JPH11119020A - Radiation sensitive composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate an electrically harmful effect due to the electric conductivity of a pigment and to form a black matrix having high light shielding property by using a specified radiation sensitive compsn. for a color filter. SOLUTION: The radiation sensitive compsn. contains a pigment, a resin binder, a multifunctional monomer, a radiation polymn. initiator and a solvent. The surfaces of particles of at least one pigment in the pigment have been coated with an alkali-soluble resin. The pigment used is, e.g. C.I. Pigment Yellow 1 or C.I. Pigment Yellow 3. The alkali-soluble resin is, e.g. a polyester or polyamide contg. one acidic group such as a carboxyl or sulfone group. The resin binder may be the same resin as a carboxyl group-contg. copolymer exampled as the alkali-soluble resin. The radiation polymn. initiator is, e.g. a compd. having an imidazole ring, a compd. having a benzoin bond or other radiation radical generator.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a radiation-sensitive composition for a color filter used in a color liquid crystal display device, a color image pickup tube element and the like.

[0002]

2. Description of the Related Art A portable personal computer or the like is equipped with a color liquid crystal display device. However, with the recent expansion of applications and demands of the color liquid crystal display device, cost reduction is desired. In particular, a color filter, which is an essential component of a color liquid crystal display device, mainly uses a black matrix in which a pattern is formed by etching a chromium thin film by a photolithography method.
However, such a color filter has an extremely high manufacturing cost, and the environmental impact of the chromium waste liquid generated at the time of manufacturing is regarded as a social problem. Therefore, in recent years, a method of using a radiation-sensitive composition containing a black colorant for forming a black matrix has attracted attention. As a main colorant used in the radiation-sensitive resin composition forming such a black matrix, carbon black, a metal oxide, a mixed system of coloring pigments and the like, among which, focusing on its large light-shielding properties Radiation-sensitive compositions using carbon black have been mainly studied. However, in the case of a black matrix using carbon black, there is a problem that the electric resistance of the carbon black is low, so that the color liquid crystal display device is electrically adversely affected, and lighting failure is likely to occur. Moreover, this black matrix
It is easy to cause loss or omission of pixel pattern during development,
In addition, there is a problem that residue or background contamination is easily generated on the substrate or the pixel in the non-irradiated portion. On the other hand, in order to solve the problem caused by the conductivity of carbon black, a method of suppressing the conductivity by coating the surface of carbon black with a resin has been proposed (JP-A-9-26571, JP-A-9-166869). Publications), those resins for coating carbon black include polyvinyl chloride, polyvinyl acetate, polystyrene, polyethylene, polypropylene,
Thermoplastic resin such as polymethyl (meth) acrylate, fluorine resin, silicon resin, silicone acrylic resin, polyimide, polyimide amide, polydiphenyl ether, epoxy resin, phenol resin, xylene resin,
Thermosetting resins such as melamine resin and alkyd resin, and functional groups (carboxyl group,
Hydroxyl group, carbonyl group) (thio)
A resin obtained from a monomer having an epoxy group, an oxazoline group, an aziridine group or a hydroxyalkylamide group is disclosed. However, black matrices using carbon black coated with these resins are particularly defective or missing in the pixel pattern during development, and residue or background contamination on the substrate or pixels in the non-radiated area, Still not enough. In addition, a dye other than a pigment is used as a coloring agent for forming each pixel of the color filter body. In recent years, a method using a pigment having excellent heat resistance, light resistance, and chemical resistance is becoming mainstream. . However, even when pixels are formed by a photolithography method using a radiation-sensitive composition containing a pigment, the pixel pattern is likely to be defective or missing at the time of development. However, there is a problem that the toner is easily left and soiled.

[0003]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a black matrix having a large light-shielding property without adversely affecting the electrical properties due to the conductivity of the pigment. Provided is a radiation-sensitive resin composition for a color filter capable of producing a black matrix and a color filter main body that do not cause chipping and do not cause residue and background contamination on a substrate and a pixel in an unirradiated portion. It is in.

[0004]

The present invention provides (A) a pigment,
(B) a binder resin, (C) a polyfunctional monomer,
A radiation-sensitive resin composition for a color filter comprising (D) a radiation polymerization initiator, and (E) a solvent,
(A) a radiation-sensitive composition for a color filter, wherein the particle surface of at least one pigment in the pigment is coated with an alkali-soluble resin.

Hereinafter, the radiation-sensitive resin composition for a color filter of the present invention will be described in detail. (A) Pigment The pigment of the present invention comprises at least one pigment contained therein.
The particle surface of the pigment is coated with an alkali-soluble resin. The color tone of the pigment in the present invention is not particularly limited, and is appropriately selected depending on the use of the color filter, and may be an organic pigment, an inorganic pigment, or an inorganic salt called an extender pigment. Examples of the organic pigment include a color index (CI; The Society)
Compounds which are classified as Pigment (of of Dyers and Colorists), specifically those having a color index (CI) number as shown below. CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20,
CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 65, CI Pigment Yellow 73, CI Pigment Yellow 74, CI
Pigment Yellow 81, CI Pigment Yellow 8
3, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI
Pigment Yellow 101, CI Pigment Yellow 1
04, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI
Pigment Yellow 110, CI Pigment Yellow 1
13, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI
Pigment Yellow 119, CI Pigment Yellow 1
20, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI
Pigment Yellow 129, CI Pigment Yellow 1
38, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI
Pigment Yellow 152, CI Pigment Yellow 1
53, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI
Pigment Yellow 166, CI Pigment Yellow 1
CI Pigment Yellow 175; CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 61, C.I.
I. Pigment Orange 71, CI Pigment Orange 7
3: CI Pigment Red 9, CI Pigment Red 8
8, CI Pigment Red 97, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 149, CI Pigment Red 168, CI Pigment Red 176, CI Pigment Red 177, C.I.
I. Pigment Red 180, CI Pigment Red 20
9, CI Pigment Red 215, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 265; CI Pigment Violet 1
9, CI Pigment Violet 23, CI Pigment Violet 29; CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15:
CI Pigment Blue 15: 6, CI Pigment Blue 60; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Brown 23, CI Pigment Brown 25; CI Pigment Black 1, Pigment Black 7.

