JP2007114803A - Color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resist composition suitable for forming a black matrix having a sufficient light shielding property without deteriorating sensitivity, developability, resolution property, adhesion and durability. <P>SOLUTION: The resist composition is a photopolymerizable composition for a color filter containing (a) a black color material, (b) a silane coupling agent and (c) at least a polyfunctional thiol compound as a photopolymerization initiation system. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a photopolymerizable composition for a color filter used in the production of an optical color filter used for a color television, a liquid crystal display element, a solid-state imaging device, a camera, and the like, and a color filter obtained from the composition, More specifically, the present invention relates to a photopolymerizable composition for a color filter suitable for producing a black matrix having high light-shielding properties but high sensitivity and excellent developability, and a color filter having a resin black matrix having high accuracy and high light-shielding properties.

  A color filter usually forms a black matrix on the surface of a transparent substrate such as glass or plastic sheet, and then sequentially applies three or more different hues such as red, green and blue in a striped or mosaic shape. It is formed with a color pattern. The pattern size varies depending on the use of the color filter and each color, but is about 5 to 700 μm. Further, the positional accuracy of superposition is several μ to several tens μ, and it is manufactured by a fine processing technique with high dimensional accuracy.

  Typical methods for producing a color filter include a dyeing method, a printing method, a pigment dispersion method, and an electrodeposition method. Among these, in particular, a pigment dispersion method for forming a color filter image by coating a photopolymerizable composition containing a color material on a transparent substrate and repeating image exposure, development, and curing as necessary is a color filter. It is widely used because it has high accuracy such as pixel position and film thickness, excellent durability such as light resistance and heat resistance, and few defects such as pinholes.

  The black matrix is generally arranged in a grid, stripe, or mosaic pattern between the red, green, and blue color patterns to prevent contrast malfunction due to color mixing suppression between colors or TFT malfunction due to light leakage. Playing a role. For this reason, the black matrix is required to have high light shielding properties. Conventionally, the black matrix is generally formed by a metal film such as chromium. In this method, a metal such as chromium is vapor-deposited on a transparent substrate, and the chromium layer is etched through a photolithography process. Therefore, a high light-shielding property can be obtained with a small thickness and high accuracy. On the other hand, it is a method with a long manufacturing process and low productivity, which is expensive, and has problems such as environmental problems caused by waste liquid of etching treatment.

  For this reason, methods for forming a low-cost, pollution-free black matrix (resin black matrix) with a photosensitive resin in which light-shielding pigments and dyes are dispersed have been energetically studied. However, since the resin black matrix has problems as described later, it has not been put into practical use yet. In order to develop the same light shielding property (optical density) as that of a black matrix made of a metal film such as chromium in the resin black matrix, it is necessary to increase the content of the light shielding pigment or dye, or to increase the film thickness. There is.

  In the method of increasing the film thickness, the flatness of the RGB colored pixels formed thereon is impaired due to the influence of the irregularities of the black matrix. For this reason, non-uniformity of the liquid crystal cell gap or disorder of the alignment of the liquid crystal occurs to cause a reduction in display capability. In addition, there is a problem that the transparent electrode ITO film provided on the color filter is disconnected.

  Further, in the method of increasing the content of the light-shielding pigment and dye, there is a problem that the sensitivity, developability, resolution, adhesion, etc. of the photosensitive resin (black resist) deteriorate, and only a decrease in productivity. Therefore, the accuracy and reliability required for color filters cannot be obtained. That is, since a photosensitive material that can exhibit sensitivity, developability, resolution, and adhesiveness under conditions of a thin film and high light-shielding properties has not been realized, practical application of a resin black matrix is hindered.

  Conventionally, methods for improving performance such as sensitivity, developability, resolution, adhesion, etc. are known in general photosensitive resins or photosensitive resins having a certain light transmission such as colored photosensitive compositions for color filters. It is in place. For example, in JP-A-1-152449, JP-A-1-254918, JP-A-2-153353, and JP-A-2-804, a coloring composition for a color filter in which a pigment is dispersed is used as a binder resin, a polyfunctional acrylic monomer, and a triazine as an initiator. JP-A-6-75372 and 6-75373 exemplify a composition comprising a compound having the same composition and the initiator being biimidazole. Therefore, in order to achieve practical sensitivity, it is necessary to provide an oxygen barrier film such as polyvinyl alcohol, which has the disadvantage that the manufacturing process becomes complicated.

  JP-A-4-340965 proposes a colored photosensitive composition containing a large amount of a polymerizable compound as a technique for reducing polymerization due to oxygen, which is the above drawback. However, the amount of the polymerizable compound is as high as 60% or more, and it is difficult to apply to a composition that requires a large amount of colorant such as a resin black matrix due to restrictions on the amount of coloring components. JP-A-6-27662 and JP-B-3-36212 propose a method for reducing polymerization inhibition by adding an amino acid derivative or a phosphorus compound. However, the improvement effect is not sufficient, and there are problems such as odor and stability. It is not practical.

  Examples of techniques for improving resolution and developability include binder resins having side chain double bonds exemplified in JP-A-5-19467, and binder resins having a controlled molecular weight distribution exemplified in JP-A-6-175362. JP-A-5-281734 includes a polyfunctional thiol compound, and JP-A-4-369653 adds an organic carboxylic acid. These are all compositions that are intended to form the RGB color pixel portion of the color filter, so that when the light-shielding pigment such as carbon black is blended, the required resolution and developability are obtained. I can't.

