JPH1046042A - Pigment composition, and highly resistant and radio active ray-sensitive black resin composition by using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a pigment composition excellent in dispersing stability, adhesion to a base plate, etc., and capable of readily imparting a highly minute black matrix pattern by dispersing a titan black with each a specific phthalocyanine compound and polymer. SOLUTION: This pigment composition is obtained by dispersing (A) a titan black with both (B) a phthalocyanine having a sulfonic group and/or a sulfonamide group, or a naphthalocyanine compound (e.g. a compound of formula I) and (C) a polymer having a monomer unit of the formulas CH2 -C(R5 ) (COOH) and/or CH(COOH)-CH(COR6 ) (R5 is H, methyl, etc.; R6 is an alkoxy or amino), e.g. a polymer of formula II. The component C is obtained, e.g. by polymerizing (meth)acrylic acid, etc., with styrene, etc. The component B of 1-10wt.% and the component C of 15-100wt.% based on component A is preferably used. A particle diameter of primary particle of component A is preferably 0.01-1μm and the specific surface area of a pigment is preferably 5-40m<2> /g.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pigment composition and a high-resistance black radiation-sensitive resin composition using the same, particularly to a black matrix used for a display material of a liquid crystal display device, an electronic display device and the like. The present invention relates to a resin composition.

[0002]

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

Conventionally, such a black matrix is usually formed by depositing a metal thin film of Cr, Ni, Al or the like on a glass substrate by vapor deposition, sputtering, vacuum film forming, or the like, and applying a photoresist on the metal thin film. After irradiating ultraviolet rays through a photomask with a desired pattern, development processing is performed to obtain a resist pattern, and the metal thin film portion other than the resist portion is removed using a means such as etching, and finally the resist is peeled. I was getting it. However, since these steps are complicated, there is a disadvantage that the production cost is high and the cost of a color filter using the same is also high. Further, there is a problem that the cost is further increased due to the necessity of equipment for removing the metal removed by etching or the like.

[0004] On the other hand, various methods for improving the problem of the black matrix using the metal thin film as described above have been studied. For example, JP-A-2-239204 discloses that a light-shielding agent such as carbon black is dispersed in a polyimide resin,
A method of forming a black matrix by using this has been proposed. 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 color filter is electrically connected to the liquid crystal drive electrode, and as a result, a problem such as inoperability of the liquid crystal or malfunction occurs, so that an insulating film is further formed. There is a disadvantage that it is necessary to do.

On the other hand, when a paint, ink, or other coating composition containing a pigment dispersion is required to have a clear color tone, gloss, high tinting strength, or transparency, it is used to obtain these properties. It is necessary to use a pigment having a small primary or secondary particle size. However, when these pigments are dispersed in a non-aqueous vehicle, it is difficult to obtain a stable dispersion, and the following problems occur very frequently.

For example, when the above-mentioned pigment is dispersed, the viscosity of the dispersion often becomes very high, making it difficult to remove the pigment from the dispersing machine or increasing the pigment concentration in the dispersion. And it was difficult to improve the productivity. In addition, the fluidity of this dispersion exhibits strong non-Newtonian properties, and the viscosity immediately after production significantly changes during storage, and further, gelation often occurs. In addition, the cohesiveness of the dispersion is strong, and when a single pigment is dispersed, further, aggregation during storage when the pigment is compounded and dispersed is likely to occur, and many problems such as sedimentation and color separation occur. .

To solve these problems, many proposals have been made mainly on phthalocyanine pigments. For example, Japanese Patent Publication No. 41-2466 and Japanese Patent Publication No. 50-40
Organic dyes such as sulfonic acid derivatives of pigments found in JP-A No. 19, aminomethyl derivatives of pigments found in JP-B-38-2713 and JP-B-39-16787, and other sulfamoyl derivatives and phthalimidomethyl derivatives. Various pigment derivatives used as bases are organic pigments and / or
Alternatively, a method has been proposed in which carbon black is used together when dispersed. However, these methods, although effective in improving non-agglomeration, have other flow characteristics,
It is not satisfactory in terms of transparency and dispersion stability.

Further, there is no description in which the above-mentioned dispersant and / or dispersing aid mainly composed of a phthalocyanine pigment derivative is applied to titanium black which is advantageous for forming a high-resistance black film.

[0011]

Therefore, a pigment composition having excellent dispersion stability, insulating properties, and excellent adhesion to a substrate, a high-resistance black radiation-sensitive resin composition, a black cured film,
And the development of the black image forming method is demanded.

