JP2010032999A - Colored photosensitive resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive resin composition containing a specific combination of pigment and dye, which is used for a film and a color filter with high lightness. <P>SOLUTION: The colored photosensitive resin composition contains a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E), wherein the colorant (A) contains an organic solvent-soluble dye containing a compound represented by formula (1) and an organic pigment. In the formula, R<SP>1</SP>-R<SP>4</SP>represent H, -R<SP>6</SP>or a 6-10C aromatic hydrocarbon group; R<SP>5</SP>represents -SO<SB>3</SB>-, -SO<SB>3</SB>H, -SO<SB>3</SB>M, -CO<SB>2</SB>H, -CO<SB>2</SB>R<SP>6</SP>, -SO<SB>3</SB>R<SP>6</SP>, -SO<SB>2</SB>NHR<SP>8</SP>or -SO<SB>2</SB>NR<SP>8</SP>R<SP>9</SP>; m represents an integer of 0-5; X represents a halogen atom; and (a) represents an integer of 0 or 1. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a colored photosensitive resin composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device or a solid-state imaging device, and a color filter using the colored photosensitive resin composition.

In recent years, color filters are desired to have high definition, high brightness, and high contrast. In order to achieve this, there is a tendency that the color filter is highly purified and the pigment concentration in the colored photosensitive resin composition is increased. However, when the pigment concentration is high, the pigment has a certain particle size and scatters light, so that there is a problem that the contrast of a color filter formed using a colored photosensitive resin composition containing the pigment becomes low. there were.
Therefore, for example, by using a combination of a pyrazole-based squarylium compound as a dye that develops a color only by light absorption and a blue pigment Pigment Blue (P.B) 15: 6 as a pigment, a high contrast of the color filter is used. A technique for achieving this is disclosed (Patent Document 1).

Japanese Patent Application Laid-Open No. 2006-079012

Furthermore, in order to achieve higher brightness of the color filter, development of a colored photosensitive resin composition containing dyes and pigments of other combinations other than the combination specifically disclosed in Patent Document 1 is desired.
As a result of intensive studies to solve the above problems, the present inventors have found that a colored photosensitive resin composition containing a specific new combination of a dye and a pigment provides a high-lightness coating film. Invented.

  The present invention is a colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the colorant (A) is a colored photosensitive resin composition which is a colorant containing an organic solvent-soluble dye containing a compound represented by the formula (1) and an organic pigment.

(In formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic hydrocarbon having 6 to 10 carbon atoms. The hydrogen atom contained in the group is a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO. _It may be substituted with ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ⁵ represents —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ . To express.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
X represents a halogen atom. a represents an integer of 0 or 1.
R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. A hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom. The methylene group contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an oxygen atom, a carbonyl group or —NR ⁶ —.
R ⁸ and R ⁹ each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms.
Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is —OH , R ⁶ , —OR ⁶ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁶ or a halogen atom.
The hydrogen atom contained in the linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms is a hydroxyl group, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ⁶ . May be substituted.
The methylene group contained in the linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms may be substituted with an oxygen atom, a carbonyl group or —NR ⁶ —.
The hydrogen atom contained in the heterocyclic ring having 1 to 10 carbon atoms may be substituted with R ⁶ , —OH or —Q.
M represents a sodium atom or a potassium atom. )

  Moreover, this invention is the said colored photosensitive resin composition whose compound represented by Formula (1) is a compound represented by Formula (1-1).

(In formula (1-1), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, —R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic having 6 to 10 carbon atoms. The hydrogen atom contained in the hydrocarbon group includes a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ Na, —CO ₂ H, —CO ₂ R ⁶ , It may be substituted with —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ¹⁵ represents a hydrogen atom, —SO ₃ ^— , —SO ₃ H, —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ¹⁶ represents —SO ₃ ^— , —SO ₃ H, —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ⁶ , R ⁸ , R ⁹ , m, X and a have the same meaning as described above. )

  Moreover, this invention is the said colored photosensitive resin composition whose compound represented by Formula (1) is a compound represented by Formula (1-2).

(In formula (1-2), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, —R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic having 6 to 10 carbon atoms. hydrogen atoms contained in the hydrocarbon group, a halogen _{^{atom, -R 26, -OH, -OR 26}} , -SO 3 -, -SO 3 Na, -CO 2 H, -CO 2 R 26, -SO 3 H, it may be substituted by -SO ₃ R ²⁶ or _-SO 2 ^{NHR 28.}
R ²⁵ represents —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ²⁶ , —SO ₃ H or SO ₂ NHR ²⁸ .
R ²⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —OR ²⁶ or a halogen atom.
R ²⁸ represents a hydrogen atom, —R ²⁶ , —CO ₂ R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is it may be substituted by -R ²⁶ or ^{-OR 26.}
m, X, and a represent the same meaning as described above. )

  Moreover, this invention is the said colored photosensitive resin composition whose compound represented by Formula (1) is a compound represented by Formula (1-3).

(In Formula (1-3), R ³¹ and R ³² each independently represent a phenyl group. The hydrogen atom contained in the phenyl group is a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R. ^26, may be substituted by _-SO 3 ^{R 26} or _-SO 2 ^{NHR 28.}
R ³³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ³⁴ represents a hydrogen atom, —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ²⁶ , R ²⁸ , X and a represent the same meaning as described above. )

  Moreover, this invention is the said colored photosensitive resin composition whose compound represented by Formula (1) is a compound represented by Formula (1-4).