  When light blocking ability is required in the entire light wavelength region, such as a resin black matrix, 1) it is extremely difficult to make a difference in crosslink density between the exposed portion and the unexposed portion, and 2) the film is exposed even in the exposed portion. Difference in crosslink density in the thickness direction occurs. That is, even if it is sufficiently cured on the light-irradiated surface, it does not cure on the base surface. 3) Since a large amount of black color material insoluble in the developer is blended, developability These are significant obstacles in imparting photosensitive properties, such as significant reduction.

  In particular, the phenomena 1) and 2) are contradictory, and as the exposed portion is hardened, the difference in cure density in the film thickness direction increases, leading to a decrease in resolution. Further, if the difference in cross-linking density between the exposed area / unexposed area and the cured density of the exposed area cannot be made uniform, it becomes difficult to use a developing solution having a strong dissolving power, so that it is difficult to improve developability. Conventionally known photosensitive compositions for forming a black matrix avoid such a situation. For example, as described in JP-A-6-51499 and JP-A-6-3518, conventional metal compositions are used. Instead of forming a resin black matrix that can block light to the same extent as the black matrix, it is light impervious to light to some extent, and the light blocking capability is extremely low and impractical. For this reason, as disclosed in Japanese Patent Laid-Open No. 8-44050, a resin black matrix having a high degree of light shielding with a thin film has also been proposed by once forming a resin black matrix having a high film thickness and low light shielding properties and then shrinking in the curing process. However, it is difficult to put into practical use due to problems such as complicated processes and reduced adhesion due to strain accumulation during film shrinkage.

In this way, the conventional technology did not respond at all to the seemingly contradictory problem of light reaction, which originally caused a photoreaction under conditions contrary to the photoreaction, and a large amount of insoluble colorant was formulated. It was difficult to realize a resin black matrix because there was no sufficient technical suggestion on how to impart developability to the photosensitive resin.
Japanese Patent Laid-Open No. 1-152449 JP-A-1-254918 JP-A-2-153353 JP-A-2-804 JP-A-6-75372 JP-A-6-75373 JP-A-4-340965 JP-A-6-27662 Japanese Patent Publication No. 3-36212 Japanese Patent Laid-Open No. 5-19467 JP-A-6-175362 Japanese Patent Laid-Open No. 5-281734 JP-A-4-369653 JP-A-6-51499 JP-A-6-3518 JP-A-8-44050

  The present invention provides a resist material having sufficient sensitivity, resolution, developability and durability that can easily form a pattern having a thin film and high light-shielding properties by a photolithography method by solving the above-mentioned problems. The resin black matrix of the color filter can be manufactured with high accuracy and low cost. In addition, by making the black matrix into a resin, the color filter is improved in image quality and pollution-free.

  As a result of diligent research, the present inventors have found that a photopolymerizable composition containing at least a polyfunctional thiol as a black color material, a silane coupling agent, and a photoinitiating system can solve such an object and completes the invention. It came to. That is, the present invention contains a black color material, a silane coupling agent, and at least a polyfunctional thiol as a photoinitiating system suitable for forming a resin black matrix of a color filter, and a photopolymerizable composition for a color filter And color filters using the same.

  The resist composition for a color filter of the present invention is excellent in sensitivity, developability, resolution, adhesion, and durability while being highly light-shielding in a thin film, so that a high-quality resin black matrix can be formed at low cost. it can. Moreover, since the development latitude is wide, production management is easy. Since the color filter using the resin black matrix of the present invention is excellent in accuracy, flatness and durability, the display quality of the liquid crystal element can be improved more than before. In addition, since the manufacturing process and the color filter itself do not contain harmful substances, the danger to the human body is reduced and the environmental safety is improved.

  Although this invention mix | blends a black color material, a polyfunctional thiol, and a silane coupling agent as an essential component, in order to set it as a photopolymerization composition, at least 1 binder resin, photoinitiating system, and an ethylenically unsaturated heavy bond which are usually mentioned below are included. It is desirable to add a compound having a single unit and a solvent.

  (Binder resin) The binder resin functions as a binder that improves compatibility, film-forming properties, developability, and adhesion. An organic polymer substance is mentioned as what has such an effect | action. The organic polymer substance is not particularly limited, but a polymer substance having a carboxyl group is preferable from the viewpoint of developability, adhesion to a substrate, and compatibility with a black color material. Such a resin can be obtained, for example, by copolymerizing a polymerizable monomer having both a double bond and a carboxyl group alone or with a polymerizable monomer having other properties.

  In the present invention, the black matrix, which is a light-shielding material, forms a highly sensitive and high-definition image and improves the film strength of the formed matrix. An organic polymer substance having a double bond is preferred, and among them, a copolymer having an ethylenically unsaturated double bond, a carboxyl group, and a hydroxyl group is more preferably used. Such a copolymer can be obtained, for example, by introducing the functional functional group into a polymer such as a styrene copolymer having a carboxyl group and an acrylic copolymer using various reactions.

