JP5080715B2 - Radiation sensitive composition for color filter, color filter, and color liquid crystal display device - Google Patents

Description

  The present invention relates to a radiation-sensitive composition for color filters, a color filter, and a color liquid crystal display device, and more specifically, manufacture of a color filter used for a transmissive or reflective color liquid crystal display device, a color imaging tube element, and the like. The present invention relates to a radiation sensitive composition for a color filter useful for a color filter, a color filter formed from the radiation sensitive composition for a color filter, and a color liquid crystal display device including the color filter.

In producing a color filter using a colored radiation-sensitive composition, a coating film of the colored radiation-sensitive composition is usually formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed. Radiation is irradiated through a mask having the pattern shape (hereinafter referred to as “exposure”), development is performed with an alkaline developer to dissolve and remove unexposed portions, and then post-baking is performed using a clean oven or a hot plate. Thus, a forming method for obtaining pixels of each color (for example, see Patent Document 1 and Patent Document 2) is known.
As a colorant used in such a colored radiation-sensitive composition, the color filter is required to have high-definition color development and heat resistance, so that it has high color developability and heat resistance, particularly high heat decomposition resistance. Organic pigments having the following are often used. However, the conventional colored radiation-sensitive composition has a drawback that the dispersibility of the pigment is poor. In order to solve such problems, for example, as disclosed in Patent Document 3, there has been a proposal of using an alkoxyalkyl acetate as a solvent. However, dispersibility is not always sufficient by itself, and application unevenness may be observed during application on a substrate, and particularly when used for application by a slit die coater, application unevenness may be noticeable. .
Therefore, development of the radiation sensitive composition for color filters which further improved the dispersibility and applicability | paintability is calculated | required strongly.

JP-A-2-144502 JP-A-3-53201 JP-A-6-289601

An object of the present invention is to provide a radiation-sensitive composition for a color filter, which does not cause uneven coating even when applied on a substrate using a slit die coater, and can form a uniform colored layer with high product yield and high efficiency. To provide things.

As a result of intensive studies on the above problems at the time of coating using a slit die coater on a substrate, the present inventors have found that the solvent type, the mixing ratio, and the radiation sensitive composition used for forming the color filter, The ratio of the total amount of each component excluding the solvent in the composition to the entire composition (hereinafter referred to as “solid content concentration”) was found to be closely related to the coating property, and the present invention was achieved. It is a thing.
The present invention firstly provides a radiation-sensitive composition containing (A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photoradical generator, and (E) a solvent. made, are those containing at least one solvent (E) is, to a 3-methoxybutyl acetate, selected from ethyl 3-ethoxypropionate and propylene glycol monomethyl ether acetate tape preparative O Li Cheng group, 3- A radiation-sensitive composition for color filters, characterized in that methoxybutyl acetate is 15 to 60% by weight of the total solvent and the solid content concentration is 10 to 30% by weight, and is used for coating with a slit die coater. .
The “radiation” as used in the present invention means a substance including visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like.

  Secondly, the present invention comprises a color filter formed from the radiation sensitive composition for color filter.

  Thirdly, the present invention comprises a color liquid crystal display device comprising the color filter.

According to the present invention, coating unevenness does not occur even when coating on a substrate, particularly when using a slit die coater, and a colored layer for a color filter having a uniform film thickness is formed with high product yield and high efficiency. be able to.
Therefore, the method for forming the radiation sensitive composition for a color filter and the colored layer for the color filter of the present invention is very suitably used for forming various color filters including color filters for color liquid crystal display devices in the electronic industry. can do.

Hereinafter, embodiments of the present invention will be described in detail.
Radiation sensitive composition for color filter- (A) Pigment-
As the pigment in the present invention, an organic pigment is preferable because the color filter is required to have high purity and high transmittance color development and heat resistance.
Examples of the organic pigment include compounds classified as pigments in a color index (CI; issued by The Society of Dyers and Colorists), specifically, a color index (CI) number as shown below. You can list what you have.

CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 211;
CI Pigment Orange 36, CI Pigment Orange 43, CI Pigment Orange 51, CI Pigment Orange 61, CI Pigment Orange 71;
CI Pigment Red 9, 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, CI Pigment Red 180, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 224, CI Pigment Red 242, CI Pigment Red 254;
CI pigment violet 19, pigment violet 23, pigment violet 29;
CI Pigment Blue 15, CI Pigment Blue 60, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6,
CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 136, CI Pigment Green 210;
CI Pigment Brown 23, CI Pigment Brown 25;
These organic pigments can be used alone or in admixture of two or more.
In the present invention, the organic pigment can be purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof.

Examples of inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide green. , Cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.
These inorganic pigments can be used alone or in admixture of two or more.
Furthermore, in the present invention, if necessary, one or more dyes or natural pigments can be used in combination with the pigment.

  In the present invention, the pigment can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the pigment particle surface include the polymers described in JP-A-8-259876, and various commercially available pigment-dispersing polymers or oligomers.

Moreover, in this invention, a pigment can be used with a dispersing agent if desired.
Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl Polyoxyethylene alkyl phenyl ethers such as phenyl ether; polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; sorbitan fatty acid esters; fatty acid modified polyesters; tertiary amine modified polyurethanes; The following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F Top (manufactured by Tochem Products), Megafu (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (Asahi Glass Co., Ltd.), Disperbyk (Bicchemy Japan Co., Ltd.), Sol Sparse (Manufactured by Zeneca Co., Ltd.), EFKA (manufactured by Fuka Chemicals Co., Ltd.), and the like.
These surfactants can be used alone or in admixture of two or more.
The amount of the dispersant used is preferably 50 parts by weight or less, more preferably 30 parts by weight or less with respect to 100 parts by weight of the pigment.

(B) Alkali-soluble resin As the alkali-soluble resin in the present invention, (A) a developer that acts as a binder for the pigment and is used in the development processing step when producing a color filter, particularly preferably alkaline Although it will not specifically limit if it has a solubility with respect to a developing solution, The alkali-soluble resin which has a carboxyl group is preferable, and especially the ethylenically unsaturated monomer (one or more carboxyl group ( Hereinafter, a copolymer of “carboxyl group-containing unsaturated monomer”) and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as “copolymerizable unsaturated monomer”). (Hereinafter referred to as “carboxyl group-containing copolymer”) is preferred.

As the carboxyl group-containing unsaturated monomer, for example,
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof;
Mono [(meth) acryloyloxyalkyl] of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;
Examples thereof include mono (meth) acrylates of polymers having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
Among these carboxyl group-containing unsaturated monomers, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively M-5300 and M-5400 (Toagosei ( (Commercially available) under the trade name.
The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

Examples of the copolymerizable unsaturated monomer include:
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether;
Indenes such as indene and 1-methylindene;

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 Rate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl Unsaturation such as (meth) acrylate, tricyclo [5.2.1.02,6] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, etc. Carboxylic acid esters;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; vinyl acetates such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Unsaturated imides such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include macromonomers having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These copolymerizable unsaturated monomers can be used alone or in admixture of two or more.

  As the carboxyl group-containing copolymer in the present invention, (meth) acrylic acid is an essential component, and in some cases, succinic acid mono [2- (meth) acryloyloxyethyl] and ω-carboxypolycaprolactone mono (meth) acrylate. A carboxyl group-containing unsaturated monomer component further containing at least one compound selected from the group consisting of styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl ( A copolymer with at least one selected from the group of (meth) acrylate, glycerol mono (meth) acrylate, N-phenylmaleimide, polystyrene macromonomer and polymethylmethacrylate macromonomer (hereinafter referred to as “carboxyl group-containing copolymer (B1) ) ". It is preferred.

