KR101813605B1 - Method for manufacturing the pigment dispersed solution - Google Patents

Abstract

And a step of simultaneously uniformly dispersing the dye and the pigment in a solvent.

Description

TECHNICAL FIELD The present invention relates to a method for manufacturing a pigment dispersion,

 The present invention relates to a process for producing a pigment dispersion.

BACKGROUND ART [0002] Pigment dispersions conventionally used for color filters and the like have been produced by dispersing pigments, dispersants, resins, viscosity reducing agents, solvents, and the like (for example, Patent Document 1, etc.). In the dispersing treatment herein, the viscosity characteristics and stability thereof are improved without adversely affecting the color characteristics by controlling the dispersing mixing order of the components, in which the viscosity reducing agent is adsorbed to a large extent by the dispersing agent and then the pigment is added .

[Patent Document 1]

Japanese Patent Application Laid-Open No. 2003-327864

However, foreign matter may be generated in the resist coating film containing the pigment dispersion obtained by such a method. In addition, there has been a problem that the brightness of the color filter decreases depending on the additive used in the dispersion.

It is an object of the present invention to provide a method for producing a pigment dispersion which can further reduce the generation of foreign matter and obtain a color filter having high brightness.

That is, the present invention provides the following [1] to [9].

[1] A method for producing a pigment dispersion, comprising the step of uniformly dispersing a dye and a pigment simultaneously in a solvent.

[2] The production method according to [1], wherein the dye is at least one dye selected from the group consisting of azo compounds, metal complexes having azo compounds as ligands, and xanthene compounds.

[3] The production method according to [1] or [2], wherein the dye is a dye containing a compound represented by formula (1).

[In the formula (1)

R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, -R ⁶ , -OH, -OR _{^{6, -SO 3 -, -SO 3}} H, -SO 3 M, -CO 2 H, -CO 2 R 6, -SO 3 R 6, -SO 2 NHR 8 Or -SO ₂ N (R ⁸ ) R ⁹ ,

R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ Or represents -SO _{^{2 N (R 8) R 9}} ,

m represents an integer of 0 to 5, and when m is an integer of 2 or more, plural R ^{5 s} may be the same or different,

X represents a halogen atom, a represents an integer of 0 or 1,

R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and -CH ₂ - included in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ^6a -, R ^6a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,

R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 30 carbon atoms which may have a substituent, or -Q, or R ⁸ and R ⁹ may be the same or different, May form a heterocyclic ring having 1 to 10 carbon atoms which may have a substituent, and -CH ₂ - contained in the alkyl group and the cycloalkyl group may be replaced by -O-, -CO-, -NH- or -NR ^{6a <} - > -,

Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 10 carbon atoms which may have a substituent,

M represents a sodium atom or a potassium atom,

The number of + electric charges and the number of electric charges of the compound represented by the formula (1) are the same)

[4] The production method according to any one of [1] to [3], wherein the dye and the pigment are contained in a mass ratio of dye: pigment = 1: 99 to 99:

[5] The pigment according to any one of the items Pigment Blue 15: 6, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 242 and C.I. Pigment Red 254. The production method according to any one of [1] to [4], wherein the pigment is at least one pigment selected from the group consisting of Pigment Red 254.

[6] The process according to [1], wherein the pigment is C.I. Pigment Blue 15: 6 as a colorant.

[7] A process for producing a pigment dispersion, which comprises a step of mixing a pigment dispersion obtained by the production method described in any one of [1] to [6] and at least one selected from the group consisting of a solvent, a resin, a photopolymerizable compound and a photopolymerization initiator ≪ / RTI >

[8] A coloring pattern formed using the coloring composition obtained by the production method described in [7].

[9] A color filter comprising a coloring pattern according to [8].

[10] A liquid crystal display device comprising the color filter according to [9].

The method for producing a pigment dispersion of the present invention includes a step of simultaneously dispersing a dye and a pigment in a solvent.

The dyes and pigments used in this method are not particularly limited to those types, and any of dyes and pigments known in the art can be used.

The dye is preferably an organic solvent soluble dye, more preferably a dye containing at least one member selected from the group consisting of an azo compound, a metal complex having an azo compound as a ligand, and a xanthene compound, And a compound represented by formula (1) to formula (3). Here, the organic solvent soluble dye means a dye dissolved in any one of the solvents used in the present invention described later.

The dye is preferably a dye containing a xanthene compound, more preferably a dye containing a compound represented by the formula (1).

[In the formula (1)

R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, -R ⁶ , -OH, -OR _{^{6, -SO 3 -, -SO 3}} H, -SO 3 M, -CO 2 H, -CO 2 R 6, -SO 3 R 6, -SO 2 NHR 8 Or -SO ₂ N (R ⁸ ) R ⁹ .

R ⁵ represents -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ Or it represents a ^{_{-SO 2 N (R 8) R}} 9.

m represents an integer of 0 to 5; When m is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different.

X represents a halogen atom. a represents an integer of 0 or 1;

R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and -CH ₂ - included in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ^6a -. R ^6a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 30 carbon atoms which may have a substituent, or -Q. However, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms which may have a substituent. The alkyl group and -CH ₂ - contained in the cycloalkyl group may be substituted with -O-, -CO-, -NH- or -NR ^6a -.

Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 10 carbon atoms which may have a substituent.

M represents a sodium atom or a potassium atom.

However, the number of positive charge and the number of negative charge of the compound represented by formula (1) are the same.)

Examples of the aromatic hydrocarbon group include an aryl group, an aralkyl group, and an aryl group substituted with an alkyl group.

Examples of the aryl group include a phenyl group, a biphenyl group, a naphthyl group, an anthryl group, and a phenanthryl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a trityl group, a naphthylmethyl group, and a naphthylethyl group.

Examples of the aryl group substituted by an alkyl group include those in which the above-mentioned aryl group is optionally combined with an alkyl group described below.

Examples of the halogen atom include fluorine, chlorine, and bromine.

The saturated hydrocarbon group may be an alkyl group, a cycloalkyl group, a cycloalkyl group substituted with an alkyl group, or an alkyl group substituted with a cycloalkyl group.

Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, hexyl, Propyl group, a 1,2-dimethylpropyl group, a 1-methylpropyl group, a 1-methylpropyl group, a 1-methylpropyl group, a 1-methylbutyl group, Dimethylpropyl group, and 2,2-dimethylpropyl group.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecanyl group.

The heterocyclic group may be aromatic or non-aromatic.

As the aromatic heterocyclic group,

As the heterocyclic ring having no aromaticity,

And the like. In addition, the combined hand of the complex ventilation can be set at any position other than the above-mentioned position.

Examples of -OR ⁶ include an alkoxy group such as a methoxy group, ethoxypropoxy group, butoxy group, hexyloxy group, and 2-ethylhexyloxy group.

Examples of -CO ₂ R ⁶ include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl , A cyclohexyloxycarbonyl group, a cyclohexyloxycarbonyl group, a heptyloxycarbonyl group, a cycloheptyloxycarbonyl group, an octyloxycarbonyl group, a 2-ethylhexyloxycarbonyl group, a cyclooctyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, a tricyclodecyloxycarbonyl group, An ethoxypropoxycarbonyl group, a hexyloxypropoxycarbonyl group, a 2-ethylhexyloxypropoxycarbonyl group, a methoxyhexyloxycarbonyl group, and the like.

Examples of -SO ₃ R ⁶ include a methoxysulfonyl group, an ethoxysulfonyl group, a hexyloxysulfonyl group, and a decyloxysulfonyl group.

Examples of -SO ₂ NHR ⁸ include sulfamoyl group, N- (methyl) sulfamoyl group, N- (ethyl) sulfamoyl group, N- (propyl) sulfamoyl group, N- (Butyl) sulfamoyl, N- (isobutyl) sulfamoyl, N- (pentyl) sulfamoyl, N- (isopentyl) sulfamoyl, N- (neopentyl) sulfamoyl, N- (Pentyl) sulfamoyl group, N- (hexyl) sulfamoyl group, N- (cyclohexyl) sulfamoyl group, N- (heptyl) sulfamoyl group, N- (cycloheptyl) sulfamoyl group, N- N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- (cyclooctyl) sulfamoyl group, N- (Decyl) sulfamoyl, N- (tricyclodecyl) sulfamoyl, N- (methoxypropyl) sulfamoyl, N- (ethoxypropyl) sulfamoyl, N- (propoxypropyl) sulfamoyl , N- (isopropoxypropyl) sulfamoyl group, N- (hexyloxypropyl) sulfamoyl group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (methoxyhexyl) sulfamoyl Group, and N- (3-phenyl-1-methylpropyl) sulfamoyl group.

Further, -SO ₂ NHR ⁸ may be a group represented by the following formula. In the following formulas, X ¹ represents a halogen atom. X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group having 1 to 3 carbon atoms, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom. X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom.

Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom include a trifluoromethyl group in addition to the above-mentioned alkyl group.

Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include the above alkyl groups, particularly methoxy group, ethoxy group and propoxy group.

-SO ₂ N (R ⁸ ) R ⁹ includes the following groups.

Examples of the heterocycle formed by bonding R ⁸ and R ⁹ to each other include groups represented by the following formulas.

Examples of the substituent of the alkyl group and the cycloalkyl group in R ⁸ and R ⁹ include a halogen atom, a hydroxyl group, -Q, -CH = CH ₂ , -CH = CHR ⁶ And the like.

Among them, examples of R ⁸ and R ⁹ include an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, an aralkyl group having 8 to 10 carbon atoms, an alkyl group having 2 to 8 carbon atoms, Group, an alkoxy group-containing alkyl group having 2 to 8 carbon atoms and an aryl group, more preferably a branched alkyl group having 6 to 8 carbon atoms, particularly preferably a 2-ethylhexyl group.

The substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably an ethyl group, a propyl group, a phenyl group, a dimethylphenyl group, -SO ₃ R ⁶ or -SO ₂ NHR ⁸ . Here, -SO ₂ R ⁸ Examples of the NHR ^8, in particular, and the alkyl group and cycloalkyl group of 3 to 30 carbon atoms having 1 to 10 carbon atoms are preferred, and more preferably an alkyl group having 1 to 10 carbon atoms, and a carbon number of 6 to 8 A branched alkyl group is more preferred, and 2-ethylhexyl is particularly preferred.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted include a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a hexylphenyl group, a decanylphenyl group, a fluorophenyl group, a chlorophenyl group, a bromophenyl group, , A methoxyphenyl group, a dimethoxyphenyl group, an ethoxyphenyl group, a hexyloxyphenyl group, a decanyloxyphenyl group, a trifluoromethylphenyl group, a biphenyl group, a dimethylphenylphenyl group, etc., and groups in which -SO ₂ NHR ⁸ is also substituted .

Examples of the substituent of the aromatic heterocyclic group having 5 to 10 carbon atoms include an ethyl group, a propyl group, a phenyl group, a dimethylphenyl group, -SO ₃ R ⁶ Or -SO ₂ NHR ⁸ may be mentioned. Here, -SO ₂ R ⁸ Examples of the NHR ^8, in particular, and the alkyl group and cycloalkyl group of 3 to 30 carbon atoms having 1 to 10 carbon atoms are preferred, and more preferably an alkyl group having 1 to 10 carbon atoms, and a carbon number of 6 to 8 More preferably a branched alkyl group, and particularly preferably a 2-ethylhexyl group.

Examples of the substituent of the saturated hydrocarbon group for R ⁶ include a halogen atom, an alkoxy group having 1 to 10 carbon atoms, and the like.

Examples of the alkoxy group include a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, pentoxy group, isopentyloxy group, neopentyloxy group, hexyloxy group, Methylbutoxy group, 3-methylbutoxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 2-methylpropoxy group, Dimethyl propoxy group, 1,2-dimethyl propoxy group, 2,2-dimethyl propoxy group and the like.

In the compound represented by the formula (1), at least one of R ¹ and R ² or at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted desirable.

At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is preferably an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted.

It is more preferable that at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted.

R ⁵ is a group selected from the group consisting of a carboxyl group, an ethoxycarbonyl group, a sulfo group, N- (2-ethylhexyloxypropyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- Methylpropyl) sulfamoyl group, and N- (isopropoxypropyl) sulfamoyl group.

The compound represented by the formula (1) is preferably at least one compound selected from the group consisting of the compounds represented by the formulas (1-1) to (1-4).

(In the formulas (1-1) to (1-4)

R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, -R ⁶ Or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO _{3 Na, -CO 2 H, -CO 2} R 6, -SO 3 R 6, -SO 2 NHR 8 or -SO ₂ may be substituted with NR ⁸ R ^9.

R ¹⁵ represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ or -SO ₂ N (R ⁸ ) R ⁹ .

R ¹⁶ represents -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ or -SO ₂ N (R ⁸ ) R ⁹ .

