JP2005215378A - Photosensitive colored composition and color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive colored composition having high sensitivity and excellent in pattern shape even in the case of a high dye content or a large film thickness, and to provide a color filter using the same. <P>SOLUTION: The photosensitive colored composition contains a dye carrier comprising a transparent resin and its precursor, a dye and a photopolymerization initiator represented by formula (1). The color filter has filter segments and/or a black matrix formed from the photosensitive colored composition on a transparent substrate. In the formula, R<SB>1</SB>and R<SB>2</SB>each independently represents a monovalent organic residue and R<SB>1</SB>and R<SB>2</SB>may bond together to form a cyclic structure but at least one of R<SB>1</SB>and R<SB>2</SB>is a π electron system functional group or a monovalent organic residue containing a hetero atom; and R<SB>3</SB>and R<SB>4</SB>each independently represents H or a monovalent organic residue. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a photosensitive coloring composition, and in particular, for color filters used in liquid crystal display devices and solid-state image sensors, formation of color filter segments such as red, green, blue, yellow, orange, cyan, and magenta, and a black matrix. It is related with the highly sensitive photosensitive coloring composition useful for. The present invention also relates to a color filter formed using the photosensitive coloring composition.

A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.
Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to form them generally at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher.

For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.
In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, and the solvent is removed by drying. After exposure, the unexposed areas are removed in the development process to form a pattern for the first color, and after processing such as heating as necessary, the same operation is sequentially repeated for all filter colors. Can be manufactured.

In recent years, color liquid crystal display devices have formed a large market for liquid crystal color televisions, car navigation and liquid crystal display integrated laptops, and monitors and televisions for desktop computers that take advantage of energy and space saving features. As it has begun to spread. Although attention is paid to a display device that replaces a conventional CRT, the color reproduction characteristic of a liquid crystal display device is inferior to that of a CRT at present.
Therefore, there is an increasing demand for high color reproducibility in color filters in which filter segments for each color are arranged.

  In order to improve contrast, a black matrix is generally arranged between the filter segments of each color of the color filter. However, the material for forming this black matrix has recently become an environmental problem, low reflection, and low cost. In view of the above, attention is focused on a resin black matrix in which a light-shielding pigment is dispersed in a resin instead of a metal chromium black matrix. However, the resin black matrix has a problem that the light shielding property (optical density) is lower than that of the metal chromium black matrix.

In order to improve the color reproduction characteristics of the color filter and to improve the light shielding property of the black matrix, it is necessary to increase the content of the dye in the photosensitive coloring composition or to increase the film thickness. However, in the method of increasing the content of the dye, problems such as a decrease in sensitivity, developability and resolution are generated. In the method of increasing the film thickness, there is a problem that the exposure light does not reach the bottom of the film and the pattern shape becomes defective.
In order to solve such problems, it is necessary to increase the sensitivity of the photosensitive coloring composition. In general, (1) provision of a reactive double bond of the resin, (2) photopolymerization initiator, Selection or increase of the sensitizer and (3) selection or increase of the monomer are performed.
JP 2001-233842 A JP 2001-264530 A JP 2003-156842 A

However, improvement in sensitivity is limited only by the provision of a double bond of the resin and the selection of a photopolymerization initiator, a sensitizer, and a monomer. In particular, when the amount of the photopolymerization initiator is increased, coloring due to a color unique to the photopolymerization initiator, a decrease in heat resistance, a decrease in light transmittance, a decrease in resolution, and the like occur. Further, when the amount of the monomer is increased, problems such as tackiness occur.
Accordingly, an object of the present invention is to provide a photosensitive coloring composition having high sensitivity and excellent pattern shape even when the pigment content is high or the film thickness is large, and a color filter using the same. .

The photosensitive coloring composition of the present invention is characterized by using a photopolymerization initiator represented by the following general formula (1) in order to obtain a high sensitivity and an excellent pattern shape. To do.
That is, the photosensitive coloring composition of the present invention is a photosensitive coloring composition containing a transparent resin and a dye carrier composed of a precursor thereof, a dye, and a photopolymerization initiator represented by the following general formula (1).
Moreover, the color filter of this invention is a color filter which comprises the filter segment and / or black matrix which are formed from the said photosensitive coloring composition.

(式中、Ｒ₁ およびＲ₂ は、それぞれ独立に１価の有機残基を表し、また、Ｒ₁ とＲ₂ は一体となって相互に結合した環状構造であってもよい。但し、Ｒ₁ およびＲ₂の少なくとも一方は、π電子系官能基もしくはヘテロ原子を含む１価の有機残基である。Ｒ₃およびＲ₄は、それぞれ独立に水素原子もしくは１価の有機残基を表す。） General formula (1)

(In the formula, R ₁ and R ₂ each independently represent a monovalent organic residue, and R ₁ and R ₂ may be a cyclic structure in which they are bonded together. _At least one of ₁ and R ₂ is a monovalent organic residue containing a π-electron functional group or a hetero atom, and R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent organic residue. )

The photosensitive coloring composition of the present invention is highly sensitive and excellent even when the pigment content is high or the formed film thickness of each color filter segment and black matrix is large by using a specific compound as a photopolymerization initiator. Each color filter segment and black matrix pattern can be formed.
Therefore, a high quality color filter can be obtained by using the photosensitive coloring composition of the present invention.

First, the photosensitive coloring composition in this invention is demonstrated concretely.
The photosensitive coloring composition of this invention contains the photoinitiator represented by the pigment | dye carrier which consists of transparent resin and its precursor, a pigment | dye, and the said General formula (1). The photopolymerization initiator represented by the general formula (1) has high sensitivity, and an excellent pattern-shaped filter segment and black matrix can be obtained by using a photosensitive coloring composition containing the photopolymerization initiator. Can be formed.
The photopolymerization initiator represented by the general formula (1) is characterized by having an O, O′-diacylglyoxime structure in which an oxime ester group is adjacent.

In the general formula (1), the substituents R ₁ and R ₂ represent a monovalent organic residue. The monovalent organic residue may have an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. Alkynyl group, optionally substituted alkoxyl group, optionally substituted aryloxy group, optionally substituted acyloxy group, optionally substituted alkylsulfanyl group, substituted An arylsulfanyl group which may have a group, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, a substituent An arylsulfonyl group that may have, an acyl group that may have a substituent, an alkoxycarbonyl group that may have a substituent, a carbamoyl group that may have a substituent, and a substituent. Good sulfamo Group, an optionally substituted amino group, an optionally substituted phosphinoyl group, heterocyclic group and the like may have a substituent. However, at least one of R ₁ and R ₂ is a monovalent organic residue containing a π-electron functional group or a hetero atom.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitrophenacyl group Etc. The.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthra Nyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a ruvicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.
The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.
As the alkoxyl group which may have a substituent, an alkoxyl group having 1 to 30 carbon atoms is preferable, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group. , T-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2 -Ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylaminocarbonylmethyloxy group Group, N- Examples include methyl-N-benzylaminocarbonylmethyloxy group, benzyloxy group, cyanomethyloxy group and the like.

