JP3230800B2 - Black radiation-sensitive resin composition, black cured film and black matrix - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a black radiation-sensitive resin composition, a high-resistance black cured film, and a black matrix for a color filter. More specifically, a multi-color display such as a color liquid crystal display device, a color facsimile, an image sensor, an ink as a black matrix for a color filter used in an optical device, etc., and a color filter having a black matrix formed by these And a television, a video monitor, a display, and the like.

[0002]

2. Description of the Related Art A purpose of a color filter used for a display material of a liquid crystal display device, an electronic display device, or the like is to block light between fine pixels colored in at least two kinds of hues to improve contrast. A black matrix is formed for the purpose of preventing a decrease in color purity.

Conventionally, for such a black matrix, a metal vapor-deposited film of Cr, Ni, Al or the like has been used on a glass substrate. Was a problem.

Therefore, various means for solving this problem have been studied. For example, JP-A-2-239204 describes that
A method has been proposed in which a light shielding agent such as carbon black is dispersed in a polyimide resin and a black matrix is formed using the light shielding agent. However, this method involves applying a composition to a glass substrate to form a film, further applying a photoresist on the film, and exposing, developing, etching, and removing the resist, thereby simplifying the process. However, it is not sufficient in terms of cost reduction.

Further, a composition in which a dye is directly added to a radiation-sensitive resin has been reported. Many of these materials use carbon black to enhance light-shielding properties. For example, JP-A-4-63870 discloses that a black matrix is formed by dispersing carbon black and an organic pigment in a photopolymerizable compound. A method has been proposed. According to this method, the composition is applied to a glass substrate, exposed,
A black matrix is formed only by the development process, which can greatly contribute to simplification of the process.

However, carbon black has a higher light-shielding property than other organic pigments, but has conductivity, and if a large amount of carbon black is added to the radiation-sensitive resin in order to enhance the light-shielding property, the formed black can be reduced. The matrix itself also has conductivity. Therefore, when a color filter is manufactured using these materials, the electric field is exposed through the liquid crystal drive electrode or through the black matrix, and as a result, the liquid crystal does not operate or malfunctions occur. There is a disadvantage that a thicker insulating film or an electric field blocking film needs to be formed.

Further, Japanese Patent Application Laid-Open No. 1-141963 proposes a coating composition using an oxide or oxynitride of titanium. This composition has a volume resistivity of 10 ⁵ Ω ·
cm or more, the composition containing titanium oxide or oxynitride does not exhibit ohmic behavior, and the higher the applied voltage, the lower its volume resistivity tends to be. The applied voltage of the measuring instrument is extremely low,
The voltage applied to a device such as a liquid crystal display device, that is, the volume resistivity at 1 to 30 V is lower than this, and has a drawback that in the worst case, dielectric breakdown may occur.

Further, a black matrix for a color filter is required to have high precision and high detail and to have a higher light-shielding property for improving contrast. However, when producing a black matrix for color filters due to black color, light due to exposure is blocked, photosensitivity is significantly reduced, and the adhesion of the pattern exposed portion to the substrate during development is reduced, so it is a practical color filter. There is a problem that a black matrix cannot be formed.

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a high light-shielding ratio, to easily form a fine pattern by photolithography, to cause a dielectric breakdown under a high applied voltage and a strong electric field. With high resistance without
An object of the present invention is to provide a black radiation-sensitive resin composition having excellent adhesion to a substrate during development. Another object of the present invention is to provide a high-resistance black cured film and a black matrix for a color filter formed using the black radiation-sensitive resin composition.

[0010]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have accomplished the present invention.

