JP4328158B2 - Dye-containing negative curable composition, color filter and method for producing the same - Google Patents

Description

  The present invention relates to a dye-containing negative curable composition suitable for forming a colored image constituting a color filter used in a liquid crystal display device (LCD), a solid-state image pickup device (CCD, CMOS, etc.), and the dye-containing negative. The present invention relates to a color filter using a mold curable composition and a method for producing the same.

  As a method for producing a color filter used for a liquid crystal display device or a solid-state imaging device, a dyeing method, a printing method, an electrodeposition method, and a pigment dispersion method are known.

  Among these, the pigment dispersion method is a method for producing a color filter by a photolithography method using a colored radiation-sensitive composition in which a pigment is dispersed in various photosensitive compositions. It has the advantage of being stable to heat and the like. In addition, since patterning is performed by a photolithography method, it has been widely used as a suitable method for manufacturing a color filter for a large-screen, high-definition color display with high positional accuracy.

  When producing a color filter by a pigment dispersion method, a radiation sensitive composition is applied on a glass substrate by a spin coater or a roll coater and dried to form a coating film, and the coating film is subjected to pattern exposure and development. Colored pixels are formed, and a color filter can be obtained by repeating this operation for each color.

  As the above-mentioned pigment dispersion method, there is a method in which a negative photosensitive composition in which a photopolymerizable monomer and a photopolymerization initiator are used in combination with an alkali-soluble resin is described (for example, see Patent Document 1).

  On the other hand, in recent years, there has been a demand for higher definition in color filters for solid-state imaging devices. However, it is difficult to further improve the resolution with conventional pigment dispersion systems, and there are problems such as color unevenness caused by coarse particles of the pigment, so that it is used for applications that require fine patterns such as solid-state imaging devices. Was not suitable.

  In view of such a problem, a technique for using a dye instead of a pigment has been conventionally proposed (for example, see Patent Document 2). However, dye-containing curable compositions generally have a problem that light resistance is inferior to pigments. Furthermore, unlike in the case of semiconductor manufacturing applications, a film thickness of 1.5 μm or less is required especially in the case of color filter manufacturing applications for solid-state imaging devices, so a relatively large amount of dye is contained in the curable composition. As a result, the adhesion to the substrate (support) becomes insufficient, and there is a problem that the film is easily peeled off by the development process.

In addition, there has been disclosed an example of adding an amine compound in a color filter using a pigment (see, for example, Patent Document 3). However, when a fine pattern having a side of 2.0 μm or less is formed, color unevenness occurs, and when such a fine pattern is formed, there is a problem in that peeling due to development is insufficient. In addition, an example in which a hindered amine compound is added to a color filter using a staining method has been reported (for example, see Patent Document 4). This example also has a problem that the adhesion to the substrate is insufficient. Some positive photosensitive resin compositions can improve storage stability by adding an amine compound or a pyridine compound (see, for example, Patent Document 5).
JP-A-2-199403 JP-A-6-75375 JP 2000-98124 A JP-A-62-102201 JP 2002-196482 A

  However, the negative curable composition containing a dye has good light resistance that hardly causes discoloration of the formed image, and can be made into a thin film and a high concentration while using the dye as a coloring material. It can be said that the technology that can sufficiently secure the adhesion to the substrate (support) even when the substrate is formed has not yet been established.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objective. That is, an object of the present invention is to provide a dye-containing negative curable composition having high light resistance and having good adhesion to a support even when a fine pattern is formed.
Further, the present invention provides a color filter comprising the dye-containing negative curable composition, having a high transmittance, a wide development latitude, a high resolution and particularly excellent light resistance, and resolution. An object of the present invention is to provide a color filter manufacturing method that can manufacture a color filter excellent in heat resistance and has high cost performance.

Specific means for solving the above problems are as follows.
At least one of <1> amine compounds, dyes with at least one, characterized in that it contains at least one of at least one, at least one photopolymerization initiator, and a radical polymerizable monomer of the alkali-soluble binder of the organic solvent-soluble acid dye It is a negative curable composition.
< 2 > The organic solvent-soluble acidic dye is the dye-containing negative curable composition according to < 1 >, which is an acidic dye having a sulfonic acid group or a salt thereof.
< 3 > The dye-containing negative curable composition according to <1> or <2>, wherein the amine compound has an oxidation potential of 0.90 V or less (vs. Ag ^/ Ag ⁺ ).
< 4 > The dye-containing negative curable composition according to any one of <1> to < 3 >, wherein the amine compound is a tertiary aniline compound, an amino compound having a nitrogen atom at a bridgehead position, or a hydrazine compound. It is.

< 5 > The dye-containing negative curable composition according to any one of <1> to < 3 >, wherein the amine compound is a tertiary aniline compound having a long-chain alkyl group.
< 6 > The dye-containing negative curable composition according to any one of <1> to < 5 >, wherein the organic solvent-soluble acidic dye is at least one of an azo-based, anthrapyridone-based, and anthraquinone-based acidic dye. It is.
< 7 > The dye-containing negative curable composition according to any one of <1> to < 6 >, wherein the organic solvent-soluble acidic dye is at least one of azo acid dyes.
< 8 > The dye-containing negative curable composition according to any one of <1> to < 7 >, wherein the organic solvent-soluble acidic dye is at least one of pyrazole azo acid dyes.

< 9 > A color filter comprising the dye-containing negative curable composition according to any one of <1> to < 8 >.
<1 0 > A step of applying a dye-containing negative curable composition according to any one of the above <1> to < 8 > onto a support, exposing through a mask, and developing to form a pattern. A method for producing a color filter characterized by the above.
<1 1 > The color filter manufacturing method according to <1 0 >, wherein the pattern size in the mask is 2.0 μm or less.
In the method for producing a color filter described in <1 0 > or <1 1 >, preferably, the step is repeated in accordance with the desired number of hues when producing a color filter having a desired hue. Moreover, the aspect which has the process of hardening | curing the said pattern by a heating and / or exposure as needed is also suitable.

  According to the present invention, it is possible to provide a dye-containing negative curable composition having high light resistance and good adhesion to a support even when a fine pattern is formed. Further, it is possible to provide a color filter which is constituted by using the dye-containing negative curable composition of the present invention, has a high transmittance and a wide development latitude, and has a high resolution and particularly excellent light resistance. Furthermore, a color filter excellent in resolution and heat resistance can be manufactured, and a method for manufacturing a color filter with high cost performance can be provided.

  Hereinafter, the dye-containing negative curable composition of the present invention, a color filter constituted using the dye-containing negative curable composition, and a method for producing the same will be described in detail.

<< Dye-containing negative curable composition >>
The dye-containing negative curable composition of the present invention comprises at least one amine compound, at least one organic solvent-soluble acidic dye, at least one alkali-soluble binder, at least one photopolymerization initiator, and a radical. It contains at least one polymerizable monomer, generally contains a solvent, and may further contain other components such as a crosslinking agent.

-Amine compound-
Examples of the amine compound according to the present invention include compounds represented by the following general formula (I).

In the general formula ^{(I), R 1, R} 2 and R ³ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aminoalkyl group having 1 to 20 carbon atoms, having 1 to 20 carbon atoms Represents a hydroxyalkyl group, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ¹ , R ² and R ³ are bonded to each other through a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom; A bicyclo ring may be formed.

