KR20090034774A - Multifunctional thiol compound-containing photosensitive resin composition for black resist, black matrix for color filter using the same, and color filter - Google Patents

Abstract

A multifunctional thiol compound-containing photosensitive resin composition for black resist, a black matrix for a color filter and a color filter using the same are provided to ensure high sensitivity, good pattern adhesion and storage stability. A photosensitive resin composition for black resist comprises (A) alkali soluble resin; (B) photopolymerizable monomer having at least ethylenically unsaturated bond; (C) a photopolymerization initiator; (D) a multi-functional thiol compound represented by the chemical formula I; and (E) one or more coloring agents selected from black organic pigment, color mixture organic pigment and light-shielding agent.

Description

MULTIFUNCTIONAL THIOL COMPOUND-CONTAINING PHOTOSENSITIVE RESIN COMPOSITION FOR BLACK RESIST, BLACK MATRIX FOR COLOR FILTER USING THE SAME, AND COLOR FILTER }

The present invention relates to a photosensitive resin composition for black resists containing a polyfunctional thiol compound having a plurality of mercapto groups in the same molecule, and to a photosensitive resin composition for black resists having high sensitivity and excellent line width retention of a fine pattern during alkali development. will be.

In recent years, photosensitive compositions have been used in all fields of color liquid crystal display devices (liquid crystal televisions, liquid crystal monitors, color liquid crystal cell phones, etc.). The color liquid crystal display includes a liquid crystal unit and a color filter which control the amount of light transmission or reflection. In general, the color filter is manufactured by forming a black matrix on the surface of transparent substrates such as glass and plastic sheets, and subsequently forming other colors of red, green, and blue in a sequential stripe pattern or a mosaic pattern. The method is used. The pattern size is different depending on the use of the color filter and the respective colors, but the red, green, and blue pixels are thinned from 200 to 300 µm to 100 µm, and the black matrix is 20 µm to 10 µm. High dimensional precision is calculated | required by the photosensitive resin composition.

Photocuring by the reaction of photoreactive resin and a photoinitiator is used for pattern formation, i line (365 nm) which is one of the line spectrums of a mercury lamp is mainly used as an exposure wavelength for hardening a pigment dispersion type negative color resist. have. In the red, green, blue, and black photosensitive resin composition, the coloring material itself absorbs ultraviolet rays, and in recent years, since the content ratio of the coloring material in the photosensitive resin composition has increased, a difference in crosslinking density with respect to the film thickness direction occurs in the exposed portion. It is difficult to obtain a color filter having good development margin, fine wire adhesiveness, and edge shape of the pattern because it is difficult to photocure at the base surface even if it is sufficiently photocured on the coating film surface. In addition, even in unexposed areas, coloring materials such as pigments, which are poorly soluble in the developing solution, are deposited on the substrate as developing residues, which results in a decrease in the transmittance of the backlight light when the other colors are sequentially formed, resulting in a decrease in the color filter brightness. Throw it away. Moreover, since adhesiveness between a coating film and a board | substrate falls, there exists a possibility of causing a fall of image development margin and a thin wire adhesiveness. And these problems are remarkable especially in the light-shielding photosensitive resin composition which forms a black matrix on the spectroscopic characteristic of a photosensitive resin composition.

In addition, in recent years, in order to increase productivity and reduce costs, color filter manufacturing lines tend to have larger mother glass substrates each year, and manufacturing has been performed on mother glass substrates larger than 1 square meter. Moreover, in order to reduce tact time and to improve productivity efficiency, the photosensitive resin composition for color filters which shortens an exposure time, ie, photocures with low exposure amount, is calculated | required. As described above, it is required to obtain a pattern having good pattern dimensional stability, pattern adhesiveness, and sharpness of the edge shape of the pattern with a wide development margin at a low exposure amount of the photosensitive resin composition for color filters having a high content of coloring material and having difficulty in photocuring. For this purpose, high sensitivity of the photosensitive resin composition is indispensable.

Under such circumstances, the photosensitive resin composition for color filters is required to be cured with lower energy, to be cured faster, and to form a clearer pattern. However, depending on the kind of pigment used for the photosensitive resin composition for color filters, sufficient energy for starting photopolymerization cannot be obtained. In particular, in the black matrix, a resin black matrix having a high optical concentration is required, and a problem arises in that the content of coloring materials such as carbon black in the photosensitive resin composition is increased and sufficient sensitivity cannot be obtained. Various problems have been devised to avoid such problems such as irradiation of larger energy, addition of excess photopolymerization initiator, and installation of an oxygen barrier film. However, it cannot be said that it is justified for saving energy and reducing production cost. This excellent composition is desired.

