JP4302075B2 - Black resist composition for forming black matrix - Google Patents

Description

The present invention relates to a light-shielding photosensitive resin composition suitable for production of a color filter used in combination with a liquid crystal display device or a solid-state imaging device. In particular, the present invention relates to a composition suitable for a black resist for forming a black pattern to be a black matrix of a color filter having a resin black matrix.
(In this specification, the black photosensitive resin composition is referred to as a black resist. The black resist composition for forming a black matrix is not limited to a black matrix on a color filter, but is used in a liquid crystal display device. It means a light-shielding black photosensitive resin composition that can be used.)

The color filter is obtained by forming fine colored pixels such as red, green, and blue on a glass substrate by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method, or the like. These known methods have the following characteristics and problems.
A color filter by a dyeing method is manufactured by forming an image with a photosensitive resin obtained by mixing dichromate as a photosensitizer with gelatin, polyvinyl alcohol or the like, and then dyeing the image. In order to form multiple colors on the same substrate, a dye-proofing process is essential, and there is a problem that the process becomes complicated. Moreover, since the dye is used, light resistance is inferior. Dichromic acid used as a photosensitizer is also a problem from the viewpoint of pollution prevention.

The color filter by printing is a method such as screen printing or flexographic printing, which transfers thermosetting or photocurable ink to a glass substrate. Since image formation and dyeing are unnecessary, the process is simple, but a high-definition image cannot be obtained, and there is a problem in the smoothness of the ink.
A color filter based on the electrodeposition method is one in which a glass substrate with an electrode is immersed in a bath containing a pigment or dye, and the hue is adhered by electrophoresis. Although it is excellent in smoothness, it is difficult to form a complicated pattern because an electrode is required on the glass substrate in advance.

In the pigment dispersion method, an image is formed with a colored resist in which a pigment is dispersed in a photocurable resin. There are advantages such as high heat resistance and no need for dyeing, and high-precision image formation is possible. The pigment dispersion method is superior to the above production method in terms of quality and production cost, and is currently the mainstream of color filter production.
In addition, a grid-like black pattern called a black matrix is generally arranged between red, blue, and green colored images for the purpose of usually improving contrast. Conventionally, the black matrix has been formed by depositing chromium on the entire glass substrate and forming a pattern by etching. However, because it uses chromium, it is costly and highly reflective, and has a problem with waste liquid treatment. is doing. For this reason, studies for forming a resin black matrix formed of a photosensitive resin have been intensively conducted.

  The resin black matrix is imaged by a photosensitive composition in which a black pigment such as carbon black or a pigment mixed with several kinds of pigments is dispersed. In order to obtain high light-shielding properties, it is necessary to add a large amount of pigment. However, the higher the pigment mixing ratio, the more difficult the pigment dispersion becomes and the lower the developability, resolution, adhesion, and stability. However, commercialization of a resin black matrix having sufficient light shielding properties has not been realized.

  An object of the present invention is to provide a black resist composition for a color filter which is excellent in developability, resolution, adhesion and stability and has a large development latitude. Furthermore, by providing a resist composition suitable for forming a black matrix having sufficient light shielding properties without impairing these characteristics, it is intended to realize a color filter excellent in high quality, low cost and safety. To do.

  As a result of intensive studies, the present inventors have been able to adopt a gloss value as an indicator of the dispersion state of solid components such as pigments in the resin black matrix, and when the gloss value of the black matrix is a specific value, the dispersibility is As a result of being good, the resolution, dimensional stability, adhesion to the substrate are good, and in the color filter having the resin black matrix, the ITO film deposited on the upper layer is not properly deposited. I found out that it is hard for trouble to occur.

Furthermore, the present inventors have found that a black resist having specific viscosity characteristics is effective in forming the resin black matrix.
That is, the gist of the present invention includes a photosensitive resin material, a black pigment, a pigment dispersant, and a solvent, and the dry coated film defined below has a 20-degree specular gloss in the range of 100 to 200, The resin material contains a binder resin, a monomer that is cured by the action of a photopolymerization initiator, and a photopolymerization initiator. The amine value of the pigment dispersant is 1 to 100 mgKOH / g, and the binder resin is in the side chain ( The present invention resides in a black resist composition for a color filter, which is a resin having a (meth) acryloyl group.
A dry coating film having a thickness of 1 μm prepared by coating the black resist composition for forming a black matrix on a glass substrate with a spin coater and drying it on a hot plate at 80 ° C. for 1 minute.

  The black resist composition for forming a black matrix according to the present invention is excellent in developability, resolution, adhesion, and coating property even when many pigments are dispersed. Can be formed stably, and a color filter for a liquid crystal display can be provided at a high quality and at a low cost, thereby providing a great industrial advantage.

Hereinafter, the present invention will be described in detail.
The feature of the present invention is that the 20 degree specular gloss of the dry coating film of the black resist composition of the present invention formed on the transparent substrate of the color filter is in the range of 100-200.
The resin black matrix is a light-shielding film formed of a black resist mainly composed of a resin and a black pigment. The resin and the black pigment are not particularly limited, and the details thereof will be described later together with the description regarding the black resist.

  The specular gloss is a method of expressing the gloss by the reflection intensity in the regular reflection direction, and the specular gloss of 20 degrees, 45 degrees, 60 degrees, 75 degrees, and 85 degrees is known depending on the measurement sample (for example, In Japanese Industrial Standard JIS Z8741), in the present invention, since the measurement sample is a resin black matrix, it is represented by a 20-degree specular gloss (corresponding to JIS method 5). "Glossiness") needs to be in the range of 100-200.

A glossiness within this range is preferable in terms of resolution, dimensional stability, and adhesion, and is less likely to cause defects such as ITO deposition defects.
If the gloss is too small, the resolution, developability, and adhesion to the substrate are poor, and it is difficult to form a resin black matrix with high accuracy.
On the other hand, if the gloss level is too high, problems such as light reflection due to the black matrix occur, which is not preferable.

  As will be described later, the present invention provides a black resist composition for forming a black matrix, which contains a black pigment, a photosensitive resin material, and a solvent, and has a 20 ° specular gloss of a dry coating film in the range of 100 to 200. However, the stability of the composition when the black resist composition is used to form a black matrix (change in image-forming ability after storage), development latitude (variation in development time when forming the black matrix) The glossiness is preferably 120 to 200, more preferably 130 to 200 in consideration of a wide allowable time).