That is, the present invention provides: (a) a polymer compound (A), titanium black (B), a dispersing aid (C), a solvent (D), and at least one ethylenically unsaturated double bond. It contains a photopolymerizable compound (E), a radical photopolymerization initiator (F) and a tertiary amine compound (G), and the amount of the component (A) used is 15 to 100% by weight based on the component (B). Wherein the amount of the component (C) used is 0.5 to 10% by weight based on the component (B), the amount of the component (E) used is 40 to 100% by weight based on the component (A), The amount of the component (F) used is 50 to 12 with respect to the component (E).
0% by weight, and the amount of the component (G) used is 1
(B) a black radiation-sensitive resin composition according to (a), further comprising an organic pigment (H); and (c) an inorganic pigment (I). (A) further comprising:
(B) The black radiation-sensitive resin composition according to any one of (b), (d), using the black radiation-sensitive resin composition according to (a), (b) or (c), by photolithography. The formed black cured film has a volume resistivity (film thickness 1).
(E) (a), (b) or (c) using a black radiation-sensitive resin composition described in (e), (a), (b) or (c). (F) A display material or a display device having the black matrix for a color filter described in (e), characterized in that the black matrix is patterned into a black matrix for a color filter.

BEST MODE FOR CARRYING OUT THE INVENTION The black radiation-sensitive resin composition and the high-resistance black cured film of the present invention will be described in detail below.

As the polymer compound (A) used in the present invention, a compound which can disperse titanium black (B) well and has dispersion stability is desired. For such a purpose, a polymer compound having a carboxyl group or a group derived therefrom is particularly useful.

Specific examples of the polymer compound having a carboxyl group or a group derived therefrom include, for example, maleic acid, a partially esterified maleic anhydride, a partially amidated maleic anhydride, or a compound having a substituent. A polymer compound having a good (meth) acrylic acid or the like as a group (repeating unit) may be used.

The high molecular compound having maleic acid, a partially esterified product of maleic anhydride, a partially amidated maleic anhydride or the like as a repeating unit may be prepared by converting maleic acid, maleic anhydride or the like into styrene such as styrene or α-alkylstyrene. Or a copolymer compound is obtained by copolymerizing with a monomer of a derivative thereof (copolymerization ratio: 1
-5, preferably 1-3), methanol, ethanol,
A method of hydrolysis or partial esterification with an alcohol such as propanol, or an acrylate ester having an alcoholic hydroxy group such as 2-hydroxyethyl acrylate, pentaerythritol triacrylate, or polyethylene glycol monoacrylate, or aniline or benzyl. It can be obtained by amidating amines such as amines.

Specific examples of the polymer compound having maleic acid, partially esterified maleic anhydride, and partially amidated maleic anhydride as a repeating unit used in the present invention are shown below.

[0016]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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Here, p indicates the number of repetitions, and the numerical value indicates that 2 to 9 units in parentheses are repeated. In addition, this invention is not limited only to these compounds.

The polymer compound containing (meth) acrylic acid as a repeating unit includes, for example, a homopolymer of (meth) acrylic acid, ethylene, vinyl acetate, styrene,
It can be obtained by copolymerizing monomers such as acrylonitrile and (meth) acrylic acid ester with (meth) acrylic acid. Specific examples of such a polymer compound will be described below. In addition, this invention is not limited only to these compounds.

[0027]

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[0028]

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[0030]

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[0031]

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[0032]

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The weight average molecular weight (M) of the component (A)
w) is from 2,000 to 200,000, preferably 5,
000-150,000, and even 8,000-8
It is 0000. When the weight average molecular weight is less than 2,000, dispersion stability is lacking, and there is a possibility that titanium black may aggregate with the standing time. When the weight average molecular weight exceeds 200,000, the dispersion stability is increased, but the viscosity of the dispersion becomes extremely high, which is not suitable for obtaining a black radiation-sensitive resin composition.

The amount of the component (A) used is 15 to 100% by weight based on the component (B). When the amount is less than 15% by weight, the dispersion stability is poor, and when it exceeds 100% by weight, the content of titanium black is low, and the black radiation-sensitive resin composition and the black cured film having sufficient light-shielding properties are provided. Not suitable to get