The inorganic or extender pigments include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, Ultramarine, navy blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black and the like can be mentioned. The average primary particle diameter of the organic pigment, the inorganic pigment and the extender is usually 500 nm or less, preferably 200 nm or less, more preferably 100 nm or less. As the pigment in the present invention, carbon black is preferable for forming a black matrix, and an organic pigment is preferable for forming a color filter body. In the present invention, the pigments can be used alone or in combination of two or more.

As the alkali-soluble resin for coating the pigment particle surface, any suitable resin can be used as long as it is soluble in an alkali developing solution used in a developing step in the production of a color filter. Examples of such alkali-soluble resins include, for example, polyesters, polyamides, polyethers, polyurethanes, polycarbonates, alkyd resins, phenolic resins, melamine resins, which contain one or more acid groups such as carboxyl groups, sulfone groups, and phenolic hydroxyl groups. Examples thereof include an epoxy resin, a novolak resin, and a vinyl-based resin. Particularly, a vinyl-based resin having one or more carboxyl groups (hereinafter, referred to as a “carboxyl-containing vinyl-based resin”) is preferable. As the carboxyl group-containing vinyl resin, an ethylenically unsaturated compound having one or more carboxyl groups (hereinafter, simply referred to as “carboxyl group-containing unsaturated compound”) and another copolymerizable ethylenically unsaturated compound ( Hereinafter, a copolymer (hereinafter simply referred to as a “carboxyl group-containing copolymer”) with an “other unsaturated compound” is preferred. Examples of the carboxyl group-containing unsaturated compound include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid Unsaturated dicarboxylic acids (anhydrides) such as itaconic anhydride, citraconic acid, citraconic anhydride, and mesaconic acid; trivalent or higher unsaturated polycarboxylic acids (anhydrides); succinic acid mono [2
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher carboxylic acids such as mono (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalate; ω- Mono- (meth) acrylates of a carboxy polymer at both ends such as carboxy-polycaprolactone mono (meth) acrylate can be exemplified. These carboxyl group-containing unsaturated compounds,
They can be used alone or in combination of two or more.

The other unsaturated compounds include, for example, styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene and o-vinyltoluene.
Chlorostyrene, m-chlorostyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene,
p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether,
aromatic vinyl compounds such as p-vinylbenzyl glycidyl ether and indene; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate , I-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) Acrylate, 2-hydroxybutyl (meth) acrylate, 3
-Hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-
Phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate Unsaturated carboxylic esters such as dicyclopentadienyl (meth) acrylate and 2-hydroxy-3-phenoxypropyl (meth) acrylate; 2-aminoethyl (meth) acrylate;
2-dimethylaminoethyl (meth) acrylate, 2-
Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, and 3-dimethylaminopropyl (meth) acrylate; glycidyl (meth) Glycidyl esters of unsaturated carboxylic acids such as acrylates; vinyl acetate,
Carboxylic acid vinyl esters such as vinyl propionate, vinyl butyrate, and vinyl benzoate; vinyl methyl ether,
Unsaturated ethers such as vinyl ethyl ether, allyl glycidyl ether and methallyl glycidyl ether; (meth) acrylonitrile, α-chloroacrylonitrile,
Vinyl cyanide compounds such as vinylidene cyanide; (meth) acrylamide, α-chloroacrylamide, N-
Unsaturated amides such as (2-hydroxyethyl) (meth) acrylamide; unsaturated imides such as maleimide, N-cyclohexylmaleimide, N-phenylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene; polystyrene, polymethyl (meth)
Acrylate, poly n-butyl (meth) acrylate,
Macromonomers having a monoacryloyl group or a monomethacryloyl group at the terminal of a polymer molecular chain such as polysilicone can be mentioned. These other unsaturated compounds can be used alone or in combination of two or more.

As the carboxyl group-containing copolymer,
(Meth) acrylic acid and at least one selected from the group consisting of styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer and polymethyl methacrylate macromonomer A copolymer with one kind is preferable, and a copolymer of a monomer mixture containing (meth) acrylic acid and benzyl (meth) acrylate is particularly preferable.

Specific examples of preferred copolymers containing a carboxyl group include (meth) acrylic acid / benzyl (meth)
Acrylate copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) ) Acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (Meth) acrylate / benzyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / styrene / Be Jill (meth) acrylate / N
-Phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide / polymethylmethacrylate macromonomer copolymer, (meth) acrylic acid / styrene / 2-hydroxy Ethyl (meth) acrylate / benzyl (meth) acrylate / N-phenylmaleimide / polystyrene macromonomer copolymer, (meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / N-phenyl Maleimide / polymethyl methacrylate macromonomer copolymer and the like can be mentioned.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually
It is 5 to 50% by weight, preferably 10 to 40% by weight.
In this case, when the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the obtained radiation-sensitive resin composition in an alkali developing solution tends to decrease, and when it exceeds 50% by weight, At the time of development with an alkali developing solution, the formed pixels tend to easily fall off the substrate and the pixel surface becomes rough. The weight average molecular weight in terms of polystyrene (hereinafter, simply referred to as “weight average molecular weight”) of the carboxyl group-containing copolymer measured by gel permeation chromatography (GPC; elution solvent: tetrahydrofuran) is preferably 3,000 to 30.
000, particularly preferably 5,000 to 100,00
0.

