JPH09263654A - Non-conductive light shading layer, composition therefor and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition for a non-conductive light shading layer, high in shading performance, non-conductive and useful as a color filter for a liquid crystal display apparatus, etc., by compounding an alkali-soluble binder, a pigment containing a spinel-type compound, a photopolymerizable monomer, a photopolymerization initiator and a solvent as main components. SOLUTION: This composition is composed of an alkali soluble binder, a pigment, a photopolymerizable monomer, a photopolymerization initiator and a solvent as main components. The pigment contains at least one kind selected from CuMn2 O4 , multiple oxide fine powder obtained by substituting a part of Mn in CuMn2 O4 with Fe, Co and/or Ni. Further, carbonaceous powder (e.g. graphite, carbon black or short fiber-shaped carbon fiber) is preferably contained as the pigment. Furthermore, a preferable pigment composition is a multiple oxide composed of 25-40wt.% of CuO, 5-30wt.% of Fe2 O3 and 40-60wt.% of Mn2 O3 .

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention has a high light shielding ability,
The present invention also relates to a composition for a light-shielding layer that is useful in applications requiring non-conductivity. More specifically, it relates to a composition for a non-conductive light-shielding layer, a non-conductive light-shielding layer, and a color filter which are useful for forming a light-shielding layer (black matrix) in a color filter used in a liquid crystal display device or the like.

[0002]

2. Description of the Related Art Conventionally, in a color filter used in a liquid crystal display device, a light-shielding layer made of a thin film metal such as chromium, nickel, or aluminum, or carbon black or titanium oxide is provided in a non-pixel region in order to enhance the contrast of a displayed image. A method of providing a light-shielding layer in which a pigment such as the above is dispersed in a binder resin is known.

[0003]

However, since the light-shielding layer is conductive in the above-mentioned conventional method, when the light-shielding layer is used between the transparent electrode layers, an insulating layer must be separately provided, and the light-shielding layer is shielded. There are problems that the layers are likely to cause a short circuit between the electrode layers and that crosstalk between adjacent electrode layers increases through the conductive light-shielding layer.
When a non-conductive inorganic compound pigment such as titanium oxide is dispersed in a binder resin and a non-conductive light-shielding layer is provided, the particle size of the pigment such as titanium oxide is large and the pigment is dispersed in the binder resin. Are difficult to achieve, and the blackness of the formed light-shielding layer (coating film) is insufficient. Therefore, an object of the present invention is to provide a composition having excellent light-shielding ability and blackness, which is suitable for producing a non-conductive light-shielding layer, and a non-conductive light-shielding layer produced using the composition. Is.

[0004]

The above object is achieved by the present invention described below. That is, the present invention is an alkali-soluble binder, a pigment, a photopolymerizable monomer, a photopolymerization initiator,
And a non-conductive light-shielding layer composition containing a solvent as a main component, wherein the pigment is CuMn ₂ O ₄ and composite oxide fine particles in which a part of Mn of CuMn ₂ O ₄ is replaced with Fe, Co and / or Ni. A non-conductive light-shielding layer composition comprising at least one pigment selected from the above, and a non-conductive light-shielding layer produced using the composition. According to the present invention, a composition suitable for producing a non-conductive light-shielding layer having excellent light-shielding ability and blackness is provided.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Next, the present invention will be described in more detail with reference to embodiments. As the alkali-soluble binder used in the composition for a non-conductive light-shielding layer of the present invention,
It is preferable that the dispersibility of the pigment is good, the compatibility with the photopolymerizable monomer and the photopolymerization initiator is good, and the solubility in an alkali developing solution, the solubility in an organic solvent, the strength, the softening temperature and the like are appropriate. These preferred binders can be selected from the wide variety of polymeric substances listed below.

Specifically, methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, etc. And a cellulose derivative having a carboxylic acid group. In addition, a carboxyl-modified polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is also useful. In addition, water-soluble polymers such as polyvinylpyrrolidone, polyethylene oxide, and polyvinyl alcohol can be used. Further, a copolymer containing an unsaturated organic acid and an unsaturated organic acid ester such as methyl acrylate, ethyl methacrylate, benzyl methacrylate, or glycidyl methacrylate as a monomer may be mentioned. Other unsaturated organic acid esters may be added to the copolymer. Those obtained by quantitative addition polymerization can also be used.