  Examples of preferred amine compounds include methylamine, ethylamine, propylamine, butylamine, amylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, isopropylamine, sec-butylamine, isobutylamine, t-butylamine, 1-methyl. Butylamine, 1-ethylpropylamine, 2-methylbutylamine, isoamylamine, 1,2-dimethylpropylamine, t-amylamine, 1,3-dimethylbutylamine, 3,3-dimethylbutylamine, 2-aminoheptane, 3-amino Heptane, 1-methylheptylamine, 2-ethylhexylamine, 1,5-dimethylhexylamine, t-octylamine, ethylenediamine, 1,3-diaminopropane, 1,2-diamino Lopan, 1,4-diaminobutane, 1,2-diamino-2-methylpropane, 1,5-diaminopentane, 2,2-dimethyl-1,3-propanediamine, hexamethylenediamine, 1,7-diaminoheptane ,

1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, dimethylamine, N-ethylmethylamine, diethylamine, N-methylpropylamine, N-methylisopropylamine, N-ethylisopropylamine, di Propylamine, diisopropylamine, N-methylbutylamine, N-ethylbutylamine, N-methyl-t-butylamine, Nt-butylisopropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, t-amyl-t- Butylamine, dipentylamine, N-methylhexylamine, dihexylamine, t-amyl-t-octylamine, dioctylamine, bis (2-ethylhexyl) amine, didecylamine, trimethylamine, N, N-diethylmethylamine , Triethylamine, tripropylamine, N, N-diisopropylethylamine, N, N, N ′, N′-tetramethyldiaminomethane, N-methylethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tris (Dimethylamino) methane, diethylenetriamine,

N, N′-bis (2-aminoethyl) -1,3-propanediamine, cyclopropylamine, cyclobutylamine, cyclopentylamine, cyclohexylamine, N-ethylcyclohexylamine, N, N-diethylcyclohexylamine, N-methyl Dicyclohexylamine, 4,4'-methylenebis (cyclohexylamine), 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, 1-adamantanamine, allylamine, diallylamine, triallylamine, allylcyclohexylamine, bis (2-methoxyethyl) ) Amine, tetrahydrofurfurylamine, ethanolamine, diethanolamine, diethylethanolamine, 1-amino-1-deoxy-D-dolbitol, pyrrolidine, 1- (2-hydroxy) Ethyl) -pyrrolidine, piperidine, 1-methylpiperidine, 4,4′-trimethylenedipiperidine, 2,2,6,6-tetramethylpiperidine, 4-dimethylamino-2,2,6,6-tetramethylpiperidine ,

Piperazine, 1,4-dimethylpiperazine, 1,4-bis (2-hydroxyethyl) -piperazine, 1,3,5-trimethylhexahydro-1,3,5-triazine, decahydroquinoline, morpholine, 4-ethyl Morpholine, thiazolidine, thiomorpholine, aniline, N-methylaniline, N-allylaniline, 2-anilinoethanol, diphenylamine, 3-aminophenol, 4,4'-methylenedianiline, p-anisidine, 4,4'- Oxydianiline, 4-aminophenyl alcohol, 1,2-phenylenediamine, 1,3-phenylenediamine, 1,2,3,4-tetrahydrocarbazole, quinuclidine, 3-chloroquinuclidine, 3-quinuclidinol, 3- Aminoquinuclidine, 1,4-diazabicyclo [2,2, ] -Octane, diphenylamine, N, N-dimethylaniline, N-ethyl-N-methylaniline, N, N-diethylaniline, N, N-dibutylaniline, 1-phenylpiperidine, triphenylamine, 2- (N- Ethylanilino) ethanol, N-phenyldiethanolamine, N- (ethoxymethyl) -N-methylaniline, N, N-dimethyl-m-toluidine, N, N-diethyl-m-toluidine, 3-dimethylaminophenol, 3-diethylamino Phenol, 2,2 ′-(p-tolylamino) diethanol, N, N, N ′, N′-tetramethylbenzidine, 4- (dimethylamino) phenylethyl alcohol, 2,6-diisopropyl-N, N-dimethylaniline N-ethyl-3,4- (methylenedioxy) -aniline N, N, 3,5-tetramethyl aniline,

N, N, 2,4,6-pentamethylaniline, N, N-dimethyl-1,3-phenylenediamine, N, N-dimethyl-1,4-phenylenediamine, N, N-diethyl-1,4- Phenylenediamine, N, N, N ′, N′-tetramethyl-p-phenylenediamine, N, N′-diphenyl-1,4-phenylenediamine, 2-methoxy-N, 4-phenyl-1,4-phenylene Diamine, N, N′-diphenylbenzidine, N-phenyl-1,4-phenylenediamine, 3-methoxydiphenylamine, 4,4′-diaminodiphenylamine, 1-aminonaphthalene, N-ethyl-1-naphthylamine, N, N -Dimethyl-1-naphthylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 2-aminonaphthalene 1-amino-2-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 3-amino-2-naphthol, 2,3-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8 -Diaminonaphthalene, 1,8-bis (dimethylamino) naphthalene, 1-aminoanthracene, 2-aminoanthracene, 9-aminophenanthrene, 9,10-diaminophenanthrene, 1-aminopyrene, 1-phenylpiperazine, 1- (2 -Methoxyphenyl) -piperazine, 1- (4-methoxyphenyl) -piperazine, 4-phenylmorpholine, 4-morpholinoaniline, 2,5-dimethoxy-4-morpholinoaniline, indoline, julolidine, phenoxazine, phenothiazine, 10- Methylphenothiazine, 4- (4-to De siloxy phenyl) - thiomorpholine 1,1-dioxide,

Methylhydrazine, 1,1-dimethylhydrazine, 2,2,2-trifluoroethylhydrazine, 2-hydroxyethylhydrazine, 1-aminopyrrolidine, 1-aminopiperidine, 1-amino-2,6-dimethylpiperidine, 1, 4-diaminopiperazine, 1-amino-4-methylpiperazine, 1-amino-4- (2-hydroxyethyl) -piperazine, 4-aminomorpholine, phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine 1-methyl-1-phenylhydrazine, benzylhydrazine, o-tolylhydrazine, 2-ethylphenylhydrazine, 2-fluorophenylhydrazine, 2-chlorophenylhydrazine, 2-bromophenylhydrazine, m-tolylphenylhydrazine, 3- ( Trifle (Romethyl) -phenylhydrazine, 3-fluorophenylhydrazine, 3-chlorophenylhydrazine, 3-bromophenylhydrazine, 4,4′-methylenebisphenylhydrazine, p-tolylphenylhydrazine, 4-isopropylphenylhydrazine, 4- (trifluoro Methyl) -phenylhydrazine, 4-fluorophenylhydrazine, 4-chlorophenylhydrazine, 4-bromophenylhydrazine, 4-methoxyphenylhydrazine, 4- (trifluoromethoxy) phenylhydrazine, 2,3-dimethylphenylhydrazine, 2,4 -Dimethylphenylhydrazine, 2,5-dimethylphenylhydrazine, 3-chloro-p-tolylhydrazine, 2,4-difluorophenylhydrazine, 2,5-difluorophenylhydra 2,6-dichlorophenylhydrazine, 2,4-dichlorophenylhydrazine, 2,5-dichlorophenylhydrazine, 3,4-dichlorophenylhydrazine, 3,5-dichlorophenylhydrazine, 2,4,6-trichlorophenylhydrazine, 2,3 , 5,6-tetrafluorophenylhydrazine, pentafluorophenylhydrazine, 3-hydroxybenzylhydrazine, and the like.