R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be a halogen atom, -R ²⁶ , -OH, -OR ²⁶ , -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H, -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ .

R ²⁵ represents -SO ₃ ^- , -SO ₃ Na, -CO ₂ H, -CO ₂ R ²⁶ , -SO ₃ H or SO ₂ NHR ²⁸ .

R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an alkoxy group having 1 to 10 carbon atoms or a halogen atom.

R ²⁸ represents a hydrogen atom, -R ²⁶ , -CO ₂ R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with -R ²⁶ or -OR ²⁶ do.

R ³¹ and R ³² each independently represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably a phenyl group, and the hydrogen atom contained in the aromatic hydrocarbon group is a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R ²⁶ , -SO ₃ R ^26, or -SO ₂ NHR ²⁸ .

R ³³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ³⁴ represents a hydrogen atom, -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ⁴¹ and R ⁴² each independently represent a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, preferably a phenyl group, and the hydrogen atom contained in the aromatic hydrocarbon group is -R ²⁶ or -SO ₂ NHR ²⁸ Or may be substituted.

R ⁴³ represents -SO ₃ ^- or -SO ₂ NHR ²⁸ .

R ⁶ , R ⁸ , R ⁹ , m, X and a have the same meanings as defined above.

In the compounds represented by formulas (1-1) to (1-4), the number of + charge and the number of charge in the compound are the same, respectively.

Among them, the formula (1-4) is preferable.

Examples of the compound represented by the formula (1) include compounds represented by the formulas (1a) to (1f). However, in the compounds represented by the formulas (1a) to (1f), the numbers of + charge and - charge are the same in the compound.

(Wherein R ^b and R ^c each independently represent a hydrogen atom, -SO ₃ ^- , -CO ₂ H or -SO ₂ NHR ^a .

R ^d , R ^e and R ^f independently represent -SO ₃ ^- , -SO ₃ Na or -SO ₂ NHR ^a .

R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, -SO ₃ ^- , -SO ₃ H or -SO ₂ NHR ^a .

R ^a represents an alkyl group of 1 to 10, preferably a 2-ethylhexyl group.

X and a have the same meanings as defined above.

The compound represented by the formula (1b) is a tautomer of the compound represented by the formula (1b-1).

Among them, the compound represented by the formula (1e) and the compound represented by the formula (1f) are preferable.

The compound represented by the formula (1) can be obtained by, for example, chlorinating a coloring matter or a dyeing intermediate having -SO ₃ H by a regular method and then converting the coloring matter or dyeing intermediate having -SO ₂ Cl into R ⁸ -NH ₂ < / RTI > The dye prepared by the method described in the right upper column to the lower column on page 3 of Japanese Patent Laid-Open Publication No. 3-78702 can be produced by chlorination and reacting with an amine in the same manner as described above.

The dye is preferably a dye containing an azo compound, more preferably a dye containing a compound represented by formula (2).

[In the formula (2), A ⁰ represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ⁰ represents a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

R ⁵¹ represents a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent, or an acyl group of 2 to 18 carbon atoms which may have a substituent.

And R ⁵² represents a hydrogen atom or a monovalent organic group.

The compound represented by the formula (2) is preferably a compound represented by the formula (2-1).

[In the formula (2-1), Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent and is included in Z ¹ , Z ² and Z ³ -CH ₂ - may be substituted with -CO- or -O-.

R ⁵³ and R ⁵⁴ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent, or an acyl group of 2 to 18 carbon atoms which may have a substituent.

A ¹ and A ² each independently represent a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

Z ¹ , Z ² and Z ³ each independently represent a divalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent. The number of carbon atoms of the substituent does not include the number of carbon atoms of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, and the number thereof is preferably 2 to 10, more preferably 2 to 8.

Examples of the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include an alkanediyl group having 1 to 16 carbon atoms, and examples thereof include methylene, ethylene, propane di, , An octanediyl group, a decanediyl group, a tetradecanediyl group and a hexadecanediyl group.

-CH ₂ - contained in the divalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with -CO- or -O-. C _{1 -16} aliphatic hydrocarbon groups include a hydrogen atom that may be substituted with a halogen atom, the fluorine atom.

Z ¹ and Z ² are preferably an alkanediyl group having 1 to 8 carbon atoms which may contain -O-, and more preferably an alkanediyl group having 5 to 7 carbon atoms which may contain -O-. Examples of preferred groups, _{e.g., - (CH 2) 3 -} , - (CH 2) 2 -O- (CH 2) 2 -, - (CH 2) 2 -O- (CH 2) 2 -O- ( CH ₂ ) ₂ - or -CH ₂ -CH (CH ₃ ) -.

Z ³ is preferably a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may contain -C (= C) -, more preferably an unsubstituted alkanediyl group having 1 to 8 carbon atoms, More preferably an unsubstituted alkanediyl group having 8 to 8 carbon atoms. Preferable groups include, for example, - (CH ₂ ) ₂ -, - (CH ₂ ) ₄ - or -CH ₂ -C (= CH ₂ ) -.

The monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms representing R ⁵³ and R ⁵⁴ may be any of linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number thereof is preferably from 6 to 10, more preferably from 1 to 4.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- Methylhexyl group (1,5-dimethylhexyl group, etc.), ethylhexyl group (2-ethylhexyl group and the like), cyclopentyl group, cyclohexyl group (1,1,3,3-tetramethylbutyl group) , A methylcyclohexyl group (such as a 2-methylcyclohexyl group), and a cyclohexylalkyl group.

The hydrogen atom contained in the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms may be substituted with an alkoxy group having 1 to 8 carbon atoms or a carboxy group. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted with an alkoxy group having 1 to 8 carbon atoms include a propoxypropyl group such as a 3- (isopropoxy) propyl group and an alkoxypropyl group such as 3- (2-ethylhexyloxy) And a propyl group). Examples of the aliphatic hydrocarbon group having 1 to 16 carbon atoms substituted with a carboxy group include a 2- (carboxy) ethyl group, a 3- (carboxy) propyl group and a 4- (carboxy) butyl group.

The hydrogen atom contained in the acyl group having 2 to 18 carbon atoms may be substituted with an alkoxy group having 1 to 8 carbon atoms. The number of carbon atoms of the acyl group having 2 to 18 carbon atoms which may have a substituent group is preferably 6 to 10, inclusive of the carbon number of the substituent. Examples of the acyl group which may have a substituent include an acetyl group, a benzoyl group, a methoxybenzoyl group (p-methoxybenzoyl group and the like) and the like.

As R ⁵³ and R ⁵⁴ , a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 4 carbon atoms, and an acyl group having 2 to 5 carbon atoms are preferable. Preferable groups include, for example, a hydrogen atom, an acetyl group or a propionyl group.

Examples of the bivalent aromatic hydrocarbon group having 6 to 14 carbon atoms which represent A ¹ and A ² include a phenylene group and a naphthalenediyl group, and among them, a phenylene group is preferable.

Examples of the substituent of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a halogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a nitro group, a sulfo group, a sulfamoyl group, .

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom, a chlorine atom or a bromine atom is preferable.

Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl and hexyl. Is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 2 carbon atoms, and particularly preferably a methyl group.

Examples of the alkoxy group having 1 to 8 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert- , An alkoxy group having 1 to 4 carbon atoms is preferable, an alkoxy group having 1 to 2 carbon atoms is more preferable, and a methoxy group is particularly preferable.

Examples of the N-substituted sulfamoyl group include SO ₂ NHR ⁵⁵ and -SO ₂ N (R ⁵⁵ ) R ^56. Specifically, -SO ₂ NHR ⁸ in the compound represented by the formula (1) A and ^{_{-SO 2 N (R 8) R}} 9 may be the same groups as either. Among them, R ⁵⁵ and R ⁵⁶ are each independently preferably an aliphatic hydrocarbon group having 1 to 16 carbon atoms which may have a substituent or an N-substituted sulfamoyl group which is an acyl group having 2 to 18 carbon atoms and may have a substituent.

B ¹ and B ² each independently represent a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group having 3 to 14 carbon atoms which may have a substituent.

Examples of the monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group and a naphthyl group.

Examples of the monovalent aromatic heterocyclic group having 3 to 14 carbon atoms include the groups shown below.

[R represents a hydrogen atom or a methyl group]

The monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms and the hydrogen atom contained in the monovalent aromatic heterocyclic group having 3 to 14 carbon atoms may be substituted with at least one selected from the group consisting of a hydroxyl group, an oxo group, a monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms, Or an N-substituted amino group.

As the N-substituted amino group, -NHR ⁵⁷ group or -NR ⁵⁷ R ⁵⁸ group is preferable. Provided that R ⁵⁷ and R ⁵⁸ each independently represent a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent or a monovalent aromatic heterocyclic group of 3 to 14 carbon atoms which may have a substituent. Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms and the monovalent aromatic heterocyclic group having 3 to 14 carbon atoms include the same groups as described above.

B ¹ and B ² each independently represent a group represented by formula (2-1a).

[In the formula (2-1a), R ⁵⁹ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent. R ⁶⁰ represents a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms which may have a substituent.]

The pyridone ring of the group represented by the formula (2-1a) may be a keto or an enol form.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 16 carbon atoms include the same groups as described above. R ⁵⁹ represents a methylbutyl group (1,1,3,3-tetramethylbutyl group, etc.), a methylhexyl group (1,5 Ethylhexyl group and the like), a methylcyclohexyl group (such as a 2-methylcyclohexyl group) and an alkoxypropyl group (such as a 3- (2-ethylhexyloxy) propyl group and the like) ), And the like are preferable.

R ⁶⁰ is preferably a methyl group.

Examples of the compound represented by formula (2) include compounds represented by formulas (I-1) to (I-18). In the table, A ¹ , A ² , Z ^1, and Z ² represent the combined hand on the right hand side closer to Z ³ .

It is more preferable that B ¹ and B ² are groups of the same kind, and it is further preferable that A ¹ and A ² , R ⁵³ and R ⁵⁴ , Z ¹ and Z ² are each a group of the same kind. With these groups, it is easy to produce the compound represented by the formula (2-1).

The compound represented by the formula (2-1) is obtained by reacting the compound represented by the formula (IA) and the compound represented by the formula (I-A ') with the compound represented by the formula (IB) at 0 to 150 캜 Can be manufactured.

Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² in the formulas (IA), (I-A ' It represents meaning.

R ⁶⁷ and R ⁶⁸ each independently represent -OR ⁶⁹ or a halogen atom. And R ⁶⁹ represents a monovalent aliphatic hydrocarbon group of 1 to 16 carbon atoms.

Examples of the compound represented by the formula (I-B) include dimethyl malonate, isobutyl succinate, dimethyl adipate, diethyl superate, malonic acid chloride, succinic acid chloride, adipic acid chloride and suberic acid chloride. The amount of the compound represented by the formula (I-B) is preferably 0.5 to 3 moles, for example, relative to 1 mole of the total amount of the compound represented by the formula (I-A) and the compound represented by the formula (I-A '). When water is contained in the solvent, it is preferable to use the compound represented by the formula (I-B) in excess of the amount described above.

When R ³¹ and R ³² of the compound represented by the formula (IB) are -OR ³³ , it is preferable to add a known acid catalyst. Examples of the acid catalyst include sulfuric acid and para-toluenesulfonic acid. The amount of the acid catalyst to be used is preferably 0.01 to 2 mol, for example, relative to 1 mol of the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A ').

The reaction between the compound represented by the formula (I-A) and the compound represented by the formula (I-A ') and the compound represented by the formula (I-B) is carried out in a solvent. As the solvent, for example, water; Ethers such as 1,4-dioxane (particularly, cyclic ethers); Halogenated hydrocarbons such as chloroform, methylene chloride, carbon tetrachloride, 1,2-dichloroethane, dichloroethylene, trichlorethylene, perchlorethylene, dichloropropane, amyl chloride and 1,2-dibromoethane; Ketones such as acetone, methyl isobutyl ketone, and cyclohexanone; Carbon-based aromatic compounds such as benzene, toluene and xylene; And alkylamides such as N, N-dimethylformamide, N, N-dibutylformamide, N, N-dimethylacetamide and N-methylpyrrolidone are preferable, and two or more kinds of solvents may be used in combination . The amount of the solvent to be used is preferably 1 to 20 parts by mass, more preferably 2 to 20 parts by mass, per 100 parts by mass of the total amount of the compound represented by the formula (IA) and the compound represented by the formula (I-A ' 10 parts by mass.

The reaction between the compound represented by the formula (IA) and the compound represented by the formula (IA ') and the compound represented by the formula (IB) is preferably carried out under a nitrogen atmosphere or an argon atmosphere, The reaction may be carried out under air.

