature, it was diluted with 29 parts of methyl ethyl ketone. Next, a mixed solution of 114 parts of ion-exchanged water and 10 parts of a 35% hydrochloric acid aqueous solution was poured into the diluted reaction mixture, and the aqueous layer was removed by a liquid separation operation. The obtained organic layer was subjected to solvent distillation under an evaporator, and then dried under reduced pressure at 60 ° C to obtain a compound represented by the formula (X0) as a blue-violet solid. The yield of the blue-violet solid was 39.4 parts.

The following reaction was carried out under a nitrogen atmosphere. In a flask equipped with a condenser and a stirring device, 38.4 parts of the compound represented by the formula (X0) and 112 parts of dichloromethane were charged, and the mixture was stirred for 30 minutes. The reaction solution was ice-cooled, and 31.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added while maintaining the internal temperature at 10 ° C, and then the reaction solution was warmed to room temperature and stirred for 9 hours. Next, the reaction solution was ice-cooled, and diluted with a mixed solution of 64 parts of N,N-dimethylformamide and 4.9 parts of ion-exchanged water while maintaining the internal temperature at 10 °C. The diluted reaction solution was poured into 1120 parts of toluene, and after stirring for 30 minutes, the viscous solid precipitated. After the oil layer was discharged by decantation, 320 parts of toluene was added to the obtained viscous solid, and the mixture was stirred for 30 minutes. The oil layer was drained by decantation, and 832 parts of 20% saline solution was added to the obtained viscous solid, and after stirring for 1 hour, the blue solid was collected by filtration. The obtained blue solid was washed with 576 parts of 20% brine, and dried under reduced pressure at 35 °C. The obtained solid and 128 parts of methanol were placed in a flask equipped with a stirring apparatus, stirred for 30 minutes, and then filtered to separate a solid and a filtrate. This filtrate was referred to as filtrate A3. The solid collected was washed with 192 parts of methanol and separated to a solid and filtrate by filtration. This filtrate was referred to as filtrate B3. The filtrate A3 and the filtrate B3 were mixed, and the solvent was removed by an evaporator, and then dried under reduced pressure at 40 ° C to obtain a compound represented by the formula (X1) as a blue-violet solid. The yield of the blue-violet solid was 38.3 parts.

28.0 parts of the compound represented by the formula (X1), 43.2 parts of cesium chloride dihydrate, and 356 parts of ion-exchanged water were placed in a flask equipped with a condenser and a stirring apparatus, and the mixture was stirred at 40 ° C for 2 hours, and then the reaction suspension was added. filter. 350 parts of the filtered solid and ion-exchanged water were placed in a flask equipped with a stirring device, and the mixture was stirred for 30 minutes, and then the suspension was filtered. The obtained solid was washed with 280 parts of ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain a compound represented by the formula (a2) as a blue-violet solid. The yield was 24.5 parts and the yield was 81.7%.

Identification of compounds represented by formula (a2)

(mass analysis) ionization mode = ESI-: m/z = 949.5 [M-Ba+2H] ^-

Exact mass [M-Ba]: 947.28

[Synthesis Example 3]

The following reaction was carried out under a nitrogen atmosphere. After adding 32.2 parts of potassium thiocyanate and 160 parts of acetone to a flask equipped with a condenser and a stirring device, the mixture was stirred at room temperature for 30 minutes. Next, 50 parts of 2-fluorobenzhydryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and then 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After the completion of the dropwise addition, the mixture was further stirred at room temperature for 30 minutes. Next, after the reaction mixture was ice-cooled, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After the end of the dropwise addition, the reaction mixture was further stirred at room temperature for 30 minutes. Next, 31.3 parts of chloroacetic acid was added dropwise to the reaction mixture at room temperature. After the end of the dropwise addition, the reaction mixture was stirred under heating and reflux for 7 hours. Next, after cooling the reaction mixture to room temperature, the reaction mixture was poured into 120 parts of ion-exchanged water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes to separate the organic layer and the aqueous layer. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, and then washed with 200 parts of ion-exchanged water, and finally washed with 200 parts of saturated brine. An appropriate amount of thenardite was added to the organic layer, and after stirring for 30 minutes, it was filtered to obtain a dried organic layer. The obtained organic layer was subjected to solvent distillation using an evaporator to obtain a pale yellow liquid. The obtained pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried under reduced pressure at 60 ° C to obtain 49.9 parts of the compound represented by formula (B-I-3). The yield was 51%.