More preferred is an amino compound having an oxidation potential of 0.90 V or less (vs. Ag ^/ Ag ⁺ ). Specifically, for example, quinuclidine, 3-chloroquinuclidine, 3-quinuclidinol, 3-aminoquinuclidine, 1,4-diazabicyclo [2,2,2] -octane, diphenylamine, N, N-dimethylaniline, N-ethyl-N-methylaniline, N, N-diethylaniline, N, N-dibutylaniline, 1-phenylpiperidine, triphenylamine, 2- (N-ethylanilino) ethanol, N-phenyldiethanolamine, N- (ethoxy Methyl) -N-methylaniline, N, N-dimethyl-m-toluidine, N, N-diethyl-m-toluidine, 3-dimethylaminophenol, 3-diethylaminophenol, 2,2 ′-(p-tolylamino) diethanol N, N, N ′, N′-tetramethylbenzidine, 4- (dimethylamino) ) Phenylethyl alcohol, 2,6-diisopropyl-N, N-dimethylaniline, N-ethyl-3,4- (methylenedioxy) -aniline, N, N, 3,5-tetramethylaniline, N, N, 2,4,6-pentamethylaniline, N, N-dimethyl-1,3-phenylenediamine, N, N-dimethyl-1,4-phenylenediamine, N, N-diethyl-1,4-phenylenediamine, N , N, N ′, N′-tetramethyl-p-phenylenediamine, N, N′-diphenyl-1,4-phenylenediamine,

2-methoxy-N, 4-phenyl-1,4-phenylenediamine, N, N′-diphenylbenzidine, N-phenyl-1,4-phenylenediamine, 3-methoxydiphenylamine, 4,4′-diaminodiphenylamine, 1 -Aminonaphthalene, N-ethyl-1-naphthylamine, N, N-dimethyl-1-naphthylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 2-aminonaphthalene, 1-amino-2-naphthol 4-amino-1-naphthol, 5-amino-1-naphthol, 3-amino-2-naphthol, 2,3-diaminonaphthalene, 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 1,8- Bis (dimethylamino) naphthalene, 1-aminoanthracene, 2-aminoanthracene 9-aminophenanthrene, 9,10-diaminophenanthrene, 1-aminopyrene, 1-phenylpiperazine, 1- (2-methoxyphenyl) -piperazine, 1- (4-methoxyphenyl) -piperazine, 4-phenylmorpholine, 4- Morpholinoaniline, 2,5-dimethoxy-4-morpholinoaniline, indoline, julolidine, phenoxazine, phenothiazine, 10-methylphenothiazine, 4- (4-tridecyloxyphenyl) -thiomorpholine-1,1-dioxide,

Methylhydrazine, 1,1-dimethylhydrazine, 2,2,2-trifluoroethylhydrazine, 2-hydroxyethylhydrazine, 1-aminopyrrolidine, 1-aminopiperidine, 1-amino-2,6-dimethylpiperidine, 1, 4-diaminopiperazine, 1-amino-4-methylpiperazine, 1-amino-4- (2-hydroxyethyl) -piperazine, 4-aminomorpholine, phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine 1-methyl-1-phenylhydrazine, benzylhydrazine, o-tolylhydrazine, 2-ethylphenylhydrazine, 2-fluorophenylhydrazine, 2-chlorophenylhydrazine, 2-bromophenylhydrazine, m-tolylphenylhydrazine, 3- ( Trifle (Romethyl) -phenylhydrazine, 3-fluorophenylhydrazine, 3-chlorophenylhydrazine, 3-bromophenylhydrazine, 4,4′-methylenebisphenylhydrazine, p-tolylphenylhydrazine, 4-isopropylphenylhydrazine, 4- (trifluoro Methyl) -phenylhydrazine, 4-fluorophenylhydrazine, 4-chlorophenylhydrazine, 4-bromophenylhydrazine, 4-methoxyphenylhydrazine, 4- (trifluoromethoxy) phenylhydrazine, 2,3-dimethylphenylhydrazine, 2,4 -Dimethylphenylhydrazine, 2,5-dimethylphenylhydrazine, 3-chloro-p-tolylhydrazine, 2,4-difluorophenylhydrazine, 2,5-difluorophenylhydra 2,6-dichlorophenylhydrazine, 2,4-dichlorophenylhydrazine, 2,5-dichlorophenylhydrazine, 3,4-dichlorophenylhydrazine, 3,5-dichlorophenylhydrazine, 2,4,6-trichlorophenylhydrazine, 2,3 , 5,6-tetrafluorophenylhydrazine, pentafluorophenylhydrazine, 3-hydroxybenzylhydrazine, and the like.

More preferred is an amino compound having an oxidation potential of 0.85 V or less (vs. Ag ^/ Ag ⁺ ). Specifically, for example, quinuclidine, 3-chloroquinuclidine, 3-quinuclidinol, 3-aminoquinuclidine, 1,4-diazabicyclo [2,2,2] -octane, N, N-dimethylaniline, N- Ethyl-N-methylaniline, N, N-diethylaniline, N, N-dibutylaniline, 1-phenylpiperidine, 2- (N-ethylanilino) ethanol, N-phenyldiethanolamine, N- (ethoxymethyl) -N-methyl Aniline, N, N-dimethyl-m-toluidine, N, N-diethyl-m-toluidine, 3-dimethylaminophenol, 2,2 '-(p-tolylamino) diethanol, N, N, N', N'- Tetramethylbenzidine, 4- (dimethylamino) phenylethyl alcohol, 2,6-diisopropyl-N, N-dimethyl Aniline, N, N, 3,5-tetramethylaniline, N, N, 2,4,6-pentamethylaniline, N, N-dimethyl-1,4-phenylenediamine, N, N-diethyl-1,4 -Phenylenediamine, N, N, N ', N'-tetramethyl-p-phenylenediamine,

N, N′-diphenyl-1,4-phenylenediamine, 2-methoxy-N, 4-phenyl-1,4-phenylenediamine, N, N′-diphenylbenzidine, N-phenyl-1,4-phenylenediamine, 4,4′-diaminodiphenylamine, 1-aminonaphthalene, N-ethyl-1-naphthylamine, N, N-dimethyl-1-naphthylamine, N-phenyl-1-naphthylamine, N-phenyl-2-naphthylamine, 2-amino Naphthalene, 1-amino-2-naphthol, 4-amino-1-naphthol, 5-amino-1-naphthol, 3-amino-2-naphthol, 2,3-diaminonaphthalene, 1,5-diaminonaphthalene, 1, 8-diaminonaphthalene, 1,8-bis (dimethylamino) naphthalene, 1-aminoanthracene, 2 Aminoanthracene, 9-aminophenanthrene, 9,10-diaminophenanthrene, 1-aminopyrene, 1-phenylpiperazine, 1- (2-methoxyphenyl) -piperazine, 1- (4-methoxyphenyl) -piperazine, 4-phenylmorpholine 4-morpholinoaniline, 2,5-dimethoxy-4-morpholinoaniline, indoline, julolidine, phenoxazine, phenothiazine, 10-methylphenothiazine, 4- (4-tridecyloxyphenyl) -thiomorpholine-1,1-dioxide,