  Specific examples of the organic polymer material according to the present invention include styrene monomers such as styrene, α-methyl-styrene, vinyltoluene; acrylic acid, methacrylic acid, silicic acid, maleic acid, fumaric acid, maleic anhydride, Unsaturated group-containing carboxylic acids such as itaconic acid; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, allyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxy Esters of (meth) acrylic acid such as ethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate benzyl (meth) acrylate; acryloni Ril; a copolymer selected from vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate, vinyl pivalate, etc. as a monomer and containing at least one unsaturated group-containing carboxylic acid as a monomer. It can be easily obtained by introducing an ethylenic double bond into the side chain by molecular reaction or the like.

  Examples of the polymer reaction in which an ethylenically unsaturated double bond is introduced into the side chain include a reaction that causes an organic bond such as an ester bond, an amide bond, an ether bond, an imide bond, and a urethane bond. As an example of the introduction reaction, a part or all of the carboxylic acid group and / or hydroxyl group of the organic polymer copolymer is glycidyl (meth) acrylate, allyl glycidyl ether, alicyclic structure of the following structure (I) The reaction with an aliphatic epoxy group-containing unsaturated compound such as an epoxy group-containing unsaturated compound can be exemplified. Since this reaction can be carried out under mild conditions and in high yield, it is desirable because it is easy to produce and low in cost. In particular, alicyclic epoxy group-containing unsaturated compounds are preferable because they can be easily introduced and have excellent physical properties in terms of resist properties such as film strength, developability, and pigment dispersibility. In the present specification, “(meth) acryl” means “acryl or methacryl”. The same applies to “(meth) acrylate”.

  In the present invention, particularly preferable organic polymer substances are styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) acrylate, for the purpose of enhancing the adhesion to the substrate. A copolymer monomer having a phenyl group such as hydroxyphenyl (meth) acrylamide and hydroxyphenyl (meth) acrylsulfamide is 10 to 90 mol%, preferably 20 to 80 mol%, more preferably 30 to 70 mol%. And a copolymer containing 2 to 50% by weight, preferably 5 to 50% by weight of (meth) acrylic acid, or 2 to 50 mol%, preferably 5 A reaction product to which ˜40 mol% of an epoxy group-containing unsaturated compound is added is desirable.

  The molecular weight of such an organic polymer substance is usually 1,000 to 1,000,000, preferably 2,000 to 300,000, more preferably 3,000 to 100,000 in terms of weight average molecular weight (Mw). It is. If the Mw of the organic polymer material is significantly lower than this range, the film veri in the image line portion occurs during development, and conversely, if the Mw of the organic polymer material is extremely high, the non-image area defect occurs during development.

  Furthermore, other organic / inorganic polymers may be added for the purpose of improving the performance as a resist and the performance as a color filter. Examples of these organic / inorganic polymers include polyethylene glycol, polypropylene glycol, polytetraethylene glycol, polyether and copolymer polyether of epichlorohydrin and bisphenol A, polyamide such as polyvinyl alkyl ether and soluble nylon, Examples thereof include polyurethane, polyethylene terephthalate / isophthalate, polyethylene adipate, polytetraethylene adipate, polyester such as polyethylene fumarate, acetyl cellulose, polyvinyl formal, and polyvinyl butyral.

  (Compound having at least one ethylenically unsaturated double bond) A compound having at least one ethylenically unsaturated double bond (hereinafter referred to as “ethylenic compound”) is generated from a photopolymerization initiator system described later. It is a compound in which a polymerization reaction is induced by the radical to be generated. The ethylenic compound may be either a monomer, an oligomer having an ethylenically unsaturated double bond in the side chain or main chain, and a macromer. In addition, the meaning of the monomer in the present invention is a concept that is opposed to a so-called polymer substance, and therefore includes dimers, trimers, and oligomers in addition to monomers in a narrow sense. .

  Examples of the ethylenic compound include unsaturated carboxylic acid, ester of aliphatic (poly) hydroxy compound and unsaturated carboxylic acid, ester of aromatic polyhydroxy compound and unsaturated carboxylic acid, unsaturated carboxylic acid and polyvalent Esters obtained from esters of carboxylic acids and aliphatic polyhydroxy compounds, ethylene oxides of aromatic polyhydroxy compounds, propylene oxide adducts and unsaturated carboxylic acids, ethylene oxides of aliphatic polyhydroxy compounds and propylene oxide adducts Esterification reaction with saturated carboxylic acid, ester of caprolactone-modified polyhydric alcohol and unsaturated carboxylic acid, reaction product of polyhydric alcohol, polyisocyanate and unsaturated carboxylic acid, styryl-terminated compound, phosphoric acid unsaturated Compound, polyepoxy and unsaturated cal Adduct of phosphate and the like.

  Among these, specific examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, neopentyl glycol diacrylate, hexanediol diacrylate, trimethylol propane tri Acrylate esters such as acrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Methacrylic acid with the acrylate of the exemplified compound replaced with methacrylate Ether, similarly itaconic acid ester instead itaconate, maleic acid esters, and the like was replaced with crotonic acid ester or maleate was replaced crotonate.

  Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. The ester obtained by the esterification reaction of an unsaturated carboxylic acid with a polyvalent carboxylic acid and a polyvalent hydroxy compound is not necessarily a single substance, but representative examples include condensation of acrylic acid, phthalic acid and ethylene glycol. Products, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

  Other examples of the ethylenic compound used in the present invention include acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate. Examples of the oligomer having an ethylenically unsaturated bond in the main chain include, for example, polyester obtained by polycondensation reaction of unsaturated divalent carboxylic acid and dihydroxy compound, and polymerization of unsaturated divalent carboxylic acid and diamine. There are polyamides obtained by condensation reaction.