Titanium black (B) used in the present invention
Means low-order titanium oxide, titanium oxynitride, or the like. Among them, the lower titanium oxide is described, for example, in JP-A-49-5432 (JP-B-52-12733).
Titanium and metallic titanium dioxide powder in vacuum or a reducing atmosphere, or a compound of blackish represented by Ti _n O _2n-1 obtained by heating at a temperature of 550 to 1,100 ° C. (n is a positive integer), JP Japanese Patent Application Laid-Open No. 64-15772 discloses a method in which hydrated titanium dioxide and metal titanium powder are heated in an inert atmosphere in the presence of a sintering treatment aid comprising a compound containing silicon, aluminum, niobium, tungsten, and the like. Compounds. Examples of titanium oxynitride include, for example, JP-A-60-65069 (JP-B-3-51).
No. 645) or JP-A-60-200827 (Japanese Patent Publication No. 42773/1990).
Black compounds obtained by reduction at a temperature of about 950 ° C. In addition, JP-A-61-201610
No. (JP-B-3-29010).
A black compound obtained by attaching vanadium to titanium dioxide or the like and reducing it at 750 to 875 ° C. in the presence of ammonia is also included. The volume resistivity of these titanium black is preferably 10 ⁰ ~10 ⁵ Ω · cm. As the titanium black (B) used in the black radiation-sensitive resin composition of the present invention, the primary particles have a particle diameter of 0.1 to provide a resistivity and further obtain a high light-shielding property and a uniform coating film.
Those having a specific surface area of 5 to 40 m < ² > / g are preferable. When the particle size is less than 0.01 μm and the specific surface area exceeds 40 m ² / g, not only the necessary and sufficient light-shielding property cannot be obtained, but also the dispersibility becomes low, and conversely, the particle size exceeds 1 μm and the specific surface area becomes large. If it is less than 5 m ² / g, not only the surface glossiness is impaired, but also the resistivity cannot be given.

The black radiation-sensitive resin composition of the present invention contains a dispersing aid (C). The component (C) has a function of preventing aggregation of titanium black, electrically and chemically adsorbing to the surface of the titanium black particles and the photosensitive resin, and further increasing the dispersion stability.

Examples of the component (C) include anionic pigment dispersants such as polycarboxylic acid type polymer activators and polysulfonic acid type polymer activators, and nonionic pigment dispersants such as polyoxyethylene and polyoxylene block polymers. Pigment dispersants such as dispersants, anthraquinones, phthalocyanines, quinacridones, azochelates, azos, isoindolinones, pyranthrones, indanthrones, anthrapyrimidines, dibromoanzanthrones, flavanthrones, Organic pigments such as perylene, perinone, quinophthalone, thioindigo, and dioxazine are used as a base, and preferably 1 to 3 substituents such as a hydroxyl group, a carboxyl group, a sulfonic acid group, a carboxamide group, and a sulfonamide group are introduced. And the like of organic pigment derivatives.
The amount of the component (C) used is 0.5 to 10% by weight based on the component (B). Disperse titanium black,
Preferred components (C) for stabilization are as follows. In addition, it is not limited only to these compounds.

[0038]

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[0040]

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[0041]

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[0042]

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[0043]

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[0045]

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[0046]

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[0047]

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The solvent (D) used for obtaining the black radiation-sensitive resin composition of the present invention is not particularly limited.
For example, ketones, alcohols, aromatics and the like can be mentioned. Specifically, benzene, toluene, benzene solvents such as xylene, cellosolves such as methyl cellosolve, ethyl cellosolve, butyl cellosolve, cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate,
Propylene glycol monomethyl ether acetate,
Propylene glycol monoethyl ether acetate,
Propylene glycol monoalkyl ether acetates such as propylene glycol monobutyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, propionates such as methyl ethoxypropionate and ethyl ethoxypropionate, methyl lactate, ethyl lactate and butyl lactate Lactic acid esters such as
Diethylene glycols such as diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; acetates such as methyl acetate, ethyl acetate, butyl acetate and amyl acetate; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dioxane; acetone, methyl ethyl ketone and methyl butyl ketone And ketones such as cyclohexanone. These may be used alone or in combination of two or more.
The component (D) is added so that the solid content of the black radiation-sensitive resin composition is in the range of 5 to 50% by weight, preferably 20 to 35% by weight.