The reaction temperature is, for example, preferably 0 to 150 占 폚, more preferably 10 to 130 占 폚. The reaction time is preferably, for example, 1 to 25 hours, more preferably 3 to 15 hours.

The order of addition of the compound represented by the formula (IA), the compound represented by the formula (I-A '), the compound represented by the formula (IB) and the solvent is not particularly limited, but the compound represented by the formula (IA) (IB) is added (added dropwise) to a solution comprising a compound represented by the formula (II) and a solvent. In the case of using an acid catalyst, it is preferable to add (drop) the compound represented by the formula (IB) to a solution comprising a compound represented by the formula (IA), a compound represented by the formula (I-A '), an acid catalyst and a solvent .

The method for obtaining the target compound represented by the formula (2-1) from the reaction mixture obtained as described above is not particularly limited, and various known methods can be adopted. For example, the reaction mixture is dissolved in an organic solvent And the like. Further, if necessary, it may be further purified by a known method such as washing with an alkaline aqueous solution or an acidic aqueous solution, recrystallization or the like.

The compound represented by the formula (2-1) can be produced by coupling reaction between the compound represented by the formula (I-C), the compound represented by the formula (I-D) and the compound represented by the formula (I-D '). (2-1) by reacting a salt of the compound represented by the formula (IC) with a compound represented by the formula (ID) and a compound represented by the formula (I-D ') in an aqueous solvent at 20 to 60 ° C, ) Can be produced.

In the formulas (IC) and (ID), Z ¹ , Z ² , Z ³ , R ⁵³ , R ⁵⁴ , A ¹ , A ² , B ¹ and B ² have the same meanings as defined above.

X ^- represents an inorganic or organic anion.]

Examples of inorganic or organic type of Anna Ian represented by (IC) compound, a fluoride ion, chloride ion, bromide ion, iodide ion water, perchloric acid ion, hypochlorous acid ion, CH ₃ -COO ^-, and the like ^-, Ph-COO there may be mentioned ^- and, preferably -COO chloride ion, bromide ion, CH _3.

The dye is preferably a dye containing a metal complex having an azo compound as a ligand, more preferably a dye containing a compound represented by the formula (3). The compound represented by the formula (3) is a salt of chromium anion or cobalt anion and cations.

R ^a1 to R ^a18 each independently represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a phenyl group, -SO ₂ NHR ^a30 , -SO ₃ ^- Or COOR ^a31 .

R ^a19 and R ^a20 each independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

R ^a30 and R ^a31 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 10 carbon atoms, and -CH ₂ - included in the hydrocarbon group may be substituted with -O- or -CO-.

M ¹ represents Cr or Co.

n ¹ represents an integer of ¹ to 5;

D ¹ represents a monovalent cation derived from a compound having a hydron, a monovalent metal cation or a xanthene skeleton.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^a1 to R ^a18 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec- N-hexyl group, n-heptyl group, n-octyl group, decyl group, 1-methylbutyl group, 1,1,3,3-tetramethylbutyl group, 1,5-dimethylhexyl group, -Dimethylheptyl group, 2-ethylhexyl group, and 1,1,5,5-tetramethylhexyl group.

Examples of the monovalent hydrocarbon group having 1 to 10 carbon atoms represented by R ^a30 and R ^a31 include a monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms, a monovalent aromatic hydrocarbon having 6 to 10 carbon atoms Group, and a group having 4 to 10 carbon atoms in combination with each other. Examples of the monovalent aliphatic hydrocarbon group having 1 to 10 carbon atoms include the same groups as described above. Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include groups similar to those of Q in the compound represented by the formula (1). Examples of the monovalent alicyclic hydrocarbon group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, and a cyclodecyl group.

Examples of the hydrocarbon group substituted with -CH ₂ - by -O- or -CO- include -R ^a32 -OR ^a33 , -R ^a32 -CO-OR ^a33 , -R ^a32 -O-CO-R ^a33 have. R ^a32 is a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, and R ^a33 is a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms representing R ^a32 include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, -1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group and octane-1,8-diyl group.

^Examples of -R ^a32 -OR ^a33 include a methoxymethyl group, an ethoxymethyl group, a propoxymethyl group, a methoxyethyl group, an ethoxyethyl group, a propoxyethyl group, a methoxypropyl group, an ethoxypropyl group, a propoxypropyl group, 4-methoxybutyl group, octyloxypropyl group, 3-ethoxypropyl group, 3- (2-ethylhexyloxy) propyl group and the like.

^Examples of -R ^a32- CO-OR ^a33 include methoxycarbonylmethyl, methoxycarbonylethyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, propoxycarbonylmethyl, propoxycarbonylethyl, butoxycarbonyl Methyl group, and butoxycarbonyl ethyl group.

^Examples of -R ^a32 -O-CO-R ^a33 include an acetyloxymethyl group, an acetyloxyethyl group, an ethylcarbonyloxymethyl group, an ethylcarbonyloxyethyl group, a propylcarbonyloxymethyl group, a propylcarbonyloxyethyl group, a butylcarbonyloxymethyl group, Butylcarbonyloxyethyl group and the like.

Examples of -SO ₂ NHR ^a30 include a sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) Substituted with an aliphatic hydrocarbon group such as a sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N- Sulfamoyl group;

(2-methoxyethyl) sulfamoyl group, N- (2-ethoxyethyl) sulfamoyl group, N- (1-methoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- (3-ethoxypropyl) sulfamoyl group, N- ) -S (-O-lower alkyl) sulfamoyl group such as N- (2-ethylhexyloxypropyl) sulfamoyl group, N- ^{31 a} sulfamoyl group substituted with -OR ³² ;

(Methoxycarbonylmethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (methoxycarbonylethyl) sulfamoyl group, N- (ethoxycarbonylethyl) sulfamoyl group, N- (Propoxycarbonylmethyl) sulfamoyl group, N- (propoxycarbonylethyl) sulfamoyl group, N- (butoxycarbonylmethyl) sulfamoyl group, N- (butoxycarbonylethyl) A sulfamoyl group substituted with -R ³¹ -CO-OR ^{32 such} as a sulfamoyl group;

N- (ethylcarbonyloxymethyl) sulfamoyl group, N- (ethylcarbonyloxyethyl) sulfamoyl group, N- (acetyloxymethyl) sulfamoyl group, N- (Propylcarbonyloxymethyl) sulfamoyl group, N- (propylcarbonyloxyethyl) sulfamoyl group, N- (butylcarbonyloxymethyl) sulfamoyl group, N- (butylcarbonyloxyethyl) sulfamoyl group and the like A sulfamoyl group substituted with -R ³¹ -O-CO-R ³² ;

(2-methylcyclohexyl) sulfamoyl group, N- (3-methylcyclohexyl) sulfamoyl group, N- (4-methylcyclohexyl) sulfamoyl group, N- 4-butylcyclohexyl) sulfamoyl group, and the like; a sulfamoyl group substituted with a cyclohexyl group having a substituent;

(2-phenylethyl) sulfamoyl group, N- (3-phenylpropyl) sulfamoyl group, N- (4-phenylbutyl) sulfamoyl group, N- ) Sulfamoyl group, N- (2- (2-naphthyl) ethyl] sulfamoyl group, N- [2- (4-methylphenyl) Pamoyl group, and sulfamoyl group substituted with an aralkyl group such as N- (3-phenyl-1-methylpropyl) sulfamoyl group.

It is preferable that at least one of R ^a1 to R ^a18 is a nitro group since heat resistance tends to be high.

Examples of R ^a30 and R ^a31 include a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ^a32 -OR ^a33 , -R ^a32- CO-OR ^a33 And -R ^a32- O-CO-R ^a33 are preferred.

In the compound represented by the formula (3), preferred examples of the pyrazole compound to be the ligand of the complex anion include compounds represented by the formulas (1-a1) to (1-a56).

In the compound represented by the formula (3), preferred examples of the anion are anions represented by the formulas (1-b1) to (1-b50).

D ¹ is a monovalent cation derived from a compound having a hydron, a monovalent metal cation or a xanthene skeleton. Of these, monovalent cationic compounds derived from a compound having a xanthene skeleton are preferable in that the resulting color filter has a high brightness. Examples of the compound having a xanthene skeleton include a compound represented by the formula (1).

The compound represented by the formula (3) is preferably a compound represented by the formula (3-1) in view of solubility in an organic solvent.

In the formula (3-1), R ^a41 ~R ^a58 are independently of each other, represent a hydrogen atom, a halogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a nitro group, a sulfo group or -SO ₂ NHR ^a34 .

R ^a34 represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a cyclohexyl group optionally substituted with an alkyl group having 1 to 4 carbon atoms, -R ^a32 -OR ^a33 , -R ^a32 -CO-OR ^a33 , R ^a32 -O-CO-R ^a33 or an aralkyl group having 7 to 10 carbon atoms.

R ^a32 represents a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ^a33 represents a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms.

R ^a59 and R ^a60 independently represent a hydrogen atom, a methyl group, an ethyl group or an amino group.

M ² represents Cr or Co.

R ^a21 to R ^a24 independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms or a monovalent aromatic hydrocarbon group of 6 to 10 carbon atoms, and the hydrogen atoms contained in the aliphatic hydrocarbon group and the aromatic hydrocarbon group May be substituted with hydroxy, -OR ³² , sulfo group, -SO ₃ Na, -SO ₃ K or a halogen atom.

R ^a25 and R ^a26 each independently represent a hydrogen atom or a methyl group.

R ^a27 represents an ethylene group, a propane-1,3- ^diyl group or a propane-1,2- ^diyl group.

R ^a28 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

n represents an integer of 1 to 4; When n is an integer of 2 or more, a plurality of R < ²⁷ > s may be the same or different.]

Examples of the monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those shown above for R ^a1 to R ^a18 .

Examples of the divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms include the same groups as those represented by R ^a32 .

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

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms include aryl groups such as a phenyl group, a methylphenyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group and a naphthyl group; An aralkyl group such as a benzyl group, a diphenylmethyl group, a phenylethyl group and a 3-phenylpropyl group.

Examples of the cyclohexyl group optionally substituted by an alkyl group having 1 to 4 carbon atoms include a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a 2-propylcyclohexyl group, a 2-isopropylcyclohexyl group, a 2-butylcyclohexyl group A 4-methylcyclohexyl group, a 4-ethylcyclohexyl group, a 4-propylcyclohexyl group, a 4-isopropylcyclohexyl group, and a 4-butylcyclohexyl group.

It is preferable that at least one of R ^a41 to R ^a58 is a nitro group since heat resistance tends to be high.

In addition, R ^a41 ~R at least one of the at least one ^a46 and R ^a50 in ^a45 ~R, sulfo or -SO ₂ NHR, and preferably in the ^a34, it is more preferably from -SO ₂ NHR ^a34. Among them, R ^a34 is preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group of 1 to 8 carbon atoms, more preferably a hydrogen atom or a 2-ethylhexyl group. If having a plurality of -SO ₂ NHR ^a34, which may be the same or different.

R ^a21 to R ^a24 are preferably a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 8 carbon atoms which may have a substituent, and more preferably a hydrogen atom or an ethyl group because the color density is high.

As R ^a27 , an ethylene group and a propane-1,2- ^diyl group are preferable, and an ethylene group is more preferable.

As R ^a28 , a hydrogen atom is preferable.

n is an integer of 1 to 4, preferably an integer of 2 to 4, more preferably 3 or 4, and still more preferably 3.

- (R ^a27 -O) n R ^a28 , 2- (2-hydroxyethoxy) ethyl group and 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group are preferable in view of solubility in organic solvents And more preferred is 2- [2- (2-hydroxyethoxy) ethoxy] ethyl group.

In the compound represented by the formula (3-1), preferred examples of the cation derived from the xanthene compound include the cations represented by the formulas (1-c1) to (1-c48).

Specific examples of the compound represented by the formula (3-1) include compounds represented by the formulas (1-1) to (1-20).

(1-1), (1-3) to (1-5), (1-7), and (1-6) in terms of solubility in an organic solvent among specific examples of the compound represented by the formula (3-1) Compounds represented by formulas (1-9), (1-11) to (1-16) and (1-18) to (1-20) Compounds and compounds represented by the formula (1-3) are more preferable.

In order to produce the compound represented by the formula (3), the compound represented by the formula (3d) and the chromium compound are used to form the chromium complex, or the compound represented by the formula (3d) and the cobalt compound are used to form the cobalt complex . Thereafter, if necessary, the compound represented by the formula (3) can be prepared by subjecting the salt having the corresponding complex salt and D ¹ to a salt exchange reaction.

[In the formula (3d), R ^a1 to R ^a5 , R ^a11 to R ^a14 And R ^a19 have the same meanings as in formula (3).]

The compound represented by the formula (3d) can be produced by a method of diazo coupling of a diazonium salt and a pyrazole compound well known in the dye field.