The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group, Examples include 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group and the like.
The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyloxy. Group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms. For example, methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropylsulfanyl group, butylsulfanyl group, hexylsulfanyl Group, cyclohexylsulfanyl group, octylsulfanyl group, 2-ethylhexylsulfanyl group, decanoylsulfanyl group, dodecanoylsulfanyl group, octadecanoylsulfanyl group, cyanomethylsulfanyl group, methoxymethylsulfanyl group and the like.
The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, 1-naphthylsulfanyl group, 2-naphthylsulfanyl group, 2-chlorophenylsulfanyl group, 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group, 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenylsulfuric group Aniru group, 4-dimethylamino-phenylsulfanyl group and the like.

As the alkylsulfinyl group which may have a substituent, an alkylsulfinyl group having 1 to 20 carbon atoms is preferable. Group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoylsulfinyl group, dodecanoylsulfinyl group, octadecanoylsulfinyl group, cyanomethylsulfinyl group, methoxymethylsulfinyl group and the like.
The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, such as a phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfuric group Iniru group, 4-dimethylaminophenyl sulfinyl group and the like.

The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms. For example, a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group. Group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group and the like.
The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, a 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminopheny Sulfonyl group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1-naphthoyl. Group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl Group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, octyl. Oxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4- Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group Group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group , 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms, for example, an N-methylcarbamoyl group, an N-ethylcarbamoyl group, an N-propylcarbamoyl group, or an N-butylcarbamoyl group. N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2- Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyanophenyl A carbamoyl group, -4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group, N, N -Dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms, for example, a sulfamoyl group, an N-alkylsulfamoyl group, an N-arylsulfamoyl group, N, N- Examples thereof include a dialkylsulfamoyl group, an N, N-diarylsulfamoyl group, and an N-alkyl-N-arylsulfamoyl group. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N— Examples include sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group, and the like. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, Nt-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenylamino group, -4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino group, N- 4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenylamino group, N N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) amino group, N N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group and the like.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphinoyl group. Group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group Group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An aryloxy group which may have a substituent, an acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, and a substituent. An arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent. An arylsulfonyl group, an optionally substituted acyl group, an optionally substituted alkoxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, Amino group which may have a substituent, a hydrogen atom of the heterocyclic group which may have a substituent may be further substituted with other substituents.

  Examples of such substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxyl groups such as methoxy group, ethoxy group and tert-butoxy group, aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acetoxy group, propionyloxy group, acyloxy group such as benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, An acyl group such as a methoxalyl group, an alkylsulfanyl group such as a methylsulfanyl group or a tert-butylsulfanyl group, an arylsulfanyl group such as a phenylsulfanyl group or a p-tolylsulfanyl group, an alkylsulfuryl group such as a methylamino group or a cyclohexylamino group; Diamino groups such as ruamino group, dimethylamino group, diethylamino group, morpholino group, piperidino group, arylamino groups such as phenylamino group, p-tolylamino group, methyl group, ethyl group, tert-butyl group, dodecyl group, etc. In addition to aryl groups such as alkyl groups, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, sulfo groups, mesyl groups , P-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumumyl group, dimethylsulfoniumumyl group, triphenylphenacylphospho And niumyl group.

Furthermore, some of the substituents for R ₁ and R ₂ may be linked by a covalent bond. For example, there are the following structures.

In these substituents R ₁ and R ₂ , at least one of them must be a monovalent organic residue containing a π-electron functional group or a hetero atom in order to give a photosensitizing effect to the skeleton of the general formula (1). There is. The π-electron functional group includes an aryl ring, a heterocyclic ring, an unsaturated double bond such as a vinyl group, a carbonyl group, a sulfonyl group, and a phosphonyl group. The hetero atom includes a nitrogen atom, an oxygen atom, a sulfur atom, a phosphorus atom, a halogen atom, and the like. Furthermore, at least one of R ₁ and R ₂ is preferably an organic residue containing an aryl ring, a heterocyclic ring, or a carbonyl group. The π-electron functional group or hetero atom may be directly bonded to the basic skeleton of the general formula (1), or may exist as a substituent such as an alkyl group.
The other of R ₁ and R ₂ may or may not be a monovalent organic residue containing a π-electron functional group or a hetero atom. Preferred examples include an alkyl group that may have a substituent, an aryl group that may have a substituent, an acyl group that may have a substituent, a heterocyclic group that may have a substituent, and the like. More preferably, methyl group, ethyl group, butyl group, 4-dimethylaminophenyl group, 4-phenylsulfanylphenyl group, 4-methoxy-1-naphthyl group, 4-phenylsulfanylbenzoyl group, 4-methoxy-1- A naphthoyl group, an N-ethyl-3-carbazoyl group, a 6-benzoyl-N-ethyl-3-carbazoyl group and the like can be mentioned, but the present invention is not limited to these examples.

The substituents R ₃ and R ₄ in the general formula (1) each independently represent a hydrogen atom or a monovalent organic residue. Examples of the monovalent organic residue include those exemplified as the organic residues for R ₁ and R ₂ . R ₃ and R ₄ may be the same substituent or different substituents.
These substituents R ₃ and R ₄ preferably have an alkyl group which may have a substituent, an aryl group which may have a substituent, an acyl group which may have a substituent, and a substituent. Phosphinyl group and the like, which may be included, more preferably methyl group, ethyl group, trifluoromethyl group, phenyl group, acetyl group, benzoyl group, diphenylphosphinyl group and the like. It is not limited to.
Specific examples of the photopolymerization initiator represented by the general formula (1) include

