JP5416434B2 - Photosensitive resin composition for black resist and color filter light-shielding film - Google Patents

Description

  The present invention relates to a photosensitive resin composition for black resist and a color filter light-shielding film, and more specifically, a photosensitive aqueous solution development type photosensitive resin composition for black resist suitable for forming a fine light-shielding film on a transparent substrate. And a color filter light-shielding film formed using the same.

  Color liquid crystal panels are used in various fields such as liquid crystal televisions, liquid crystal monitors, and color liquid crystal mobile phones. A color liquid crystal panel has a structure in which a substrate on which a color filter is formed and a counter substrate (TFT substrate) are bonded together with a sealing material, and liquid crystal is filled between both substrates. Among these, as a method for producing a color filter, a black matrix is usually formed on the surface of a transparent substrate such as glass or plastic sheet, which plays a role in improving contrast by suppressing color mixing between red, green, and blue colors. A method is used in which different hues of red, green, and blue, which play a role in expressing all natural colors, are sequentially formed in a color pattern such as a stripe shape or a mosaic shape.

  By the way, a PCT (Pressure Cooker Test) is generally performed as a durability test (reliability test) in a liquid crystal panel. This test method is performed under severe conditions of a temperature of 120 ° C., a humidity of 100%, and an atmospheric pressure of 2 atm. The liquid crystal panel is left for a period of time, and the presence or absence of liquid crystal leakage sealed between the color filter substrate and the TFT substrate of the liquid crystal panel is checked. As described above, the black matrix exists between each color of red, green, and blue. In addition to improving the contrast, the black matrix also functions as an outer frame light shielding film for the color filter. Is attached to the counter substrate. The black matrix is also required to have a high adhesion strength that does not peel off from the glass substrate even under severe conditions such as PCT. In particular, in recent years, there is a high need for a high light-shielding effect in order to improve the visibility of liquid crystal panels.

  In order to achieve high light shielding, it is conceivable to increase the thickness of the black matrix. However, if the film thickness is increased too much, the black, black, and black pixels are formed in the subsequent manufacturing process. The film thickness of red, green, and blue in the part superimposed on the matrix is increased, and so-called “two” steps are generated. Since this “two” steps cause the alignment disorder of the liquid crystal and lead to a decrease in the visibility of the panel, it is necessary to achieve high light shielding without increasing the thickness of the black matrix (that is, high light shielding of the thin film). It has been.

  In order to ensure high light-shielding of the thin film, it is usually necessary to increase the content of the black pigment in the resin composition. As a result, the blending ratio of the binder resin or acrylate component that contributes to curability is relatively Therefore, there is a problem that the coating film is hardly cured, the adhesion between the coating film and the glass substrate is lowered, and peeling or the like is likely to occur.

  As described above, since the demand for the adhesion of the black matrix to the substrate in recent years has become more advanced, there is a demand for a black matrix having a higher adhesion to the glass substrate than ever before. ing. Therefore, for example, in Patent Document 1, the black matrix is peeled after the PCT test by adding at least one selected from amine-based silane compounds, ketimine-based silane compounds, and isocyanate-based silane compounds to the light-shielding resin composition. There has been proposed a photosensitive resin composition having no adhesion and good adhesion. However, in the examples, the concentration of carbon black is at most 40% by mass with respect to the solid content in the photosensitive resin composition, and there is room for studying the adhesion at a higher pigment concentration. Further, evaluation items other than adhesion to the glass substrate, such as photolithography characteristics, storage stability, etc., cannot be fully understood. Also. There is no description of adhesion before PCT.

JP 2006-330209 A

  An object of the present invention is to provide a photosensitive resin composition for a black resist that can form a black matrix (or a light-shielding film) with high adhesion with a glass substrate before and after PCT and having good quality. Moreover, it is providing the color filter light shielding film formed from this photosensitive resin composition.

  As a result of diligent research to solve the problems of the above-mentioned prior art, the present inventors have added a group selected from the group consisting of an acryloyl group and a methacryloyl group together with a pigment, a binder resin, and a photopolymerization initiator. It was found that by containing a bifunctional monomer having 2 in the above, it was possible to achieve high adhesion and a high light-shielding property of the thin film, thereby completing the present invention.

That is, the present invention
(A) a bifunctional monomer having a total of two of any one or both of groups selected from the group consisting of an acryloyl group and a methacryloyl group;
(B) an unsaturated group-containing resin obtained by further reacting a reaction product of a compound having two or more epoxy groups and (meth) acrylic acid with a polybasic acid carboxylic acid or an anhydride thereof,
(C) a photopolymerization initiator, and (d) a light-shielding dispersion containing one or more light-shielding components selected from the group consisting of black organic pigments, mixed-color organic pigments and light-shielding materials , and an acryloyl group and A black resist comprising a polyfunctional monomer having a total of 3 or more of any one or both of groups selected from the group consisting of methacryloyl groups in an amount of 20% by mass or less based on component (a). Photosensitive resin composition.

  When the photosensitive resin composition for black resist of the present invention satisfies any one or more of the following, a more preferable photosensitive resin composition for black resist is provided.