Photopolymerizable compound (E) having at least one ethylenically unsaturated double bond used in the present invention
Examples thereof include photocrosslinkable or photopolymerizable monomers, oligomers, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, ethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipenta as a prepolymer. Esters of acrylic acid or methacrylic acid of monohydric or polyhydric alcohol such as erythritol hexaacrylate, dipentaerythritol hexamethacrylate, and polyester prepolymer obtained by condensing polyhydric alcohol with monobasic acid or polybasic acid (meth) ) Polyester (meth) acrylate obtained by reacting acrylic acid, after reacting a compound having a polyol group and two isocyanate groups (meth) Polyurethane (meth) acrylate, bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, novolak type epoxy resin, polycarboxylic acid glycidyl ester, polyol glycidyl ester, obtained by reacting crylic acid, Aliphatic or cycloaliphatic epoxy resin,
Photopolymerizable compounds such as epoxy (meth) acrylate obtained by reacting (meth) acrylic acid with an epoxy resin such as an amine epoxy resin, a triphenolmethane type epoxy resin, and a dihydroxybenzene type epoxy resin. These components (E) are used alone or in combination of two or more. The amount of these (E) components used is
It is 40 to 100% by weight based on the component (A).

The photopolymerization initiator (F) used in the black radiation-sensitive resin composition of the present invention includes acetophenone,
2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p
Acetophenones such as tert-butyl acetophenone, benzophenones such as benzophenone and 2-chlorobenzophenone, benzoin ethers such as benzyl, benzoin, benzoin methyl ether, benzoin butyl ether and benzoin propyl ether, benzyl dimethyl ketal, thioxanthone and 2-chlorobenzene Sulfur compounds such as thioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone and 2-isopropylthioxanthone; 2-ethylanthraquinone;
Anthraquinones such as benzanthraquinone, 2,3-diphenylanthraquinone, organic peroxides such as azobisisobutylnitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole,
Thiol compounds such as 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, and 2,2′-bis ( And biimidazole compounds such as 2-chlorophenyl) -4,4 ', 5,5'-tetra- (4-methoxyphenyl) bisimidazole. These components (F) can be used alone or in combination of two or more. In particular, g-line (436 nm) and h-line (405 n) of ultraviolet rays emitted from an ultra-high pressure mercury lamp generally used as an exposure light source
In order to have sensitivity to m) and i-line (365 nm), it is preferable to use two or more kinds in combination. A suitable amount of the component (F) is 50 to 120% by weight based on the component (E).

When a black cured film is produced, the light transmittance in the ultraviolet region required for photocuring is significantly reduced, so that it does not act as a photopolymerization initiator by itself. Thus, a tertiary amine compound (G) is added in order to increase the ability of the photopolymerization initiator and increase the photocurability and adhesion. As the component (G), for example, triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate,
Isoamyl 4-dimethylaminobenzoate, benzoic acid (2
-Dimethylamino) ethyl, (n-butoxy) ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone and the like. As the amount of the component (G), (F)
1 to 10% by weight of the components is suitable.

In the present invention, for example, an organic content (H) and an inorganic pigment (I) can be used as needed for the purpose of improving optical characteristics. Examples of the organic pigment (H) that can be used in the present invention include anthraquinone, phthalocyanine, benzimidazolone, quinacridone, azochelate, azo, isoindolinone, pyranthrone, indanthrone, and anthrapyrimidine. And dibromoanzanthrone-based, flavanthrone-based, perylene-based, perinone-based, quinophthalone-based, thioindigo-based, and dioxazine-based pigments. For details, those described in the organic pigment section of the Coloring Material Engineering Handbook (edited by the Coloring Material Association) can be used, but are not limited thereto. Further, if necessary, they can be used alone or in combination of two or more.

The inorganic pigment (I) which can be used in the present invention includes barium sulfate, zinc white, lead sulfate, titanium oxide, yellow lead, red iron oxide, ultramarine blue, navy blue, chromium oxide,
Metal oxides such as antimony white, iron black, lead red, zinc sulfide, cadmium yellow, cadmium red, zinc, manganese purple, cobalt purple, barium sulfate, magnesium carbonate,
Metal sulfide, sulfate, metal hydroxide, metal carbonate and the like can be mentioned. Further, conventionally known carbon-based inorganic pigments such as carbon black can be used to the extent that the resistivity is not impaired. For details, those described in the inorganic pigment section of the Coloring Material Engineering Handbook (edited by the Coloring Material Association) can be used, but are not limited thereto. Further, if necessary, they can be used alone or in combination of two or more.