The following reaction was carried out under a nitrogen atmosphere. 8.2 parts of the compound represented by the formula (BI-3), 10 parts of the compound represented by the formula (CI-2), and 20 parts of toluene were placed in a flask equipped with a condenser and a stirring device, and then 12.2 parts of phosphorus oxychloride was added thereto. Stir at 95 to 100 ° C for 3 hours. Next, after cooling the reaction mixture to room temperature, it was diluted with 170 parts of isopropyl alcohol. Next, the diluted reaction mixture was poured into 300 parts of saturated brine, and then 100 parts of toluene was added, followed by stirring for 30 minutes. Then, the stirring was stopped, and the mixture was allowed to stand for 30 minutes to separate the organic layer and the aqueous layer. After the water layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of thenardite was added to the organic layer, stirred for 30 minutes, and filtered to give an organic layer. The obtained organic layer was subjected to solvent distillation using an evaporator to obtain a blue-purple solid. Further, the blue-violet solid was dried under reduced pressure at 60 ° C to obtain 18.4 parts of the compound represented by formula (X-II-2). The yield was 100%.

Identification of compounds represented by formula (X-II-2)

(mass analysis) ionization mode = ESI+: m/z = 687.3 [M-Cl] ⁺

Exact quality: 722.3

The following reaction was carried out under a nitrogen atmosphere. After 2.0 parts of the compound represented by the formula (X-II-2) and 7.3 parts of dichloromethane were placed in a flask equipped with a condenser and a stirring device, the reaction solution was ice-cooled. Next, 1.6 parts of chlorosulfonic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred overnight while warming to room temperature. Next, the reaction solution was diluted with 34 parts of N,N-dimethylformamide while being ice-cooled. Next, the diluted reaction solution was poured into 140 parts of toluene, followed by stirring for 30 minutes. Next, the stirring was stopped and decantation was carried out to obtain a blue-violet viscous solid. Further, the blue-violet viscous solid was dried under reduced pressure at 60 ° C to obtain 2.3 parts of the compound represented by the formula (X-I-2). The yield was 100%.

Identification of compounds represented by formula (X-I-2)

(mass analysis) ionization mode = ESI +: m / z = 847.3 [M + H] ⁺

ESI-:m/z=845.5[MH] ^-

Exact quality: 846.2

The following reaction was carried out under a nitrogen atmosphere. Into a flask equipped with a condenser and a stirring device, 2.0 parts of a compound represented by the formula (X-I-2) and 167 parts of ion-exchanged water were placed, and the mixture was stirred at 40 ° C for 30 minutes. 5.8 parts of cerium chloride dihydrate and 35 parts of ion-exchanged water were placed in a beaker, and stirred for 30 minutes. In the aqueous solution of the compound represented by the formula (X-I-2) prepared above, the aqueous solution of ruthenium chloride was added dropwise while maintaining the liquid temperature of the aqueous solution at 40 ° C, and the mixture was stirred for 1 hour and 20 minutes. The obtained reaction suspension was filtered, and the filtered solid was suspended and washed with 67 parts of ion-exchanged water, and then washed with 20 parts of ion-exchanged water. The obtained solid was dried under reduced pressure at 60 ° C to obtain 1.9 parts of the compound represented by formula (a3). The yield was 89%.

[Synthesis Example 4]

The compound represented by the formula (XI-4) was obtained in the same manner as in the synthesis example 3 except that the compound represented by the formula (CI-2) was changed to the compound represented by the formula (BP-2). In the formula, -SO ₃ ^- means that any of the hydrogen atoms contained in the partial structure in the parentheses is substituted.