(R ₁ = alkyl, R ₂ = aryl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1-phenyl-1,2-propanedione glyoxime, O, O′-diacetyl-1- (1-naphthyl) -1,2-propanedione glyoxime, O, O′-diacetyl -1-phenyl-1,2-butanedione glyoxime, O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -1,2-butanedione glyoxime, O, O′-diacetyl-1- ( 4-methoxy-1-naphthyl) -1,2-butanedione glyoxime, O, O′-dipropionyl-1-phenyl-1,2-propanedione glyoxime, O, O′-dibutyryl-1-phenyl- 1,2-propanedione glyoxime, O, O′-diisobutyryl-1-phenyl-1,2-propanedione glyoxime, O, O′-divalyl-1- (4-phenylsulfanylphenyl) -1,2 -Bu Dioneglyoxime, O, O′-dihexanoyl-1- (4-phenylsulfanylphenyl) -1,2-butanedioneglyoxime, O, O′-dioctanoyl-1- (4-phenylsulfanylphenyl) -1, 2-butanedione glyoxime, O, O′-didecanoyl-1- (4-ethoxy-1-naphthyl) -1,2-butanedione glyoxime, O, O′-dilauroyl-1- (4-ethoxy-1) -Naphthyl) -1,2-pentanedione glyoxime, O, O'-diacetyl-1- (9-anthryl) -1,2-propanedione glyoxime, O, O'-diacetyl-1- (1-pyrenyl) ) -1,2-butanedione glyoxime, O, O′-diacetyl-1- (4-biphenyl) -1,2-propanedione glyoxime, O, O′-diacetyl-1- (2-naphthyl)- 2-phenacyl- 1,2-ethanedione glyoxime, O, O′-dipropionyl-1- (p-tolyl) -1,2-hexanedione glyoxime, O, O′-bis (trifluoromethylcarbonyl) -1- ( 4-phenylsulfanylphenyl) -1,2-butanedione glyoxime, O, O′-diacetyl-1- (2,4,6-trimethyl) -1,2-butanedione glyoxime,

(R ₁ = aryl, R ₂ = aryl, R ₃ , R ₄ = alkyl)
O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-phenyl-1,2-ethanedione glyoxime, O, O′-diacetyl-1- (1-naphthyl) -2-phenyl-1 , 2-ethanedione glyoxime, O, O′-diacetyl-1- (1-naphthyl) -2-biphenyl-1,2-ethanedione glyoxime, O, O′-diacetyl-1- (1-naphthyl) 2- (p-tolyl) -1,2-ethanedione glyoxime, O, O′-diacetyl-1- (4-methoxy-1-naphthyl) -2-phenyl-1,2-ethanedione glyoxime, O, O′-dipropionyl-1- (2-naphthyl) -2- (2-naphthyl) -1,2-ethanedione glyoxime, O, O′-diacetyl-1- (1-naphthyl) -2- (4-Phenylsulfanylphenyl) -1,2-ethanediol O, O'-dioctanoyl-1- (4-methylsulfanylphenyl) -2-phenyl-1,2-ethanedione glyoxime, O, O'-diacetyl-1- (4-methoxyphenyl) -2- Phenyl-1,2-ethanedione glyoxime, O, O′-diacetyl-1,2-bis (4-dimethylaminophenyl) -1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = aryl, R ₃ , R ₄ = aryl)
O, O′-dibenzoyl-1- (4-phenylsulfanylphenyl) -2-phenyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1,2-bis (1-naphthyl) -1, 2-ethanedione glyoxime, O, O′-di (2-methylbenzoyl) -1,2-bis (4-dimethylaminophenyl) -1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = aryl, R ₃ , R ₄ = acyl)
O, O′-di (acetylcarbonyl) -1,2-diphenyl-1,2-ethanedione glyoxime, O, O′-di (acetylcarbonyl) -1- (1-naphthyl) -2-phenyl-1 , 2-ethanedione glyoxime, O, O′-di (acetylcarbonyl) -1- (4-methoxyphenyl) -2-phenyl-1,2-ethanedione glyoxime, O, O′-di (acetylcarbonyl) ) -1- (4-cyanophenyl) -2-phenyl-1,2-ethanedione glyoxime, O, O′-di (acetylcarbonyl) -1- (4-trifluoromethylphenyl) -2- (1 -Naphthyl) -1,2-ethanedione glyoxime, O, O'-di (acetylcarbonyl) -1- (4-dimethylaminophenyl) -2-phenyl-1,2-ethanedione glyoxime, O, O '-Di (acetylcarbonyl) -1- (4-phenyls Fanylphenyl) -2- (4-methoxyphenyl) -1,2-ethanedioneglyoxime, O, O′-di (benzoylcarbonyl) -1- (4-phenylsulfanylphenyl) -2-phenyl-1,2 -Ethanedione glyoxime, O, O'-di (acetylcarbonyl) -1- (4-methoxy-1-naphthyl) -2- (4-biphenyl) -1,2-ethanedione glyoxime, O, O ' -Di (acetylcarbonyl) -1- (4-phenylsulfanylphenyl) -2- (1-naphthyl) -1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = aryl, R ₃ , R ₄ = phosphinyl)
O, O′-bis (diphenylphosphinoyl) -1,2-diphenyl-1,2-ethanedione glyoxime, O, O′-bis (diethoxyphosphinoyl) -1- (1-naphthyl)- 2-Phenyl-1,2-ethanedione glyoxime, O, O′-bis (dimesitylphosphinoyl) -1- (4-methoxy-1-naphthyl) -2-phenyl-1,2-ethanediol Lioxime, O, O′-bis (diphenylphosphinoyl) -1- (4-phenylsulfanylphenyl) -2- (4-diethylaminophenyl) -1,2-ethanedione glyoxime, O, O′-bis (Diphenylphosphinoyl) -1- (4-dimethylaminophenyl) -2- (1-naphthyl) -1,2-ethanedione glyoxime, O, O′-bis (diphenylphosphinoyl) -1- ( 4-cyanophenyl) -2- (2-naphthyl) -1 , 2-ethanedione glyoxime, O, O′-bis (diphenylphosphinoyl) -1- (3-cyanophenyl) -2-phenyl-1,2-ethanedione glyoxime, O, O′-bis ( Diphenylphosphinoyl) -1- (3-trifluoromethylphenyl) -2-phenyl-1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = alkenyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (1-naphthyl) -2-vinyl-1,2-ethanedione glyoxime, O, O′-diacetyl-1- (4-butoxyphenyl) -2-allyl-1, 2-ethanedione glyoxime, O, O′-diacetyl-1- (1-naphthyl) -2-styryl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (4-methoxy-1) -Naphthyl) -2-allyl-1,2-ethanedione glyoxime, O, O'-di (acetylcarbonyl) -1- (1-naphthyl) -2-allyl-1,2-ethanedione glyoxime, O , O′-bis (diphenylphosphinoyl) -1- (1-naphthyl) -2-vinyl-1,2-ethanedione glyoxime, O, O′-bis (trifluoromethylcarbonyl) -1- (2 -Naphthyl) -2-allyl-1,2-ethanedione glyoxime, O, '- diacetyl-1- (4-phenylsulfanyl-phenyl) -2-vinyl-1,2-ethane MSN-02 ZEONG Li oxime,

