JP5931319B2 - Colored curable composition - Google Patents

Description

  The present invention relates to a colored curable composition used for forming a color filter such as a liquid crystal display panel.

  In order to obtain a bright and clear image, a display device using a color filter has a problem that the brightness is low because an image is displayed by light transmitted through the color filter, compared to a self-luminous display such as a plasma display. There is a need for a color filter with high brightness.

“This is the whole picture of the display!” P. 114 (by Wataru Izumiya; Kanki Publishing April 18, 2005)

  An object of the present invention is to provide a colored curable composition capable of forming a color filter having excellent brightness and contrast.

  As a result of intensive studies to find a colored curable composition that can solve the above-described problems, the present inventors have completed the present invention.

That is, the present invention provides the following inventions.
1. A colored curable composition containing (A) a colorant and (B) a polymerizable compound, wherein (A) the colorant contains a pigment represented by formula (1) and a yellow dye.

Wherein ^{(1), A} 1 ^{~A 16} each independently represent a hydrogen atom, a chlorine atom or a bromine atom. ]

2. The coloring according to claim 1, wherein the yellow dye is a yellow dye containing at least one dye selected from the group consisting of barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes. Curable composition.
3. 3. The colored curable composition according to item 1 above, wherein the barbituric acid azo dye is a dye represented by formula (2).

[In Formula (2), T ¹ and T ² each independently represent an oxygen atom or a sulfur atom.
R ^{31 to} R ³⁴ are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an optionally substituted group having 6 to 20 carbon atoms. It represents an aryl group, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or an acyl group having 2 to 10 carbon atoms which may have a substituent.
R ^{35 to} R ⁴² are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group. Represents. A hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom. ]

4). 3. The pyridone azo dye is a dimer formed from a compound represented by formula (3), a salt of a compound represented by formula (3), or a compound represented by formula (3). Colored curable composition.

[In Formula (3), Z is a halogen atom, the C1-C12 aliphatic hydrocarbon group which may have a substituent, a C1-C8 alkoxyl group, a hydroxyl group, a carboxyl group, carbamoyl. A phenyl group having one or two substituents selected from the group consisting of a group, a sulfo group, a sulfamoyl group, and an N-substituted sulfamoyl group, or a halogen atom and an optionally substituted carbon At least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, and an N-substituted sulfamoyl group. Represents a naphthyl group having 1 to 3 substituents.
R ²¹ represents a hydrogen atom, a linear, branched or cyclic C 1-10 aliphatic hydrocarbon group, carboxyl group or trifluoromethyl group.
R ²² represents a hydrogen atom, a cyano group, a carbamoyl group, an N-position-substituted carbamoyl group, a sulfamoyl group or a sulfo group.
R ²³ is a hydrogen atom, an optionally substituted linear, branched or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 6 carbon atoms. 30 aryl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted heterocyclic group having 3 to 20 carbon atoms, carbamoyl group, N-substituted carbamoyl Group, an optionally substituted alkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms, and a substituent. A C2-C20 acyl group, a C1-C30 aliphatic sulfonyl group which may have a substituent or a C6-C30 arylsulfonyl group which may have a substituent. . ]

5. The colored curable composition according to any one of 1 to 4 above, further comprising (C) a binder resin.
6). The pattern formed with the photolithographic method or the inkjet method using the coloring curable composition in any one of the preceding 1-5.
7). A color filter comprising the pattern described in the previous item 6.
8). 8. A liquid crystal display device comprising the color filter according to item 7.

  When the colored curable composition of the present invention is used, a color filter having excellent brightness and contrast can be produced.

  The colored curable composition of this invention contains the pigment represented by Formula (1) as (A) a coloring agent.

Wherein ^{(1), A} 1 ^{~A 16} each independently represent a hydrogen atom, a chlorine atom or a bromine atom. ]

In the formula (1), the number of substituents represented by A ^{1 to} A ¹⁶ is preferably 0 to 6 chlorine atoms, 10 to 16 bromine atoms, and a chlorine atom and a bromine atom. The sum is 10 to 16, more preferably 0 to 3 chlorine atoms, 13 to 16 bromine atoms, and 13 to 16 sum of chlorine and bromine atoms, Preferably, there are 1 to 3 chlorine atoms, 13 to 15 bromine atoms, and 14 to 16 sum of chlorine and bromine atoms.

  When the number of substituents is in the above range, the hue becomes yellowish, and the brightness becomes high without lowering the color reproduction range when a color filter is formed.

  The method for producing the pigment represented by the formula (1) is described in publications such as JP2007-284589, JP2007-284592, JP2007-291232, and JP2008-19383. It can be manufactured by a method.

  The content of the pigment represented by the formula (1) is 0.5 to 99.5% by mass, preferably 1 to 99% by mass, based on the total amount of the colorant (A), and more preferably 1 to 99% by mass. Preferably it is 2-98 mass%.

  The colored curable composition of the present invention further contains a yellow dye as the colorant (A). The yellow dye is preferably at least one dye selected from the group consisting of barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes, and cyanine dyes.

  Although it does not specifically limit as a barbituric acid azo dye, Although a well-known substance can be used, Preferably the barbituric acid azo dye represented by Formula (2) is used.

[In Formula (2), T ¹ and T ² each independently represent an oxygen atom or a sulfur atom.
R ^{31 to} R ³⁴ are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an optionally substituted group having 6 to 20 carbon atoms. It represents an aryl group, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or an acyl group having 2 to 10 carbon atoms which may have a substituent.
R ^{35 to} R ⁴² are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group. Represents. A hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom. ]

T ¹ and T ² each independently represent an oxygen atom or a sulfur atom, and may be the same or different, but are preferably the same.

The aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ^{31 to} R ³⁴ may be linear, branched or cyclic. Carbon number of a C1-C10 aliphatic hydrocarbon group becomes like this. Preferably it is 2-8, More preferably, it is 3-6. Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and an ethylhexyl group. (2-ethylhexyl group etc.), cyclopentyl group, cyclohexyl group, cyclohexyl alkyl group and the like.
Moreover, the hydrogen atom contained in a C1-C10 aliphatic hydrocarbon group is a hydroxyl group, a C1-C8 (preferably C1-C4) alkoxyl group, or a C1-C8 (preferably It may be substituted with a thioalkoxyl group having 1 to 4 carbon atoms. Examples of the substituted aliphatic hydrocarbon group include a hydroxyethyl group (such as 2-hydroxyethyl group), an ethoxyethyl group (such as 2-ethoxyethyl group), and an ethylhexyloxypropyl group (3- (2-ethylhexyloxy)). Propyl group, etc.) and methylthiopropyl group (3-methylthiopropyl group, etc.).

The aryl group having 6 to 20 carbon atoms in R ^{31 to} R ³⁴ may be unsubstituted and has a substituent such as an aliphatic hydrocarbon group, an alkoxyl group, a carboxyl group, a sulfo group, or a group containing an ester bond. You may do it. The carbon number of the aryl group is counted including the carbon number of the substituent, and preferably 6 to 10. Examples of the aryl group include a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 2-methoxyphenyl group, a 3-methoxyphenyl group, a 4-methoxyphenyl group, and a 2-sulfophenyl group. , 3-sulfophenyl group, 4-sulfophenyl group, and ethoxycarbonylphenyl group (such as 4- (COOC ₂ H ₅ ) Ph group).

The alkyl part of the aralkyl group having 7 to 20 carbon atoms in R ^{31 to} R ³⁴ may be linear, branched or cyclic. The carbon number of the aralkyl group is counted including the carbon number of the substituent, and is preferably 7 to 10. Examples of the aralkyl having 7 to 20 carbon atoms include a benzyl group and a phenethyl group.

The acyl group having 2 to 10 carbon atoms in R ^{31 to} R ³⁴ may be unsubstituted, or a substituent such as an aliphatic hydrocarbon group or an alkoxyl group may be bonded thereto. The carbon number of the acyl group is counted including the carbon number of the substituent, and the number is preferably 2 to 10. Examples of the acyl group include an acetyl group, a benzoyl group, a methoxybenzoyl group (such as a p-methoxybenzoyl group), and the like.

Aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ³⁵ to R ^{42 include} those similar to the case of R 31 ^{to R 34.} The hydrogen atom contained in the aliphatic hydrocarbon group of R ^{35 to} R ⁴² may be substituted with a halogen atom, and the halogen atom is preferably a fluorine atom. Specific examples of the aliphatic hydrocarbon group substituted with a halogen atom include a trifluoromethyl group.

The number of carbon atoms of the alkoxyl group having 1 to 8 carbon atoms in R ³⁵ to R ⁴² is preferably from 1 to 4. Examples of the alkoxyl group include methoxy group, ethoxy group, isopropoxy group, n-propoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group.