Methylhydrazine, 1,1-dimethylhydrazine, 2,2,2-trifluoroethylhydrazine, 2-hydroxyethylhydrazine, 1-aminopyrrolidine, 1-aminopiperidine, 1-amino-2,6-dimethylpiperidine, 1, 4-diaminopiperazine, 1-amino-4-methylpiperazine, 1-amino-4- (2-hydroxyethyl) -piperazine, 4-aminomorpholine, phenylhydrazine, 1,1-diphenylhydrazine, 1,2-diphenylhydrazine 1-methyl-1-phenylhydrazine, benzylhydrazine, o-tolylhydrazine, 2-ethylphenylhydrazine, 2-fluorophenylhydrazine, 2-chlorophenylhydrazine, 2-bromophenylhydrazine, m-tolylphenylhydrazine, 3- ( Trifle (Romethyl) -phenylhydrazine, 3-fluorophenylhydrazine, 3-chlorophenylhydrazine, 3-bromophenylhydrazine, 4,4′-methylenebisphenylhydrazine, p-tolylphenylhydrazine, 4-isopropylphenylhydrazine, 4- (trifluoro Methyl) -phenylhydrazine, 4-fluorophenylhydrazine, 4-chlorophenylhydrazine, 4-bromophenylhydrazine, 4-methoxyphenylhydrazine, 4- (trifluoromethoxy) phenylhydrazine, 2,3-dimethylphenylhydrazine, 2,4 -Dimethylphenylhydrazine, 2,5-dimethylphenylhydrazine, 3-chloro-p-tolylhydrazine, 2,4-difluorophenylhydrazine, 2,5-difluorophenylhydrazine 2,6-dichlorophenylhydrazine, 2,4-dichlorophenylhydrazine, 2,5-dichlorophenylhydrazine, 3,4-dichlorophenylhydrazine, 3,5-dichlorophenylhydrazine, 2,4,6-trichlorophenylhydrazine, 2,3, 5,6-tetrafluorophenyl hydrazine, pentafluorophenyl hydrazine, 3-hydroxybenzyl hydrazine, etc. are mentioned.
Note that the oxidation potential is preferably 0.1 V or more (vs. Ag ^/ Ag ⁺ ).

  Among the above amine compounds, a tertiary amine compound, a tertiary aniline compound, or a hydrazine compound is preferable in that the effects of the present invention can be effectively achieved. A tertiary aniline compound, an amino compound having a nitrogen atom at the bridgehead position, or a hydrazine compound is more preferable, and a tertiary aniline compound is more preferable. Most preferred is a tertiary aniline compound having a long-chain alkyl group from the viewpoint of solubility. The long chain alkyl group herein is a saturated hydrocarbon group having 6 or more carbon atoms, more preferably a saturated hydrocarbon group having 8 or more carbon atoms, and still more preferably 10 or more carbon atoms.

When determining the oxidation potential, first, sweeping is started so as to increase the potential to the plus side (example: ± 0 V → + 2.0 V). Then, the oxidation wave is measured when oxidation occurs. Usually, the results of the oxidation and reduction potential measurement are plotted with the horizontal axis representing the potential and the vertical axis representing the amount of current flowing between the electrodes. That is, the oxidation wave means a waveform having a peak (vertex) that swings above the base line indicating a state in which no current flows. This waveform is expressed as a half wave of the oxidation potential, and the peak (vertex) potential of the waveform is expressed as E _pa . E _pa in the present invention is a value measured by the following method.

Using a measuring instrument connected with an arbitrary function generator, potentiostat, and measuring vessel, 0.1M n-Bu ₄ N · ClO ₄ (for Hanai Polaro) is measured as a supporting electrolyte in the measuring vessel. It was dissolved in acetonitrile (manufactured by Kanto Chemical) as a solvent and used. The electrode used was a Pt electrode as the working electrode and Ag / AgCl (saturated KCl) as the reference electrode. As the salt bridge connecting the reference electrode and the measurement container, agar containing 1 M KNO ₃ supporting salt was filled and used. Under the above conditions, the sample was melted in a measurement container so as to be 1 × 10 ⁻⁴ M, and measured at a sweep rate of 50 mV / cm ² to 1 V / cm ² at 25 ° C.

  The concentration of the amine compound in the dye-containing negative curable composition will be described. The concentration of the amine compound in the total solid component of the dye-containing negative curable composition varies depending on the dye, but is preferably 0.5 to 80% by mass, more preferably 1 to 60% by mass, and 5 to 50% by mass. Is particularly preferred.

-Organic solvent soluble acid dyes-
As the organic solvent-soluble acid dye, at least one kind can be appropriately selected and used without particular limitation, and conventionally known acid dyes for color filters can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 And dyes described in JP-A-6-194828. As the chemical structure, dyes such as triphenylmethane, anthraquinone, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, and indigo can be used. Particularly preferred are pyrazole azo dyes, anilinoazo dyes, pyrazolotriazole azo dyes, pyridone azo dyes and anthrapyridone dyes .

When used in a resist system as in the present invention, the acid dye and / or derivative thereof is used in combination with the amine compound according to the present invention, and in particular, the adhesion to the support is improved, and peeling that causes problems during development is effective. that obtained and prevented. Good Mashiku is a combination manner with a sulfonic acid group or an amine compound according to the present invention the acid dye and / or a derivative thereof with a salt thereof.

<Acid dye>
The acid dye will be described. The acidic dye is not particularly limited as long as it is a pigment having an acidic group such as a sulfonic acid group, a carboxylic acid group, or a phenolic hydroxyl group, but is soluble in an organic solvent or a developer, salt-forming with a basic compound, absorbance, It is selected in consideration of all of the required performance such as interaction with other components in the curable composition, light resistance, heat resistance and the like.

  As the acidic dye in the present invention, those having a sulfonic acid group and / or a salt thereof are particularly suitable. Hereinafter, specific examples of the acid dye according to the present invention will be given. However, the present invention is not limited to these. For example,

acid alizarin violet N;
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103, 112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324: 1, 335, 340;
acid chroma violet K;
acid Fuchsin;
acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106,109;
acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66,73,80,87,88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217, 227,228,249,252,257,258,260,261,266,268,270,274,277,280,281,195,308,312,315,316,339,341,345,346,349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98,99,111,112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 190,193,196,197,199,202,203,204,205,207,212,214,220,221,228,230,232,235,238,240,242,243,251;

Direct Yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129, 136, 138, 141;
Direct Orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189, 190, 192, 193 194,196,198,199,200,207,209,210,212,213,214,222,228,229,237,238,242,243,244,245,247,248,250,251,252, 256, 257, 259, 260, 268, 274, 275, 293;
Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82;
Modern Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 50, 61, 62, 65;
Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

Modern Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
Modern Violet 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
Modern Blue 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84;
Modern Green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53;
Food Yellow 3;
And derivatives of these dyes.