(R ₁ = aryl, R ₂ = alkynyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-ethynyl-1,2-ethanedione glyoxime, O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-propynyl -1,2-ethanedione glyoxime, O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-propargyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- ( 1-naphthyl) -2-ethynyl-1,2-ethanedione glyoxime, O, O′-bis (acetylcarbonyl) -1- (4-methoxy-1-naphthyl) -2-propynyl-1,2-ethane Dione glyoxime, O, O′-bis (diphenylphosphinoyl) -1- (4-cyanophenyl) -2-propargyl-1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = alkoxy, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-methoxy-1,2-ethanedione glyoxime, O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-ethoxy -1,2-ethanedione glyoxime, O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-propyloxy-1,2-ethanedione glyoxime, O, O′-diacetyl-1- (4-Phenylsulfanylphenyl) -2-butoxy-1,2-ethanedione glyoxime, O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-octyloxy-1,2-ethanedione glyoxime Oxime, O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-dodecyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl- -(4-Phenylsulfanylphenyl) -2-methoxy-1,2-ethanedioneglyoxime, O, O'-bis (acetylcarbonyl) -1- (4-phenylsulfanylphenyl) -2-ethoxy-1,2 -Ethanedione glyoxime, O, O'-bis (diphenylphosphinoyl) -1- (4-phenylsulfanylphenyl) -2-methoxy-1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = aryloxy, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-phenoxy-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (4-phenylsulfanylphenyl) -2-phenoxy -1,2-ethanedione glyoxime, O, O′-bis (acetylcarbonyl) -1- (4-phenylsulfanylphenyl) -2-phenoxy-1,2-ethanedione glyoxime, O, O′-bis (Diphenylphosphinoyl) -1- (4-phenylsulfanylphenyl) -2-phenoxy-1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = acyloxy, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-benzoyloxy-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (1-naphthyl) -2-acetyloxy -1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1- (4-methoxyphenyl) -2-propanoyloxy-1,2-ethanedione glyoxime, O, O′-bis (diphenyl) Phosphinoyl) -1- (4-methoxy-1-naphthyl) -2-trifluoromethylcarbonyloxy-1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = alkylsulfanyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (4-methoxyphenyl) -2-methylsulfanyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (4-phenylsulfanylphenyl) -2-ethyl Sulfanyl-1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1- (1-naphthyl) -2-butylsulfanyl-1,2-ethanedione glyoxime, O, O′-bis (diphenylphos Finoyl) -1- (4-phenylsulfanylphenyl) -2-methylsulfanyl-1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = arylsulfanyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-phenylsulfanyl-1,2-ethanedioneglyoxime, O, O′-dibenzoyl-1- (4-methoxy-1-naphthyl)- 2- (1-naphthylsulfanyl) -1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1-phenyl-2- (2-methoxyphenylsulfanyl) -1,2-ethanedione glyoxime, O , O′-bis (diethoxyphosphinoyl) -1- (1-naphthyl) -2- (3-cyanophenylsulfanyl) -1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = alkylsulfinyl, R ₃ , R ₄ = no limitation)
O, O′-dipropanoyl-1- (4-phenoxyphenyl) -2-methylsulfinyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (4-phenylsulfanylphenyl) -2-ethyl Sulfinyl-1,2-ethanedione glyoxime, O, O′-dipropanoylcarbonyl-1- (2-naphthyl) -2-butylsulfinyl-1,2-ethanedione glyoxime, O, O′-bis ( Diphenylphosphinoyl) -1- (4-dimethylaminophenyl) -2-methylsulfinyl-1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = arylsulfinyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (4-diethylaminophenyl) -2-phenylsulfinyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1-phenyl-2- (1-naphthylsulfinyl)- 1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1- (4-phenylsulfanylphenyl) -2- (3-nitrophenylsulfinyl) -1,2-ethanedione glyoxime, O, O ′ -Bis (dimesitylphosphinoyl) -1- (p-tolyl) -2- (2-naphthylsulfinyl) -1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = alkylsulfonyl, R ₃ , R ₄ = no limitation)
O, O′-bis (trifluoromethylcarbonyl) -1- (4-dibutylaminophenyl) -2-methylsulfonyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (2-naphthyl) ) -2-ethylsulfonyl-1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1- (3-cyanophenyl) -2-butylsulfonyl-1,2-ethanedione glyoxime, O, O '-Bis (diphenylphosphinoyl) -1- (4-methylsulfanylphenyl) -2-octylsulfonyl-1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = arylsulfonyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1-phenyl-2-phenylsulfonyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (1-naphthyl) -2- (1-naphthylsulfonyl) -1 , 2-ethanedione glyoxime, O, O′-dipropanoylcarbonyl-1- (4-methylsulfanylphenyl) -2-phenylsulfonyl-1,2-ethanedione glyoxime, O, O′-bis (diphenyl) Phosphinoyl) -1-phenyl-2- (4-cyanophenylsulfonyl) -1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = acyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2-acetyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (4-dimethylaminophenyl) -2- ( 1-naphthoyl) -1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1- (4-methoxy-1-naphthyl) -2-benzoyl-1,2-ethanedione glyoxime, O, O '-Bis (diethoxyphosphinoyl) -1- (4-cyanophenyl) -2- (4-dimethylaminobenzoyl) -1,2-ethanedione glyoxime, O, O'-diacetyl-1- (4 -Phenylsulfanylphenyl) -2- (4-methoxy-1-naphthoyl) -1,2-ethanedioneglyoxime, O, O'-diacetyl-1- (4-phenylsulfanylphenyl) -2- (trifluoromethyl Carbonyl) -1,2-ethane MSN-02 ZEONG Li oxime,

(R ₁ = alkyl, R ₂ = acyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1-benzoyl-1,2-butanedione glyoxime, O, O′-dibenzoyl-1- (4-diphenylaminobenzoyl) -1,2-pentanedione glyoxime, O, O ′ -Diacetylcarbonyl-1- (1-naphthoyl) -1,2-butanedione glyoxime, O, O'-bis (dibenzoylphosphinoyl) -1- (3-cyanobenzoyl) -1,2-hexanediong Lioxime,