Until now, in order to improve the sensitivity of a photosensitive composition, it has been proposed to use the polyfunctional thiol compound which has several mercapto group in the same molecule. However, the use of the polyfunctional thiol compound proposed so far has a drawback of poor storage stability. For example, about using a polyfunctional thiol compound in the photopolymerizable composition for color filters suitable for black matrix formation, although the photopolymerizable composition containing a polyfunctional thiol is disclosed by patent document 1, using a polyfunctional thiol Under high light shielding (CB concentration of 52% or more), there is a problem in that storage stability is sacrificed to achieve high sensitivity by such a polyfunctional thiol, and high sensitivity is not achieved when no sensitizer is used. Accordingly, there is a demand for development of a black matrix resist for color filters excellent in developability under high light shielding and high sensitivity and excellent in storage stability and a photosensitive composition using the same.

Patent Document 1: Japanese Patent Application Laid-Open No. 2004-325733

Therefore, the objective of this invention is providing the photosensitive resin composition for black resists with high sensitivity, favorable pattern adhesiveness, and storage stability also in high light shielding area | region. Moreover, another object of this invention is to provide the black matrix for color filters and the color filter formed using this photosensitive resin composition for color filters.

MEANS TO SOLVE THE PROBLEM As a result of carrying out examination in order to solve the said problem, according to the photosensitive resin composition which mix | blended the specific thiol compound in combination with a photoinitiator, it discovered that the said problem was solved and completed this invention.

That is, this invention is the following (A)-(E) component,

(A) alkali-soluble resin,

(B) a photopolymerizable monomer having at least one ethylenically unsaturated bond,

(C) photoinitiator,

(D) Polyfunctional thiol compound represented by the following general formula (I)

(In formula, R <^1> is an alkyl group, R <^2> is an n-valent aliphatic group which may contain atoms other than carbon, R <^0> is an alkyl group which is not H, n represents 2-4., And

(E) As a photosensitive resin composition for black resists containing as an essential component one or more coloring materials selected from black organic pigments, mixed organic pigments, and light-shielding materials,

The weight ratio (A / B) of (A) component and (B) component is 60/40-90/10, and (C) component is 5-about 100 weight part of total of (A) component and (B) component. It is 50 weight part containing, The photosensitive resin composition for black resists characterized by the above-mentioned.

In addition, the present invention, after applying the photosensitive resin composition for black resist on a transparent substrate and dried, the steps of (a) exposure by ultraviolet light exposure apparatus, (b) development by alkaline aqueous solution and (c) thermoplasticity It is obtained by passing through, and it is a black matrix for color filters.

Moreover, this invention is a color filter which has the said black matrix.

Hereinafter, the photosensitive resin composition for black resists (henceforth only a "photosensitive resin composition" or a "composition" of this invention) is demonstrated in detail. The composition of this invention contains the said (A)-(E) component as an essential component.

As a preferable example of alkali-soluble resin of (A) component, if alkali developing is possible and if it is a high molecular compound which has a film forming ability, there will be no restriction | limiting in particular, The following compounds are mentioned as a specific example. 1) polyolefin-based polymers such as polyethylene, polypropylene and polyisobutylene, 2) diene-based polymers such as polybutadiene and polyisoprene, 3) polymers having conjugated polyene structures such as polyacetylene-based polymers and polyphenylene-based polymers 4) vinyl polymers such as polyvinyl chloride, polystyrene, polyvinyl acetate, polyvinyl alcohol, polyacrylic acid, polyacrylic acid ester, polyacrylamide, polyacrylonitrile, polyvinylphenol, etc. 5) polyphenylene ether, poly Polyethers such as oxirane, polyoxetane, polytetrahydrofuran, polyetherketone, polyetheretherketone, polyacetal, 6) phenol resins such as novolak resins, resol resins, 7) polyethylene terephthalates, polyphenolphthalein teres Polyesters such as phthalates, polycarbonates, alkyd resins, unsaturated polyester resins, 8) nylon 6, nylon 66, water Polyamides such as nylon, polyphenyleneamide, 9) polypeptides such as gelatin, casein, 10) epoxy resins such as novolac epoxy resins, bisphenol epoxy resins, modified resins with novolac epoxy acrylates and acid anhydrides and the like 11) Polyurethane, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole, polypyrrole, polyaniline, polysulfide, polysulfone, cellulose, etc. can be illustrated besides a modified product.