The method for coating the surface of the pigment particles with the alkali-soluble resin is not particularly limited.
For example, after mixing the alkali-soluble resin solution and the pigment particles, the pigment particles coated with the alkali-soluble resin solution,
A method of removing the solvent from the coated pigment particles by separating by filtration, centrifugation, etc., mixing the alkali-soluble resin solution and the aqueous suspension of the pigment particles, and then coating the pigment particles with the alkali-soluble resin solution Is separated by filtration, centrifugation, etc., and the coated pigment particles are dried.The molten alkali-soluble resin and the pigment particles are mixed under heating, then cooled, and then the mixture is pulverized, A method of obtaining a mixture of soluble resin particles and pigment particles coated with an alkali-soluble resin, mixing the alkali-soluble resin particles and the pigment particles while applying a mechanical impact between the two particles to melt the alkali-soluble resin A method of adhering the monomer constituting the alkali-soluble resin to the pigment particles, polymerizing the pigment particles, and causing the pigment particles to adhere to the surface of the pigment particles. A method of forming a coating layer made of a soluble resin can be used. The mixture of the alkali-soluble resin particles obtained by the above method and the coated pigment particles, the alkali-soluble resin particles are separated in advance, and only the coated pigment particles are used for preparing a radiation-sensitive composition for a color filter. Alternatively, the mixture may be used as it is in the preparation of the radiation-sensitive composition for a color filter. In the above method, a mixture of the alkali-soluble resin particles and the coated pigment particles may be obtained in some cases. In this case, too, the alkali-soluble resin particles are separated in advance, and only the coated pigment particles are used as a color filter. It may be used for the preparation of the radiation-sensitive composition or the mixture as it is for the preparation of the radiation-sensitive composition for color filters.

In the present invention, the alkali-soluble resin that coats the surface of the pigment particles can be used alone or in combination of two or more, and can also be used in combination with a resin other than the alkali-soluble resin. When coating the pigment particle surface with a combination of two or more resins including an alkali-soluble resin, two or more resins may be mixed and coated, or two or more resins may be sequentially laminated and coated. May be. The resin amount when coating the particle surface of the pigment in the present invention with a resin containing an alkali-soluble resin,
Usually, 0.1 to 500 parts by weight, preferably 1 to 100 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the pigment.
５０50 parts by weight. In the present invention, at least one
By coating the particle surface of the kind pigment with an alkali-soluble resin, it is possible to produce a black matrix having a large light-shielding property without giving an adverse electric effect due to the conductivity of the pigment, and also to provide a defective pixel pattern. And a radiation-sensitive resin composition for a color filter capable of producing a black matrix and a color filter main body, which does not cause chipping and does not cause residue and background contamination on a substrate and a pixel in an unirradiated portion. can do.

In the present invention, the pigments coated as described above can be used alone or in admixture of two or more, and used in admixture with one or more uncoated pigments. be able to. When a mixture of a coated pigment and an uncoated pigment is used, the proportion of the coated pigment used is usually the weight of the pigment before being coated,
It is at least 5% by weight, preferably at least 20% by weight. The pigment in the present invention can be used together with a dispersant or a dispersing aid, if desired. Examples of such a dispersing agent or dispersing aid include cationic, anionic, nonionic, amphoteric, silicone-based, and fluorine-based surfactants. Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; and polyoxyethylene octyl phenyl ether and polyoxyethylene nonyl phenyl ether. Polyoxyethylene alkyl phenyl ethers; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid-modified polyesters; tertiary amine-modified polyurethanes; In the trade name, for example, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Yushi Kagaku Kogyo), F-Top (Tochem Products) ), Megafac (produced by Dainippon Ink and Chemicals, Inc.), Fluorad (Sumitomo 3M), Asahi Guard, Surflon (above, mention may be made of Asahi Glass Co., Ltd.) and the like. These surfactants can be used alone or in combination of two or more. The amount of the surfactant to be used is generally 50 parts by weight or less, preferably 10 to 40 parts by weight, based on 100 parts by weight of the total pigment before coating.