[0012]

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, titanium black, phthalocyanine or naphthalocyanine compound having a sulfonic acid group and / or sulfonic acid amide groups of formula _{-CH 2 -C (R 5) (} COOH) - and / or -C
H (COOH) —CH (COR ₆ ) — (wherein R ₅ and R ₆
Is a pigment composition obtained by dispersing with a polymer having a monomer unit represented by the following formula (1):

[0013]

Embedded image (In the formula (1), a represents 0 or 1, PcMa represents a metal-free phthalocyanine when a is 0, represents a metal phthalocyanine nucleus when a is 1, M represents a metal atom,
l and m are integers and 1 ≦ l + m ≦ 4, and R ₁ is

[0014]

Embedded image Or

[0015]

Embedded image Is shown. (In the formula (2), A represents an oxygen atom, and n is
0 or 1, when n = 0, y = 0, and x is 1 ≦
x represents an integer of 3 or less, and when n = 1, x and y are 1 ≦
x, y represents an integer of 3 or less. R ₂ and R ₃ represent a hydrogen atom or a C _{1 to} C ₁₂ optionally substituted alkyl group;
R ₂ and R ₃ do not simultaneously become hydrogen atoms. Equation (3)
In the formula, z represents an integer of 1 ≦ z ≦ 3, B represents a hydrogen atom or an oxygen atom, and R ₄ represents a hydrogen atom or a C _{1 to} C ₄ optionally substituted alkyl group. )) And a compound of formula (4)

[0016]

Embedded image (In the formula (4), R ₅ represents a hydrogen atom, a halogen atom, or a methyl group.) And / or the formula (5)

[0017]

Embedded image (In the formula (5), R ₆ represents an optionally substituted alkoxy group or an optionally substituted amino group.) And is dispersed by a polymer having a monomer unit. , Pigment composition

(B) The primary particles of titanium black have a particle size of 0.01 to 1 μm and a pigment has a specific surface area of 5 to 4 μm.
A 0m ² / g (a) a pigment composition according

(C) A radiation-sensitive resin containing a compound and / or a resin capable of causing a cross-linking reaction upon irradiation with radiation and optionally other resins, a photopolymerization initiator and a pigment composition described in (a). High resistance black radiation-sensitive resin composition characterized by the following:

(D) A radiation-sensitive resin, a photopolymerization initiator, an organic pigment and a pigment composition described in (a) containing a compound and / or a resin capable of causing a crosslinking reaction by irradiation with radiation and optionally other resins. High resistance black radiation-sensitive resin composition characterized by containing

(E) a radiation-sensitive resin containing a compound and / or a resin capable of causing a cross-linking reaction upon irradiation with radiation and optionally other resins, a photopolymerization initiator, the pigment composition described in (a), carbon black and High-resistance black radiation-sensitive resin composition comprising an organic pigment (f) The solid content in the high-resistance black radiation-sensitive resin composition is 1
When the amount is 00 parts by weight, the ratio of titanium black is 1 to 7
0 parts by weight, the proportion of carbon black is 10 parts by weight or less,
The high-resistance black radiation-sensitive resin composition according to any one of (c) to (e), wherein the proportion of the organic pigment is 60 parts by weight or less, and the total pigment proportion is 30 to 80 parts by weight. (c) a black cured film obtained by using the high-resistance black radiation-sensitive resin composition of any of (c) to (f); (h) having a volume resistance of 10 ⁵ Ω · cm or more;
(I) using the high-resistance black radiation-sensitive resin composition according to any one of (c) to (f) to form a black film by a photolithography method; An object of the present invention is to provide an image forming method.

[0022]

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

The phthalocyanine nucleus represented by the formula (1) used in the present invention includes:

[0024]

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[0025]

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[0026]

Embedded image

[0027]

Embedded image

[0028]

Embedded image And the like. In the formula (1), examples of the metal atom M include atoms such as Cu, Zn, Ni, Fe, T, and Sn, but are not limited thereto. In some cases, M is a ligand other than phthalocyanine. May be provided.

The group of the formula (2) used in the present invention includes:

[0030]

Embedded image And the like.

The group of the formula (3) used in the present invention includes:

[0032]

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[0033]

Embedded image

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image And the like.