In these resin, what has a carboxyl group, a phenolic hydroxyl group, etc. in a resin side chain or main chain is preferable. In particular, resins having a carboxyl group, such as acrylic acid (co) polymers, styrene maleic anhydride resins, acid anhydride modified resins of novolac epoxy acrylates, and the like are preferred because they are highly alkaline developable. Moreover, acrylic resin is preferable because it is excellent in developability, and the copolymer is more preferable from a viewpoint of performance and manufacturing control, since polymerization can be carried out by selecting various monomers.

More specifically, as an acrylic resin containing a carboxyl group, the monomer which has carboxyl groups, such as (meth) acrylic acid, (anhydride) maleic acid, crotonic acid, itaconic acid, fumaric acid, and styrene, (alpha) -methylstyrene, (meth) acrylic acid Methyl, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, Allyl glycidyl ether, ethyl acrylate glycidyl, crotonic acid glycidyl ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl, (meth) acrylate, N-metholacrylamide, N Examples thereof include polymers obtained by copolymerizing comonomers such as N-dimethylacrylamide, N-methacryloyl morpholine, N, N-dimethylaminoethyl (meth) acrylate, and N, N-dimethylaminoethylacrylamide. Among them, preferred is an acrylic resin containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ether as the constituent monomer, and more preferably acrylic resin containing (meth) acrylic acid and styrene.

Moreover, it is also possible to add ethylenic double bond to the resin side chain to acrylic resin which has these carboxyl groups. Since a photocurability becomes high by providing a double bond to a resin side chain, since resolution and adhesiveness can be improved further, it is preferable.

The preferable range of the weight average molecular weight measured by GPC of the acrylic resin which has these carboxyl groups is 1000-100,000, and when it exceeds this, there exists a tendency for resolution to fall. In addition, the range of preferable content of a carboxyl group is 5-200 by acid value. If the acid value is 5 or less, it is insoluble in alkali developability, and if it exceeds 200, the sensitivity may be lowered.

Among the alkali-soluble resins of the above (A) component, a propylene glycol monomethyl ether acetate solution of an acid anhydride polycondensate of an epoxy acrylate having a fluorene skeleton is particularly preferably used.

As a photopolymerizable monomer which has at least 1 or more ethylenically unsaturated bond of (B) component, it is well-known, such as a monomer which radically polymerizes by the action of the radical which a photoinitiator generate | occur | produces, and the monomer which addition-condenses by the action of the acid generated from a photoinitiator. Any of can be used. As typical examples of the former, monomers having ethylenic double bonds are exemplified, more specifically isobutyl acrylate, t-butyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, cyclohexyl acrylate, Isobornyl acrylate, benzyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, ethylcarbitol acrylate, phenoxyethyl acrylate, tetrahydrofuryl acrylate, phenoxy polyethylene glycol acrylate, Methoxypropylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloyloxyethylhydrogen phthalate, 2-acryloyloxypropylhydrogen phthalate, 2-acryloyl Oxypropyltetrahydrohydrophthalphthalate, morpholinoethyl methacrylate, triple Fluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorododecyl Acrylate, trimethylsiloxyethyl methacrylate, 1,4-butanedioldiacrylate, 1,6-hexanedioldiacrylate, 1,9-nonanedioldiacrylate, neopentylglycoldiacrylate, tetraethylene glycol Diacrylate, tripropylene glycol diacrylate, propylene glycol diacrylate, glycerin methacrylate acrylate, bisphenol A ethylene oxide adduct diacrylate, trimetholpropane triacrylate, pentaerythritol triacrylate, pentaerythritol Tetraacrylate, Trimetholpropane Ethylene Oxide Adduct Triacrylate , Glycerin propylene oxide adduct triacrylate, trisacryloyloxyethyl phosphate, dipentaerythritol hexaacrylate, acrylic acid modification of novolac epoxy, acrylic acid of novolac epoxy and modified product of acid anhydride, N-vinylpi Lollidon, N-vinyl caprolactam, acrylated isocyanurate, dipentaerythritol monohydroxypentaacrylate, urethane acrylate, unsaturated polyester acrylate, etc. are mentioned, These mixtures are 1 type, or 2 or more types Can be used.

Among these monomers, in the acrylic monomer, especially an acrylic monomer having three or more double bonds, since the photosensitivity is increased, trimetholpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) Poly (meth) acrylates, such as) acrylate, are especially preferable. These monomers are used individually or in combination of two or more.

