KR20140141543A - Colored photosensitive resin composition - Google Patents

Abstract

The present invention relates to a colored photosensitive resin composition that includes a coloring agent (A), a binder resin (B), a photopolymeric compound (C), a photopolymerization initiator (D), and a solvent (E). The coloring agent (A) includes an organic solvent soluble dye represented by Chemical Formula (1), and an organic pigment.

Description

COLORED PHOTOSENSITIVE RESIN COMPOSITION [0002]

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 element or a solid-state imaging element, and a color filter using the colored photosensitive resin composition.

BACKGROUND ART [0002] In recent years, there has been a demand for a high definition, a high definition, and a high contrast in a color filter. In order to achieve this, color filters tend to have higher color purity and the pigment concentration in the colored photosensitive resin composition tends to be higher. However, when the concentration of the pigment is high, the pigment has a certain particle diameter and scattered light, so that there is a problem that the contrast of the color filter formed using the colored photosensitive resin composition containing the pigment is low.

Specifically, for example, by using a pyrazole-based squarylium compound as a dye that exhibits color by absorbance alone and a blue pigment pigment blue (PB) 15: 6 as a pigment in combination, And a technique of achieving contrast is disclosed (Patent Document 1).

Japanese Patent Application Laid-Open No. 2006-079012

In addition, in order to achieve high definition of a color filter, development of a colored photosensitive resin composition containing dyes and pigments of other combinations other than those specifically disclosed in Patent Document 1 is desired.

The inventors of the present invention have found that the colored photosensitive resin composition containing any kind of dye and pigment provides a high-definition coating film.

The present invention provides 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) ), And a coloring agent comprising an organic pigment.

(In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ Or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ Or it may be substituted by -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 it represents a -SO ₂ NR ⁸ R ^9.

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

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

R ⁶ represents a saturated hydrocarbon group of 1 to 10 carbon atoms. The 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. Or R ⁸ and R ⁹ may combine with 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 the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be substituted with -OH, R ⁶ , -OR ⁶ , -NO ₂ , -CH = CH ₂ , -CH = CHR ⁶ Or a halogen atom.

The hydrogen atom contained in the straight chain or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms is preferably a hydroxyl group, a halogen atom, -Q, -CH = CH ₂ Or -CH = CHR < ^{6 &} gt ;.

The methylene group contained in the straight chain 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 heterocycle 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 present invention also relates to the colored photosensitive resin composition, wherein the compound represented by formula (1) is a compound represented by formula (1-1).

(In the formula (1-1), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, -R ⁶ Or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ Na, -CO ₂ H, CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ Or it may be substituted by -SO ₂ NR ⁸ R ^9.

R ¹⁵ represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ Or it represents a -SO ₂ NR ⁸ R ^9.

R ¹⁶ is -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ Or it represents a -SO ₂ NR ⁸ R ^9.

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

The present invention also relates to the above-mentioned colored photosensitive resin composition, wherein the compound represented by the formula (1) is a compound represented by the formula (1-2).

(In the formula (1-2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms It is a halogen ^{atom, -R 26, -OH, -OR 26} , -SO 3 -, -SO 3 Na, -CO 2 H, -CO 2 R 26, -SO 3 H, -SO 3 R 26 or -SO ₂ NHR < ²⁸ >

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

R ²⁶ represents a 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 -R ²⁶ or -OR ²⁶ Or may be substituted.

m, X and a have the same meanings as defined above.

The present invention also relates to the above-mentioned colored photosensitive resin composition, 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 phenyl group. The hydrogen atom contained in the phenyl group is preferably a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R ²⁶ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ .

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

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

R ²⁶ , R ²⁸ , X and a have the same meanings as defined above.

The present invention also relates to the above-mentioned colored photosensitive resin composition, wherein the compound represented by the formula (1) is a compound represented by the formula (1-4).

(In the formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group. The hydrogen atom contained in the phenyl group may be substituted with -R ²⁶ or -SO ₂ NHR ²⁸ .

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

R ²⁶ , R ²⁸ , X and a have the same meanings as defined above.

Further, the present invention provides a coloring composition comprising an organic pigment. Pigment Blue 15: 6. ≪ / RTI >

In addition, the present invention relates to a colorant (C) having a colorant (C). Pigment Blue 15: 6 and an organic solvent-soluble dye containing a compound represented by the formula (1) is 97: 3 to 50:50.