(R ₁ = aryl, R ₂ = alkoxycarbonyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (1-naphthyl) -2-methoxycarbonyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (4-phenylsulfanylphenyl) -2-ethoxycarbonyl -1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1- (4-diethylaminophenyl) -2-phenoxycarbonyl-1,2-ethanedione glyoxime, O, O′-bis (diethoxy Phosphinoyl) -1- (3-cyanophenyl) -2- (1-naphthyloxy) carbonyl-1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = carbamoyl, R ₃ , R ₄ = no limitation)
O, O′-dibutanoyl-1- (4-phenylsulfanylphenyl) -2- (N, N-dimethylcarbamoyl) -1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (4-ethoxy -1-naphthyl) -2- (N, N-diphenylcarbamoyl) -1,2-ethanedioneglyoxime, O, O′-dipropanoylcarbonyl-1-phenyl-2- (N-3-cyanophenylcarbamoyl) ) -1,2-ethanedione glyoxime, O, O′-bis (dimesitylphosphinoyl) -1-phenyl-2- (N, N-dimethylcarbamoyl) -1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = sulfamoyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (1-naphthyl) -2- (N, N-dimethylsulfamoyl) -1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (4-biphenyl) ) -2- (N, N-diphenylsulfamoyl) -1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1- (4-phenylsulfanylphenyl) -2- (N-methyl-N -Phenylsulfamoyl) -1,2-ethanedione glyoxime, O, O'-bis (diethoxyphosphinoyl) -1- (4-dimethylaminophenyl) -2- (N, N-diethylsulfa Moyl) -1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = amino, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1-phenyl-2- (N, N-diphenylamino) -1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (2-naphthyl) -2- (N , N-dimethylamino) -1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1- (4-phenylsulfanylphenyl) -2- (N, N-ditolylamino) -1,2-ethanediol Lioxime, O, O′-bis (diphenylphosphinoyl) -1- (4-methylphenyl) -2- (N, N-dibutylamino) -1,2-ethanedione glyoxime,

(R ₁ = aryl, R ₂ = phosphinoyl, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (4-phenylsulfanylphenyl) -2- (dibenzoylphosphinoyl) -1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (1-naphthyl) 2- (diethoxyphosphinoyl) -1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1-phenyl-2- (dimesitylphosphinoyl) -1,2-ethanedione Oxime, O, O′-diacetyl-1- (4-dimethylaminophenyl) -2- (dibenzoylphosphinoyl) -1,2-ethanedione glyoxime,

(R ₁ = alkyl, R ₂ = phosphinoyl, R ₃ , R ₄ = no limitation)
O, O′-dipropanoyl-1- (dibenzoylphosphinoyl) -1,2-butanedione glyoxime, O, O′-diacetylcarbonyl-1- (dimesitylphosphinoyl) -1,2-hexane Dione glyoxime, O, O′-dibenzoyl-1- (diphenylphosphinoyl) -1,2-pentanedione glyoxime, O, O′-diacetyl-1- (diethoxyphosphinoyl) -1,2- Butanedione glyoxime,

(R ₁ = aryl, R ₂ = heterocycle, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (4-dimethylaminophenyl) -2- (2-thienyl) -1,2-ethanedione glyoxime, O, O′-dibenzoyl-1-phenyl-2- (N— Ethyl-3-carbazolyl) -1,2-ethanedione glyoxime, O, O′-diacetylcarbonyl-1-phenyl-2- (2-thioxanthryl) -1,2-ethanedione glyoxime, O, O '-Diacetyl-1- (p-tolyl) -2- (N-ethyl-6-benzoyl-3-carbazolyl) -1,2-ethanedione glyoxime,

(R ₁ = alkyl, R ₂ = heterocycle, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (N-ethyl-3-carbazolyl) -1,2-butanedione glyoxime, O, O′-dibenzoyl-1- (N-ethyl-3-phenothiazinyl) -1, 2-octanedione glyoxime, O, O′-diacetylcarbonyl-1- (N-ethyl-2-acridinyl) -1,2-butanedione glyoxime, O, O′-bis (dibenzoylphosphinyl)- 1- (N-ethyl-3-carbazolyl) -1,2-hexanedione glyoxime,

(R ₁ = acyl, R ₂ = heterocycle, R ₃ , R ₄ = no limitation)
O, O′-diacetyl-1- (N-ethyl-3-carbazolyl) -2-benzoyl-1,2-ethanedione glyoxime, O, O′-dibenzoyl-1- (N-ethyl-3-phenothiazinyl) ) -2-acetyl-1,2-ethanedione glyoxime, O, O′-diacetyl-1- (2-thioxanthryl) -2- (1-naphthoyl) -1,2-ethanedione glyoxime, O O′-bis (dimesitylphosphinyl) -1- (3-phenoxathiinyl) -2-propanoyl-1,2-ethanedione glyoxime,
However, the present invention is not limited to these examples.
Specific examples of the photopolymerization initiator represented by the general formula (1) exemplified above include the following compounds (where Me is a methyl group, Et is an ethyl group, and Pr is a propyl group). Represents).

(式中、Ｒ₁，Ｒ₂は一般式（１）と同義である。) The starting material for synthesizing the photopolymerization initiator represented by the general formula (1) is a glyoxime represented by the general formula (2).
General formula (2)

(In the formula, R ₁ and R ₂ have the same meaning as in the general formula (1).)

The glyoxime represented by the general formula (2) is, for example, Chem. Ber., 50, <1917>, 952, Chem. Ber., 22, <1889>, 540, edited by The Chemical Society of Japan, 4th edition experiment. It can be obtained by various methods described in Chemistry Course, Vol. 14, page 1326 (Maruzen). Furthermore, it can also be obtained from a method for synthesizing oximes described in commercially available chemistry texts (for example, J. March, Advanced Organic Organic Chemistry, 4th Edition, Wiley Interscience, 1992).
One of the most convenient methods for synthesizing oximes is the reaction of ketones with hydroxylamine or salts thereof in a polar solvent such as ethanol or aqueous ethanol. In this case, it is well known to add a base such as sodium acetate to adjust the pH of the reaction mixture. The rate of this reaction is pH dependent and the base can be added initially or continuously during the reaction. A basic solvent such as pyridine is used as the base and / or solvent or co-solvent. The reaction temperature is generally the boiling temperature of the mixture, usually 60-120 ° C.

  Another convenient synthesis of oximes is nitrosation of active methylene groups with nitrous acid or alkyl nitrites. Both alkaline conditions are described for example in Organic Syntheses Coll. Vol. VI (J. Wiley & Sons, New York, 1988), pp 199 and 840, and acidic conditions are described for example in Organic Syntheses Coll. Vol. pp 32 and 373, Organic Syntheses Coll. Vol. III, pp 191 and 513, Organic Syntheses Coll. Vol. II, pp 202, 204 and 363, and is suitable for the production of oximes. Nitrous acid is usually produced from sodium nitrite. The nitrite alkyl ester is, for example, methyl nitrite, isopropyl nitrite, butyl nitrite, isoamyl nitrite.