Preferred examples of the alkali-soluble binder used in the present invention include terpolymers of terpolymers of (meth) acrylic acid, styrene and benzyl (meth) acrylate. The copolymerization ratio of these copolymers is arbitrary, but the preferable range is 15 to 40% by weight of (meth) acrylic acid and styrene 2 when the total amount is 100% by weight.
5 to 45% by weight, and benzyl (meth) acrylate 10
５０50% by weight. The copolymer also has the purpose of stabilizing the pigment in the composition of the present invention together with the dispersant described below. Further, in order to impart appropriate alkali developer resistance, the acid value thereof is preferably in the range of about 70 to 250 mgKOH / g.

This means that if the copolymerization ratio and the acid value are poorly balanced, pattern resolution will occur after exposure and development, but there will be no resistance to alkaline developers, and small wrinkles and cracks will occur on the developed pattern surface. The permeation of the alkaline developer from here rapidly causes the resist peeling (peeling) from the glass substrate surface. The molecular weight of these alkali-soluble binders is 10,000 to 7
The range of ten thousand is preferable. The preferred amount of the alkali-soluble binder is in the range of 5 to 80% by weight based on the total solids in the liquid composition. Further, in the present invention, an isocyanate having glycidyl (meth) acrylate, vinyl group, (meth) acryloyl group, etc. in the above-mentioned copolymer of (meth) acrylic acid, styrene and benzyl (meth) acrylate of 3 or more groups. By reacting a compound or the like to introduce a reactive double bond group into the above copolymer to form a polymerizable binder, various strengths of the light shielding layer to be formed can be improved. The reactive double bond group to be introduced is 0.1 to 2
A range of 0 mol% is preferred.

In addition to the binders described above, in order to improve various properties such as strength of the light-shielding layer to be formed, in the range that does not adversely affect the developability and resolution of the light-shielding layer to be formed. An alkali-insoluble polymer can be added. Examples of these polymers include alcohol-soluble nylon and epoxy resin.

Examples of the photopolymerizable monomer used in the composition of the present invention include monofunctional acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate, and monofunctional acrylates. Methacrylate,
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethane triacrylate, trimethylolpropane triacrylate, trimethylolpropane diacrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate , Pentaerythritol tri (meth) acrylate,
Dipentaerythritol penta (meth) acrylate,
Dipentaerythritol hexaacrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, tri Poly (meth) acrylates after addition reaction of ethylene oxide or propylene oxide to polyfunctional alcohols such as methylolpropane or glycerin, polyester acrylates,
Examples include polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resin and (meth) acrylic acid. In addition to monomers, prepolymers,
That is, dimers and trimers are also effective. The preferred amount of the above monomers is in the range of 5 to 50% by weight of the total solids in the liquid composition.

Examples of the photopolymerization initiator used in the composition of the present invention include thioxanthone type compounds, acetophenone type compounds, benzophenone type compounds, benzoin ether type compounds, and peroxide type compounds, and amines may be used as necessary to improve sensitivity. It is effective to add a system or quinone type photopolymerization accelerator. The preferred amount of the photopolymerization initiator or photopolymerization accelerator is in the range of 0.5 to 40% by weight based on the total solids in the liquid composition.

The pigment used in the composition of the present invention is obtained by a wet method as disclosed in JP-A-4-50119, and is non-conductive, has excellent blackness and can be made into fine particles. CuMn ₂ O ₄ and / or part of Mn of the CuMn ₂ O ₄ is Fe, Co and / or N
It is at least one pigment selected from the composite oxide fine particles substituted with i.

The above pigment is a spinel type compound,
It is known as a pigment excellent in weather resistance, heat resistance and insulation. According to JP-A-4-50119, Cu, M
An alkaline agent was added to a water-soluble metal salt of n, Fe, Co, and Ni for neutralization and precipitation, and an oxidizing agent such as hydrogen peroxide was added to the precipitated slurry to perform oxidation in a liquid phase. After that, the inorganic pigment is obtained by washing, drying, firing and pulverizing. By this manufacturing method, a fine pigment having a high specific surface area can be obtained at a low manufacturing cost. Furthermore, a part of Mn of the composite oxide of CuM ₂ O ₄ is F
Substitution with e, Co or Ni gives fine pigments with even greater specific surface area. The preferred composition of the pigment used in the present invention is CuO, Fe ₂ O ₃ and Mn ₂
A complex oxide of O ₃ can be mentioned. As its composition ratio,
CuO of 25 to 40% by weight, Fe ₂ O ₃ of 5 to 30% by weight and Mn ₂ O ₃ of 40 to 60% by weight are particularly preferable.