The N-position-substituted sulfamoyl group in R ^{35 to} R ⁴² is preferably, for example, an N-position-monosubstituted sulfamoyl group, and represented by —SO ₂ NHR ¹³ .
R ¹³ has an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 20 carbon atoms, and a substituent. Or an aralkyl group having 7 to 20 carbon atoms or an acyl group having 2 to 10 carbon atoms which may have a substituent.

The C1-C10 aliphatic hydrocarbon group for R ¹³ may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group does not include the carbon number of the substituent, and the number is preferably 6 to 10.
Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ¹³ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. , Methylbutyl group (1,1,3,3-tetramethylbutyl group etc.), methylhexyl group (1-methylhexyl group, 1,5-dimethylhexyl group etc.), ethylhexyl group (2-ethylhexyl group etc.), cyclopentyl Group, cyclohexyl group, methylcyclohexyl group (such as 2-methylcyclohexyl group) and cyclohexylalkyl group.

The C1-C10 aliphatic hydrocarbon group in R < ¹³ > may be substituted with a C1-C8 (preferably C1-C4) alkoxyl group, for example, a propoxypropyl group (3- (Isopropoxy) propyl group, etc.).

The aryl group having 6 to 20 carbon atoms in R ¹³ may be unsubstituted or may have a substituent such as an aliphatic hydrocarbon group or a hydroxyl group. The carbon number of the aryl group is counted including the carbon number of the substituent, and preferably 6 to 10. Examples of the aryl group include a phenyl group, a hydroxyphenyl group (such as a 4-hydroxyphenyl group), and a trifluoromethylphenyl group (such as a 4-trifluoromethylphenyl group).

The alkyl part of the aralkyl group having 7 to 20 carbon atoms in R ¹³ may be either linear or branched. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 10. Examples of the aralkyl group include phenylalkyl groups such as a benzyl group, a phenylpropyl group (such as 1-methyl-3-phenylpropyl group), and a phenylbutyl group (such as 3-amino-1-phenylbutyl group).

The acyl group having 2 to 10 carbon atoms in R ¹³ may be unsubstituted, and a hydrogen atom contained in the acyl group may be substituted with an aliphatic hydrocarbon group or an alkoxyl group. The carbon number of the acyl group is counted including the carbon number of the substituent, and the number is preferably 6 to 10. Examples of the acyl group include an acetyl group, a benzoyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group, and a methoxybenzoyl group (such as a p-methoxybenzoyl group).

  Examples of the N-substituted sulfamoyl group include groups represented by formulas (4) to (10).

  Examples of the barbituric acid azo dyes include compounds represented by the formulas (2-1) to (2-8), and preferably the formulas (2-1) and (2-3) to (2- 5), compounds represented by (2-7) and (2-8), and the like.

  The pyridone azo dye is not particularly limited, and a known substance can be used, but a dye represented by the formula (3) is preferably used.

[In Formula (3), Z is a halogen atom, the C1-C12 aliphatic hydrocarbon group which may have a substituent, a C1-C8 alkoxyl group, a hydroxyl group, a carboxyl group, carbamoyl. A phenyl group having one or two substituents selected from the group consisting of a group, a sulfo group, a sulfamoyl group, and an N-substituted sulfamoyl group, or a halogen atom and an optionally substituted carbon At least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, and an N-substituted sulfamoyl group. Represents a naphthyl group having 1 to 3 substituents.
R ²¹ represents a hydrogen atom, a linear, branched or cyclic C 1-10 aliphatic hydrocarbon group, carboxyl group or trifluoromethyl group.
R ²² represents a hydrogen atom, a cyano group, a carbamoyl group, an N-position-substituted carbamoyl group, a sulfamoyl group or a sulfo group.
R ²³ is a hydrogen atom, an optionally substituted linear, branched or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 6 carbon atoms. 30 aryl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted heterocyclic group having 3 to 20 carbon atoms, carbamoyl group, N-substituted carbamoyl Group, an optionally substituted alkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms, and a substituent. A C2-C20 acyl group, a C1-C30 aliphatic sulfonyl group which may have a substituent or a C6-C30 arylsulfonyl group which may have a substituent. . ]

In formula (3), the C1-C12 aliphatic hydrocarbon group in Z may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group includes all the carbon numbers of the substituents, and the number is usually 1 to 12, preferably 2 to 11. Examples of the aliphatic hydrocarbon group include an n-octyl group, a methylhexyl group (such as 1,5-dimethylhexyl group), an ethylhexyl group (such as 2-ethylhexyl group), a cyclooctyl group, and a methylcyclohexyl group (2, 2). -Dimethylcyclohexyl group and the like) and cyclohexylalkyl group. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an alkoxyl group having 1 to 8 carbon atoms or a carboxyl group. Examples of the aliphatic hydrocarbon group having a substituent include an alkoxypropyl group (such as 3- (2′-ethylhexyloxy) propyl group) and an 8- (carboxy) octyl group.
Examples of the alkoxyl group having 1 to 8 carbon atoms in Z include a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, and a tert-butoxy group. It is done.
Examples of the halogen atom in Z include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom.
The N-position-substituted sulfamoyl group in Z is represented by —SO ₂ N (R ²⁴ ) R ²⁵ .
R ²⁴ and R ²⁵ are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 16 carbon atoms, or an optionally substituted substituent having 6 to 20 carbon atoms. An aryl group, an optionally substituted aralkyl group having 7 to 20 carbon atoms, or an optionally substituted acyl group having 2 to 15 carbon atoms (wherein R ²⁴ and R ²⁵ are They are not hydrogen atoms at the same time).
The aliphatic hydrocarbon group having 1 to 16 carbon atoms may be linear, branched or cyclic, and the aliphatic hydrocarbon group preferably has 6 to 16 carbon atoms.

The aliphatic hydrocarbon group having 1 to 16 carbon atoms in R ²⁴ and R ²⁵ may be 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 usually 1 to 16, preferably 6 to 10. Examples of the aliphatic hydrocarbon group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, methylbutyl group (1,1,3, 3-tetramethylbutyl group), methylhexyl group (1,5-dimethylhexyl group etc.), ethylhexyl group (2-ethylhexyl group etc.), cyclopentyl group, cyclohexyl group, methylcyclohexyl group (2-methylcyclohexyl group etc.) And a cyclohexylalkyl group. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an alkoxyl group having 1 to 8 carbon atoms or a carboxyl group. Examples of the aliphatic hydrocarbon group having a substituent include a propoxypropyl group (such as 3- (isopropoxy) propyl group), a 2- (carboxy) ethyl group, a 3- (carboxy) ethyl group, and a 4-carboxyethyl group. Can be mentioned.

The aryl group having 6 to 20 carbon atoms in R ²⁴ and R ²⁵ may have a substituent such as an aliphatic hydrocarbon group or a hydroxyl group. Carbon number of an aryl group is counted including carbon number of a substituent, and is 6-20 normally, Preferably it is 6-10. The aryl group includes a phenyl group, a carboxyphenyl group (such as a 2-carboxyphenyl group and a 2,4-carboxyphenyl group), a hydroxyphenyl group (such as a 4-hydroxyphenyl group), and a trifluoromethylphenyl group (4-trifluoro). A methylphenyl group) and a methoxyphenyl group (4-methoxyphenyl group).

The alkyl part of the aralkyl group having 7 to 20 carbon atoms in R ²⁴ and R ²⁵ may be either linear or branched. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 10. Aralkyl includes benzyl group, phenylethyl group (2-phenylethyl group, 2- (4-hydroxyphenyl) ethyl group, etc.), phenylethylene group (2-phenylethylene group, etc.), phenylpropyl group (1-methyl- And phenylalkyl groups such as 3-phenylpropyl group and phenylbutyl group (3-amino-1-phenylbutyl group).

The acyl group having 2 to 15 carbon atoms in R ²⁴ and R ²⁵ may be unsubstituted or may have a substituent such as an aliphatic hydrocarbon group, an alkoxyl group, or a carboxyl group. Carbon number of an acyl group is counted including carbon number of a substituent, and the number is 2-15 normally, Preferably it is 6-10. As the acyl group, for example, acetyl group, benzoyl group, methoxybenzoyl group (p-methoxybenzoyl group etc.), carboxyacetyl group, 2-carboxypropionyl group, 3-carboxypropionyl group, 2-carboxybutyryl group, 3-carboxy Examples include butyryl group and 4-carboxybutyryl group.

R ²¹ represents a hydrogen atom, a linear, branched or cyclic C 1-10 aliphatic hydrocarbon group, carboxyl group or trifluoromethyl group.

The carbon number of the aliphatic hydrocarbon group having 1 to 10 carbon atoms in R ²¹ does not include the carbon number of the substituent. The carbon number is preferably 2 to 8, more preferably 3 to 6. Examples of the aliphatic hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a cyclopentyl group, and a cyclohexyl group.