The present invention is also a coating film formed using the colored photosensitive resin composition.

Further, the present invention is a color filter formed using the colored photosensitive resin composition.

Further, the present invention is the color filter formed by photolithography.

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 sometimes referred to as "dye (1) ). ≪ / RTI >

As the dye (1), a plurality of dyes may be mixed and used in accordance with the color of the objective color filter. It is preferable that the compound has a sufficient solubility in a solvent contained in the colored photosensitive resin composition and a sufficient solubility in a developer to such an extent that a pattern can be formed in a development step at the time of pattern formation.

(In the formula (1), R ¹ to R ⁴ each independently represent a hydrogen atom, -R ⁶ Or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ M, -CO ₂ H, CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ Or -SO ₂ 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 it represents a -SO ₂ NR ⁸ R ^9.

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

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

R ⁶ represents a saturated hydrocarbon group of 1 to 10 carbon atoms. The 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. Or R ⁸ and R ⁹ may combine with 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 the hydrogen atom contained in the aromatic hydrocarbon group and the aromatic heterocyclic group may be substituted with -OH, R ⁶ , -OR ⁶ , -NO ₂ , -CH = CH ₂ , -CH = CHR ⁶ Or a halogen atom.

The hydrogen atom contained in the straight chain or branched alkyl group having 1 to 10 carbon atoms and the cycloalkyl group having 3 to 30 carbon atoms is preferably a hydroxyl group, a halogen atom, -Q, -CH = CH ₂ Or -CH = CHR < ^{6 &} gt ;.

The methylene group contained in the straight chain 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 heterocycle 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 is preferably} methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, isopentyl, neopentyl, cyclopentyl, hexyl, cyclohexyl, heptyl, cycloheptyl, , Decanyl, tricyclodecanyl, 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 as the substituent of the above-mentioned 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.

Examples of -CO ₂ R ⁶ include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, isobutyloxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, N-pentyloxycarbonyl, cyclopentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, cycloheptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, Cyclohexyloxycarbonyl, octyloxycarbonyl, decyloxycarbonyl, tricyclodecanyloxycarbonyl, methoxypropyloxycarbonyl, ethoxypropyloxycarbonyl, hexyloxypropyloxycarbonyl, 2-ethylhexyl Hydroxypropyloxycarbonyl, methoxyhexyloxycarbonyl and the like.

Examples of -SO ₂ NHR ⁸ include sulfamoyl, methanesulfamoyl, ethanesulfamoyl, propanesulfamoyl, isopropanesulfamoyl, butanesulfamoyl, isobutanesulfamoyl, pentanesulfamoyl, isopentanesulfamoyl, neopentanesulfamoyl, But are not limited to, cyclopentylsulfamoyl, cyclopentanesulfamoyl, hexanesulfamoyl, cyclohexanesulfamoyl, heptanesulfamoyl, cycloheptanesulfamoyl, octanesulfamoyl, 2-ethylhexanesulfamoyl, 1,5-dimethylhexanesulfamoyl, Propylsulfamoyl, propylsulfanyl, propylsulfamoyl, isopropylsulfamoyl, hexyloxypropanesulfamoyl, 2-ethylhexyloxypropane sulfamoyl, isopropylsulfamoyl, isobutylsulfamoyl, Methoxyhexanesulfamoyl, 3-phenyl-1-methylpropanesulfamoyl, and the like.

-SO ₂ NHR ⁸ And -SO ₂ NR ⁸ R ⁹ may further include groups represented by the following formulas.

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

In the above formula, X ³ represents an alkyl group having 1 to 3 carbon atoms or an alkoxyl group having 1 to 3 carbon atoms, and the hydrogen atom of the alkyl group and the alkoxy group may be substituted with a halogen atom.

Examples of the alkyl group having 1 to 3 carbon atoms which may be substituted with a halogen atom include methyl, ethyl, propyl, isopropyl, and perfluoromethyl.

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

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 may be substituted with a halogen atom.

Examples of the halogen atom in 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, and perfluoromethyl.

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

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

In the above formula, X < ³ >

Examples of 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, An aralkyl group, a hydroxyl group-containing alkyl group having 2 to 8 carbon atoms and an aryl group or an alkoxyl group-containing alkyl or aryl group having 2 to 8 carbon atoms, and particularly preferably 2-ethylhexyl.