Identification of compounds represented by formula (X-I-4)

(mass analysis) ionization mode = ESI +: m / z = 931.5 [M + H] ⁺

Exact quality: 930.3

The compound represented by the formula (a4) was obtained in the same manner as in Synthesis Example 3 except that the compound represented by the formula (X-I-2) was changed to the compound represented by the formula (X-I-4).

[Synthesis Example 5]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was flowed in, and it was replaced with a nitrogen atmosphere, and 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were placed, and heated while stirring. To 85 ° C. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxy tricycloacrylate [5.2.1.0] were added dropwise over 5 hours. 25 parts of a mixture of ^2,6 ]decane-9-yl ester (content: 1:1), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, propylene glycol monomethyl ether A mixed solution of 338 parts of an acid ester. On the other hand, a mixed solution obtained by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-1)) having a solid content of 25.6%. The resulting copolymer had a weight average molecular weight Mw of 8,000, a degree of dispersion of 2.1, and an acid value of 111 mg-KOH/g in terms of solid content. The resin (B-1) has the following structural unit.

[Synthesis Example 6]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, an appropriate amount of nitrogen was introduced, and the mixture was replaced with a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 80 ° C while stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and acrylic acid 3 were dropped into the flask using a drip pump for about 5 hours. A mixture of 4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl ester (content: 1:1) 289 parts of a solution obtained by dissolving 125 parts of propylene glycol monomethyl ether acetate. On the other hand, an additional drip pump was used to drip into the flask for about 6 hours, and 33 parts of the polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl. A solution obtained from 235 parts of ether acetate. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (B-2)) having a solid content of 35.1%. The resulting copolymer had a weight average molecular weight Mw of 9,200, a degree of dispersion of 2.08, and an acid value of 77 mg-KOH/g in terms of solid content. The resin (B-2) has the following structural unit.

The measurement of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin was carried out under the following conditions by the GPC method.

Device: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF

Flow rate: 1.0 ml / min (mL / min)

Solid concentration of the tested liquid: 0.001 to 0.01% by mass

Injection volume: 50 microliters (μL)

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as the degree of dispersion.

[Production of Dispersion 1]

41.4 parts of the compound represented by the formula (a1), 17.3 parts of a dispersing agent (BYKLPN-6919, a propylene glycol monomethyl ether acetate 60% solution), and 16.5 parts of a resin (B-2) (solid content conversion), 270 parts of propylene glycol monomethyl ether acetate was mixed, and 600 parts of 0.4 micron zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Then, the zirconia beads were removed by filtration to obtain a dispersion 1.

[Production of Dispersion 2]

23.1 parts of the compound represented by the formula (a2), 28.8 parts of a dispersing agent (BYKLPN-6919, a propylene glycol monomethyl ether acetate 60% solution), and 5.8 parts of a resin (B-2) (solid content conversion), 28.9 parts of diacetone alcohol and 202 parts of propylene glycol monomethyl ether acetate were mixed, and 600 parts of 0.4 micron zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Then, the zirconia beads were removed by filtration to obtain a dispersion 2.

[Production of Dispersion 3]

21.1 parts of CI Pigment Blue 15:6 (pigment), dispersing agent (BYKLPN-6919 manufactured by BYK Co., Ltd.; propylene glycol monomethyl ether acetate 60% solution) 12.3 parts, resin (B-2) (converted solid content) 8.4 A portion, 16.1 parts of ethyl lactate, and 153 parts of propylene glycol monomethyl ether acetate were mixed, and 600 parts of 0.4 micron zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Then, the zirconia beads were removed by filtration to obtain a dispersion 3.

[Production of Dispersion 4]

13.6 parts of the compound represented by the formula (a3), 17.0 parts of a dispersing agent (BYKLPN-6919 manufactured by BYK Corporation; 60% solution of propylene glycol monomethyl ether acetate), and 3.4 parts of a resin (B-2) (solid content conversion), 146 parts of propylene glycol monomethyl ether acetate was mixed, and 600 parts of 0.4 micron zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Then, the zirconia beads were removed by filtration to obtain a dispersion 4.