(In Formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group. The hydrogen atom contained in the phenyl group is substituted with —R ²⁶ or —SO ₂ NHR ^28. Also good.
R ⁴³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ²⁶ , R ²⁸ , X and a represent the same meaning as described above. )

  In the present invention, the organic pigment is C.I. I. It is the said colored photosensitive resin composition which is an organic pigment containing pigment blue 15: 6.

  The present invention also relates to C.I. in the colorant (A). I. It is the said colored photosensitive resin composition whose mass ratio of pigment blue 15: 6 and the organic-solvent soluble dye containing the compound represented by Formula (1) is 97: 3-50: 50.

  Moreover, this invention is a coating film formed using the said colored photosensitive resin composition.

  Moreover, this invention is a color filter formed using the said colored photosensitive resin composition.

  Moreover, this invention is the said color filter formed by the photolithographic method.

  According to the colored photosensitive resin composition of the present invention, a coating film with high brightness can be obtained.

  The colored photosensitive resin composition of the present invention contains a colorant (A), and the colorant (A) is an organic solvent-soluble dye containing a compound represented by the formula (1) (hereinafter “dye (1)”). A coloring agent containing

  The dye (1) can be selected according to the color of the target color filter, and a plurality of dyes can be blended and used. Those having sufficient solubility in the solvent contained in the colored photosensitive resin composition and sufficient solubility in the developing solution to such an extent that the pattern can be formed in the development step during pattern formation are preferred.

(In formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic hydrocarbon having 6 to 10 carbon atoms. The hydrogen atom contained in the group is a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO. _It may be substituted with ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ⁵ represents —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ . To express.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
X represents a halogen atom. a represents an integer of 0 or 1.
R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. A hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom. The methylene group contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an oxygen atom, a carbonyl group or —NR ⁶ —.
R ⁸ and R ⁹ each independently represents a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms.
Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group is —OH , R ⁶ , —OR ⁶ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁶ or a halogen atom.
The hydrogen atom contained in the linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms is a hydroxyl group, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ⁶ . May be substituted.
The methylene group contained in the linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms may be substituted with an oxygen atom, a carbonyl group or —NR ⁶ —.
The hydrogen atom contained in the heterocyclic ring having 1 to 10 carbon atoms may be substituted with R ⁶ , —OH or —Q.
M represents a sodium atom or a potassium atom. )

R ⁶ includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, octyl, 2-ethylhexyl, cyclooctyl, nonyl, decanyl, tricyclodecane Nyl, methoxypropyl, ethoxypropyl, hexyloxypropyl, 2-ethylhexyloxypropyl, methoxyhexyl, ethoxypropyl and the like.

Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include phenyl and naphthyl.
Examples of the halogen atom exemplified as the substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms include fluorine, chlorine, bromine and the like.
Examples of —SO ₃ R ⁶ include methanesulfonyl, ethanesulfonyl, hexanesulfonyl, decanesulfonyl, and the like.
-CO ₂ R ⁶ includes methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, cyclopentyloxycarbonyl, Hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, cyclooctyloxycarbonyl, nonyloxycarbonyl, decanyloxycarbonyl, tricyclodecanyloxycarbonyl, methoxypropyl Oxycarbonyl, ethoxypropyloxycarbonyl, hex B propyl oxycarbonyl, 2-ethylhexyloxy propyloxy, methoxy hexyloxycarbonyl, and the like.

—SO ₂ NHR ⁸ includes sulfamoyl, methanesulfamoyl, ethanesulfamoyl, propanesulfamoyl, isopropanesulfamoyl, butanesulfamoyl, isobutanesulfamoyl, pentansulfamoyl, isopentansulfamoyl, Neopentanesulfamoyl, cyclopentanesulfamoyl, hexanesulfamoyl, cyclohexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanessulfamoyl, 2-ethylhexanesulfamoyl, 1,5- Dimethylhexanesulfamoyl, cyclooctanesulfamoyl, nonanesulfamoyl, decanesulfamoyl, tricyclodecanesulfamoyl, methoxypropanesulfamoyl, ethoxypropanesulfa , Propoxypropane sulfamoyl, isopropoxypropane sulfamoyl, hexyloxypropane sulfamoyl, 2-ethylhexyloxypropane sulfamoyl, methoxyhexanesulfamoyl, 3-phenyl-1-methylpropanesulfamoyl, etc. Is mentioned.

Examples of —SO ₂ NHR ⁸ and —SO ₂ NR ⁸ R ⁹ further include a group represented by the following formula.

In the above formula, X ¹ represents a halogen atom. Examples of the halogen atom for X ¹ include a fluorine atom, a chlorine atom, and a bromine atom.

In the above formula, X ³ represents an alkyl group or an alkoxyl group having 1 to 3 carbon atoms having 1 to 3 carbon atoms, hydrogen atoms of the alkyl group and alkoxy group may be substituted with a halogen atom.
Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom include methyl, ethyl, propyl, isopropyl, perfluoromethyl and the like.
Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include methoxy, ethoxy and propoxy.

In the above formula, X ² represents an alkyl group having 1 to 3 carbon atoms, an alkoxyl group having 1 to 3 carbon atoms, a halogen atom or a nitro group, and the hydrogen atom of the alkyl group and the alkoxy group is substituted with a halogen atom. It may be.
Examples of the halogen atom for X ² include a fluorine atom, a chlorine atom and a bromine atom.
Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom include methyl, ethyl, propyl, isopropyl, perfluoromethyl and the like.
Examples of the alkoxy group having 1 to 3 carbon atoms which may be substituted with a halogen atom include methoxy, ethoxy and propoxy.