Examples of the substituent of the aromatic hydrocarbon group having 6 to 10 carbon atoms include ethyl, propyl, phenyl, dimethylphenyl, -SO ₃ R ⁶ Or -SO ₂ NHR ⁸ is preferred.

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

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

R ¹ And R < ² >, and at least one of R < ^{3 &} And R ⁴ Is preferably an alkyl group having 1 to 4 carbon atoms or an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted.

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

R ⁵ is a group selected from the group consisting of carboxyl, ethyloxycarbonyl, sulfoxyl, 2-ethylhexyloxypropanesulfamoyl, 1,5-dimethylhexanesulfamoyl, 3-phenyl-1-methylpropanesulfamoyl, isopropoxypropanesulfamoyl .

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

(In the formula (1-1), R ¹¹ to R ¹⁴ each independently represent a hydrogen atom, -R ⁶ Or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms is preferably a halogen atom, -R ⁶ , -OH, -OR ⁶ , -SO ₃ ^- , -SO ₃ H, -SO ₃ Na, -CO ₂ H, CO ₂ R ⁶ , -SO ₃ R ⁶ , -SO ₂ NHR ⁸ Or it may be substituted by -SO ₂ NR ⁸ R ^9.

R ¹⁵ represents a hydrogen atom, -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ Or it represents a -SO ₂ NR ⁸ R ^9.

R ¹⁶ is -SO ₃ ^- , -SO ₃ H, -SO ₂ NHR ⁸ Or it represents a -SO ₂ NR ⁸ R ^9.

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

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

(In the formula (1-2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms It is a halogen ^{atom, -R 26, -OH, -OR 26} , -SO 3 -, -SO 3 Na, -CO 2 H, -CO 2 R 26, -SO 3 H, -SO 3 R 26 or -SO ₂ NHR < ²⁸ >

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

R ²⁶ represents a 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 -R ²⁶ or -OR ²⁶ Or may be substituted.

m, X and a have the same meanings as defined above.

It is preferable that 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 phenyl group. The hydrogen atom contained in the phenyl group is preferably a halogen atom, -R ²⁶ , -OR ²⁶ , -CO ₂ R ²⁶ , -SO ₃ R ²⁶ or -SO ₂ NHR ²⁸ .

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

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

R ²⁶ , R ²⁸ , X and a have the same meanings as defined above.

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

(In the formula (1-4), R ⁴¹ and R ⁴² each independently represent a phenyl group. The hydrogen atom contained in the phenyl group may be substituted with -R ²⁶ or -SO ₂ NHR ²⁸ .

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

R ²⁶ , R ²⁸ , X and a have the same meanings as defined above.

Examples of the compound represented by the formula (1) include compounds represented by the formulas (1a) to (1f).

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

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

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

(In the formula (1b-1), R ^b , X and a have the same meanings as defined above.)

(In the formulas (1c) and (ld), 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.)

In (formula (1e) and formula (1f), R ^g, R ^h and R ⁱ are, each independently, a hydrogen atom, -SO ₃ ^-. Represents a, -SO ₃ H or -SO ₂ NHR ^a R ^a is , 2-ethylhexyl.)

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

The colorant (A) is a colorant further comprising an organic pigment in addition to the dye (1). As the organic pigment, specifically, for example,

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, and 38, and the like. Among them, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 3, and 15: 6, and preferably at least one pigment selected from the group consisting of C.I. Pigment Blue 15: 6 is particularly preferable. These pigments may be used alone or in combination of two or more.

The organic pigment in the above-mentioned pigments may be subjected to a surface treatment using a rosin treatment, a pigment derivative into which an acidic group or a basic group is introduced, graft treatment on the surface of the pigment with a polymer compound or the like, an atomization treatment with a sulfuric acid atomization method, Or a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed.

The organic pigment preferably has a uniform particle diameter. By containing a pigment dispersant and performing a dispersion treatment, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.

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

When a pigment dispersant is used, its amount to be 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 is within the above range, a pigment dispersion in a uniformly dispersed state tends to be obtained, which is preferable.

The content of the colorant (A) is preferably from 5 to 60 mass%, more preferably from 8 to 55 mass%, and still more preferably from 10 to 50 mass%, based on the solid content in the colored photosensitive resin composition, to be. Here, the solid content refers to the total of the components from which the solvent in the colored photosensitive resin composition has been removed.