  The optical density of the resin black matrix formed according to the present invention is usually 2.8 or higher, preferably 3.0 or higher, more preferably 3.5 or higher. In the present invention, the dispersibility of the solid component in the mixture containing at least a resin, a black pigment and a solvent is good, and in order to achieve the above glossiness, a large amount of black pigment is contained and a high optical density is achieved. Nevertheless, the resolution and adhesion are also good.

  Next, the black resist composition for forming a black matrix will be described. The black resist for forming a black matrix of the present invention is characterized in that it contains a photosensitive resin material, a black pigment and a solvent as described above, and the dry coated film has a 20-degree specular gloss of 100 to 200.

The photosensitive resin material used in the composition of the present invention usually contains (a) a binder resin, (b) a monomer that is cured by the action of a photopolymerization initiator, and (c) a photopolymerization initiator. You can choose from a wide range used for seed resists.
The (a) binder resin is not particularly limited as long as it is a polymer compound having a coating film-forming ability, and specific examples thereof include the following compounds.

1) Polyolefin polymer Polyethylene, polypropylene, polyisobutylene, etc. 2) Diene polymer, polybutadiene, polyisoprene, etc. 3) Polymer having conjugated polyene structure Polyacetylene polymer, polyphenylene polymer, etc. 4) Vinyl polymer Polyvinyl chloride, polystyrene, vinyl acetate , Polyvinyl alcohol, polyacrylic acid, polyacrylic acid ester, polyacrylamide, polyacrylonitrile, polyvinylphenol, etc. 5) Polyether Polyphenylene ether, polyoxirane, polyoxetane, polytetrahydrofuran, polyetherketone, polyetheretherketone, polyacetal, etc. 6 ) Phenolic resin Novolak resin, resole resin, etc. 7) Polyester Polyethylene terephthalate, Poly Phenolphthalein terephthalate, polycarbonate, alkyd resin, unsaturated polyester resin, etc. 8) Polyamide, nylon-6, nylon 66, water-soluble nylon, polyphenyleneamide, etc. 9) Polypeptide gelatin, casein, etc. 10) Epoxy resin and its modified products, novolak epoxy Resin, modified resin with bisphenol epoxy resin, novolac epoxy acrylate and acid anhydride, etc. 11) Others Polyurethane, polyimide, melamine resin, urea resin, polyimidazole, polyoxazole, polypyrrole, polyaniline, polysulfide, polysulfone, celluloses, etc.

Among these resins, when a resin having a carboxyl group or a phenolic hydroxyl group in the resin side chain or main chain is contained, the resist composition can be alkali-developed, which is preferable from the viewpoint of pollution prevention. In particular, a resin having a carboxyl group, for example, an acrylic acid (co) polymer, a styrene / maleic anhydride resin, an acid anhydride-modified resin of novolak epoxy acrylate, and the like are preferable because of high alkali developability.
Furthermore, acrylic resins are preferable because they are excellent in developability, and since various copolymers can be obtained by selecting various monomers, they are more preferable from the viewpoint of performance and production control.

  More specifically, the acrylic resin containing a carboxyl group is, for example, a monomer having a carboxyl group such as (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, styrene, α-methyl, etc. Styrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) ) Acrylate, allyl glycidyl ether, glycidyl ethyl acrylate, glycidyl crotonic acid ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylol acrylamide, N, N-dimethylacrylamido , N- methacryloyl morpholine, N, N- dimethylaminoethyl (meth) acrylate, N, N- dimethylaminoethyl acrylamide, polymers obtained by copolymerizing comonomers like. Among them, an acrylic resin containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ether as a constituent monomer is preferable, and an acrylic resin containing (meth) acrylic acid and styrene is more preferable.

  Moreover, these resins can also add an ethylenic double bond to the side chain. Since the photocurability is increased by imparting a double bond to the resin side chain, the resolution and adhesion can be further improved, which is preferable. Examples of the synthesis means for introducing an ethylenic double bond include the methods described in JP-B-50-34443, JP-B-50-34444 and the like. Specific examples include a method of reacting a compound having both a glycidyl group, an epoxycyclohexyl group and a (meth) acryloyl group with a carboxyl group or a hydroxyl group, or acrylic acid chloride. For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By using a compound such as acrylic acid chloride or (meth) allyl chloride and reacting with a resin having a carboxyl group or a hydroxyl group, a resin having a polymer group in the side chain can be obtained. In particular, a resin obtained by reacting an alicyclic epoxy compound such as (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable.

In the present specification, “(meth) acryl-”, “(meth) acrylate” and the like mean “acrylic or methacrylic”, “acrylate or methacrylate” and the like, for example, “(meth) acrylic”. "Acid" shall mean "acrylic acid or methacrylic acid".
The preferable range of the weight average molecular weight measured by GPC of these acrylic resins is 1,000 to 100,000. When the weight average molecular weight is 1,000 or less, it is difficult to obtain a uniform coating film, and when it exceeds 100,000, the developability tends to decrease. Moreover, the range of preferable content of a carboxyl group is 5-200 in an acid value. When the acid value is 5 or less, it becomes insoluble in an alkaline developer, and when it exceeds 200, the sensitivity may be lowered.

(B) Monomers that are cured by the action of a photopolymerization initiator include monomers that undergo radical polymerization by the action of radicals generated by the photopolymerization initiator and monomers that undergo addition condensation by the action of acids generated from the photopolymerization initiator. Any one can be used.
Typical examples of the former include monomers having an ethylenic double bond, and 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, ethyl carbitol acrylate, phenoxyethyl acrylate, tetrahydrofuryl acrylate, phenoxy polyethylene glycol acrylate, methoxypropylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 2-acryloyloxyethyl hydrogen phthalate, 2-acryloyloxyp Pyrhydrogen phthalate, 2-acryloyloxypropyl tetrahydro phthalate, morpholinoethyl methacrylate, trifluoroethyl acrylate, trifluoroethyl methacrylate, tetrafluoropropyl (meth) acrylate, hexafluoropropyl (meth) acrylate, octafluoropentyl (meth) acrylate , Heptadecafluorododecyl acrylate, trimethylsiloxyethyl methacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, tetraethylene glycol diacrylate , Tripropylene glycol diacrylate, propylene glycol diac Rate, glycerin methacrylate acrylate, bisphenol A, ethylene oxide adduct diacrylate, trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane ethylene oxide addition triacrylate, glycerin propylene oxide addition triacrylate, trisacryloyl Oxyethylene phosphate, dipentaerythritol hexaacrylate, modified acrylic acid of novolac epoxy, modified acrylic acid and anhydride of novolak epoxy, N-vinylpyrrolidone, N-vinylcaprolactam, acrylated isocyanurate, dipentaerythritol Monohydroxypentaacrylate, urethane acrylate And unsaturated polyester acrylates.
Among these monomers, acrylic monomers, particularly acrylic monomers having 3 or more ethylenic double bonds are preferred. These monomers are used alone or in combination.