R ²² represents a hydrogen atom, a cyano group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group or a sulfo group.

Examples of the N-position-substituted carbamoyl group for R ²² include —CON (R ²⁶ ) R ²⁷ . R ²⁶ and R ²⁷ are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an optionally substituted substituent having 6 to 20 carbon atoms. It represents an aryl group, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or an acyl group having 2 to 10 carbon atoms which may have a substituent.
The explanation and specific examples of the aliphatic hydrocarbon group, aryl group, aralkyl group and acyl group of R ²⁶ and R ²⁷ are the same as those of R ²⁴ and R ²⁵ described above. However, the acyl group may have a halogen atom. Examples of the acyl group having a halogen atom include a bromobenzoyl group (such as a p-bromobenzoyl group).

R ²³ is a hydrogen atom, an optionally substituted linear, branched or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 6 carbon atoms. 30 aryl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted heterocyclic group having 3 to 20 carbon atoms, carbamoyl group, N-substituted carbamoyl Group, an optionally substituted alkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms, and a substituent. A C2-C20 acyl group, a C1-C30 aliphatic sulfonyl group which may have a substituent, or a C6-C30 arylsulfonyl group which may have a substituent. .

Examples of the aliphatic hydrocarbon group for R ²³ include the same groups as the aliphatic hydrocarbon group for R ²¹ described above.

The aryl group in R ^23, the carbon number is usually 6 to 30, preferably 6 to 20, more preferably 6 to 16. Specific examples of the aryl group include a phenyl group, a 4-nitrophenyl group, a 2-nitrophenyl group, a 2-chlorophenyl group, a 2,4-dichlorophenyl group, a 2,4-dimethylphenyl group, and a 2-methylphenyl group. 4-methoxyphenyl group, 2-methoxyphenyl group, 2-methoxycarbonyl-4-nitrophenyl group, and the like.

The aralkyl group for R ²³ may be linear or branched, and the carbon number is preferably 7 to 10. Specific examples of aralkyl include phenylalkyl groups such as benzyl group, phenylpropyl group (such as 1-methyl-3-phenylpropyl group) and phenylbutyl group (such as 3-amino-1-phenylbutyl group). It is done.

The heterocyclic group having 3 to 20 carbon atoms in R ^23, may be saturated or unsaturated, carbon number, preferably from 3 to 20, more preferably 5 to 15. Specific examples of the heterocyclic group include pyrazole group, 1,2,4-triazole group, isothiazole group, benzoisothiazole group, thiazole group, benzothiazole group, oxazole group and 1,2,4-thiadiazole group. Etc. Furthermore, you may have a substituent.

The N-substituted carbamoyl group for R ²³ is the same as the N-substituted carbamoyl group described above for R ²² .

The alkyloxycarbonyl group for R ²³ may be unsubstituted or substituted, or may be cyclic. As carbon number of an alkyloxycarbonyl group, it is 2-20 normally, Preferably it is 2-16, More preferably, it is 2-10. Examples of the alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group.

The aryloxycarbonyl group for R ²³ may be unsubstituted or substituted, and the number of carbon atoms is usually 7 to 30, preferably 7 to 20, and more preferably 7 to 16. It is. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a 4-methylphenoxycarbonyl group.

The acyl group for R ²³ may be an aliphatic carbonyl group or an arylcarbonyl group, may be saturated or unsaturated, may be cyclic, and may further have a substituent. Good. As carbon number, it is 2-20 normally, Preferably it is 2-15, More preferably, it is 2-10. Examples of the acyl group include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, and benzoyl group.

The aliphatic sulfonyl group for R ²³ may be saturated, unsaturated, or cyclic. As carbon number, it is 1-30 normally, Preferably it is 1-20, More preferably, it is 1-16. Examples of the aliphatic sulfonyl group include a methanesulfonyl group, a butanesulfonyl group, a methoxymethanesulfonyl group, a methoxyethanesulfonyl group, and an ethoxyethanesulfonyl group.

The arylsulfonyl group for R ²³ may have a substituent, and the number of carbon atoms is usually 6 to 30, preferably 6 to 20, and more preferably 6 to 18. Examples of the arylsulfonyl group include benzenesulfonyl and toluenesulfonyl groups.

  Examples of the pyridone azo dye include the following compounds, and compounds represented by formulas (3-1) to (3-9) are preferable.

The compound represented by Formula (3) may form any of an ammonium salt, a lithium salt, a sodium salt, or a potassium salt.
The compound represented by the formula (3) may form a dimer or higher multimer.
The multimer in the formula (3) is a compound having a group derived from two or more compounds represented by the formula (3) in one molecule, specifically, the formula (3-12) -The compound etc. which are represented by Formula (3-15) are mentioned.

  The pyrazolone azo dye is not particularly limited, and a known substance can be used. For example, pyrazolone azo described in JP 2006-276512 A, JP 2005-263926 A, and JP 2006-015669 A, for example. Series dyes can be used.

  Specifically, C.I. I. Acid Yellow 17, C.I. I. Solvent Orange 56 and C.I. I. Examples thereof include Solvent Yellow 82 and compounds represented by Formulas (11) to (14).

  The quinophthalone dye is not particularly limited, and a known substance can be used. For example, quinophthalone dyes described in JP-A-5-39269, JP-A-6-220339, JP-A-8-171201, and the like. Is mentioned.

  Specifically, C.I. I. Solvent Yellow 33, C.I. I. Disperse Yellow 54, C.I. I. Disperse yellow 64 and compounds represented by formulas (15) to (19) are exemplified.

The cyanine dye is not particularly limited, and a known substance can be used.
Examples thereof include cyanine dyes described in JP 2005-194509 A, JP 2007-131818 A, JP 2005-297406 A, and the like.
Specific examples include compounds represented by formulas (20) to (23).

  Furthermore, the (A) colorant may contain other dyes and pigments as long as the effects of the present invention are not impaired.

  Examples of the dye include compounds classified as dyes in the color index (published by The Society of Dyers and Colorists) and known dyes described in dyeing notes (color dyeing companies). C. I. Solvent Yellow 4 (hereinafter, the description of CI Solvent Yellow is omitted, and only the number is described. Other dye types and hues are also omitted) 14, 15, 23 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, C.I. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, C.I. I. Solvent orange 2, 7, 11, 15, 26, 45, 56 etc. are mentioned. In addition, C.I. I. As an acid dye, C.I. I. Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 and derivatives thereof. Can be mentioned. In addition, C.I. I. C. as a direct dye I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 136, 138, 141, C.I. I. Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107, C.I. I. Examples include direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82. Furthermore, C.I. I. As a modern dye, C.I. I. Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65, C.I. I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, C.I. I. Modern green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53 and the like can be mentioned. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162, Acid Green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, C.I. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251,23,25 29, 34, 40, 42, 72, 76, 99, 111, 112, 114, 116, 163, 243 and derivatives thereof.

  Examples of the pigment include compounds classified as pigments by Color Index (published by The Society of Dyers and Colorists). 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, 214 and the like, C.I. I. And green pigments such as C.I. Pigment Green 7 and 36. I. Pigment yellow 138, 139, 150, C.I. I. Pigment Green 7, 36.

  The pigment can be obtained as a dispersion in which the pigment is uniformly dispersed in the solution by carrying out a dispersion treatment by containing a pigment dispersant as necessary.

  Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, and polyamine surfactants. The pigment dispersant may be used alone or in combination of two or more.

  Examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid-modified polyesters, tertiary amine-modified polyurethanes, polyethyleneimines, etc. In addition, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoei Chemical Co., Ltd.), F-Top (manufactured by Tochem Products), MegaFuck (manufactured by Dainippon Ink Chemical Co., Ltd.) , FLORARD (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by EFKA CHEMICALS Co., Ltd.), PB821 (manufactured by Ajinomoto Co., Inc.) And Disperbic (by Big Chemie)

  When using a dispersing agent, the usage-amount is a mass fraction with respect to 100 mass% of pigments, Preferably it is 0.1-100 mass%, More preferably, it is 5-50 mass%.

  The average particle diameter of the pigment in the pigment dispersion is 10 to 150 nm, preferably 15 to 120 nm, and more preferably 20 to 100 nm.

(A) Content of a coloring agent is 10-95 mass% by mass fraction with respect to solid content of a colored curable composition, Preferably it is 15-90 mass%, More preferably, it is 20-88 mass%. is there.
In this specification, solid content means the total amount of the component except the solvent contained in a colored curable composition.