The compound of the formula (1) obtained from the above compound group includes

[0040]

Embedded image

[0041]

Embedded image

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

Embedded image

[0047]

Embedded image

[0048]

Embedded image

[0049]

Embedded image

And the like. Examples of the polymer having a monomer unit of the formula (4) used in the present invention include:

[0051]

Embedded image

[0052]

Embedded image

[0053]

Embedded image

[0054]

Embedded image

[0055]

Embedded image

[0056]

Embedded image

And the like. Here, Mn indicates the number average molecular weight in terms of polystyrene, and the value outside the parentheses indicates the ratio occupied by each monomer unit when the whole is 100 mol% (the same applies hereinafter).

These compounds are known compounds and can be copolymerized with monomers such as (meth) acrylic acid and α-halogenoacrylic acid, for example, styrene,
Radical polymerization or in combination with monomers such as (meth) acrylates, (meth) acrylamide, (meth) acrylonitrile, vinyl acetate, vinylphenol, vinylbenzoic acid, vinylbutyral, chloroprene, vinyl chloride, vinylpyrrolidone, etc. It can be obtained by polymerizing by an ionic polymerization method or the like.

Examples of the polymer having a monomer unit of the formula (5) used in the present invention include:

[0060]

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[0061]

Embedded image

[0062]

Embedded image

[0063]

Embedded image

[0064]

Embedded image

[0065]

Embedded image

[0066]

Embedded image

[0067]

Embedded image

And the like. Here, p indicates the number of repetitions, and the numerical value indicates that 2 to 9 units in parentheses are repeated.

These compounds are known compounds and are prepared by reacting maleic anhydride with a copolymerizable monomer such as styrene or α-methylstyrene by a radical polymerization method to obtain (α-methyl) styrene-maleic anhydride. After obtaining the copolymer, methanol, ethanol, alcohols such as propanol, 2-hydroxyethyl acrylate,
A method of half-esterification with a polyol acrylate having an alcoholic hydroxy group remaining, such as pentaerythritol triacrylate and polyethylene glycol monoacrylate, and an amidation of amines such as aniline and benzylamine can be obtained. The number average molecular weight (Mn) of the polymer having the monomer units represented by the formulas (4) and (5) of the present invention is 2,000.
~ 50,000, preferably 3,000 ~ 30,000
When the number average molecular weight is less than 2,000, the dispersion stability is lowered and the sensitivity is also lowered. When the number average molecular weight is more than 50,000, the dispersion stability is improved. There is a risk that it will be lower. Also,
The content of the monomer unit represented by the formula (5) in each polymer is 2 to 70 mol%, preferably 5 to 70 mol%.
６０60 mol%, and when this amount is less than 2 mol%,
Dispersion stability is low. Conversely, if it exceeds 70 mol%, dispersion stability increases, but the solubility of the developer becomes unnecessarily large, and there is a risk that patterning becomes difficult.

In the pigment composition of the present invention, the amount of the compound represented by the formula (1) is
It is 0.5 to 15% by weight, preferably 1 to 10% by weight, and the amount of the polymer having the monomer unit represented by the formula (4) and / or the formula (5) is 10 to 10% with respect to titanium black. It is 150% by weight, preferably 15 to 100% by weight.

The method for dispersing titanium black with a polymer having monomer units represented by the formulas (1), (4) and / or (5) to obtain the pigment composition of the present invention is as follows. Method. That is, titanium black, a compound represented by the formula (1), a compound represented by the formula (4) and / or
Alternatively, after a polymer having a monomer unit represented by the formula (5) is suspended or dissolved in an organic solvent, the polymer is dispersed for a predetermined time using a disperser such as a ball mill, a sand mill, or a dissolver.

As described above, when the compound of the present invention is used for dispersing titanium black, gravure ink such as rosin varnish, polyamide resin varnish, vinyl chloride resin varnish, nitrocellulose lacquer, amino alkyd resin paint, acrylic lacquer, amino acrylic resin In non-aqueous vehicles such as urethane resin paints, the dispersion viscosity, structure viscosity, color separation, sedimentation prevention, aggregation stability, dispersion stability, etc. are lower than when titanium black is used alone. A remarkable effect can be obtained with respect to the adhesion of the film applied to the substrate surface.