Among the above acidic dyes, those having a sulfonic acid group and / or a salt thereof are preferable. In particular,
acid black 1, 2, 24, 48;
acid blue 1,7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,90,92,96,103,112, 113, 120, 129, 138, 147, 150, 158;
acid chroma violet K;
acid green 1,3,5,9,16,25,27,50;
acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74;

acid red 1,4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,52,57,66,73,80,88,97,103, 111, 114, 133, 134, 138, 145, 150, 151, 158, 176, 183, 198, 249, 266;
acid violet 6B, 7, 9, 17, 19;
acid yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,76,99,172,199,228;

Direct Yellow 33, 34, 50, 69, 70, 86;
Direct Orange 34, 39, 41, 46, 61, 70, 96;
Direct Red 79, 83, 84, 98, 99, 173, 176, 181, 243, 250;
Direct Violet 47, 54, 66, 79, 80, 81, 103;
Direct Blue 80, 81, 84, 86, 93, 95, 98, 106, 107, 108, 109, 149, 150, 158, 159, 162, 163, 164, 166, 167, 190, 199, 214;
Direct Green 34;

Modern Yellow 8, 10, 20, 26, 30, 33, 45;
Modern Orange 3, 4, 29, 35, 37;
Modern Red 2, 3, 9, 17, 19, 26, 30, 41, 71, 90, 94;
Modern Violet 2, 4, 5, 30, 40, 41, 44;
Modern Blue 3, 7, 9, 13, 23, 31, 44, 48;
Modern Green 10, 15, 26, 34;
Food Yellow 3;
And derivatives of these dyes.

Among the acid dyes and derivatives of these dyes, azo, anthrapyridone, or anthraquinone acid dyes are preferable. Among them, azo acid dyes and derivatives of these dyes are more preferable. Specifically,
acid black 24;
acid blue 29, 92, 158;
acid orange 8, 51, 56, 74, 63;
acid red 1,4,8,34,37,42,52,57,97,114,145,151,183,249;
acid violet 7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 99, 172, 228;
Preferred examples include dyes such as these and derivatives of these dyes.

Furthermore, pyrazole azo dyes are particularly preferable. In particular,
acid orange 56, 74, 63;
acid red 183;
acid violet 7;
acid yellow 17, 25, 29, 34, 42, 72, 76, 172;
And other dyes and derivatives of these dyes.

  As the derivative of the acid dye, an inorganic salt of an acid dye having a sulfonic acid group or a carboxylic acid group, a salt of an acid dye having a sulfonic acid group or a carboxylic acid group and a nitrogen-containing compound can be preferably used, and a curable composition It is not particularly limited as long as it can be dissolved as a solution, but it needs solubility, absorbance, interaction with other components in the curable composition, light resistance, heat resistance, etc. in an organic solvent or developer. It is selected in consideration of all the performance to be performed.

  The salt of an acid dye and a nitrogen-containing compound will be described. The method of forming a salt of an acid dye and a nitrogen-containing compound may be effective for improving the solubility of the acid dye (providing solubility in an organic solvent) and improving heat resistance and light resistance.

  Nitrogen-containing compounds that form salts with acidic dyes are: salt solubility in organic solvents and developers, salt formation, absorbance / color value of dyes, interactions with other components in curable compositions, colorants Is selected in consideration of all of heat resistance, light resistance and the like. When selecting only in terms of absorbance and color value, the nitrogen-containing compound is preferably as low as possible in molecular weight, more preferably having a molecular weight of 300 or less, more preferably having a molecular weight of 280 or less, and a molecular weight of 250 or less. Those are particularly preferred.

  Hereinafter, the specific example of the said nitrogen-containing compound is given. However, the present invention is not limited to these.

  The molar ratio of nitrogen-containing compound / acid dye (hereinafter referred to as n) in the salt of the acid dye and the nitrogen-containing compound will be described. n is a value that determines the molar ratio between the acid dye molecule and the amine compound that is a counter ion, and can be freely selected according to the salt forming conditions of the acid dye-amine compound. Specifically, a number between 0 <n ≦ 5 of the number of functional groups of the acid in the acid dye is practically used, and the solubility in organic solvents and developers, salt formation, absorbance, and curable composition It is selected in consideration of all necessary performance such as interaction with other components, light resistance, heat resistance and the like. When selecting from the standpoint of absorbance only, n is preferably a value between 0 <n ≦ 4.5, more preferably a value between 0 <n ≦ 4, and 0 <n. It is particularly preferable to take a numerical value between ≦ 3.5.

The content concentration of the organic solvent-soluble acidic dye will be described. The concentration of the organic solvent-soluble acidic dye in the total solid components of the dye-containing negative curable composition of the present invention varies depending on the dye, but is preferably 0.5 to 80% by mass, and preferably 0.5 to 60% by mass. Is more preferable, and 0.5 to 50% by mass is particularly preferable.

-Alkali-soluble binder Next, an alkali-soluble binder is demonstrated. The alkali-soluble binder according to the present invention is not particularly limited as long as it is water-soluble or alkali-soluble, and at least one kind can be appropriately selected and contained, and is selected from the viewpoints of heat resistance, developability, availability, and the like. Is preferred.

  The alkali-soluble binder is preferably a linear organic polymer, soluble in an organic solvent, and developable with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-54-25957. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, as described in JP-A-59-53836 and JP-A-59-71048. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

In addition to the above, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), polyvinylpyrrolidone and polyethylene oxide, Polyvinyl alcohol, etc. are also useful.
Moreover, you may copolymerize the monomer which has hydrophilic property, As an example, alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, Secondary or tertiary alkylacrylamide, dialkylaminoalkyl (meth) acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate Branched or linear propyl (meth) acrylate, branched or linear butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like.

  Other examples of the hydrophilic monomer include tetrahydrofurfuryl group, phosphoric acid, phosphoric ester, quaternary ammonium salt, ethyleneoxy chain, propyleneoxy chain, sulfonic acid and its salt, and morpholinoethyl group. Useful.

  In order to improve the crosslinking efficiency, a polymerizable group may be included in the side chain, and a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is also useful. Examples of the polymer containing a polymerizable group include KS resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins.

  Examples of the acrylic resin include a copolymer composed of monomers selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, KS resist-106 (Osaka Organic Chemical Industry). And Cyclomer P series (manufactured by Daicel Chemical Industries, Ltd.).

As the alkali-soluble binder, a polymer having a weight average molecular weight (polystyrene conversion value measured by GPC method) of 1000 to 2 × 10 ⁵ is preferable, a polymer of 2000 to 1 × 10 ⁵ is more preferable, and 5000 to 5 is preferable. A polymer of × 10 ⁴ is particularly preferred.

  The content of the alkali-soluble binder in the dye-containing negative curable composition is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total solid content (mass) of the composition. 30-70 mass% is especially preferable.

<Radically polymerizable monomer>
Next, the radical polymerizable monomer will be described. As the radically polymerizable monomer, a compound having at least one addition-polymerizable ethylenic double bond and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable. By containing at least one kind together with a photopolymerization initiator, which will be described later, the dye-containing negative curable composition can be formed into a negative type.

  Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate,

Trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, polymethic alcohol such as glycerin and trimethylolethane, and (meth) acrylate after addition of ethylene oxide or propylene oxide, Urethane acrylates as described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Mention polyfunctional acrylates and methacrylates such as polyester acrylates, epoxy resins and epoxy acrylates which are reaction products of (meth) acrylic acid and mixtures thereof described in JP-B-52-30490 Can do. Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, which are introduced as photocurable monomers and oligomers.

  The content of the radical polymerizable monomer in the dye-containing negative curable composition is preferably 0.1 to 90 mass, and 1.0 to 80 mass with respect to the total solid content (mass) of the composition. % Is more preferable, and 2.0 to 70% by mass is particularly preferable.

