JP2012208474A - Colored composition for color filter, color filter and display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored radiation-sensitive composition for color filter that contains a yellow dye and is excellent in process durability.SOLUTION: A colored composition for color filter contains (A) colorant including a yellow dye, (B) binder resin with an acid value of 85-300 mgKOH/g, (C) polyfunctional monomer, and (D) photopolymerization initiator including a biimidazole-based compound.

Description

  The present invention relates to a coloring composition for a color filter, a color filter, and a display element. More specifically, the present invention relates to a color filter used for a transmissive or reflective color liquid crystal display element, a color imaging tube element, an organic EL display element, and the like. The present invention relates to a colored composition used for forming a useful colored layer, a color filter including a colored layer formed using the colored composition, and a display element including the color filter.

  In producing a color filter using a colored radiation-sensitive composition, a colored radiation-sensitive composition in which an organic pigment is dispersed is applied on a substrate or a substrate on which a light-shielding layer having a desired pattern is formed in advance. There is known a method (Patent Documents 1 and 2) of obtaining a pixel of each color by irradiating a dry coating film with a desired pattern shape after drying (hereinafter referred to as “exposure”) and developing. . A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. Furthermore, a method for obtaining pixels of each color by an ink jet method using a colored resin composition in which an organic pigment is dispersed (Patent Document 4) is also known.

  By the way, it is known that it is effective to use a dye as a colorant in order to realize high luminance and high color purity of a display element or high definition of a solid-state imaging element. For example, Patent Document 5 proposes the use of a specific yellow dye.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2010-168531 A

However, since the coloring composition containing the yellow dye proposed in Patent Document 5 has insufficient process resistance such as heat resistance, the obtained color filter has reduced chromaticity characteristics.
Therefore, the subject of this invention is providing the coloring composition for color filters which contains yellow dye and was excellent in process resistance. Furthermore, the subject of this invention is providing the color filter provided with the colored layer excellent in chromaticity characteristic, and the display element which comprises the said color filter.

  In view of this situation, the present inventors have conducted extensive research and have solved the above problem by using a yellow dye together with a specific binder resin, a polyfunctional monomer and a specific photopolymerization initiator. The present invention has been completed.

  That is, the present invention includes (A) a colorant containing a yellow dye, (B) a binder resin having an acid value of 85 to 300 mgKOH / g, (C) a polyfunctional monomer, and (D) a biimidazole compound. The coloring composition for color filters characterized by containing the photoinitiator containing this is provided.

  Moreover, this invention provides the color filter provided with the colored layer formed from the said coloring composition, and the display element which comprises the said color filter. Here, the “colored layer” means each color pixel, black matrix, etc. used in the color filter.

If the coloring composition of the present invention is used, a color filter having each color pixel having extremely excellent chromaticity characteristics can be obtained.
Therefore, the colored composition of the present invention is extremely suitable for the production of various color filters including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, and color filters for organic EL display elements. Can be used for

Hereinafter, the present invention will be described in detail.
Color Filter Color Composition Hereinafter, the components of the color filter color composition of the present invention (hereinafter simply referred to as “color composition”) will be described.

-(A) Colorant-
The coloring composition of the present invention is characterized by containing a yellow dye as the colorant (A). The yellow dye is preferably at least one 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, the barbituric acid azo dye represented by following formula (2) is suitable.

[In Formula (2),
Q ¹ and Q ² each independently represents an oxygen atom or a sulfur atom.
R ^{11 to} R ¹⁴ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an aryl having 6 to 20 carbon atoms which may have a substituent. The C7-C20 aralkyl group which may have a group and a substituent, or the C2-C10 acyl group which may have a substituent is shown.
R ^{15 to} R ²² are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms that may be substituted with a halogen atom, an alkoxy group having 1 to 8 carbon atoms, a carboxyl group, a sulfo group, or a sulfamoyl group. Group or N-substituted sulfamoyl group. ]

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

The saturated hydrocarbon group for R ^{11 to} R ¹⁴ may be linear, branched or cyclic. The carbon number of the saturated hydrocarbon group does not include the carbon number of the substituent, and the number thereof is 1 to 10, preferably 2 to 8, more preferably 3 to 6. Specific examples of the saturated hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-ethylhexyl group, cyclopentyl group, Examples include a cyclohexyl group and a cyclohexylalkyl group. The saturated hydrocarbon group is substituted with a hydroxy group, an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms), or a thioalkoxy group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms). May be. Examples of the saturated hydrocarbon group having a substituent include a hydroxy-substituted alkyl group (such as 2-hydroxyethyl group), an alkoxy-substituted alkyl group (2-ethoxyethyl group, 3- (isopropoxy) propyl group, 3- (2-ethylhexyl). Oxy) propyl group and the like, and alkylthio-substituted alkyl groups (such as 3-methylthiopropyl group) and the like.

The aryl group in R ^{11 to} R ¹⁴ may be unsubstituted or may have a substituent. The number of carbon atoms of the aryl group does not include the number of carbon atoms of the substituent, and the number thereof is 6 to 20, but preferably 6 to 10. As a substituent, a C1-C10 (preferably 1-6) saturated hydrocarbon group which may have a halogen atom, a C1-C8 (preferably 1-4) alkoxy group, a carboxyl group , A sulfo group, or a group containing an ester bond. Examples of the aryl group include a phenyl group. Examples of the aryl group having a substituent include an alkyl-substituted phenyl group (2-methylphenyl group, 3-methylphenyl group, 4-methylphenyl group, etc.), an alkoxy-substituted phenyl group (2-methoxyphenyl group, 3-methoxyphenyl group). Phenyl group, 4-methoxyphenyl group, etc.), carboxy-substituted phenyl group (2-carboxyphenyl group, 2,4-dicarboxyphenyl group etc.), hydroxy-substituted phenyl group (4-hydroxyphenyl group etc.), perfluoroalkyl substitution Phenyl group (4-trifluoromethylphenyl group, etc.), sulfo-substituted phenyl group (2-sulfophenyl group, 3-sulfophenyl group, 4-sulfophenyl group), alkoxycarbonyl-substituted phenyl group (4-ethoxycarbonylphenyl group, etc.) ) And the like.

The alkyl part of the aralkyl group in R ^{11 to} R ¹⁴ may be linear, branched or cyclic. The number of carbon atoms of the aralkyl group does not include the number of carbon atoms of the substituent, and the number thereof is 7 to 20, but preferably 7 to 10. Examples of the substituent include a hydroxy group, an amino group, an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4), a carboxyl group, a sulfo group, or a group containing an ester bond. Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylbutyl group, and a 1-methyl-3-phenylpropyl group. Examples of the aralkyl group having a substituent include a hydroxy-substituted aralkyl group (such as 2- (4-hydroxyphenyl) ethyl group) and an amino-substituted aralkyl group (such as 3-amino-1-phenylbutyl group). it can.