When the content of the colorant (A) is in the above-mentioned range, it is preferable since the color density when the color filter is formed is sufficient and a required amount of the binder polymer can be contained in the composition so that a pattern having sufficient mechanical strength can be formed .

The content of the dye (1) in the colorant (A) is usually 3 to 80% by mass, preferably 3 to 70% by mass, and more preferably 3 to 50% by mass.

The content of the organic pigment in the colorant (A) is usually from 20 to 97% by mass, preferably from 30 to 97% by mass, and more preferably from 50 to 97% by mass.

Especially C.I. The mass ratio of Pigment Blue 15: 6 to the dye (1) is preferably 97: 3 to 50:50.

When the content of the organic pigment in the colorant (A) is in the above-mentioned range, it is preferable that the transmission spectrum is easily optimized, and it is good for obtaining high contrast and high brightness, and is excellent in heat resistance and chemical resistance.

The colored photosensitive resin composition used in the production of the color filter of the present invention comprises a binder resin (B). The above-mentioned binder resin (B) preferably contains a constituent unit derived from (meth) acrylic acid. Here, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. The content of the constituent unit derived from (meth) acrylic acid is preferably 16 mol% or more and 40 mol% or less, more preferably 18 mol% or less, and still more preferably 20 mol% or less, in terms of the mole fraction of all the constituent units constituting the binder resin (B) Or more and 38 mol% or less. When the content of the constitutional unit derived from (meth) acrylic acid is within the above-mentioned range, the solubility of the non-hydrogenated portion at the time of development is favorable and the residue tends to remain in the non-calcined portion after development.

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

(In the formulas (II) and (III), R ⁵³ and R ⁵⁵ each independently represent a hydrogen atom or a methyl group, and R ⁵⁴ and R ⁵⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms Lt; / RTI >

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

The acid value of the binder resin (B) used in the present invention is usually 50 to 150, preferably 60 to 135, and particularly preferably 70 to 135. When the acid value is in the above-mentioned range, the solubility in the developer is improved, the unexposed portion is easily dissolved, and the sensitivity is increased, so that the pattern of the exposed portion remains at the time of development and the residual film ratio tends to be improved. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic acid-based polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

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

A binder resin having a constituent component represented by the formula (II), for example, a methacrylic acid / a structural component represented by the formula (II) wherein R ⁵³ represents a methyl group and R ⁵⁴ represents a A benzyl methacrylate copolymer is obtained by polymerizing methacrylic acid and benzyl methacrylate to obtain a two-component polymer, and the resulting two-component polymer is reacted with a compound represented by the formula (IV) IV), R ⁵⁷ represents a hydrogen atom).

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

The weight average molecular weight of the binder resin in terms of polystyrene 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-mentioned range, the hardness of the coating film is improved, the residual film ratio is high, the solubility in the developing solution of the unexposed portion is good, and the resolution tends to be improved.

In particular, the binder resin (B) represented by the formula (V) is preferable from the viewpoints of curability and developability.

The copolymerization is generally carried out in a solvent using a polymerization initiator. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutylonitrile and 2,2'-azobis (methyl 2-methylpropionate), peroxides such as benzoyl peroxide and -tert-butyl peroxide Etc. are used. The solvent is not particularly limited as long as it dissolves the respective monomers and includes, for example, glycol ether esters such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate Is used. The reaction temperature may be determined in consideration of the decomposition temperature of the polymerization initiator, the boiling point of the solvent and the monomer, and the like. The side chain of the copolymer thus obtained may be modified with a compound having a polymerizable group to obtain a photosensitive binder resin (B). At this time, a catalyst for introducing a polymerizable group into the resin may be added. As the catalyst, for example, trisdimethylaminomethylphenol can be mentioned. Further, an additive for preventing the secondary reaction may be added. As the additive, for example, hydroquinone can be mentioned.

The colored photosensitive resin composition of the present invention comprises a photopolymerizable compound (C). The photopolymerizable compound (C) is a compound which can be polymerized by an active radical, an acid, or the like generated from the photopolymerization initiator (D) by being irradiated with light, and includes, for example, a compound having a polymerizable carbon- .