Compounds and / or resins capable of causing a crosslinking reaction upon irradiation with radiation used in the present invention include bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-S type epoxy resin, novolak type epoxy resin, Obtained by reacting epoxy group such as glycidyl ester of polycarboxylic acid, polyol glycidyl ester, aliphatic or alicyclic epoxy resin, amine epoxy resin, triphenolmethane type epoxy resin, dihydroxybenzene type epoxy resin and (meth) acrylic acid. Epoxy acrylate resin, methanol,
Ester compounds obtained by reacting lower alcohols such as ethanol and propanol, and polyhydric alcohols such as (poly) ethylene glycol, (poly) propylene glycol, glycerin, methylolpropane, pentaerythritol and dipentaerythritol with (meth) acrylic acid , N-methylol melamine, N-methylol benzoguanamine, (poly) N-methylol (meth) acrylamide and the like, and an ester compound obtained by reacting (meth) acrylic acid, and a monomer copolymerizable with maleic anhydride Polymer obtained by the reaction with hydroxyethyl (meth) acrylic acid, azide compounds such as azidobenzophenone, azidochalcone, azidostilbene, azidobenzalcyclohexanone, methanol, ethanol, propanol, etc. Grade alcohols, (poly) ethylene glycol, (poly) propylene glycol, glycerin, trimethylolpropane, pentaerythritol, condensates of polyhydric alcohols and azidobenzoic acid dipentaerythritol and the like.

Other resins to be included in the high-resistance black radiation-sensitive resin composition of the present invention include a film-forming polymer binder. As the film-forming polymer binder, any polymerizable compound and / or a polymer compound that is compatible with the polymerizable resin that can cause a cross-linking reaction by the above-mentioned radiation irradiation can be used. For example, (meth) acrylic acid , (Meth) acrylic acid ester, acrylamide, acrylonitrile, vinyl acetate, vinyl phenol, vinyl benzoic acid, styrene, maleic anhydride, vinyl butyral, chloroprene, vinyl chloride, vinyl pyrrolidone, and other monomers alone or in combination of two or more And polymerized by a radical polymerization method or an ionic polymerization method. Among the obtained polymer compounds, those having a carboxyl group or a phenolic hydroxy group are particularly preferable because they can be developed with an aqueous alkali solution.

The photopolymerization initiator used in the high-resistance black radiation-sensitive resin composition of the present invention includes benzyl, benzoin ether, benzoin butyl ether, benzoin propyl ether, benzophenone, 3,3'-dimethyl-4-methoxybenzophenone. Benzoylbenzoic acid, esterified product of benzoylbenzoic acid, 4-benzoyl-4′-methyldiphenylsulfide, benzyldimethylketal, 2-butoxyethyl-4-methylaminobenzoate, chlorothioxanthone, methylthioxanthone, ethylthioxanthone, isopropylthioxanthone, Dimethylthioxanthone, diethylthioxanthone, diisopropylthioxanthone, dimethylaminomethylbenzoate, dimethylaminobenzoic acid isoamyl ester, 1- (4 Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2
-Methyl-1-phenylpropan-1-one, 1- (4
-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, methylbenzoylformate, 2-methyl-1- (4-methylthiophenyl) -2
-Morpholinopropan-1-one, 2-benzyl-2-
Dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbisimidazole, 2,2′- Bis (2-chlorophenyl) -4,
4 ', 5,5'-tetra- (4-methoxyphenyl) bisimidazole and the like. These photopolymerization initiators can be used alone or in combination of two or more. These amounts are desirably 0.5 to 30 parts by weight, preferably 1 to 25 parts by weight based on 100 parts by weight of the solid content of the composition.

The organic pigments of different colors used in the present invention are anthraquinone, phthalocyanine, benzimidazolone, quinacridone, azochelate, azo, isoindolinone, pyranthrone, indanthrone, and the like. Anthrapyrimidines, dibromoanzanthrones, flavanthrones, perylenes, perinones,
It can be obtained by using one kind or a combination of two or more kinds of pigments such as quinophthalone type, thioindigo type and dioxazine type.

The ratio of each of the pigments used in the present invention is 1 to 100 parts by weight of the solid content (other than the organic solvent) of the high-resistance black radiation-sensitive resin composition. 70 parts by weight, preferably 5 to 60 parts by weight,
The proportion of carbon black is 15 parts by weight or less, preferably 10 parts by weight or less, the proportion of the blackening organic pigment is 60 parts by weight or less, preferably 50 parts by weight or less, and the total pigment proportion is 20 to 80 parts by weight. Parts, preferably 30 to 75 parts by weight. When the total pigment ratio is less than 20 parts by weight, the light-shielding property is not sufficient, and when it exceeds 80 parts by weight, there is a possibility that patterning may not be performed.