The acyl group having 2 to 10 carbon atoms in R ^{11 to} R ¹⁴ may be unsubstituted or may have a substituent. Examples of the substituent include an alkoxy group having 1 to 8 (preferably 1 to 4) carbon atoms. The carbon number of the acyl group does not include the carbon number of the substituent, and the number thereof is 2 to 10, but preferably 2 to 8. Examples of the acyl group include an acetyl group and a benzoyl group. In addition, examples of the acyl group having a substituent include an alkoxy-substituted benzoyl group (such as a p-methoxybenzoyl group).

Examples of the saturated hydrocarbon group in R ^{15 to} R ²² include the same as the saturated hydrocarbon group having 1 to 10 carbon atoms in R ^{11 to} R ¹⁴ , and the specific configuration thereof has been described in R ^{11 to} R ¹⁴ . However, it may be further substituted with a halogen atom. Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom, and an iodine atom, and among them, a fluorine atom is preferable. Examples of the halogen-substituted saturated hydrocarbon group include a perfluoroalkyl group (such as a trifluoromethyl group).

The alkoxy group in R ^{15 to} R ²² may be either linear or branched. The alkoxy group has 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms. Examples of the alkoxy group 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.

The N-substituted sulfamoyl group in R ^{15 to} R ²² is represented by —SO ₂ N (R ²³ ) R ²⁴ .
R ²³ and R ²⁴ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or an aryl having 6 to 20 carbon atoms which may have a substituent. Group, an optionally substituted aralkyl group having 7 to 20 carbon atoms or an optionally substituted acyl group having 2 to 10 carbon atoms (provided that R ²³ and R ²⁴ are simultaneously It cannot be a hydrogen atom).
The saturated hydrocarbon group, aryl group, aralkyl group and acyl group in R ²³ and R ²⁴ are the same as the saturated hydrocarbon group, aryl group, aralkyl group and acyl group in R ^{11 to} R ¹⁴ , respectively. Is as described for R ^{11 to} R ¹⁴ .

The N-substituted sulfamoyl group in R ^{15 to} R ²² is preferably a mono-substituted sulfamoyl group, and specifically represented by —SO ₂ NHR ²³ . Suitable N-substituted sulfamoyl groups include, for example, groups represented by formulas (i) to (vii).

  Examples of the barbituric acid azo dyes include compounds represented by formulas (2-1) to (2-8), among which formulas (2-1) and (2-3) to (2) The compounds represented by -5), (2-7) and (2-8) are preferred.

  The pyridone azo dye is not particularly limited, and a known substance can be used, but those represented by the following formula (1) are preferable.

[In Formula (1),
Z is a halogen atom, a C1-C12 saturated hydrocarbon group which may have a substituent, a C1-C8 alkoxy group, a hydroxy group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, and A phenyl group having one or two substituents selected from the group consisting of N-substituted sulfamoyl groups, or a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, A naphthyl group having 1 to 3 substituents selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group; Show.
R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group.
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a cyano group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, a sulfo group or an amino group.
R ³ has a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, and a substituent. An optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted heterocyclic group having 3 to 20 carbon atoms, a carbamoyl group, an N-substituted carbamoyl group, and a substituent. An aliphatic oxycarbonyl group having 2 to 20 carbon atoms, an aromatic oxycarbonyl group having 7 to 30 carbon atoms which may have a substituent, and an acyl group having 2 to 20 carbon atoms which may have a substituent The C1-C30 aliphatic sulfonyl group which may have a substituent, or the C6-C30 aromatic sulfonyl group which may have a substituent is shown. ]

In formula (1), the saturated hydrocarbon group for Z may be linear, branched or cyclic. The carbon number of the saturated hydrocarbon group does not include the carbon number of the substituent, and the number thereof is 1 to 12, but preferably 2 to 11. Examples of the substituent include a hydroxy group, an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms), a carboxyl group, and the like. Examples of the saturated hydrocarbon group for Z include the same as the saturated hydrocarbon group for R ^{11 to} R ¹⁴ , and further include a carboxy-substituted alkyl group (2-carboxyethyl group, 3-carboxypropyl group, 4-carboxybutyl group). , 8-carboxyoctyl group, etc.).

Examples of the alkoxy group for Z include the same groups as the alkoxy groups for R ^{15 to} R ²² , and the specific configuration thereof is as described for R ^{15 to} R ²² .
Examples of the halogen atom in Z include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom.

The N-substituted sulfamoyl group in Z is represented by —SO ₂ N (R ⁴ ) R ⁵ .
R ⁴ and R ⁵ are each independently a hydrogen atom, a saturated hydrocarbon group having 1 to 16 carbon atoms which may have a substituent, or an aryl having 6 to 20 carbon atoms which may have a substituent. A group, an optionally substituted aralkyl group having 7 to 20 carbon atoms or an optionally substituted acyl group having 2 to 15 carbon atoms (provided that R ⁴ and R ⁵ are simultaneously It cannot be a hydrogen atom).
The N-substituted sulfamoyl group in Z is preferably a monosubstituted sulfamoyl group, and specific examples include the monosubstituted sulfamoyl group exemplified in R ^{15 to} R ²² .

The saturated hydrocarbon group for R ⁴ and R ⁵ may be linear, branched or cyclic. The number of carbon atoms of the saturated hydrocarbon group does not include the number of carbon atoms of the substituent, and the number thereof is 1 to 16, but preferably 6 to 10. Such a saturated hydrocarbon group may be substituted with a hydroxy group, an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms), or a carboxyl group. As the saturated hydrocarbon group, the same as the saturated hydrocarbon group for Z can be mentioned.

Examples of the aryl group and aralkyl group in R ⁴ and R ⁵ include those similar to the aryl group and aralkyl group in R ²³ and R ²⁴ , respectively, and specific configurations thereof are as described for R ²³ and R ²⁴ . .

The acyl group in R ⁴ and R ⁵ may be unsubstituted or may have a substituent. Examples of the substituent include an alkoxy group having 1 to 8 carbon atoms (preferably 1 to 4) or a carboxyl group. The number of carbon atoms of the acyl group does not include the number of carbon atoms of the substituent, and the number thereof is 2 to 15, but preferably 6 to 10. Examples of the acyl group having an acyl group and a substituent include the same acyl groups as in R ^{11 to} R ¹⁴ , and further a carboxy-substituted acyl group (carboxyacetyl group, 2-carboxypropionyl group, 3-carboxypropionyl group, 2-carboxybutyryl group, 3-carboxybutyryl group, 4-carboxybutyryl group and the like.