The content of the yellow dye used in the colored curable composition of the present invention is 0.5 to 100% by mass, preferably 1 to 100% by mass, and more preferably 1% to 100% by mass with respect to all yellow pigments. Preferably it is 2-100 mass%.
Moreover, content of the yellow dye used for the colored curable composition of this invention is 0.5-99.5 mass% by mass fraction with respect to all the pigment | dyes of (A) colorant whole quantity yellow, Preferably Is 1 to 99 mass%, more preferably 2 to 98 mass%.
It is preferable that the content of the yellow dye is in the above-mentioned range because the brightness and contrast when used as a color filter tend to be high.

  (B) As a polymeric compound, the monomer or oligomer which hardens | cures with a heat | fever or light, or both can be used, Furthermore, you may use these together. A known substance can be used as the monomer or oligomer.

  Specific examples of monomers include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate derivatives having a carboxyl group, ethylene oxide glycerin triacrylate, ethylene Oxidized trimethylolpropane triacrylate, propylene oxided glycerin triacrylate and the like can be mentioned.

  Examples of the oligomer include epoxy acrylate, urethane acrylate, polyester acrylate, and the like. For example, the current state and prospects of UV / EB curing technology (CMC Publishing) pages 18 to 20 can be used.

  (B) Content of a polymeric compound is a mass fraction with respect to solid content of a colored curable composition, Preferably it is 5-90 mass%, More preferably, it is 10-85 mass%, Most preferably It is 12-80 mass%.

  The colored curable composition of the present invention may further contain (C) a binder resin. (C) The binder resin preferably contains a repeating unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the repeating unit derived from (meth) acrylic acid is a molar fraction in all repeating units constituting the binder resin, preferably 10 mol% or more and 40 mol% or less, more preferably 13 mol% or more and 35 mol. % Or less.

  Examples of other monomers that lead to the repeating unit of the binder resin other than the repeating unit derived from (meth) acrylic acid include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, and unsaturated compounds. Carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl groups and mono Examples thereof include macromonomers having a methacryloyl group, and examples thereof include a repeating unit represented by the formula (24) and a repeating unit represented by the formula (25).

[In Formula (24) and Formula (25), R ⁵¹ and R ⁵² each independently represent a hydrogen atom or a saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms. ]

R ⁵¹ and R ⁵² include a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 2-ethylpropyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group 1-ethylbutyl group, 2-ethylbutyl group, 3-ethylbutyl group, etc., preferably hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group or tert. -A butyl group is mentioned, More preferably, a hydrogen atom, a methyl group, or an ethyl group is mentioned.

(C) Specific examples of the binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, methacrylic acid / Styrene / benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / repeating unit represented by formula (25) (wherein, in formula (25), R ³¹ represents a methyl group, and R ³² represents hydrogen Represents an atom.) / N-benzylmaleimide / benzyl methacrylate copolymer, methacrylic acid / repeating unit represented by formula (25) (wherein, in formula (25), R ⁵¹ represents a methyl group, R ⁵² represents a hydrogen atom.) / N-cyclohexylmaleimide / benzyl methacrylate Rate copolymer, methacrylic acid / repeating unit represented by formula (24) (wherein, in formula (24), R ⁵¹ represents a methyl group and R ⁵² represents a hydrogen atom) / benzyl methacrylate. A copolymer, a repeating unit represented by formula (24) (wherein, in formula (24), R ⁵¹ represents a methyl group and R ⁵² represents a hydrogen atom) / benzyl methacrylate copolymer, Methacrylic acid / Repeating unit represented by formula (25) (wherein, in formula (25), R ⁵¹ represents a methyl group and R ⁵² represents a hydrogen atom) / styrene / dicyclopentanyl methacrylate A copolymer or the like is preferred.

(C) The acid value of the binder resin is preferably 30 to 150, more preferably 35 to 135, and particularly preferably 40 to 120.
Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and can usually be obtained by titration with an aqueous potassium hydroxide solution. .

  (C) Content of binder resin is a mass fraction with respect to solid content of a colored curable composition, Preferably it is 5-40 mass%, More preferably, it is 8-35 mass%, Most preferably 10 to 32% by mass.

(C) Binder resin having a repeating unit represented by the formula (24), for example, a repeating unit derived from methacrylic acid / a repeating unit represented by the formula (24) (here, in the formula (24), R ⁵¹ represents a methyl group, and R ⁵² represents a hydrogen atom.) / A copolymer containing a repeating unit derived from benzyl methacrylate is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer. Thus, the obtained two-component polymer can be obtained by reacting the compound represented by the formula (26) (here, R ⁵³ represents a hydrogen atom in the formula (26)).

Repeating units represented by repeating units / expressions derived from methacrylic acid (25) (However, in this case, the formula ^{(25), R 51} represents a methyl ^{group, R 52} represents a hydrogen atom.) / Benzyl methacrylate A copolymer comprising a repeating unit derived from a dicyclopentanyl methacrylate and a copolymer comprising a repeating unit derived from dicyclopentanyl methacrylate is obtained by reacting a copolymer of benzyl methacrylate, methacrylic acid and dicyclopentanyl methacrylate with glycidyl methacrylate. Can do.

  (C) The weight average molecular weight in terms of polystyrene of the binder resin is preferably 5,000 to 100,000, more preferably 6,000 to 80,000, and particularly preferably 7,000 to 60,000. . When the molecular weight is within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved, which is preferable.

  The colored curable composition of the present invention may further contain (D) a polymerization initiator. Examples of the polymerization initiator include triazine compounds, acetophenone compounds, biimidazole compounds, active radical generators, and acid generators.

  Examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 -[2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl]- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl)- -[2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine are preferable, 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- (4-methoxystyryl) -1,3,5-triazine or 2,4-bis (trichloromethyl) -6-piperonyl-1,3, 5-triazine is mentioned, More preferably, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine is mentioned.

  Examples of acetophenone compounds include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one Benzyl dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- Preferred examples include [4- (1-methylvinyl) phenyl] propan-1-one oligomers. Or 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- ( 4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, more preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1 -One or 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butan-1-one.

  Examples of biimidazole compounds include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2-chlorophenyl) -4,4 ′. , 5,5′-tetra (4-carboethoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (4-bromophenyl) biimidazole, 2, , 2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (2,4-dichlorophenyl) biimidazole, 2,2′-bis (2-bromophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 , 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′- Bis (2,6-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole Examples include imidazole and 2,2′-bis (2-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, preferably 2,2′-bis (2-chlorophenyl) -4, Examples thereof include 4 ′, 5,5′-tetraphenylbiimidazole or 2,2′-bis (2,3-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole.

  An active radical generator generates an active radical when irradiated with light. Examples of the active radical generator include benzoin compounds, benzophenone compounds, thioxanthone compounds, and oxime compounds.

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

  Examples of the benzophenone compounds include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxy). Carbonyl) benzophenone and 2,4,6-trimethylbenzophenone.

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

  Examples of oxime compounds include O-acyl oxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O-benzoate. 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1-one oxime-O-acetate and 1 -(4-Phenylsulfanyl-phenyl) -butan-1-one oxime-O-acetate and the like.

  As active radical generators other than the above, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphor Examples include quinone, methyl phenylglyoxylate, and titanocene compounds.

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium-p-toluenesulfonate, 4-acetoxyphenylmethylbenzyl. Onium salts such as sulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium-p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples include benzoin tosylate.

  In addition, among the above-mentioned compounds, there are compounds that generate an acid simultaneously with an active radical. For example, a triazine polymerization initiator is also used as an acid generator.

  (D) Content of a polymerization initiator is a mass fraction with respect to the total amount of (B) polymeric compound and (C) binder resin, Preferably it is 0.1-25 mass%, More preferably, it is 1 ˜20 mass%.

The colored curable composition of the present invention may further contain (E) a polymerization initiation assistant. (E) A polymerization initiation assistant is a compound that is usually used in combination with (D) a polymerization initiator, and is used to accelerate the polymerization of a polymerizable compound that has been polymerized by (D) polymerization initiator. .
(E) Examples of polymerization initiation assistants include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminoethyl benzoate. 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethyl) Methylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred.

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

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

  (E) The polymerization initiation assistant may be used alone or in combination of two or more. Moreover, as (E) polymerization start adjuvant, a commercially available thing can also be used, and as a commercially available (E) polymerization start adjuvant, it is EAB-F (Hodogaya Chemical Co., Ltd. product) by a brand name, for example. , 4,4′-bis (diethylamino) benzophenone) and the like.

  Examples of combinations of (D) polymerization initiator / (E) polymerization initiation assistant include 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine / 4,4′-bis ( Diethylamino) benzophenone, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) Benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4,4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2 -Methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4'- Sus (diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one Oligomer / 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) And benzophenone, preferably 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, 2,4-bis (trichloromethyl) ) -6-piperonyl-1,3,5-triazine / 4,4′-bis (diethylamino) benzophenone, 2- (4-methylbenzyl) -2-dimethylamino-1- (4-morpholinophenyl) butane-1 -On / 4,4'-bis (diethylamino) benzophenone.