The proportion of each pigment used in the present invention depends on the solid content (other than the organic solvent) of the black radiation-sensitive resin composition.
Based on the amount, the proportion of organic or inorganic pigments is used up to 60% by weight, preferably up to 50% by weight, and the total pigment proportion is from 20 to 80% by weight, preferably from 30 to 7%.
It can be used at 5% by weight. When the total pigment ratio is less than 20% by weight, the light-shielding property is not sufficient, and when it exceeds 80% by weight, there is a possibility that the sensitivity may decrease and patterning may not be performed.

The black radiation-sensitive resin composition of the present invention is usually prepared by first dispersing the components (A), (B), (C) and (D) using a disperser such as a ball mill, a sand mill or a dissolver. (E), dispersed in the obtained black pigment composition,
It is prepared by adding the components (F) and (G) and, if necessary, the components (H) and (I) and performing a dispersion treatment using a dispersing machine such as a ball mill, a sand mill or a dissolver. The order of preparation is not limited to this. Further, if necessary, a redispersion treatment such as a high-pressure dispersion treatment is performed, or filtration is performed to remove contaminants before use. Also, if necessary, a silane coupling agent or a titanate coupling agent for improving the adhesion to the substrate, a fluorine-based, silicon-based, hydrocarbon-based surfactant for improving the smoothness of the film, and ultraviolet rays Various additives such as an absorbent and an antioxidant can be used.

The formation of a black cured film from the black radiation-sensitive resin composition of the present invention is usually carried out as follows. That is, the black radiation-sensitive resin composition obtained by the above method is applied on a substrate such as a glass substrate by a method such as spin coating, roll coating, printing, or bar coating to have a film thickness of usually 0%. It is applied so as to have a thickness of 0.5 to 5 μm, and is soft-baked to form a film. Next, the entire surface is irradiated with radiation (for example, an electron beam or ultraviolet light, preferably ultraviolet light), and a treatment such as post baking is performed to obtain a black cured film. The obtained black cured film has a volume resistance value of 10 ⁷ Ω · cm or more, has sufficient insulation properties, and has high light-shielding properties and high adhesion to substrates. Also,
When forming a pattern, after soft baking, a mask of a predetermined shape such as a dot pattern or a stripe pattern is brought into close contact with the mask, and the pattern is exposed by irradiating radiation through the mask, followed by processing such as development and post baking. Can be obtained. At that time, by adding the tertiary amine compound (G), the adhesion to the substrate is increased as compared with the black radiation-sensitive resin composition not containing this component, the development margin is increased, and a practical black matrix for a color filter is used. Could be formed.

The above-mentioned black radiation-sensitive resin composition can be used as a coating material, and the cured black film has a high resistivity, excellent light-shielding properties, excellent adhesion to a substrate, and especially a liquid crystal. A high-precision and high-detail black matrix used for a display material such as a display device or an electronic display device can be easily manufactured.

[0058]

EXAMPLES The present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Reference Example (Preparation of Black Pigment Composition) As the component (A), a polymer compound of 1-2 7.96
g, as component (B), 19.90 g of titanium black 13M (titanium oxynitride manufactured by Mitsubishi Materials) (primary particle diameter 0.2 μm, specific surface area 13 m ² / g), and as component (C), 2-1 dispersion aid 0.5 g of the component (D)
Propylene glycol monomethyl ether acetate
In addition to 71.64 g, the mixture was dispersed with a sand mill to obtain a black pigment composition. The viscosity of this dispersed black pigment composition was measured with a B-type viscometer (at a temperature of 25 ° C.), and the thixotropy was low and very good. Also, apply the obtained black pigment composition on a glass substrate,
When the film was formed and observed with a microscope, no aggregation was observed, and the film was glossy and uniform.