The titanium black used in the present invention means low-order titanium oxide, titanium oxynitride or the like. Among them, the lower titanium oxide is prepared, for example, by mixing titanium dioxide and metallic titanium powder in a vacuum or a reducing atmosphere as described in JP-A-49-5432 (Japanese Patent Publication No. 52-12733).
It is obtained by heating at a temperature of 50 to 1100 ° C. Ti _n O
Black compounds represented by _2n-1 (n is a positive integer), hydrated titanium dioxide and metallic titanium powder described in JP-A-64-11572, silicon, aluminum, niobium, tungsten, etc. Compounds obtained by heating in an inert atmosphere in the presence of a sintering treatment aid consisting of a compound containing the compound. Examples of titanium oxynitride include, for example, JP-A-60-65069 (Japanese Patent Publication No. 3-51645) and JP-A-60-200827 (Japanese Patent Publication No. 2-4).
No. 2773), a black compound obtained by reducing a powder of titanium dioxide or titanium hydroxide at a temperature of about 550 to 950 ° C. in the presence of ammonia. In addition, vanadium described in JP-A-61-201610 (Japanese Patent Publication No. 3-29010) is adhered to titanium dioxide or the like and 750 in the presence of ammonia.
Black compounds obtained by reduction at 〜875 ° C. are also included. The particle size of the primary particles used in the high-resistance black radiation-sensitive resin composition of the present invention is 0.01 to 1 μm, and the specific surface area of the pigment is 5 to 40 m ² / g. It is used for imparting and enhancing light-shielding properties. If the particle size is less than 0.01 μm, the necessary and sufficient light-shielding properties cannot be obtained, and if the particle size exceeds 1 μm, the dispersibility becomes low, and aggregation or precipitation tends to occur. Become. Specific surface area is 5m ² / g
If it is less than 40 m ² / g, it will not be practical because a large amount of dispersing agent and dispersing agent will be required.

Each component (solid content) used in the high-resistance black radiation-sensitive resin composition of the present invention is usually used by dissolving and / or dispersing it in an organic solvent. Examples of the solvent include benzene solvents such as benzene, toluene, and xylene; cellosolves such as methyl cellosolve, ethyl cellosolve, and butyl cellosolve; cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate; and butyl cellosolve acetate; and propylene glycol monomethyl ether. Acetate, propylene glycol monoalkyl ether acetates such as propylene glycol monoethyl ether acetate propylene glycol monobutyl ether acetate, methyl methoxypropionate, ethyl methoxypropionate, methyl ethoxypropionate, methyl propionate such as ethyl ethoxypropionate, Lactic esters such as methyl lactate, ethyl lactate and butyl lactate, diethylene glycol Bruno methyl ether, diethylene glycol, and diethylene glycol monoethyl ether, methyl acetate, ethyl acetate, butyl acetate, esters such as acetic aluminum,
Ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dioxane; and ketones such as acetone, methyl ethyl ketone, methyl butyl ketone, and cyclohexanone. These may be used alone or as a mixture of two or more. The obtained solution and / or dispersion liquid is used after being subjected to redispersion treatment or filtration as necessary to remove impurities.

The black cured film obtained from the high-resistance black radiation-sensitive resin composition of the present invention is usually prepared as follows.
That is, the solution and / or dispersion obtained by the above method is applied onto a substrate such as a glass substrate by a method such as a spin coating method, a roll coating method, a printing method, or a bar coating method, so that the film thickness is usually 0.1 μm. Coating is performed so as to have a thickness of 5 to 5 μm, and soft baking is performed to form a film. Next, radiation can be applied through a desired mask pattern by a photolithography method, followed by processing steps such as development and post-baking. The resulting black cured film had a volume resistance of 10 ⁵ Ω.
-It has a value of cm or more, has sufficient insulation properties, and has high adhesion to substrates.

The high-resistance black radiation-sensitive resin composition, the black cured film and the black image forming method of the present invention have high resistance, are excellent in photosensitivity, light-shielding properties and dispersion stability, and have a high-definition black matrix. Can be easily produced.

[0082]

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

Example 1 19.90 g of titanium black 13M (trade name: titanium oxynitride manufactured by Mitsubishi Materials; the same applies hereinafter) (primary particle diameter)
0.2 μm, specific surface area 13 m ² / g) As a compound of the formula (1), 0.5 g of (1-1), and as a compound of the formula (5), 7.96 g of (5-7) were obtained by adding propylene glycol monomethyl In addition to 71.64 g of ether acetate,
Dispersion was performed by a sand mill to obtain a pigment composition of the present invention. The dispersed pigment composition was measured with a B-type viscometer (temperature 2
(5 ° C.), the thixotropy was low and very good. In addition, when the obtained pigment composition was applied on a glass substrate and observed with a microscope, no aggregation was observed, and a uniform film was obtained.