In the photosensitive resin composition of this invention, (B) component is used in 10-40 weight part with respect to a total of 100 weight part of (A) component and (B) component. When the component (B) is less than 10 parts by weight, the proportion of the photoreactive functional group in the photosensitive resin composition of the present invention is small, resulting in lack of photosensitivity, so that the pattern to be formed becomes narrower than the target line width or the pattern is easily lost. Lose. On the other hand, when it exceeds 40 weight part, on the contrary, light sensitivity is too strong and a pattern line width becomes thick with respect to a pattern mask, and faithful line width cannot be reproduced with respect to a mask. Moreover, since developability deteriorates, there exists a possibility that the problem that a pattern edge becomes nonuniform and does not become sharp may arise.

Although at least 1 type of photoinitiator is used as a photoinitiator of (C) component, it will not specifically limit, if it is a compound which can start superposition | polymerization of the compound which has an ethylenically unsaturated bond and can be polymerized. For example, an acetophenone type compound, a triazine type compound, a benzoin type compound, a benzophenone type compound, a thioxanthone type compound, an imidazole type compound, an acyl oxime type compound, etc. are illustrated.

Among these, as an acetophenone type compound, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1 -One, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] And oligomers of propane-1-one.

Examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -1,3,5-triazine and 2-methyl-4,6-bis (trichloromethyl) -1,3,5 -Triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1 , 3,5-triazine, 2- (4-methoxybutyl) -4,6-bis (trichloromethyl) -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 ( Trichloromethyl) -1,3,5-triazine and the like.

As a benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As a benzophenone type compound, for example, benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4'- tetra (tert- Butyl peroxycarbonyl) benzophenone, 2, 4, 6-trimethyl benzophenone, etc. are mentioned.

As a thioxanthone type compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- Propoxy city oxanthone etc. are mentioned.

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 And 4,5-triarylimidazole dimers.

As the acyl oxime compound, for example, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -bicycloheptyl-1-one oxime-O-acetate , 1- [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-onoxime-O-acetate, 1- [9-ethyl-6- (2- Methylbenzoyl) -9.H.-carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9 .H.-carbazol-3-yl] -tetrahydrofuranylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazole -3-yl] -thiophenylmethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -thio Phenylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -morphonylmethane-1-one oxime -O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carr Zol-3-yl] -Morofonylmethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane -1-onoxime-O-bicycloheptancarboxylate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-onoxime- O-tricyclodecanecarboxylate, 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime-O-adamantanecarboxy Rate, 1,2-octanediene, 1- [4- (phenylthio) -2- (O-benzoyloxime)] (product name monosaccharide OXE01 by the Chiba specialty chemicals company), ethanone, 1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl oxime) (product name: Monocure OXE02 by the Chiba Specialty Chemicals company), etc. are mentioned.

As a photoinitiator of (C) component, an active radical generator and an acid generator can also be used. As an active radical generator, for example, 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, phenylglyoxalate, titanocene compound, etc. may also be used. have. As the acid generator, for example, 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate , 4-acetoxyphenyl methyl benzylsulfonium hexafluoro antimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluenesulfonate, Onium salts, such as diphenyl iodonium hexafluoro antimonate, nitrobenzyl tosylates, benzoin tosylate, etc. are mentioned. Moreover, as an active radical generating agent, there exist some compounds which generate | occur | produce an acid simultaneously with an active radical among the said compounds, For example, a triazine type compound is used also as an acid generator.

The photoinitiator of (C) component can be used individually or in mixture of 2 or more types. Moreover, although it is not used as a photoinitiator or the sensitizer mentioned later by itself, it is also possible to add the compound which can increase the ability of a photoinitiator and a sensitizer by using it in combination with the photoinitiator of the said (C) component. Do. As such a compound, the amine compound which is effective when used in combination with benzophenone, for example is mentioned.

Examples of the amine compound include triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4,4'- Bis (ethylmethylamino) benzophenone etc. are mentioned.

Among the photoinitiators of the said (C) component, the triazine type photoinitiator and the acyl oxime type photoinitiator which trichloromethyl group is introduce | transduced are especially used preferably.