<Photopolymerization initiator>
Next, the photopolymerization initiator will be described. A photoinitiator is contained with at least 1 type of said radically polymerizable monomer, when comprising a negative type curable composition containing a dye. The photopolymerization initiator is not particularly limited as long as it can polymerize the radical polymerizable monomer, but is preferably selected from the viewpoints of properties, initiation efficiency, absorption wavelength, availability, cost, and the like.

  Examples of the photopolymerization initiator include at least one active halogen compound selected from a halomethyloxadiazole compound and a halomethyl-s-triazine compound, a 3-aryl-substituted coumarin compound, a lophine dimer, a benzophenone compound, and an acetophenone. Examples thereof include compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, and oxime compounds.

  Examples of the active halogen compound which is a halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxadiazole compounds described in JP-B-57-6096, 2-trichloromethyl- 5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (p-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) ) -1,3,4-oxadiazole.

  Examples of the active halogen compound which is a halomethyl-s-triazine compound include vinyl-halomethyl-s-triazine compounds described in JP-B-59-1281 and 2- (naphtho-) described in JP-A-53-133428. 1-yl) -4,6-bis-halomethyl-s-triazine compound and 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound.

  Specifically, 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,6-bis (trichloromethyl) -4- (3,4-methylenedioxyphenyl) -1 , 3,5-triazine, 2,6-bis (trichloromethyl) -4- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (1-p -Dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine, 2- (naphth-1-yl) -4,6- Bis-trichloromethyl-s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl)- , 6-Bis-trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -Naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine,

2- [4- (2-Ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-butoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-5- Methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2 -(5-Methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl -S-triazine, 2- 6-Ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s -Triazine,

4- [pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonyl) Methyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (p-N-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [p-N, -Di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine ,

4- [pN- (p-methoxyphenyl) carbonylaminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [mN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s- Triazine, 4- [m-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) Minophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl)- s-triazine,

4- [o-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N- Di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trick Romechiru) -s- triazine,

4- [m-Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylamino) Phenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4 -(M-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (o-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloro) Methyl) -s-triazine,

4- (o-Fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2 , 6-Di (trichloromethyl) -s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro -PN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) ) -S-triazine, 4- (o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloro) Ethylamino) -2,6-di (trichloromethyl) -s-triazine.

  In addition, TAZ series (for example, TAZ-107, TAZ-110, TAZ-104, TAZ-109, TAZ-140, TAZ-204, TAZ-113, TAZ-123) manufactured by Midori Chemical, T manufactured by PANCHIM Series (for example, T-OMS, T-BMP, TR, TB), Irgacure series (for example, Irgacure 651, Irgacure 184, Irgacure 500, Irgacure 1000, Irgacure 149, Irgacure 819, Irgacure 261), Darocur series (eg Darocur 1173), 4,4'-bis (diethylamino) -benzophenone, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione 2-benzyl-2-dimethyl Amino-4-morpholinobutyrophenone Ciro acetophenone, 2,2-dimethoxy-2-phenylacetophenone,

2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5 -Diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (2, 4-Dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, benzoin isopropyl ether, and the like are also useful.

A sensitizer and a light stabilizer can be used in combination with these photopolymerization initiators.
Specific examples thereof include benzoin, benzoin methyl ether, benzoin, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9. Anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-methoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p- (dimethylamino) phenylstyryl ketone, p- ( Dimethylamino) phenyl-p-methyls Rilketone, benzophenone, p- (dimethylamino) benzophenone (or Michler's ketone), p- (diethylamino) benzophenone, benzoanthrone, benzothiazole compounds described in Japanese Patent Publication No. 51-48516, tinuvin 1130, 400, etc. Is mentioned.

In addition to the above-mentioned photopolymerization initiator, other known initiators can be used in the dye-containing negative curable composition of the present invention.
Specifically, the vicinal polykettle aldonyl compound disclosed in US Pat. No. 2,367,660, disclosed in US Pat. Nos. 2,367,661 and 2,367,670. Substituted α-carbonyl compounds, acyloin ethers disclosed in US Pat. No. 2,448,828, α-hydrocarbons disclosed in US Pat. No. 2,722,512 Aromatic acyloin compounds, polynuclear quinone compounds disclosed in US Pat. Nos. 3,046,127 and 2,951,758, disclosed in US Pat. No. 3,549,367. Triarylimidazole dimer / p-aminophenyl ketone combination, benzothiazole compound / trihalome disclosed in Japanese Patent Publication No. 51-48516 Examples thereof include a teal-s-triazine compound.

  The total amount of the photopolymerization initiator (and known initiator) is preferably 0.01% by mass to 50% by mass, and preferably 1% by mass to 30% by mass with respect to the solid content (mass) of the radical polymerizable monomer. % Is more preferable, and 1% by mass to 20% by mass is particularly preferable. When the amount used is less than 0.01% by mass, the polymerization may be difficult to proceed. When the amount used exceeds 50% by mass, the polymerization rate increases, but the molecular weight decreases and the film strength may decrease.

<Crosslinking agent>
In the present invention, it is also possible to obtain a film that has been further cured by using a crosslinking agent. Hereinafter, the crosslinking agent will be described.
The crosslinking agent that can be used in the present invention is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. At least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, which is substituted with at least one substituent selected from Substituted phenol compounds, naphthol compounds or hydroxyanthracene compounds. Of these, polyfunctional epoxy resins are preferred.

  The epoxy resin (a) may be any epoxy resin as long as it has an epoxy group and has crosslinkability, for example, bisphenol A diglycidyl ether, ethylene glycol diglycidyl ether, butanediol diglycidyl ether. , Hexanediol diglycidyl ether, dihydroxybiphenyl diglycidyl ether, diphthalic acid diglycidyl ester, N, N-diglycidyl aniline and other divalent glycidyl group-containing low molecular weight compounds, as well as trimethylolpropane triglycidyl ether, Trivalent glycidyl group-containing low molecular weight compounds represented by methylolphenol triglycidyl ether, TrisP-PA triglycidyl ether, etc., as well as pentaerythritol tetraglycidyl ether, tetramethylol vinyl Tetravalent glycidyl group-containing low molecular weight compounds typified by phenol A tetraglycidyl ether, polyvalent glycidyl group-containing low molecular weight compounds such as dipentaerythritol pentaglycidyl ether and dipentaerythritol hexaglycidyl ether, polyglycidyl ( And glycidyl group-containing polymer compounds represented by 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol and the like. .

The number of methylol groups, alkoxymethyl groups, and acyloxymethyl groups substituted in the crosslinking agent (b) is 2 to 6 in the case of melamine compounds, in the case of glycoluril compounds, guanamine compounds, and urea compounds. Although it is 2-4, Preferably it is 5-6 in the case of a melamine compound, and 3-4 in the case of a glycoluril compound, a guanamine compound, and a urea compound.
Hereinafter, the melamine compound, guanamine compound, glycoluril compound, and urea compound of (b) are collectively referred to as a compound (methylol group-containing compound, alkoxymethyl group-containing compound, or acyloxymethyl group-containing compound) according to (b).

  The methylol group-containing compound according to (b) can be obtained by heating the alkoxymethyl group-containing compound according to (b) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like. The acyloxymethyl group-containing compound according to (b) can be obtained by mixing and stirring the methylol group-containing compound according to (b) with acyl chloride in the presence of a basic catalyst.