  The oligomer having an ethylenically unsaturated double bond in the side chain includes a divalent carboxylic acid having an unsaturated bond in the side chain, such as itaconic acid, propylidene succinic acid, ethylidene malonic acid and the like, and a dihydroxy or diamine compound. There is a condensed compound of Also, compounds having functional groups having reactive activity such as hydroxy groups and methyl halide groups in the side chain, such as polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, and acrylic acid, methacrylic acid, crotonic acid, etc. Oligomer obtained by polymer reaction with an unsaturated carboxylic acid can also be suitably used.

  Among the ethylenic compounds listed above, the most preferable ones have 2 or more, more preferably 3 or more ethylenically unsaturated groups in the same molecule. The unsaturated group is preferably a (meth) acryl group, more preferably an acrylic group. Such compounds include trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, etc. Is mentioned.

  (Photopolymerization initiator system) One feature of the photopolymerization initiation system of the present invention is that it contains at least a polyfunctional thiol compound. By using a polyfunctional thiol as a part of the initiation system, in the photopolymerizable composition for color filters containing a large amount of the black color material which is the main object of the present invention, in other words, the light transmittance is greatly increased. In a limited photopolymerizable composition for a color filter, the details of the mechanism are unknown, but a significant improvement in sensitivity can be exhibited without impairing the image forming properties such as resolution. Usually, in a photocurable resist, a polymerization reaction proceeds only at a portion irradiated with light, and an image is formed by utilizing a fact that a polymerization reaction does not proceed at an unirradiated portion. However, in a system containing a large amount of a light-shielding pigment (in the case of the present invention, in particular, carbon black, etc.) as in the present invention, the film thickness from the light-irradiated surface also in the light-irradiated portion. The amount of light transmission decreases in proportion to (Lambert-Beer's law), the amount of light transmission to the back surface is 1% to 0.01% or less of the surface, and polymerization reaction is hardly induced on the back surface. It is. However, when the photopolymerization initiator system to which the polyfunctional thiol of the present invention is added is used, the photopolymerization reaction proceeds to the resist film back surface, which is the interface with the substrate, to form a cured film, and between the resist and the substrate. Adhesion can be improved and high sensitivity and image formability can be achieved.

  The polyfunctional thiol compound used in the present invention has two or more mercapto (SH) groups in the same molecule. In particular, a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as methylene or ethylene group is preferable. Specifically, for example, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiol Glycolate, butanediol bisthiopropionate, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, etc. Is mentioned. These polyfunctional thiols can be used alone or in combination.

  Since the blending amount of the polyfunctional thiol is used as the starting system, it is 0.01 to 10% by weight, more preferably 0.02 to 7% by weight, still more preferably 0.03 to 5% based on the total solid content excluding the solvent. It is desirable to add in the range of% by weight. When the blending ratio is out of the above range, the stability, odor, sensitivity, resolution, developability, adhesion, etc. of the photosensitive solution are deteriorated. Low addition amount decreases sensitivity and adhesion, and high addition amount decreases stability, odor, resolution and developability.

  It is uncertain about the cause of such deterioration, but it is related to the fact that polyfunctional thiol is radically or ionically added to the carbon-carbon double bond in an anti-Markownikoff, that is, a compound that can also take monomeric behavior. It seems to do. That is, since the function as a monomer is lower than the above-mentioned desirable acrylic monomer, if it is added in the same amount as a normal monomer, the function of the acrylic monomer will be inhibited. Therefore, as described above, a small amount should be added as an initiator. It is thought that it exhibits a high function.

  The photopolymerization initiator of the present invention is preferably a complex initiator system further containing a compound that polymerizes an ethylenically unsaturated double bond with actinic rays. Examples of the compound that polymerizes an ethylenically unsaturated double bond with actinic rays include 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl)- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6 -Halomethylated triazine derivatives such as bis (trichloromethyl) -s-triazine, halomethylated oxadiazole derivatives, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'- Chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole dimer, 2- (2'-fluorophenyl) -4,5 Imidazole derivatives such as diphenylimidazole dimer, 2- (2′-methoxyphenyl) -4,5-diphenylimidazole dimer, (4′-methoxyphenyl) -4,5-diphenylimidazole dimer, benzoin methyl Benzoin such as ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, benzoin alkyl ethers, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, anthraquinone derivatives such as 1-chloroanthraquinone, benzanthrone Derivatives, benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone Benzophenone derivatives such as 2-carboxybenzophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy- 1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1 , 1,1-trichloromethyl- (p-butylphenyl) ketone acetophenone derivatives, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthio Oxa And thioxanthone derivatives such as 2,4-diisopropylthioxanthone, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate, 9-phenylacridine, 9- (p-methoxyphenyl) acridine and the like Acridine derivatives, phenazine derivatives such as 9,10-dimethylbenzphenazine, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti- Bis-2,3,4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclo Pentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di-cyclo Interdienyl-Ti-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis -2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-di-fluorophen-1-yl, di-cyclopentadienyl And titanocene derivatives such as -Ti-2,6-di-fluoro-3- (pyr-1-yl) -phen-1-yl.