On the other hand, as a monomer that undergoes addition condensation by the action of an acid generated from a photopolymerization initiator, melamine, benzoguanamine, glycoluril, or a compound obtained by acting formaldehyde on urea or an alkyl-modified compound thereof, an epoxy compound, a resole compound, or the like Examples thereof include compounds having an action.
Specifically, Mitsui Cyanamid's Cymel (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158 are examples of compounds in which formaldehyde is allowed to act on melamine or alkyl modified products thereof. Cymel (registered trademark) 1123, 1125, and 1128 are examples of a compound obtained by allowing formaldehyde to act on benzoguanamine or an alkyl-modified product thereof. Cymel (registered trademark) 1170, 1171, 1174, and 1172 are examples of compounds obtained by allowing formaldehyde to act on glycoluril or alkyl-modified products thereof. UFR (registered trademark) 65, 300 of Mitsui Cyanamid Co., Ltd. can be given as an example of a compound obtained by reacting urea with formaldehyde or an alkyl modified product thereof.

  Examples of epoxy compounds include triglycidyl trishydroxyethyl isocyanurate, allyl glycidyl ether, ethylhexyl glycidyl ether, phenyl glycidyl ether, phenol glycidyl ether, lauryl alcohol glycidyl ether, adipic acid glycidyl ether, phthalic acid glycidyl ether, dibromophenyl glycidyl ether, Dibromoneopentyl glycol diglycidyl ether, glycidyl phthalimide, (poly) ethylene glycol glycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, glycerin polyglycidyl ether, trimethylolpropane polyglycidyl ether, butyl glycidyl ether, etc. It is possible .

Among these, particularly preferred compounds include compounds having a —N (CH ₂ OR) ₂ group in the molecule (wherein R represents a hydrogen atom or an alkyl group). Specifically, a compound obtained by reacting formaldehyde with urea or melamine or an alkyl-modified product thereof is particularly preferable.
Examples of the resol compound include PP-3000s, PP-3000A, RP-2978, SP-1974, SP-1975, SP-1976, SP-1977, and RP-3972 manufactured by Gunei Chemical Co., Ltd.
Among these binder resins and monomers, the combination of the above acrylic resin containing a carboxyl group and an acrylic monomer is most preferable in that the color filter resist composition can be alkali-developed.

(C) As the photopolymerization initiator, any known photopolymerization initiator can be used, and examples thereof include a compound capable of generating a radical that polymerizes an ethylenically unsaturated group by ultraviolet rays and a compound capable of generating an acid by ultraviolet rays. .
Specifically, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, Halomethyl such as 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine, etc. Triazine derivatives, halomethylated oxadiazole derivatives, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) ) Imidazole dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) 4,5-diphenylimidazole dimer, imidazole derivatives such as (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, benzoin such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether Benzoin alkyl ethers, 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, anthraquinone derivatives such as 1-chloroanthraquinone, benzanthrone derivatives, benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, Benzophenone derivatives such as 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2,2 Dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ) Acetophenone derivatives such as ketones, thioxanthone such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone Conductor, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine, 9,10-dimethylbenzphenazine, etc. Phenazine derivatives, di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6 -Pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4 , 6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluorophen-1-yl, di Cyclopentadienyl-Ti-2,4-di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, Di-methylcyclopentadienyl-Ti-bis-2,6-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-di-fluoro-3- (pyr-1-yl) ) -Phen-1-yl and the like titanocene derivatives. These photopolymerization initiators are used alone or in combination. For example, combinations of initiators described in JP-B-53-12802, JP-A-1-279903, JP-A-2-48664, JP-A-4-164902, JP-A-6-75373 and the like can be mentioned.

Among these photopolymerization initiators, halomethylated triazine derivatives, halomethylated oxadiazole derivatives, biimidazole derivatives, and titanocene derivatives are particularly preferable because of their high sensitivity, high stability, and high solubility.
The black pigment used in the present invention is not particularly limited, and a known organic pigment or inorganic pigment such as red, green, and blue can be mixed to make a black color. It is preferable to use strong carbon black, graphite, or titanium black. Of these, carbon black is preferred.

Specifically, carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, # 650, MA600 manufactured by Mitsubishi Chemical Corporation , MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40, # 33 , # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N339, Diamond Black SH, Ear black SHA, Diablack LH, Diablack H, Diablack HA, Diablack SF, Diablack N550M, Diablack E, Diablack G, Diablack R, Diablack N
760M, Diamond Black LR. Carbon black thermax N990, N991, N907, N908, N990, N991, N908 made by Cancarb. Carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal. Degussa AG of carbon black ColorBlack Fw200, ColorBlack Fw2, ColorBlack Fw2V, ColorBlack Fw1, ColorBlack Fw18, ColorBlack S170, ColorBlack S160, SpecialBlack6, SpecialBlack5, SpecialBlack4, SpecialBlack4A, SpecialBlack250, SpecialBlack
350, PrintexU, PrintexV, Printex140U, Printex140V (all are trade names), and the like.

Among these carbon blacks, those having a specific surface area of 110 m ² / g or less and a pH of 2 to 9 are particularly preferred. When the specific surface area exceeds 110 m ² / g, a large amount of a polymer dispersant necessary for stabilizing the dispersion is required. However, since the polymer dispersant is insoluble in the developer, resolution and developability are deteriorated. It becomes easy to do. Moreover, when the pH value exceeds 9, the polymer dispersant is difficult to adsorb and dispersion stabilization is difficult. Carbon black having a pH of less than 2 is extremely difficult to industrially manufacture and is not practical.