  When (E) a polymerization initiation assistant is used, the amount used is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 1 part by mass of (D) polymerization initiator.

  The colored curable composition of the present invention may further contain (F) a solvent. Examples of the solvent (F) include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides, and the like.

  Examples of ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol. Monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate Methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether acetate, methoxybutyl acetate, methoxy pentyl acetate, anisole, and the like phenetol and methyl anisole.

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

  Examples of ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and 4-hydroxy-4-methyl-2 pentanone. Is mentioned.

  Examples of alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, diacetone alcohol, and glycerin.

  Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate , Methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, 2-metho Methyl cypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.

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

Examples of other solvents include N-methylpyrrolidone and dimethyl sulfoxide.
(F) You may use a solvent individually or in combination of 2 or more types, respectively.

  (F) As a solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate or diacetone alcohol is preferable.

  (F) Content of a solvent is a mass fraction with respect to a colored curable composition, Preferably it is 70-90 mass%, More preferably, it is 75-88 mass%.

  The colored curable composition of the present invention may further contain (G) a surfactant. Examples of the surfactant (G) include silicone surfactants, fluorine surfactants, and silicone surfactants having a fluorine atom.

  Examples of the silicone surfactant include a surfactant having a siloxane bond. Specifically, it is the Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (manufactured by Torresilicone), KP321, KP322, KP323 under the trade names. , KP324, KP326, KP340, KP341 (made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (made by GE Toshiba Silicone Co., Ltd.).

  Examples of the fluorosurfactant include a surfactant having a fluorocarbon chain. Specifically, under the product names Florard FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck F142D, F171, F172, F173, F177, F183, F470, F475, and R30 ( Dainippon Ink & Chemicals Co., Ltd.), EFTOP EF301, EF303, EF351, EF352 (made by Shin-Akita Kasei), Surflon S381, S382, SC101, SC105 (made by Asahi Glass Co., Ltd.) ), E5844 (manufactured by Daikin Fine Chemical Laboratory), BM-1000, BM-1100 (manufactured by BM Chemie), and the like.

Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specific examples include Megafax R08, BL20, F475, F477, F443 (Dainippon Ink Chemical Co., Ltd.).
Surfactants may be used alone or in combination of two or more.

  The colored curable composition of the present invention may contain an organic acid having a molecular weight of 1,000 or less. As an organic acid, the organic acid disclosed by Unexamined-Japanese-Patent No. 5-343631 is mentioned, for example. Specifically, malonic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, citraconic acid, itaconic acid, mesaconic acid, fumaric acid, phthalic acid, acrylic acid and A methacrylic acid is mentioned, Preferably malonic acid, an oxalic acid, a fumaric acid, or a phthalic acid is mentioned. By containing an organic acid having a molecular weight of 1,000 or less, the residue tends to be even better, which is preferable.

  The colored curable composition of the present invention further includes a filler, (C) a polymer compound other than the binder resin, an adhesion promoter, an antioxidant, an ultraviolet absorber, an aggregation inhibitor, an organic amine compound, and (H) curing. An additive such as an agent may be contained.

  Examples of the filler include fine particles such as glass and alumina.

  Examples of the polymer compound other than (C) the binder resin include polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate.

  Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-amino). Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Examples include methoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.

  Examples of the antioxidant include 4,4′-thio-bis (6-tert-butyl-3-methylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-). Hydroxyphenyl) propionate], 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], pentaerythrityl-tetrakis [3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6- Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, 2,6-di-tert-butyl-4-methyl Phenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 4,4'-thio-bis (3-methyl-6- tert-butylphenol), 4,4′-butylidene-bis (3-methyl-6-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane and Examples include 1,3,5-tris (4-hydroxybenzyl) benzene and tetrakis [methylene-3- (3,5′-di-tert-butyl-4′-hydroxyphenylpropionate)] methane.

Examples of the ultraviolet absorber include benzotriazoles such as 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole;
Benzophenone series such as 2-hydroxy-4-octyloxybenzophenone;
Benzoate UV absorbers such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate;
Examples include triazine ultraviolet absorbers such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Examples of the aggregation inhibitor include sodium polyacrylate.

Examples of the organic amine compound include n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine. Monoalkylamines such as n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine;
Monocycloalkylamines such as cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine;
Methylethylamine, diethylamine, methyl-n-propylamine, ethyl-n-propylamine, di-n-propylamine, diisopropylamine, di-n-butylamine, diisobutylamine, di-sec-butylamine, di-tert-butylamine, Dialkylamines such as di-n-pentylamine and di-n-hexylamine;
Monoalkylmonocycloalkylamines such as methylcyclohexylamine and ethylcyclohexylamine;
Dicycloalkylamines such as dicyclohexylamine;
Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl-n-propylamine, diethyl-n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, triisopropylamine, tri-n -Trialkylamines such as butylamine, triisobutylamine, tri-sec-butylamine, tri-tert-butylamine, tri-n-pentylamine, tri-n-hexylamine;
Dialkylmonocycloalkylamines such as dimethylcyclohexylamine and diethylcyclohexylamine;
Monoalkyldicycloalkylamines such as methyldicyclohexylamine, ethyldicyclohexylamine, tricyclohexylamine;
Monoalkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, and 6-amino-1-hexanol Kind;
Monocycloalkanolamines such as 4-amino-1-cyclohexanol;
Dialkanolamines such as diethanolamine, di-n-propanolamine, diisopropanolamine, di-n-butanolamine, diisobutanolamine, di-n-pentanolamine, di-n-hexanolamine;
Dicycloalkanolamines such as di (4-cyclohexanol) amine;
Trialkanolamines such as triethanolamine, tri-n-propanolamine, triisopropanolamine, tri-n-butanolamine, triisobutanolamine, tri-n-pentanolamine, tri-n-hexanolamine;
Tricycloalkanolamines such as tri (4-cyclohexanol) amine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 , 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, aminoalkanediols such as 2-diethylamino-1,3-propanediol;
Aminocycloalkanediols such as 4-amino-1,2-cyclohexanediol and 4-amino-1,3-cyclohexanediol;
Amino group-containing cycloalkanone methanols such as 1-aminocyclopentanone methanol and 4-aminocyclopentanone methanol;
Amino group-containing cycloalkanemethanols such as 1-aminocyclohexanone methanol, 4-aminocyclohexanone methanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4-diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisoacetic acid, 3-aminoisoacetic acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, 4-aminocyclohexanecarboxylic acid;
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, p-isopropylaniline, pn-butylaniline, p-tert-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples include aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.
By adding the organic amine compound, a residue is not generated on the unexposed substrate during development, and a pixel having excellent adhesion to the substrate can be provided.

  (H) As a curing agent, for example, (C) a compound capable of reacting with a carboxyl group in the binder resin to crosslink the (C) binder resin when heated, polymerizing alone to cure the colored pattern The compound etc. which can be made to be mentioned are mentioned, For example, an epoxy compound, an oxetane compound, etc. are mentioned, An oxetane compound is used preferably.

  Here, as the epoxy compound, for example, bisphenol A type epoxy resin, hydrogenated bisphenol A type epoxy resin, bisphenol F type epoxy resin, hydrogenated bisphenol F type epoxy resin, novolac type epoxy resin, other aromatic epoxy resins , Alicyclic epoxy resins, heterocyclic epoxy resins, glycidyl ester resins, glycidyl amine resins, epoxy resins such as epoxidized oil, brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof Aliphatic, alicyclic or aromatic epoxy compounds, epoxidized products of butadiene (co) polymers, epoxidized products of isoprene (co) polymers, (co) polymers of glycidyl (meth) acrylates, triglycidyl Examples include isocyanurate.

  Examples of the oxetane compound include carbonate bisoxetane, xylylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, and cyclohexanedicarboxylate bisoxetane.

  When an epoxy compound, an oxetane compound, or the like is contained as a curing agent, it preferably contains a compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. Examples of the compound include polyvalent carboxylic acids and polyvalent carboxylic acid anhydrides.

Examples of the polyvalent carboxylic acids include phthalic acid, 3,4-dimethylphthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid, trimellitic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 3,3 Aromatic polycarboxylic acids such as', 4,4'-benzophenonetetracarboxylic acid;
Aliphatic polycarboxylic acids such as succinic acid, glutaric acid, adipic acid, 1,2,3,4-butanetetracarboxylic acid, maleic acid, fumaric acid, itaconic acid;
Hexahydrophthalic acid, 3,4-dimethyltetrahydrophthalic acid, hexahydroisophthalic acid, hexahydroterephthalic acid, 1,2,4-cyclopentanetricarboxylic acid, 1,2,4-cyclohexanetricarboxylic acid, cyclopentanetetracarboxylic acid And alicyclic polyvalent carboxylic acids such as 1,2,4,5-cyclohexanetetracarboxylic acid.