  Z in the formula (1) is preferably a phenyl group having a substituent, and any of the above substituents can be selected as appropriate. However, sulfo has a high solubility in a solvent. Group, N-substituted sulfamoyl group is preferred. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

R ^{1 in the} formula (1) is preferably a trifluoromethyl group or a linear, branched or cyclic hydrocarbon group, particularly a saturated hydrocarbon group. The number of carbon atoms of the hydrocarbon group does not include the number of carbon atoms of the substituent, and the number thereof is 1 to 10, preferably 1 to 8, more preferably 1 to 4. Examples of the saturated hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, cyclopentyl group, and cyclohexyl group.

The hydrocarbon group for R ² may be linear, branched or cyclic. As the hydrocarbon group for R ^2, the same groups as those hydrocarbon group in R ^1, the specific configuration is as described in R ^1.
As the amino group in R ² , an aliphatic amino group, an aromatic amino group, an acylamino group, a carbamoylamino group, a sulfamoylamino group, an aliphatic oxycarbonylamino group, an aryloxycarbonylamino group, an aliphatic sulfonylamino group, An aromatic sulfonylamino group is exemplified.

Examples of the N-substituted carbamoyl group for R ² include —CON (R ⁶ ) R ⁷ .
R ⁶ and R ⁷ are each independently a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 6 to 20 carbon atoms. Group, an optionally substituted aralkyl group having 7 to 20 carbon atoms or an optionally substituted acyl group having 2 to 10 carbon atoms (provided that R ⁶ and R ⁷ are simultaneously It cannot be a hydrogen atom).
Examples of the saturated hydrocarbon group, aryl group, aralkyl group and acyl group in R ⁶ and R ⁷ include the same as the saturated hydrocarbon group, aryl group, aralkyl group and acyl group in R ^{11 to} R ¹⁴ , respectively. Although the specific structure is as having demonstrated in R < ¹¹ > -R < ¹⁴ >, the acyl group may have a halogen atom further. Examples of the acyl group having a halogen atom include a halogen-substituted benzoyl group (such as a p-bromobenzoyl group).

As R < ² > of Formula (1), a C1-C10 saturated hydrocarbon group, a cyano group, a carbamoyl group, and an amino group are preferable, and a cyano group and a carbamoyl group are more preferable.

The saturated hydrocarbon group for R ³ may be linear, branched or cyclic. Examples of the saturated hydrocarbon group for R ³ include the same as the saturated hydrocarbon group for R ¹ , and the specific configuration is as described for R ¹ .

The aryl group in R ³ may be unsubstituted or may have a substituent. The number of carbon atoms of the aryl group does not include a substituent, and the number thereof is 6-30, preferably 6-20, and more preferably 6-16. Examples of the substituent include a halogen atom, a nitro group, a saturated hydrocarbon group having 1 to 10 (preferably 1 to 6) carbon atoms, an alkoxy group having 1 to 8 (preferably 1 to 4) carbon atoms, and 1 to 10 carbon atoms. (Preferably 1 to 6) alkoxycarbonyl groups and combinations of two or more thereof.
Examples of the aryl group include a phenyl group, and examples of the aryl group having a substituent include a nitro-substituted phenyl group (4-nitrophenyl group, 2-nitrophenyl group, etc.), a halogen-substituted phenyl group (2-chlorophenyl group). , 2,4-dichlorophenyl group), alkyl-substituted phenyl group (2,4-dimethylphenyl group, 2-methylphenyl group, etc.), alkoxy-substituted phenyl group (4-methoxyphenyl group, 2-methoxyphenyl group, etc.), Examples include alkoxycarbonyl and nitro-substituted phenyl groups (such as 2-methoxycarbonyl-4-nitrophenyl group).

The alkyl part of the aralkyl group in R ³ may be either linear or branched. The number of carbon atoms of the aralkyl group does not include the number of carbon atoms of the substituent, and the number thereof is 7 to 20, but preferably 7 to 10. As a substituent, a saturated hydrocarbon group, a hydroxy group, an amino group, or a C 1-8 (preferably 1 to 4 C) optionally having a halogen atom having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms). And the like. Examples of the aralkyl group and the aralkyl group having a substituent include the same aralkyl groups as in Z.

The heterocyclic group for R ³ may be saturated or unsaturated. The number of carbon atoms in the heterocyclic group does not include the number of carbon atoms in the substituent, and the number is 3 to 20, preferably 5 to 15. Examples of the heterocyclic group include a pyrazole group, 1,2,4-triazole group, isothiazole group, benzoisothiazole group, thiazole group, benzothiazole group, oxazole group, and 1,2,4-thiadiazole group. The heterocyclic group further has a substituent such as a saturated hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6), a hydroxy group, or an alkoxyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms). It may be.

Examples of the N-substituted carbamoyl group in R ³ include the same as the N-substituted carbamoyl group in R ² , and the specific configuration thereof is as described in R ² .
The aliphatic oxycarbonyl group for R ³ may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxy group and an alkoxy group having 1 to 8 (preferably 1 to 4) carbon atoms. The carbon number of the aliphatic oxycarbonyl group does not include the carbon number of the substituent, and the number thereof is 2 to 20, preferably 2 to 16, and more preferably 2 to 10. Examples of the aliphatic oxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a butoxycarbonyl group.

The aromatic oxycarbonyl group in R ³ may be unsubstituted or may have a substituent. Examples of the aromatic group include a phenyl group. Examples of the substituent include a hydroxy group, a saturated hydrocarbon group having 1 to 10 (preferably 1 to 6) carbon atoms, and an alkoxy group having 1 to 8 (preferably 1 to 4) carbon atoms. The number of carbon atoms of the aromatic oxycarbonyl group does not include the number of carbon atoms of the substituent, and the number thereof is 7 to 30, preferably 7 to 20, and more preferably 7 to 16. Examples of the aromatic oxycarbonyl group include a phenoxycarbonyl group and a 4-methylphenoxycarbonyl group.

The acyl group for R ³ may be an aliphatic carbonyl group, an alicyclic carbonyl group, or an aromatic carbonyl group, and the aliphatic group and the alicyclic group may be saturated or unsaturated. Further, the acyl group in R ³ may have a substituent. The carbon number of the acyl group does not include the carbon number of the substituent, and the number thereof is 2 to 20, preferably 2 to 15, and more preferably 2 to 10. As a substituent, a C1-C10 (preferably 1-6) saturated hydrocarbon group, a C1-C8 (preferably 1-4) alkoxy group, a carboxyl group, etc. are mentioned. 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 ³ may be saturated or unsaturated. The carbon number of the aliphatic sulfonyl group does not include the carbon number of the substituent, and the number thereof is 1 to 30, preferably 1 to 20, and more preferably 1 to 16. The aliphatic sulfonyl group in R ³ may have a substituent, and examples of the substituent include a hydroxy group, a saturated hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 6), and 1 to 8 carbon atoms. (Preferably 1 to 4) alkoxyl group and the like. Examples of the aliphatic sulfonyl group include a methanesulfonyl group, a butanesulfonyl group, a methoxymethanesulfonyl group, a methoxyethanesulfonyl group, and an ethoxyethanesulfonyl group.