The photopolymerization initiator represented by the general formula (1) is a method described in literature, for example, an oxime and an acyl chloride obtained by the above method or an acid anhydride, starting from the glyoxime represented by the general formula (2). Product in an inert solvent such as tetrahydrofuran, benzene or dimethylformamide, in the presence of a base, for example a tertiary amine such as triethylamine, or in a basic solvent such as pyridine. Is done.
Such reactions are known to those skilled in the art and are generally carried out at -15 to + 50 ° C, preferably 0 to 30 ° C.
All oxime ester groups exist in two configurations, (Z) or (E). Although this isomer can be separated by a conventional method, a mixture of isomers can also be used as a photopolymerization initiator. Therefore, the photopolymerization initiator represented by the general formula (1) may be a mixture of configurational isomers.
The photopolymerization initiator represented by the general formula (1) can be identified by elemental analysis values and ¹ H-NMR.

In the photosensitive coloring composition of the present invention, other photopolymerization initiators can be used in combination with the compound represented by the general formula (1).
Other photopolymerization initiators include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, Acetophenone compounds such as 1-hydroxycyclohexyl phenyl ketone and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin compounds such as benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2, Thioxanthone compounds such as 4-diisopropylthioxanthone and 2,4-diethylthioxanthone, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- ( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (tri (Loromethyl) -6-styryl-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-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], O- (acetyl) -N- (1-phenyl-2-oxo-2- (4 ′ Oxime ester compounds such as -methoxy-naphthyl) ethylidene) hydroxylamine, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6 Phosphine compounds such as trimethylbenzoyldiphenylphosphine oxide, quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone, borate compounds, carbazole compounds, imidazole compounds, titanocene compounds, and the like are used. . These photopolymerization initiators can be used alone or in combination.
The content of the photopolymerization initiator is preferably 0.5 to 50% by weight, more preferably 3 to 30% by weight, based on the total solid content of the photosensitive coloring composition.

Furthermore, the photosensitive coloring composition of the present invention can contain a sensitizer. The content of the sensitizer is preferably 0.5 to 60% by weight, more preferably 3 to 40% by weight based on the total amount of the photopolymerization initiator and the sensitizer.
Sensitizers include unsaturated ketones typified by chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, Michler's ketone derivatives and the like.

Specific examples include Okawara Nobu et al., “Dye Handbook” (1986, Kodansha), Okawara Nobu et al., “Functional Dye Chemistry” (1981, CMC), Ikemori Chusaburo et al., “Special Examples include, but are not limited to, sensitizers described in “Functional Materials” (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.
Two or more kinds of sensitizers may be used in any ratio as required.
Among the sensitizers, examples of the sensitizer capable of particularly suitably sensitizing the photopolymerization initiator represented by the general formula (1) include thioxanthone derivatives and Michler ketone derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4′-bis (Dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl- Examples thereof include N-ethylcarbazole. Among these, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is more preferable.

Moreover, the photosensitive coloring composition of the present invention can contain an amine compound having a function of reducing dissolved oxygen.
Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

Further, the photosensitive coloring composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimerca DOO -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used alone or in combination.
The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight, based on the total solid content of the photosensitive coloring composition. If it is less than 0.1% by mass, the effect of adding a polyfunctional thiol is insufficient, and if it exceeds 30% by mass, the sensitivity is too high and the resolution is lowered.

  As described above, the dye carrier contained in the photosensitive coloring composition of the present invention is composed of a transparent resin and a precursor thereof. The transparent resin is a resin having a transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. The transparent resin includes a thermoplastic resin, a thermosetting resin, and a photosensitive resin, and its precursor includes a monomer or an oligomer that is cured by irradiation with radiation to form a transparent resin. Or a mixture of two or more.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.

  Monomers and oligomers include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate , Polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neo Pentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, urethane Various acrylates and methacrylates such as acrylates, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide , N-vinylformamide, acrylonitrile and the like. These can be used alone or in admixture of two or more.

In the photosensitive coloring composition, the ratio M / P between the weight (P) of the transparent resin and the weight (M) of the precursor is preferably 0.10 to 1.20, and 0.15 to 1. 00 is more preferable, and 0.20 to 0.98 is particularly preferable. When the M / P is less than 0.10, the sensitivity is low, and when the M / P exceeds 1.20, a pattern-shaped linearity defect or tack is caused.
The ratio I _a / M of the weight (I _a ) of the photopolymerization initiator and the weight (M) of the precursor of the transparent resin is preferably 0.20 to 1.50, preferably 0.25 to 1 .40 is more preferable, and 0.30 to 1.30 is particularly preferable.
Further, when the photosensitive coloring composition contains a sensitizer, the ratio of the total weight (I _b ) of the photopolymerization initiator and the sensitizer to the weight (M) of the precursor of the transparent resin I _b / M is preferably 0.20 to 1.50, more preferably 0.25 to 1.40, and particularly preferably 0.60 to 1.30.
When I _a / M and I _b / M are less than 0.20, the sensitivity is low, and when I _a / M and I _b / M exceeds 1.50, a pattern-shaped linearity defect occurs.

As a pigment | dye contained in the photosensitive coloring composition of this invention, an organic or inorganic pigment can be used individually or in mixture of 2 or more types. Among the pigments, pigments having high color developability and high heat resistance, particularly pigments having high heat decomposition resistance are preferred, and organic pigments are usually used.
Below, the specific example of the organic pigment which can be used for the photosensitive coloring composition of this invention is shown with a color index number.
Examples of the red photosensitive coloring composition for forming the red filter segment include CI Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81. : 2, 81: 3, 97, 122, 123, 146, 149, 168, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220 Red pigments such as 223, 224, 226, 227, 228, 240, 246, 254, 255, 264, 272, and 279 can be used. A yellow pigment and an orange pigment can be used in combination with the red photosensitive coloring composition.

  For example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18 may be used as the yellow photosensitive coloring composition for forming the yellow filter segment. 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166 167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214, etc. Can be used.

Orange pigments such as CI Pigment orange 36, 43, 51, 55, 59, 61, 71, 73 can be used for the orange photosensitive coloring composition for forming the orange filter segment.
As the green photosensitive coloring composition for forming the green filter segment, for example, a green pigment such as CI Pigment Green 7, 10, 36, 37 can be used. A yellow pigment can be used in combination with the green photosensitive coloring composition.
Blue photosensitive coloring compositions for forming blue filter segments include, for example, CI Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64. , 80 and the like can be used. Purple pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 can be used in combination with the blue photosensitive coloring composition.

For example, CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 or the like is used as a cyan photosensitive coloring composition for forming a cyan filter segment. Can be used.
For the magenta color photosensitive coloring composition for forming the magenta color filter segment, purple pigments and red pigments such as CI Pigment Violet 1, 19, CI Pigment Red 144, 146, 177, 169, 81 can be used. . A yellow pigment can be used in combination with the magenta photosensitive coloring composition.