(B) Binder Resin As the binder resin in the present invention, as long as it acts as a binder with respect to the (A) pigment and is soluble in an alkali developing solution used in a developing step in the production of a color filter, An appropriate resin can be used. Preferred binder resin in the present invention,
(A) A resin similar to the carboxyl group-containing copolymer mentioned as the alkali-soluble resin for coating the pigment particle surface, and in particular, (A) the alkali-soluble resin and the binder resin for coating the pigment particle surface are the same. Is preferred. The copolymerization ratio of the carboxyl group-containing unsaturated compound in the carboxyl group-containing copolymer used as the binder resin is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated compound is less than 5% by weight, the solubility of the obtained radiation-sensitive resin composition in an alkali developing solution tends to decrease, and if it exceeds 50% by weight, At the time of development with an alkali developing solution, the formed pixels tend to easily fall off the substrate and the pixel surface becomes rough. In particular, a carboxyl group-containing copolymer containing a carboxyl group-containing unsaturated monomer at the specific copolymerization ratio is one having excellent solubility in an alkali developer, and the copolymer was used as a binder. The radiation-sensitive composition has very little undissolved material remaining after development with an alkali developing solution, and is unlikely to cause background fouling, film residue, and the like in a region other than a portion on which a pixel is formed on a substrate. The pixels obtained from the product do not dissolve excessively in the alkaline developer,
It has excellent adhesion and does not have a risk of falling off the substrate. Gel permeation chromatography of binder resin (GPC; elution solvent: tetrahydrofuran)
The polystyrene-equivalent weight average molecular weight (hereinafter, simply referred to as “weight average molecular weight”) measured in the above is usually 3,000.
~ 300,000, particularly preferably 5,000 ~ 10
It is 0000. By using a binder resin having such a specific weight average molecular weight, a radiation-sensitive resin composition having excellent developability can be obtained, whereby a pixel array having a sharp pattern edge can be formed, Residues on the substrate or pixels of the non-irradiated portion, background contamination, and the like hardly occur. In the present invention, the binder resins can be used alone or in combination of two or more. The amount of the binder resin used in the present invention is generally 10 to 1000 parts by weight based on 100 parts by weight of the total pigment before coating with the alkali-soluble resin.
Parts by weight, preferably 20 to 500 parts by weight. In this case, when the amount of the binder resin used is less than 10 parts by weight, for example, alkali developability is reduced, residues on the substrate or pixels of the non-irradiated portion are easily generated, and background stains and the like are easily generated. If the amount exceeds the above range, the pigment concentration relatively decreases, so that it may be difficult to achieve the target color density as a thin film.

(C) Polyfunctional Monomer The polyfunctional monomer in the present invention includes, for example, di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; and polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Di (meth) acrylates; poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol; polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins, Oligo (meth) acrylates such as spirane resin; hydroxyl-terminated at both ends such as hydroxy-poly-1,3-butadiene at both ends, hydroxy-polyisoprene at both ends and hydroxy-polycaprolactone at both ends Examples thereof include polymer di (meth) acrylates and tris [2- (meth) acryloyloxyethyl] phosphate.

Of these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols are preferred. Specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate
Acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dicarboxylic acid-modified pentaerythritol tri (meth) acrylate, and the like,
Trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate, and the compound represented by the following formula (1) have high pixel strength, excellent smoothness of the pixel surface, and are not exposed to radiation on the substrate. Alternatively, it is preferable in that a residue on a pixel, a background stain, and the like hardly occur.

[0018]

Embedded image

In the present invention, the polyfunctional monomers can be used alone or in combination of two or more.
A part of the polyfunctional monomer used in the present invention can be replaced with a monofunctional monomer. Examples of such a monofunctional monomer include, for example, the aforementioned (A)
As the constituent monomer of the alkali-soluble resin used for coating the surface of the pigment particle, there may be mentioned the same compounds as the carboxyl group-containing unsaturated compounds and other unsaturated compounds exemplified above. These monofunctional monomers can be used alone or in combination of two or more. The usage ratio of the monofunctional monomer is 0 to 90% by weight, preferably 0 to 50% by weight, based on the total of the polyfunctional monomer and the monofunctional monomer. The amount of the polyfunctional monomer used in the present invention is usually 5 to 500 parts by weight, preferably 20 to 100 parts by weight of the binder resin (B).
３００300 parts by weight. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the pixel strength or the smoothness of the pixel surface tends to decrease, while if it exceeds 500 parts by weight, for example, alkali developability decreases, There is a tendency that residues, non-irradiated portions on the substrate or pixels, background contamination, and the like are likely to occur.

(D) Radiation polymerization initiator The radiation polymerization initiator in the present invention refers to irradiation of radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray (hereinafter, referred to as “ radiation polymerization initiator”) .
This is called "exposure". ) Means a compound which generates an active species capable of initiating polymerization of the (C) polyfunctional monomer such as a radical species, a cationic species, an anionic species, etc. As such a radiation polymerization initiator, a compound having an imidazole ring,
Examples thereof include a compound having a benzoin bond, another radiation radical generator, a compound having a trihalomethyl group, and the like. As the compound having an imidazole ring, a biimidazole compound described in JP-A-8-259876 is preferable. Among these biimidazole compounds, in particular, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-biimidazole,
2,2′-bis (2-bromophenyl) -4,4 ′,
5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-
Tetraphenyl-1,2'-biimidazole, 2,2 '
-Bis (2,4-dibromophenyl) -4,4 ', 5
5′-tetraphenyl-1,2′-biimidazole,
2,2'-bis (2,4,6-trichlorophenyl)-
4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and 2,2'-bis (2,4,6-tribromophenyl) -4,4', 5,5'-tetra Phenyl-1,2'-biimidazole is preferred.

Examples of the compound having a benzoin bond and other radiation radical generators include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 1- (4-i-propylphenyl)- 2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2,2-dimethoxy-2-phenyl Acetophenone, 2-methyl- (4-methylthiophenyl) -2-
Morpholino-1-propan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, benzophenone, 3,3-dimethyl-4-methoxybenzophenone, 2,4 -Diethylthioxanthone, 4-azidobenzaldehyde, 4-azidoacetophenone, 4-azidobenzalacetophenone, azidopyrene, 4-diazodiphenylamine, 4-
Diazo-4'-methoxydiphenylamine, 4-diazo-3-methoxydiphenylamine, bis (2,4,6-
Trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4
Examples thereof include 4-trimethylpentylphosphine oxide, dibenzoyl, benzoin isobutyl ether, N-phenylthioacridone, triphenylpyrylium perchlorate, and the like, and trade names such as Irgacure and Darocure (all manufactured by Ciba Geigy). A series can be mentioned. Among these compounds having a benzoin bond and other radiation radical generators, in particular, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl Preferred are -1-phenylpropan-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and the like.