[Production of Dispersion 5]

13.6 parts of the compound represented by the formula (a4), a dispersing agent (BYKLPN-6919 manufactured by BYK Co., Ltd.; propylene glycol monomethyl ether acetate 60% solution), 17.1 parts, and a resin (B-2) (in terms of solid content), 3.4 parts, 145 parts of propylene glycol monomethyl ether acetate was mixed, and 600 parts of 0.4 micron zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU Corporation). Then, the zirconia beads were removed by filtration to obtain a dispersion 5.

[Examples 1 to 17 and Comparative Example 1]

[Preparation of Colored Curable Resin Composition]

The components shown in Tables 10 to 12 were mixed to obtain each colored curable resin composition.

‧Resin (B): Resin (B-1) (converted in solid content)

‧Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)

‧ Polymerization initiator (D): N-benzylideneoxy-1-(4-phenylhydrothiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01 ; manufactured by BASF; 肟 compound)

‧Solvent (E):

Solvent (E-1): ethyl lactate

Solvent (E-2): propylene glycol monomethyl ether acetate

‧Leveling agent (F): Polyether modified eucalyptus oil (solid content conversion) (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

‧Adhesion promoter (G): 3-methacryloxypropyltrimethoxydecane (KBM-503; manufactured by Shin-Etsu Chemical Co., Ltd.)

‧Antioxidant (H)

Antioxidant (H-1): GPA-5001 (made by Edigo, molecular weight = 1577, OH equivalent = 294)

Antioxidant (H-2): Sumilizer GA80 (manufactured by Sumitomo Chemical Co., Ltd., molecular weight = 741, OH equivalent = 371)

Antioxidant (H-3): ADEKA STAB AO-20 (made by Eddy, molecular weight = 784, OH equivalent = 261)

Antioxidant (H-4): ADEKA STAB AO-60 (made by Eddy, molecular weight = 1177, OH equivalent = 294)

Antioxidant (H-5): ADEKA STAB TPP (made by Eddy, molecular weight 310)

Antioxidant (h-1): Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd., molecular weight = 661, OH equivalent = 661)

<heating quality reduction rate>

With respect to the antioxidant, the change in the thermal mass at the time of heating was measured under the following conditions, and the heating mass reduction rate was calculated according to the following formula. The results are shown in Table 13.

Device: Differential heat and mass weight measurement device TG/DTA6200 (manufactured by Seiko Instruments Co., Ltd.)

Reference: empty dish (aluminum)

Atmosphere: air (flow: 200 ml / min)

Measurement conditions: 230 ° C / hold for 100 minutes

Heating mass reduction rate (%) = 100 - (mass after 100 minutes after reaching 230 ° C / mass at 230 ° C) × 100

<Production of Colored Coating Film>

The colored curable resin composition was applied by spin coating on a glass substrate (Eagle 2000; manufactured by Corning Incorporated) of 5 cm square to have a film thickness of 2.0 μm after post-baking, and then prebaked at 100 ° C for 3 minutes to form a film. Coloring the composition layer. After cooling, an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used, and an exposure amount of 60 mJ/cm ² (mJ/cm ² ) (365 nm basis) was used for the color combination in an air atmosphere. The layer is irradiated with light. Then, it was baked in an oven at 230 ° C for 20 minutes to obtain a colored coating film.

<Residual film rate evaluation>

The film thickness measurement apparatus (DEKTAK3, manufactured by Nippon Vacuum Technology Co., Ltd.) was used to measure the film thickness before and after the post-baking, and the residual film ratio was calculated according to the following formula. The results are shown in Table 14.

Residual film rate (%) = (film thickness after post-baking / film thickness before post-baking) × 100

A large value indicates that the residual film ratio before and after post-baking is high and good.

If the residual film ratio is high, it is difficult to cause an unfavorable situation such as cracking or haze caused by film shrinkage during heating.