The aromatic sulfonyl group in R ³ may be unsubstituted or may have a substituent. The number of carbon atoms of the aromatic sulfonyl group does not include the number of carbon atoms of the substituent, and the number thereof is 6-30, preferably 6-20, and more preferably 6-18. Examples of the aromatic group include a phenyl group. Examples of the substituent include a hydroxy group, a saturated hydrocarbon group having 1 to 10 (preferably 1 to 6) carbon atoms, and an alkoxyl group having 1 to 8 (preferably 1 to 4) carbon atoms. Examples of the aromatic sulfonyl group include benzenesulfonyl and toluenesulfonyl groups.

As R < ³ > of Formula (1), the sulfo group, the C1-C10 saturated hydrocarbon group which may have a substituent, and the phenyl group which has a substituent are preferable. Any one of the above substituents can be selected as appropriate, but a sulfo group and an N-substituted sulfamoyl group are preferable from the viewpoint of high solubility in a solvent. In addition, the position and number of substituents are arbitrary, and when having two or more substituents, the substituents may be the same or different.

  Examples of the pyridone azo dye include compounds represented by formulas (1-1) to (1-11), and among them, compounds represented by formulas (1-1) to (1-9) are preferable. It is.

  The compound represented by Formula (1) may form a dimer. The dimer here is a compound having a group derived from two compounds represented by the formula (1) in one molecule, and two compounds represented by the formula (1) are arbitrary. A dimer is formed by binding at a position. Examples of the dimer include a compound represented by the formula (1a), a compound represented by the formula (1b), or a compound represented by the formula (1c).

[In the formulas (1a), (1b) and (1c),
R ⁶ , independently of each other, is an alkanediyl group or —C _m H _2m (OC _n H _2n ) _p — (m and n each independently represents an integer of 1 to 4, and p is 1 to 10 Indicates an integer)
R ⁷ is independently of each other a halogen atom, an optionally substituted saturated hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, a carboxyl group, a carbamoyl group, A phenyl group having one or two substituents selected from the group consisting of a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group;
R ⁸ is independently of each other a halogen atom, an optionally substituted saturated hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, a carboxyl group, a carbamoyl group, A phenylene group having one or two substituents selected from the group consisting of a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group, or a halogen atom, an optionally substituted carbon atom having 1 to 2 carbon atoms At least one substituent selected from the group consisting of 12 hydrocarbon groups, alkoxy groups having 1 to 8 carbon atoms, hydroxy groups, carboxyl groups, carbamoyl groups, sulfo groups, sulfamoyl groups and N-substituted sulfamoyl groups; A naphthylene group having three is shown.
R ¹ , R ² , R ³ and Z are as defined above. ]

Examples of the alkanediyl group for R ⁶ include a methylene group and an alkylene group having 2 to 6 carbon atoms. The alkylene group may be linear or branched. As the alkanediyl group, a methylene group, an ethylene group, a trimethylene group, a propane-1,2-diyl group, and a tetramethylene group are preferable.
m and n are integers of 1 to 4, but an integer of 2 to 4 is preferable. Although p is an integer of 1-10, the integer of 1-3 is preferable. The group represented by, for _{example, -C 2 H 4 (OC 2} H 4) - - -C m H 2m (OC n H 2n) p, - C 2 H 4 (OC 2 H 4) 2 -, - C ₃ H ₆ (OC ₂ H ₄ ) ₂ — can be mentioned.
The substituent of the phenyl group in R ⁷ is the same as the phenyl group having a substituent in Z, and the specific configuration thereof is as described in Z.
R ⁸ represents a phenylene group or a naphthylene group formed by bonding two compounds represented by the formula (1) at the Z position, and the specific structure of the substituent in R ⁸ is described in Z. As you did.

  Examples of the dimer formed from the compound represented by formula (1) include compounds represented by formula (1-12) to formula (1-15).

  Examples of the compound represented by the formula (1) and a dimer salt formed from the compound include organic amine salts such as ammonium salt, ethanolamine salt, and alkylamine salt, lithium salt, sodium salt, potassium salt, and the like. Examples include alkali metal salts.

  The method for producing the compound represented by the formula (1) is not particularly limited, and a conventionally known method can be appropriately used. For example, as is well known in the dye field, it can be produced by coupling a diazonium salt and a pyridone.

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

  Specifically, C.I. I. Acid Yellow 17, C.I. I. Solvent Orange 56, C.I. I. Solvent yellow 82, compounds represented by formulas (3-1) to (3-4), and the like can be given.

  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. Dyes.

  Specifically, C.I. I. Solvent Yellow 33, C.I. I. Disperse Yellow 54, C.I. I. Disperse yellow 64, compounds represented by formulas (4-1) to (4-5), and the like can be given.

The cyanine dye is not particularly limited, and a known substance can be used. Examples thereof include cyanine dyes described in JP-A-2005-194509, JP-A-2007-131818, JP-A-2005-297406, and the like.
Specific examples include compounds represented by formulas (5-1) to (5-4).

  In this invention, a yellow dye can be used individually or in mixture of 2 or more types. The coloring composition of this invention can contain another coloring agent further with a specific yellow dye as a coloring agent. The other colorant is not particularly limited. For example, by using a specific yellow dye together with a red colorant, a color composition for forming a red pixel can be obtained. By using with an agent, it can be set as the coloring composition for forming a green pixel.

  As the other colorant, any of pigments, dyes and natural pigments can be used, but organic pigments and organic dyes are preferable in terms of obtaining pixels having high luminance and color purity. As organic pigments, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the following color index (CI) names are given. Things can be mentioned.

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment red 272;

C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211;

C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;
C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60, C.I. I. Pigment blue 80;
C. I. Pigment green 7, C.I. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.

  Examples of the organic dye include those having the following color index (CI) names.

C. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Azo dyes such as Moldant Black 7;

C. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Anthraquinone dyes such as Disperse Blue 60;

C. I. Phthalocyanine dyes such as Pad Blue 5;
C. I. Basic Blue 3, C.I. I. Quinone imine dyes such as Basic Blue 9;
C. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Quinoline dyes such as Disperse Yellow 64;
C. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Nitro dyes such as Disperse Yellow 42.

  In the present invention, other colorants can be used alone or in admixture of two or more.