Specific examples of the solvent of the present invention include diisopropyl ether, mineral spirit, n-pentane, amyl ether, ethyl caprylate, n-hexane, diethyl ether, isoprene, ethyl isobutyl ether, butyl stearate, n-octane, valsol # 2, Apco # 18 solvent, diisobutylene, amyl acetate, butyl butyrate, apcocinner, butyl ether, diisobutyl ketone, methylcyclohexene, methyl nonyl ketone, propyl ether, dodecane, Socal solvent No. 1 and no. 2, amyl formate, dihexyl ether, diisopropyl ketone, Solvesso # 150, butyl acetate (n, sec, t), hexene, shell TS28 solvent, butyl chloride, ethyl amyl ketone, ethyl benzoate, amyl chloride, ethylene glycol diethyl ether , Ethyl orthoformate, methoxymethylpentanone, methyl butyl ketone, methyl hexyl ketone, methyl isobutyrate, benzonitrile, ethyl propionate, methyl cellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, propyl acetate, amyl acetate, Amylformate, bicyclohexyl, diethylene glycol monoethyl ether acetate, dipentene, methoxymethylpentanol, methylamino Ketone, methyl isopropyl ketone, propyl propionate, propylene glycol-t-butyl ether, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, ethyl acetate, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxypropionic acid, 3- Ethoxypropionic acid , Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, dipropylene glycol monomethyl ether, ethylene glycol acetate, ethyl carb Examples include organic solvents such as tol, butyl carbitol, ethylene glycol monobutyl ether, propylene glycol-t-butyl ether, 3-methyl-3-methoxybutanol, tripropylene glycol methyl ether, and 3-methyl-3-methoxybutyl acetate.
It is preferable to select a solvent having a boiling point in the range of 100 to 200 ° C. More preferably, it has a boiling point of 120-170 ° C. These solvents are used alone or in combination.

In the present invention, a pigment dispersant can be added in addition to these components. It is preferable to add a pigment dispersant since the viscosity characteristic and gloss value can be easily controlled by further adding a pigment dispersant.
The pigment dispersant has an affinity for both the pigment and the binder resin, and examples thereof include surfactants such as nonions, cations, and anions, and polymer dispersants. Among these, polymer dispersants are preferable.
The compounding ratio of each component of the black resist composition of the present invention is usually 50 to 250 parts by weight of a black pigment, 300 to 2500 parts by weight of a solvent, and 0 to 50 parts by weight of a polymer dispersant with respect to 100 parts by weight of the photosensitive resin material. It is.

In a preferred embodiment of the composition of the present invention, the monomer is 5 to 100 parts by weight, the initiator is 0.01 to 30 parts by weight, the black pigment is 50 to 500 parts by weight, and the solvent with respect to 100 parts by weight of the binder resin. Is contained in an amount of 200 to 10,000 parts by weight, and the polymer dispersant is contained in an amount of 0 to 50 parts by weight.
If the monomer is less than the above range, the image-exposed image area has insufficient crosslinking density, and it is difficult to obtain a good image, and if it exceeds the above range, the resist film after drying becomes more sticky, resulting in workability. Become inferior. When the addition amount of the photopolymerization initiator is less than the above range, sufficient sensitivity cannot be obtained, and when it exceeds the above range, the initiator sometimes precipitates from the resist composition. When the addition amount of the black pigment is less than the above range, it is difficult to obtain a sufficient color density and the light shielding ability is also inferior. On the other hand, if the above range is exceeded, the pigment dispersion stability, developability, resolution and adhesion will be reduced. If the addition amount of the solvent is less than the above range, coating unevenness is likely to occur and the film thickness is not uniform, and if it exceeds the above range, a sufficient film thickness cannot be obtained, and coating defects such as pinholes may occur. It becomes easy.
The black pigment concentration in the total solid content is usually 20 to 80% by weight, preferably 25 to 75% by weight, more preferably 35 to 75% by weight, and most preferably 45 to 75% by weight. In addition to these essential components, a sensitizer, a coating property improver, a polymerization inhibitor, a plasticizer, a flame retardant, and the like can be suitably added to the present invention. These can be used alone or in combination of several kinds.

  When preparing the black resist composition of the present invention, it is necessary to finely disperse the pigment in advance. For the dispersion treatment, methods such as a ball mill, a sand mill, a bead mill, a three roll, a paint shaker, an ultrasonic wave, and a bubble homogenizer can be used. Two or more of these processing methods can be combined. The dispersion treatment is preferably carried out with a composition in which a solvent is added to the pigment and the pigment dispersant or binder resin. Dispersion treatment in a state where all the essential components of the resist are added is not preferable because it may cause deterioration of highly reactive components such as an initiator and a monomer. The other components are preferably added and dissolved after the dispersion treatment. The particle diameter of a preferable pigment obtained by the dispersion treatment is, for example, in the range of 0.005 to 0.7 μ, more preferably 0.01 to 0.5 μ in the case of carbon black. The carbon black particle size is measured by a laser Doppler particle size measuring device. When the particle size exceeds the upper limit of the above range, the developability, resolution and stability are lowered. Moreover, in order to make it below the lower limit, it is necessary to make the pigment particles finer than the primary particles of carbon black or higher, so that the production is extremely difficult.

  The black resist composition thus obtained needs to have a 20-degree specular gloss of the dry coating film in the range of 100 to 200. Such glossiness is determined by forming a dry coating film on a transparent substrate using the black resist composition of the present invention according to the image forming method described later and measuring the glossiness.