（式中、Ｒ_１及びＲ_２は水素原子又はメチル基を表し、互いに同じか異なってもよく、ＡＯ及びＢＯは炭素数２〜４の互いに異なるオキシアルキレン基を表す。また、ｍ及びｎは０以上の整数であり、ｍ＋ｎ＝４〜３０の範囲である。）

（式中、Ｒ_１及びＲ_２は水素原子又はメチル基を表し、互いに同じか異なってもよく、Ｒ_３〜Ｒ_１０は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のアルケニル基、炭素数１〜５のアルキニル基、炭素数５〜９のシクロアルキル基、炭素数６〜１０のアリール基、又は炭素数１〜５のアルコキシ基を表し、Ｘは‐CO‐、−SO_２−、‐C(CF₃)₂−、-Si(CH₃)₂‐、-CH₂‐、-C(CH₃)₂‐、-O-、9,9-フルオレニル基又は単結合を示す。ＡＯ及びＢＯは炭素数２〜４の互いに異なるオキシアルキレン基を表す。また、ｍ及びｎは０以上の整数であり、ｍ＋ｎ＝４〜３０の範囲である。） 1) The bifunctional monomer having a total of two of any one or both of groups selected from the group consisting of (a) acryloyl group and methacryloyl group is represented by the following general formula (1) or general formula (2). Be a compound.

(Wherein R ₁ and R ₂ represent a hydrogen atom or a methyl group and may be the same or different from each other, AO and BO represent different oxyalkylene groups having 2 to 4 carbon atoms, and m and n are (It is an integer of 0 or more, and m + n = 4 to 30)

(Wherein R ₁ and R ₂ represent a hydrogen atom or a methyl group and may be the same or different from each other, and R _{3 to} R ₁₀ are each independently a hydrogen atom, a halogen atom, or an alkyl having 1 to 5 carbon atoms. Group, an alkenyl group having 1 to 5 carbon atoms, an alkynyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 9 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an alkoxy group having 1 to 5 carbon atoms. , X is —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—, 9, 9-fluorenyl group or a single bond, AO and BO represent different oxyalkylene groups having 2 to 4 carbon atoms, and m and n are integers of 0 or more, and m + n = 4 to 30. .)

（但し、式（３）中、Ｒ_１１及びＲ_１２は水素原子、炭素数１〜５のアルキル基又はハロゲン原子であり、互いに同じか異なってもよくＸは‐CO‐、−SO₂−、‐C(CF₃)₂−、-Si(CH₃)₂‐、-CH₂‐、-C(CH₃)₂‐、-O-、9,9-フルオレニル基又は単結合を示し、ｎは０〜１０の整数である）

（但し、式(４)中、ｎは１以上５以下の整数を表し、Ｒ_１３〜Ｒ_１６は、それぞれ独立に、水素原子、炭素数１〜５のアルキル基、炭素数５〜９のシクロアルキル基、又は炭素数６〜１０のアリール基を表し、Ｒ_１７〜Ｒ_２７は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のアルケニル基、炭素数１〜５のアルキニル基、炭素数５〜９のシクロアルキル基、炭素数６〜１０のアリール基、又は炭素数１〜５のアルコキシ基を表す。） 2) At least one compound selected from the group consisting of compounds represented by the following general formula (3) and general formula (4), wherein the compound having two or more epoxy groups used for obtaining the component (b): Be.

(In the formula (3), R ₁₁ and R ₁₂ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and may be the same or different from each other, and X is —CO—, —SO ₂ —, -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9,9-fluorenyl group or a single bond, n is (It is an integer from 0 to 10)

(However, in Formula (4), n represents an integer of 1 to 5, and R _{13 to} R ₁₆ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cyclohexane having 5 to 9 carbon atoms. Represents an alkyl group or an aryl group having 6 to 10 carbon atoms, and R _{17 to} R ₂₇ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, A C1-C5 alkynyl group, a C5-C9 cycloalkyl group, a C6-C10 aryl group, or a C1-C5 alkoxy group is represented.)

3) The light shielding component in component (d) is carbon black.

4) Content of the light-shielding component in (d) component is 40-60 mass% with respect to solid content in the photosensitive resin composition for black resists.

5) (c) The photopolymerization initiator is one or more selected from acyloxime photopolymerization initiators.

  In addition, the photosensitive resin composition for black resist of the present invention can be preferably used for forming a color filter light-shielding film, and the present invention further provides the photosensitive resin composition for black resist as a transparent substrate. A color filter light-shielding film obtained by applying each step of (i) exposure with an ultraviolet light exposure device, (ii) development with an aqueous alkali solution, and (iii) thermal baking after coating and drying.