In the above formula, X ² represents the same meaning as described above.

上記式中、Ｘ^３は、上記と同じ意味を表す。

In the above formula, X ³ represents the same meaning as described above.

R ⁸ and R ⁹ contained in —SO ₂ NR ⁸ R ⁹ include a branched alkyl group having 6 to 8 carbon atoms, an alicyclic alkyl group having 5 to 7 carbon atoms, an allyl group, a phenyl group, and a carbon number. An aralkyl group having 8 to 10 carbon atoms, a hydroxyl group-containing alkyl and aryl group having 2 to 8 carbon atoms, or an alkyl group or aryl group having 2 to 8 carbon atoms is preferable, and 2-ethylhexyl is particularly preferable.

As the substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms, ethyl, propyl, phenyl, dimethylphenyl, —SO ₃ R ⁶ or —SO ₂ NHR ⁸ is preferable.

  Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl, hexylphenyl, decanylphenyl, fluorophenyl, chlorophenyl, bromophenyl, hydroxyphenyl, methoxyphenyl , Dimethoxyphenyl, ethoxyphenyl, hexyloxyphenyl, decanyloxyphenyl, trifluoromethylphenyl and the like.

At least one of R ¹ and R ² or at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or an optionally substituted aromatic carbon atom having 6 to 10 carbon atoms. A hydrogen group is preferred.
At least one of R ¹ and R ² and at least one of R ³ and R ⁴ is an alkyl group having 1 to 4 carbon atoms or an optionally substituted aromatic carbon atom having 6 to 10 carbon atoms. A hydrogen group is preferred.
More preferably, at least one of R ¹ and R ² and at least one of R ³ and R ⁴ is an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms.
R ⁵ is carboxyl, ethyloxycarbonyl, sulfoxyl, 2-ethylhexyloxypropane sulfamoyl, 1,5-dimethylhexanesulfamoyl, 3-phenyl-1-methylpropanesulfamoyl, isopropoxypropane sulfamoyl It is preferable that

  It is preferable that the compound represented by Formula (1) is a compound represented by Formula (1-1).

(In formula (1-1), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, —R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic having 6 to 10 carbon atoms. The hydrogen atom contained in the hydrocarbon group includes a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ Na, —CO ₂ H, —CO ₂ R ⁶ , It may be substituted with —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ¹⁵ represents a hydrogen atom, —SO ₃ ^— , —SO ₃ H, —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ¹⁶ represents —SO ₃ ^— , —SO ₃ H, —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ⁶ , R ⁸ , R ⁹ , m, X and a have the same meaning as described above. )

  It is preferable that the compound represented by Formula (1) is a compound represented by Formula (1-2).

(In formula (1-2), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, —R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic having 6 to 10 carbon atoms. hydrogen atoms contained in the hydrocarbon group, a halogen _{^{atom, -R 26, -OH, -OR 26}} , -SO 3 -, -SO 3 Na, -CO 2 H, -CO 2 R 26, -SO 3 H, it may be substituted by -SO ₃ R ²⁶ or _-SO 2 ^{NHR 28.}
R ²⁵ represents —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ²⁶ , —SO ₃ H or SO ₂ NHR ²⁸ .
R ²⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —OR ²⁶ or a halogen atom.
R ²⁸ represents a hydrogen atom, —R ²⁶ , —CO ₂ R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is it may be substituted by -R ²⁶ or ^{-OR 26.}
m, X, and a represent the same meaning as described above. )

  It is preferable that the compound represented by Formula (1) is a compound represented by Formula (1-3).

(In Formula (1-3), R ³¹ and R ³² each independently represent a phenyl group. The hydrogen atom contained in the phenyl group is a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R. ^26, may be substituted by _-SO 3 ^{R 26} or _-SO 2 ^{NHR 28.}
R ³³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ³⁴ represents a hydrogen atom, —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ²⁶ , R ²⁸ , X and a represent the same meaning as described above. )

  It is preferable that the compound represented by Formula (1) is a compound represented by Formula (1-4).

(In Formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group. The hydrogen atom contained in the phenyl group is substituted with —R ²⁶ or —SO ₂ NHR ^28. Also good.
R ⁴³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ²⁶ , R ²⁸ , X and a represent the same meaning as described above. )

（式（１ａ）中、Ｒ^ｂ及びＲ^ｃは、それぞれ独立に、水素原子、−ＳＯ_３ ⁻、−ＣＯ_２Ｈ又は−ＳＯ_２ＮＨＲ^ａを表す。Ｒ^ａは、２−エチルヘキシルを表す。Ｘ及びａは、上記と同じ意味を表す。） Examples of the compound represented by formula (1) include compounds represented by formula (1a) to formula (1f).

(In formula (1a), R ^b and R ^c each independently represent a hydrogen atom, —SO ₃ ^— , —CO ₂ H, or —SO ₂ NHR ^a . R ^a represents 2-ethylhexyl. X And a represent the same meaning as described above.)

（式（１ｂ）中、Ｒ^ｂは、上記と同じ意味を表す。）

(In formula (1b), R ^b represents the same meaning as described above.)

（式（１ｂ−１）中、Ｒ^ｂ、Ｘ及びａは、上記と同じ意味を表す。） The compound represented by the formula (1b) is a tautomer of the compound represented by the formula (1b-1).

(In formula (1b-1), R ^b , X and a represent the same meaning as described above.)