The compound represented by the formula (3-1) is prepared by subjecting the complex salt to a salt exchange reaction with the xanthene compound represented by the formula (b).

[In the formula (b), R ^a21 to R ^a28 And n have the same meanings as in the formula (3-1). A ^- represents a monovalent anion.]

Examples of univalent anions include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , PF ₆ ^- or BF ₄ ^- and the like.

The xanthene compound represented by the formula (b) can be produced by reacting a compound represented by the formula (bO) with a compound represented by the formula (b1) in an organic solvent.

[In formulas (b0) and (b1), R ^a21 to R ^a28 and n have the same meanings as in formula (2-1). A ^- has the same meaning as in formula (b).]

In the above reaction, the reaction temperature is preferably 15 ° C to 60 ° C, and the reaction time is preferably 1 hour to 12 hours. From the viewpoint of shortening the reaction time or improving the yield, it is preferable to use an acid catalyst and / or a dehydrating agent.

Examples of the acid catalyst include sulfuric acid, p-toluenesulfonic acid and the like.

Examples of the dehydrating agent include carbodiimides such as dicyclohexylcarbodiimide, diisopropylcarbodiimide and 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride; 1-alkyl-2-halopyridinium salts; 1,1'-carbonyldiimidazole; Bis (2-oxo-3-oxazolidinyl) phosphine acid chloride; Di-2-pyridyl carbonate, and the like. Among them, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride is preferable as the dehydrating agent since post treatment and purification are easy.

Examples of the organic solvent used in the reaction include dichloromethane, chloroform, tetrahydrofuran, toluene, acetonitrile and the like.

The compound represented by the formula (3-1) can be produced by allowing the complex salt and the xanthene compound represented by the formula (b) to undergo a salt exchange reaction in a solvent. It is preferable to react the cobalt complex salt with the xanthene compound (b) in a molar ratio of 1: 1 to 1: 4.

As the pigment, any of an organic pigment and an inorganic pigment may be used, but an organic pigment is preferable.

As the organic pigment, for example, any of those described in JP-A-2003-327864 and the like can be used. Among them, C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60; C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38; C.I. Green pigments such as Pigment Green 7, 10, 15, 25, 36, 47 and 58; C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 , 147, 148, 150, 153, 154, 166, 173, 194 and 214; C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, .

When a coloring composition is used to make a color filter, the coloring composition is adjusted as a blue composition, a green composition and a red composition, respectively.

The blue composition was prepared by mixing C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 3, and 15: 6, and preferably at least one pigment selected from the group consisting of C.I. It is more preferable to contain Pigment Blue 15: 6. The green composition may be selected from the group consisting of C.I. Pigment Green 36, 58, C.I. Pigment Yellow 138, and 150. It is preferable that at least one selected from the group consisting of Pigment Yellow 138 and Pigment Yellow 138 is contained. The red composition comprises C.I. Pigment Yellow 138, 139, 150, C.I. Pigment Red 177, 242, and 254, based on the total weight of the composition. These pigments may be used alone or in combination of two or more.

The pigment, particularly, the organic pigment may be subjected to a surface treatment using a pigment derivative or the like to which a rosin treatment, an acidic group or a basic group is introduced, a graft treatment on the surface of a pigment with a polymer compound or the like, A cleaning treatment with water or the like, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. The pigment preferably has a uniform particle diameter.

As the pigment used in the method for producing a pigment dispersion of the present invention, it is preferable to use a pigment subjected to a fineness treatment. Examples of the fineness treatment include a salt milling treatment and a sulfuric acid atomization treatment, and preferably a salt milling treatment.

The salt milling treatment is a treatment in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically heated while being kneaded using a kneader, a 2 roll mill, a 3 roll mill, a ball mill, an attritor, , And then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid. The pigment is broken due to the high hardness of the inorganic salt at the time of salt milling. Since the crushing of the pigment and the crystal growth on the active surface caused by the crushing occur simultaneously, the primary particle diameter of the resulting pigment is different if the kneading conditions are different.

The kneading temperature is preferably 40 to 150 占 폚. When the kneading temperature is within the above-mentioned range, the crystal growth during kneading is promoted, and the shape of the resulting pigment particles tends to become uniform. On the other hand, when the heating temperature is lower than 40 캜, crystal growth does not sufficiently take place, and the shape of the pigment particles becomes close to amorphous. On the other hand, when the heating temperature exceeds 150 캜, the crystal growth proceeds excessively and the primary particle diameter of the pigment becomes large, so that it is not preferable as a coloring agent for a coloring composition for a color filter. The kneading time of the salt milling treatment is preferably 2 to 24 hours in terms of the particle size distribution of the primary particles of the salt milled pigment and the cost required for the salt milling treatment.

By optimizing the conditions under which the pigment is subjected to the salt milling treatment, it is possible to obtain a pigment having a very small primary particle diameter, narrow distribution width, and sharp particle size distribution. A color filter obtained by using a coloring composition containing such a pigment has excellent color characteristics.

As the water-soluble inorganic salt used in the salt milling treatment, sodium chloride, barium chloride, potassium chloride, and sodium sulfate can be used, but it is preferable to use sodium chloride (salt) in view of cost. The water-soluble inorganic salt is preferably used in an amount of from 50 to 2,000 mass%, and most preferably from 300 to 1,000 mass%, based on the whole amount of the pigment in both treatment efficiency and production efficiency.

The water-soluble organic solvent is not particularly limited as far as it has a function of wetting the pigment and the water-soluble inorganic salt, dissolving in water (miscible) and not substantially dissolving the inorganic salt to be used, From the viewpoints of difficulty in evaporation and safety, it is preferable that the solvent is a solvent having a boiling point of 120 deg. For example, there can be mentioned 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl Diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, liquid propylene glycol, 1-methoxy- Monoethyl ether, and liquid polypropylene glycol. The water-soluble organic solvent is preferably used in an amount of 5 to 1,000 mass%, more preferably 50 to 500 mass%, based on the entire amount of the pigment.

When the salt milling treatment is carried out, a resin may be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin to be used is preferably solid at room temperature, hardly soluble or insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin to be used is preferably in the range of 5 to 200 mass% with respect to the total amount of the pigment.

In the method for producing a pigment dispersion of the present invention, it is preferable to use a pigment dispersant for improving the dispersibility of the pigment and improving the dispersion stability. Examples of the pigment dispersant include surfactants such as cationic surfactants, anionic surfactants, nonionic surfactants, amphoteric surfactants, polyester surfactants, polyamine surfactants, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more.

When a pigment dispersant is used, the amount of the pigment to be used is preferably not more than 2 parts by mass, more preferably not more than 1 part by mass, more preferably not less than 0.05 parts by mass and not more than 0.5 parts by mass, per 1 part by mass of the pigment. When the amount of the pigment dispersant is within this range, a pigment dispersion in a uniformly dispersed state tends to be obtained.

In the method for producing a pigment dispersion of the present invention, a pigment derivative (different from a dye) or the like may be used as a dispersing aid for improving the dispersibility of the pigment and improving the dispersion stability. Examples of the pigment derivative include azo pigments, phthalocyanine pigments, quinacridone pigments, benzimidazolone pigments, quinophthalone pigments, isoindolinone pigments, isoindolin pigments, dioxadine pigments, anthraquinone pigments, indanthrene pigments, And derivatives such as pyranthrone, pyranthrone, pyranthrone, pyranthrone, pyranthrone, pyranthrone, and the like. Usually, pigment derivatives are poorly soluble in organic solvents. Examples of the substituent of the pigment derivative include a sulfo group, a sulfamoyl group and a quaternary salt thereof, a phthalimidemethyl group, an N, N-dialkylaminoalkyl group, a hydroxyl group, a carboxyl group and a carbamoyl group directly to the pigment skeleton or an alkyl group, , A heterocyclic group, and the like, and preferred examples thereof include a sulfamoyl group, a quaternary salt thereof, and a sulfo group, and more preferably a sulfo group. These substituents may be plurally substituted on one pigment skeleton or may be a mixture of compounds having different substitution numbers. Specific examples of the pigment derivative include sulfonic acid derivatives of azo pigments, sulfonic acid derivatives of phthalocyanine pigments, sulfonic acid derivatives of quinophthalone pigments, sulfonic acid derivatives of isoindoline pigments, sulfonic acid derivatives of anthraquinone pigments, sulfonic acid derivatives of quinacridone pigments, A sulfonic acid derivative of a pyrrolopyr pigment, a sulfonic acid derivative of a dioxadine pigment, and the like.

In the method for producing a pigment dispersion of the present invention, a part or all of the resin selected from the resin (B) described later may be contained. Concretely, in the dispersion treatment step in the preparation of the pigment dispersion to be described later, the binder resin is preferably contained in combination with the above-mentioned pigment dispersant, because the binder resin contributes to the dispersion stability by the synergistic effect with the dispersant.

In the present invention, the dye and the pigment are contained preferably in a mass ratio of dye: pigment = 1: 99 to 99: 1, more preferably 1:99 to 60:40, and even more preferably 5:95 to 40:60 Is more preferable. By setting the ratio to the above range, it is possible to easily optimize the transmission spectrum, to obtain a high contrast and a high-definition coloring pattern, and to improve the heat resistance and chemical resistance of the obtained coloring pattern.

When the coloring composition is a blue composition, C.I. The mass ratio of Pigment Blue 15: 6 to the dye is preferably 99: 1 to 40:60, more preferably 97: 3 to 50:50, and even more preferably 97: 3 to 70:30. In the case of a green composition, C.I. Pigment Green 36, C.I. Pigment Green 58, C.I. Pigment Yellow 138 and C.I. It is preferable that the mass ratio of at least one species selected from Pigment Green 150 and the dye is 99: 1 to 40:60, more preferably 99: 1 to 50:50, and 95: 5 to 55:45 More preferable. In the case of a red composition, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Red 177, C.I. Pigment Red 242 and C.I. Pigment Red 254 and the dye is preferably 99: 1 to 40:60, more preferably 99: 1 to 50:50, and most preferably 97: 3 to 65:35 More preferable.

In the method for producing a pigment dispersion of the present invention, the above-mentioned dye and pigment are simultaneously dispersed in a solvent.

Examples of the solvent used in the present invention include the following.

For example, alcohols such as monoalcohol and polyhydric alcohol.

Examples of such alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.

Also, glycol ethers such as ethylene glycols and propylene glycols can be mentioned.

Ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monoisopropyl ether and ethylene glycol monobutyl ether;

Propylene glycol monoalkyl ethers such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and propylene glycol monobutyl ether;

Propylene glycol dialkyl ethers such as propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol ethyl methyl ether, propylene glycol dipropyl ether propylene glycol propyl methyl ether and propylene glycol ethyl propyl ether

Dipropylene glycol dialkyl ethers such as dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether and dipropylene glycol methyl ethyl ether;

Dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether and dipropylene glycol monopropyl ether;

Butyldiol monoalkyl ethers such as 3-methoxybutanol, ethoxybutyl alcohol, propoxybutyl alcohol and butoxybutyl alcohol;

Diethylene glycol dimethyl ether, and the like.

And ethers including ether acetates and ether propionates.

Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate and ethylene glycol monoethyl ether acetate;

Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate and propylene glycol monopropyl ether acetate;

Propylene glycol alkyl ether propionates such as propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate and propylene glycol butyl ether propionate;

Butanediol monoalkyl ether acetates such as methoxybutyl acetate, ethoxybutyl acetate, propoxybutyl acetate and butoxybutyl acetate;

Butanediol monoalkyl ether propionates such as methoxy butyl propionate, ethoxy butyl propionate, propoxy butyl propionate and butoxy butyl propionate;

Diethylene glycol monoalkyl ether acetates such as diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate;

Dipropylene glycol monoalkyl ether acetates such as dipropylene glycol monomethyl ether acetate;

Propylene glycol monoethyl ether acetate and the like;

Methoxypentyl acetate, and the like.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, and mesitylene.

Examples of the hydrocarbons include cyclohexane and the like.

Examples of the ketones include methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, N-methylpyrrolidone, 4-hydroxy- Heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, isophorone and the like.

Examples of esters include methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy- Hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, 3-hydroxypropionate, Propyl methoxyacetate, butyl hydroxypropionate, methyl 2-hydroxy-3-methylbutanoate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, ethoxy Propyl acetate, propyl acetate, butyl ethoxyacetate, methyl propoxyacetate, ethyl propoxyacetate, propoxyacetic acid propyl, Butyl methoxypropionate, propyl 2-methoxypropionate, propyl 2-methoxypropionate, butyl 2-methoxypropionate, butyl 2-methoxypropionate, butyl 2-methoxypropionate, Ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, propyl 2-butoxypropionate, 2-ethoxypropionate, Methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3- Propoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, butyl 3-propoxypropionate, Butyl, and 3-butoxy-ethyl, 3-butoxy propyl propionate, butyl 3-butoxy-propionic acid, pyruvic acid acetate.