The usage-amount of the photoinitiator of (C) component is 5-50 weight part with respect to a total of 100 weight part of each component of (A) and (B) which are resin components, Preferably it is 20-45 weight part. When the blending ratio of the component (C) is less than 5 parts by weight, the speed of photopolymerization is slowed and the sensitivity is lowered. On the other hand, when it exceeds 50 parts by weight, the sensitivity is excessively strong and the pattern line width becomes thicker with respect to the pattern mask and the mask A faithful line width cannot be reproduced with respect to. Moreover, there exists a possibility that the problem that a pattern edge becomes nonuniform and does not become sharp may arise.

It is also possible to mix | blend a sensitizer separately from the photoinitiator of (C) component. As a sensitizer, although the general sensitizer used for a normal photoinitiator can be used, In order to raise a sensitivity more preferably, it is 1 chosen from the group which consists of a benzophenone type compound, a thioxanthone type compound, and a ketocoumarin type compound. More than one compound is used.

Specifically, benzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 4,4'-bis (dimethylamino) benzophenone, 4 Benzophenone compounds such as 4'-bis (diethylamino) benzophenone, thioxanthone, 2-methyl thioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone and iso Thioxanthone type compounds, such as a propyl thioxanthone, 2, 4- diisopropyl thioxanthone, and 2-chloro- thioxanthone, 3-acetyl coumarin, 3-acetyl-7- diethylamino coumarin, 3-benzoyl coumarin, 3 -Benzoyl-7-diethylaminocoumarin, 3-benzoyl-7-methoxycoumarin, 3,3'-carbonylbiscoumarin, 3,3'-carbonylbis (7-methoxycoumarin), 3,3 ' Ketocoumarin type compounds, such as carbonylbis (5,7- dimethoxy coumarin), can be used. You may use these 1 type or in mixture of 2 or more types.

Although the compounding ratio of the said sensitizer with respect to a photoinitiator is not specifically limited, Preferably it is 5-40 mass% in the total amount of a photoinitiator and a sensitizer, More preferably, it is 10-30 mass%. If the blending ratio of these sensitizers is too small, the sensitivity is lowered. If the sensitizer is too large, light transmission to the bottom of the resist is inhibited, so that the cross section of the resist becomes inverse rhombic and resolution resolution is not preferable.

The polyfunctional thiol compound as the component (D) of the present invention has two or more mercapto (SH) groups in the same molecule, and can be represented by the following general formula (I).

(In formula, R <^1> is an alkyl group, R <^2> is an n-valent aliphatic group which may contain atoms other than carbon, R <^0> is an alkyl group which is not H, and n shows 2-4.)

Specific examples of the polyfunctional thiol compound represented by the general formula (I) include 1,4-bis (3-mercaptobutyryloxy) butane [formula (II)] having 1,3, 5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazian-2,4,6 (1H, 3H, 5H) -trione [formula (III)], and pentaerythritol tetrakis ( 3-mercaptobutyrate) [formula (IV)] etc. are mentioned. These polyfunctional thiols can be used 1 type or in combination.

About the compounding quantity of the polyfunctional thiol in the photosensitive resin composition, it is preferable to add in 0.3-0.8 weight%, More preferably, it is 0.8-6.4 weight% with respect to the total solid except a solvent. When the blending ratio is out of the above range, the stability, odor, sensitivity, resolution, developability, adhesion, and the like of the photosensitive resin composition are deteriorated. In the low addition amount, the sensitivity and the adhesiveness decrease, and in the high addition amount, the ratio of the initiator to the thiol compound decreases, the speed of photopolymerization slows down, the sensitivity decreases, hardening, and the resist solubility also decreases.

While it is unclear what causes such deterioration, it is thought that the polyfunctional thiol is related to a compound that can also take an anti-Markownikoff addition, ie monomeric behavior, to a carbon-carbon double bond radically or ionically. That is, since the function as a monomer is lower than the preferable acrylic monomer of (B) component mentioned above, when the addition amount like a monomer will normally inhibit the function of an acryl monomer, it exhibits high function by adding a small amount by initiator as mentioned above. I think.

The coloring material of (E) component is at least 1 sort (s) chosen from black organic pigment which is a light-shielding pigment, mixed organic pigment, or light-shielding material. As black organic pigment, perylene black, cyanine black, etc. are mentioned, for example. Examples of the mixed color organic pigment include those which are pseudo blackened by mixing at least two or more pigments selected from red, blue, green, purple, yellow, cyanine, magenta and the like. Examples of the light shielding material include carbon black, chromium oxide, iron oxide, titanium black, aniline black, and cyanine black. Although it is also possible to select and use 2 or more types as a coloring material suitably, carbon black is especially preferable at the point which is favorable in light-shielding property, surface smoothness, dispersion stability, and compatibility with resin.