（式（１ｃ）及び式（１ｄ）中、Ｒ^ｄ、Ｒ^ｅ及びＲ^ｆは、それぞれ独立に、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ又は−ＳＯ_２ＮＨＲ^ａを表す。Ｒ^ａは、２−エチルヘキシルを表す。）

(In Formula (1c) and Formula (1d), R ^d , R ^e and R ^f each independently represent —SO ₃ ^— , —SO ₃ Na or —SO ₂ NHR ^a . R ^a represents 2- Represents ethylhexyl.)

（式（１ｅ）及び式（１ｆ）中、Ｒ^ｇ、Ｒ^ｈ及びＲ^ｉは、それぞれ独立に、水素原子、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ又は−ＳＯ_２ＮＨＲ^ａを表す。Ｒ^ａは、２−エチルヘキシルを表す。）

(In the formula (1e) and the formula ^{(1f), R g, R} h and ^{R i} each independently represent a hydrogen _atom, ^-SO 3 -, is .R ^a representative of the -SO ₃ H or _-SO 2 NHR ^a Represents 2-ethylhexyl.)

The compound represented by formula (1) is obtained by, for example, chlorinating a dye or dye intermediate having —SO ₃ H by a conventional method, and converting the obtained dye or dye intermediate having —SO ₂ Cl into R ⁸ —NH. It can manufacture by making it react with the amine represented by ₂ . Moreover, it can manufacture by making the pigment | dye manufactured by the method of Unexamined-Japanese-Patent No. 3-78702 page 3 right upper column-lower left column react with an amine after chlorination like the above.

The colorant (A) is a colorant further containing an organic pigment in addition to the dye (1).
As an organic pigment, specifically, for example,
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. And violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, and 38. Among them, C.I. I. Pigment red violet 23, C.I. I. Pigment Blue 15: 3, preferably containing at least one pigment selected from 15: 6, C.I. I. It is particularly preferable that pigment blue 15: 6 is contained. These pigments may be used alone or in combination of two or more.

Among the above pigments, organic pigments are optionally treated with rosin, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment onto the pigment surface with a polymer compound, sulfuric acid fine particles, etc. A pulverization process such as an atomization method, a cleaning process using an organic solvent or water for removing impurities, a removal process using an ion exchange method for ionic impurities, or the like may be performed.
The organic pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.
Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants, which may be used alone or in combination of two or more. Good.
When the pigment dispersant is used, the amount used is preferably 1 part by mass or less, more preferably 0.05 part by mass or more and 0.5 part by mass or less, per 1 part by mass of the pigment (A). When the amount of the pigment dispersant used is in the above range, it is preferable because a pigment dispersion in a uniform dispersion state tends to be obtained.

Content of a coloring agent (A) is a mass fraction with respect to solid content in a coloring photosensitive resin composition, Preferably it is 5-60 mass%, More preferably, it is 8-55 mass%, Furthermore, Preferably it is 10-50 mass%. Here, solid content means the sum total of the components except a solvent in a coloring photosensitive resin composition.
When the content of the colorant (A) is in the above range, the color density when a color filter is obtained is sufficient, and a necessary amount of the binder polymer can be contained in the composition. It is preferable because a sufficient pattern can be formed.
The content of the dye (1) in the colorant (A) is 3 to 80% by mass ratio, preferably 3 to 70% by mass, and more preferably 3 to 50% by mass.
Content of the organic pigment in a coloring agent (A) is 20 to 97% by mass ratio, Preferably it is 30 to 97 mass%, More preferably, it is 50 to 97 mass%.

In particular, C.I. I. It is preferable that the mass ratio of Pigment Blue 15: 6 and Dye (1) is 97: 3 to 50:50.
When the content of the organic pigment in the colorant (A) is in the above range, it is easy to optimize the transmission spectrum, and it is good for obtaining high contrast and high brightness, and further, heat resistance and chemical resistance. It is preferable because of its good properties.

  The colored photosensitive resin composition used for producing the color filter of the present invention contains a binder resin (B). The binder resin (B) preferably contains a structural unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the structural unit derived from the (meth) acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 18 in terms of mole fraction in all the structural units constituting the binder resin (B). It is from mol% to 38 mol%. When the content of the structural unit derived from (meth) acrylic acid is within the above range, the solubility of the non-pixel portion is good during development, and the residue tends not to remain in the non-pixel portion after development. Yes, it is preferable.

  Examples of the other monomer that leads to the constituent unit of the binder resin other than the constituent unit derived from (meth) acrylic acid include, for example, aromatic vinyl compounds, unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, and unsaturated compounds. Carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides, unsaturated imides, aliphatic conjugated dienes, monoacryloyl group or mono at the end of the polymer molecular chain Examples thereof include macromonomers having a methacryloyl group, units represented by the formula (II), and units represented by the formula (III).

(In Formula (II) and Formula (III), R ⁵³ and R ⁵⁵ each independently represent a hydrogen atom or a methyl group. R ⁵⁴ and R ⁵⁶ each independently represent a hydrogen atom or a C 1-6 carbon atom. Represents an alkyl group of

Specific examples of the binder resin include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / isobornyl methacrylate copolymer, and methacrylic acid / styrene. / Benzyl methacrylate / N-phenylmaleimide copolymer, methacrylic acid / constituent component represented by formula (II) (wherein, in formula (II), R ⁵³ represents a methyl group and R ⁵⁴ represents a hydrogen atom) / Benzyl methacrylate copolymer, a constituent represented by the formula (II) (in the formula (II), R ⁵³ represents a methyl group and R ⁵⁴ represents a hydrogen atom). / Benzyl methacrylate copolymer, methacrylic acid / constituent component represented by formula (III) In formula (III), R ⁵⁵ represents a methyl group, and R ⁵⁶ represents a hydrogen atom.) / Styrene copolymer / Tricyclodecanyl methacrylate copolymer and the like are preferable.