Further, in order to improve the light-shielding property of the light-shielding layer formed, a carbonaceous powder can be mixed with the composite oxide fine particles. Examples of the carbonaceous powder include, for example, carbon black such as Ketjen black, acetylene black, furnace black, and channel black,
There are natural or artificial graphite and the like, and other carbon whiskers and short fibers such as carbon fiber and graphite fiber can be mentioned. These carbonaceous powders can be used alone or in combination of two or more.

By using a mixture of the non-conductive composite oxide fine particles and the carbonaceous powder, the chain of carbonaceous powder particles in the light-shielding layer to be formed is non-conductive. By preventing the oxide fine particles, the light-shielding layer also has excellent light-shielding properties, and a non-conductive light-shielding layer can be obtained. The mixing ratio of the composite oxide fine particles and the carbonaceous powder is 50% by weight or more because the light shielding layer formed when the carbonaceous powder is too much exhibits conductivity. On the other hand, it is desirable that the carbonaceous powder is 50% or less.

It is important that the above pigment is well dispersed in the composition of the present invention. Considering the dispersibility of the pigment, at least a part of the surface of each of the composite oxide fine particles and the carbonaceous powder, or either one of them is coated with a hydrolyzate and / or a partial hydrolyzate of a metal compound. be able to. As the hydrolyzate or partial hydrolyzate of the metal compound, at least one kind of hydrolyzate or partial hydrolyzate of an inorganic metal salt, an organic metal salt, an organometallic compound, an organometallic complex, or a derivative thereof is used. can do. Further, when at least a part of the surface of the carbonaceous powder is coated with a hydrolyzate and / or a partial hydrolyzate of a metal compound, not only the dispersibility of the carbonaceous powder is improved but also a conductor is used. It is also possible to make a certain carbonaceous powder non-conductive.

As the solvent used in the composition of the present invention, coating suitability of liquid composition, polymer and monomer,
Considering the solubility of the photopolymerization initiator and the dispersibility of the pigment, one or more solvents can be selected and used, and the solvent contains at least one polyhydric alcohol or its derivative. It is preferable. Considering especially the dispersibility of the pigment, among the polyhydric alcohols or their derivatives, water 10
Those having a solubility of 20 parts by weight or more with respect to 0 parts by weight are particularly effective for the present invention.

Specific examples of the solvent include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether,
Ethylene glycol isoamyl ether, methoxy methoxy ethanol, ethylene glycol monoacetate,
Diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether, 1 -Butoxyethoxy propanol, dipropylene glycol monomethyl ether,
Butanediol etc. are mentioned.

In addition to the above components, the composition of the present invention has a silane coupling agent, a titanate coupling agent, and an aluminum cup in order to impart adhesion to the substrate to which the composition is applied. A ring agent or the like can be added. Further, known additives such as a dispersant, a plasticizer, and a surfactant can be added if necessary.
Known dispersants and surfactants can be used, but in view of the surface potential of the pigment, anionic surfactants, amphoteric surfactants, and nonionic surfactants are particularly preferable. Specific examples of the anionic surfactant include an aliphatic compound and a cyclic compound having a carboxylate or sulfate ester salt, a sulfonate salt, a phosphate ester salt, and a phosphonate salt group at the terminal, and Styrene-maleic anhydride copolymer called a molecular surfactant,
Olefin-maleic anhydride copolymer, formalin condensate of naphthalene sulfonate, sodium polyacrylate,
Partially hydrolyzed polyacrylamide, sodium alginate and the like can be used.

Specific examples of the amphoteric surfactant include betaine-based compounds such as carboxybetaine and sulfobetaine, aminocarboxylic acid-based compounds, and phosphoric acid ester salts. Specific examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, ethers such as polyoxyethylene polyoxypropylene glycol, polyhydric esters such as glycerin esters, sorbitan esters, and sucrose esters. Ether ester system such as alcohol partial ester, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester polyoxyethylene ether, etc., nitrogen-containing system such as fatty acid alkanolamide, polyoxyethylene fatty acid amide, amine oxide, etc. And polyvinyl alcohol, a copolymer of polyoxyethylene ether ester, polyacrylamide, etc., which are called polymer surfactants, can be used.