Examples of the compound having a trihalomethyl group include 1,3,5-tris (trichloromethyl) triazine and 2- (2′-furylethylidene)
-4,6-bis (trichloromethyl) -s-triazine, 2- (3 ', 4'-dimethoxystyryl) -4,6
-Bis (trichloromethyl) -s-triazine, 2-
(4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2'-bromo-
4'-methylphenyl) -4,6-bis (tric15methyl) -s-triazine, 2- (2'-thiophenylethylidene) -4,6-bis (trichloromethyl) -s-
Triazine and the like can be mentioned. Further, as radiation polymerization initiators other than the above, 4-azidobenzaldehyde, azidopyrene, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, N-phenylthioacridone, triphenylpyridone Lium perchlorate can also be used.
In the present invention, the radiation polymerization initiator may be used alone or
A mixture of more than one species can be used.

In the present invention, together with the radiation polymerization initiator, a sensitizer, a curing accelerator, or a radiation cross-linking agent or a radiation sensitizer comprising a polymer compound (hereinafter referred to as a “polymer radiation cross-linking / sensitizer”) ) May be used in combination. Examples of the sensitizer include 4,
4'-bis (dimethylamino) benzophenone, 4,
4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl-4-dimethylaminobenzoate, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4 ′ -Diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4
-Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone and the like. These sensitizers can be used alone or in combination of two or more. Further, as the curing accelerator, for example,
2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole,
2,5-dimercapto-1,3,4-thiadiazole,
2-mercapto-4,6-dimethylaminopyridine, 1
-Phenyl-5-mercapto-1H-tetrazole, 3
-Mercapto-4-methyl-4H-1,2,4-triazole and the like. These curing accelerators can be used alone or in combination of two or more. Further, the polymer radiation crosslinking / sensitizer is a polymer compound having a functional group capable of functioning as a radiation crosslinking agent and / or a radiation sensitizer in a main chain and / or a side chain. Condensates of 4-azidobenzaldehyde and polyvinyl alcohol, condensates of 4-azidobenzaldehyde and phenol novolak resin,
A homopolymer or a copolymer of 4-acryloylphenylcinnamoyl ester, 1,4-polybutadiene,
Examples thereof include 1,2-polybutadiene. These polymer radiation crosslinking / sensitizers can be used alone or in combination of two or more. In the present invention, as the radiation polymerization initiator, it is preferable to use the compound having a benzoin bond, or to use the compound in combination with the sensitizer and / or the curing accelerator. Hydroxy-2-methyl-
1-phenylpropan-1-one, 2-methyl- (4-
At least one selected from the group consisting of methylthiophenyl) -2-morpholino-1-propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, or Combination of at least one member selected from the group consisting of compounds of formula (I) with at least one member selected from the group consisting of 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone and 2-mercaptobenzothiazole Is preferred because formed pixels are less likely to fall off the substrate during development and have higher pixel strength and sensitivity.

The amount of the radiation polymerization initiator used in the present invention is usually 0.01 to 200 parts by weight, preferably 1 to 120 parts by weight, more preferably 100 to 100 parts by weight of the polyfunctional monomer (C). 1 to 50 parts by weight. In this case, if the amount of the radiation polymerization initiator is less than 0.01 part by weight, curing by exposure becomes insufficient, and the pattern is missing,
There is a risk of causing breakage or undercut.
If the amount is more than 0 parts by weight, the formed pattern tends to fall off the substrate during development, and the unexposed portion tends to be left on the substrate or the pixel, to cause background stain, and the like. The amount of the sensitizer and / or the curing accelerator used in the present invention is preferably 80% by weight or less of the total amount of the radiation polymerization initiator and the sensitizer and / or the curing accelerator.

(E) Solvent The solvent in the present invention dissolves or disperses the above-mentioned components (A) to (D) and additive components described below, and does not react with these components, and has an appropriate volatility. As long as it has, it can be appropriately selected and used. Such solvents include, for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
Ethylene glycol monoalkyl ethers such as ethylene glycol mono-n-propyl ether and ethylene glycol mono-n-butyl ether; diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol Ethylene glycol monomethyl ether,
Polyethylene glycol monoalkyl ethers such as triethylene glycol monoethyl ether; propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-
Propylene glycol monoalkyl ethers such as propyl ether and propylene glycol mono-n-butyl ether; dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether Propylene glycol monoalkyl ethers such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether; ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate; propylene glycol monomethyl ether acetate; Propylene glycol monoethyl ether Propylene glycol monoalkyl ether acetates such as acetate; diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, other ethers such as tetrahydrofuran; methylethylketone, cyclohexanone, 2-heptanone, 3
Ketones such as -heptanone; alkyl lactates such as methyl 2-hydroxypropionate and ethyl 2-hydroxypropionate; ethyl 2-hydroxy-2-methylpropionate; methyl 3-methoxypropionate;
-Ethyl methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutyl acetate, 3- Methyl-3-methoxybutyl propionate, ethyl acetate, n-butyl acetate, i-acetic acid
-Butyl, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate , Other esters such as ethyl acetoacetate and ethyl 2-oxobutanoate; aromatic hydrocarbons such as toluene and xylene; N-methylpyrrolidone; N, N-dimethylformamide;
Examples thereof include amides such as N-dimethylacetamide. These solvents can be used alone or in combination of two or more.