Example 2 Titanium black 13M (trade name: manufactured by Mitsubishi Materials)
19.61 g (primary particle diameter 0.2 μm, specific surface area
13 m ² / g), as a compound of the formula (1), (1-1)
1.96 g, as a compound of the formula (5), (5-7) 7.
84 g was added to 70.59 g of propylene glycol monomethyl ether acetate, and the mixture was dispersed with a sand mill to obtain a pigment composition of the present invention. When the dispersed pigment composition was measured with a B-type viscometer (at a temperature of 25 ° C.), the thixotropy was low and very good. In addition, when the obtained pigment composition was applied on a glass substrate and observed with a microscope, no aggregation was observed, and a uniform film was obtained.

Example 3 Titanium Black 13R (trade name: manufactured by Mitsubishi Materials)
19.90 g (primary particle diameter 0.04 μm, specific surface area 35 m ² / g), as a compound of the formula (1), (1-
1) 0.5 g of the compound of the formula (5) as (5-7)
7.96 g was added to 71.64 g of propylene glycol monomethyl ether acetate, and the mixture was dispersed with a sand mill to obtain a pigment composition of the present invention. When the dispersed pigment composition was measured with a B-type viscometer (at a temperature of 25 ° C.), the thixotropy was low and very good. In addition, when the obtained pigment composition was applied on a glass substrate and observed with a microscope, no aggregation was observed, and a uniform film was obtained.

Example 4 Titanium Black 13R (trade name, manufactured by Mitsubishi Materials Corporation)
19.61 g (primary particle diameter 0.04 μm, specific surface area 35 m ² / g), as a compound of the formula (1), (1-
1) 1.96 g of the compound of the formula (5) as (5-7)
7.84 g was added to 70.59 g of propylene glycol monomethyl ether acetate, and the mixture was dispersed with a sand mill to obtain a pigment composition of the present invention. When the dispersed pigment composition was measured with a B-type viscometer (at a temperature of 25 ° C),
The thixotropy was low and very good. In addition, when the obtained pigment composition was applied on a glass substrate and observed with a microscope, no aggregation was observed, and a uniform film was obtained.

Example 5 Titanium Black 13R (trade name: manufactured by Mitsubishi Materials)
20.94 g (primary particle diameter 0.04 μm, specific surface area 35 m ² / g), as a compound of the formula (1), (1-
4) 0.52 g of the compound of the formula (4), (5-2)
6.28 g was added to 72.25 g of propylene glycol monomethyl ether acetate, and the mixture was dispersed with a sand mill to obtain a pigment composition of the present invention. When the dispersed pigment composition was measured with a B-type viscometer (at a temperature of 25 ° C.), the viscosity was very low and very good. In addition, when the obtained pigment composition was applied on a glass substrate and observed with a microscope, no aggregation was observed and a uniform film was obtained.

Example 6 50.0 g of the pigment composition obtained in Example 1, Example 3
3.4.3 g of the pigment composition obtained in the above, 21.5% of CI Pigment Red 177, and a sorbistane dispersant.
13. A pigment paste composed of 0% and 74.5% of a solvent was used.
2 g, DPHA (trade name Nippon Kayaku acrylate resin) as a resin capable of causing a crosslinking reaction upon irradiation with radiation
8.7 g, Irgacure 3 as a mixed photopolymerization initiator
1.7 (trade name Ciba-Geigy) 1.7 g, DETX
-S (trade name, manufactured by Nippon Kayaku) 0.8 g, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole 0.8 g, as a solid content adjusting solvent, 10.5 g of propylene glycol monomethyl ether acetate was added, mixed well and dispersed to obtain a high-resistance black radiation-sensitive resin composition of the present invention.

The obtained resin composition was treated with 2% RBS-2
5 (trade name Chemical Products Co., Ltd. weak alkaline detergent) for 10 minutes with ultrasonic cleaning and pure water cleaning, then 200
Spin coated on a glass substrate dehydrated and baked on a hot plate at 10 ° C for 10 minutes, pre-soft baked in a circulating oven at 50 ° C for 1 minute, and then soft baked on a hot plate with a surface temperature of 100 ° C for 100 seconds Was done. Next, using a 500 W ultra-high pressure mercury lamp, 350 mJ / cm ² was passed through a mask on which a black matrix pattern was drawn.
Of energy. Thereafter, a liquid temperature of 25 consisting of 0.19% tetramethylammonium hydroxide and 0.19% emulgen A-60 (trade name, manufactured by Kao)
Flow rate: 500 ml / min, discharge pressure:
Shower development was performed at 1 kg / cm ² for 35 seconds. After washing with water, post-baking on a hot plate with a surface temperature of 200 ° C., and observing the transfer pattern with a microscope,
A 10 μm pattern without any residue was resolved.