In addition, the coloring material of (E) component can be used with a dispersing agent as needed. As such a dispersing agent, surfactant, such as a cationic type, an anionic type, an amphoteric, a silicone type, and a fluorine type, is mentioned, for example. Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether and polyoxyethylene stearyl ether.

Moreover, it is good to mix | blend so that the addition amount of the coloring material of (E) component may be 50%-60% of solid content concentration except the solvent of the photosensitive resin composition. When this concentration is low, the light shielding property is not sufficient, and in order to obtain the desired contrast, the film thickness must be thickened, so that the surface smoothness of the black matrix is difficult to be obtained. On the contrary, when the addition amount is too large, the dispersion stability of the photosensitive resin composition for black matrices containing the component (E) decreases, and the content of the photosensitive resin serving as the original binder also decreases. There may be a problem.

About the compounding ratio of (E) component, it is 40 to 70 weight% in weight fraction with respect to solid content except the solvent which consists of (A)-(E) component in the composition of this invention, Preferably it is 50 to 60 weight%. good. If it is less than 40 weight%, light shielding will become inadequate. If the content exceeds 70% by weight, the content of the photosensitive resin serving as the original binder decreases, which leads to an unfavorable problem of impairing the manifestation characteristics and impairing the film forming ability.

In the photosensitive resin composition for black resists of this invention, it is preferable to use a solvent other than the said (A)-(E) component. 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. Ketones such as methyl-2-pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methylcarbitol, ethylcarbitol and butyl Glycol ethers such as carbitol, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and ethyl acetate Butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol Lactate, and the like can be butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, esters such as acetates. It can be set as a uniform solution composition by melt | dissolving and mixing using these.

Moreover, a hardening accelerator, a thermal polymerization inhibitor, a plasticizer, a filler, a solvent, a leveling agent, an antifoamer, etc. can be mix | blended with the photosensitive resin composition for black resists of this invention as needed. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, pyrogarol, tert-butyl catechol, phenothiazine, and the like. Examples of the plasticizer include dibutyl phthalate, dioctyl phthalate and tricresyl. Examples of the filler include glass fiber, silica, mica, alumina and the like. As an antifoamer and a leveling agent, a silicon type, a fluorine type, and an acryl type compound are mentioned, for example.

The photosensitive resin composition for black resists of this invention contains the said (A)-(E) component or these and a solvent as a main component. In solid content (solid content contains the monomer used as solid content after hardening) except a solvent, it is preferable that (A)-(E) component contain 80 weight% in total, Preferably it is 90 weight% or more. Although the quantity of a solvent changes according to the target viscosity, it is preferable to be contained in 70 to 90weight% of a range in the photosensitive resin composition.

The photosensitive resin composition for black resists of this invention is excellent as a resin composition for black matrix formation. In addition, the black matrix of this invention is formed by the photolithographic method, for example using the photosensitive resin composition for black resists of this invention. As the manufacturing step, first, the photosensitive resin composition is applied as a solution to the surface of the substrate, and then the solvent is dried (prebaked), and then the ultraviolet rays are irradiated with a photomask on the film thus obtained to cure the exposed portion, Moreover, the method of eluting the unexposed part using aqueous alkali solution is performed, the pattern is formed, and the method of post-baking (thermoplastic) as post-drying is illustrated.

As the substrate to which the solution of the composition of the present invention is applied, a transparent electrode such as ITO, gold, or the like is deposited or patterned on glass or a transparent film (for example, polycarbonate, polyethylene terephthalate, polyether sulfone, etc.). do.

As a method of apply | coating the solution of this composition to a board | substrate, in addition to a well-known solution immersion method and a spray method, any method, such as a method of using a roller coater, a land coater, or a spinner, can be employ | adopted. By these methods, after apply | coating to desired thickness, a film is formed by removing a solvent (prebaking). Prebaking can be performed by adding with an oven, a hotplate, etc., The heating temperature and heating time in prebaking are suitably selected according to the solvent used, For example, it carries out for 1 to 10 minutes at the temperature of 80-120 degreeC. You can do that.

Exposure performed after prebaking is performed by an exposure machine, and only the resist of the part corresponding to a pattern is exposed by exposing through a photomask. The exposure apparatus and the exposure irradiation conditions thereof are appropriately selected, for example, exposure using a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp, an ultraviolet ray, or the like, and the short wavelength (313 nm, 334 nm or less) is blocked. Then, the resin composition for black resists in a coating film is photocured.