In this invention, it is preferable to set it as the coloring composition for forming a green pixel by using a yellow dye with a green coloring agent. As the green colorant, a green pigment is preferable. I. Pigment green 7, C.I. I. Pigment green 36 and C.I. I. At least one selected from the group consisting of CI Pigment Green 58 is preferable. I. Pigment Green 58 is preferable.
In this case, the content ratio of the yellow dye in the total colorant is preferably 10 to 99% by mass, particularly preferably 30 to 95% by mass, and the content ratio of the green colorant is preferably 1 to 90% by mass. Especially preferably, it is 5-70 mass%.

  When a pigment is used as the colorant in the present invention, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. Moreover, it is preferable to use a pigment by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  (A) The content ratio of the colorant is usually 5 to 70% by mass in the solid content of the coloring composition, preferably from the point of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass. Solid content here is components other than the solvent mentioned later.

  In the present invention, when a pigment is used as a colorant, it can be used together with a dispersant and a dispersion aid as desired. As the dispersing agent, for example, an appropriate dispersing agent such as a cationic type, an anionic type, or a nonionic type can be used, and a polymer dispersing agent is preferable. Specifically, urethane dispersant, polyethyleneimine dispersant, polyoxyethylene alkyl ether dispersant, polyoxyethylene alkylphenyl ether dispersant, polyethylene glycol diester dispersant, sorbitan fatty acid ester dispersant, polyester Examples thereof include an acrylic dispersant and an acrylic dispersant.

  Such dispersants are commercially available. For example, acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN21324 (above, BYK Corporation (BYK)) Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (Lubrisol Co., Ltd.) ), Polyethylene imine-based dispersant, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), polyester-based dispersant, Azisper PB821, Jisupa PB822, Adisper PB880, mention may be made of Ajisper PB881 (Ajinomoto Fine-Techno Co., Ltd.), and the like.

  Examples of the dispersion aid include pigment derivatives, and specific examples include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivatives of quinophthalone. The contents of the dispersant and the dispersion aid can be appropriately determined within a range that does not impair the object of the present invention.

-(B) Binder resin-
The binder resin (B) in the present invention is not particularly limited as long as the acid value is 85 to 300 mgKOH / g. When the acid value is less than 85 mgKOH / g, the thermal stability of the yellow dye is lowered. On the other hand, when it exceeds 300 mgKOH / g, the yellow dye is easily eluted during alkali development. (B) The lower limit of the acid value of the binder resin is preferably 100 mgKOH / g or more from the viewpoint that the thermal stability of the specific yellow dye can be enhanced. On the other hand, the upper limit of the acid value of the (B) binder resin is preferably 270 mgKOH / g or less from the viewpoint that the elution of the specific yellow dye during alkali development can be further suppressed. Here, the “acid value” is the number of mg of KOH required to neutralize 1 g of the resin, and specifically, it is measured by the method described in the examples below. Moreover, in this invention, the acid value of binder resin means the acid value as the whole binder resin. That is, even when a plurality of types of binder resins having different acid values are used, it means an acid value measured in a mixed state.

  In the present invention, examples of the acidic functional group that expresses an acid value include a carboxyl group, a phenolic hydroxyl group, an imido acid group (—CO—NH—CO—), a sulfo group, a sulfino group, and a sulfeno group. Among them, a carboxyl group is preferable from the viewpoint of solubility in a solvent described later. Examples of the polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) include, for example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer (b1)”. ) ") And other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomer (b2) ").

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (b1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; aromatics such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene Vinyl compounds;

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol (n = 2 -10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) ) Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, Glyce Mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meta ) (Meth) acrylic acid esters such as acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane A macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, and the like.
These unsaturated monomers (b2) can be used alone or in admixture of two or more.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. No. 10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, etc. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000. If Mw is too small, the remaining film rate of the resulting film may be reduced, pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. On the other hand, if Mw is too large, resolution may be reduced. In addition, the pattern shape may be damaged, and dry foreign matter may be easily generated during application by the slit nozzle method.

  Further, the ratio (Mw / Mn) of Mw of the binder resin in the present invention to the number average molecular weight (Mn) in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran) is preferably 1.0 to 5.0, More preferably, it is 1.0-3.0.

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, Mw, and Mw / Mn can be controlled by the method.

In this invention, binder resin can be used individually or in mixture of 2 or more types.
In this invention, content of binder resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(C) polyfunctional monomer-
In the present invention, the (C) polyfunctional monomer is a monomer having two or more polymerizable unsaturated bonds, and is a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups. Preferably there is. Examples of such compounds include polyfunctional (meth) acrylates obtained by reacting aliphatic polyhydroxy compounds with (meth) acrylic acid, caprolactone-modified polyfunctional (meth) acrylates, and alkylene oxide-modified polyfunctional compounds. Functional (meth) acrylate, polyfunctional urethane (meth) acrylate obtained by reacting hydroxyl-containing (meth) acrylate and polyfunctional isocyanate, carboxyl group obtained by reacting hydroxyl-containing (meth) acrylate and acid anhydride The polyfunctional (meth) acrylate etc. which have can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, and dipentaerythritol. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di It can be mentioned pointer ethylene oxide erythritol and / or propylene oxide-modified hexa (meth) acrylate.

Of these polyfunctional monomers, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, Polyfunctional urethane (meth) acrylate and polyfunctional (meth) acrylate having a carboxyl group are preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate is obtained by reacting pentaerythritol triacrylate and succinic anhydride, and reacting dipentaerythritol pentaacrylate and succinic anhydride. A compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residue are hardly generated on the unexposed substrate and the light shielding layer.
In the present invention, the polyfunctional monomer (C) can be used alone or in admixture of two or more.

  In the present invention, the content of the (C) polyfunctional monomer is preferably 5 to 500 parts by mass, particularly preferably 20 to 300 parts by mass with respect to 100 parts by mass of the (B) binder resin. In this case, if the content of the polyfunctional monomer is too small, sufficient curability may not be obtained. On the other hand, if the content of the polyfunctional monomer is too large, the alkali developability is lowered, and there is a tendency that background stains, film residues, etc. are likely to occur on the unexposed substrate or the light shielding layer.

-(D) Photopolymerization initiator-
(D) The photopolymerization initiator generates an active species capable of initiating polymerization of the (C) polyfunctional monomer by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound.
The (D) photopolymerization initiator used in the present invention contains a biimidazole compound. The present inventors considered that the active species generated from the photopolymerization initiator upon exposure attacked the dye molecules and deteriorated the chromaticity characteristics, and conducted intensive research. It has been found that by using a biimidazole compound as a photoradical generator as a photopolymerization initiator, a colored composition capable of forming a pixel having extremely excellent chromaticity characteristics can be obtained.

  The biimidazole compound is a compound having at least one skeleton represented by the following formula (6), formula (7) or formula (8).