Further, benzyl ethyl ether, dihexyl ether, acetonylacetone,
Isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate , Etc., can be used in combination. These high-boiling solvents can be used alone or in combination of two or more.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, from the viewpoints of solubility, pigment dispersibility, coatability and the like.
Diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, 3-methyl-3-methoxybutylpropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3- Ethyl ethoxypropionate, n-butyl acetate, i-butyl acetate,
Preferred are n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl pyruvate and the like, and as the high boiling solvent, γ-butyrolactone and the like preferable. The amount of the solvent used in the present invention is not particularly limited, but from the viewpoints of coatability, stability of the composition and the like, the above (A) to (A)
The total concentration of the component (D) and the additive component described below is 5 to 5
An amount of 0% by weight, preferably 10 to 40% by weight is desirable.

Additives The radiation-sensitive composition for a color filter of the present invention contains the above-mentioned components (A) to (E) as essential components, and further improves the solubility of the composition in an alkali developing solution. And
In order to further reduce the remaining undissolved matter after the development processing, an organic acid may be contained. As such an organic acid, an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having a molecular weight of 1,000 or less is preferable. Examples of the aliphatic carboxylic acid include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, and amber Acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, cyclohexanedicarboxylic acid, itaconic acid ,
Examples thereof include dicarboxylic acids such as citraconic acid, maleic acid, fumaric acid, and mesaconic acid; and tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid. Examples of the phenyl group-containing carboxylic acid include, for example, an aromatic carboxylic acid in which a carboxyl group is directly bonded to a phenyl group, and a carboxylic acid in which a carboxyl group is bonded to a phenyl group via a carbon chain. Specifically, aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, and terephthalic acid; trimellitic acid, trimesic acid, and melophane acid,
Trivalent or higher aromatic polycarboxylic acids such as pyromellitic acid, phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidenic acid, coumaric acid, umbellic acid, etc. Can be mentioned. Of these organic acids, malonic acid,
Aliphatic dicarboxylic acids and aromatic dicarboxylic acids such as adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, and phthalic acid are alkali-soluble, (E) solvent-soluble, on unexposed portions of the substrate or pixels It is preferable from the viewpoint of reduction of the residue on the top and background dirt. The organic acids can be used alone or in combination of two or more. The amount of the organic acid used in the present invention is usually 10% by weight or less, preferably 5% by weight or less, more preferably 1% by weight or less, based on the whole radiation-sensitive composition. In this case, if the amount of the organic acid used exceeds 10% by weight, the adhesion of the formed pixel to the substrate tends to decrease.

Further, the radiation-sensitive composition for a color filter of the present invention may contain various additives other than the above-mentioned organic acids, if necessary. Examples of such additives include dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives; fillers such as glass and alumina; polyvinyl alcohol, polyethylene glycol monoalkyl ether, and polyfluoroalkyl acrylate. High molecular compounds; nonionic, cationic,
Surfactants such as anionic surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl)-
3-aminopropylmethyldimethoxysilane, N- (2
-Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2 -Promotion of adhesion of (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; 2- (3-t-butyl-5-methyl-2-hydroxy) Phenyl) -5-chlorobenzotriazoe Ultraviolet absorbers such as alkoxy benzophenone; aggregation inhibitor such as sodium polyacrylate, epoxy compounds, melamine compounds, mention may be made of thermal crosslinking agents such as bis-azido compounds.

Color filter body and black matrix
Next, a method of forming a color filter body and a black matrix using the radiation-sensitive composition for a color filter of the present invention will be described. First, on the surface of a transparent substrate, if necessary, a light-shielding layer is formed so as to partition a portion where a pixel pattern is to be formed.On this substrate, for example, a radiation-sensitive composition in which a red pigment is dispersed is used. After application, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Next, after this coating film is exposed through a photomask, it is subjected to a developing treatment to dissolve and remove the unexposed portions of the coating film, and is preferably post-baked, and red pixels are arranged in a predetermined pattern. To form a pixel array. Thereafter, using each radiation-sensitive composition in which the green or blue pigment is dispersed, in the same manner as described above, coating, pre-baking, exposure and development treatment of each composition, preferably post-baking afterwards, By sequentially forming a green pixel array and a blue pixel array on the same substrate, a color filter main body in which three primary color pixel arrays of red, green and blue are arranged on the substrate is obtained. Examples of the transparent substrate used when forming the color filter main body include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide imide, and polyimide. In addition, these transparent substrates can be subjected to an appropriate pretreatment such as a chemical treatment with a silane coupling agent or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, or a vacuum deposition, if desired. . When applying the radiation-sensitive composition to the transparent substrate, an appropriate coating method such as spin coating, casting coating, and roll coating can be employed. The coating thickness is
The film thickness after drying is usually 0.1 to 10 μm, preferably 0.2 to 5.0 μm, more preferably 0.2 to 5.0 μm.
3.0 μm. As the radiation used when forming the color filter main body, visible light, ultraviolet light, far ultraviolet light, an electron beam, X-ray, or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable. The irradiation energy amount of the radiation is preferably 1 to 1000 m
J / cm ² . Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, and 1,8-diazabicyclo- [5.4.0] -7-.
Undecene, 1,5-diazabicyclo- [4.3.0]
An aqueous solution such as -5-nonene is preferred. Further, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkali developer. After the alkali development, the film is usually washed with water. As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid puddle) developing method, or the like can be applied. The developing condition is preferably 5 to 300 seconds at room temperature. Furthermore, a black matrix can be formed by using the radiation-sensitive composition for a color filter of the present invention containing a black pigment in the same manner as in the case of each pixel array. The color filter main body and the black matrix formed in this manner are, for example, a desktop calculator, a wristwatch, a clock, a coefficient display board, a word processor, a personal computer, a color liquid crystal display device such as a liquid crystal television, a color image pickup tube element, a color Very useful for sensors and the like.