Hereinafter, specific examples of the compound according to (b) having the substituent will be given.
Examples of the melamine compound include hexamethylol melamine, hexamethoxymethyl melamine, a compound in which 1 to 5 methylol groups of hexamethylol melamine are methoxymethylated, or a mixture thereof, hexamethoxyethyl melamine, hexaacyloxymethyl melamine, hexamethylol. Examples thereof include compounds in which 1 to 5 methylol groups of melamine are acyloxymethylated, or mixtures thereof.

  Examples of the guanamine compound include tetramethylol guanamine, tetramethoxymethyl guanamine, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol guanamine, or a mixture thereof, tetramethoxyethyl guanamine, tetraacyloxymethyl guanamine, tetramethylol. Examples thereof include compounds obtained by acyloxymethylating 1 to 3 methylol groups of guanamine or a mixture thereof.

  Examples of the glycoluril compound include tetramethylol glycoluril, tetramethoxymethylglycoluril, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylolglycoluril, or a mixture thereof, or a methylol group of tetramethylolglycoluril. Examples thereof include compounds in which 1 to 3 are acyloxymethylated or a mixture thereof.

Examples of the urea compound include tetramethylol urea, tetramethoxymethyl urea, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol urea, a mixture thereof, and tetramethoxyethyl urea.
These compounds according to (b) may be used alone or in combination.

  The crosslinking agent (c), that is, a phenol compound, a naphthol compound, or a hydroxyanthracene compound substituted with at least one group selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group is the crosslinking agent (b As in the case of), intermixing with the overcoated photoresist is suppressed by thermal crosslinking, and the film strength is further increased. Hereinafter, these compounds may be collectively referred to as a compound according to (c) (a methylol group-containing compound, an alkoxymethyl group-containing compound, or an acyloxymethyl group-containing compound).

The number of methylol groups, acyloxymethyl groups or alkoxymethyl groups contained in the crosslinking agent (c) is at least 2 per molecule, and from the viewpoint of thermal crosslinkability and storage stability, phenol as a skeleton Compounds in which the 2nd and 4th positions of the compound are all substituted are preferred. In addition, the naphthol compound and hydroxyanthracene compound as the skeleton are preferably compounds in which all of the ortho-position and para-position of the OH group are substituted. The 3-position or 5-position of the phenol compound may be unsubstituted or may have a substituent.
The naphthol compound may be unsubstituted or substituted except for the ortho position of the OH group.

The methylol group-containing compound according to the above (c) uses a compound in which the phenolic OH group is a hydrogen atom at the 2nd or 4th position as a raw material, and this is used as sodium hydroxide, potassium hydroxide, ammonia, tetraalkylammonium hydroxide. It can be obtained by reacting with formalin in the presence of a basic catalyst.
The alkoxymethyl group-containing compound according to (c) can be obtained by heating the methylol group-containing compound according to (c) in an alcohol in the presence of an acid catalyst such as hydrochloric acid, sulfuric acid, nitric acid, methanesulfonic acid or the like.
The acyloxymethyl group-containing compound according to (c) can be obtained by reacting the methylol group-containing compound according to (c) with an acyl chloride in the presence of a basic catalyst.

  Examples of the skeleton compound in the crosslinking agent (c) include phenol compounds, naphthols, hydroxyanthracene compounds, etc., in which the ortho-position or para-position of the phenolic OH group is unsubstituted. , 3-xylenol, 2,5-xylenol, 3,4-xylenol, 3,5-xylenol, bisphenols such as bisphenol A, 4,4'-bishydroxybiphenyl, TrisP-PA (Honshu Chemical Industry) Naphthol, dihydroxynaphthalene, 2,7-dihydroxyanthracene, etc. are used.

  Specific examples of the crosslinking agent (c) include, as a phenol compound or a naphthol compound, for example, trimethylolphenol, tri (methoxymethyl) phenol, a compound obtained by methoxymethylating one or two methylol groups of trimethylolphenol, Trimethylol-3-cresol, tri (methoxymethyl) -3-cresol, compounds obtained by methoxymethylating 1 to 2 methylol groups of trimethylol-3-cresol, 2,6-dimethylol-4-cresol and the like Methylol cresol, tetramethylol bisphenol A, tetramethoxymethyl bisphenol A, a compound obtained by methoxymethylating 1 to 3 methylol groups of tetramethylol bisphenol A, tetramethylol-4,4′-bishydroxybiphenyl, tetramethyl A compound obtained by methoxymethylating 1 to 5 methylol groups of cymethyl-4,4′-bishydroxybiphenyl, hexamethylol of TrisP-PA, hexamethoxymethyl of TrisP-PA, hexamethylol of TrisP-PA, Bishydroxymethyl naphthalene diol, etc. are mentioned.

  Examples of the hydroxyanthracene compound include 1,6-dihydroxymethyl-2,7-dihydroxyanthracene, and examples of the acyloxymethyl group-containing compound include, for example, a part of the methylol group of the methylol group-containing compound. Examples include compounds that are all acyloxymethylated.

Among these compounds, trimethylolphenol, bishydroxymethyl-p-cresol, tetramethylolbisphenol A, trisP-PA (manufactured by Honshu Chemical Industry Co., Ltd.) or a methylol group thereof is preferable. Examples thereof include an alkoxymethyl group and a phenol compound substituted with both a methylol group and an alkoxymethyl group.
These compounds according to (c) may be used alone or in combination.

  The total content of the crosslinking agent in the dye-containing negative curable composition varies depending on the material, but is preferably 1 to 70% by mass, preferably 5 to 50%, based on the solid content (mass) of the curable composition. % By mass is more preferable, and 7 to 30% by mass is particularly preferable.

<Thermal polymerization inhibitor>
In addition to the above, it is preferable to add a thermal polymerization inhibitor to the dye-containing negative curable composition of the present invention. For example, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), 2,2 ' -Methylenebis (4-methyl-6-tert-butylphenol), 2-mercaptobenzimidazole, etc. are useful.

<solvent>
In preparing the dye-containing negative curable composition of the present invention, a solvent is generally used. The solvent is not particularly limited as long as the solubility of each component and the coating property of the dye-containing negative curable composition are satisfied, but the solvent is particularly selected in consideration of the solubility, coating property, and safety of the dye and binder. It is preferable that

  Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, and methyl lactate. , Ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc .;

3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate, such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Ethyl propionate, etc .; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, 2-methoxypropion Acid ethyl, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, 2-methoxy- 2-methylpropio Methyl acid, 2-ethoxy-2-methylpropionic acid ethyl, etc; methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, etc .;

Ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether, propylene glycol methyl Ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone are preferred; aromatic hydrocarbons such as toluene and xylene are preferred.

  Among these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate and the like are more preferable.

<Various additives>
In the dye-containing negative curable composition of the present invention, various additives such as a filler, a polymer compound other than the above, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, An anti-aggregation agent or the like can be blended.

  Specific examples of the various additives include fillers such as glass and alumina; polymer compounds other than binder resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate; nonionic, cationic And anionic surfactants: vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltrimetoki Adhesion promoters such as silane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl- 6-t-butylphenol), 2,6-di-t-butylphenol and other antioxidants; 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenone, etc. And an anti-aggregation agent such as sodium polyacrylate.