  The acid value of binder resin (B) used by this invention is 50-150 normally, Preferably it is 60-135, Most preferably, it is 70-135. When the acid value is in the above range, the solubility in the developer is improved and the unexposed area is easily dissolved, and the sensitivity is increased so that the pattern of the exposed area remains during development and the remaining film ratio tends to be improved. Is preferable. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic acid polymer, and is usually obtained by titration with an aqueous potassium hydroxide solution. it can.

  Content of binder resin (B) is a mass fraction with respect to solid content of a coloring photosensitive resin composition, and is 7-65 mass% normally, Preferably it is 13-60 mass%, More preferably 17-55 mass%. When the content of the binder resin (B) is in the above range, a pattern can be formed and the resolution and the remaining film ratio tend to be improved.

Binder resin having a component represented by formula (II), for example, methacrylic acid / component represented by formula (II) (wherein, in formula (II), R ⁵³ represents a methyl group, R ⁵⁴ represents a hydrogen atom.) / Benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the obtained two-component polymer is represented by the formula (IV). Wherein R ⁵⁷ represents a hydrogen atom in formula (IV).

Methacrylic acid / constituent component represented by formula (III) (wherein, in formula (III), R ⁵⁵ represents a methyl group and R ⁵⁶ represents a hydrogen atom) / styrene copolymer / tricyclo The decanyl methacrylate copolymer can be obtained by reacting benzyl methacrylate, methacrylic acid, or a monomethacrylate copolymer having a tricyclodecane skeleton with glycidyl methacrylate.

The weight average molecular weight in terms of polystyrene of the binder resin is usually 5,000 to 35,000, preferably 6,000 to 30,000, and particularly preferably 7,000 to 28,000. When the molecular weight is within the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution tends to be improved, which is preferable.
In particular, the binder resin (B) represented by the formula (V) is preferable in terms of curability and developability.

  Copolymerization is generally carried out in a solvent using a polymerization initiator. Examples of the polymerization initiator include azo compounds such as 2,2′-azobisisobutyronitrile and 2,2′-azobis (methyl 2-methylpropionate), benzoyl peroxide and tert-butyl peroxide. A peroxide such as is used. The solvent may be any solvent that dissolves each monomer. For example, glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, etc. Is used. The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator and the boiling points of the solvent and the monomer. The side chain of the copolymer thus obtained can be modified with a compound having a polymerizable group to form a photosensitive binder resin (B). At this time, a catalyst for introducing a polymerizable group into the resin may be added. An example of the catalyst is trisdimethylaminomethylphenol. Moreover, you may add the additive for preventing a side reaction. Examples of the additive include hydroquinone.

  The colored photosensitive resin composition of the present invention contains a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound that can be polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator (D) when irradiated with light, and is, for example, polymerizable carbon-carbon unsaturated. Examples thereof include compounds having a bond.

  The photopolymerizable compound (C) is preferably a trifunctional or higher polyfunctional photopolymerizable compound. Examples of the trifunctional or higher polyfunctional photopolymerizable compound include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, and the like. Is mentioned. The photopolymerizable compound (C) may be used alone or in combination of two or more, and the content thereof is 7 to 65% by mass with respect to the solid content of the colored photosensitive resin composition. It is preferable that it is, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When the content of the photopolymerizable compound (C) is within the above range, curing is sufficiently performed, the film thickness ratio before and after the development is improved, and the pattern is less likely to be undercut and adhesion is improved. It is preferable because it tends to be good.

The colored photosensitive resin composition of the present invention contains a photopolymerization initiator (D). Examples of the photopolymerization initiator (D) include acetophenone compounds, active radical generators, and acid generators.
Examples of the acetophenone compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, and 2-hydroxy-2-methyl-1-phenylpropane-1. -One, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1 -[4- (1-methylvinyl) phenyl] propan-1-one oligomers, and the like, preferably 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and the like. It is done.

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

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

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

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

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl ] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- Bis (trichloromethyl) ) Such -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

  Examples of the oxime compounds include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanyl-phenyl) -butane-1,2-dione 2-oxime-O—. Benzoate, 1- (4-phenylsulfanyl-phenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole- 3-yl] ethanone 1-O-acetate, 1- [9-ethyl-6- (2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl) -9H -Carbazol-3-yl] ethanone 1-O-acetate and the like.

  Examples of active radical generators other than those exemplified above include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl- 1,2′-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound, etc. can also be used. .

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

  Among the compounds described above as the active radical generator, there are compounds that generate an acid simultaneously with the active radical. For example, a triazine photopolymerization initiator is also used as an acid generator.

  Content of a photoinitiator (D) is a mass fraction with respect to the total amount of binder resin (B) and a photopolymerizable compound (C), Preferably it is 0.1-30 mass%, More preferably Is 1-20 mass%. When the content of the photopolymerization initiator is within the above range, the sensitivity is increased, the exposure time is shortened, and the productivity is improved.