  Hereinafter, the photosensitive resin composition for black resist of the present invention (hereinafter also referred to as a photosensitive resin composition or a composition) will be described in detail. The composition of the present invention contains components (a) to (d) as essential components. That is, (a) a bifunctional monomer having a total of two of either or both groups selected from the group consisting of an acryloyl group and a methacryloyl group, (b) a compound having two or more epoxy groups, and (meth) acrylic acid; An unsaturated group-containing resin obtained by further reacting the reaction product with a polybasic acid carboxylic acid or an anhydride thereof, (c) a photopolymerization initiator, and (d) a black organic pigment, a mixed color organic pigment, and a light shielding material. A light-shielding dispersion containing one or more light-shielding components selected from the group consisting of:

  Regarding the bifunctional monomer having a total of two of any one or both of groups selected from the group consisting of acryloyl group and methacryloyl group as component (a), preferably the above general formula (1) or general formula (2) Specific examples thereof include diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nonaethylene glycol di (meth) acrylate, and dipropylene. Glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, tetrapropylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,5-pentanediol di (meth) acrylate, 1 , 6-Hexanedi Di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, di (meth) acrylate of neopentyl glycol ethylene oxide adduct, dipentyl glycol propylene oxide adduct (Meth) acrylate, di (meth) acrylate of bisphenol A ethylene oxide adduct, di (meth) acrylate of propylene oxide adduct of bisphenol A, di (meth) acrylate of hydrogenated bisphenol A ethylene oxide adduct, hydrogenated bisphenol A propylene oxide adduct di (meth) acrylate and the like.

  Moreover, in addition to the bifunctional monomer of the component (a), if necessary, any one of groups selected from the group consisting of an acryloyl group and a methacryloyl group, in terms of improvement in pattern strength and excellent smoothness of the pattern surface, or A polyfunctional monomer having a total of three or more of both can also be added. For example, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol tetramethacrylate, dipentaerythritol hexa Examples thereof include acrylate and dipentaerythritol hexamethacrylate. However, the blending ratio of these polyfunctional monomers is desirably 20% by mass or less of the bifunctional monomer. When it exceeds 20% by mass, the substrate adhesion is reduced as compared with the case of the bifunctional monomer alone.

  The unsaturated group-containing resin as the component (b) is obtained by adding “(meth) acrylic acid” (this means “acrylic acid and / or methacrylic acid”) to the “compound having two or more epoxy groups”. It is an “epoxy (meth) acrylate acid adduct” obtained by reacting a “polybasic acid carboxylic acid or its anhydride” with the obtained “compound having a hydroxy group”. A polyester is produced by a reaction between a hydroxy group and a polybasic acid carboxylic acid, and a low molecular weight resin having an average degree of polymerization of about 2 to 500 is preferable.

（但し、式（３）中、Ｒ_１１及びＲ_１２は水素原子、炭素数１〜５のアルキル基又はハロゲン原子であり、互いに同じか異なってもよくＸは‐CO‐、−SO₂−、‐C(CF₃)₂−、-Si(CH₃)₂‐、-CH₂‐、-C(CH₃)₂‐、-O-、9,9-フルオレニル基又は単結合を示し、ｎは０〜１０の整数である）

（但し、式(４)中、ｎは１以上５以下の整数を表し、Ｒ_１３〜Ｒ_１６は、それぞれ独立に、水素原子、炭素数１〜５のアルキル基、炭素数５〜９のシクロアルキル基、又は炭素数６〜１０のアリール基を表し、Ｒ_１７〜Ｒ_２７は、それぞれ独立に、水素原子、ハロゲン原子、炭素数１〜５のアルキル基、炭素数１〜５のアルケニル基、炭素数１〜５のアルキニル基、炭素数５〜９のシクロアルキル基、炭素数６〜１０のアリール基、又は炭素数１〜５のアルコキシ基を表す。）

As the “compound having two or more epoxy groups” in the component (b), (o, m, p-) cresol novolac type epoxy resin, phenol novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, A trisphenol methane type epoxy resin etc. can be illustrated, In detail, it is good that it is a compound shown by following General formula (3) or (4), More specifically, it is a compound shown by following General formula (5) It is good to be.

(In the formula (3), R ₁₁ and R ₁₂ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and may be the same or different from each other, and X is —CO—, —SO ₂ —, -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9,9-fluorenyl group or a single bond, n is (It is an integer from 0 to 10)

(However, in Formula (4), n represents an integer of 1 to 5, and R _{13 to} R ₁₆ are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cyclohexane having 5 to 9 carbon atoms. Represents an alkyl group or an aryl group having 6 to 10 carbon atoms, and R _{17 to} R ₂₇ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, A C1-C5 alkynyl group, a C5-C9 cycloalkyl group, a C6-C10 aryl group, or a C1-C5 alkoxy group is represented.)

  The component (b) is preferably derived from the epoxy compound represented by the general formula (3) or (4). Among these, the epoxy compound of the general formula (3) is derived from bisphenols. Therefore, by explaining the bisphenols, the epoxy compound of the general formula (3), the reaction product with (meth) acrylic acid, and further the component (b) can be understood. To do.