The glossiness, which is a feature of the present invention, can be controlled by selecting the chemical structure of each component, the amount added, and the dispersion treatment conditions described above.
As one of the preferable embodiments capable of achieving the glossiness of the present invention, the viscosity at 25 ° C. is in the range of 2 to 20 mPs, and the viscosity ratios η5 / η50 measured at 5 rpm and 50 rpm are 1 to 1. And a resist composition in the range of 5. In this case, the glossiness and viscosity can be controlled by the dispersion treatment conditions, for example, as follows. Usually, the gloss value with respect to dispersion time and the change in viscosity behavior are low gloss value and high viscosity at the initial stage of dispersion, but the gloss value increases, viscosity and η5 / η50 decrease as the dispersion proceeds, When the dispersion is advanced, the dispersion becomes overdispersed, the gloss value is saturated, and the viscosity and η5 / η50 tend to increase rapidly. However, the glossiness is presumed that the maximum glossiness changes depending on the components of the composition. Therefore, by setting the dispersion time at which the glossiness is maximum and the viscosity is minimum, a pigment dispersion and a resist composition having preferable glossiness and viscosity characteristics can be obtained.
In addition, regarding the control by the resist component, there are many complicated and unclear points in relation to the behavior of the viscosity and gloss and the resist component. For example, the gloss value and the viscosity can be controlled as follows.
With respect to the gloss value, it is possible to obtain a high gloss value by increasing the molecular weight and addition amount of the binder resin.
The viscosity and η5 / η50 can be controlled, for example, by controlling the molecular weight and addition amount of the binder resin. As is well known, the higher the molecular weight of the binder resin, the higher the solution viscosity. However, in the pigment dispersion system, the binder resin has a function of suppressing aggregation between the pigments, and the higher the molecular weight, the greater the suppression effect.
Therefore, the dispersion system has an optimum molecular weight of the binder resin with respect to the viscosity and η5 / η50, and the viscosity can be controlled by optimizing the molecular weight. The same applies to the addition amount. If the addition amount is large, the viscosity of the resin itself is increased. Conversely, if the addition amount is small, the increase in viscosity due to the pigment aggregation effect occurs. Therefore, the viscosity and η5 / η50 are minimum. By obtaining the added amount, a pigment dispersion having a preferable viscosity characteristic and a resist composition can be obtained.
The reason why the glossiness or the viscosity characteristic has a great influence on the photosensitive characteristics of the resist is unknown, but in a system containing a large amount of fine pigment particles such as a color resist, it is not between fine particles. Since the interaction is very large, its control becomes important in order to obtain favorable photosensitive characteristics. The physical property values seem to indicate a range in which the fine particle interaction is preferably reflected as resist characteristics.
When the viscosity at 25 ° C. is less than the range of 2 to 20 mPs, it is difficult to ensure the film thickness necessary for the color filter, and there is a tendency that defects such as a decrease in contrast due to insufficient light shielding and pinholes are likely to occur. If the above range is exceeded, film thickness unevenness, resolution unevenness, development unevenness and the like become significant.
When the viscosity ratios η5 / η50 measured at the rotation speeds of 5 rpm and 50 rpm are out of the range of 1 to 1.5, the resolution, developability, and adhesion are deteriorated. Therefore, the quality and productivity of the color filter. Will drop significantly.

On the other hand, the composition of the present invention preferably contains a polymer dispersant. If a chemical structure preferable as the polymer dispersant is specifically exemplified, for example, at least a polyisocyanate compound, and 1 hydroxyl group in the molecule is included. Examples thereof include one or two compounds having a number average molecular weight of 300 to 10,000 and a dispersion resin obtained by reacting a compound having an active hydrogen and a tertiary amino group in the same molecule.
Examples of the polyisocyanate compound include aroma such as paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, and tolidine diisocyanate. Aliphatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate and other aliphatic diisocyanates, isophorone diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), ω, ω ' -Alicyclic diisocyanates such as diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α ', α'-tetramethyl Aliphatic diisocyanates having aromatic rings such as xylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate , Triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, and trimers thereof, water adducts, and polyol adducts thereof.
Preferred as the polyisocyanate is a trimer of an organic diisocyanate, and most preferred is a trimer of tolylene diisocyanate and a trimer of isophorone diisocyanate, which may be used alone or in combination.

  As a method for producing an isocyanate trimer, the polyisocyanate may be converted into an isocyanate group using an appropriate trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like. And the trimerization is stopped by adding a catalyst poison, and then the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

  Examples of the compound having one or two hydroxyl groups in the same molecule (number average molecular weight 300 to 10,000) include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and one terminal hydroxyl group of these compounds is carbon. Examples thereof include those alkoxylated with an alkyl group of 1 to 25 and a mixture of two or more of these.

  Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of polyether diols are those obtained by homopolymerizing or copolymerizing alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and the like. The mixture of 2 or more types of these is mentioned. Polyether ester diols include those obtained by reacting mixtures of ether group-containing diols or other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly (poly And oxytetramethylene) adipate. Most preferred as the polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

  Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Propylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 , 6-hexanediol, 2-methyl-2,4- Nanthanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -N-alkyl dialkanolamines such as methyldiethanolamine) obtained by polycondensation, such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc., or the diols or carbon number 1-25 Polylactone diol or polylactone monool obtained by using polyhydric alcohol as an initiator, for example, polycaprolactone glycol, poly methyl valerolactone and mixtures of two or more thereof. Most preferred as the polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator, more specifically, a compound obtained by ring-opening addition polymerization of ε-caprolactone to a monool.

Polycarbonate glycol includes poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, and polyolefin glycol includes polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, and the like. Can be mentioned.
Of the compounds having one or two hydroxyl groups in the same molecule, polyether glycol and / or polyester glycol are particularly preferable.
The molecular weight of the compound having one or two hydroxyl groups in the same molecule is 300 to 10,000, preferably 500 to 6,000, and more preferably 1,000 to 4,000.

The compound having an active hydrogen and a tertiary amino group in the same molecule will be described. Examples of the active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom include a hydrogen atom in a functional group such as a hydroxyl group, an amino group, and a thiol group. Of these, the hydrogen atom of the amino group is preferred. The tertiary amino group is not particularly limited.
Moreover, as a tertiary amino group, the amino group which has a C1-C4 alkyl group, or a heterocyclic structure, More specifically, an imidazole ring or a triazole ring is mentioned.

  Examples of such compounds having an active hydrogen and a tertiary amino group in the same molecule include N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  In addition, the tertiary amino group is an N-containing heterocycle, such as pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring, benzoxazole ring, benzo Examples thereof include N-containing hetero 5-membered rings such as thiazole ring and benzothiadiazole ring, N-containing hetero 6-membered rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, and isoquinoline ring. Preferred as these N-containing heterocycles are an imidazole ring or a triazole ring.

Specific examples of these compounds having an imidazole ring and an NH2 group include 1- (3-aminopropyl) imidazole, histidine, 2-aminoimidazole, 1- (2-aminoethyl) imidazole and the like.
Further, specific examples of the compound having a triazole ring and an NH2 group include 3-amino-1,2,4-triazole, 5- (2-amino-5-chlorophenyl) -3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole and the like.

Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4-triazole Is preferred.
A preferable blending ratio of the dispersant raw material is 10 to 200 parts by weight, preferably 20 to 200 parts by weight of a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule with respect to 100 parts by weight of the polyisocyanate compound. 190 parts by weight, more preferably 30 to 180 parts by weight, and the compound having an active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight.