As specific examples of the carboxyl group-containing copolymer (B1),
(Meth) acrylic acid / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / methyl (meth) acrylate / polymethyl methacrylate macromonomer 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,
Methacrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono [2- ( (Meth) acryloyloxyethyl] / styrene / allyl (meth) acrylate / N-phenylmaleimide copolymer (meth) acrylic acid / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer Coalescence,
Examples thereof include (meth) acrylic acid / ω-carboxypolycacrolactone mono (meth) acrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate / N-phenylmaleimide copolymer.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. In this case, if the copolymerization ratio is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkali developer tends to be reduced, whereas if it exceeds 50% by weight, the solubility in an alkali developer is low. Therefore, when developing with an alkaline developer, the colored layer tends to drop off from the substrate or the pixel surface becomes rough.
Mw measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of an alkali-soluble resin is usually 3,000 to 300,000, preferably 5,000 to 100,000.
The polystyrene-equivalent number average molecular weight (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of an alkali-soluble resin is usually 3,000 to 60,000, preferably 5,000 to 25,000.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin is preferably 1 to 5, and more preferably 1 to 4.
In the present invention, by using such an alkali-soluble resin having specific Mw and Mn, a radiation-sensitive composition having excellent developability can be obtained, and thereby a pixel pattern having sharp pattern edges can be obtained. In addition to being able to be formed, residues, background stains, film residues and the like are less likely to occur on the unexposed substrate and the light shielding layer during development.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.
The usage-amount of the alkali-soluble resin in this invention is 10-1,000 weight part normally with respect to 100 weight part of (A) pigments, Preferably it is 20-500 weight part. In this case, if the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, the alkali developability may be lowered, or background stains or film residues may be generated on the substrate or the light shielding layer in the unexposed area. When the amount exceeds 1,000 parts by weight, the pigment concentration is relatively lowered, and it may be difficult to achieve the target color concentration as a thin film.

(C) Polyfunctional monomer The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds.
As the multifunctional monomer, for example,
Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;
Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;
Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol and the like and their dicarboxylic acid modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene, both terminal hydroxypolycaprolactone,
And tris [2- (meth) acryloyloxyethyl] phosphate.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid-modified products, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tri ( (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are preferred, especially trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexa Acrylates are preferred in that they are excellent in strength and surface smoothness of the colored layer, and are less likely to cause background stains and film residue on the unexposed substrate and the light shielding layer.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of (B) alkali-soluble resin, Preferably it is 20-300 weight part. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to be reduced. There is a tendency that background contamination, film residue, etc. are likely to occur on the unexposed substrate or the light shielding layer.
In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include (B) a monomer similar to the carboxyl group-containing unsaturated monomer and copolymerizable unsaturated monomer exemplified for the alkali-soluble resin, and N- (meta ) In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, trade names include M-5600 (manufactured by Toagosei Co., Ltd.).
These monofunctional monomers can be used alone or in admixture of two or more.

The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total amount of the polyfunctional monomer and the monofunctional monomer. In this case, when the usage ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the obtained pixel may be insufficient.
The total use amount of the polyfunctional monomer and the monofunctional monomer in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the (B) alkali-soluble resin. Part. In this case, if the total amount used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to be lowered. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability is lowered or unexposed parts There is a tendency that soiling, film residue, etc. are likely to occur on the substrate or the light shielding layer.

(D) Photoradical generator The photoradical generator in the present invention is used by (C) the polyfunctional monomer and optionally by exposure to visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like. It is a compound capable of generating a radical capable of initiating polymerization of a monofunctional monomer.
Examples of such photo radical generators include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds. A compound etc. can be mentioned.
In the present invention, the photoradical generator can be used alone or in admixture of two or more. As the photoradical generator in the present invention, acetophenone compounds, biimidazole compounds and triazine compounds can be used. At least one selected from the group is preferred.

  Among preferred photoradical generators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl. ] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-1,2-diphenyl And ethane-1-one.

Among these acetophenone compounds, in particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) Butanone-1 and the like are preferable.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, when the acetophenone-based compound is used as the photoradical generator, the amount used is usually 0 with respect to 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. 0.01 to 80 parts by weight, preferably 1 to 60 parts by weight, more preferably 1 to 30 parts by weight. In this case, if the amount of the acetophenone compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a pixel pattern in which pixels are arranged according to a predetermined arrangement. When it exceeds the weight part, the formed colored layer tends to be detached from the substrate during development.