As a method for dispersing the pigment in the liquid composition, an alkali-soluble binder, a solvent, a pigment,
And, if necessary, a method of dispersing and mixing a mixture comprising a dispersion aid with a three-roll mill, a ball mill, a sand mill, an attritor, a paint shaker, an annular bead mill, or the like can be used. Further, a pigment dispersion liquid in which a solvent, a pigment and a dispersion aid are previously dispersed, and a photosensitive resin liquid in which an alkali-soluble binder, a photopolymerizable monomer, a photopolymerization initiator and a solvent are previously dissolved and mixed are combined. The composition of the present invention can be prepared by mixing. The method of dispersing and mixing the pigment is not limited to the above method, and other suitable methods can be used depending on the mixing system of each component.

The above-mentioned composition for non-conductive light-shielding layer of the present invention,
By coating and drying on a substrate by a known method,
A non-conductive light shielding layer can be formed on the substrate. Specific examples of the coating method include a spinner, a whiler, a roller coater, a curtain coater, a knife coater, a bar coater, an extruder and the like, and the non-conductive light-shielding layer of the present invention is formed on a substrate by drying the coating layer. Can be provided. Upon exposure of the substrate having the non-conductive light-shielding layer of the present invention, the light source is selected according to the photosensitivity of the non-conductive light-shielding layer, an ultra-high pressure mercury lamp, a xenon lamp,
Known ones such as a carbon arc lamp and an argon laser can be used.

An alkaline water-based developer is preferably used as a developer for developing the pattern-exposed non-conductive light-shielding layer. The alkaline water-based developer referred to in the present invention means that when the development is carried out in an aqueous system, the O
It is a developer that releases H ⁻ . The pH of the alkaline aqueous developer is optimally in the range of 7.5 to 12, and the alkaline component used is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, or an organic ammonium compound, for example, Tetraethylammonium hydroxide,
Other examples include those hydrolyzed with sulfides, oxides, or weak acid anions (for example, F ⁻ , CN ^−, etc.). Further, a buffer solution in this pH range may be prepared and used as an alkaline aqueous developer. Furthermore, in the present invention,
According to a known method, in a color filter in which red, green and blue pixels and a black matrix are provided on a transparent substrate, and a transparent electrode layer is further provided on the surface, the black matrix is replaced with the non-conductive light shielding layer of the present invention. Provided is a color filter formed from a composition for use.

[0024]

The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Example 1 (1) Preparation of Black Pigment Dispersion Liquid TM Black # 3550 23 wt% (Compound oxide pigment in which a part of Mn of CuMn ₂ O ₄ is replaced with Fe, manufactured by Dainichiseika Kogyo Co., Ltd.) Disperbyk 111 2% by weight (polymer dispersant, manufactured by BYK Japan KK) 75% by weight Ethylene glycol monobutyl ether The above components were mixed and sufficiently dispersed in a sand mill.

(2) Preparation of composition for non-conductive light-shielding layer Black pigment dispersion prepared in (1) 61% by weight Benzyl methacrylate / styrene / methacrylic acid copolymer 3% by weight (weight ratio 1/1/1 , Molecular weight of about 30,000) Dipentaerythritol hexaacrylate 4% by weight 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1.6% by weight 4,4'-diethylaminobenzophenone 0 0.3% by weight 2,4-diethylthioxanthone 0.1% by weight Ethylene glycol monobutyl ether 30% by weight The above components were sufficiently mixed to obtain a non-conductive light-shielding layer composition of the present invention.

(3) Preparation of Light-Shielding Layer The composition for non-conductive light-shielding layer prepared in (2) was coated on a glass substrate with a roll coater and dried at 100 ° C. for 3 minutes to form a light-shielding layer having a thickness of about 1 μm. Was formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with a super-high pressure mercury lamp under a nitrogen stream and then developed with a 1% sodium carbonate aqueous solution.

Example 2 (1) Preparation of Black Pigment Dispersion TM Black # 3550 23% by weight (composite oxide pigment in which a part of Mn of CuMn ₂ O ₄ is replaced with Fe, manufactured by Dainichiseika Kogyo Co., Ltd.) ) Disperbyk 161 2% by weight (polymer dispersant, manufactured by BYK Japan KK) Propylene glycol monomethyl ether acetate 75% by weight The above components were mixed and sufficiently dispersed with a paint shaker to obtain a black pigment dispersion. .