Examples of the cyclic ethers include tetrahydrofuran, pyran, tetrahydropyran and the like.

As the cyclic esters,? -Butylolactone and the like can be given.

Examples of amides include N, N'-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

As the solvent used in the dispersion step, ethers including ether acetates and ether propionates are preferable, ether acetates are more preferable, and propylene glycol monomethyl ether acetate is more preferable. If these solvents are used, foreign matter tends to be difficult to come out from the surface of the resulting color filter.

These solvents may be used alone or in combination of two or more. In addition, there may be a solvent classified into a plurality of streams.

In the method for producing a pigment dispersion of the present invention, the pigment and the dye are uniformly dispersed simultaneously in a solvent. The term " simultaneous " here does not mean an instantaneous time, but means that the same solvent in the above-mentioned solvents is continuously supplied to the same solvent, that is, without substantially performing other operations such as heating, cooling, In the same solvent, and then optionally heating, cooling, stirring, mixing, and the like are carried out to uniformly disperse them. That is, as one step, it means that both are put into the same solvent and dispersed.

The method of dispersing the dye and the pigment at the same time is not particularly limited and can be carried out by a known apparatus and a known method in the field. A pigment, a dye, a pigment dispersant, a solvent, a dispersant, and a resin may be mixed and dispersed at the same time, or the dye, the pigment dispersant and the resin may be dissolved in a solvent in advance and then mixed and dispersed. The dispersion is preferably performed using a dispersing machine such as a paint shaker, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homodizer, or the like. As described above, since the pigment is made into fine particles by dispersing, the coating properties of the coloring composition are improved, and the transmittance and contrast of the color filter obtained from the coloring composition are improved.

In the case of dispersing using a paint shaker, glass beads or zirconia beads having a diameter of 0.1 to 2 mm are preferably used. The temperature at which dispersion is carried out is preferably 0 to 100 DEG C or higher, more preferably 20 to 80 DEG C or higher. The time for carrying out the dispersion may be from 1 to 20 hours, preferably from 1 to 10 hours, but it may be suitably adjusted according to the composition of the pigment dispersion and the size of the paint shaker apparatus.

The method for producing a colored composition according to the present invention comprises mixing at least one kind of the group consisting of the solvent (E), the resin (B), the photopolymerizable compound (C) and the photopolymerization initiator (D) in the pigment dispersion (A) .

The solvent contained in the pigment dispersion may be used as is, or the solvent may be appropriately selected and mixed.

The total amount of the dye and the pigment in the coloring composition to be produced is preferably 5 to 60 mass%, more preferably 8 to 55 mass%, and still more preferably 10 to 50 mass%, based on the solid content in the coloring composition. Mass%. Here, the solid content refers to the sum of components excluding the solvent in the coloring composition.

When the content of the dye and the pigment is within this range, the obtained coloring pattern or the color density of the color filter is sufficient, and a required amount of the binder polymer can be contained in the composition, so that a coloring pattern or color filter excellent in mechanical strength can be formed .

The resin (B) is not particularly limited, but for example, it preferably contains an alkali-soluble resin.

The alkali-soluble resin is not particularly limited, and any resin may be used. For example, the alkali-soluble resin contains a constituent unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the constituent unit derived from (meth) acrylic acid is preferably from 16 mol% to 40 mol%, more preferably from 18 mol% to 38 mol%, inclusive of the total constituent units constituting the alkali- to be. When the content of the constituent unit derived from (meth) acrylic acid is within the above-mentioned range, solubility of the non-combustible part becomes good at the time of development. In addition, there is a tendency that residues are hard to remain in the non-combusted portions after development.

Examples of other monomers for deriving constituent units other than the constituent units derived from (meth) acrylic acid constituting the alkali-soluble resin include aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, Unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl groups or monomethacryloyl groups at the ends of the polymer molecular chain, and monoacryloyl groups or monoacryloyl groups at the ends of the polymer molecular chains. , A unit represented by the formula (II) and a unit represented by the formula (III).

[In the formulas (II) and (III), R ⁸⁰ and R ⁸² each independently represent a hydrogen atom or a methyl group. R ⁸¹ and R ⁸³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Specific examples of the alkali-soluble resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer , A methacrylic acid / styrene / benzyl methacrylate / N-phenylmaleimide copolymer, a methacrylic acid / a structural component represented by the formula (II) wherein R ⁵³ represents a methyl group, R ⁵⁴ represents a hydrogen atom] / benzyl methacrylate copolymer, a structural unit represented by the formula (II) (wherein, in the formula (II), R ⁵³ represents a methyl group and R ⁵⁴ represents a hydrogen atom ] / Benzyl methacrylate copolymer, methacrylic acid / structural unit represented by formula (III) (wherein, in formula (III), R ⁵⁵ represents a methyl group and R ⁵⁶ represents a hydrogen atom.] / Styrene copolymer / tricyclodecyl methacrylate copolymer The like are preferable.

In particular, an alkali-soluble resin represented by the formula (IV) is preferable from the viewpoints of curability and developability.

An alkali-soluble resin having a structural unit represented by the formula (II), for example, a methacrylic acid / structural unit represented by the formula (II) / benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to produce 2 To obtain a component polymer, and reacting the obtained two-component polymer with a compound represented by the formula (V).

The methacrylic acid / structural unit / styrene copolymer / tricyclodecyl methacrylate copolymer represented by the formula (III) is obtained by copolymerizing a monomethacrylate copolymer of benzyl methacrylate, methacrylic acid and tricyclodecane skeleton with a monomer With a compound represented by the formula (VI).

[In the formulas (V) and (VI), R ⁸¹ and R ⁸³ have the same meanings as defined above.]

The copolymerization is generally carried out in a solvent using a polymerization initiator.

Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutylonitrile and 2,2'-azobis (methyl 2-methylpropionate), peroxides such as benzoyl peroxide and peroxide-tert- Etc. are used.

The solvent is not particularly limited as long as it dissolves the respective monomers and includes, for example, glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate, A solvent or the like may be used.

The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator, the boiling point of the solvent and the monomer, and the like.

The side chain of the copolymer thus obtained may be modified with a compound having a polymerizable group to form a photosensitive alkali-soluble resin. At this time, a catalyst for introducing a polymerizable group into the resin may be added.

Examples of the catalyst include trisdimethylaminomethylphenol and the like. In addition, an additive for preventing side reaction may be added. Examples of the additive include hydroquinone and the like.

As the alkali-soluble resin, for example, the following copolymers [K1] to [K4] and the like are exemplified.

(B1) (hereinafter sometimes simply referred to as "(B1)") and the monomer (B2) having a ring-shaped ether structure having 2 to 4 carbon atoms [ (Hereinafter sometimes simply referred to as " (B2) ").

[K2] A copolymer obtained by polymerizing (B1) and (B2) and a monomer (B3). Here, the monomer B3 (hereinafter sometimes simply referred to as (B3)) is a monomer copolymerizable with (B1) and / or (B2), which is a monomer different from (B1) and (B2) .

[K3] A copolymer obtained by reacting a part of carboxyl groups derived from (B1) with a cyclic ether structure having 2 to 4 carbon atoms derived from (B2) in the copolymer of (B1) and (B3).

[K4] Copolymer of (B1) and (B3).

Among them, the copolymer is preferably a copolymer obtained by polymerizing at least (B1) and (B2).

(B1) include, for example, an aliphatic unsaturated carboxylic acid and / or an aliphatic unsaturated carboxylic acid anhydride. Specifically,

Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid;

Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, Anhydrides of unsaturated dicarboxylic acids such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride (hydroamic anhydride);

(Meth) acryloyloxyalkyl] unsaturated monocarboxylic acid mono [(meth) acryloyloxyethyl] phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

and? - (hydroxymethyl) acrylic acid, and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule.

Of these, acrylic acid, methacrylic acid or maleic anhydride are preferable from the viewpoint of copolymerization reactivity and alkali solubility.

These may be used alone or in combination of two or more. In the present specification, any of the exemplified compounds, components, and agents may be used singly or in combination of two or more, unless otherwise specified.

In the present specification, the term "(meth) acrylic acid" refers to at least one member selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as "(meth) acryloyl" and "(meth) acrylate" have the same meaning.

(B2) may have at least one structure selected from the group consisting of, for example, a cyclic ether structure having 2 to 4 carbon atoms (for example, an oxylen structure, an oxetane structure and a tetrahydrofuran structure) , And is preferably a monomer having an unsaturated bond.

(B2) include, for example, a monomer having an oxiranyl group, a monomer having an oxetanyl group, a monomer having a tetrahydrofuryl group, and the like.

The monomer having an oxiranyl group as described above means, for example, a polymerizable compound having at least one group selected from the group consisting of an aliphatic epoxy group and an alicyclic epoxy group.

The monomer having an epoxy group is preferably a compound having an unsaturated bond and at least one structure selected from the group consisting of a structure obtained by epoxidizing an alkene and a structure obtained by epoxidizing a cycloalkene and a structure obtained by epoxidizing an alkene, And a monomer having at least one structure selected from the group consisting of a structure obtained by epoxidizing an alkene and a (meth) acryloyloxy group.

Specific examples of the compound having an alkenyl epoxidized structure include glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) Compounds represented by the following formula (VI) described in JP-A-7-248625, and the like.

[In the formula (VI), R ⁸⁴ to R ⁸⁶ are each independently a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and m ¹ is an integer of ¹ to 5. ).

Examples of the compound represented by the above formula (VI) include o-vinylbenzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether,? -Methyl- Glycidyl ether,? -Methyl-m-vinylbenzyl glycidyl ether,? -Methyl-p-vinylbenzyl glycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4- Diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyl Methylstyrene, dodecylmethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, and 2,4,6-triglycidyloxymethylstyrene.

Examples of monomers having a structure in which a cycloalkene is epoxidized include monomers having a structure obtained by epoxidizing a monocyclic cycloalkene, monomers having a structure obtained by epoxidizing a polycyclic cycloalkene, and the like. The monomer having an oxirane structure is preferably a compound having an unsaturated bond and at least one structure selected from the group consisting of a structure obtained by epoxidizing a monocyclic cycloalkene and a structure obtained by epoxidizing a polycyclic cycloalkene, Is more preferably a monomer having at least one structure selected from the group consisting of a structure obtained by epoxidizing a cycloalkene and a structure obtained by epoxidizing a cycloalkene and a (meth) acryloyloxy group.

Examples of the above monocyclic cycloalkane include cyclopentene, cyclohexene, cycloheptene, cyclooctene, and the like. Among them, a compound having 5 to 7 carbon atoms is preferable.

Specific examples of the monomer having a structure in which a monocyclic cycloalkene is epoxidized include vinylcyclohexene monoxide 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide 2000; Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl acrylate (for example, Cyclomer-A400; Manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl methacrylate (for example, Cyclomer-M100; (Manufactured by Daicel Chemical Industries, Ltd.).

Examples of the polycyclic cycloalkenes include dicyclopentene, tricyclodecene, norbornene, isonorbornene, bicyclooctene, bicyclo- nene, bicyclo- undecene, tricyclo- undecene, bicyclo dodecene Tricyclododecene, and the like.

Among them, a compound having 8 to 12 carbon atoms is preferable.

Examples of the monomer having a structure in which the polycyclic cycloalkene is epoxidized include 3,4-epoxy norbornyl acrylate, 3,4-epoxy norbornyl methacrylate, a compound represented by the formula (VII) And at least one compound selected from the group consisting of compounds represented by the formula (VIII).

In the formulas (VII) and (VIII), R ⁸⁷ and R ⁸⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

X ⁸⁷ and X ⁸⁸ each independently represent a single bond, an alkanediyl group having 1 to 6 carbon atoms or * - (CH ₂ ) _s -X '- (CH ₂ ) _t -.

X 'represents -S-, -O- or -NH-.

s represents an integer of 1 to 6, and t represents an integer of 0 to 6; Where s + t ≤ 6.

* Indicates a hand joined with 0.]

Specific examples of R ⁸⁷ and R ⁸⁸ include a hydrogen atom; An alkyl group such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group;

Hydroxyethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, Hydroxy-substituted alkyl groups such as a hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.

Among them, preferred are a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group. More preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms for X ⁷¹ and X ⁷² include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, Pentane-1,5-diyl group, hexane-1,6-diyl group and the like.

Among them, a single bond, a methylene group, an ethylene group, -O-CH ₂ -, and -O- (CH ₂ ) ₂ - are preferable. More preferably a single bond, -O- (CH ₂ ) ₂ -.