  Examples of the bisphenols that give the preferred component (b) include the following. Bis (4-hydroxyphenyl) ketone, bis (4-hydroxy-3,5-dimethylphenyl) ketone, bis (4-hydroxy-3,5-dichlorophenyl) ketone, bis (4-hydroxyphenyl) sulfone, bis (4 -Hydroxy-3,5-dimethylphenyl) sulfone, bis (4-hydroxy-3,5-dichlorophenyl) sulfone, bis (4-hydroxyphenyl) hexafluoropropane, bis (4-hydroxy-3,5-dimethylphenyl) Hexafluoropropane, bis (4-hydroxy-3,5-dichlorophenyl) hexafluoropropane, bis (4-hydroxyphenyl) dimethylsilane, bis (4-hydroxy-3,5-dimethylphenyl) dimethylsilane, bis (4- Hydroxy-3,5-dichlorophenyl) dimethyl Silane, bis (4-hydroxyphenyl) methane, bis (4-hydroxy-3,5-dichlorophenyl) methane, bis (4-hydroxy-3,5-dibromophenyl) methane, 2,2-bis (4-hydroxyphenyl) ) Propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-) 3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-3,5-dimethylphenyl) ether, bis (4 -Hydroxy-3,5-dichlorophenyl) ether and the like. Furthermore, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, wherein X in the general formula (3) is a 9,9-fluorenyl group, 9 , 9-bis (4-hydroxy-3-chlorophenyl) fluorene, 9,9-bis (4-hydroxy-3-bromophenyl) fluorene, 9,9-bis (4-hydroxy-3-fluorophenyl) fluorene, 9 , 9-bis (4-hydroxy-3-methoxyphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (4-hydroxy-3,5-dichlorophenyl) ) Fluorene, 9,9-bis (4-hydroxy-3,5-dibromophenyl) fluorene, and the like. Still further, compounds such as 4,4'-biphenol and 3,3'-biphenol are exemplified.

  Examples of the epoxy compound of the general formula (4) include (o, m, p-) cresol novolak type epoxy resins and phenol novolak type epoxy resins as described above.

  Examples of the “polybasic acid carboxylic acid or its anhydride” used for obtaining the component (b) include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and methylendomethylene. Tetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, trimellitic acid, pyromellitic acid, etc. and their anhydrides, as well as aromatic polyvalents such as benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid Examples thereof include carboxylic acids and acid dianhydrides thereof. And about the use ratio of an acid anhydride and an acid dianhydride, the ratio suitable for forming a fine pattern by exposure and alkali image development operation can be selected.

  In addition, the reaction between “compound having two or more epoxy groups” and “(meth) acrylic acid”, and “epoxy (meth) acrylate” (compound having a hydroxy group) obtained by this reaction and “polybasic acid” The reaction with `` or its anhydride '' employs a known method described in JP-A-8-278,629, for example, by reaction under heating in a cellosolve solvent such as ethyl cellosolve acetate or butyl cellosolve acetate. However, it is not particularly limited. And about the unsaturated group containing resin of the obtained (b) component, only 1 type may be used and 2 or more types of mixtures can also be used. The component (b) thus obtained has both an ethylenically unsaturated double bond and a carboxyl group, so that it has a function as a binder and gives excellent photocurability to the photosensitive resin composition for black resist. In addition, good developability and patterning characteristics (alkali solubility, alkali developability) are imparted to improve the physical properties of the light shielding film.

  The blending ratio of the component (a) and the component (b) is preferably 10/90 to 50/50 in weight ratio (a) / (b), and preferably 20/80 to 40/60. It is good. When the blending ratio of the component (a) is less than 10/90, the cured product after photocuring becomes brittle, and the acid value of the coating film is low in the unexposed area, so that the solubility in an alkali developer is lowered. There is a risk that the pattern edges may not be jagged and sharp. On the contrary, if the ratio is more than 50/50, the proportion of the photoreactive functional group in the resin is small and the formation of a crosslinked structure is not sufficient, and the acid value in the resin component is too high, so that the alkaline developer in the exposed area Therefore, there is a possibility that the formed pattern is narrower than the target line width or a pattern is easily lost.

  As the photopolymerization initiator of component (c), at least one photopolymerization initiator is used, and any compound that has an ethylenically unsaturated bond and can initiate addition polymerization can be used. It is not limited. Examples include acetophenone compounds, triazine compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, imidazole compounds, acyloxime compounds, and the like.

  Here, as the acetophenone compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- ( 2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino Examples include oligomers of -1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one.

  Examples of triazine compounds include 2,4,6-tris (trichloromethyl) -1,3,5-triazine, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloroRmethyl) -1,3,5 -Triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis ( Trichloromethyl) -1,3,5-triazine, 2- (4-methylthiostyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (pipronyl) -4,6-bis And (trichloromethyl) -1,3,5-triazine.

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

  Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like. Examples of the imidazole compound include 2- (o-chlorophenyl) -4,5-phenylimidazole dimer and 2- (o-chlorophenyl) -4,5-di (m-methoxyphenyl) imidazole dimer. 2- (o-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole 2 Examples include masses.