The photopolymerizable compound (C) is preferably a multifunctional photopolymerizable compound having three or more functional groups. Examples of the polyfunctional photopolymerizable compound having three or more functional groups include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol hexaacrylate, Dipentaerythritol hexamethacrylate, and the like. The above-mentioned photopolymerizable compound (C) may be used alone or in combination of two or more kinds. The content thereof is preferably 7 to 65% by mass with respect to the solid content of the colored photosensitive resin composition, Preferably from 13 to 60 mass%, and more preferably from 17 to 55 mass%. When the content of the photopolymerizable compound (C) is within the above range, the curing is sufficiently carried out, the ratio of the film thickness before and after the development is improved, the undercut is difficult to be introduced into the pattern, Do.

The colored photosensitive resin composition of the present invention comprises a photopolymerization initiator (D). Examples of the photopolymerization initiator (D) include an acetophenone-based compound, an active radical generator, and an acid generator.

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

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

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

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

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

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

Examples of the oxime compound include O-acyloxime compounds, and specific examples thereof include 1- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O- Benzoate, 1- (4-phenylsulfanylphenyl) -octane-1,2-dione 2-oxime-O-benzoate, 1- [ Ethyl] -6- (2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl) - 9H-carbazol-3-yl] ethanone 1-O-acetate.

As examples of the active radical generator other than the above-mentioned examples, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis (o-chlorophenyl) -4,4 ' -Tetraphenyl-1,2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphaquinone, methyl phenylglyoxylate, A titanocene compound or the like may be used.

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

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

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

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

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2-dimethylamino Ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (usually Mihira ketone), 4,4'- ) Benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of 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- Propanedioxanthone, and the like.

The photopolymerization initiator (F) may be used alone or in combination of two or more. As commercially available photopolymerization initiator (F), for example, trade name "EAB-F" (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used as the photopolymerization initiator (F) .

Examples of the combination of the photopolymerization initiator (D) and the photopolymerization initiator (F) in the colored photosensitive resin composition of the present invention include diethoxyacetophenone / 4,4'-bis (diethylamino) benzophenone, 2- (4-methylthiophenyl) propan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy- (Diethylamino) benzophenone, benzyldimethyl ketal / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy- (Diethylamino) benzophenone, 1-hydroxycyclohexyl phenyl ketone / 4,4'-bis (diethylamino) ) Oligomer / 4,4'-bis (diethylamino) benzophenone, 2-hydroxy-2-methyl-1- [4- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one / 4,4'-bis (diethylamino) benzophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one / 4,4-bis (diethylamino) benzophenone may be mentioned.

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

The colored photosensitive resin composition of the present invention comprises a solvent (E). Examples of the solvent (E) include ethers, aromatic hydrocarbons, ketones other than the above, alcohols, esters, amides, N-methylpyrrolidone, dimethylsulfoxide 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 But are not limited to, 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, And methyl anisole. There.

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

Examples of the ketones include acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, Pentanone, cyclopentanone, cyclohexanone, and the like.

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, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl esters, alkyl esters , Methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, ethoxyacetate, ethoxyacetate, methyl 3-oxypropionate, Ethoxypropionate, ethyl 3-methoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, ethyl 2-oxypropionate, Propyl, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-epoxypropionate, 2-ethoxypropionate Methyl 2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy- But are not limited to, ethyl acetate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, 3-methoxybutylacetate, Butyrolactone, and the like.

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

Of 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 them in combination.

The above-mentioned solvents may be used alone or in combination of two or more.

The content of the solvent (E) in the colored photosensitive resin composition is preferably 70 to 95% by mass, more preferably 75 to 90% by mass, based on the mass of the colored photosensitive resin composition. When the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color characteristic is not insufficient when the color filter is formed, so that the display characteristic tends to be good.

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 fluorinated surfactant, and a silicon surfactant having a fluorine atom.

Examples of the silicone surfactants include surfactants having a siloxane bond. Specific examples of the silicone oil include silicone oils such as silicone oils such as silicone oils such as silicone oils such as silicone oils such as silicone oils such as silicone rubber, silicone rubber, silicone rubber, , 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 Co., ) And the like.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain. Specific examples of the solvents include Fluoride (trade name) FC430, Fluoride FC431 (manufactured by Sumitomo 3M Corporation), Megafac F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, (Trade name) S381, Saphron S382, and Saphron SC101 (manufactured by DIC Corporation), Eftop (trade name) EF301, Efopto EF303, Efopto EF351 and Efopto EF352 , BM-1000 and BM-1100 (both trade names: manufactured by BM Chemie), and the like, and the like.