At least one compound selected from the group consisting of the compound represented by the formula (VII) and the compound represented by the formula (VIII) is a compound selected from the group consisting of a compound represented by the following formula (VII ') and a compound represented by the formula (VIII' It is preferable that the compound is at least one kind of compound selected.

In the formulas (VII ') and (VIII'), R ⁸⁹ and R ⁹⁰ are the same as R ⁸⁷ and R ⁸⁸ , respectively.

Examples of the compound represented by the formula (VII) include compounds represented by the formula (VII-1) to (VII-15). (VII-1), VII-3, VII-5, VII-7, VII-9, )to be. (VII-1), (VII-7), (VII-9) and (VII-15).

Examples of the compound represented by the formula (VIII) include compounds represented by the formula (VIII-1) to (VIII-15). (VIII-1), VIII-3, VIII-5, VIII-7, VIII-9, VIII- )to be. (VIII-1), (VIII-7), (VIII-9) and (VIII-15).

The at least one compound selected from the group consisting of the compound represented by the formula (VII) and the compound represented by the formula (VIII) may be used alone. In addition, they can be mixed at an arbitrary ratio. When mixed, the mixing ratio thereof is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10, and even more preferably from 20: 80 to 80:20.

The above-mentioned oxetanyl group-containing monomer is preferably a compound having an oxetanyl group and an unsaturated bond, more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group.

Specific examples of the monomer having an oxetanyl group include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxymethyloxetane, 3- 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-acryloxy methyl oxetane, 3-methyl- Or 3-ethyl-3-acryloxyethyloxetane.

The monomer having a tetrahydrofuryl group is preferably a compound having a tetrahydrofuryl group and an unsaturated bond, more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group.

Specific examples of the monomer having a tetrahydrofuryl group include tetrahydrofurfuryl acrylate (for example, Viscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like. have.

As the copolymerizable monomer (B3), for example,

Acrylic acid alkyl ester such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate and tert-butyl (meth) acrylate;

(Meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decan- (Meth) acrylic acid esters such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

(Meth) acrylic acid aryl esters such as phenyl (meth) acrylate and benzyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;

Hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [ 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept- 2,1-hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cycarbonylbicyclo [ 2.2.1] hept-2-ene, 5,6-di (tertiary butoxycarbonyl) bicyclo [2.2.1] hept- Non-cyclic unsaturated compounds such as cyclo [2.2.1] hept-2-ene;

N-alkylmaleimides such as N-methylmaleimide, N-ethylmaleimide and N-propylmaleimide;

N-cycloalkyl maleimides such as N-cyclopentyl maleimide, N-cyclohexyl maleimide and N-cyclooctyl maleimide;

N-bridged carbocyclic group substituted maleimides such as N-adamantyl maleimide and N-norbornyl maleimide;

N-aryl maleimides such as N-phenyl maleimide;

N-aralkyl maleimides such as N-benzyl maleimide;

N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide caproate, N- Dicarbonylimide derivatives such as phionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among them, styrene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hept-2-ene are preferred from the viewpoint of copolymerization reactivity and alkali solubility.

The copolymers [K1] to [K4] can be prepared, for example, by the method described in the "Experimental Method of Polymer Synthesis" (published by KODOKI Corporation, 1st Ed., 1st Ed., March 1, 1972, And can be produced by referring to the reference documents listed in the document.

Specifically, a predetermined amount of the monomers (B1) and (B2) and optionally (B3) constituting the copolymer, the polymerization initiator and the solvent are placed in a reaction vessel, oxygen is replaced by nitrogen, By heating and warming, a polymer is obtained. The polymerization 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 generated by polymerization, and the like.

As the polymerization initiator and the solvent to be used herein, any of those conventionally used in the field can be used. For example, the polymerization initiator and solvent described above may be used.

The solution obtained after the reaction may be used as it is, or a concentrated or diluted solution may be used, or a solution extracted as a solid (powder) by re-precipitation or the like may be used.

In particular, by using the above-mentioned solvent as a solvent in the polymerization, the solution after the reaction can be used as it is, and the manufacturing process can be simplified.

It is preferable that the copolymer [K1] has a ratio of the constitutional unit derived from each monomer to the total molar number of the constitutional unit constituting the copolymer [K1] in the following range.

, 5 to 95 mol%, more preferably 10 to 90 mol%

(B2), more preferably 10 to 90 mol%.

It is preferable that the proportion of the constituent units derived from each monomer in the copolymer [K2] is in the following range with respect to the total molar number of the constituent units constituting the copolymer [K2].

(B1) in an amount of 2 to 40 mol%, more preferably 5 to 35 mol%

(B2) in an amount of 2 to 95 mol%, more preferably 5 to 80 mol%

(B3) is 1 to 65 mol%, more preferably 1 to 60 mol%.

The copolymer [K3] can be produced through a two-step process.

First, (B1) and (B3) are copolymerized in the same manner as described above to obtain a copolymer.

In this case, it is preferable that the ratio of each monomer is within the following range with respect to the total number of moles of the constituent units constituting the resin.

(B1) of 5 to 50 mol%, preferably 10 to 45 mol%

(B3) is 50 to 95 mol%, preferably 55 to 90 mol%.

Next, a part of the carboxylic acid and / or carboxylic anhydride of (B1) derived from the copolymer of (B1) and (B3) is reacted with a cyclic ether derived from (B2) (oxiranyl, oxetanyl or tetra Hydrofuryl group).

To this end, the atmosphere in the flask is replaced by air from nitrogen, (B2), the reaction catalyst and the polymerization inhibitor are placed in a flask, and the reaction is continued at 60 to 130 DEG C for 1 to 10 hours, for example do. The reaction conditions such as the feeding method, the reaction temperature and the time can be suitably adjusted in consideration of the amount of heat generated by the production equipment or polymerization.

In this case, the number of moles of (B2) is preferably 5 to 80 mol%, more preferably 10 to 75 mol%, still more preferably 15 to 70 mol% with respect to the number of moles of (B1).

The reaction catalyst is preferably used as a reaction catalyst between a carboxyl group and a cyclic ether (oxiranyl, oxetanyl or tetrahydrofuryl group). Specific examples thereof include trisdimethylaminomethylphenol and the like.

The amount of the reaction catalyst to be used is preferably 0.001 to 5 mass% with respect to the total amount of (B1) to (B3).

As the polymerization inhibitor, for example, hydroquinone is exemplified.

The amount of the polymerization inhibitor to be used is, for example, preferably 0.001 to 5% by mass based on the total amount of (B1) to (B3).

It is preferable that the copolymer [K4] has a ratio of the constituent units derived from the respective monomers to the total number of moles of the monomers constituting the copolymer [K4] in the following range.

(B1) in an amount of 2 to 40 mol%, more preferably 5 to 35 mol%

(B2), more preferably 65 to 95 mol%.

The dispersion degree (molecular weight distribution) and [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the copolymers [K1] to [K4] are preferably 1.1 to 6.0 and more preferably 1.2 to 4.0 .

The weight average molecular weight of the resin (B) in terms of polystyrene is from 5,000 to 35,000, more preferably from 6,000 to 30,000, and particularly preferably from 7,000 to 28,000. When the molecular weight is within the above-mentioned range, the hardness of the coating film is improved, the residual film ratio is high, the solubility in the developing solution of the unexposed portion is good, and the resolution tends to be improved.

The acid value of the resin (B) is preferably 50 to 150, more preferably 60 to 135, and particularly preferably 70 to 135. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic acid-based polymer, and is usually determined by appropriately using an aqueous solution of potassium hydroxide.

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and particularly preferably from 17 to 55% by mass, based on the solid content of the coloring composition. When the content of the resin (B) is in the above-mentioned range, a pattern can be formed and the resolution and the residual film ratio tend to be improved.

The photopolymerizable compound (C) is not particularly limited so long as it is a compound which can be polymerized by an active radical, an acid generated from the photopolymerization initiator (D) upon irradiation with light. For example, a compound having a polymerizable carbon-carbon unsaturated bond.

The photopolymerizable compound (C) is preferably a multifunctional photopolymerizable compound having three or more functional groups. Examples of the polyfunctional photopolymerizable compound having three or more functional groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, Dipentaerythritol hexamethacrylate, and the like. The photopolymerizable compound (C) may be used singly or in combination of two or more kinds.

The content of the photopolymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the solid content of the colored composition. When the content of the photopolymerizable compound (C) is within the above range, the curing is sufficiently carried out, the ratio of the film thickness before and after the development is improved, the undercut is difficult to be introduced into the pattern, and the adhesion tends to be good.

The photopolymerization initiator (D) is preferably a compound capable of generating an active radical, an acid or the like by irradiation with light to polymerize the polymerizable compound (C) and generating a radical by ultraviolet rays. Examples of the photopolymerization initiator (D) include an active radical generator and an acid generator.

The active radical generator generates active radicals by being irradiated with light. Examples of the active radical generator include acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, oxime compounds, and the like.

Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2- Phenylpropan-1-one, benzyldimethylketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) Oligomers of phenyl ketone and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, -1- (4-methylthiophenyl) propan-1-one, and the like.

The active radical generator generates active radicals by being irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, triazine compounds, oxime compounds, and the like.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- Tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propoxyoctanoate and the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl ) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- Triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- Methyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4- dimethoxyphenyl) ethenyl] -1,3 , 5-triazine, and the like.

Examples of the above oxime compounds include O-acyloxime compounds, and specific examples thereof include N-benzoyloxy-1- (4-phenylsulfanylphenyl) -butan-1-one-2- Imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan- 1-one-2-imine, N-acetoxy- 1- [ 3-yl] ethan-1-imine, N-acetoxy-1- [ Oxy) benzoyl} -9H-carbazol-3-yl] ethan-1-imine.

As the active radical generator, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra Phenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphaquinone, methyl phenylglyoxylate, Or the like may be used.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p- Toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluene sulfonate, p-toluene sulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p- Onium salts such as diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroantimonate and the like, nitrobenzyl tosylates, benzoin tosylates and the like.

Among the compounds described above as the above-mentioned active radical generator, there are compounds which generate an acid at the same time as an active radical. For example, a triazine-based photopolymerization initiator is also used as an acid generator.

The content of the photopolymerization initiator (D) is preferably from 0.1 to 30 mass%, more preferably from 1 to 20 mass%, based on the total amount of the alkali-soluble resin and the photopolymerizable compound (C). When the content of the photopolymerization initiator is within the above-mentioned range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

The coloring composition of the present invention may further contain a photopolymerization initiator. The photopolymerization initiator (F) is generally used in combination with the photopolymerization initiator (D), and is a compound or sensitizer used for promoting polymerization of the photopolymerizable compound initiated by the photopolymerization initiator.

Examples of the photopolymerization initiator (F) include an amine compound, an alkoxyanthracene compound, and a thioxanthone compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylbenzoic acid Aminoethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- ) Benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Among them, 4,4'-bis (diethylamino) benzophenone is preferable.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxy Anthracene, 9,10-dibutoxyanthracene, and 2-ethyl-9,10-dibutoxyanthracene.

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propoxyoctanoate and the like.

The photopolymerization initiator (F) may be used alone or in combination of two or more. Examples of commercially available photopolymerization initiator (F) include trade name "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) and the like can be used as the photopolymerization initiator (F) have.

Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiator (F) include diethoxyacetophenone / 4,4'-bis (diethylamino) benzophenone, 2-methyl- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy- (Diethylamino) benzophenone, benzyldimethylketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl- 1- [4- (2- hydroxyethoxy) (Diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy- (Diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-methylphenyl) (4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone, and preferably 2-methyl- - methylthiophenyl) ph 1-one / 4,4'-bis (diethylamino) benzophenone.

When these photopolymerization initiators (F) are used, the amount thereof to be used is preferably 0.01 to 10 mol, more preferably 0.01 to 5 mol, per 1 mol of the photopolymerization initiator (D).

The solvent (E) is not particularly limited, and a solvent commonly used in the field can be used. The above-mentioned solvents can be appropriately selected and used. The solvent (E) contained in the coloring composition is preferably selected from the group consisting of propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, cyclohexanone, ethyl lactate and 4-hydroxy-4-methyl- A solvent containing at least one kind is preferable, and a solvent containing at least one kind selected from the group consisting of propylene glycol monomethyl ether acetate and 4-hydroxy-4-methyl-2-pentanone is more preferable, More preferred are solvents comprising glycol monomethyl ether acetate. When the solvent (E) is one of these solvents, generation of foreign matter is suppressed, and a color filter having high contrast can be obtained.

The content of the solvent (E) in the coloring composition is 70 to 95 mass%, and more preferably 75 to 92 mass%, with respect to the coloring composition. In other words, the solid content is preferably 5 to 30 mass%, more preferably 8 to 25 mass%, based on the coloring composition. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color characteristics are not insufficient when the color filter is formed, so that display characteristics tend to be good.