The colored photosensitive resin composition of the present invention may further contain a photopolymerization initiation assistant (F). The photopolymerization initiation assistant (F) is usually used in combination with the photopolymerization initiator (D), and is a compound used for promoting the polymerization of the photopolymerizable compound whose polymerization has been initiated by the photopolymerization initiator. is there.
Examples of the photopolymerization initiation assistant (F) include amine compounds, alkoxyanthracene compounds, and thioxanthone compounds.
Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylbenzoate. Aminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4, Examples thereof include 4′-bis (ethylmethylamino) benzophenone, and among these, 4,4′-bis (diethylamino) benzophenone is preferable.

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

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

  The photopolymerization initiation assistant (F) may be used alone or in combination of two or more. Moreover, as a photopolymerization start adjuvant (F), a commercially available thing can also be used, and as a commercially available photopolymerization start adjuvant (F), brand name "EAB-F" (Hodogaya Chemical Industry ( Etc.).

  Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiation assistant (F) in the colored photosensitive resin composition of the present invention include, for example, diethoxyacetophenone / 4,4′-bis (diethylamino) benzophenone, 2- Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one / 4 4′-bis (diethylamino) benzophenone, benzyldimethyl ketal / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one / 4,4′-bis (diethylamino) benzophenone, 1-hydroxycyclohexylphenylke / 4,4′-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one oligomer / 4,4′-bis (diethylamino) Benzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4′-bis (diethylamino) benzophenone, etc., preferably 2-methyl-2-morpholino Examples include -1- (4-methylthiophenyl) propan-1-one / 4,4′-bis (diethylamino) benzophenone.

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

  The colored photosensitive resin composition of the present invention contains a solvent (E). Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, amides, N-methylpyrrolidone, dimethyl sulfoxide, and the like.

  Examples of the ethers include tetrahydrofuran, tetrahydropyran, 1,4-dioxane, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Propylene glycol monopropyl ether acetate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl carbitol acetate, butyl carbitol acetate, anisole, phenetole, and the like methyl anisole.

Examples of the aromatic hydrocarbons include benzene, toluene, xylene, mesitylene and the like.
Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, 4-hydroxy-4-methyl-2-pentanone, and cyclopentanone. And cyclohexanone.
Examples of the alcohols include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, and glycerin.

Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate, 3 -Methyl methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, Methyl methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, 2-oxy-2- Ethyl methyl propionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 2-oxobutane Examples include methyl acid, ethyl 2-oxobutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and γ-butyrolactone.
Examples of the amides include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.
Among these, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether and 4-hydroxy-4-methyl-2-pentanone are preferable, and it is more preferable to use these in combination.
Furthermore, the said solvent may be used individually or in combination of 2 or more types.

  Content of the solvent (E) in a colored photosensitive resin composition is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 70-95 mass%, More preferably, it is 75-90 mass%. . If the content of the solvent (E) is in the above range, the flatness at the time of application is good, and when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good. preferable.

The colored photosensitive resin composition of the present invention may further contain a surfactant (G). Examples of the surfactant (G) include at least one selected from the group consisting of a silicone surfactant, a fluorine surfactant, and a silicone surfactant having a fluorine atom.
Examples of the silicone surfactant include surfactants having a siloxane bond. Specifically, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH28PA, 29SHPA, SH30PA, polyether-modified silicone oil SH8400 (trade name: manufactured by Torresilicone Co., Ltd.), KP321, KP322, KP323 , KP324, KP326, KP340, KP341 (made by Shin-Etsu Silicone), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 (made by Momentive Performance Materials Japan GK) .

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain. Specifically, Florard (product name) FC430, FC431 (Sumitomo 3M Co., Ltd.), MegaFuck (product name) F142D, F171, F172, F173, F177, F177, F183, R30 (DIC) ), Ftop (trade name) EF301, EF303, EF351, EF351, EF352 (manufactured by Shin-Akita Kasei Co., Ltd.), Surflon (tradename) S381, S382, SC101, SC105 (Asahi Glass ( Co., Ltd.), E5844 (Daikin Fine Chemical Laboratory Co., Ltd.), BM-1000, BM-1100 (both trade names: manufactured by BM Chemie), and the like.
Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain. Specifically, MegaFuck (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation) and the like can be mentioned.
These surfactants may be used alone or in combination of two or more.
Content of surfactant (G) is a mass fraction with respect to a colored photosensitive resin composition, Preferably it is 0.00001-0.1 mass%, More preferably, it is 0.00005-0.01 mass%. It is. When the content of the surfactant (G) is in the above range, the flatness tends to be good, which is preferable.

  As a method for forming a color filter pattern using the colored photosensitive resin composition of the present invention, for example, the colored photosensitive resin composition of the present invention is applied to a substrate or another resin layer (for example, on a substrate). To another colored photosensitive resin composition layer, etc. formed on the substrate, removes volatile components such as a solvent to form a colored layer, exposes the colored layer through a photomask, and develops it. Examples thereof include a method using an inkjet apparatus that does not require a method and a photolithography method.

  According to the colored photosensitive resin composition of the present invention, it is possible to obtain a coating film having high brightness.

  Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “%” and “parts” are by weight and parts by weight unless otherwise specified.

Synthesis example 1
Into a flask equipped with a condenser and a stirrer, 15 parts of sulforhodamine B (manufactured by Kanto Chemical Co., Inc.), 150 parts of chloroform and 9.8 parts of N, N-dimethylformamide were added, and the temperature was maintained at 20 ° C. or lower with stirring. 12.0 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 13.9 parts of 2-ethylhexylamine and 24.5 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C. to obtain 14.7 parts of Dye A1.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 15 parts of a dye represented by the formula A0-2 (manufactured by Chugai Kasei), 150 parts of chloroform and 7.1 parts of N, N-dimethylformamide, and stirred at 20 ° C. While maintaining the following, 8.7 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 10 parts of 2-ethylhexylamine and 17.7 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed thoroughly with ion exchange water, and dried under reduced pressure at 60 ° C. to obtain 12.7 parts of dye A2 (mixed dye of dye A2-1 to dye A2-7).