  Examples of the acyloxime compounds include 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptyl-1-one oxime-O-acetate, [9-Ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -adamantylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2- Methylbenzoyl) -9.H.-carbazol-3-yl] -adamantylmethane-1-oneoxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazole- 3-yl] -tetrahydrofuranylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -tetra Drofuranylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -thiophenylmethane-1-one oxime-O -Benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -thiophenylmethane-1-one oxime-O-acetate, 1- [9-ethyl -6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -morophonylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) ) -9.H.-Carbazol-3-yl] -morophonylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazole- 3-Ile] Ethane-1-one oxime-O-bicycloheptanecarboxylate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-tri Cyclodecane carbocichelate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-adamantane carbochelate, 1,2 -Octanediene, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (product name Irgacure OXE01, manufactured by Ciba Specialty Chemicals), Ethanone, 1- [9-Ethyl-6- -Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (product name Irgacure OXE02 manufactured by Ciba Specialty Chemicals).

As the photopolymerization initiator of component (c), an active radical generator and an acid generator can also be used. Examples of the active radical generator include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like can also be used. Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl. Onium salts such as benzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, Examples thereof include benzoin tosylate. Among the compounds described above as active radical generators, there are compounds that generate an acid simultaneously with active radicals. For example, triazine compounds are also used as acid generators.

Among the photopolymerization initiators of component (c), acyloxime photopolymerization initiators are particularly preferably used. (C) The photoinitiator of a component can be used individually or in mixture of 2 or more types. In addition, although it does not act as a photopolymerization initiator or sensitizer by itself, it is also possible to add a compound that can increase the ability of the photopolymerization initiator or sensitizer by using in combination with the above compound. it can. Examples of such compounds include amine compounds that are effective when used in combination with benzophenone. Here, examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-benzoic acid 2-benzoate. Dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′- And bis (ethylmethylamino) benzophenone.

  The amount of the photopolymerization initiator used as the component (c) is suitably 10 to 50 parts by weight based on 100 parts by weight of the total of the components (a) and (b). When the blending ratio of component (c) is less than 10 parts by weight, the rate of photopolymerization becomes slow and the sensitivity is lowered. On the other hand, when it exceeds 50 parts by weight, the sensitivity is too strong and the pattern line The width becomes thicker than that of the pattern mask, and there is a possibility that a line width that is faithful to the mask cannot be reproduced, or that the pattern edge becomes jagged and does not become sharp.

  The light shielding component such as the black organic pigment, the mixed color organic pigment or the light shielding material as the component (d) is preferably excellent in heat resistance, light resistance and solvent resistance. Here, examples of the black organic pigment include perylene black and cyanine black. Examples of the mixed color organic pigment include those obtained by mixing two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta, and the like into a pseudo black color. Examples of the light-shielding material include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. Two or more kinds can be appropriately selected and used. It is preferable in terms of smoothness, dispersion stability, and compatibility with the resin. Then, these light shielding components are dispersed in a dispersion medium to obtain a light shielding dispersion liquid as component (d). Here, examples of the dispersion medium include propylene glycol monomethyl ether acetate and 3 methoxybutyl acetate.

  About the mixture ratio of the light-shielding component in the light-shielding dispersion liquid of (d) component, it is used in 20-60 mass% with respect to the total solid of the composition of this invention, Preferably it is used in the range of 40-60 mass%. Good. When the amount is less than 20% by mass, the light shielding property is not sufficient. If it exceeds 60% by mass, the content of the photosensitive resin, which is the original binder, decreases, so that undesired problems occur in that the development characteristics are impaired and the film forming ability is impaired. The composition of the present invention has a particularly high pigment concentration range, specifically, a pigment (light shielding component) in an amount exceeding 40% by weight based on the total solid content in the photosensitive resin composition, and further 45% by weight. A high effect is exhibited with respect to the composition containing the above pigment.

  In the photosensitive resin composition for black resist in the present invention, it is preferable to use a solvent in addition to the components (a) to (d). Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol, and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, and N-methyl-2-pyrrolidone. Ketones such as toluene, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol Glycol ethers such as ethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Examples include acetic acid esters such as ethyl ether acetate, and the like, and these can be dissolved and mixed to form a uniform solution-like composition.

  The black resist resin composition of the present invention may contain a silane coupling agent as an adhesion improver. Examples of silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, vinyl Trimethoxysilane, vinyltriethoxysilane and the like are preferable because of easy availability of raw materials. Since the silane coupling agent has an effect of improving adhesion in a small amount, it is not necessary to add a large amount, and is preferably 0.2 to 10% by mass, more preferably 0, based on the total solid content of the composition. It is good that it is 5-5 mass%.

  Furthermore, a surfactant can be added for the purpose of preventing coating properties, smoothness of the colored coating, and Benard cell. The addition amount of the surfactant is usually 0.001 to 5% by mass, preferably 0.01 to 1% by mass of the resin composition. If the amount added is too small, the coating properties, smoothness of the colored coating and Benard cell are not effective, and if too large, the physical properties of the coating film may be poor. Specific examples of the surfactant include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine, cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride, lauryldimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethylhydroxyethyl imidazolium betaine, nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate, polydimethylsiloxane, etc. An activator, a fluorosurfactant, etc. are mentioned. In the present invention, the surfactant is not limited to these, and one or more surfactants can be used.