  Among these compounds, biimidazole compounds, titanocene compounds, triazine compounds, and oxadiazole compounds are particularly effective in combination with polyfunctional thiols, and exhibit excellent performance in sensitivity, resolution, developability, and adhesion. Therefore, it is preferable. The compounding amount of the compound capable of polymerizing the ethylenically unsaturated double bond with actinic rays is preferably added in the range of 0.03 to 5% by weight based on the total solid content.

  In addition to the above components, a sensitizing dye can be further added to the photoinitiating system of the present invention. The addition of a sensitizing dye is preferable because it can achieve a wider photosensitive wavelength and higher sensitivity. Examples of such a sensitizing dye include a coumarin compound having a heterocyclic ring described in JP-A-3-239703 and JP-A-5-289335, and 3-ketocoumarin described in JP-A-63-221110. Compounds, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, pyromethene dyes described in JP-A-6-19240, JP-A-47-2528, JP-A-54- (P-dialkylaminobenzylidene) ketone, styryl dye described in JP-A-56-166154, JP-A-59-56403, and a julolidyl group described in Japanese Patent Application No. 5-83588. And sensitizing dyes, diaminobenzene compounds described in Japanese Patent Application No. 7-10109, and the like.

  Of these sensitizing dyes, amino group-containing sensitizing dyes are particularly preferred, and more specifically compounds having an amino group and a phenyl group in the same molecule. Specifically, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, 3,3'- Benzophenone compounds such as diaminobenzophenone and 3,4-diaminobenzophenone, 2- (p-dimethylaminophenyl) benzoxazole, 2- (p-diethylaminophenyl) benzoxazole, 2- (p-dimethylaminophenyl) benzo [4 , 5] benzoxazole, 2- (p-dimethylaminophenyl) benzo [6,7] benzoxazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-oxazole, 2- (p-dimethylamino) Phenyl) benzothiazole, 2- ( -Diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) 1,3,4-thiadiazole, ( p-dimethylaminophenyl) pyridine, (p-diethylaminophenyl) pyridine, 2- (p-dimethylaminophenyl) quinoline, 2- (p-diethylaminophenyl) quinoline, 2- (p-dimethylaminophenyl) pyrimidine, 2- Examples thereof include p-dialkylaminophenyl group-containing compounds such as (p-diethylaminophenyl) pyrimidine.

(Color material) The black color material can be a single color black material or a plurality of black color materials, or a black color material obtained by mixing red, green, blue, or the like. These color materials can be appropriately selected from inorganic or organic pigments and dyes. Specific examples of color materials that can be mixed are Victoria Pure Blue (42595), Auramin O (41000), Catillon Brilliant Flavin (Basic 13), Rhodamine 6GCP (45160), Rhodamine B (45170), Safranin OK70: 100 ( 50240), Erioglaucine X (42080), No. 120 / Lionol Yellow (21090), Lionol Yellow GRO (21090), Shimla First Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimler First Red 4015 (12355), Lionol Red 7B4401 (15850), Fast Gen Blue TGR-L (74160), Lionol Blue SM (26150), Lionol Blue ES (Pigment Blue 15: 6), Lionogen Red GD (Pigment Red 168), Lionol Green 2YS (Pigment Green 36), etc. (Note that the above (
The numbers in () mean the color index (C.I.)).

  In addition, other pigments that can be used in combination are C.I. I. For example, C.I. I. Yellow pigments 20, 24, 86, 93, 109, 110, 117, 125, 137, 138, 147, 148, 153, 154, 166, C.I. I. Orange pigment 36, 43, 51, 55, 59, 61, C.I. I. Red pigments 9, 97, 122, 123, 149, 168, 177, 180, 192, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, C.I. I. Violet pigments 19, 23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I. I. Green pigment 7, C.I. I. Examples thereof include brown pigments 23, 25, and 26.

  Examples of the black color material that can be used alone include carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, and cyanine black. Among these, carbon black is particularly preferable from the viewpoints of light shielding rate and image characteristics. Examples of carbon black include the following carbon black.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA100, MA220, MA230, # 52, # 50, # 47, # 45, # 2700, # 2650, # 2200, # 1000, # 990, # 900
Made by Degussa: Printex95, Printex 90, Printex85, Printex75, Printex55, Printex45, Printex40, Printex30, Printex3, PrintexA, PrintexG, SpecialBlack550, SpeckB350550, SpeckSc350

Manufactured by Cabot Corporation: Monarch 460, Monarch 430, Monarch 280, Monarch 120, Monarch 800, Monarch 4630, REGAL99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, BLACK
PEARLS 480, PEARLS 130
Made by Colombian Carbon: Raven11, Raven15, Raven30, Raven35, Raven40, Raven410, Raven420, Raven450, Raven500, Raven780, Raven850, Raven890H, Raven1000, Raven1000, Raven1020, Raven1040 Further, it may be used in combination with an organic pigment. Other pigments naturally have a light shielding property or image characteristic lower than that of carbon black, so the mixing ratio is naturally limited.

  (Silane Coupling Agent) The silane coupling agent used in the present invention is a silicon-containing compound having two or more different reactive groups in the molecule. That is, a silicon compound having a reactive group chemically bonded to an inorganic material such as glass and a reactive group chemically bonded to an organic material. Examples of reactive groups that chemically bond with inorganic materials such as glass include alkoxy groups such as methoxy groups and ethoxy groups, and reactive groups that chemically bond with organic materials include vinyl groups, epoxy groups, amino groups, and (meth). An acrylic group and a mercapto group are mentioned.