（式（Ａ２）中、Ｒ^ｄ、Ｒ^ｅ及びＲ^ｆは、それぞれ独立に、−ＳＯ_３ ⁻、−ＳＯ_３Ｎａ又は−ＳＯ_２ＮＨＲ^ａを表す。Ｒ^ａは、２−エチルヘキシルを表す。）

(In formula (A2), R ^d , R ^e and R ^f each independently represent —SO ₃ ^— , —SO ₃ Na or —SO ₂ NHR ^a . R ^a represents 2-ethylhexyl.)

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 15 parts of a dye represented by the formula A0-3 (manufactured by Chugai Kasei), 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide, and stirred at 20 ° C. While maintaining the following, 10.9 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C., the reaction was continued for 5 hours at the same temperature, and then cooled to 20 ° C. While maintaining the reaction solution after cooling at 20 ° C. or lower with stirring, a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine was added dropwise. Then, it was made to react by stirring at the same temperature for 5 hours. Next, after the solvent of the obtained reaction mixture was distilled off with a rotary evaporator, a small amount of methanol was added and stirred vigorously. This mixture was added to a mixture of 375 parts of ion exchange water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C. to obtain 11.3 parts of dye A3 (mixed dye of dye A3-1 to dye A3-8).

（式（Ａ３）中、Ｒ^ｇ、Ｒ^ｈ及びＲ^ｉは、それぞれ独立に、水素原子、−ＳＯ_３ ⁻、−ＳＯ_３Ｈ又は−ＳＯ_２ＮＨＲ^ａを表す。Ｒ^ａは、２−エチルヘキシルを表す。）

(In formula (A3), R ^g , R ^h and R ⁱ each independently represent a hydrogen atom, —SO ₃ ^— , —SO ₃ H or —SO ₂ NHR ^a . R ^a represents 2-ethylhexyl. To express.)

Synthesis example 4
After introducing 182 g of propylene glycol monomethyl ether acetate into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, and changing the atmosphere in the flask from air to nitrogen, the temperature was raised to 100 ° C., 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) ) And 136 g of propylene glycol monomethyl ether acetate, a solution obtained by adding 3.6 g of 2,2′-azobisisobutyronitrile was added dropwise, and stirring was continued at 100 ° C. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol, 0.5%. 9 g and 0.145 g of hydroquinone were charged into the flask, and the reaction was continued at 110 ° C. to obtain a resin solution B1 having a solid content acid value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000.
About the measurement of the polystyrene conversion weight average molecular weight of said resin, it carried out on condition of the following using GPC method.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column; TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: THF
Flow rate: 1.0 mL / min
Test liquid solid concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-1, A-2500, A-500
(Manufactured by Tosoh Corporation)

Example 1
[Preparation of colored photosensitive resin composition 1]
(A) Colorant: C.I. I. Pigment Blue 15: 6 20 parts Acrylic pigment dispersant 5 parts Propylene glycol monomethyl ether acetate 137 parts are mixed and the pigment is sufficiently dispersed using a bead mill,
(A) Colorant: Dye A1 3.5 parts (B) Resin: Resin solution B1 157 parts (C) Photopolymerizable compound: Dipentaerythritol hexaacrylate (Nippon Kayaku Co., Ltd.) 50 parts (D) Light Polymerization initiator: OXE-01
(Ciba Specialty Chemicals) 15 parts (E) Solvent: 289 parts of 4-hydroxy-4-methyl-2-pentanone were mixed to obtain a colored photosensitive resin composition 1.

[Formation of pattern]
The colored photosensitive resin composition 1 was applied by spin coating on a 2-inch square glass substrate (Eagle 2000; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes. After cooling, the distance between the substrate coated with the colored photosensitive resin composition and the photomask made of quartz glass having a pattern is set to 100 μm, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) , And was irradiated with light at an exposure dose of 150 mJ / cm ² (based on 365 nm). After light irradiation, the coating film was immersed and developed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 80 seconds, washed with water, and 220 ° C. in an oven. And post-baked for 20 minutes. After standing to cool, the film thickness of the obtained cured pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.) and found to be 2.2 μm.

[Evaluation]
About the coating film on the obtained glass substrate, spectroscopy was measured using a colorimeter (OSP-SP-200; Olympus Co., Ltd.), and xy chromaticity in the XYZ color system of CIE using a C light source. Coordinates (Bx, By) and brightness were measured. The results are shown in Table 1.

Examples 2-5
A colored photosensitive resin composition and a coating film were obtained in the same manner as in Example 1 except that the dye A1 was changed to the dye shown in Table 1. The results are shown in Table 1.

※ 染料Ａ５：ローダミンＢベース（アルドリッチ製）

* Dye A4: Rhodamine B (manufactured by Taoka Chemical)

* Dye A5: Rhodamine B base (Aldrich)

  High brightness was confirmed in the coating films formed using the colored photosensitive resin compositions of Examples 1 to 5.

  According to the colored photosensitive resin composition of the present invention, a high-lightness coating film and a color filter can be obtained.