As a specific example, for example,
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole, 2,2′-bis (2-bromophenyl) ) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole and the like bis (halogen-substituted phenyl) tetrakis (alkoxycarbonylphenyl) biimidazole;
2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'-tetraphenyl-1, 2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4 -Dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5 Bis (halogen-substituted phenyl) tetraphenylbiimidazole such as 5,5'-tetraphenyl-1,2'-biimidazole Rukoto can.
Biimidazole compounds can be used alone or in admixture of two or more.

  Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-Dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole is preferred, in particular 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole. Imidazole is preferred.

  In this invention, content of a biimidazole type compound is 0.01-50 mass parts normally with respect to 100 mass parts of (C) polyfunctional monomers, Preferably it is 1-40 mass parts, More preferably 1 to 30 parts by mass.

In the present invention, it is preferable to further use the following hydrogen donor in view of further improving the sensitivity.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.

A mercaptan compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ A mercaptan hydrogen donor).
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , "Amine-based hydrogen donor").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor will be described more specifically.
The mercaptan hydrogen donor may have one or more benzene rings or heterocyclic rings, or may have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, a condensed ring may be formed.
Further, when the mercaptan-based hydrogen donor has two or more mercapto groups, one or more of the remaining mercapto groups are substituted with an alkyl group, an aralkyl group or an aryl group as long as at least one free mercapto group remains. May be. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are in the form of a disulfide. Can have structural units bonded together.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- Examples include mercapto-substituted heterocyclic compounds such as 2,5-dimethylaminopyridine.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

The amine-based hydrogen donor can have one or more benzene rings or heterocyclic rings, or both a benzene ring and a heterocyclic ring. When two or more of these rings are present, a condensed ring may be formed.
In the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group may be substituted at a position other than the amino group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such amine hydrogen donors include amino-substituted benzophenones such as 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone; 4-diethylaminoacetophenone, 4- Examples thereof include dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of a photopolymerization initiator other than a biimidazole compound.

In the present invention, C.I. I. When using CI Pigment Green 58, it is preferable to use a mercaptan compound as the hydrogen donor.
In this invention, a hydrogen donor can be used individually or in mixture of 2 or more types.

  In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the content of the hydrogen donor is preferably 0.01 to 40 parts by mass with respect to 100 parts by mass of the (C) polyfunctional monomer. More preferably, it is 1-30 mass parts, Most preferably, it is 1-20 mass parts. When the content of the hydrogen donor is too small, the sensitivity improving effect tends to be lowered. On the other hand, if the amount is too large, the formed colored layer tends to fall off the substrate during development.

In the present invention, as the photopolymerization initiator, another photopolymerization initiator can be used in combination with the biimidazole compound. Other photopolymerization initiators include, for example, thioxanthone compounds, acetophenone compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear compounds. Examples thereof include quinone compounds, diazo compounds, imide sulfonate compounds, and the like. Other photopolymerization initiators are preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, triazine compounds, and O-acyloxime compounds.
In this invention, another photoinitiator can be used individually or in mixture of 2 or more types.

In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (C) polyfunctional monomers, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.
Further, the content ratio of the biimidazole compound in the total photopolymerization initiator is preferably 5% by mass or more, and more preferably 10% by mass or more. By using the photopolymerization initiator in this manner, a colored composition having extremely excellent chromaticity characteristics can be obtained.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And a siloxane oligomer having a reactive functional group disclosed in JP-A-2008-242078 and the like.

-Solvent-
Although the coloring composition of this invention contains the said (A)-(D) component and the other component added arbitrarily, normally, a solvent is mix | blended and it prepares as a liquid composition. As said solvent, (A)-(D) component which comprises a coloring composition, and another component are disperse | distributed or melt | dissolved, and it does not react with these components, but suitably has volatility. You can choose to use.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, lactic acid Ethyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl lopionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate N-butyl butyrate, ethyl pyruvate, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

  Although content of a solvent is not specifically limited, From viewpoints of the applicability | paintability of a coloring composition obtained, stability, etc., the total density | concentration of each component except the solvent of the said coloring composition is 5-50. An amount of mass% is preferred, and an amount of 10 to 40 mass% is particularly preferred.

  The coloring composition of the present invention can be prepared by an appropriate method, and examples of the preparation method include methods disclosed in JP 2008-58642 A, JP 2010-132874 A, and the like. be able to. When both a yellow dye and a pigment are used as the colorant, as disclosed in Japanese Patent Application Laid-Open No. 2010-132874, after passing a dye solution containing a yellow dye through the first filter, A method can be employed in which the dye solution that has passed is mixed with a separately prepared pigment dispersion or the like, and the resulting colored composition is passed through a second filter. Moreover, after dissolving yellow dye, said (B)-(D) component, and an additive component as needed in a solvent, let the obtained solution pass a 1st filter, it passes a 1st filter. A method may also be employed in which the prepared solution is mixed with a separately prepared pigment dispersion and the resulting colored composition is passed through a second filter. In addition, after passing the dye solution containing the yellow dye through the first filter, the dye solution that has passed through the first filter, the components (B) to (D), and the additive component as necessary are mixed. Dissolve the obtained solution through the second filter, mix the solution that has passed through the second filter with the pigment dispersion prepared separately, and pass the resulting colored composition through the third filter. It is also possible to employ a method of preparing by.

Color filter and method for producing the same The color filter of the present invention includes a colored layer formed using the colored composition of the present invention.

  As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying the red radiation-sensitive composition of the present invention on this substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

  Next, each colored radiation-sensitive composition of green or blue is used, and each colored radiation-sensitive composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that the green pixel array and blue Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation-sensitive composition, it can be formed in the same manner as in the case of forming the pixel.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When the colored radiation-sensitive composition is applied to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

  The coating thickness is usually 0.6 to 8 μm, preferably 1.2 to 5 μm, as the film thickness after drying.

  Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples of the light source include a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.

Exposure of the radiation is generally preferred 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 120 to 280 ° C. and about 10 to 60 minutes. The post-baking temperature is preferably 240 ° C. or less, particularly preferably 230 ° C. or less, from the viewpoint of the heat resistance of the yellow dye.
The film thickness of the pixel thus formed is usually 0.5 to 5 μm, preferably 1 to 3 μm.

  The color filter of the present invention thus obtained is extremely useful for a color liquid crystal surface element, a color imaging tube element, an organic EL display element, and the like because it has excellent chromaticity characteristics.

Display element The display element of the present invention comprises the color filter of the present invention. Examples of the display element include a color liquid crystal display element and an organic EL display element.
A color liquid crystal display device including the color filter of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that faces each other via the The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

  The color liquid crystal display device including the color filter of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light by color mixing by combining a red LED, a green LED, and a blue LED, a white LED that obtains white light by color mixing by combining a blue LED, a red LED, and a green phosphor, and a blue LED White LED that obtains white light by mixing colors, red LED and green light emitting phosphor, white LED that obtains white light by mixing colors of blue LED and YAG phosphor, blue LED, orange light emitting phosphor and green light emitting fluorescence A white LED that obtains white light by color mixing by combining the body, a white LED that obtains white light by color mixing by combining an ultraviolet LED, a red light emitting phosphor, a green light emitting phosphor, and a blue light emitting phosphor can be exemplified.