(2) Preparation of composition for non-conductive light-shielding layer Black pigment dispersion prepared in (1) 61% by weight Benzyl methacrylate / styrene / methacrylic acid copolymer 3% by weight (weight ratio 1/1/1 , Molecular weight of about 20,000) Dipentaerythritol hexaacrylate 4% by weight 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1.6% by weight 4,4′-diethylaminobenzophenone 0 0.3% by weight 2,4-diethylthioxanthone 0.1% by weight Ethylene glycol monobutyl ether 30% by weight The above components were sufficiently mixed to obtain a non-conductive light-shielding layer composition of the present invention.

(3) Formation of Light-Shielding Layer The composition for non-conductive light-shielding layer prepared in the above (2) was applied onto a glass substrate with a spinner and dried at 100 ° C. for 3 minutes to form a light-shielding layer having a thickness of about 1 μm. Was formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with a super-high pressure mercury lamp under a nitrogen stream and then developed with a 1% sodium carbonate aqueous solution.

Example 3 (1) Preparation of Black Pigment Dispersion TM Black # 3550 23 wt% (composite oxide pigment in which part of Mn of CuMn ₂ O ₄ is replaced with Fe, manufactured by Dainichiseika Kogyo Co., Ltd.) ) SOLSPERSE S27000 2% by weight (polymer dispersant, manufactured by Zeneca Corp.) Ethylene glycol monomethyl ether 75% by weight The above components were mixed and sufficiently dispersed with an annular bead mill to obtain a black pigment dispersion.

(2) Preparation of composition for non-conductive light-shielding layer Black pigment dispersion prepared in (1) 61% by weight Benzyl methacrylate / styrene / methacrylic acid copolymer 3% by weight (weight ratio 1/1/1 , Molecular weight of about 30,000) Dipentaerythritol hexaacrylate 4% by weight 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1.6% by weight 4,4'-diethylaminobenzophenone 0 0.3% by weight 2,4-diethylthioxanthone 0.1% by weight Ethylene glycol monomethyl ether 30% by weight The above components were sufficiently mixed to obtain a non-conductive light-shielding layer composition of the present invention.

(3) Formation of Light-Shielding Layer The composition for non-conductive light-shielding layer prepared in (2) above was coated on a glass substrate with a bar coater and dried at 100 ° C. for 3 minutes to form a light-shielding film having a thickness of about 1 μm. Layers were formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with a super-high pressure mercury lamp under a nitrogen stream and then developed with a 1% sodium carbonate aqueous solution.

Example 4 (1) Preparation of Black Pigment Dispersion TM Black # 3550 23 wt% (composite oxide in which a part of Mn of CuMn ₂ O ₄ is replaced with Fe, manufactured by Dainichiseika Kogyo Co., Ltd.) Acetoalkoxyaluminum diisopropylate 1% by weight Disperbyk 111 1% by weight (polymer dispersant, manufactured by BYK Japan KK) Propylene glycol monomethyl ether acetate 75% by weight The above components are mixed and sufficiently dispersed with a paint shaker. A black pigment dispersion was obtained.

(2) Preparation of composition for non-conductive light-shielding layer Black pigment dispersion prepared in (1) 61% by weight Benzyl methacrylate / styrene / methacrylic acid copolymer 3% by weight (weight ratio 1/1/1 , Molecular weight of about 30,000) Dipentaerythritol hexaacrylate 4% by weight 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1.6% by weight 4,4'-diethylaminobenzophenone 0 0.3% by weight 2,4-diethylthioxanthone 0.1% by weight Ethylene glycol monobutyl ether 30% by weight The above components were sufficiently mixed to obtain a non-conductive light-shielding layer composition of the present invention.

(3) Formation of Light-Shielding Layer The composition for non-conductive light-shielding layer prepared in (2) above was coated on a glass substrate with a spinner and dried at 100 ° C. for 3 minutes to form a light-shielding layer having a thickness of about 1 μm. Was formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with a super-high pressure mercury lamp under a nitrogen stream and then developed with a 1% sodium carbonate aqueous solution.