[0031]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Here, embodiments of the radiation-sensitive composition for a color filter of the present invention are more specifically exemplified as follows (a) to (d). (A) (A) pigment, (B) binder resin, (C) polyfunctional monomer, (D) radiation polymerization initiator, and (E)
A radiation-sensitive resin composition for a color filter containing a solvent, wherein (A) at least one pigment in the pigment has a particle surface coated with a carboxyl group-containing vinyl resin. Composition. (B) The (A) carboxyl group-containing vinyl resin coating the particle surface of at least one pigment in the pigment is (meth)
The radiation-sensitive composition for a color filter according to the above (a), which is a copolymer of a monomer mixture containing acrylic acid and benzyl (meth) acrylate. (C) the particle surface of at least one pigment in the pigment (A) is coated with a carboxyl group-containing vinyl resin, and the carboxyl group-containing vinyl resin is the same as the binder resin (B); The radiation-sensitive composition for a color filter according to (a) or (b). (D) (A) wherein the pigment contains carbon black coated with a carboxyl group-containing vinyl resin,
The radiation-sensitive composition for a color filter according to (b) or (c).

Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Comparative Example 1 As a component (A), 120 parts by weight of carbon black was used.
A pigment dispersion liquid dispersed in propylene glycol monomethyl ether acetate using a polyester dispersant, and as a component (B), a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 15/70/15) ) 40 parts by weight, dipentaerythritol pentaacrylate 3 as component (C)
0 parts by weight, as the component (D), 25 parts by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one,
As a component (E), 700 parts by weight of propylene glycol monomethyl ether acetate (including the solvent for the pigment dispersion) and 100 parts by weight of cyclohexanone were mixed to prepare a radiation-sensitive composition. Next, on a surface of a transparent substrate made of soda glass on which a silica (SiO ₂ ) film for preventing elution of sodium ions was formed on the surface, the radiation-sensitive composition was applied using a spin coater, and then heated to 80 ° C. Pre-bake for 4 minutes on a hot plate to obtain a film thickness of 1.
A coating film of 4 μm was formed. Then, after cooling the substrate, a high-pressure mercury lamp was used to apply a wavelength of 365 nm to the coating film.
400 mJ / cm including light at 05 nm and 436 nm
² were exposed to UV light. Next, post-baking was performed for 30 minutes in a clean oven at 220 ° C.
A substrate on which a coating film was formed was prepared. As a result of measuring the surface resistivity of the obtained coating film, it was found to be 10 ⁶ Ω / □. In addition, silica (S
iO ₂ ) The radiation-sensitive resin composition was applied using a spin coater on the surface of a transparent substrate made of soda glass on which the film was formed, and then prebaked on a hot plate at 80 ° C. for 4 minutes to obtain a film thickness. A coating film of 1.4 μm was formed.
Then, after cooling the substrate, using a high-pressure mercury lamp,
The wavelength of 365 nm, 405 is applied to the coating film through a photomask.
It was exposed to ultraviolet light of 400 mJ / cm ² including light of nm and 436 nm. Next, the substrate was developed and washed under the following conditions, air-dried, and then post-baked in a clean oven at 220 ° C. for 30 minutes to produce a lattice-shaped black matrix having a line width of 20 μm. <Developing conditions> Developing solution: 0.1% by weight aqueous solution of tetramethylammonium hydroxide Developing device: Shower developing device Developing temperature: 23 ° C. Shower pressure: 1 kg / cm ² Developing time: 1 minute <Washing condition> Washing solution: Ultrapure water Shower pressure: 2 kg / cm ² Cleaning time: 1 minute As a result, pattern defects and omissions were observed on the obtained black matrix substrate, and residue and background stain were observed on the unexposed portion of the substrate and pixels. Was done. Further, lighting failure occurred in the color liquid crystal display device incorporating the obtained black matrix.

Comparative Example 2 As a component (A), a pigment dispersion obtained by dispersing 132 parts by weight of carbon black whose particle surface was coated with 12 parts by weight of an epoxy resin in propylene glycol monomethyl ether acetate using a polyester dispersant. , (B)
Methacrylic acid / benzyl methacrylate /
Polystyrene macromonomer copolymer (copolymerization weight ratio =
25/65/10) 40 parts by weight, as component (C), 30 parts by weight of dipentaerythritol pentaacrylate,
(D) As component, 2-hydroxy-2-methyl-1-
25 parts by weight of phenylpropan-1-one, 700 parts by weight of propylene glycol monomethyl ether acetate (including the solvent for the pigment dispersion) and 100 parts by weight of cyclohexanone as the component (E) were mixed to prepare a radiation-sensitive composition. Prepared. Comparative Example 1 using the radiation-sensitive composition
After forming a coating film in the same manner as in the above, the surface resistivity was measured. As a result, it was 10 ¹¹ Ω / □. Further, a black matrix was prepared in the same manner as in Comparative Example 1 using the radiation-sensitive composition. In the obtained black matrix substrate, pattern defects and omissions were observed, and residues and background stains were observed on the unexposed portions of the substrate and on the pixels.