Example 7 The same operation as in Example 6 was carried out except that the entire surface of the glass substrate was irradiated, to obtain a black cured film of the present invention. Next, this glass substrate was set in an electronic spectrum measuring apparatus, and 780 to 38
The absorbance at 0 nm was measured and normalized to the absorbance per 1 μm of film thickness. Convert the normalized absorbance to transmittance, J
The Y value with the C light source was calculated according to IS Z8722.
When the optical density (OD) in the XYZ color system was calculated by the following equation, it was 2.34, indicating a sufficient light-shielding property.

[0091]

(Equation 1)

Example 8 The same operation as in Example 6 was carried out except that the entire surface of the glass substrate was irradiated, to obtain a black cured film of the present invention. Next, the cross-sectional area 0.2
A 7 cm ² cylindrical rod was adhered to the black film with an adhesive (epoxy adhesive made by Araldite Rapid Ciba Geigy) and left in an oven at 70 ° C. for 1 hour to cure the adhesive. Then, when the adhesion strength was measured with a tensile strength tester (tensile speed: 10 mm / min),
4 kg / cm ² , showing high strength.

Example 9 A black cured film of the present invention was obtained by performing the same operation as in Example 6 except that the glass substrate was a chromium-deposited substrate and the entire surface of the substrate was irradiated. Next, an area of 0.28 cm was formed on the black film.
² A circular electrode of (S) was formed of silver paste, and a constant voltage was generated between this electrode and a chromium deposition surface as a counter electrode using a constant voltage generator (PA36-2A regulated DC power supply manufactured by Kenwood). 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 ¹² Ω · cm, indicating an extremely high resistivity. The results are shown in FIG.

[0094]

(Equation 2)

Example 10 47.0 g of the pigment composition obtained in Example 2, Example 4
3.3.4 g of the pigment composition obtained in the above, 21.5% of CI Pigment Red 177, and a sorbistane dispersant.
11. A pigment paste consisting of 0% and 74.5% of a solvent is used.
4 g, MA-600 (trade name: Mitsubishi Chemical carbon black) 24.37%, sorbistane-based dispersant 7.3
Pigment paste consisting of 1% and solvent 68.32%
5.9 g, 8.2 g of DPHA (trade name, Nippon Kayaku acrylate resin) as a resin capable of causing a cross-linking reaction upon irradiation with radiation, 1.6 g of Irgacure 369 (trade name, Ciba Geigy) as a mixed photopolymerization initiator, DE
TX-S (trade name, manufactured by Nippon Kayaku) 0.8 g, 2, 2 '
-Bis (2-chlorophenyl) -4,4 ', 5,5'-
0.8 g of tetraphenylbisimidazole and 9.9 g of propylene glycol monomethyl ether acetate as a solid content adjusting solvent were added, mixed well and dispersed to obtain a high-resistance black radiation-sensitive resin composition of the present invention. This composition was pattern-transferred according to the method of Example 6 except that the developer concentration was changed to 0.12%, and showed a resolution of 15 μm. When various items were measured according to the methods of Examples 7 to 9, the concentration was 2.80, and the adhesion strength was 67 k.
g / cm ² , and the resistivity was 10 ⁷ at an applied voltage of 10 V, which was sufficiently high.

Comparative Example MA-600 (trade name: Mitsubishi Chemical carbon black)
24.37%, sorbistane-based dispersant 7.31% Solvent 6
16.0 g of a 8.32% pigment paste was used as a resin capable of causing a crosslinking reaction upon irradiation with radiation.
6.0 g of the resin of 7) and 4.0 g of DPHA (trade name Nippon Kayaku acrylate resin), Irgacure 369 (trade name, manufactured by Ciba Geigy) as a mixed photopolymerization initiator
1.6 g, DETX-S (trade name, manufactured by Nippon Kayaku) 0.8
g, 2,. 2'-bis (2-chlorophenyl) -4.
4 ', 5,5'-tetraphenylbisimidazole 0.
8 g and 9.9 g of propylene glycol monomethyl ether acetate as a solid content adjusting solvent were added, mixed well and dispersed to obtain a black radiation-sensitive resin composition. When this composition was measured for various items in accordance with the methods of Examples 7 and 9, the concentration was 2.5 and the composition was light-shielding, but had a resistivity of 10 ³ units even when the applied voltage was 5 V or less. Yes, it had conductivity.