Example 1 (Preparation of Black Radiation-Sensitive Resin Composition) 88.17 g of the black pigment composition obtained in Reference Example,
2.90 g of DPHA (multifunctional acrylate resin manufactured by Nippon Kayaku) as a component (E), 1.74 g of Irgacure 369 (acetophenone-based polymerization initiator manufactured by Ciba-Geigy) as a component (F), DETX-S (Nippon Kayaku) 0.87 g, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole (manufactured by Kurokin Kasei) 0.87 g
g, 2-mercaptobenzothiazole (Kawaguchi Chemical)
0.87 g and 0.22 g of 4,4′-diethylaminobenzophenone (manufactured by Hodogaya Chemical) as a component (G) are added, well mixed and dispersed, and filtered under pressure to obtain a black radiation-sensitive resin composition of the present invention. Obtained.

Example 2 (Preparation of Black Radiation-Sensitive Resin Composition) 88.17 g of the black pigment composition obtained in Reference Example,
2.90 g of DPHA (multifunctional acrylate resin manufactured by Nippon Kayaku) as a component (E), 1.74 g of Irgacure 369 (acetophenone-based polymerization initiator manufactured by Ciba-Geigy) as a component (F), DETX-S (Nippon Kayaku) 0.87 g, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole (manufactured by Kurokin Kasei) 0.87 g
g, 2-mercaptobenzothiazole (Kawaguchi Chemical)
0.84 g and 0.44 g of 4,4′-diethylaminobenzophenone (manufactured by Hodogaya Chemical Co., Ltd.) are added as the component (G), mixed and dispersed well, and filtered under pressure to obtain the black radiation-sensitive resin composition of the present invention. Obtained.

Example 3 (Preparation of Black Radiation-Sensitive Resin Composition) 88.17 g of the black pigment composition obtained in Reference Example,
2.90 g of DPHA (multifunctional acrylate resin manufactured by Nippon Kayaku) as a component (E), 1.74 g of Irgacure 369 (acetophenone-based polymerization initiator manufactured by Ciba-Geigy) as a component (F), DETX-S (Nippon Kayaku) 0.87 g, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole (manufactured by Kurokin Kasei) 0.87 g
g, 2-mercaptobenzothiazole (Kawaguchi Chemical)
0.87 g, and as a component (G), 0.87 g of 4,4′-diethylaminobenzophenone (manufactured by Hodogaya Chemical Co., Ltd.) was added, mixed and dispersed well, and filtered under pressure to obtain a black radiation-sensitive resin composition of the present invention. Obtained.

Example 4 (Preparation of a cured black film) The black radiation-sensitive resin composition obtained in Example 1 was used in an amount of 2%
RBS-25 (trade name Chemical Products Co., Ltd., weak alkaline detergent) ultrasonic cleaning for 10 minutes with an aqueous solution, pure water cleaning, spin coating on a glass substrate dehydrated and baked on a hot plate at 200 ° C. for 10 minutes, and spin coating at 50 ° C. Was prebaked in a circulating oven for 1 minute, and then softbaked on a hot plate having a surface temperature of 100 ° C. for 150 seconds. Next, using a 500 W ultra-high pressure mercury lamp, 200 m
Irradiation with energy of J / cm ² was performed. Thereafter, post-baking was performed on a hot plate having a surface temperature of 200 ° C. to obtain a black cured film of the present invention. Next, this glass substrate was set in an electronic spectrum measuring apparatus, and the Y value at 380 to 780 nm was measured. At this time, Y = 0.01, and the film thickness at that time was 1.1 μm. The optical density (OD) was calculated by the following equation, which was 3.0, indicating a sufficient light-shielding property.

[0064]

OD = log (100 / Y)

Example 5 (Preparation of a cured black film) A black cured film of the present invention was obtained in the same manner as in Example 4, except that the glass substrate was a chromium-deposited substrate. Next, a circular electrode having an area of 0.28 cm ² (S) was formed from a silver paste on the black cured film, and a constant voltage generator (Kenwood PA) was formed between this electrode and the chromium-deposited surface as the counter electrode.
36-2A regulated DC power supply)
, A constant voltage (V) was applied, and the current (A) flowing through the film was measured with an ammeter (R644C digital multimeter manufactured by Advantest). Next, the thickness (d) cm of the black film was measured, and the resistivity was calculated by the following equation. As a result, even at an applied voltage of 10 V, the resistivity was on the order of 10 ⁷ Ω · cm, showing an extremely high resistivity.