The coloring composition of the present invention may optionally contain a surfactant (G) (however, different from the pigment dispersant). As the surfactant (G), a surfactant having a fluorine atom or a silicon atom is suitable. Specific examples include at least one selected from the group consisting of a silicone surfactant, a fluorinated surfactant, and a silicon surfactant having a fluorine atom.

Examples of the silicone surfactants include surfactants having a siloxane bond. Specifically, the following materials are used: Dore silicon DC3PA, Dole silicone SH7PA, Dore silicon DC11PA, Dore silicon SH21PA, Dore silicon SH28PA, Dore silicon SH29PA, Dole silicone SH30PA, Dore silicon SH8400 (Dow Corning Co., Ltd.), KP321, KP323, KP324, KP340, KP341 [Shin-Etsu Chemical Co., Ltd.], TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 [Momentive Performance Materials, .

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specific examples of such a solvent include Fluoride (trade name) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (trade name) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, (Trade name) EF301, Epson EF303, Epson EF351, Epson EF352 (manufactured by Mitsubishi Material Electronics Co., Ltd.)], Megapack F489, Megapack F554, Megapack R30 (Manufactured by Daikin Fine Chemical Research Institute, Ltd.), BM-1000, BM-1100 [manufactured by Asahi Glass Co., Ltd.], E5844 Trade name: BM Chemie).

Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain. Specific examples include Megapac (registered trademark) R08, Megapack BL20, Megapack F475, Megapack F477, Megapack F443 (manufactured by DIC Corporation) and the like.

These surfactants may be used singly or in combination of two or more kinds.

The content of the surfactant (G) is preferably 0.0005 to 0.3 mass%, more preferably 0.001 to 0.1 mass% with respect to 100 mass parts of the coloring composition. When the content of the surfactant (F) is in the above-mentioned range, the flatness tends to be good.

The coloring composition of the present invention is preferably a negative-type coloring composition.

The coloring composition of the present invention can be suitably used for forming a color filter or a coloring pattern, and it is possible to obtain a coloring pattern and a color filter having good color density, brightness, contrast, sensitivity, resolution, heat resistance and the like. An optical film, an array substrate, a color filter substrate, and the like having these color filters or colored patterns as a part of their constituent parts, and also a color filter or a color pattern, an optical film or array substrate, It can be used in a known manner in a display device, for example, a device related to various colored images such as a known liquid crystal display device, an organic EL device, and a solid-state image pickup device.

As a method for forming a color filter or a pattern thereof using the coloring composition of the present invention, for example, a method of forming the coloring composition of the present invention on a substrate or a separate resin layer (for example, a separate coloring composition Layer or the like) to remove or dry volatile components such as a solvent to form a colored layer, exposing and developing the colored layer through a photomask, a method of using an inkjet device that does not require a photolithographic method And the like.

The film thickness of the coating film in this case is not particularly limited and can be appropriately adjusted depending on the material to be used and the application. For example, it is 0.1 to 30 탆, preferably 1 to 20 탆, more preferably 1 to 6 Mu m.

Examples of the application method of the coloring composition include an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a CAP coating method and a die coating method. It may also be coated using a coater such as a dip coater, a bar coater, a spin coater, a slit & spin coater, a slit coater (die coater, curtain flow coater, or spinless coater). Among them, it is preferable to apply by using a spin coater.

The removal / drying of the solvent includes, for example, natural drying, air drying, and vacuum drying. The specific heating temperature is preferably 10 to 120 占 폚, more preferably 25 to 100 占 폚. The drying time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. In the case of performing the reduced-pressure drying, it is preferably carried out at a temperature of 20 to 25 캜 under a pressure of 50 to 150 Pa.

Example

Hereinafter, the method for producing the pigment dispersion of the present invention, the method for producing the coloring composition, the color filter as the coloring pattern and the like will be described in more detail with reference to Examples. In the examples, "% " and " part " are by mass% and mass part, respectively, unless otherwise specified.

Synthesis Example 1

≪ Synthesis of Dye A1 >

In a flask equipped with a cooling tube and a stirrer, 15 parts of a coloring matter represented by the formula A-0-1 (a jugation agent), 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were fed, And 10.9 parts of thionyl chloride was added dropwise thereto while being kept. After completion of the dropwise addition, the temperature was raised to 50 占 폚, and the reaction was carried out at the same temperature for 5 hours, followed by cooling to 20 占 폚. The cooled reaction solution was added dropwise with a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine with stirring while maintaining the temperature at 20 ° C or lower. Followed by stirring at the same temperature for 5 hours. Then, the solvent was distilled off using a rotary evaporator, and a small amount of methanol was added to the reaction mixture. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were filtered, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain 11.3 parts of dye A1 (mixed dye of dye A1-1 to dye A1-8).

[Wherein, in the formula (A1), each R _c independently represents -SO ₂ NH-R _a , -SO ₃ H, -SO ₃ ^- Or -H. R _a represents 2-ethylhexyl.

Synthesis Example 2

≪ Synthesis of resin B1 >

In a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping rod and a nitrogen inlet tube, 133 g of propylene glycol monomethyl ether acetate was introduced, and the atmosphere in the flask was changed from nitrogen to nitrogen. The temperature was raised to 100 占 폚 and 22.0 g (0.47 mol) of benzyl methacrylate, 0.37 mol of methacrylic acid, 0.43 mol of methacrylate and mono methacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 0.10 mole) and propylene glycol monomethyl ether acetate (164 g) was added dropwise to a mixture of 2,2'-azobisisobutylonitrile (3.6 g), followed by further stirring at 100 ° C.

Next, 21.5 g of glycidyl methacrylate (0.15 mol, 50 mol% with respect to the carboxyl group of the methacrylic acid used in the present reaction)) and 0.9 g of trisdimethylaminomethylphenol And 0.145 g of hydroxyquinone were placed in a flask, and the reaction was continued at 110 캜 to obtain a resin solution B1 (solid content: 38%) having a solid acid value of 97 mgKOH / g.

The weight average molecular weight in terms of polystyrene measured by GPC was 9.0 × 10 ³ .

The measurement of the polystyrene reduced weight average molecular weight of the above resin was carried out by the GPC method under the following conditions.

Device ; HLC-8120 GPC (manufactured by TOSOH CORPORATION)

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

Solid concentration of the test solution; 0.001 to 0.01 mass%

Dose; 50 μL

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE

                      F-40, F-4, F-1, A-2500 and A-500 (manufactured by TOSOH CORPORATION)

Examples 1 and 2, Comparative Examples 1 and 2

≪ Production of Pigment Dispersion >

The ingredients listed in Table 22 were put in turn into the beaker to mix all the components. Thereafter, zirconia beads of 0.65 mm in diameter were used for dispersion treatment for 5 hours by means of a paint shaker. The resulting uniform dispersion was filtered to remove the beads to obtain a pigment dispersion.

Pigment: C.I. Pigment Blue 15: 6

Dye: Dye A1

Dispersant 1: Disperbyk-161 (manufactured by Big Chemical)

Dispersant 2: Copper phthalocyanine derivative (Solus Pass 5000, available from Avicia)

Solvent 1: Propylene glycol monomethyl ether acetate

Solvent 2: ethyl lactate

Examples 3 to 5 and Comparative Examples 3 to 5

≪ Preparation of colored composition >

The components described in Table 23 were mixed to obtain a colored composition.

In Table 23, the components are as follows.

Photopolymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure OXE01; Manufactured by Chiba, Specialty Chemicals Co., Ltd.]

Surfactant: polyether-modified silicone oil (SH8400, manufactured by Dow Corning Toray Co., Ltd.)

Solvent 1: Propylene glycol monomethyl ether acetate

Solvent 2: ethyl lactate

Solvent 3: 4-Hydroxy-4-methyl-2-pentanone

≪ Fabrication of color filter &

On the glass substrate (Eagle 2000; manufactured by Corning) having a 2-inch square, the coloring composition obtained above was applied by the spin coat method.

Next, prebaking was performed in a clean oven at 100 占 폚 for 3 minutes. After cooling, the substrate was irradiated with light at an exposure (365 nm) of 150 mJ / cm 2 in an atmosphere of an exposure apparatus (TME-150RSK; manufactured by Topcon Co., Ltd.) and heated at 220 캜 for 20 minutes, Respectively. The film thickness of the obtained color filter was measured with a film thickness measuring device [DEKTAK3; Manufactured by Nippon Vacuum Technology Co., Ltd.).

[Evaluation of foreign object]

The obtained color filter surface was visually confirmed. The results were as follows. ○: no foreign substance at all ○: no foreign substance was observed △: a large amount of foreign substance was observed ×: no foreign substance was obtained due to a large amount of foreign matter. The results are shown in Table 24.

[Brightness evaluation]

With respect to the obtained color filter, a colorimeter [OSP-SP-200; (X, y) and brightness (Y) in an XYZ colorimetric system of CIE were measured using a C light source. The results are shown in Table 24.

[Evaluation of contrast]

The resulting color filter was applied to two polarizing plates [POLAX-38S; (BM-5A, manufactured by Topcon Technohouse Co., Ltd.) as a light source, a cold cathode tube F10 lamp as a light source (manufactured by Fuji Photo Film Co., Ltd.) , The luminance of the transmitted light of the sample in the parallel Nicol and the luminance in the quadrature Nicol were measured and the ratio of the luminance in the parallel Nicol and the luminance in the orthogonal Nicol (parallel Nicol / quadrature Nicol) was taken as a contrast . Before the contrast of the color filter was measured, the intensity of the light source was adjusted so that the measured contrast was 10000 without interposing the color filter. The results are shown in Table 24.

Synthesis Example 3

≪ Synthesis of Dye A2 >

After adding 75 parts of water to 7.7 parts of 2-amino-4-nitrophenol (manufactured by Wako Pure Chemical Industries, Ltd.), 2.0 parts of sodium hydroxide was added to dissolve the mixture. And 9.5 parts of 35% aqueous solution of sodium nitrite (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, followed by dissolving 30.0 parts of 35% hydrochloric acid in small portions and stirring for 2 hours to obtain a suspension containing the diazonium salt. Subsequently, an aqueous solution prepared by dissolving 8.9 parts of amide sulfuric acid (manufactured by Wako Pure Chemical Industries, Ltd.) in 36 parts of water was slowly added to quench excess sodium nitrite.

Subsequently, 13 parts of 3-methyl-1- (3'-sulfamoyl) -5-pyrazolone (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 100 parts of water and sodium hydroxide was used to adjust the pH to 8.0 Respectively. The suspension containing the diazonium salt was added dropwise over 15 minutes while appropriately adding 10% sodium hydroxide solution so that the pH was in the range of 7 to 7.5. After completion of the dropwise addition, stirring was continued for another 30 minutes to obtain a yellow suspension. And stirred for 1 hour. The yellow solid obtained by filtration was dried at 60 ° C under reduced pressure to obtain 17.9 parts (yield: 85%) of a compound represented by the formula (p-1).

10 parts of the compound represented by the formula (p-1) were dissolved in 100 parts of dimethylformamide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.1 parts of ammonium chromate (III) sulfate (manufactured by Wako Pure Chemical Industries, And 1.1 parts of sodium acetate (manufactured by Wako Pure Chemical Industries, Ltd.) were added thereto, and the mixture was heated to reflux for 4 hours and a half. After cooling to room temperature, the reaction solution was poured into 1500 parts of 20% saline, and the resulting red colored solid obtained after filtration was dried at 60 캜 to obtain 12.8 parts (60%) of a compound represented by the formula (z-1).

, 170 parts of anhydrous chloroform (manufactured by KANTO CHEMICAL CO., LTD.), 1.0 part of camphorsulfonic acid [manufactured by Aldrich Co., Ltd.], 4- (N, N-dimethylamino) , 1.4 parts of pyridine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 18 parts of triethylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred for about 30 minutes. Thereafter, a solution prepared by adding 47 parts of anhydrous chloroform to 10.5 parts of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added slowly, And stirred for 2 hours. The separation operation was performed twice with a 1N hydrochloric acid aqueous solution (150 parts), and then the organic layer was washed twice with 150 parts of 10% brine. Subsequently, 43 parts of anhydrous magnesium sulfate was added and stirred for about 30 minutes. The drying agent was filtered off and the solvent was distilled off to obtain 20.6 parts (yield: 90%) of a compound represented by the formula (g-1).

Identification of the compound represented by the formula (g-1)

(Mass Spec.) Ionization mode = ESI +: m / z = 575.3 [M-Cl -] +.