The molecular weight of the dispersion resin is 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000 in terms of polystyrene-equivalent weight average molecular weight measured by GPC. . If the molecular weight is less than 1,000, the dispersibility and dispersion stability are poor, and if it exceeds 200,000, the solubility is lowered and the dispersibility is inferior, and at the same time, it becomes difficult to control the reaction.
The dispersion resin is produced according to a known method for producing a polyurethane resin. As a solvent for production, usually, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone, esters such as ethyl acetate, butyl acetate, cellosolve acetate, benzene, toluene, xylene, hexane Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tert-butanol, etc., chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used.

  A normal urethanization reaction catalyst is used as a catalyst for production. Examples include tin series such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stanas octoate, iron series such as iron acetylacetonate and ferric chloride, and tertiary amine series such as triethylamine and triethylenediamine. It is done.

The introduction amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mgKOH / g in terms of the amine value after the reaction. More preferably, it is the range of 5-95 mgKOH / g. When the amine value is less than the above range, the dispersing ability tends to decrease, and when it exceeds the above range, the developability tends to decrease.
In addition, when an isocyanate group remains in the dispersion resin by the above reaction, it is preferable to crush the isocyanate group with an alcohol or an amino compound because the dispersion resin has high temporal stability.

The black resist composition of the present invention is particularly advantageous in that it contains the above-described polymer dispersant from the viewpoint of stability (presence or absence of change in image-forming ability after storage of the resist solution). The black pigment is 50 to 250 parts by weight, the polymer dispersant is 0.01 to 50 parts by weight, and the solvent is 300 to 2500 parts by weight with respect to 100 parts by weight of the photosensitive resin material.
More specifically, the monomer is 5 to 100 parts by weight, preferably 10 to 95 parts by weight, more preferably 15 to 90 parts by weight, and the photopolymerization initiator is 0.01 to 30 parts by weight with respect to 100 parts by weight of the binder resin. , Preferably 0.05 to 28 parts by weight, more preferably 0.1 to 25 parts by weight, pigments 50 to 500 parts by weight, preferably 60 to 490 parts by weight, more preferably 70 to 480 parts by weight, and the dispersion resin 0.01-50 parts by weight, preferably 0.05-49 parts by weight, more preferably 0.1-48 parts by weight, the solvent is 200-10,000 parts by weight, preferably 250-9500 parts by weight, more preferably It is contained in the range of 300 to 9000 parts by weight.

By using the dispersant of the present invention, it becomes possible to produce a highly dispersible black resist composition containing carbon black at a high concentration. When a black matrix is produced using such a black resist composition, carbon black However, it is possible to produce a black matrix having no coating unevenness, high resolving power, good adhesion and storage stability, and high light shielding properties.
In addition to these essential components, a sensitizer, a coating property improver, a polymerization inhibitor, a plasticizer, a flame retardant, and the like can be suitably added to the present invention. These can be used alone or in combination of several kinds.

The composition of this invention is apply | coated to a transparent substrate by well-known methods, such as a spin coater, a roll coater, a curtain coater, and screen printing. In addition to glass, plastics such as PET, acrylic, and polycarbonate can be used as the transparent substrate.
The coating film thickness is preferably 0.2 to 10 μm. More preferably, it is 0.3-5 micrometers. A convection oven or a hot plate is used to dry the coating film. The drying temperature is preferably 50 to 150 ° C., and the drying time is preferably 30 seconds to 60 minutes. For the exposure, a light source emitting ultraviolet rays such as a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp can be used, and a latent image is formed on the resist film by exposing through a mask. Then, an image is formed by developing with the solvent which dissolves an unexposed part. As the developer, an organic solvent such as acetone, toluene, MEK or the like can be used. However, an alkaline developer is preferable in view of environmental problems. For example, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate, ammonia water, tetramethylammonium hydroxide aqueous solution, etc. are used. A surfactant, an antifoaming agent or the like may be added to the alkaline developer. There is no restriction | limiting in particular as a developing method, It can carry out by well-known methods, such as a paddle method, a dipping method, and a spray method. A pre-wet may be adopted. Post-baking, post-photocuring, or the like may be employed for the purpose of enhancing the drying of the developer after the image formation and the curing of the resist film.

Next, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
Synthesis Example 1 (Synthesis of dispersion resin)
32 g of tolylene diisocyanate trimer (Mittech GP750A manufactured by Mitsubishi Chemical Co., Ltd., resin solid content 50 wt%, butyl acetate solution) and 0.02 g of dibutyltin dilaurate as a catalyst were diluted with 47 g of PGMEA (propylene glycol monomethyl ether acetate). Dissolved. Under stirring, 14.4 g of polyethylene glycol having a methoxy group at one end and having a number average molecular weight of 1,000 (Niox M-1000, manufactured by NOF Corporation) and polypropylene glycol having a molecular weight of 1,000 (Sanyo Chemical Industries) 9.6 g of Sannicks PP-1000 (manufactured by Co., Ltd.) and the mixture were added dropwise, followed by further reaction at 70 ° C. for 3 hours. Next, 1 g of N, N-dimethylamino-1,3-propanediamine was added, and the mixture was further reacted at 40 ° C. for 1 hour.
The amine value of the solution containing the dispersion resin thus obtained was determined by neutralization titration to be 14 mg KOH / g. Further, when the resin content was determined by a dry-up method (at 150 ° C. for 30 minutes, the solvent was removed on a hot plate and the resin concentration was calculated from the amount of change in weight), the resin content was 40 wt%.

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

Examples 1-2 and Comparative Examples 1-2, 4-5
Manufacture of carbon black dispersion liquid 50% by weight of carbon black MA-220 (manufactured by Mitsubishi Chemical Corporation) and 5 parts by weight of dispersion resin shown in Table 1 (in terms of solid content) so that the solid content concentration becomes 50 wt%. PGMEA was added. The weight of the dispersion was 50 g. This was thoroughly stirred with a stirrer and premixed.
Next, the dispersion | distribution process of Table-1 was performed in 25-45 degreeC with the paint shaker. As beads, 0.5 mmφ zirconia beads were used, and the same weight as the dispersion was added.
After the completion of dispersion, the beads and the dispersion were separated by a filter.

Preparation of Black Resist Composition Each component was added using the carbon black dispersion described above so that the solid content would be the following blending ratio, and stirred and dissolved with a stirrer.