The color liquid crystal display device having the color filter of the present invention includes a TN (twisted nematic) type, an STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical alignment) type, and an OCB (Optic Optical). An appropriate liquid crystal mode such as a birefringence type can be applied.
Moreover, the organic EL display element provided with the color filter of the present invention can take an appropriate structure, and examples thereof include a structure disclosed in JP-A-11-307242.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Preparation of pigment dispersion>
Preparation Example 1
As a coloring agent, C.I. I. 15 parts by mass of Pigment Green 58, 12.5 parts by mass of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration = 40% by mass), and 72.5 parts by mass of propylene glycol monomethyl ether acetate as a solvent The pigment dispersion (A-1) was prepared by using a bead mill.

Preparation Example 2
As a coloring agent, C.I. I. 15 parts by weight of Pigment Yellow 150, 12.5 parts by weight of BYK-LPN21116 (produced by BYK) as a dispersant (solid content concentration = 40% by weight), and 72.5 parts by weight of propylene glycol monomethyl ether acetate as a solvent Then, it was processed by a bead mill to prepare a pigment dispersion (A-2).

<Preparation of dye solution>
Preparation Example 3
10 parts by weight of yellow dye 1 represented by the following formula as a colorant (CI solvent yellow 162, which is a pyridone azo dye) and 90 parts by weight of cyclohexane non as a solvent are mixed to prepare a dye solution (A-3). Was prepared.

Preparation Example 4
10 parts by weight of yellow dye 2 (cyanine dye) represented by the following formula as a colorant and 90 parts by weight of cyclohexanenone as a solvent were mixed to prepare a dye solution (A-4).

Preparation Example 5
10 parts by mass of yellow dye 3 (barbituric acid azo dye) represented by the following formula as a colorant and 90 parts by mass of cyclohexanenone as a solvent were mixed to prepare a dye solution (A-5).

Preparation Example 6
10 parts by weight of yellow dye 4 (pyridone azo dye forming a dimer) represented by the following formula as a colorant and 90 parts by weight of cyclohexanenon as a solvent are mixed to prepare a dye solution (A-6). Prepared.

<Synthesis of binder resin>
Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 20 parts by mass of methacrylic acid, 15 parts by mass of styrene, 25 parts by mass of butyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, N-phenylmaleimide A mixed solution of 25 parts by mass and 2,2′-azobis (2,4-dimethylvaleronitrile) 6 parts by mass was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 10,500 and Mn = 5,500. This binder resin is referred to as “binder resin (B1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 16 parts by mass of methacrylic acid, 15 parts by mass of styrene, 29 parts by mass of butyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, N-phenylmaleimide A mixed solution of 25 parts by mass and 2,2′-azobis (2,4-dimethylvaleronitrile) 6 parts by mass was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 10,300 and Mn = 5,200. This binder resin is referred to as “binder resin (B2)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of cyclohexanone, 40 parts by mass of methacrylic acid, 15 parts by mass of styrene, 10 parts by mass of butyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, 25 parts by mass of N-phenylmaleimide, And a mixed solution of 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 11,000 and Mn = 5,600. This binder resin is referred to as “binder resin (B3)”.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of cyclohexanone, 46 parts by mass of methacrylic acid, 15 parts by mass of styrene, 4 parts by mass of butyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, 25 parts by mass of N-phenylmaleimide, And a mixed solution of 6 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 10,000 and Mn = 5,100. This binder resin is referred to as “binder resin (B4)”.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 12 parts by mass of methacrylic acid, 15 parts by mass of styrene, 33 parts by mass of butyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, N-phenylmaleimide A mixed solution of 25 parts by mass and 2,2′-azobis (2,4-dimethylvaleronitrile) 6 parts by mass was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 10,700 and Mn = 5,500. This binder resin is referred to as “binder resin (B5)”.

Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 22 parts by mass of methacrylic acid, 15 parts by mass of styrene, 23 parts by mass of butyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, N-phenylmaleimide A mixed solution of 25 parts by mass and 2,2′-azobis (2,4-dimethylvaleronitrile) 6 parts by mass was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 11,000 and Mn = 5,300. This binder resin is referred to as “binder resin (B6)”.

Synthesis example 7
A flask equipped with a condenser and a stirrer was charged with 100 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen. Heat to 80 ° C., and at the same temperature, 100 parts by mass of propylene glycol monomethyl ether acetate, 26 parts by mass of methacrylic acid, 15 parts by mass of styrene, 19 parts by mass of butyl methacrylate, 10 parts by mass of 2-hydroxyethyl methacrylate, N-phenylmaleimide A mixed solution of 25 parts by mass and 2,2′-azobis (2,4-dimethylvaleronitrile) 6 parts by mass was added dropwise over 1 hour, and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C. and further polymerized for 1 hour to obtain a binder resin solution (solid content concentration = 33% by mass). The obtained binder resin was Mw = 11,000 and Mn = 5,200. This binder resin is referred to as “binder resin (B7)”.

<(B) Measurement of acid value of binder resin>
The acid value of the binder resin obtained in each of the above synthesis examples was measured as follows. Table 1 shows the measurement results.
0.5 g of the binder resin solution was precisely weighed to a unit of 1 mg and separated into a glass container. After diluting to 50 mL with cyclohexanone, phenolphthalein was added, titrated with 0.1N ethanolic potassium hydroxide aqueous solution, and the point colored pink was the end point. Similarly, a blank test was performed. The acid value (unit: mgKOH / g) was calculated from the binder resin and the drop amount of 0.1N ethanolic potassium hydroxide aqueous solution in the blank test.

Example 1
<Preparation of colored radiation-sensitive composition>
32.7 parts by mass of the pigment dispersion (A-1), 22.0 parts by mass of the dye solution (A-3) obtained in Preparation Example 3, 12.2 parts by mass of the binder resin (B1) solution as the binder resin, M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd. as a polyfunctional monomer, and 2,2′-bis (2-chlorophenyl) as a photopolymerization initiator ) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Hodogaya Chemical Co., Ltd.) 1.2 parts by mass and 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.4 mass Part, 0.04 parts by mass of DIC's MegaFac F-554 as a fluorosurfactant and propylene glycol monomethyl ether acetate as a solvent are mixed to obtain a solid content concentration of 20 A mass% colored radiation-sensitive composition was prepared.