  The photosensitive resin composition for a black resist of the present invention contains the above components (a) to (d) or these and a solvent as main components. It is desirable that the components (a) to (d) are contained in a total of 80% by mass, preferably 90% by mass or more, in the solid content excluding the solvent (the solid content includes a monomer that becomes a solid content after curing). Although the quantity of a solvent changes with target viscosity, it is good to make it contain in the range of 70-90 mass% in the photosensitive resin composition.

  The photosensitive resin composition for black resist in the present invention is excellent as a resin composition for forming a color filter light-shielding film. For example, a color filter light-shielding film can be obtained by the following photolithography method. First, the photosensitive resin composition is applied as a solution on a transparent substrate, and then the solvent is dried (pre-baked). Then, a photomask is applied to the coating film thus obtained and irradiated with ultraviolet rays. Examples include a method in which the exposed portion is cured, development is performed to elute the unexposed portion using an alkaline aqueous solution, a pattern is formed, and post-baking (thermal baking) is performed as post-drying.

  As a transparent substrate to which the solution of the photosensitive resin composition is applied, a transparent electrode such as ITO or gold is vapor-deposited or patterned on a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.) in addition to a glass substrate. The thing etc. can be illustrated. As a method for applying the solution of the photosensitive resin composition on the transparent substrate, any method such as a method using a roller coater machine, a land coater machine or a spinner machine in addition to a known solution dipping method or spray method is adopted. can do. After applying to a desired thickness by these methods, the film is formed by removing the solvent (pre-baking). Pre-baking is performed by heating with an oven, a hot plate or the like. The heating temperature and heating time in the pre-baking are appropriately selected according to the solvent to be used, and are performed, for example, at a temperature of 60 to 110 ° C. for 1 to 5 minutes.

  The exposure performed after pre-baking is performed by an ultraviolet exposure apparatus, and only the resist corresponding to the pattern is exposed by exposing through a photomask. The exposure apparatus and the exposure irradiation conditions are appropriately selected, and exposure is performed using a light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, or a deep ultraviolet lamp, and the photosensitive resin composition for black resist in the coating film is exposed to light. Harden.

  The alkali development after the exposure is performed for the purpose of removing the resist in the unexposed portion, and a desired pattern is formed by this development. Examples of the developer suitable for the alkali development include, for example, an aqueous solution of an alkali metal or alkaline earth metal carbonate, an aqueous solution of an alkali metal hydroxide, and the like. Particularly, sodium carbonate, potassium carbonate, lithium carbonate, and the like. It is better to develop at a temperature of 23 to 28 ° C. using a weakly alkaline aqueous solution containing 0.05 to 3% by mass of carbonate such as a commercially available developing machine or ultrasonic cleaner. It can be formed precisely.

  After the development, heat treatment (post-bake) is preferably performed at a temperature of 180 to 250 ° C. and a condition of 20 to 60 minutes. This post-baking is performed for the purpose of improving the adhesion between the patterned light-shielding film and the substrate. This is performed by heating with an oven, a hot plate or the like, as in the pre-baking. The patterned light-shielding film of the present invention is formed through each step by the above photolithography method.

  As described above, the photosensitive resin composition of the present invention is suitable for forming a fine pattern by an operation such as exposure or alkali development. A light-shielding film having excellent light-shielding properties, adhesion, electrical insulation, heat resistance, and chemical resistance can be obtained. Further, the photosensitive resin composition for black resist of the present invention can be suitably used as a coating material, and is particularly suitable as a color filter ink used for a liquid crystal display device or a photographing element. The light-shielding film is useful as a color filter, a black matrix for liquid crystal projection, and the like.

  According to the present invention, it is possible to form a black matrix (or a light shielding film) with good adhesion to a glass substrate before and after PCT and having good quality. In particular, even when a light shielding component is contained at a high concentration, high adhesion can be maintained, and so-called high light shielding of a thin film can be achieved.

  Hereinafter, although an embodiment of the present invention is described concretely based on an example and a comparative example, the present invention is not limited to these. Here, the raw materials and abbreviations used in the production of the black matrices of Examples and Comparative Examples are as follows.

(monomer)
(a) -1: alkoxylated neopentyl glycol diacrylate (trade name CD9043, manufactured by Sartomer Japan)
(a) -2: alkoxylated hexanediol diacrylate (trade name CD564, manufactured by Sartomer Japan)
(a) -3: Polyethylene glycol diacrylate (trade name Blemmer ADE-600 manufactured by NOF Corporation)
(a) -4: Polyethylene glycol diacrylate (trade name Blemer ADE-400, manufactured by NOF Corporation)
(a) -5: Ethoxylated (10) Bisphenol A diacrylate (trade name SR602, manufactured by Sartomer Japan)
(a) -6: Pentaerythritol tetraacrylate (manufactured by Sartomer Japan, trade name SR295)
(a) -7: Mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate (Nippon Kayaku Co., Ltd., trade name DPHA)