2) Evaluation of resist The viscosity of the black resist composition was measured under the conditions of 5 rpm and 50 rpm with an E-type viscometer (manufactured by Tokyo Seimitsu Co., Ltd.) at a constant temperature of 25 ° C. Next, the black resist composition was applied to a glass substrate (7059, manufactured by Corning) with a spin coater, and dried on a hot plate at 80 ° C. for 1 minute. The film thickness of the resist after drying was measured with a stylus type film thickness meter (α-step, manufactured by Tencor Corporation) and found to be 1 μm. The 20-degree glossiness of the resist film after drying was measured with a gloss meter (manufactured by Big Chemie). Further, the coating unevenness was evaluated by visual observation. The case where a uniform coating was obtained was marked with ◯, and the case where coating unevenness was observed was marked with x. Further, the optical density (OD) was measured with a Macbeth reflection densitometer TR927 (manufactured by Kolmorgun).

Next, this sample was image-exposed at 2,000 mj / cm ² with a high-pressure mercury lamp through a mask. The resist pattern was obtained by immersion development in an aqueous potassium hydroxide solution having a temperature of 25 ° C. and a concentration of 0.05% while changing the development time. The resist pattern that can be formed was observed with a microscope at a magnification of 200 times to determine the resolving power. The resolving power was rated to be 10 μm or less, and that exceeding 10 μ was rated as x. Further, the development latitude was evaluated based on the width of the development time when a resist pattern corresponding to a mask size of 20 μ was formed with a width of 20 ± 1 μ. In addition, the adhesion was evaluated by a cellophane (registered trademark) test (cellotape (registered trademark) was applied to the resist pattern and then peeled off). A case where the resist pattern was not peeled off was marked with ◯, and a case where the resist pattern was peeled off was marked with ×.
The results are shown in Table-1.

Synthesis Examples-3 to 12 (Synthesis of dispersion resin)
A dispersion resin was synthesized in the same manner as in Synthesis Example 1 except that the compounds shown in Table 2 were used.

Examples 5 to 19 and Comparative Example 3
Production of Carbon Black Dispersion PGMEA was added so that the solid concentration was 50 wt% at a ratio of 50 parts by weight of carbon black shown in Table 3 and 5 parts by weight of the dispersion resin (in terms of solid content). The weight of the dispersion was 50 g. This was thoroughly stirred with a stirrer and premixed.
Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 8 hours.
After the completion of dispersion, the beads and the dispersion were separated by a filter.

Measurement of Gloss of Carbon Black Dispersion In order to determine the quality of the dispersion of the above dispersion , the gloss was measured by the following method. The better the dispersion state, the smaller the particle size of the carbon black, so that irregular reflection is suppressed and a high gloss value is obtained. That is, a dispersion with higher gloss represents a better dispersion state.
The dispersion was applied onto a glass substrate with a spin coater and dried on a hot plate at 80 ° C. for 1 minute. This sample was measured for 20-degree specular gloss by a gloss meter (Hick Chemie). The results are shown in Table-3.

Preparation of Black Resist Composition Each component was added using the carbon black dispersion described above so that the solid content would be the following blending ratio, and stirred and dissolved with a stirrer.
1) Resist composition a) Binder resin (synthesized in Synthesis Example 2) 25 g
b) Acrylic monomer; Dipentaerythritol hexaacrylate
15g
c) Initiator (3 types in combination)
c-1: 2- (2-chlorophenyl) -4,5-diphenylimidazole
Dimer 2g
c-2: 4,4'-bis (diethylamino) benzophenone 1.0 g
c-3: 2-mercaptobenzothiazole 1 g
d) Pigment 50 g of carbon black described in Table 3
e) Polymer dispersing agent Table-3 5g
f) Solvent Propylene glycol monomethyl ether acetate 300g

2) Evaluation of resist The composition of the black resist composition was applied to a glass substrate (7059, manufactured by Corning) using a spin coater, and dried on a hot plate at 80 ° C. for 1 minute. The film thickness of the resist after drying was measured with a stylus type film thickness meter (α-step, manufactured by Tencor Corporation) and found to be 1 μm. Further, the 20-degree glossiness of the resist film after drying was measured with a gloss meter (manufactured by Big Chemie). Furthermore, the coating unevenness of the resist film thickness after drying was evaluated by visual observation. The case where a uniform coating was obtained was marked with ◯, and the case where coating unevenness was observed was marked with x. Further, the optical density (OD) was measured with a Macbeth reflection densitometer TR927 (manufactured by Kolmorgun).

Next, this sample was exposed to 2,000 mj / cm ² image with a high-pressure mercury lamp through a mask. A resist pattern was obtained by immersion development for 1 minute in an aqueous potassium hydroxide solution at a temperature of 25 ° C. and a concentration of 0.05%. The resist pattern that can be formed was observed with a microscope at a magnification of 200 times to determine the resolving power. A resolving power of 10 μm or less was evaluated as “Good”, and a value exceeding 10 μm was evaluated as “Poor”. In addition, the adhesion was evaluated by a cellophane (registered trademark) test (cellotape (registered trademark) was applied to the resist pattern and then peeled off). A case where the resist pattern was not peeled off was marked with ◯, and a case where the resist pattern was peeled off was marked with ×.
Further, the black resist composition was allowed to stand at room temperature for 1 day, and the same image formation was performed. Those that can form a resist pattern of 10 μm or less were designated as stability ○, and those that were not so were designated as ×. The results are shown in Table-3.

Specific surface area (m ² / g) pH
Asahi Thermal 24 8.8
MA-220 31 3.0
SP 250 40 3.1
SP 350 65 3.5
MA-11 104 3.5

Example 20 (Preparation of color filter)
In preparing the color filter, a color resist photosensitive solution for forming RGB pixels was prepared as follows.
<Manufacture of red, blue and green inks>
Red ink (diketopyrrolopyrrole PR-254) 20 g, yellow pigment (isoindoline yellow PY-139) 5 g, polymer dispersant BYK-161 (Pick Chemie) 5 g, and PGMEA 70 g are thoroughly stirred with a stirrer and premixed. Went.
Next, the dispersion process was performed in the range of 25-45 degreeC with the paint shaker for 6 hours. As beads, 0.5 mmφ zirconia beads were used and added in the same weight as the dispersion. After the completion of dispersion, the beads and the dispersion were separated by a filter.

Blue ink 25 g of a blue pigment (phthalocyanine blue PB-15; 3), 5 g of a polymer dispersant BYK-161 (Bic Chemie), and 70 g of PGMEA were thoroughly stirred with a stirrer and premixed. Subsequent processing was carried out in the same manner as the red ink.
Green ink Green pigment (phthalocyanine green PG-36) 20 g, yellow pigment (isoindoline yellow PY-139) 5 g, polymer dispersant BYK-161 (Bic Chemie) 5 g, PGMEA 70 g are thoroughly stirred with a stirrer and premixed. It was. Subsequent processing was carried out in the same manner as the red ink.