  Specifically, vinyl silanes such as vinyl tris (β methoxyethoxy) silane, vinyl ethoxy silane, vinyl trimethoxy silane, (meth) acryl silanes such as γ-methacryloxypropyl trimethoxy silane, β- (3 , 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane , Γ-glycidoxypropyltriethoxysilane, and other epoxy silanes, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (Aminoethyl) γ-aminopropylmethyl Aminosilanes such as ethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, γ- Examples thereof include thiosilanes such as mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. Among these silane coupling agents, (meth) acryl silanes and epoxy silanes have high stability in the photosensitive solution, and the developability and resolution of the photosensitive composition are particularly good. . Moreover, since the durability improvement effect at the time of forming a color filter is also high, it is preferable.

(Solvent) In the present invention, the solvent is not particularly limited as long as it dissolves and disperses the above-described components. Specifically, diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene , Methyl nonyl ketone, propyl ether, dodecane, Socal
solvent no. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec, t), hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amyl formate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methyl amyl Ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3- Ethoxypropionic acid Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carbitol And organic solvents such as butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, 3-methyl-3-methoxybutyl acetate.

  It is preferable to select a solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120-170 ° C. These solvents are used alone or in combination. The content of each component of the photopolymerizable composition for a color filter of the present invention is 0 to 95% by weight, preferably 10 to 10% by weight, based on the solid content excluding the solvent and the black color material. 80% by weight, more preferably 20-70% by weight, and the compounding amount of the compound having at least one ethylenically unsaturated double bond is 0-95% by weight, preferably 10-80% by weight, more preferably 20-70%. The blending amount of the photopolymerization initiator system containing% by weight and the polyfunctional thiol compound is preferably 0.1 to 40% by weight, particularly 0.5 to 30% by weight, especially 0.5 to 20% by weight. In addition, the compounding quantity of polyfunctional thiol is as having mentioned above. The amount of the silane coupling agent is preferably in the range of 0.05 to 15% by weight. The black material content is preferably 20 to 80% by weight, particularly 30 to 70% by weight, based on the total solid content in the photopolymerizable composition excluding the solvent. In particular, when carbon black is used as the black pigment, the amount of carbon black blended is light to form a black matrix having a light shielding ratio of 3.0 μm and a high light shielding ratio of 3.5 or more at a film thickness of 1 μm. The total solid content in the polymerizable composition is preferably 30 to 80% by weight, preferably 35 to 75% by weight, and more preferably 40 to 70% by weight.

  In addition, the photopolymerizable composition of the present invention is desirably prepared using these solvents so that the solid content concentration is in the range of 5 to 50% by weight, preferably 10 to 30% by weight. In the present invention, in addition to the components described above, for example, coating property improvers such as F-based surfactants, pigment derivatives, surfactants, pigment dispersants such as polymers, and polymerization prohibition for stabilizing the photosensitive solution are prohibited. Components such as an agent can be suitably added.

  Next, the manufacturing method of the photopolymerizable composition for color filters of this invention is demonstrated. In the present invention, it is usually preferable to disperse the black color material in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer or the like. Since the black color material is finely divided by the dispersion treatment, the light shielding ability of the resist and the coating characteristics are improved.

  In the dispersion treatment, the treatment is preferably carried out in a system in which a black color material and a solvent, a binder resin having a dispersion function, or a dispersant is further used in combination. In particular, it is preferable to use a polymer dispersant because it is excellent in dispersion stability over time. Further, in the dispersion treatment with a solution in which all components to be blended as a resist solution are mixed, there is a possibility that highly reactive components are denatured due to heat generated at the time of dispersion.

  In the case of dispersing with a sand grinder, glass beads or zirconia beads having a diameter of 0.1 to several millimeters are preferably used. The conditions for the dispersion are usually that the temperature is from 0 ° C. to 100 ° C., and preferably from room temperature to 80 ° C. The dispersion time is appropriately adjusted because the appropriate time varies depending on the composition of the ink (black color material, solvent, dispersant) and the size of the sand grinder.

  Next, the black ink obtained by the dispersion treatment and the other components necessary as a resist component are added and mixed to obtain a uniform solution. In the manufacturing process, fine dust is often mixed with the photosensitive solution. Therefore, the obtained resist photosensitive solution is preferably filtered through a filter or the like. Then, the manufacturing method of the color filter using the photopolymerizable composition for color filters of this invention is demonstrated.

  First, the photopolymerizable composition for a light-shielding film of the present invention is coated on a transparent substrate by a spinner, a wire bar, a flow coater, a die coater, a roll coater, a spray or the like, and then dried. A photomask is placed on the photomask, and a black matrix image for shading is formed through image exposure, development, and heat curing or photocuring as necessary, and this operation is repeated for each of the three RGB colors to obtain a color filter image. Let it form.

  In addition, when forming a pixel of a color filter using the photopolymerizable composition of the present invention, since it has very high sensitivity and high resolution, exposure and development can be performed without providing an oxygen blocking layer such as polyvinyl alcohol. Thus, an image can be formed. The transparent substrate used here is a transparent substrate for a color filter, and its material is not particularly limited. For example, polyester such as polyethylene terephthalate, polypropylene, polyolefin such as polyethylene, polycarbonate, polymethyl methacrylate, Examples thereof include a thermoplastic resin sheet of polysulfone, an epoxy resin, a polyester resin, a thermosetting plastic sheet such as poly (meth) acrylic resin, and various glass plates. In particular, a glass plate and a heat resistant plastic are preferably used from the viewpoint of heat resistance.