Example 5 (1) Preparation of Black Pigment Dispersion TM Black # 3550 16% by weight (composite oxide pigment in which a part of Mn of CuMn ₂ O ₄ is replaced by Fe, manufactured by Dainichiseika Kogyo Co., Ltd.) ) Regal250R 7% by weight (carbon black manufactured by Cablack Co., Ltd.) Disperbyk 161 2% by weight (polymer dispersant, manufactured by BYK Japan KK) 75% by weight Propylene glycol monomethyl ether acetate 75% by weight The above components are mixed to prepare a paint shaker To obtain a black pigment dispersion.

(2) Preparation of composition for non-conductive light-shielding layer Black pigment dispersion prepared in (1) 61% by weight benzyl methacrylate / styrene / glycidyl methacrylate / acrylic acid (weight ratio 40/33/11/27, Molecular weight: about 40,000) 3% by weight Dipentaerythritol hexaacrylate 4% by weight 2-Benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1.6% by weight 4,4'-diethylamino Benzophenone 0.3% by weight 2,4-Diethylthioxanthone 0.1% by weight Erylene glycol monobutyl ether 30% by weight The above components were sufficiently mixed to obtain a non-conductive light-shielding layer composition of the present invention.

(3) Formation of Light-Shielding Layer The composition for non-conductive light-shielding layer prepared in (2) above was coated on a glass substrate with a spinner and dried at 100 ° C. for 3 minutes to form a light-shielding layer having a thickness of about 1 μm. Was formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with a super-high pressure mercury lamp under a nitrogen stream and then developed with a 1% sodium carbonate aqueous solution.

Example 6 (1) Preparation of Black Pigment Dispersion TM Black # 3550 23 wt% (composite oxide pigment in which part of Mn of CuMn ₂ O ₄ is replaced with Fe, manufactured by Dainichiseika Kogyo Co., Ltd.) ) MA-100 7% by weight (carbon black manufactured by Mitsubishi Chemical Corporation) acetoalkoxyaluminum diisopropylate 1% by weight Disperbyk 111 1% by weight (polymer dispersant, manufactured by BYK Japan KK) Propylene glycol monomethyl ether acetate 68% by weight The above components were mixed and sufficiently dispersed by a sand mill to obtain a black pigment dispersion liquid.

(2) Preparation of composition for non-conductive light-shielding layer Black pigment dispersion prepared in (1) 61% by weight benzyl methacrylate / styrene / glycidyl methacrylate / acrylic acid (weight ratio 40/33/11/27, Molecular weight: about 30,000) 3% by weight 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1.6% by weight 4,4'-diethylaminobenzophenone 0.3% by weight 2, 4-Diethylthioxanthone 0.1% by weight Ethylene glycol monobutyl ether 30% by weight The above components were sufficiently mixed to obtain a non-conductive light-shielding layer composition of the present invention.

(3) Formation of Light-Shielding Layer The composition for non-conductive light-shielding layer prepared in (2) above was applied onto a glass substrate with a spinner and dried at 100 ° C. for 3 minutes to form a light-shielding layer having a thickness of about 1 μm. Was formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with a super-high pressure mercury lamp under a nitrogen stream and then developed with a 1% sodium carbonate aqueous solution.

Example 7 (1) Preparation of Black Pigment Dispersion TM Black # 3550 23 wt% (composite oxide pigment in which a part of Mn of CuMn ₂ O ₄ is replaced by Fe, manufactured by Dainichiseika Kogyo Co., Ltd.) ) Disperbyk 111 2% by weight (polymer dispersant, manufactured by BYK Japan KK) Ethylene glycol monobutyl ether 75% by weight The above components were mixed and sufficiently dispersed in a sand mill to obtain a black pigment dispersion.

(2) Preparation of composition for non-conductive light-shielding layer Black pigment dispersion prepared in (1) 61% by weight benzyl methacrylate / styrene / methacrylic acid copolymer (weight ratio 1/1/1, molecular weight) Approximately 30,000) glycidyl methacrylate 7.3 mol% adduct) 3 wt% dipentaerythritol hexaacrylate 4 wt% 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1 0.6 wt% 4,4′-diethylaminobenzophenone 0.3 wt% 2,4-diethylthioxanthone 0.1 wt% ethylene glycol monobutyl ether 30 wt% The non-conductive light-shielding layer of the present invention by sufficiently mixing the above components. A composition for use was obtained.