<Preparation of color resist solution>
Each color resist sensitizing solution was prepared using the color ink so as to have the following ratio.
a) Binder resin (Synthesis example-2) 25 g
b) 15 g of dipentaerythritol hexaacrylate
c) Initiator (3 types in combination)
c-1) 2- (2-Chlorophenyl) -4,5-diphenylimidazole
Dimer 2g
c-2) 4,4'-bis (diethylamino) benzophenone 1 g
c-3) 2-mercaptobenzothiazole 1 g
d) Additive Maleic anhydride 1g
FC-430 (Sumitomo 3M) 100ppm
e) 70 g of the above pigment ink (red, blue or green, each color)
f) 270 g of propylene glycol monomethyl ether acetate
The above components were stirred and homogenized with a stirrer and then filtered through a 0.5 μm Teflon (registered trademark) membrane filter.

<Production of color filter>
The black resist composition of Example-1 was applied to a glass substrate having a plate size of 300 × 400 mm and a plate thickness of 1.1 mm (7059 manufactured by Corning) with a spin coater. It was dried at 80 ° C. for 1 minute on a hot plate. The black resist dry film thickness under these conditions was 1.0 μm as measured by α step (manufactured by Tencor). The 20 ° glossiness was 138, and the optical density OD was 3.5.
Next, the black resist film was exposed at an exposure amount of 2000 mj / cm ² with an exposure apparatus having a high-pressure mercury lamp through a chromium mask on which a transparent grid pattern with a line width of 25 μm was formed. After spray development with a potassium hydroxide aqueous solution at a temperature of 25 ° C. and a concentration of 0.05% for 50 seconds, it was thoroughly rinsed with pure water.

Post baking was performed at 200 ° C. for 20 minutes in a convection oven. The 20-degree glossiness and optical density after post-baking were measured, and showed the same numerical values as those measured after pre-baking. Further, when the edge portion of the formed resin black matrix was observed with a 200 × optical microscope, it was found that the edge portion was very sharp and there were no defects such as pinholes.
A red resist was applied on the sample with a spin coater and dried on a hot plate at 80 ° C. for 1 minute. The film thickness of the red resist was 1.5 μm on the glass substrate without the resin BM.

Next, the red resist film was exposed at an exposure amount of 200 mj / cm ² with an exposure apparatus having a high-pressure mercury lamp through a chromium mask on which a transparent stripe pattern with a line width of 100 μm was formed. After spray development with a potassium hydroxide aqueous solution at a temperature of 25 ° C. and a concentration of 0.05% for 50 seconds, it was thoroughly rinsed with pure water.
Post baking was performed at 200 ° C. for 20 minutes in a convection oven. When the formed red pattern was observed with an optical microscope of 200 times, it was very sharp. Further, even when the red pattern was formed, the resin black matrix was completely peeled off, and damage such as surface roughness did not occur, and the 20 ° gloss value maintained the initial value.
The same operation was performed on the blue and green resists to form patterns. Even after the red, blue, and green color patterns were formed, the edge portion of the resin plaque matrix was observed with a 200 × optical microscope and found to be very sharp and free from defects such as pinholes. It was. The 20-degree gloss value also kept the initial value.

The color filter having the resin black matrix produced as described above has very good dimensional accuracy, pattern edge cuts, and no defects such as pinholes.
Therefore, a liquid crystal display device having good image quality can be manufactured by using this color filter.
In Example 20, it is possible to manufacture a liquid crystal display device with good image quality by using a black resist other than Example 1 and processing in the same manner to produce a color filter and using the color filter. is there.

The black resist composition for forming a black matrix according to the present invention is excellent in developability, resolution, adhesion, and coating property even when many pigments are dispersed. Can be stably formed, and can provide color filters for liquid crystal displays, etc. at high quality and low cost, and provide great industrial benefits, and the industrial applicability is extremely large. .

Claims (12)

It contains a black pigment, a photosensitive resin material, a pigment dispersant, and a solvent, and the 20-degree specular gloss of the dry coating film defined below is 100 to 200. The photosensitive resin material is a binder resin, photopolymerization It contains a monomer that cures by the action of an initiator and a photopolymerization initiator, the amine value of the pigment dispersant is 1 to 100 mgKOH / g, and the binder resin is a resin having a (meth) acryloyl group in the side chain A black resist composition for forming a black matrix.
A dry coating film having a thickness of 1 μm prepared by coating the black resist composition for forming a black matrix on a glass substrate with a spin coater and drying it on a hot plate at 80 ° C. for 1 minute.   The viscosity at 25 ° C is in the range of 2 to 20 mPs, and the viscosity ratio η5 / η50 measured at 5 rpm and 50 rpm, respectively, is in the range of 1 to 1.5. A black resist composition for forming a black matrix.   The pigment dispersant is a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule, and a compound having an active hydrogen and a tertiary amino group in the same molecule. The black resist composition for forming a black matrix according to claim 1, wherein the black resin composition is a dispersion resin obtained by this.   The resist composition for forming a black matrix according to claim 3, wherein the polyisocyanate compound is a trimer of an organic diisocyanate compound.   The black resist composition for forming a black matrix according to claim 3 or 4, wherein the compound having a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule is polyether glycol and / or polyester glycol.   The black matrix formation according to any one of claims 3 to 5, wherein the tertiary amino group of the compound having active hydrogen and a tertiary amino group has an alkyl group having 1 to 4 carbon atoms and / or a heterocyclic structure. Black resist composition.   The black resist composition for forming a black matrix according to any one of claims 3 to 6, wherein the weight average molecular weight in terms of polystyrene measured by GPC of the dispersion resin is 1,000 to 200,000.   The black resist composition for forming a black matrix according to any one of claims 1 to 7, wherein the black pigment is carbon black. The black resist composition for forming a black matrix according to claim 8, wherein the carbon black has a specific surface area of 110 m ² / g or less and a pH of 2 to 9.   The black resist composition for black matrix formation in any one of Claims 1-9 in which the said binder resin contains the acrylic resin which has a carboxyl group in at least 1 part of the structural unit.   The black resist composition for forming a black matrix according to claim 10, wherein the binder resin is a resin having a double bond in a side chain.   The black resist composition for a color filter according to claim 1, wherein the pigment concentration in the total solid content of the composition is 25 to 70%.