  Examples of the black photosensitive coloring composition for forming the black matrix include carbon black, aniline black, anthraquinone black pigment, perylene black pigment, specifically CI pigment black 1, 6, 7, 12, 20, 31 or the like can be used. For the black photosensitive coloring composition, a mixture of a red pigment, a blue pigment, and a green pigment can also be used. As the black pigment, carbon black is preferable from the viewpoint of price and light shielding properties, and the carbon black may be surface-treated with a resin or the like. Moreover, in order to adjust a color tone, a blue pigment and a purple pigment can be used together in a black photosensitive coloring composition.

Carbon black having a specific surface area of 50 to 200 m ² / g by the BET method is preferable from the viewpoint of the shape of the black matrix. When carbon black having a specific surface area of less than 50 m ² / g is used, the black matrix shape is deteriorated. When carbon black of more than 200 m ² / g is used, the dispersion aid is excessively adsorbed on the carbon black. This is because it is necessary to add a large amount of a dispersion aid in order to express various physical properties.

Carbon black preferably has an oil absorption of dibutyl phthalate (hereinafter referred to as “DBP”) of 120 ml / 100 g or less from the viewpoint of sensitivity.
Furthermore, the average primary particle diameter of carbon black is preferably 20 to 50 nm. Carbon black having an average primary particle diameter of less than 20 nm is difficult to disperse at a high concentration, and it is difficult to obtain a photosensitive black composition having good stability over time. This is because the matrix shape may be deteriorated.

Also, inorganic pigments include barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber, titanium black. Examples thereof include metal oxide powders such as synthetic iron black, titanium oxide, and iron tetroxide, metal sulfide powders, and metal powders. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The photosensitive coloring composition of the present invention may contain a dye within a range that does not reduce heat resistance for color matching.

  In the photosensitive coloring composition of the present invention, the dye is sufficiently dispersed in a dye carrier, and applied to a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. A solvent can be included to facilitate the formation of the matrix. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n amyl ketone, propylene glycol monomethyl ether toluene, methyl ethyl ketone. , Ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent and the like, and these are used alone or in combination.

  The photosensitive coloring composition of the present invention comprises a dye or a dye composition comprising two or more dyes, together with the photopolymerization initiator, in a three-roll mill, two-roll mill, sand mill, kneader, atomizer in a dye carrier and a solvent. It can be produced by finely dispersing using various dispersing means such as a lighter. Moreover, the photosensitive coloring composition containing 2 or more types of pigment | dyes can also mix and manufacture what each disperse | distributed finely in the pigment | dye carrier and a solvent separately. When the dye is dispersed in the dye carrier and the solvent, a dispersion aid such as a resin-type pigment dispersant, a surfactant, and a dye derivative can be appropriately contained. Since the dispersion aid is excellent in pigment dispersion and has a great effect of preventing re-aggregation of the pigment after dispersion, a photosensitive coloring composition obtained by dispersing the pigment in a dye carrier and a solvent using the dispersion aid is used. When used, a color filter excellent in transparency can be obtained.

  The resin-type pigment dispersant has a pigment-affinity part that has the property of adsorbing to the pigment and a part that is compatible with the dye carrier, and adsorbs to the pigment to stabilize the dispersion of the pigment on the dye carrier. It works. Specific examples of resin-type pigment dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamines. Salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, their modified products, amides formed by the reaction of poly (lower alkyleneimines) with polyesters having free carboxyl groups, and the like Water-based dispersants such as oily dispersants such as salts, (meth) acrylic acid-styrene copolymers, (meth) acrylic acid- (meth) acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone Resin, water-soluble polymer, polyester Modified polyacrylate, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate. , Lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Anionic surfactants such as: polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene Nonionic surfactants such as nylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; chaotic properties such as alkyl quaternary ammonium salts and their ethylene oxide adducts Surfactants: Examples include amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetic acid betaine and alkylimidazolines, and these can be used alone or in admixture of two or more.

  The dye derivative is a compound in which a substituent is introduced into an organic dye, and the organic dye includes naphthalene-based and anthraquinone-based light yellow aromatic polycyclic compounds that are not generally called dyes. Examples of the dye derivatives are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. These can be used alone or in combination of two or more.

  The photosensitive coloring composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time, and in order to improve the adhesion to the transparent substrate, such as a silane coupling agent. An adhesion improver can also be included. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples thereof include phosphine and phosphite.

  Examples of the silane coupling agent include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) ) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopro Lutriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N Examples include aminosilanes such as -phenyl-γ-aminopropyltriethoxysilane, thiosilanes such as γ-mercaptopropyltrimethoxysilane, and γ-mercaptopropyltriethoxysilane.

The photosensitive coloring composition of the present invention can be prepared in the form of a solvent developing type or alkali developing type colored resist material. The coloring resist material is obtained by dispersing a pigment in a composition containing a thermoplastic resin, a thermosetting resin or a photosensitive resin, a monomer, a photopolymerization initiator, and a solvent.
The pigment is preferably contained in a proportion of 5 to 70% by weight based on the total solid content of the photosensitive coloring composition. More preferably, it is contained in a proportion of 20 to 50% by weight, and the remainder consists essentially of a resinous binder provided by a dye carrier.
The photosensitive coloring composition is formed by means of centrifugal separation, sintering filter, membrane filter, or the like, coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more and mixed dust. Is preferably removed.

Next, the color filter of the present invention will be described.
The color filter of the present invention comprises a filter segment or a black matrix formed from the photosensitive coloring composition of the present invention on a transparent substrate, and a general color filter has at least one red filter segment, at least It comprises one green filter segment and at least one blue filter segment, or comprises at least one magenta filter segment, at least one cyan filter segment, and at least one yellow filter segment.

As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material has a dry film thickness of 0. 0 on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It apply | coats so that it may become 2-10 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove uncured portions and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

EXAMPLES The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” means “parts by weight”.
First, preparation of acrylic resin solutions used in Examples and Comparative Examples will be described. The molecular weight of the resin is a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography).

[Preparation of acrylic resin solution]
A reaction vessel was charged with 800 parts of cyclohexanone, heated to 100 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator was added dropwise at the same temperature over 1 hour to carry out a polymerization reaction.
60.0 parts of styrene
Methacrylic acid 60.0 parts
Methyl methacrylate 65.0 parts
Butyl methacrylate 65.0 parts
Azobisisobutyronitrile 10.0 parts After the addition, the mixture was further reacted at 100 ° C. for 3 hours, and then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added. The reaction was continued for 1 hour to obtain an acrylic resin solution. The weight average molecular weight of the acrylic resin was about 40,000.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. To prepare an acrylic resin solution.