  In order to improve physical properties such as surface adhesion, such a transparent substrate can be previously subjected to corona discharge treatment, ozone treatment, thin film treatment of various polymers such as silane coupling agents and urethane polymers, and the like. . The coating method is not particularly limited, but the thickness of the resin black matrix after coating and drying is 0.1 to 2 μ, preferably 0.1 to 1.5 μ, and more preferably 0.1 to 1 μ. good.

  In drying, a hot plate, IR oven, convection oven or the like can be used, and preferable drying conditions are 40 to 150 ° C., and drying time is in the range of 10 seconds to 60 minutes. The light source used for exposure is, for example, a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, or the like, an argon ion laser, a YAG laser, an excimer laser, A laser light source such as a nitrogen laser may be used. In the case where only the wavelength of specific irradiation light is used, an optical filter can also be used.

  The development treatment is not particularly limited as long as it is a solvent capable of dissolving the resist film in the unexposed area. For example, an organic solvent such as acetone, methylene chloride, trichlene, and cyclohexanone can be used. However, since many organic solvents have environmental pollution, harmfulness to human body, fire risk, etc., it is preferable to use an alkaline developer without such danger. Examples of such an alkali developer include inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or diethanolamine, triethanolamine, tetraalkylammonium hydroxide salt, etc. And an aqueous solution containing an organic alkali agent. If necessary, the alkaline developer may contain a surfactant, a water-soluble organic solvent, a low molecular compound having a hydroxyl group or a carboxylic acid group, and the like. In particular, it is preferable to add a surfactant since many surfactants have an improving effect on developability, resolution, and background stains.

  For example, as a surfactant for a developer, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group Can be mentioned. Although there is no restriction | limiting in particular about the image development processing method, Usually, it is carried out by methods, such as immersion image development, spray image development, brush image development, ultrasonic wave development, at 10-50 degreeC, Preferably it is 15-45 degreeC.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated still in detail, this invention is not limited to a following example, unless the summary is exceeded.

Synthesis Example-1
32 g of tolylene diisocyanate trimer (Mittech GP750A manufactured by Mitsubishi Chemical Corporation, resin solid content 50 wt%, butyl acetate solution) and 0.02 g of dibutyltin dilaurate as a catalyst were diluted with 47 g of PGMEA (propylene glycol monomethyl ether acetate) Dissolved. Under stirring, 14.4 g of polyethylene glycol having a molecular weight of 1,000 with one end being a methoxy group (Niox M-1000, manufactured by NOF Corporation) and polypropylene glycol having a molecular weight of 1,000 (Sanyo Chemical Industries, Ltd.) ), Sanix PP-1000) and 9.6 g of the mixture were added dropwise, and the mixture was further reacted at 70 ° C. for 3 hours. Next, 1 g of N, N-dimethylamino-1,3-propanediamine was added, and the mixture was further reacted at 40 ° C. for 1 hour. The amine value of the solution containing the dispersion resin thus obtained was determined by neutralization titration to be 14 mg KOH / g. Further, when the resin content was determined by a dry-up method (at 150 ° C. for 30 minutes, the hot plate solvent was removed and the resin concentration was calculated based on the weight change), the resin content was 40 wt%. )

Synthesis Example-2
A flask was charged with 20 g of a styrene / acrylic acid resin having an acid value of 200 and a molecular weight of 5,000, 0.2 g of p-methoxyphenol, 0.2 g of dodecyltrimethylammonium chloride, and 40 g of propylene glycol monomethyl ether acetate, and (3,4-epoxycyclohexyl). ) 7.6 g of methyl acrylate was added dropwise and reacted at a temperature of 100 ° C. for 30 hours. The reaction solution was reprecipitated in water and dried to obtain a resin. When neutralization titration with KOH was performed, the acid value of the resin was 80.

Examples 1-11 and Comparative Examples 1-7
Carbon Black Dispersed Carbon Black MA-220 (Mitsubishi Chemical Co., Ltd.) 50 parts by weight, PGMEA was added so that the solid content of the dispersion resin shown in Synthesis Example-1 was 5 parts by weight and the solid content concentration was 50 wt%. added. The weight of the dispersion was 50 g. This was thoroughly stirred with a stirrer and premixed. Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added. After the completion of dispersion, the beads and the dispersion were separated by a filter.

Preparation of Resist Solution Using the carbon black dispersion ink described above, each component was added so as to have the following mixing ratio as a solid content, and stirred and dissolved with a stirrer to prepare a black resist photosensitive solution.
1) Composition of resist

[Table 1]
Pigment Carbon black MA-220 50g
Polyfunctional thiol described in Table-1 Silane coupling agent described in Table-1 binder resin (synthesized in Synthesis Example-2) 25g
Acrylic monomer; Dipentaerythritol hexaacrylate 15g
Photopolymerization initiator system (described in Table-1) 4g in total
Solvent propylene glycol monomethyl ether acetate 300g
Polymer dispersing agent (Synthesis example-1) 5 g

2) Evaluation and evaluation conditions for resist-1
A black resist photosensitive solution was applied to a glass substrate (7059, manufactured by Corning) using a spin coater, and dried on a hot plate at 80 ° C. for 1 minute. The film thickness of the resist after drying was measured with a stylus type film thickness meter (α-step, manufactured by Tencor Corporation) and found to be 1 μm. Next, this sample was image-exposed through a mask while changing the exposure amount with a high-pressure mercury lamp. A resist pattern was obtained by immersing and developing in an aqueous potassium hydroxide solution having a temperature of 25 ° C. and a concentration of 0.05% for 1 minute.