(3) Formation of Light-Shielding Layer The composition for non-conductive light-shielding layer prepared in the above (2) was coated on a glass substrate with a roll coater and dried at 100 ° C. for 3 minutes to form a light-shielding film having a thickness of about 1 μm. Layers were formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with a super-high pressure mercury lamp under a nitrogen stream and then developed with a 1% sodium carbonate aqueous solution.

Example 8 (1) Preparation of Black Pigment Dispersion TM Black # 3550 23 wt% (composite oxide pigment in which a part of Mn of CuMn ₂ O ₄ is replaced by Fe, manufactured by Dainichiseika Kogyo Co., Ltd.) ) Disperbyk 111 2% by weight (polymer dispersant, manufactured by BYK Japan KK) Ethylene glycol monobutyl ether 75% by weight The above components were mixed and sufficiently dispersed in a sand mill to obtain a black pigment dispersion.

(2) Preparation of composition for non-conductive light-shielding layer Black pigment dispersion liquid prepared in (1) 61 wt% Benzylmethacrylate / styrene / acrylic acid copolymer (weight ratio 4/3/3, molecular weight approx. 30,000) glycidyl methacrylate 7.5 mol% adduct) 3 wt% dipentaerythritol hexaacrylate 4 wt% 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1. 6% by weight 4,4'-diethylaminobenzophenone 0.3% by weight 2,4-diethylthioxanthone 0.1% by weight ethylene glycol monobutyl ether 30% by weight For the non-conductive light-shielding layer of the present invention by thoroughly mixing the above components A composition was obtained.

(3) Formation of Light-Shielding Layer The composition for non-conductive light-shielding layer prepared in (2) above was coated on a glass substrate with a roll coater and dried at 100 ° C. for 3 minutes to form a light-shielding film having a thickness of about 1 μm. Layers were formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with a super-high pressure mercury lamp under a nitrogen stream and then developed with a 1% sodium carbonate aqueous solution.

Example 9 (1) Preparation of Black Pigment Dispersion TM Black # 3550 23 wt% (composite oxide pigment in which a part of Mn of CuMn ₂ O ₄ is replaced with Fe, manufactured by Dainichiseika Kogyo Co., Ltd.) ) Disperbyk 111 2% by weight (polymer dispersant, manufactured by BYK Japan KK) Ethylene glycol monobutyl ether 75% by weight The above components were mixed and sufficiently dispersed in a sand mill to obtain a black pigment dispersion.

(2) Preparation of composition for non-conductive light-shielding layer Black pigment dispersion liquid prepared in (1) 61% by weight benzyl methacrylate / styrene / acrylic acid copolymer (weight ratio 4/4/2, molecular weight approx. 30,000) glycidyl methacrylate 2.0 mol% adduct) 3 wt% dipentaerythritol hexaacrylate 4 wt% 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1. 6% by weight 4,4'-diethylaminobenzophenone 0.3% by weight 2,4-diethylthioxanthone 0.1% by weight ethylene glycol monobutyl ether 30% by weight For the non-conductive light-shielding layer of the present invention by thoroughly mixing the above components A composition was obtained.

(3) Formation of Light-Shielding Layer A non-conductive light-shielding layer composition prepared in (2) above was coated on a glass substrate with a roll coater and dried at 100 ° C. for 3 minutes to form a light-shielding film having a thickness of about 1 μm. Layers were formed. (4) Exposure and Development The light-shielding layer was exposed to a light-shielding layer pattern with a super-high pressure mercury lamp under a nitrogen stream and then developed with a 1% sodium carbonate aqueous solution.

Comparative Example 1 A light-shielding layer pattern was prepared in the same manner as in Example 2, except that the pigment was carbon black alone and the composition was as follows. (1) Preparation of Black Pigment Dispersion Liquid 250R (Carbon Black Co., Ltd. carbon black) 23% by weight Disperbyk 161 2% by weight (polymer dispersant, manufactured by BYK Japan KK) Propylene glycol monomethyl ether acetate 75% by weight % The above components were mixed and sufficiently dispersed with a paint shaker to obtain a black pigment dispersion.