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

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

The content of the surfactant (G) is preferably 0.00001 to 0.1 mass%, and more preferably 0.00005 to 0.01 mass%, based on the mass of the colored photosensitive resin composition. When the content of the surfactant (G) is within the above-mentioned range, the flatness tends to be good, which is preferable.

As a method of forming a pattern of a color filter using the colored photosensitive resin composition of the present invention, for example, a method of forming a colored photosensitive resin composition of the present invention on a substrate or a separate resin layer (for example, A colored photosensitive resin composition layer or the like), removing volatile components such as a solvent to form a colored layer, exposing the colored layer through a photomask to develop and a method of developing the inkjet apparatus And the like.

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

Example

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

Synthesis Example 1

15 parts of sulfolodamine B (manufactured by KANTO CHEMICAL CO., LTD.), 150 parts of chloroform and 9.8 parts of N, N-dimethylformamide were fed into a flask equipped with a stirrer, a cooling tube and a stirrer, 12.0 parts of thionyl was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 占 폚, and the reaction was carried out at the same temperature for 5 hours, followed by cooling to 20 占 폚. The cooled reaction solution was added dropwise with a mixed solution of 13.9 parts of 2-ethylhexylamine and 24.5 parts of triethylamine while maintaining the temperature at 20 ° C or lower with stirring. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. Then, the solvent was distilled off using a rotary evaporator, and a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separately filtered, washed well with ion-exchanged water, and dried under reduced pressure at 60 ° C to obtain dye Al (14.7 parts).

                             A1

Synthesis Example 2

In a flask equipped with a cooling tube and a stirrer, 15 parts of a coloring matter represented by the formula A0-2 (primary hydrogen curable agent), 150 parts of chloroform and 7.1 parts of N, N-dimethylformamide were charged and maintained at 20 ° C or lower , 8.7 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 占 폚, held at the same temperature for 5 hours for reaction, and then cooled to 20 占 폚. The cooled reaction solution was added dropwise with a mixed solution of 10 parts of 2-ethylhexylamine and 17.7 parts of triethylamine while stirring at 20 占 폚 or lower. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. Then, the solvent was distilled off using a rotary evaporator, and a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separately filtered, washed well with ion-exchanged 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).

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

Synthesis Example 3

In a flask equipped with a cooling tube and a stirrer, 15 parts of a dye represented by the formula A0-3 (primary hydrogen curable agent), 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were charged, , 10.9 parts of thionyl chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 占 폚, held at the same temperature for 5 hours for reaction, and then cooled to 20 占 폚. The cooled reaction solution was added dropwise with a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine while maintaining the temperature at 20 ° C or lower while stirring. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. Then, the solvent was distilled off using a rotary evaporator, and a small amount of methanol was added thereto, followed by vigorous stirring. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separately filtered, 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).

(In the 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 Lt; / RTI >

Synthesis Example 4

182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, the atmosphere in the flask was changed from nitrogen to nitrogen, 22.0 g (0.10 mol) of mono-methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) of tricyclodecane skeleton and 43.0 g (0.5 mol) of methacrylic acid were mixed with 70.5 g (0.40 mol) And 136 g of ether acetate, to which 3.6 g of 2,2'-azobisisobutylonitrile had been added was added dropwise, followed by further stirring at 100 ° C. Next, 35.5 g (0.25 mol) of glycidyl methacrylate (50 mol% with respect to the carboxyl group of the methacrylic acid used in the present reaction)) and 0.9 g of trisdimethylaminomethylphenol And hydroquinone (0.145 g) were charged into a flask, and the reaction was continued at 110 DEG C to obtain a resin solution B1 having a solid dispersion value of 79 mgKOH / g. The weight average molecular weight in terms of polystyrene measured by GPC was 30,000.