1. Sensitivity is defined as the exposure amount (appropriate exposure amount) that can form a mask pattern with a sensitivity of 20 μm as the dimensions. That is, a resist with a small exposure amount has high sensitivity because an image can be formed with a low exposure amount.

2. The minimum resist pattern size that can be resolved at an exposure amount that faithfully reproduces a mask pattern having a resolution of 20 μm was observed with a microscope at a magnification of 200 times. The minimum pattern dimension was 10 μm or less, and the resolution power was more than 10 μm.

3. The optical density of the light-shielding image area was measured with a Macbeth reflection densitometer TR927 (manufactured by Kolmorgun) (OD). The OD value is a numerical value indicating the light shielding ability, and the larger the numerical value, the higher the light shielding property.

4). Adhesiveness was evaluated by an adhesive cello tape test (the adhesive tape was applied to the resist pattern and then peeled off). A case where the resist pattern was not peeled off was marked with ◯, and a case where the resist pattern was peeled off was marked with ×.
Evaluation condition-2
Conditions other than fixing the appropriate exposure amount under evaluation condition-1 and varying the development time were to form a resist image according to evaluation condition-1, and to obtain development latitude and durability based on the following evaluation criteria. .

5. The development latitude was determined to have a development time width in which a resist pattern corresponding to a development latitude mask size of 20 μm could be formed with a width of 20 ± 1 μm. That is, the larger the development time width, the larger the allowable development width.

6). 3. Durability evaluation A 20 μm patterned sample patterned was thermally cured at 200 ° C. for 10 minutes, and then exposed to 2 atmospheres at 120 ° C. in a steam atmosphere for 2 hours. A cellophane test was conducted in the same manner as described above. Those that could not be peeled off by the resist pattern were evaluated as “good” and those that could be seen as “poor”. The results are shown in Table 1. In addition, the color which has the black matrix excellent in light-shielding property by forming a black matrix on a glass substrate using the black resist photosensitive solution of Examples 1-11, and then forming each pixel of red, green, and blue The filter could be manufactured.

BI: 2,2 '-(o-chlorophenyl) -4,5,4', 5'-tetraphenyl-1,2'-biimidazole DEAB: 4,4'-bis- (diethylamino) benzophenone BDTP: butanediol Bisthiopropionate EGTP: Ethylene glycol bisthiopropionate TMTP: Trimethylolpropane tristhiopropionate THEIC: Trimercaptopropionate tris (2-hydroxyethyl) isocyanurate PETP: Pentaerythritol tetrakisthiopropionate BDTG: Butanediol bisthioglycolate EGTG: ethylene glycol bisthioglycolate TMTG: trimethylolpropane tristhioglycolate PETG: pentaerythritol tetrakisthioglycolate 2MBT: 2 Mercaptobenzothiazole c-1: .gamma.-methacryloxypropyltrimethoxysilane c-2: β- (3,4- epoxycyclohexyl) ethyltrimethoxysilane c-3: .gamma.-glycidoxypropyltrimethoxysilane

Claims (14)

  A photopolymerizable composition for a color filter, comprising (a) a black color material, (b) a silane coupling agent, and (c) at least a polyfunctional thiol compound as a photopolymerization initiation system.   The photopolymerizable composition for a color filter according to claim 1, further comprising (d) a binder resin, (e) a compound having at least one ethylenically unsaturated double bond, and (f) a solvent.   The photopolymerizable composition for a color filter according to claim 1 or 2, wherein the silane coupling agent is epoxy silane and / or (meth) acryl silane.   4. The photopolymerizable composition for a color filter according to claim 2, wherein the binder resin is an organic polymer substance having an ethylenically unsaturated double bond in the side chain.   The photopolymerizable composition for a color filter according to claim 2, wherein the binder resin is a copolymer having an ethylenically unsaturated double bond, a carboxyl group, and a hydroxyl group.   The photopolymerizable composition for a color filter according to claim 2, wherein the binder resin is a styrene copolymer or an acrylic copolymer having an ethylenically unsaturated double bond, a carboxyl group, and a hydroxyl group.   The photopolymerizable composition for a color filter according to claim 1, wherein the photopolymerization initiator system further contains a biimidazole derivative.   (E) The photopolymerizable composition for color filters according to claim 2, wherein the compound containing at least one ethylenically unsaturated double bond is a compound containing three or more acrylic groups.   The photopolymerizable composition for a color filter according to claim 2, wherein the solvent has a boiling point in the range of 120 to 170 ° C.   The photopolymerizable composition for a color filter according to claim 1, wherein the black color material contains at least carbon black.   The photopolymerizable composition for a color filter according to claim 1, wherein the content of the black color material is 30 to 80 wt% of the total solid content.   The color filter which has a black matrix formed with the composition in any one of Claims 1-11 on a transparent substrate.   The color filter according to claim 12, wherein the black matrix has a light shielding factor of 2.0 or more when the film thickness is 1 μm.   The color filter according to claim 12 or 13, wherein the black matrix has a thickness of 1 µm or less.