Alkali development after exposure is performed in order to remove the resist of the unexposed part, and a desired pattern is formed by this phenomenon. Examples of suitable developer for the alkali development include, for example, aqueous solutions of carbonates of alkali metals and alkaline earth metals, aqueous solutions of hydroxides of alkali metals, and the like, and especially 0.05 to 3% by weight of carbonates such as sodium carbonate, potassium carbonate and lithium carbonate. It is good to form at the temperature of 20-30 degreeC using the weakly alkaline aqueous solution mentioned above, and a fine image can be formed precisely using a commercially available developer, an ultrasonic cleaner, etc.

After developing in this manner, heat treatment (post-baking) is performed at a temperature of 180 to 250 ° C. and a condition of 20 to 60 minutes. This postbaking is performed for the purpose of enhancing the adhesion between the patterned black matrix and the substrate. This is done by heating with an oven, hot plate or the like as in the prebaking. The patterned black matrix of this invention is formed through each process by the above photolithographic method.

As described above, the composition of the present invention is suitable for forming a fine pattern by an operation such as exposure and alkali development, but the same light shielding properties, adhesiveness, electrical insulation, heat resistance, A black matrix excellent in chemical resistance can be obtained.

The photosensitive resin composition for black resists of this invention can be used suitably as a coating material, Especially the color filter ink used for the display apparatus or imaging element of a liquid crystal, and the light shielding film formed by this are a color filter, the black matrix for liquid crystal projection It is useful as such.

The color filter of this invention can be obtained by well-known methods, such as apply | coating, developing, and hardening | curing ink of each color in a predetermined pattern for each color on the board | substrate with which the said black matrix was provided, and forming a protective film.

(Effects of the Invention)

The photosensitive resin composition for black resists of this invention does not have image development residue even if it is a light-shielding photosensitive resin composition with many content rates of a coloring material, and photocuring is difficult, and also the pattern dimensional stability, pattern adhesiveness, and sharpness of the edge shape of a pattern are favorable. A pattern can be obtained with a wide development margin, and a favorable light shielding film is provided.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described concretely based on an Example and a comparative example, this invention is not limited to these. Here, the waste material and the symbol used in manufacture of the black matrix of an Example and a comparative example are as follows.

(A): The propylene glycol monomethyl ether acetate solution of the acid anhydride polycondensate of the epoxy acrylate which has a fluorene skeleton (resin solid content concentration: 56.1 weight%, the Shin-Nitetsu Kagaku Co., Ltd. make, brand name V259ME)

(B): trimethylolpropane triacrylate (Satoma Japan Co., Ltd. product, brand name SR351S)

(C) -1: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (made by Chiba Specialty Chemicals Co., Ltd.) , Product name monocure OXE02)

(C) -2: 4- (4'-ethylbiphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine (made by Resve Chemical, brand name STR-2BP)

(D) -1: 1,4-bis (3-mercaptobutyryloxy) butane (Brand name: Kalenz MT BD1 (hereinafter referred to as BD1 abbreviation: manufactured by Denko Co.))

(D) -2: 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazian-2,4,6 (1H, 3H, 5H) -trione (brand name: Karenz MT NR1 (hereinafter referred to as NR1 abbreviation: manufactured by Hyddenco)

(D) -3: pentaerythritol tetrakis (3-mercaptobutyrate) (brand name: Karenz MT PE1 (hereinafter, referred to as PE1 abbreviation: manufactured by Soda Denko Co., Ltd.))

(D) -4: pentaerythritol tetrakistiopionionate (trade name: PETP (manufactured by Yodo Kagaku Co., Ltd.))

(E): A propylene glycol monomethyl ether acetate dispersion having a carbon black concentration of 20% by weight and a polymer dispersant concentration of 4.0% by weight (solid content 24.0%).

(F) -1: Propylene glycol monomethyl ether acetate

(F) -2: cyclohexanone

(Example)

The said compounding component was mix | blended in the ratio of Table 1, and Examples 1-10 and Comparative Examples 1-6 (resist) were prepared. In Table 1, the number in () of (A) component represents solid content, and the number in () of (E) component represents solid amount which a pigment (coloring material) occupies.