(Unsaturated group-containing resin)
(b) -1: Propylene glycol monomethyl ether acetate solution of an acid anhydride polycondensate of epoxy acrylate having a fluorene skeleton (resin solid content concentration = 56.5% by mass, manufactured by Nippon Steel Chemical Co., Ltd., trade name V259ME)
(b) -2: Mw (weight average molecular weight) 9000, acid value 80 N-phenylmaleimide / acrylic acid / styrene copolymer propylene glycol monomethyl ether acetate solution (resin solid content concentration = 35.5% by mass), (N -Phenylmaleimide: acrylic acid: styrene = 19: 22: 59 mol%)

(Photopolymerization initiator)
(c) -1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime), (Ciba Japan, product) Name Irgacure OXE02)
(c) -2: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (manufactured by Ciba Japan, product name Irgacure 369)
(c) -3: 2- (pipronyl) -4,6-bis (trichloromethyl) -1,3,5-triazine (product name: Triazine PP, manufactured by Nippon Sebel Hegner)

(Light-shielding dispersion)
(d): Propylene glycol monomethyl ether acetate dispersion having a carbon black concentration of 25.0% by mass and a polymer dispersant concentration of 4.75% by mass (solid content 29.75%)

(Silane coupling agent)
(e): 3-Methacryloxypropyltrimethoxysilane (trade name: KBM-503: manufactured by Shin-Etsu Chemical Co., Ltd.)

(solvent)
(f) -1: Propylene glycol monomethyl ether acetate
(f) -2: Cyclohexanone

(Surfactant)
(g): Megafuck F475 (manufactured by Dainippon Ink & Chemicals, Inc.)

[Examples 1-6, Comparative Examples 1-5]
The above-described blending components were blended in the proportions shown in Table 1 to prepare black resist photosensitive resin compositions according to Examples 1 to 6 and Comparative Examples 1 to 5. In Table 1, the number in () of the component (b) indicates the solid content (g) in the unsaturated group-containing resin, and the number in () of the component (d) indicates the solid content (g) of the light shielding component. .

It mixed uniformly with the combination of each component described in Table 1, and obtained each photosensitive resin composition for black resist which concerns on Examples 1-6 and Comparative Examples 1-5 using a spin coater. It apply | coated so that the film thickness after a post-baking might be set to 1.0 micrometer on a 125 mm glass substrate (Corning 1737), and it prebaked at 90 degreeC for 1 minute. Thereafter, the exposure gap was adjusted to 80 μm, and on the dried coating film, line / space = 2 μm / 2 μm, 4 μm / 4 μm, 5 μm / 5 μm, 6 μm / 6 μm, 8 μm / 8 μm, 10 μm / 10 μm, 20 μm / 20 μm negatives. A photomask was applied to the photosensitive portion to irradiate 100 mj / cm ² with an ultrahigh pressure mercury lamp with an I-line illuminance of 30 mW / cm ² . Next, this exposed coated plate is +10 seconds and +20 from the development time (break time = BT) at which the pattern begins to appear at 23 ° C. in a 0.05% potassium hydroxide aqueous solution at a shower developing pressure of 1 kgf / cm ^2. After developing for 2 seconds, spray water washing at 5 kgf / cm ² pressure is performed to remove the unexposed portion of the coating film to form a pixel pattern on the glass substrate, and then heat post at 230 ° C. for 30 minutes using a hot air dryer. The line width, pattern linearity, and resolution with respect to the mask width of the 20 μm line after baking were evaluated. The results are shown in Tables 2 and 3. The evaluation method is as follows.

<Pattern line width>
The pattern line width with a mask width of 20 μm was measured using a length measuring microscope (trade name: XD-20, manufactured by Nikon Corporation).

<Pattern linearity>
The 20 μm mask pattern after development was observed with a microscope, and the case where peeling to the substrate and the jaggedness of the pattern edge portion were not recognized was evaluated as “◯”, and the case where it was recognized as “×”.

<Resolution>
Of the 2 μm, 4 μm, 5 μm, 6 μm, 8 μm, 10 μm, and 20 μm mask patterns, the minimum pattern size remaining on the substrate was defined as the resolution. The case where the resolution was 2, 4, 5, 6 or 8 μm was evaluated as ◯, and the case where the resolution was 10 μm or more was evaluated as x.

Further, in order to evaluate the adhesion strength (seal strength), a photosensitive resin composition for black resist obtained by uniformly mixing the respective compositions shown in Table 1 above was applied to a 125 mm × 125 mm glass substrate (using a spin coater). The film was applied on Corning 1737) so that the film thickness after post-baking was 1.0 μm, and prebaked at 90 ° C. for 1 minute. Thereafter, solid exposure was performed at 100 mJ / cm ² without using a negative photomask, and heat post-baking was performed at 230 ° C. for 30 minutes using a hot air dryer.

  Then, the seal strength of the post-baked substrate obtained above was evaluated as follows by an evaluation method according to the three-point bending adhesion test method of JIS K6856-1994. Each of the post-baked substrate and the glass substrate (Corning 1737) not coated with the resin composition was cut into 20 mm × 63 mm strips to prepare test pieces. Both substrates (test pieces) were bonded so that the post-baked coated plate and the glass substrate not coated with the resin composition were overlapped with a certain amount of sealant so that the overlap width was 8 mm. . When stacked, the sealant has a circular shape and a diameter of about 5 mm. Thereafter, the superposed test pieces were pre-baked at 90 ° C. for 20 minutes, followed by post-baking at 150 ° C. for 2 hours to prepare three-point bent test pieces. Furthermore, a sample for a comparative test in which 20 mm × 63 mm glass pieces not coated with the resin composition were bonded together by the same method as described above was also prepared.