Further, when the alkali solubility of the non-image area is promoted and the developability of the dye-containing negative curable composition of the present invention is further improved, the composition has an organic carboxylic acid, preferably a molecular weight of 1000 or less. Of low molecular weight organic carboxylic acids can be added.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

<< Color filter and manufacturing method thereof >>
Next, the color filter of the present invention will be described in detail through its manufacturing method.
In the method for producing a color filter of the present invention, the above-described dye-containing negative curable composition of the present invention is used.
The dye-containing negative curable composition of the present invention is coated on a support by a coating method such as spin coating, cast coating, roll coating, etc. to form a radiation-sensitive composition layer, and the layer is formed into a predetermined mask, That is, a negative colored pattern is formed by exposing through a mask pattern and developing with a developer (image forming step). Moreover, the hardening process which hardens | cures the formed coloring pattern by heating and / or exposure as needed may be included.

  In the production of a color filter, a color filter having a desired hue can be produced by repeating the image forming step (and the curing step if necessary) according to the desired number of hues. The mask preferably has a mask pattern provided on the mask having a pattern size of 2.0 μm or less. As light or radiation used at this time, ultraviolet rays such as g-line, h-line and i-line are particularly preferably used.

Examples of the support include soda glass, Pyrex (R) glass, and quartz glass used for liquid crystal display elements and the like, a transparent conductive film attached thereto, a photoelectric conversion element substrate used for an imaging element, and the like. For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These supports may be formed with black stripes that separate pixels.
In addition, an undercoat layer may be provided on these supports, if necessary, for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the support surface.

  Any developer can be used as long as it has a composition that dissolves the uncured portion of the dye-containing negative curable composition of the present invention but does not dissolve the irradiated portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used. As said organic solvent, the above-mentioned solvent used when preparing the dye-containing negative curable composition of this invention is mentioned.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide. , Choline, pyrrole, piperidine, alkaline compounds such as 1,8-diazabicyclo- [5.4.0] -7-undecene, the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. An alkaline aqueous solution obtained by dissolution is preferable. When a developer composed of such an alkaline aqueous solution is used, it is generally washed with water after development.

  The color filter of the present invention can be used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.

1) Preparation of dye-containing negative curable composition Propylene glycol monomethyl ether acetate 20.2 parts (PGMEA)
-Ethyl lactate-29.8 parts-Allyl methacrylate / methacrylic acid copolymer (= 80/20 [molar ratio])
(Alkali-soluble binder) ... 36.28 parts-Dipentaerythritol hexaacrylate ... 12.20 parts-Polymerization inhibitor (p-methoxyphenol) ... 0.0061 parts-Fluorosurfactant ... 0.83 parts-Photopolymerization Initiator (TAZ-107, manufactured by Midori Chemical Co., Ltd.) 0.586 parts Organic acid- soluble acid dyes listed in Table 1 0.05 parts Amine compounds listed in Table 1 0.05 parts mixed The dye-containing negative curable composition of the present invention was prepared.

2) Creation of glass substrate with undercoat layer A glass substrate (Corning 1737) was ultrasonically washed with 1% NaOH water, and then washed with water and dehydrated (200 ° C./30 minutes). Next, a resist CT-2000L solution (manufactured by Fuji Film Arch Co., Ltd.) is applied onto the glass substrate after washing with a spin coater so as to have a film thickness of 2 μm, and is heated and dried at 220 ° C. for 1 hour to be cured. A film (undercoat layer) was formed.

3) Exposure and development of dye-containing negative curable composition (image forming process)
The dye-containing negative curable composition obtained in 1) above was applied on the undercoat layer of the glass substrate with an undercoat layer obtained in 2) above using a spin coater so that the film thickness became 1 μm. And prebaking at 120 ° C. for 120 seconds.
Next, using an i-line reduction projection exposure apparatus, the coating film was irradiated at a wavelength of 365 nm through a mask having a light transmission portion of 2 μm square with an exposure amount of 800 mJ / cm ² . After irradiation, development was performed at 23 ° C. for 60 seconds using a 60% CD-2000 (Fuji Film Arch Co., Ltd.) developer. Subsequently, after rinsing with running water for 20 seconds, spray drying was performed to obtain a yellow pattern image. The image formation was confirmed by an ordinary method using an optical microscope and SEM photograph observation.

4) Evaluation
(1) Light resistance After irradiating a glass substrate with an undercoat layer on which a yellow pattern image is formed with a xenon lamp at 200,000 lux for 10 hours (equivalent to 2 million lux · h), the chromaticity change in the pattern image, that is, The ΔEab value was measured. A smaller ΔEab value indicates better light resistance.
(2) Substrate adhesion The pattern remaining ratio (%) after development and rinsing of the portion irradiated to the 2.0 μm square pattern in the formed yellow pattern image was determined by SEM photograph observation and evaluated. A larger residual ratio indicates better adhesion.
The results of the above evaluations are shown in Table 2 below.

(Examples 2 to 40, Comparative Examples 1 to 5)
In the preparation of the dye-containing negative curable composition of Example 1, an organic solvent-soluble acidic dye and an amine compound were replaced with each other as shown in Table 1 in the same manner as in Example 1, except that the dye-containing A negative curable composition was prepared, a pattern image was further formed, and the same evaluation was performed.

As shown in Table 2 above, in the examples containing the amine compound in the composition of the dye-containing negative curable composition, the light resistance of the formed image is excellent, the pattern remaining rate is high, and the substrate (support) is applied. Good adhesion was shown. In particular, in Examples 1 to 32 containing an amine compound having a high oxidation potential, superior light resistance and substrate adhesion can be obtained as compared with Examples 33 to 40 in which the oxidation potential of the amine compound is not so high. It was.
On the other hand, in the comparative example which did not contain an amine compound, both the light resistance and the substrate adhesion were inferior. Furthermore, when a coloring material not containing a sulfonic acid group was used (Comparative Example 5), sufficient substrate adhesion could not be obtained even if an amine compound was added.

Claims (10)

At least one, at least one organic solvent-soluble acid dye of the amine compound, at least one, at least one, and dye-containing negative type, characterized in that it contains at least one radical polymerizable monomer of the photopolymerization initiator of the alkali-soluble binder Curable composition. The dye-containing negative curable composition according to claim 1, wherein the organic solvent-soluble acidic dye is an acidic dye having a sulfonic acid group or a salt thereof. The oxidation potential of the amine compound is 0.90 V or less (vs. Ag / Ag ⁺ The dye-containing negative curable composition according to claim 1 or 2, wherein The dye-containing negative curable composition according to any one of claims 1 to 3, wherein the amine compound is a tertiary aniline compound, an amino compound having a nitrogen atom at a bridgehead position, or a hydrazine compound. The dye-containing negative curable composition according to any one of claims 1 to 3, wherein the amine compound is a tertiary aniline compound having a long-chain alkyl group. The dye-containing negative curable composition according to any one of claims 1 to 5, wherein the organic solvent-soluble acidic dye is at least one of an azo-based, anthrapyridone-based, and anthraquinone-based acidic dye. The dye-containing negative curable composition according to any one of claims 1 to 6, wherein the organic solvent-soluble acid dye is at least one of azo acid dyes. The dye-containing negative curable composition according to any one of claims 1 to 7, wherein the organic solvent-soluble acid dye is at least one of pyrazole azo acid dyes. A color filter comprising the dye-containing negative curable composition according to any one of claims 1 to 8 . It has the process of apply | coating the dye containing negative curable composition of any one of Claims 1-8 on a support body, exposing through a mask, and developing, and forming a pattern, It is characterized by the above-mentioned. A method for manufacturing a color filter.