[0097]

The black pigment composition of the present invention is excellent in dispersion stability, and the black radiation-sensitive resin composition prepared by using the same has sufficient photosensitivity, light-shielding property, and resistivity. A fine black matrix pattern can be easily produced.

[Brief description of the drawings]

FIG. 1 is a diagram showing a relationship between an applied voltage and a volume resistance value.

Claims (10)

[Claims] 1. A method according to claim 1, wherein the titanium black comprises a sulfonic group and / or
Or phthalocyanine or naphthalocyanine compound having a sulfonic acid amide group of formula _{-CH 2 -C (R 5) (} C
OOH)-and / or -CH (COOH) -CH (CO
R ₆ )-(wherein R ₅ and R ₆ mean the following ones). A pigment composition obtained by dispersing with a polymer having a monomer unit. 2. Titanium black as a free acid of the formula (1) (In the formula (1), a represents 0 or 1, and PcMa represents that a is 0.
Represents a metal-free phthalocyanine nucleus, a represents a metal phthalocyanine nucleus when a is 1, M represents a metal atom,
l and m are integers and 1 ≦ l + m ≦ 4, and R ₁ is Or Is shown. (In the formula (2), A represents an oxygen atom, and n is
0 or 1, when n = 0, y = 0, and x is 1 ≦
x represents an integer of 3 or less, and when n = 1, x and y are 1 ≦
x, y represents an integer of 3 or less. R ₂ and R ₃ represent a hydrogen atom or a C _{1 to} C ₁₂ optionally substituted alkyl group, and R ₂ and R ₃ are not hydrogen atoms at the same time. In the formula (3), z represents an integer of 1 ≦ z ≦ 3, and B represents —C
H ₂ - or an oxygen atom, R ₄ is a hydrogen atom or a C ₁
-C _{4 represents} an optionally substituted alkyl group. ))
And a compound represented by the formula (4): (In the formula (4), R ₅ represents a hydrogen atom, a halogen atom or a methyl group.) And / or the formula (5) (In the formula (5), R ₆ represents an optionally substituted alkoxy group or an optionally substituted amino group.) Characteristic pigment composition 3. The primary particles of titanium black having a particle size of 0.
01 to 1 μm, and the specific surface area of the pigment is 5 to 40 m ² /
The pigment composition according to claim 1 or 2, wherein g is g. 4. A radiation-sensitive resin, a photopolymerization initiator and / or a radiation-sensitive resin containing a compound and / or a resin capable of causing a cross-linking reaction by irradiation with radiation and optionally other resins.
-Resistive black radiation-sensitive resin composition, characterized by containing the pigment composition described in the above. 5. A radiation-sensitive resin, a photopolymerization initiator, an organic pigment, and a pigment composition according to claim 1, which contain a compound and / or a resin capable of causing a cross-linking reaction by irradiation with radiation and optionally other resins. High resistance black radiation-sensitive resin composition characterized by containing 6. A radiation-sensitive resin containing a compound and / or a resin capable of causing a cross-linking reaction by irradiation with radiation and optionally another resin, a photopolymerization initiator, the pigment composition according to claim 1 or 2, carbon black, High resistance black radiation-sensitive resin composition characterized by comprising an organic pigment 7. When the solid content (excluding the organic solvent) in the high-resistance black radiation-sensitive resin composition is 100 parts by weight, the proportion of titanium black is 1 to 70 parts by weight and the proportion of carbon black is 1 to 70 parts by weight. 10 parts by weight or less, the proportion of the organic pigment is 6
0 parts by weight or less, and the total pigment ratio of these three is 3 parts by weight.
The high-resistance black radiation-sensitive resin composition according to any one of claims 4 to 6, which is 0 to 80 parts by weight. 8. A black cured film obtained by using the high-resistance black radiation-sensitive resin composition according to any one of claims 4 to 6. 9. The black cured film according to claim 8, having a volume resistance of at least 10 ⁵ Ω · cm. 10. A black image forming method comprising forming a black film by photolithography using the high-resistance black radiation-sensitive resin composition according to any one of claims 4 to 6.