Claims (10)

A colored photosensitive resin composition comprising a colorant (A), a binder resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D) and a solvent (E), wherein the colorant (A) is The coloring photosensitive resin composition which is a coloring agent containing the organic solvent soluble dye containing the compound represented by Formula (1), and an organic pigment.

(In formula (1), R ^{1 to} R ⁴ each independently represents a hydrogen atom, —R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic hydrocarbon having 6 to 10 carbon atoms. The hydrogen atom contained in the group is a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO. _It may be substituted with ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ⁵ represents —SO ₃ ^— , —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁶ , —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ . To express.
m represents an integer of 0 to 5. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
X represents a halogen atom. a represents an integer of 0 or 1.
R ⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. A hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with a halogen atom. The methylene group contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an oxygen atom, a carbonyl group or —NR ⁶ —.
R ⁸ and R ⁹ each independently represent a linear or branched alkyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, or -Q. Alternatively, R ⁸ and R ⁹ may be bonded to each other to form a heterocyclic ring having 1 to 10 carbon atoms.
Q represents an aromatic hydrocarbon group having 6 to 10 carbon atoms or an aromatic heterocyclic group having 5 to 10 carbon atoms, and a hydrogen atom contained in the aromatic hydrocarbon group and aromatic heterocyclic group is —OH , R ⁶ , —OR ⁶ , —NO ₂ , —CH═CH ₂ , —CH═CHR ⁶ or a halogen atom.
The hydrogen atom contained in the linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms is a hydroxyl group, a halogen atom, -Q, -CH = CH ₂ or -CH = CHR ⁶ . May be substituted.
The methylene group contained in the linear or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms may be substituted with an oxygen atom, a carbonyl group or —NR ⁶ —.
The hydrogen atom contained in the heterocyclic ring having 1 to 10 carbon atoms may be substituted with R ⁶ , —OH or —Q.
M represents a sodium atom or a potassium atom. ) The colored photosensitive resin composition according to claim 1, wherein the compound represented by formula (1) is a compound represented by formula (1-1).

(In formula (1-1), R ^{11 to} R ¹⁴ each independently represents a hydrogen atom, —R ⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic having 6 to 10 carbon atoms. The hydrogen atom contained in the hydrocarbon group includes a halogen atom, —R ⁶ , —OH, —OR ⁶ , —SO ₃ ^— , —SO ₃ H, —SO ₃ Na, —CO ₂ H, —CO ₂ R ⁶ , It may be substituted with —SO ₃ R ⁶ , —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ¹⁵ represents a hydrogen atom, —SO ₃ ^— , —SO ₃ H, —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ¹⁶ represents —SO ₃ ^— , —SO ₃ H, —SO ₂ NHR ⁸ or —SO ₂ NR ⁸ R ⁹ .
R ⁶ , R ⁸ , R ⁹ , m, X and a have the same meaning as described above. ) The colored photosensitive resin composition according to claim 1, wherein the compound represented by the formula (1) is a compound represented by the formula (1-2).

(In formula (1-2), R ^{21 to} R ²⁴ each independently represents a hydrogen atom, —R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The aromatic having 6 to 10 carbon atoms. hydrogen atoms contained in the hydrocarbon group, a halogen _{^{atom, -R 26, -OH, -OR 26}} , -SO 3 -, -SO 3 Na, -CO 2 H, -CO 2 R 26, -SO 3 H, it may be substituted by -SO ₃ R ²⁶ or _-SO 2 ^{NHR 28.}
R ²⁵ represents —SO ₃ ^— , —SO ₃ Na, —CO ₂ H, —CO ₂ R ²⁶ , —SO ₃ H or SO ₂ NHR ²⁸ .
R ²⁶ represents a saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with —OR ²⁶ or a halogen atom.
R ²⁸ represents a hydrogen atom, —R ²⁶ , —CO ₂ R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms, and the hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is it may be substituted by -R ²⁶ or ^{-OR 26.}
m, X, and a represent the same meaning as described above. ) The colored photosensitive resin composition according to any one of claims 1 to 3, wherein the compound represented by the formula (1) is a compound represented by the formula (1-3).

(In the formula ^{(1-3), R 31} and ^{R 32} each independently represent a hydrogen atom contained in. The phenyl group represents a phenyl group, a halogen _{^{atom, -R 26, -OR 26, -CO}} 2 R ^26, may be substituted by _-SO 3 ^{R 26} or _-SO 2 ^{NHR 28.}
R ³³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ³⁴ represents a hydrogen atom, —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ²⁶ , R ²⁸ , X and a represent the same meaning as described above. ) The colored photosensitive resin composition according to any one of claims 1 to 4, wherein the compound represented by the formula (1) is a compound represented by the formula (1-4).

(In Formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group. The hydrogen atom contained in the phenyl group is substituted with —R ²⁶ or —SO ₂ NHR ^28. Also good.
R ⁴³ represents —SO ₃ ^— or —SO ₂ NHR ²⁸ .
R ²⁶ , R ²⁸ , X and a represent the same meaning as described above. )   The organic pigment is C.I. I. The colored photosensitive resin composition according to claim 1, which is an organic pigment containing CI Pigment Blue 15: 6.   C. in the colorant (A) I. The colored photosensitive resin composition according to claim 6, wherein a mass ratio of Pigment Blue 15: 6 to an organic solvent-soluble dye containing a compound represented by Formula (1) is 97: 3 to 50:50.   The coating film formed using the colored photosensitive resin composition in any one of Claims 1-7.   A color filter formed using the colored photosensitive resin composition according to claim 1.   The color filter according to claim 9, which is formed by a photolithography method.