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

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

column ; TSK-GELG2000HXL

Column temperature; 40 ℃

Solvent; THF

Flow rate; 1.0 mL / min

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

Injection volume: 50 μL

Detector; RI

Calibration standards; 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. Pigment Blue 15: 6 20 parts

Acrylic pigment dispersant 5 parts

Propylene glycol monomethyl ether acetate 137 parts

And the pigment is sufficiently dispersed using a bead mill, and then,

(A) Colorant: 3.5 parts of dye A1

(B) Resin: Resin solution B1 157 parts

(C) Photopolymerizable compound: dipentaerythritol hexaacrylate

(Manufactured by Nippon Kayaku Co., Ltd.) 50 parts

(D) Photopolymerization initiator: OXE-01

(Manufactured by Chiba Specialty Chemicals Co., Ltd.) 15 parts

(E) Solvent: 4-hydroxy-4-methyl-2-pentanone 289 parts

To obtain a colored photosensitive resin composition 1.

[Formation of pattern]

The colored photosensitive resin composition 1 was applied on a glass substrate (Eagle 2000: Corning) having a 2-inch square by a spin coat method, and then prebaked at 100 ° C for 3 minutes. After cooling, the space between the substrate coated with the colored photosensitive resin composition and the quartz glass photomask having the pattern was set to 100 μm in an atmosphere of 150 (cm) using an exposure machine (TME-150 RSK, manufactured by Topcon Co.) mJ / cm < 2 > (based on 365 nm). After the light irradiation, the coating film was immersed in an aqueous developing solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 DEG C for 80 seconds, washed with water and then subjected to postbaking in an oven at 220 DEG C for 20 minutes Respectively. After cooling, the film thickness of the obtained cured pattern was measured using a film thickness measuring device DEKTAK3 (manufactured by Japan Vacuum Technology Co., Ltd.) to find that it was 2.2 탆.

[evaluation]

Spectroscopy was measured using a colorimeter (OSP-SP-200, manufactured by Olympus Corporation) with respect to the obtained coating film on the glass substrate, and xy chromaticity coordinates (Bx, By ) And lightness were measured. The results are shown in Table 1.

Examples 2 to 5

A colored photosensitive resin composition and a coated film were obtained in the same manner as in Example 1 except that the dye A1 was changed to the dyes shown in Table 1. [ The results are shown in Table 1.

Example 1 Example 2 Example 3 Example 4 Example 5 dyes A1 A2 A3 A4 ^※ A5 ^※ Bx 0.141 0.138 0.141 0.141 0.141 By 0.085 0.085 0.085 0.085 0.085 brightness 9.7 9.7 9.7 9.6 9.5

※ Dye A4: Rhodamine B (made by Daoka Chemical)

※ Dye A5: Rhodamine B base (made by Aldrich)

A high brightness was confirmed in the coating film formed using the colored photosensitive resin compositions of Examples 1 to 5.

According to the present invention, a coating film and a color filter with high brightness can be obtained. The obtained color filter is suitably used for a liquid crystal display element or a solid-state image pickup element.

Claims (6)

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 colorant comprising an organic solvent-soluble dye containing a compound represented by the formula (1-2) and an organic pigment, wherein the organic pigment is at least one selected from the group consisting of a blue pigment and a violet pigment Sensitive resin composition.

(In the formula (1-2), R ²¹ to R ²⁴ each independently represent a hydrogen atom, -R ²⁶ or an aromatic hydrocarbon group having 6 to 10 carbon atoms. The hydrogen atoms contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms It is a halogen ^{atom, -R 26, -OH, -OR 26} , -SO 3 -, -SO 3 Na, -CO 2 H, -CO 2 R 26, -SO 3 H, -SO 3 R 26 or -SO ₂ NHR < ²⁸ >
R ²⁵ represents -CO ₂ H or -CO ₂ R ²⁶ .
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 -R ²⁶ or -OR ²⁶ Or may be substituted.
m represents an integer of 0 to 5; When m is an integer of 2 or more, a plurality of R ^{25 s} may be the same or different.
X represents a halogen atom. and a represents an integer of 0 or 1.) The method according to claim 1,
Wherein the organic pigment is an organic pigment comprising CI Pigment Blue 15: 6. 3. The method of claim 2,
Wherein the mass ratio of the CI Pigment Blue 15: 6 in the colorant (A) to the organic solvent-soluble dye containing the compound represented by the formula (1-2) is 97: 3 to 50:50. A coating film formed using the colored photosensitive resin composition according to claim 1. A color filter formed using the colored photosensitive resin composition according to claim 1. 6. The method of claim 5,
A color filter formed by photolithography.