                         Exact Mass: 610.3

To 253 parts of the compound represented by the formula (z-1), 4030 parts of methanol was added to adjust the solution (s1). To 153 parts of the compound represented by the formula (g-1), 1080 parts of methanol was added to adjust the solution (t1). Then, solution (s1) and solution (t1) were mixed at room temperature and stirred for about 1 hour. The obtained red solid was dried under reduced pressure at 60 占 폚, washed with 3500 parts of water, filtered and dried under reduced pressure at 60 占 폚 to obtain 263 parts (yield 65%) of a compound represented by the formula (1-1) (dye A2).

The structure of the compound represented by the formula (1-1) was determined by elemental analysis. The analytical instrument is an ICP emission analyzer [ICPS-8100; (Manufactured by Shimadzu Corporation) was used.

C 55.6 H 4.7 N 12.0 Cr 3.57

Synthesis Example 4

≪ Synthesis of dye A3 >

After adding 200 parts of water to 10.0 parts of m-toluidine-4-sulfonic acid represented by the formula (a-2), the mixture was adjusted to a pH of 7 to 8 with 30% aqueous sodium hydroxide solution under ice cooling. The following operation was performed under ice-cooling. 11.1 parts of sodium nitrite was added, and the mixture was stirred for 30 minutes. 39.0 parts of 35% hydrochloric acid was added in small portions to make a brown solution, which was then stirred for 2 hours. And 10.1 parts of amide sulfuric acid in 101 parts of water was added to the reaction solution and stirred to obtain a suspension containing the diazonium salt.

  To 14.0 parts of 1- (2-ethylhexyl) -3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (c-2), 125 parts of water and N-methylpyrrolidone 25.0 And the mixture was adjusted to pH 8-9 with 30% aqueous sodium hydroxide solution under ice-cooling.

The following operation was performed under ice-cooling. The pyridone aqueous solution was stirred to obtain a colorless solution, and the suspension containing the diazonium salt was added dropwise over 2 hours while adjusting the pH to 8 to 9 with 30% aqueous sodium hydroxide solution. After completion of the dropwise addition, stirring was continued for another 2 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 캜 under reduced pressure to obtain 21.4 parts (yield: 87%) of a compound represented by the formula (d-3).

0.35 g of the compound (d-3) was dissolved in N, N-dimethylformamide to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with water to make a volume of 100 cm 3 (concentration: 0.028 g / Absorption spectra were measured using a photometer [quartz cell, cell length 1 cm]. This compound exhibited an absorbance of 2.9 (arbitrary unit) at? Max = 433 nm.

5.0 parts of the compound (d-3), 35 parts of acetonitrile and 1.6 parts of N, N-dimethylformamide were fed into a flask equipped with a stirrer, a cooling tube and a stirrer. Thionyl chloride 2.4 parts was added dropwise. After completion of dropwise addition, the temperature was raised to 40 占 폚, and the reaction was carried out at the same temperature for 2 hours, followed by cooling to 20 占 폚. The cooled reaction solution was poured into 150 parts of ice water while stirring, followed by stirring for 30 minutes. The precipitated yellow crystals were filtered, washed well with tap water, and dried at room temperature for 1 hour. A flask equipped with a cooling tube and a stirrer was separately prepared, 2.0 parts of 1-amino-2-propanol and 20 parts of N-methylpyrrolidone were charged, and while adjusting the stirring temperature to 20 ° C or less, Over a period of 1 hour. After the yellow solid was added, the temperature of the solution was raised to room temperature, and then the reaction solution was stirred for 30 minutes. After 40 parts of methanol was added to the reaction solution and stirred, the mixed solution was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were filtered, washed well with ion-exchanged water and dried under reduced pressure at 60 ° C to obtain 3.9 parts (yield: 69%) of a compound represented by the formula (III-3).

0.35 g of the compound (III-3) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with deionized water to make a volume of 100 cm 3 (concentration: 0.028 g / L) Absorption spectra were measured using a photometer (quartz cell, optical path length: 1 cm). This compound exhibited an absorbance of 2.3 (arbitrary unit) at? Max = 431 nm.

The following reaction was carried out in a nitrogen atmosphere. 2.0 parts of the compound (III-3) was added 4.0 parts of N-methylpyrrolidone, and the mixture was stirred for 30 minutes to adjust the reaction solution. While stirring the reaction solution at room temperature, 0.1 part of sebacic acid chloride was added dropwise. After completion of the dropwise addition, stirring was continued for another 8 hours. After the reaction solution was poured into 300 parts of water, 80 parts of ethyl acetate was added and the mixture was stirred for 30 minutes. The organic phase was separated using a separating rod, and then washed with 500 parts of water, 500 parts of 10% sodium carbonate aqueous solution, 500 parts of 10% acetic acid aqueous solution, and 500 parts of ion exchange water. The separated organic phase was subjected to solvent distillation to obtain 2.0 parts of the dye A3 represented by the formula (I-6). Yield 85%.

The structure of compound (I-6) was determined by mass spectrometry. JMS-700 (manufactured by Nippon Denshoku Co., Ltd.) was used as the mass spectrometer.

Mass spectrometry: ionization mode = FD +: m / z = 1200

0.35 g of Compound (I-6) was dissolved in ethyl lactate to make a volume of 250 cm 3, and 2 cm 3 of the solution was diluted with ion-exchanged water to make a volume of 100 cm 3 (concentration: 0.028 g / Quartz cell, optical path length: 1 cm) was used to measure the absorption spectrum. This compound exhibited an absorbance of 2.2 (arbitrary unit) at? Max = 431 nm.

Synthesis Example 5

≪ Synthesis of Resin Solution B2 >

Nitrogen was flowed at 0.02 L / min in a flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping load to make a nitrogen atmosphere, and 935 parts by mass of ethyl lactate was added and heated to 70 캜 with stirring. Subsequently, 140 parts by mass of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl acrylate [compound represented by the following formula (I-1-1) and compound represented by the formula (I- 240 parts by mass in a molar ratio of 50:50) and 140 parts by mass of ethyl lactate to prepare a solution. The solution was dropped into a flask heated to 70 ° C over 4 hours using a dropping rod Respectively. On the other hand, a solution obtained by dissolving 30 parts by mass of polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) in 225 parts by mass of ethyl lactate was added dropwise to the flask over 4 hours using another dropping rod. After the dropwise addition of the polymerization initiator solution was completed, the solution was maintained at 70 占 폚 for 4 hours and then cooled to room temperature to obtain a solution having a weight average molecular weight (Mw) of 9.0 占⁰³ , a solid content of 26% To obtain a resin solution B2 of KOH / g.

Synthesis Example 6

≪ Synthesis of Resin Solution B3 >

250 parts by mass of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping rod and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 DEG C, and then a mixture composed of 152.6 parts by mass of benzyl methacrylate, 41.7 parts by mass of methacrylic acid, 1.5 parts by mass of azobisisobutylonitrile, and 150 parts by mass of propylene glycol monomethyl ether acetate Was added dropwise to the flask over a period of 2 hours using a dropping rod. After completion of the dropwise addition, stirring was further continued at 100 DEG C for 2.5 hours to obtain a polymer having a weight average molecular weight (Mw) of 2.3x10 < ⁴ >, a solid content of 34% To obtain a resin solution B3 of 47 mg-KOH / g.

Examples 6 and 7

≪ Production of Pigment Dispersion >

The ingredients listed in Table 25 were added in turn to the beaker to mix all the components. Thereafter, zirconia beads of 0.65 mm in diameter were used and the dispersion treatment was carried out by a paint shaker for 5 hours. The obtained uniform dispersion liquid was filtered to remove beads to obtain pigment dispersions 5 and 6. [

Pigment 2: C.I. Pigment Red 254

Pigment 3: C.I. Pigment Green 58

Dispersant 3: Acrylic pigment dispersant

Solvent 1: Propylene glycol monomethyl ether acetate

Examples 8 and 9

≪ Preparation of colored composition >

The components described in Table 26 were mixed to obtain a colored composition.

In Table 26, the components are as follows.

Photopolymerizable compound: dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd.)

Photopolymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure OXE01;

Surfactant: polyether-modified silicone oil (SH8400, manufactured by Dow Corning Toray Co., Ltd.)

Solvent 1: Propylene glycol monomethyl ether acetate

Solvent 4: Cyclohexanone

≪ Fabrication of color filter &

The coloring composition was coated on a 2 inch square glass substrate (Eagle 2000, manufactured by Corning) by spin coating.

Next, prebaking was performed in a clean oven at 100 占 폚 for 3 minutes. After cooling, the substrate was irradiated with light at an exposure (365 nm) of 150 mJ / cm 2 in an atmospheric environment using an exposure machine (TME-150 RSK, manufactured by Topcon Co., Ltd.) and heated at 230 캜 for 30 minutes, Respectively.

The obtained color filter was evaluated for foreign matters, brightness and contrast in the same manner as in Example 5.

[Evaluation of contrast]

The resultant color filter was sandwiched between two polarizing plates (POLAX-38S, manufactured by Luke), and a contrast meter (CT-1, manufactured by Tsubosaka Electric Co., Ltd.) Using a cold cathode tube F10 lamp as a light source, the luminance of the transmitted light of the sample in the parallel Nicol and the luminance in the quadrature Nicol were measured, and the luminance in the parallel Nicol and the luminance in the orthogonal Nicol The results are shown in Table 27. Before the contrast of the color filter was measured, the intensity of the light source was set so that the contrast measured was 3000 without interposing the color filter. Respectively.

In the color compositions of Examples 3 to 5, 8 and 9, a good color filter with few foreign matters was obtained. Also, excellent brightness and contrast were confirmed.

On the other hand, in Comparative Examples 3 to 5, a large amount of foreign matter was generated. In addition, the value of x is large, the red color is strong, and the contrast is also inferior. Particularly, in Comparative Example 5, since there were many foreign matters, normal evaluation could not be performed.

Since the method of producing a pigment dispersion of the present invention can uniformly disperse a dye and a pigment by a simple method, it is possible to produce various coloring compositions, coloring members, and the like used in various manufacturing processes as well as semiconductor manufacturing processes It is widely available.

According to the present invention, it is possible to provide a method for producing a pigment dispersion capable of further reducing the generation of foreign matter, and it becomes possible to produce a high-performance coloring pattern, a color filter, a liquid crystal display, etc. by using the obtained pigment dispersion .

Claims (10)

And a step of uniformly dispersing the dye and the pigment simultaneously in a solvent,
Wherein the dye is a dye comprising a xanthene compound,
Wherein the pigment is selected from the group consisting of CI Pigment Blue 15: 6, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Yellow 138, CI Pigment Yellow 150, CI Pigment Red 177 and CI Pigment Red 242 Wherein the pigment is at least one selected from the group consisting of a pigment and a pigment. delete The method according to claim 1,
Wherein the dye is a dye containing a compound represented by the formula (1).

[In the formula (1)
R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a halogen atom, -R ⁶ , -OH, -OR _{^{6, -SO 3 -, -SO 3}} H, -SO 3 M, -CO 2 H, -CO 2 R 6, -SO 3 R 6, -SO 2 NHR 8 or ^{_{-SO 2 N (R 8) R}} 9 , ≪ / RTI >
R ⁵ is selected from the group consisting of -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, -CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ or -SO ₂ N (R ⁸ ) R ⁹ ,
m represents an integer of 0 to 5, and when m is an integer of 2 or more, a plurality of R ^{5 s} may be the same or different,
X represents a halogen atom, a represents an integer of 0 or 1,
R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and -CH ₂ - included in the saturated hydrocarbon group may be substituted with -O-, -CO- or -NR ^6a -, R ^6a represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms,
R ⁸ and R ⁹ each independently represent an alkyl group having 1 to 10 carbon atoms which may have a substituent, a cycloalkyl group having 3 to 30 carbon atoms which may have a substituent, or -Q, or R ⁸ and R ⁹ may be the same or different, May form a heterocyclic ring having 1 to 10 carbon atoms which may have a substituent, and -CH ₂ - contained in the alkyl group and the cycloalkyl group may be replaced by -O-, -CO-, -NH- or -NR ^{6a <} - > -,
Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent or an aromatic heterocyclic group having 3 to 10 carbon atoms which may have a substituent,
M represents a sodium atom or a potassium atom,
The number of + electric charges and the number of electric charges of the compound represented by the formula (1) are the same) The method according to claim 1,
Wherein the dye and the pigment are contained in a mass ratio of dye: pigment = 1: 99 to 99: 1. delete The method according to claim 1,
Wherein the pigment is a pigment comprising CI Pigment Blue 15: 6. A process for producing a coloring composition comprising a pigment dispersion obtained by the production method according to claim 1 and at least one selected from the group consisting of a solvent, a resin, a photopolymerizable compound and a photopolymerization initiator. A coloring pattern characterized by being formed using the coloring composition obtained by the manufacturing method according to claim 7. A color filter comprising the coloring pattern according to claim 8 A liquid crystal display device comprising the color filter according to claim 9.