[0066]

## EQU2 ## Volume resistance (Ω · cm) = (V · S) / (A · d)

Example 6 (Formation of Pattern) The high-resistance black radiation-sensitive resin composition obtained in Examples 1, 2 and 3 was replaced with 2% RBS-25 (trade name: a weak alkaline detergent manufactured by Chemical Products). After ultrasonic cleaning with an aqueous solution for 10 minutes and pure water cleaning, place on a hot plate at 200 ° C for 1 minute.
Spin coating on a glass substrate dehydrated and baked for 0 minutes, 50
After pre-soft baking for 1 minute in a circulating oven at a temperature of 100 ° C., soft baking was performed for 150 seconds on a hot plate having a surface temperature of 100 ° C. Next, using a 500 W ultra-high pressure mercury lamp, irradiation was performed at an energy of 200 mJ / cm ² through a mask on which a black matrix pattern was drawn.
Thereafter, 0.19% tetramethylammonium hydroxide, 0.19% emulgen A-60 (trade name)
Flow rate using a developer having a liquid temperature of 25 ° C.)
Shower development was performed for 50 seconds at 500 ml / min and a discharge pressure of 1 kg / cm ² . After washing with water and post-baking on a hot plate having a surface temperature of 200 ° C., the transfer pattern was observed with a microscope. As a result, a 10 μm pattern without any residue was resolved. Further, R, G, and B pixels were formed in a pattern on a glass substrate on which a black matrix pattern had been formed, to create a color filter.

[0068]

The black radiation-sensitive resin composition of the present invention comprises:
By including the tertiary amine compound (G), the adhesion to the substrate is increased, the development margin is increased, and an excellent black matrix for a color filter is formed, as compared with a black radiation-sensitive resin composition containing no this component. can do. Further, a high-definition black matrix pattern having sufficient light-shielding properties and high resistivity and used for a display material of a liquid crystal display device, an electronic display device or the like can be easily manufactured. Further, when the color filter having the black matrix pattern is used for a liquid crystal display device, the liquid crystal operates stably without conducting to the liquid crystal driving electrode or applying an electric field through the black matrix.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C09D 5/00 C09D 5/00 C G02B 5/20 101 G02B 5/20 101 G03F 7/027 G03F 7/027 // C08F 2 / 50 C08F 2/50 (56) References JP-A-5-61196 (JP, A) JP-A-4-340965 (JP, A) JP-A-8-82928 (JP, A) (58) Fields studied Int.Cl. ⁷ , DB name) G03F 7/004 C07D 233/54 C08L 35/00 C08L 101/00 C09D 4/06 C09D 5/00 G02B 5/20 101 G03F 7/027 C08F 2/50

Claims (6)

(57) [Claims] 1. A polymer compound (A), titanium black (B), a dispersing aid (C), a solvent (D), a photopolymerizable compound (E) having at least one ethylenically unsaturated double bond. A radical photopolymerization initiator (F) and a tertiary amine compound (G), the amount of the component (A) used is 15 to 100% by weight based on the component (B), and the component (C) Is used in an amount of 0.5 to 10% by weight based on the component (B), and the used amount of the component (E) is 40 to 10% by weight based on the component (A).
0% by weight, the amount of component (F) used is 50 to 120% by weight with respect to component (E), and the amount of component (G) used is 1 to 10% by weight with respect to component (F). Black radiation-sensitive resin composition characterized by the following 2. The method according to claim 1, further comprising an organic pigment (H).
Black radiation-sensitive resin composition described in 3. The black radiation-sensitive resin composition according to claim 1, further comprising an inorganic pigment (I). 4. A black cured film formed by a photolithography method using the black radiation-sensitive resin composition according to claim 1, wherein the volume resistivity is
Black cured film characterized in that the thickness of the cured black film is 10 ⁷ Ω · cm or more. 5. A black matrix for a color filter, wherein the black radiation-sensitive resin composition according to claim 1, 2 or 3 is patterned into a black matrix for a color filter. 6. A display material or display device having the black matrix for a color filter according to claim 5.