Examples of the polyvalent carboxylic acid anhydrides include aromatic polyvalent carboxylic acids such as phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, and 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride. Acid anhydrides;
Aliphatic polycarboxylic anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarballylic anhydride, maleic anhydride, 1,2,3,4-butanetetracarboxylic dianhydride Kind;
Hexahydrophthalic anhydride, 3,4-dimethyltetrahydrophthalic anhydride, 1,2,4-cyclopentanetricarboxylic anhydride, 1,2,4-cyclohexanetricarboxylic anhydride, cyclopentanetetracarboxylic dianhydride Alicyclic polycarboxylic acid anhydrides such as 1,2,4,5-cyclohexanetetracarboxylic dianhydride, hymic anhydride, and nadic anhydride;
Examples thereof include ester bond-containing carboxylic acid anhydrides such as ethylene glycol bistrimellitic acid and glycerin tristrimellitic anhydride.

  As carboxylic acid anhydrides, those commercially available as epoxy resin curing agents may be used. Examples of the epoxy resin curing agent include ADEKA HARDNER EH-700 (manufactured by Asahi Denka Kogyo Co., Ltd.), RIKACID HH, MH-700 (both manufactured by Shin Nippon Rika Co., Ltd.) and the like.

  A hardening | curing agent may be used individually or in combination of 2 or more types.

  As a method of forming a color filter pattern using the colored curable composition of the present invention, for example, the colored curable composition of the present invention is first formed on a substrate or another resin layer (for example, on the substrate). Applied to another colored curable composition layer, etc.), removing a volatile component such as a solvent to form a colored layer, exposing the colored layer through a photomask, developing, and In response to this, the so-called photolithography method or a colored curable composition is applied to a substrate or another resin layer using an inkjet apparatus, and a volatile component such as a solvent is removed to form a colored layer. And an ink jet method for curing by at least one of the above.

  The color filter thus obtained is preferably used for a liquid crystal display device.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Synthesis example 1
<Synthesis of Colorant (A-1)>
In a 1000 mL four-necked flask, 106.4 g (400 mmol) of tetrachlorophthalonitrile, 14.3 g (105 mmol) of zinc chloride, 84.0 g (3000 mmol) of urea, 19.9 g of ammonium molybdate tetrahydrate ( 30 mmol) and 100 mL of methylnaphthalene were charged and heated at 200 ° C. for 6 hours in a nitrogen atmosphere. The precipitate was collected by filtration, washed with methanol and then with hot water at 60 ° C., and then dried under reduced pressure at 60 ° C. to obtain 29.7 g of hexadecachlorozinc phthalocyanine.
Next, 90.7 g (680 mmol) of anhydrous aluminum chloride and 11.7 g (200 mmol) of sodium chloride were mixed at 40 ° C. in a 500 mL four-necked flask, and 25.0 g (22 mmol) of hexadecachlorozinc phthalocyanine was mixed. Then, 60.0 g (751 mmol) of bromine was added dropwise with stirring, and the temperature was raised to 130 ° C. over 20 hours and held for 1 hour. The obtained reaction product was taken out into water, and a chlorinated brominated phthalocyanine crude pigment was precipitated. This crude chlorinated brominated phthalocyanine pigment slurry was filtered, washed with warm water at 60 ° C., then washed with 1% aqueous sodium hydrogen sulfate solution, further washed with warm water at 60 ° C., and dried under reduced pressure at 60 ° C. .3 g of purified chlorinated brominated phthalocyanine crude pigment was obtained.
Next, 20 g of the chlorinated brominated phthalocyanine crude pigment obtained by the above operation, 60 g of sodium chloride and 20 g of diethylene glycol were charged into a kneader, ground at 90 ° C. for 5 hours, taken out into 100 parts by weight of an 80 ° C. aqueous solution, and stirred for 30 minutes. Thereafter, filtration, washing with hot water at 60 ° C., drying under reduced pressure at 60 ° C., and pulverization were performed to obtain 12.8 g of a chlorinated brominated zinc phthalocyanine pigment.
As a result of analyzing the obtained chlorinated brominated phthalocyanine pigment by flask combustion treatment ion chromatography, the ratio of substituents on the zinc phthalocyanine skeleton was bromine 14.6, chlorine 1.4, and hydrogen 0. .

Synthesis example 2
<Synthesis of Colorant (A-2)>
In a 1000 mL four-necked flask, 89.1 g (660 mmol) of sulfuryl chloride, 90.7 g (680 mmol) of anhydrous aluminum chloride and 12.3 g (210 mmol) of sodium chloride were mixed at 40 ° C. and 25.0 g of zinc phthalocyanine was mixed. (43.3 mmol) was added and stirred, and then 60.0 g (751 mmol) of bromine was added dropwise with stirring, and the temperature was raised to 130 ° C. over 20 hours and held for 1 hour. The obtained reaction product was taken out into water, and a chlorinated brominated phthalocyanine crude pigment was precipitated. The chlorinated brominated phthalocyanine crude pigment slurry was filtered, then washed with warm water at 60 ° C., then washed with 1% aqueous sodium hydrogen sulfate solution, further washed with warm water at 60 ° C., and then dried under reduced pressure at 60 ° C. 0.5 g of purified chlorinated brominated phthalocyanine crude pigment was obtained.
Next, 20 g of the chlorinated brominated phthalocyanine crude pigment obtained by the above operation, 60 g of sodium chloride and 20 g of diethylene glycol were charged into a kneader, ground at 90 ° C. for 5 hours, taken out into 100 parts by weight of an 80 ° C. aqueous solution, and stirred for 30 minutes. Thereafter, filtration, washing with hot water at 60 ° C., drying under reduced pressure at 60 ° C., and pulverization were performed to obtain 14.3 g of a chlorinated brominated zinc phthalocyanine pigment.
As a result of analyzing the obtained chlorinated brominated phthalocyanine pigment by flask combustion treatment ion chromatography, the ratio of substituents on the zinc phthalocyanine skeleton was as follows: bromine 13.4, chlorine 2.2, hydrogen 0.4 It was.

Synthesis example 3
<Synthesis of Colorant (A-3)>
Synthesis of Barbituric Acid Azo Dye Represented by Formula (2-4) 300 g of water was added to 30 g (61 mmol) of 2,2′-benzidinedisulfonic acid (containing 30% water) represented by Formula (27) Thereafter, the pH was adjusted to 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were performed under ice cooling. 12.6 g (183 mmol) of sodium nitrite was added and stirred for 30 minutes. After adding 38.1 g of 35% hydrochloric acid little by little to give a brown solution, the mixture was stirred for 2 hours. An aqueous solution in which 5.3 g (61 mmol) of amidosulfuric acid was dissolved in 57.4 g of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

  After adding 372 g of water to 18.6 g (146 mmol) of N, N′-dimethylbarbituric acid represented by the formula (28), the pH was adjusted to 8-9 with 30% aqueous sodium hydroxide solution under ice cooling.

  The following operations were performed under ice cooling. The aqueous barbiturate aqueous solution was stirred to give a colorless solution, and then a suspension containing a diazonium salt was added dropwise with a pump while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 15 g (21 mmol, yield 34%) of the azo compound represented by the formula (29).

  A flask equipped with a condenser and a stirrer is charged with 5 g (7 mmol) of the azo compound represented by the formula (29), 50 g of chloroform, and 2 g (3 mmol) of N, N-dimethylformamide, and is stirred at 20 ° C. or lower. While maintaining the temperature, 6 g (54 mmol) of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., maintained at the same temperature for 5 hours for reaction, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 3 g (20 mmol) of 3-aminophenylbutane and 10 g (103 mmol) of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixed liquid of 29 g of acetic acid and 300 g of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 6 g (6 mmol, yield 78%) of the azo compound represented by the formula (7-4).

The azo compound obtained in this example was subjected to LC-MS analysis under the following conditions.
Apparatus: Agilent 1100 (manufactured by Agilent Technology)
Detector; UV detector; 254 nm
Column; Sumipax ODS (manufactured by Sumika Chemical Analysis Co., Ltd.)
Elution solvent: Solvent system in which 0.1% of trifluoromethylacetic acid was added to water-acetonitrile mixed solvent The content of each azo compound was calculated from the peak area. As a result, the azo compound represented by formula (7-4) was detected as a compound having a molecular weight of 940, and the area percentage value with respect to the total peak area was 98%.