  Specific examples of the biimidazole compound include 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- Chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl -1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2 '-Bis (2-bromophenyl) -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-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like can be mentioned.

Among these biimidazole compounds, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 , 4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole and the like are more preferable, and in particular, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole is preferred.
The biimidazole compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved matter and precipitates, has high sensitivity, and sufficiently proceeds with a curing reaction by exposure with a small amount of energy, and is not exposed. The coating film after exposure is clearly divided into a cured part that is insoluble in the developer and an uncured part that has high solubility in the developer. Thus, it is possible to form a high-definition pixel pattern in which pixels without undercuts are arranged according to a predetermined arrangement.
The biimidazole compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used in the case of using a biimidazole compound as a photoradical generator is usually (C) with respect to a total of 100 parts by weight of the polyfunctional monomer and the monofunctional monomer, 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the amount of biimidazole compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a pixel pattern in which pixels are arranged according to a predetermined arrangement, If it exceeds 40 parts by weight, the formed colored layer tends to fall off the substrate during development.

-Hydrogen donor-
In the present invention, when a biimidazole compound is used as the photoradical generator, it is preferable to use the following hydrogen donor in combination because the sensitivity can be further improved.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As the hydrogen donor in the present invention, mercaptan compounds, amine compounds and the like defined below are preferable.
The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “ Mercaptan-based hydrogen donor ").
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). , "Amine-based hydrogen donor").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, these hydrogen donors will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and the like are preferable, and 2-mercaptobenzothiazole is particularly preferable.

Next, the amine-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When these two or more rings are present, A condensed ring may or may not be formed.
In addition, in the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxy group may be substituted at a position other than the amino group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Of these amine-based hydrogen donors, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of a photopolymerization initiator other than a biimidazole compound.

In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed colored layer does not easily fall off the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of the combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-bis. (Diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,
4′-bis (diethylamino) benzophenone and the like can be mentioned, and more preferable combinations are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis ( Diethylamino) benzophenone and the like, and a particularly preferred combination is 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

  In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the amount used is preferably 0 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the hydrogen donor used is less than 0.01 parts by weight, the effect of improving the sensitivity tends to decrease. On the other hand, if it exceeds 40 parts by weight, the formed colored layer is detached from the substrate during development. It tends to be easy to do.

Specific examples of triazine compounds include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) ) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy) Triazine compounds having a halomethyl group such as styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.
Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.
The triazine compounds can be used alone or in admixture of two or more.

  In the present invention, when the triazine-based compound is used as the photoradical generator, the amount used is usually 0 with respect to 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the use amount of the triazine-based compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a pixel pattern in which pixels are arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the formed colored layer tends to be easily detached from the substrate during development.

Additive component The radiation-sensitive composition in the present invention may contain various additive components as required.
The additive component may be an organic acid or an organic amino compound (provided to improve the solubility of the radiation-sensitive composition in an alkaline developer and to further suppress the remaining undissolved product after development) , Excluding the hydrogen donor).

-Organic acid-
The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.
Examples of the aliphatic carboxylic acid include
Aliphatic 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, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid , Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
Examples thereof include aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoric acid.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, and compounds in which a carboxyl group is bonded to a phenyl group via a divalent carbon chain.
Examples of the phenyl group-containing carboxylic acid include
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples thereof include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

Among these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in a solvent described later, prevention of soiling and film residue on the substrate or the light-shielding layer in the unexposed area, and the like. Dicarboxylic acids are preferred. In particular, malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are preferred. As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferred, and phthalic acid is particularly preferred.
The organic acids can be used alone or in admixture of two or more.
The amount of the organic acid used is usually 15 parts by weight or less, preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the components (A) to (D) and the additive component. In this case, when the usage-amount of organic acid exceeds 15 weight part, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

-Organic amino compounds-
The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule.
Examples of the aliphatic amine include:
mono (cyclo) alkylamines such as n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec- Di (cyclo) alkylamines such as butylamine and di-t-butylamine;
Dimethyl ethylamine, methyl diethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyl di-n-propylamine, ethyl di-n-propylamine, tri-n-propylamine, tri -Tri (cyclo) alkylamines such as i-propylamine, tri-n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine;

Mono (cyclo) alkanolamines such as 2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol;
Di (cyclo) alkanolamines such as diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine;
Tri (cyclo) alkanolamines such as triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine;
3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 3-dimethylamino-1 Amino (cyclo) alkanediols such as 2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol, 2-diethylamino-1,3-propanediol;
Examples thereof include aminocarboxylic acids such as β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, and 3-aminoisobutyric acid.