The glass substrate of 125 mm x 125 mm (Spinning) was used for the photosensitive resin composition for black resists which concerns on Examples 1-10 and Comparative Examples 1-6 which were obtained by mixing each component of Table 1 uniformly using a spin coater. 1737) was applied so that the film thickness after the postbaking was 1.1 µm and prebaked at 80 ° C for 2 minutes. Thereafter, the exposure gap was adjusted to 80 µm, and a negative photomask of line / space = 10 µm / 10 µm and 20 µm / 20 µm was coated on the dry coating film, and the ultra-high pressure of i-line roughness 30 µs / cm 2 was observed. The photocuring reaction of the photosensitive part was performed by irradiating 80mj / cm <2> ultraviolet-rays with the mercury lamp.

Next, the pattern of the exposed coating plate (where the photosensitive portion was photocured by applying the photosensitive resin composition to the glass substrate) was started to appear in a shower developing pressure of 1 kgf / cm 2 in 0.04% potassium hydroxide aqueous solution. After development of ± 30 seconds from the development time (break time = BT), spray washing at 5 kgf / cm 2 was performed to form a pixel pattern on the glass substrate from which the unexposed portions of the coating film were removed. Then, the line width and saturation exposure amount with respect to each mask width | variety after 230 degreeC hot-baking for 30 minutes using the hot air dryer were measured. The results are shown in Table 2.

Moreover, what preserve | saved each photosensitive resin composition for black resists which concerns on Examples 1-10 and Comparative Examples 1-6 at room temperature (22 degreeC-24 degreeC) for 2 weeks, and 1 month is line / space = 20micrometer / 20 It exposed and developed similarly using the negative photomask of micrometer, and evaluated the line width, the line | wire width reduction rate, and the external appearance of the surface. The results are shown in Table 3.

The evaluation items and the method of the black matrix obtained by the Example and the comparative example are as follows, and the result is shown to Table 2 and Table 3.

Line width: After developing further +30 second from the developing time (break time) in which a pattern starts to appear, it measured using the side microscope (The Nikon Corporation make, brand name XD-20).

OD: optical density when converted to thickness 1 탆

Appearance of the surface: The value of the surface roughness (Ra) of the coating film after image development and baking evaluated <good | favorableness> and 150 Å or more as less than 150 GPa as x <defect>.

When comparing Comparative Examples 5, 6, in which a primary thiol compound was added, and Examples 1 to 10, in which a secondary thiol compound was added, the addition of the primary thiol compound was performed at +30 seconds from the break time for 2 weeks over time. Significant line narrowing was shown by the 20 micrometer pattern, and the pattern of 20 micrometer did not remain in 1 month. However, the addition of the secondary thiol compound can leave a good line width even for one month for two weeks over time. In addition, in Comparative Example 3 in which the thiol compound was added excessively with respect to the initiator, aging stability is poor, and in Comparative Example 4 in which the excess is added, pattern formation itself becomes difficult.

In addition, as is apparent from the results of Tables 2 and 3, the results of Examples 1 to 10 compared to Comparative Examples 1 and 2 that are not thiol compounds added show a significant line width improvement by adding a polyfunctional thiol compound. It became clear.

Claims (6)

Following (A)-(E) component, (A) alkali-soluble resin, (B) a photopolymerizable monomer having at least one ethylenically unsaturated bond, (C) photoinitiator, (D) Polyfunctional thiol compound represented by the following general formula (I)

(In formula, R <^1> is an alkyl group, R <^2> is an n-valent aliphatic group which may contain atoms other than carbon, R <^0> is an alkyl group which is not H, n represents 2-4., And (E) As a photosensitive resin composition for black resists containing as an essential component one or more colorants selected from black organic pigments, mixed organic pigments and light-shielding materials: The weight ratio (A / B) of (A) component and (B) component is 60/40-90/10, and (C) component is 5-about 100 weight part of total of (A) component and (B) component. It contains 50 weight part, The photosensitive resin composition for black resists characterized by the above-mentioned. The photosensitive resin composition for black resists according to claim 1, wherein R ⁰ in the general formula (I) is an ethyl group or a methyl group. The photosensitive resin composition for black resists according to claim 1, wherein the multifunctional thiol compound is composed of one kind or a mixture of two or more kinds selected from the following formulas (II), (III) and (IV).

The photosensitive resin composition for black resists of Claim 1 or 2 whose content concentration of the said coloring agent is 40 to 70 weight%. After applying the photosensitive resin composition for black resists of Claim 1 on a transparent board | substrate, and drying, it carries out each process of (a) exposure by the ultraviolet-ray exposure apparatus, (b) image development by aqueous alkali solution, and (c) thermocalcination. Black matrix for color filters obtained, obtained. It has a black matrix of Claim 5, The color filter characterized by the above-mentioned.