Claims (4)

 A colored curable resin composition comprising a colorant, a resin, a polymerizable compound, a polymerization initiator, and an antioxidant, wherein the colorant comprises a triarylmethane lake, and the antioxidant is used to utilize a thermal analysis device The antioxidant having a heating mass reduction rate of 8.0% or less, which is measured by the following formula, has a heating mass reduction rate (%) = 100 - (mass after holding at 230 ° C for 100 minutes / quality at 230 ° C) × 100.   The colored curable resin composition according to claim 1, wherein the triarylmethane lake is at least one selected from the group consisting of a compound represented by the formula (1) and a compound represented by the formula (2). In the formula (1), R ^41a to R ^44a each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number 7 which may have a substituent. In the aralkyl group of 30, in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an unsubstituted amino group or a halogen atom, and the carbon number at the saturated hydrocarbon group is In the case of 2 to 20, the methylene group contained in the saturated hydrocarbon group may be substituted by an oxygen atom or -CO-; however, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent methylene group may not be simultaneously Substituted by an oxygen atom, the terminal methylene group is not substituted by an oxygen atom or -CO-; R ^41a and R ^42a may be bonded to form a ring together with the bonded nitrogen atoms, and R ^43a and R ^44a may be bonded. And forming a ring together with the nitrogen atom to which the bond is bonded, and each of R ^47a to R ^54a independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group having 1 to 8 carbon atoms, and a methylene group constituting the alkyl group. may be substituted with an oxygen atom or -CO-; R ^48a and R ^52a may be bonded to each other to form a -NH -, - O -, - S- or -SO ₂ -, ring T ^1a represents a substituent having a carbon number of 3 10 is an aromatic heterocycle, [Y] ^m- represents an arbitrary m-valent oxygen containing at least one element selected from tungsten, molybdenum, silicon and phosphorus in the anion, m represents an arbitrary natural number, comprising a plurality in one molecule In the case of a cation represented by the following formula, the same may be the same structure or a different structure. Wherein the rings T ^1a , R ^41a to R ^44a and R ^47a to R ^54a are respectively synonymous with the above, In the formula (2), R ^41b to R ^44b each independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or a carbon number 7 which may have a substituent. The aralkyl group to 30, the aromatic hydrocarbon group and the substituent which the aralkyl group may have may be -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , and the hydrogen atom contained in the saturated hydrocarbon group It may be substituted with an unsubstituted amino group or a halogen atom, and in the case where the saturated hydrocarbon group has a carbon number of 2 to 20, -CH ₂ - contained in the saturated hydrocarbon group may be replaced with -O- and - At least one of CO-; however, in the saturated hydrocarbon group having 2 to 20 carbon atoms, the adjacent -CH ₂ - is not simultaneously substituted with -O-, and the terminal -CH ₂ - is not replaced with -O - or -CO-; R ^41b and R ^42b may be bonded and form a ring together with the bonded nitrogen atoms, and R ^43b and R ^44b may be bonded to form a ring together with the bonded nitrogen atoms, R ^47b to R ^54b each independently represent a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, -SO ₃ ^- , -SO ₂ -N ^- -SO ₂ -R ^f , or an alkyl group having 1 to 8 carbon atoms, constituting the alkane. The base -CH ₂ - may be replaced by at least one of -O- and -CO-, R ^48b and R ^52b may be bonded to each other to form -NH-, -S- or -SO ₂ -, however, in the alkyl group, the adjacent -CH ₂ - may not be simultaneously substituted by -O-, and the terminal -CH ₂ - not substituted by -O- or -CO-, ring T ^1b represents an aromatic heterocyclic ring having 3 to 10 carbon atoms, and the aromatic heterocyclic ring may have a saturated hydrocarbon group having 1 to 20 carbon atoms, or unsubstituted An amine group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent; the aromatic hydrocarbon group may have a substituent of -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f , M ^r+ represents a r-valent metal ion, and k represents the number of -SO ₃ ^- and -SO ₂ -N ^- -SO ₂ -R ^{f in} R ^41b to R ^44b , R ^47b to R ^54b and ring T ^1b And r represents an integer of 1 or more, and R ^f represents a fluoroalkyl group having 1 to 12 carbon atoms; however, R ^41b to R ^44b , R ^47b to R ^54b and ring T ^1b have at least one -SO ₃ ^- or -SO ₂ -N ^- -SO ₂ -R ^f .  A color filter formed of the colored curable resin composition according to claim 1 or 2.    A display device comprising the color filter as claimed in claim 3.