Example 1 As component (A), 132 parts by weight of carbon black whose particle surface was coated with 12 parts by weight of a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 15/70/15) Is dispersed in propylene glycol monomethyl ether acetate using a polyester-based dispersant, and as a component (B), a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 25 /
65/10) 40 parts by weight, as component (C), 30 parts by weight of dipentaerythritol pentaacrylate, (D)
As a component, 25 parts by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one, as a component (E),
Propylene glycol monomethyl ether acetate 7
00 parts by weight (including the solvent for the pigment dispersion) and 100 parts by weight of cyclohexanone were mixed to prepare a radiation-sensitive composition. Using the radiation-sensitive composition, a coating film was formed in the same manner as in Comparative Example 1, and the surface resistivity was measured. The result was 10 ¹¹ Ω / □. Further, a black matrix was prepared in the same manner as in Comparative Example 1 using the radiation-sensitive composition. In the obtained black matrix substrate, no loss or omission of the pattern was observed, and no residue or background stain was observed on the unexposed portion of the substrate and on the pixels. In addition, no lighting failure occurred in the color liquid crystal display device incorporating the obtained black matrix.

Comparative Example 3 As a component (A), a pigment dispersion obtained by dispersing 120 parts by weight of a red pigment (CI Pigment Red 177) in propylene glycol monomethyl ether acetate using a polyurethane dispersant, As the component (B), a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 15/70/1)
5) 40 parts by weight, 30 parts by weight of dipentaerythritol pentaacrylate as the component (C), 30 parts by weight of 2-hydroxy-2-methyl-1-phenylpropan-1-one as the component (D), (E) As components, 700 parts by weight of propylene glycol monomethyl ether acetate (including the solvent for the pigment dispersion) and cyclohexanone 1
Then, 00 parts by weight were mixed to prepare a radiation-sensitive composition.
Silica (SiO ₂ ) that prevents sodium ions from eluting to the surface
After a light-shielding layer having a desired pattern is formed in advance on the surface of the soda glass transparent substrate on which the film is formed, the radiation-sensitive resin composition is applied using a spin coater, and then is applied on a hot plate at 80 ° C. Pre-baking was performed for 4 minutes to form a coating film having a thickness of 2.0 μm. Then, after cooling the substrate, the wavelength of 365 nm, 405 nm and 4
It was exposed to ultraviolet light of 100 mJ / cm ² including light of 36 nm. Next, the substrate was developed and washed under the same conditions as in Comparative Example 1, air-dried, and further post-baked in a clean oven at 220 ° C. for 30 minutes to produce a red pixel array. In the obtained substrate, pattern defects and omissions were observed, and residues and background stains were observed on the unexposed portion of the substrate and on the pixels.

Comparative Example 4 As a component (A), a red pigment (CI Pigment Red 17) coated on the particle surface with 12 parts by weight of an epoxy resin was used.
7) 132 parts by weight of a pigment dispersion obtained by dispersing 132 parts by weight in propylene glycol monomethyl ether acetate using a polyurethane-based dispersant, and as a component (B), a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymer weight) Ratio = 15/70/15) 40
Parts by weight, as component (C), 30 parts by weight of dipentaerythritol pentaacrylate, and as component (D), 2-
Hydroxy-2-methyl-1-phenylpropane-1-
A radiation-sensitive composition was prepared by mixing 30 parts by weight of ON, 700 parts by weight of propylene glycol monomethyl ether acetate (including the solvent for the pigment dispersion) and 100 parts by weight of cyclohexanone as the component (E). A red pixel array was produced in the same manner as in Comparative Example 3 using the radiation-sensitive composition. In the obtained substrate, pattern defects and omissions were observed, and residues and background stains were observed on the unexposed portion of the substrate and on the pixels.

Example 2 As a component (A), a red pigment (C.I.) coated with 12 parts by weight of a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymer weight ratio = 15/70/15) was used. I. Pigment Red 177) 13
2 parts by weight of a pigment dispersion obtained by dispersing 2 parts by weight in propylene glycol monomethyl ether acetate using a polyurethane-based dispersant, and as a component (B), a methacrylic acid / benzyl methacrylate / polystyrene macromonomer copolymer (copolymerization weight ratio = 15/70/15) 40 parts by weight,
As the component (C), 30 parts by weight of dipentaerythritol pentaacrylate, and as the component (D), 2-hydroxy-2-methyl-1-phenylpropan-1-one 30
The radiation-sensitive composition was prepared by mixing 700 parts by weight of propylene glycol monomethyl ether acetate (including the solvent for the pigment dispersion) and 100 parts by weight of cyclohexanone as the component (E). A red pixel array was produced in the same manner as in Comparative Example 3 using the radiation-sensitive composition. In the obtained substrate, no loss or omission of the pattern was observed, and no residue or background stain was observed on the unexposed portion of the substrate and on the pixels.

[0038]

By using the radiation-sensitive composition for a color filter of the present invention, an adverse electrical effect due to the conductivity of the pigment can be suppressed. Not only can produce a black matrix having a large size, but also a black matrix and a color filter main body that do not have a pattern defect or omission and that do not cause residue or background stain on an unexposed portion of a substrate and pixels. Thus, a color liquid crystal display device, a color image pickup tube element, a color sensor, and the like having high reliability and excellent characteristics can be manufactured.

Claims (1)

[Claims] (A) a pigment, (B) a binder resin,
A radiation-sensitive resin composition for a color filter containing (C) a polyfunctional monomer, (D) a radiation polymerization initiator, and (E) a solvent, wherein (A) at least one pigment particle in the pigment A radiation-sensitive composition for a color filter, the surface of which is coated with an alkali-soluble resin.