Synthesis example 4
<Synthesis of Colorant (A-4)>
Synthesis of Pyridoneazo Dye Represented by Formula (3-12) After adding 3000 g of water to 100 g (203 mmol) of 2,2′-benzidinedisulfonic acid (containing 30% water) represented by Formula (27), Under ice cooling, the pH was adjusted to 7-8 with a 30% aqueous sodium hydroxide solution. The following operations were performed under ice cooling. 56 g (812 mmol) of sodium nitrite was added and stirred for 30 minutes. After adding 150 g of 35% hydrochloric acid little by little to make a brown solution, the mixture was stirred for 2 hours. An aqueous solution in which 38 g (406 mmol) of amidosulfuric acid was dissolved in 380 g of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.
After adding 1000 g of water to 76 g (426 mmol) of 1-ethyl-3-cyano-4-methyl-6-hydroxypyrid-2-one represented by the formula (30), 30% hydroxylation was performed under ice cooling. The pH was adjusted to 8-9 with an aqueous sodium solution.

  The following operations were performed under ice cooling. The aqueous alkaline solution of pyridones was stirred to give a colorless solution, and then a suspension containing a diazonium salt was added dropwise with a pump while adjusting the pH to 8 to 9 with a 30% aqueous sodium hydroxide solution. After completion of dropping, the mixture was further stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried at 60 ° C. under reduced pressure to obtain 137 g (204 mmol, yield 100%) of the azo compound represented by the formula (31).

  In a flask equipped with a condenser and a stirrer, 5 g (7 mmol) of the azo compound represented by the formula (31) obtained by the above operation, 50 g of chloroform and 2.4 g (33 mmol) of N, N-dimethylformamide. Then, 7 g (59 mmol) of thionyl chloride was added dropwise while maintaining the temperature at 20 ° C. or lower with stirring. After completion of the dropwise addition, the temperature was raised to 50 ° C., maintained at the same temperature for 5 hours for reaction, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 4 g (30 mmol) of 1,5-dimethylhexylamine and 12 g (119 mmol) of triethylamine was added dropwise. Thereafter, the reaction was carried out by stirring overnight at the same temperature. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixed liquid of 29 g of acetic acid and 300 g of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C. to obtain 6 g (6 mmol, yield 80%) of the azo compound represented by the formula (3-12).

  When the same structural analysis as described above was performed on the azo compound obtained in this example, the azo compound represented by the formula (3-12) was detected as a compound having a molecular weight of 944, and the area relative to the total peak area. The percentage value was 58.3%. Furthermore, the monosulfonamidated azo compound represented by the formula (40) was detected as a compound having a molecular weight of 833, and the area percentage value with respect to the total peak area was 30.1%.

Synthesis example 5
<Synthesis of Resin (C-1)>
333 g of propylene glycol monomethyl ether acetate was introduced into a 1000 ml flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and 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 temperature of the solution in the flask was raised to 100 ° C., and then 22.0 g (0.10 mol) of dicyclopentanyl methacrylate (FA-513M; manufactured by Hitachi Chemical Co., Ltd.), 70.5 g (0 mol) of benzyl methacrylate. .40 mol), 43.0 g (0.5 mol) of methacrylic acid, 3.6 g of azobisisobutyronitrile and 164 g of propylene glycol monomethyl ether acetate were added dropwise to the flask using a dropping funnel over 2 hours. After completion of the dropwise addition, stirring was further continued at 100 ° C. for 5 hours.

  After the stirring was completed, air was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was changed to air, and then 35.5 g of glycidyl methacrylate [0.25 mol (moles relative to methacrylic acid used in this reaction). 50% by mole)), 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a solution containing the resin (C-1). Obtained (solid content: 38.7% by mass, acid value: 82 mgKOH / g).

Here, the acid value is a value measured as an amount (mg) of potassium hydroxide necessary to neutralize 1 g of a polymer having an acid group such as carboxylic acid, and is usually a potassium hydroxide aqueous solution having a known concentration. It is calculated | required by titrating using.
The obtained resin (C-1) had a weight average molecular weight in terms of polystyrene of 9,800.

The measurement of the weight average molecular weight in terms of polystyrene of the (C-1) binder resin was performed using the GPC method under the following conditions.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent; THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Standard material for calibration; TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)

Synthesis Example 6
<Synthesis of Resin (C-2)>
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel and nitrogen inlet 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 temperature of the solution in the flask was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, monomethacrylate having a tricyclodecane skeleton (Hitachi Chemical Co., Ltd.) ) FA-513M) 22.0 g (0.10 mol) and propylene glycol monomethyl ether acetate 136 g of a mixture of 2,2′-azobisisobutyronitrile added thereto was added dropwise, and further 100 Stirring was continued at ° C.
After completion of the stirring, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0 .9 g and hydroquinone 0.145 g were charged into the flask and reacted at 110 ° C. to obtain a solution containing the resin (C-2) (solid content 28.9% by mass, acid value 79 mgKOH / g).
The weight average molecular weight in terms of polystyrene was measured in the same manner as for the resin (C-1). The weight average molecular weight in terms of polystyrene of the resin (C-2) was 3.0 × 10 ⁴ .

The components used in this example are as follows, and may be omitted below.
(A-1) Colorant (pigment): Dye obtained in Synthesis Example 1 (A-2) Colorant (pigment): Dye obtained in Synthesis Example 2 (A-3) Colorant (dye): Synthesis Colorant (dye) obtained in Example 3 Colorant (dye): Colorant (A-5) colorant (dye) obtained in Synthesis Example 4 Compound (C) represented by formula (3-1) I. Solvent Yellow 162)
(A-6) Colorant (dye): compound represented by formula (21) (cyanine dye; NK-3212: manufactured by Hayashibara Biochemical Laboratories)

(A-7) Colorant (pigment): C.I. I. Pigment Yellow 150

(A-8) Colorant (dye): compound represented by formula (A-8)

(A-9) Colorant (dye): Compound represented by formula (A-9)

(A-10) Colorant (pigment): C.I. I. Pigment Green 58

(B-1) Polymerizable compound: DPHA (manufactured by Nippon Kayaku Co., Ltd.)
(C-1) Binder resin: Resin (C-1) obtained in Synthesis Example 5 (Propylene glycol monomethyl ether acetate solution having a solid content of 38.7% by mass)
(C-2) Binder resin: Resin (C-2) obtained in Synthesis Example 6 (Propylene glycol monomethyl ether acetate solution having a solid content of 28.9% by mass)
(D-1) Polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (D-2) Polymerization initiator: OXE-01 (Ciba Specialty Chemicals) Made)
(E-1) Polymerization initiation assistant: 4,4′-bis (diethylamino) benzophenone (F-1) Solvent: Propylene glycol monomethyl ether (F-2) Solvent: Propylene glycol monomethyl ether acetate (F-3) Solvent: Ethyl 3-ethoxypropionate (G-1) surfactant: Megafac F475 (manufactured by Dainippon Ink & Chemicals, Inc.)
Pigment dispersant 1: Dispersic 2001 (manufactured by Big Chemie) (mixed solution of propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate and ethylene glycol monobutyl ether having a solid content of 46.0% by mass)

Example 1
[Preparation of Pigment Dispersion 1]
(A-1) 8.500 parts by mass (C-1) 6.589 parts by mass (solid content conversion value: 2.550 parts by mass)
(Pigment dispersant) 7.761 parts by mass (solid content conversion value: 3.570 parts by mass)
(F-1) 13.575 parts by mass (F-2) 13.575 parts by mass The above composition was placed in a mayonnaise bottle having a capacity of 143 ml, and 166.500 parts by mass of zirconia beads having a diameter of 0.5 mm were further added and sealed. The mixture was shaken with a paint conditioner for 20 hours and then filtered to obtain pigment dispersion 1.

[Preparation of colored curable composition 1]
Next, each component was mixed by the following mixing | blending, and the colored curable composition 1 was obtained.
Pigment Dispersion 1 3.775 parts by mass (A-6) 0.200 parts by mass (B-1) 0.399 parts by mass (C-1) 1.050 parts by mass (solid content conversion value: 0.406 parts by mass) )
(D-1) 0.142 parts by mass (E-1) 0.047 parts by mass (F-1) 4.000 parts by mass (F-3) 0.385 parts by mass (G-1) 0.001 parts by mass

[Formation of coating film]
Next, after applying the colored curable composition 1 obtained above on glass (EAGLE 2000; manufactured by Corning) by a spin coating method, the volatile components are volatilized at 100 ° C. for 3 minutes to form a colored curable composition film. Formed. After cooling, the colored curable composition film was exposed to i-line (wavelength 365 nm) for exposure. An ultra-high pressure mercury lamp was used as the i-line light source, and the light was irradiated after being converted into parallel light. The amount of irradiation light was 200 mJ / cm ² . Subsequently, post-baking was performed at 220 ° C. for 20 minutes to obtain a colored curable composition film having y = 0.600 in the CIE-XYZ color system. The film thickness of the colored curable composition film was 2.2 μm.