  In the test piece obtained above, a coated plate and a counter substrate (non-coated substrate) or a non-coated glass substrate for comparison test are supported by two supports so that the overlapping portion is centered ( The length of the support at the two points is 3 cm), and the load is applied at a speed of 1 mm / min using ORIENTEC product name UCT-100 from directly above to below the overlapped part. The observation and the load at that time were read, and divided by the application area of the sealant, and the load per unit area was defined as the adhesion strength. Further, after performing a PCT (pressure cooker) test under the conditions of 121 ° C., 100% RH, 2 atm, and 4 hours, the same adhesion strength test was performed to determine the adhesion strength before and after the PCT. The adhesion strength of each composition was shown as a relative value when the adhesion strength between glasses not coated with resist (resin composition) before and after PCT was 100, respectively. Before and after PCT, 60 or more was marked as ◯, and less than 60 was marked as x. The results are shown in Tables 2 and 3.

  As a result of the above, the coating films obtained from the photosensitive resin compositions of Examples 1 to 6 were good in line width, pattern linearity, resolution, and seal strength. On the other hand, none of the coating films obtained from the photosensitive resin compositions of Comparative Examples 1 to 5 had good line width, pattern linearity, resolution, and seal strength.

  When a liquid crystal panel was prepared using a color filter formed with a black matrix such as obtained using the photosensitive resin compositions of Examples 1 to 6, there was almost no peeling of the black matrix even under severe conditions. Leakage can be prevented. Further, development characteristics such as development adhesion, pattern linearity, and resolution are not sacrificed. For this reason, even when a black matrix having a high light-shielding ratio is produced by increasing the pigment concentration in the coating film containing black pigment and relatively reducing the resin component, peeling of the coating film from the glass substrate is reduced. High productivity (yield) and reliability can be secured.

Claims (5)

(A) a bifunctional monomer having a total of two of any one or both of groups selected from the group consisting of an acryloyl group and a methacryloyl group represented by the following general formula (1) or general formula (2) ;
(B) It was obtained by further reacting a reaction product of a compound having two or more epoxy groups represented by the following general formula (3) and (meth) acrylic acid with a polybasic acid carboxylic acid or its anhydride. Unsaturated group-containing resin,
(C) one or more photopolymerization initiators selected from acyloxime photopolymerization initiators, and (d) one or more selected from the group consisting of black organic pigments, mixed color organic pigments and light-shielding materials A polyfunctional monomer containing a light-shielding dispersion containing a light-shielding component and having a total of 3 or more of either one or both of groups selected from the group consisting of an acryloyl group and a methacryloyl group as the component (a) A photosensitive resin composition for a black resist, which is contained in an amount of 20% by mass or less .

[In Formula (1), R < ₁ > and R < ₂ > represents a hydrogen atom or a methyl group, and may mutually be the same or different, AO and BO represent a C2-C4 different oxyalkylene group. M and n are integers of 0 or more, and m + n = 4-30. ]

Wherein (2), R ₁ and R ₂ represents a hydrogen atom or a methyl group, may be the same or different from each other, R ₃ to R ₁₀ are independently a hydrogen atom, a halogen atom, 1 to carbon atoms 5 alkyl groups, alkenyl groups having 1 to 5 carbon atoms, alkynyl groups having 1 to 5 carbon atoms, cycloalkyl groups having 5 to 9 carbon atoms, aryl groups having 6 to 10 carbon atoms, or alkoxy having 1 to 5 carbon atoms X represents —CO—, —SO ₂ —, —C (CF ₃ ) ₂ —, —Si (CH ₃ ) ₂ —, —CH ₂ —, —C (CH ₃ ) ₂ —, —O—. , 9,9-fluorenyl group or a single bond. AO and BO represent different oxyalkylene groups having 2 to 4 carbon atoms. M and n are integers of 0 or more, and m + n = 4-30. ]

[In the formula (3), R ₁₁ and R ₁₂ are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or a halogen atom, and may be the same or different from each other, and X is —CO—, —SO ₂ —, -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9,9-fluorenyl group or a single bond, n is It is an integer from 0 to 10.] (D) shielding component in component, the black resist photosensitive resin composition according to claim 1 is carbon black. The photosensitive resin composition for a black resist according to claim 1 or 2 , wherein the content of the light shielding component in the component (d) is 40 to 60% by mass with respect to the solid content in the photosensitive resin composition for a black resist. . The photosensitive resin composition for black resist according to claim 1 , which is used for forming a color filter light-shielding film. Each of the photosensitive resin composition for black resist according to claim 4 is applied onto a transparent substrate and dried, and then (i) exposure with an ultraviolet exposure device, (ii) development with an alkaline aqueous solution, and (iii) thermal baking. A color filter light-shielding film obtained by requiring a process.