(2) Preparation of composition for light-shielding layer Black pigment dispersion prepared in (1) 38% by weight Benzyl methacrylate / styrene / methacrylic acid copolymer 5% by weight (weight ratio 1/1/1, molecular weight approx. 30,000) Dipentaerythritol hexaacrylate 3% by weight 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 1.6% by weight 4,4'-diethylaminobenzophenone 0.3% by weight % 2,4-Diethylthioxanthone 0.1% by weight Ethylene glycol monobutyl ether 52% by weight The above components were sufficiently mixed to obtain a light-shielding layer composition of Comparative Example. A light-shielding layer was obtained using the above composition for a carbon black-dispersed light-shielding layer in the same manner as in (3) and (4) of Example 2. Table 1 shows a comparison of the volume resistivity of the light shielding layer.

Table 1 As described above, as compared with Comparative Example 1, it was confirmed that the non-conductive light-shielding layer of the composition for a non-conductive light-shielding layer of the present invention exhibits excellent non-conductivity.

[0054]

According to the present invention, it is possible to obtain a non-conductive light-shielding layer composition and a non-conductive light-shielding layer which are non-conductive and have a high light-shielding ability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location G02F 1/1335 505 G02F 1/1335 505

Claims (14)

[Claims] 1. A non-conductive light-shielding layer composition comprising an alkali-soluble binder, a pigment, a photopolymerizable monomer, a photopolymerization initiator, and a solvent as main components, wherein the pigment is CuMn.
₂ O ₄ and part of Mn of the CuMn ₂ O ₄ are Fe, Co
And / or at least one kind of pigment selected from Ni-substituted composite oxide fine particles, and a composition for a non-conductive light-shielding layer. 2. The composition for a non-conductive light-shielding layer according to claim 1, which further contains carbonaceous powder as a pigment. 3. The composition for a non-conductive light-shielding layer according to claim 2, wherein the carbonaceous powder is one kind or two or more kinds selected from graphite, carbon black and short fiber carbon fiber. 4. At least a part of the surface of the carbonaceous powder is
The non-conductive light-shielding layer composition according to claim 2, which is coated with a hydrolyzate and / or a partial hydrolyzate of a metal compound. 5. The composition for a non-conductive light-shielding layer according to claim 1, wherein at least a part of the surface of the composite oxide fine particles is coated with a hydrolyzate and / or a partial hydrolyzate of a metal compound. 6. The hydrolyzate or partial hydrolyzate of a metal compound is a hydrolyzate or a partial hydrolyzate of an inorganic metal salt, an organometallic salt, an organometallic compound, an organometallic complex or a derivative thereof. The composition for a non-conductive light-shielding layer according to 4 or 5. 7. The non-conductive light-shielding material according to claim 1, wherein the solvent contains at least one polyhydric alcohol or a derivative thereof, and the solvent has a solubility of 20 parts by weight or more in 100 parts by weight of water. Layer composition. 8. The alkali-soluble binder is (meth)
The composition for a non-conductive light-shielding layer according to claim 1, which is a copolymer of acrylic acid, styrene and benzyl (meth) acrylate of 3 or more. 9. The alkali-soluble binder is (meth)
A binder obtained by introducing 0.1 to 20 mol% of a reactive double bond group into a copolymer of acrylic acid, styrene and benzyl (meth) acrylate of 3 or more types.
3. The composition for a non-conductive light-shielding layer according to item 1. 10. The copolymerization ratio of the 3 type copolymer is 1 as a whole.
When set to 00% by weight, (meth) acrylic acid 15 to 40
The composition for a non-conductive light-shielding layer according to claim 9, which is 10 to 50% by weight of benzyl (meth) acrylate and 25 to 45% by weight of styrene. 11. The non-conductive light-shielding layer composition according to claim 8, wherein the alkali-soluble binder has a molecular weight of 10,000 to 70,000. 12. The acid value of the alkali-soluble binder is
It is 70-250 mgKOH / g, The composition for nonelectroconductive light-shielding layers of Claims 8-11. 13. A non-conductive layer, which is formed by a pattern forming process including at least exposure and development after coating and drying the non-conductive light-shielding layer composition according to claim 1 on a substrate. Light shielding layer. 14. A color filter in which red, green and blue pixels and a black matrix are provided on a transparent substrate, and a transparent electrode layer is further provided on the surface of the transparent substrate, wherein the black matrix is a non-woven fabric according to any one of claims 1 to 13. A color filter formed of a composition for a conductive light-shielding layer.