<Evaluation of chromaticity characteristics and contrast ratio>
The obtained colored radiation-sensitive composition was applied onto a glass substrate using a spin coater, and then pre-baked on an 80 ° C. hot plate for 10 minutes to form a coating film. Three coating films having different film thicknesses were formed by the same operation while changing the rotation speed of the spin coater.
Next, after cooling these substrates to room temperature, a high-pressure mercury lamp is used, and a radiation containing each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without using a photomask at an exposure dose of 2,000 J / m ² . And exposed. Then, shower development was performed for 90 seconds on these substrates by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter: 1 mm). . Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 230 ° C. for 30 minutes to form a cured film for evaluation.

  Using the color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), the chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. Moreover, the film thickness of the obtained cured film was measured using the alpha step IQ made from KLA-Tencor. From the measurement results, the chromaticity coordinate value x, the stimulus value (Y), and the film thickness at the chromaticity coordinate value y = 0.590 were obtained. The evaluation results are shown in Table 1. The larger the stimulus value (Y), the higher the luminance, and the thinner the film thickness, the higher the coloring power.

  Further, the substrate on which the cured film is formed is sandwiched between two deflecting plates, and the front side deflecting plate is rotated while irradiating with a fluorescent lamp (wavelength range of 380 to 780 nm) from the back side, and the luminance meter LS-100 (Minolta The maximum value and the minimum value of the transmitted light intensity were measured. And about each cured film, the value which remove | divided the maximum value by the minimum value was made into the contrast ratio. From the measurement result, the contrast ratio at the chromaticity coordinate value y = 0.590 was determined. The evaluation results are shown in Table 1.

Examples 2 to 6 and Comparative Example 1
A colored radiation-sensitive composition was prepared in the same manner as in Example 1 except that the type of (B) binder resin component in Example 1 was as shown in Table 1. Then, the chromaticity characteristics and the contrast ratio were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Example 7
In Example 1, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (manufactured by Hodogaya Chemical Co., Ltd.) 0 as a photopolymerization initiator .9 parts by mass and 0.3 parts by mass of 2-mercaptobenzothiazole (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.3 parts by mass of NCI-930 (manufactured by ADEKA, Inc., O-acyloxime compound) In the same manner as in Example 1, a colored radiation-sensitive composition was prepared. Then, the chromaticity characteristics and the contrast ratio were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Examples 8-10
In Example 1, a colored radiation-sensitive composition was prepared in the same manner as in Example 1 except that the type of the dye solution was as shown in Table 1. Then, the chromaticity characteristics and the contrast ratio were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Examples 2-5
In Example 1 and Examples 5 to 7, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole (residue) was used as a photopolymerization initiator. Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H- in place of 1.2 parts by mass (made by Tsuchiya Chemical Co.) and 0.4 parts by mass of 2-mercaptobenzothiazole (made by Tokyo Chemical Industry Co., Ltd.) Carbazol-3-yl]-, 1- (O-acetyloxime) (Ciba Specialty Chemicals, trade name IRGACURE OXE-02) Except for using 1.3 parts by mass, Example 1 and Example were carried out, respectively. Colored radiation sensitive compositions were prepared in the same manner as in Examples 5-7. Then, the chromaticity characteristics and the contrast ratio were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 6
28.0 parts by mass of the pigment dispersion (A-1), 18.7 parts by mass of the pigment dispersion (A-2), 11.4 parts by mass of the binder resin (B1) solution as a binder resin, and as a polyfunctional monomer 5.6 parts by mass of M-402 (mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) manufactured by Toagosei Co., Ltd., 2,2′-bis (2-chlorophenyl) -4,4 ′, as a photopolymerization initiator 5,5′-Tetraphenyl-1,2′-biimidazole (Hodogaya Chemical Co., Ltd.) 1.2 parts by mass, 2-mercaptobenzothiazole (Tokyo Chemical Industry Co., Ltd.) 0.4, DIC as a fluorosurfactant Colored radiation-sensitive composition having a solid content of 20% by mass by mixing 0.04 parts by mass of Megafac F-554 manufactured by KK and propylene glycol monomethyl ether acetate as a solvent A product was prepared. Then, the chromaticity characteristics and the contrast ratio were evaluated in the same manner as in Example 1. The evaluation results are shown in Table 1.

In Table 1, “G58” means C.I. I. Pigment Green 58, “Y150” is C.I. I. Pigment Yellow 150, “D1” is 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, “D2” is 2 -Mercaptobenzothiazole, “D3” is ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), “D4” means NCI-930 (manufactured by ADEKA Corporation, O-acyloxime compound).

Claims (6)

(A) a colorant containing a yellow dye,
(B) a binder resin having an acid value of 85 to 300 mgKOH / g,
A coloring composition for a color filter comprising (C) a polyfunctional monomer, and (D) a photopolymerization initiator containing a biimidazole compound.   The coloring for color filter according to claim 1, wherein the yellow dye contains at least one selected from the group consisting of barbituric acid azo dyes, pyridone azo dyes, pyrazolone azo dyes, quinophthalone dyes and cyanine dyes. Composition.   The colored composition for a color filter according to claim 1 or 2, further comprising a green colorant as the colorant (A). The color according to claim 1 or 3, wherein the yellow dye comprises at least one selected from the group consisting of a compound represented by the following formula (1), a dimer formed from the compound, and a salt thereof. Coloring composition for filters.

[In Formula (1),
Z is a halogen atom, a C1-C12 saturated hydrocarbon group which may have a substituent, a C1-C8 alkoxy group, a hydroxy group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group, and A phenyl group having one or two substituents selected from the group consisting of N-substituted sulfamoyl groups, or a halogen atom, a hydrocarbon group having 1 to 12 carbon atoms which may have a substituent, A naphthyl group having 1 to 3 substituents selected from the group consisting of an alkoxy group having 1 to 8 carbon atoms, a hydroxy group, a carboxyl group, a carbamoyl group, a sulfo group, a sulfamoyl group and an N-substituted sulfamoyl group; Show.
R ¹ represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a carboxyl group or a trifluoromethyl group.
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, a cyano group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, a sulfo group or an amino group.
R ³ has a hydrogen atom, an optionally substituted saturated hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted aryl group having 6 to 30 carbon atoms, and a substituent. An optionally substituted aralkyl group having 7 to 20 carbon atoms, an optionally substituted heterocyclic group having 3 to 20 carbon atoms, a carbamoyl group, an N-substituted carbamoyl group, and a substituent. An aliphatic oxycarbonyl group having 2 to 20 carbon atoms, an aromatic oxycarbonyl group having 7 to 30 carbon atoms which may have a substituent, and an acyl group having 2 to 20 carbon atoms which may have a substituent The C1-C30 aliphatic sulfonyl group which may have a substituent, or the C6-C30 aromatic sulfonyl group which may have a substituent is shown. ]   The color filter provided with the colored layer formed using the coloring composition for color filters of any one of Claims 1-4.   A display device comprising the color filter according to claim 5.