[Adjustment of red pigment dispersion]
A mixture having the following composition was uniformly stirred and mixed, dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a red pigment dispersion.
Diketopyrrolopyrrole pigment (CI Pigment Red 254) 10.0 parts ("Irga Four Red B-CF" manufactured by Ciba Specialty Chemicals)
1.6 parts of anthraquinone pigment (CI Pigment Red 177) (“Chromophthal Red A2B” manufactured by Ciba Specialty Chemicals)
0.4 parts of anthraquinone pigment (CI Pigment Yellow 199) (“Chromoval Yellow GT-AD” manufactured by Ciba Specialty Chemicals)
Dispersant (“Solsperse 20000” manufactured by Zeneca) 2.4 parts Acrylic resin solution 28.0 parts Cyclohexanone 57.6 parts

[Adjustment of green pigment dispersion]
A green pigment dispersion was prepared in the same manner as the red pigment dispersion except that the pigment was changed to the following pigment.
7.0 parts of halogenated copper phthalocyanine pigment (CI Pigment Green 36) (“Rionol Green 6YK” manufactured by Toyo Ink Co., Ltd.)
Monoazo pigment (CI Pigment Yellow 150) 5.0 parts ("Funcheon First Yellow Y-5688" manufactured by Bayer)
[Adjustment of black pigment dispersion]
A black pigment dispersion was prepared in the same manner as the red pigment dispersion except that the pigment was changed to the following pigment.
Carbon black ("MA77" manufactured by Mitsubishi Chemical Corporation) 12.0 parts

[Examples 1 to 9 and Comparative Examples 1 and 2] (Adjustment of photosensitive coloring composition)
With the blending composition shown in Table 4, the mixture was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain each color resist material.

Monomer: Trimethylolpropane triacrylate
(Shin Nakamura Chemical "NK Ester ATMPT")
Photopolymerization initiator A: Compound (1) in Table 1 [Examples 1-6, 8, 9]
Photopolymerization initiator B: Compound (3) in Table 1 [Example 7]
Photopolymerization initiator C: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1
("Irgacure 369" manufactured by Ciba Specialty Chemicals)
Sensitizer: 2,4-diethylthioxanthone ("DETX-S" manufactured by Nippon Kayaku Co., Ltd.)

[Filter segment and black matrix pattern formation]
The obtained resist material was applied to a 10 cm × 10 cm glass substrate by spin coating so that the film thickness after post-baking was as shown in Table 5, and then pre-baked at 70 ° C. for 15 minutes in a clean oven. did. Next, after cooling the substrate to room temperature, ultraviolet rays were exposed through a photomask using an ultrahigh pressure mercury lamp. Thereafter, the substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, and air-dried. Thereafter, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form a stripe-shaped filter segment or black matrix on the substrate.

[Evaluation]
The sensitivity of the obtained resist material and the pattern shape of the filter segment or black matrix formed by the above method were evaluated by the following methods. The results are shown in Table 5.
(sensitivity)
The sensitivity of the resist was determined by the irradiation exposure amount at which the formed filter segment or black matrix pattern was finished according to the image size of the photomask. The rank of evaluation is as follows.
○: Less than 100 mJ / cm ² Δ: 100 mJ / cm ² or more and less than 300 mJ / cm ² ×: 300 mJ / cm ² or more

(Pattern shape)
The shape of the formed filter segment or black matrix pattern was evaluated by (1) the linearity of the pattern and (2) the cross-sectional shape of the pattern.
(1) was evaluated by observing with an optical microscope. The rank of evaluation is as follows.
◯: Good linearity Δ: Partially good linearity ×: Poor linearity (2) was evaluated by observing with a scanning electron microscope (SEM). The rank of evaluation is as follows.
○: Forward tapered shape.
Δ: Non-tapered shape.
X: Reverse taper shape.

膜厚：各色フィルタセグメントおよびブラックマトリックスの形成膜厚。
色素含有量：感光性着色組成物の全固形分量を基準とした色素の割合。
Ｍ／Ｐ＝（モノマーの重量）／（アクリル樹脂の重量）
Ｉ_a／Ｍ＝（光重合開始剤の重量）／（モノマーの重量）
Ｉ_b／Ｍ＝（光重合開始剤と増感剤との合計重量）／（モノマーの重量）

Film thickness: film thickness of each color filter segment and black matrix.
Dye content: Ratio of dye based on the total solid content of the photosensitive coloring composition.
M / P = (weight of monomer) / (weight of acrylic resin)
I _a / M = (weight of photopolymerization initiator) / (weight of monomer)
I _b / M = (total weight of photopolymerization initiator and sensitizer) / (weight of monomer)

As shown in Table 5, the photosensitive coloring compositions of Examples 1 to 9 using the photopolymerization initiator represented by the general formula (1) have high sensitivity, and the linearity of the obtained pattern. In addition, the photosensitive coloring compositions of Comparative Examples 1 and 2 using other photopolymerization initiators had poor sensitivity, pattern linearity, or cross-sectional shape. Nothing was obtained that was all good.

Claims (7)

A photosensitive coloring composition comprising a dye carrier comprising a transparent resin and a precursor thereof, a dye, and a photopolymerization initiator represented by the following general formula (1).
General formula (1)

(1)
(In the formula, R ₁ and R ₂ each independently represents a monovalent organic residue, and R ₁ and R ₂ may be a cyclic structure in which they are bonded together. _At least one of ₁ and R ₂ is a monovalent organic residue containing a π-electron functional group or a hetero atom, and R ₃ and R ₄ each independently represent a hydrogen atom or a monovalent organic residue. ) The photosensitive coloring composition according to claim 1, wherein the ratio of the weight (P) of the transparent resin to the weight (M) of the precursor is in the following relationship.
M / P = 0.10-1.20 The photosensitive coloring composition according to claim 1 or 2, wherein the ratio of the weight (I _a ) of the photopolymerization initiator and the weight (M) of the precursor of the transparent resin is in the following relationship.
I _a /M=0.20-1.50 A sensitizer is further included, and the ratio between the total weight (I _b ) of the photopolymerization initiator and the sensitizer and the weight (M) of the precursor of the transparent resin is in the following relationship: The photosensitive coloring composition of 2.
I _b /M=0.20-1.50   Furthermore, polyfunctional thiol is contained, The photosensitive coloring composition of any one of Claims 1-4 characterized by the above-mentioned.   A color filter comprising a filter segment formed from the photosensitive coloring composition according to claim 1 on a transparent substrate. A color filter comprising a black matrix formed from the photosensitive coloring composition according to claim 1 on a transparent substrate.