[Evaluation 1] Lightness Evaluation As a result of measuring the chromaticity of the obtained colored curable composition film using a colorimeter (OSP-SP-200; manufactured by OLYMPUS), x = 0.289, y = 0. 600, Y (lightness) = 58.62.

[Evaluation 2] Contrast Evaluation When the contrast value of the obtained colored curable composition film was measured using a contrast colorimeter (CT-1; manufactured by Aisaka Electric Co., Ltd.) with a blank value of 10,000, it was 9180. It was.
As a criterion for evaluating the contrast of the colored curable composition film, if the contrast value is 8000 or more, depolarization is hardly recognized, and the color filter exhibits good characteristics, and the contrast value exceeds 5800 and is 8000 or less. For example, a slight degree of depolarization is recognized, but it is at a level where there is no problem in practical use of the color filter. If the contrast value is 5800 or less, clear depolarization can be confirmed, and there is a problem as a color filter. Is a level.

[Evaluation 3] Evaluation of heat resistance The chromaticity of the obtained colored curable composition film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS).
Next, the obtained colored curable composition film was further heated in an oven in an air atmosphere at 230 ° C. for 120 minutes, and the chromaticity of the colored curable composition film after heating was measured in the same manner, and heated. The color difference before and after (ΔEab *) was determined to be 4.6.
As an evaluation standard for color difference, if ΔEab * is 5 or less, almost no hue change is observed, showing good characteristics as a color filter, and if ΔEab * is more than 5 and less than 10, slight hue change is recognized. However, if the color filter has a practically no problem level and ΔEab * is 10 or more, a clear hue change can be confirmed, which is a problematic level for the color filter.

[Evaluation 4] Light Resistance Evaluation An ultraviolet cut filter (COLORED OPICAL GLASS L38; manufactured by Hoya Co., Ltd .; cuts light of 380 nm or less) is placed on the obtained colored curable composition film, and a light resistance tester ( XUNON lamp light was irradiated for 48 hours using SUNTEST CPS + (manufactured by Toyo Seiki Co., Ltd.).
The chromaticity of the colored curable composition film after irradiation was measured, and the color difference before and after irradiation was determined to be 2.8.
As the evaluation criteria for the color difference, as described above, when ΔEab * is 5 or less, there is almost no change in hue, showing good characteristics as a color filter, and when ΔEab * is more than 5 and 10 or less, However, when ΔEab * is 10 or more, a clear hue change can be confirmed, which is a problematic level for a color filter.

Examples 2-6
Colored curable compositions 2 to 6 were obtained in the same manner as in Example 1 except that the composition of the colored curable composition was changed as described in Table 1.
In addition, about coloring agent (A-2) and (A-7), the coloring agent (A-1) of [preparation of pigment dispersion 1] is changed to (A-2) and (A-7), respectively. A pigment dispersion was prepared in the same manner except that it was changed, and used for evaluation.
The obtained colored curable compositions 2 to 6 were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

Example 7
[Preparation of Pigment Dispersion 2]
(A-10) 40 parts by mass (pigment dispersant) 5 parts by mass (F-2) 137 parts by mass were mixed, and the pigment was sufficiently dispersed using a bead mill to obtain pigment dispersion 2.

[Preparation of colored curable composition 7]
Next, each component was mixed by the following mixing | blending, and the colored curable composition 7 was obtained.
Pigment Dispersion 2 182 parts by mass (A-8) 24 parts by mass (B-1) 50 parts by mass (C-2) 157 parts by mass (D-2) 15 parts by mass (F-2) 289 parts by mass

[Formation of pattern]
The colored curable composition 7 was applied by spin coating on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored curable composition and the quartz glass photomask having the pattern is set to 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), in an air atmosphere, Light irradiation was performed at an exposure amount of 150 mJ / cm ² (based on 365 nm). After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and 220 ° C. in an oven. And post-baked for 20 minutes. After standing to cool, the film thickness of the obtained cured pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.2 μm.

[Evaluation]
About the coating film on the obtained glass substrate, xy chromaticity coordinates (x, y) in the XYZ color system of CIE using a C light source with a colorimeter (OSP-SP-200; manufactured by Olympus Corporation) The brightness (Y) was measured, and the contrast was measured using a contrast meter (color difference meter BM-5A; manufactured by Topcon Corporation). The results are shown in Table 3. Good results are also obtained for the heat resistance evaluation and the light resistance evaluation.

Example 8
A colored curable composition 8 was obtained in the same manner as in Example 7 except that (A-8) was changed to (A-9). In the same manner as in Example 7, a pattern having a thickness of 2.2 μm was formed and evaluated. The results are shown in Table 3. Good results are also obtained for the heat resistance evaluation and the light resistance evaluation.

Example 9
The colored curable compositions 1 to 8 are applied to a substrate provided with a bank using an ink jet apparatus to form a colored coating film.

  When the colored curable composition of the present invention is used, a color filter having excellent brightness and contrast can be produced.

Claims (7)

(A) contains a colorant and (B) a polymerizable compound,
(A) A colorant contains a pigment represented by the formula (1), a yellow dye, and a fluorosurfactant, and the yellow dye is a barbituric acid azo dye represented by the formula (2) The content of the pigment represented by the formula (1) is 2 to 98% by mass with respect to the total amount of the colorant (A), and the yellow dye content is A colored curable composition having a mass fraction of 2 to 100% by mass.

Wherein ^{(1), A} 1 ^{~A 16} each independently represent a hydrogen atom, a chlorine atom or a bromine atom. ]

[In Formula (2), T ¹ and T ² each independently represent an oxygen atom or a sulfur atom.
R ^{31 to} R ³⁴ are each independently a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, or an optionally substituted group having 6 to 20 carbon atoms. It represents an aryl group, an aralkyl group having 7 to 20 carbon atoms which may have a substituent, or an acyl group having 2 to 10 carbon atoms which may have a substituent.
R ^{35 to} R ⁴² are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, a sulfamoyl group, or an N-substituted sulfamoyl group. Represents. A hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with a halogen atom. ] (A) contains a colorant and (B) a polymerizable compound,
(A) The colorant contains a pigment represented by the formula (1), a yellow dye, and a fluorosurfactant, the yellow dye contains a pyridone azo dye represented by the formula (3), The content of the pigment represented by the formula (1) is 2 to 98% by mass with respect to the total amount of the colorant (A), and the content of the yellow dye is mass with respect to all the yellow pigments. A colored curable composition having a fraction of 2 to 100% by mass.

Wherein ^{(1), A} 1 ^{~A 16} each independently represent a hydrogen atom, a chlorine atom or a bromine atom. ]

[In Formula (3), Z is a halogen atom, the C1-C12 aliphatic hydrocarbon group which may have a substituent, a C1-C8 alkoxyl group, a hydroxyl group, a carboxyl group, carbamoyl. A phenyl group having one or two substituents selected from the group consisting of a group, a sulfo group, a sulfamoyl group, and an N-substituted sulfamoyl group, or a halogen atom and an optionally substituted carbon At least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 12 carbon atoms, an alkoxyl group having 1 to 8 carbon atoms, a hydroxyl group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, and an N-substituted sulfamoyl group. Represents a naphthyl group having 1 to 3 substituents.
R ²¹ represents a hydrogen atom, a linear, branched or cyclic C 1-10 aliphatic hydrocarbon group, carboxyl group or trifluoromethyl group.
R ²² represents a hydrogen atom, a cyano group, a carbamoyl group, an N-position-substituted carbamoyl group, a sulfamoyl group or a sulfo group.
R ²³ is a hydrogen atom, an optionally substituted linear, branched or cyclic aliphatic hydrocarbon group having 1 to 10 carbon atoms, and an optionally substituted carbon atom having 6 to 6 carbon atoms. 30 aryl group, optionally substituted aralkyl group having 7 to 20 carbon atoms, optionally substituted heterocyclic group having 3 to 20 carbon atoms, carbamoyl group, N-substituted carbamoyl Group, an optionally substituted alkyloxycarbonyl group having 2 to 20 carbon atoms, an optionally substituted aryloxycarbonyl group having 7 to 30 carbon atoms, and a substituent. A C2-C20 acyl group, a C1-C30 aliphatic sulfonyl group which may have a substituent or a C6-C30 arylsulfonyl group which may have a substituent. . ]   The colored curable composition according to claim 1 or 2, further comprising (C) a binder resin. The hardening pattern which consists of a coloring curable composition in any one of Claims 1-3. A color filter comprising the cured pattern according to claim 4.   A liquid crystal display device comprising the color filter according to claim 5. The manufacturing method of the hardening pattern formed by the photolithographic method or the inkjet method using the coloring curable composition in any one of Claims 1-3.