Examples of the phenyl group-containing amine include compounds in which an amino group is directly bonded to the phenyl group, and compounds in which the amino group is bonded to the phenyl group via a divalent carbon chain.
As the phenyl group-containing amine, for example,
Aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, p-methyl-N, Aromatic amines such as N-dimethylaniline;
aminobenzyl alcohols such as o-aminobenzyl alcohol, m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol, p-diethylaminobenzyl alcohol;
aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol, p-diethylaminophenol;
Examples thereof include aminobenzoic acids such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid, and p-diethylaminobenzoic acid.

Among these organic amino compounds, mono (cyclo) alkanolamines are used as aliphatic amines from the viewpoints of solubility in the solvent described later, prevention of soiling and film residue on the unexposed portion of the substrate or the light shielding layer, and the like. And amino (cyclo) alkanediols are preferred, especially 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino -1,3-propanediol, 4-amino-1,2-butanediol and the like, and as the phenyl group-containing amine, aminophenols are preferable, and in particular, o-aminophenol, m-aminophenol, p- Aminophenol and the like are preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The amount of the organic amino compound used is usually 15 parts by weight or less, preferably 10 parts by weight or less based on 100 parts by weight of the total of the components (A) to (D) and the additive component. In this case, when the usage-amount of an organic amino compound exceeds 15 weight part, there exists a tendency for the adhesiveness with the board | substrate of the formed colored layer to fall.

-Other additive components-
Moreover, as other additive components, for example,
Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl-methyl-dimethoxysilane, N- (2-aminoethyl) -3-amino Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyl methyl dimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, Adhesion promoters such as 3-chloropropyl, methyl, dimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Examples thereof include thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

(E) Solvent The solvent in the present invention contains 3-methoxybutyl acetate.
(E) The solvent further contains at least one selected from the group consisting of propylene glycol monomethyl ether acetate, cyclohexanone and ethyl 3-ethoxypropionate as another solvent.
The other solvents can be used alone or in admixture of two or more.

The amount of 3-methoxybutyl acetate used is 15-60% by weight of the total solvent. By making the usage-amount of 3-methoxybutyl acetate into such a range, the dispersibility of a pigment and the applicability | paintability will be balanced.

  The amount of the solvent used is desirably an amount such that the solid content concentration is usually 10 to 30% by weight, preferably 15 to 25% by weight, from the viewpoint of applicability and stability of the liquid composition to be obtained. In this case, if the solid content concentration is less than 10% by weight, it becomes difficult to obtain a coating film having a prescribed film thickness, whereas if it exceeds 30% by weight, coating defects such as coating unevenness tend to occur. is there.

Method for Forming Color Filter Next, a method for forming the color filter of the present invention using the radiation sensitive composition for color filter of the present invention will be described.
The method for forming a color filter of the present invention includes at least the following steps (1) to (4).
(1) The coating film formation process which forms the coating film of the radiation sensitive composition for color filters of this invention on a board | substrate.
(2) An exposure step of exposing at least a part of the coating film.
(3) A development step for developing the coated film after exposure.
(4) A heat treatment step of post-baking the coated film after development.
Hereinafter, these steps will be sequentially described.

(1) Coating film forming step.
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming pixels, and a liquid composition of the radiation sensitive composition for a color filter of the present invention is formed on this substrate. After coating, pre-baking is performed to evaporate the solvent, and a coating film can be formed.
Examples of the substrate used in this step include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, cyclic olefin ring-opening polymer, and hydrogenated products thereof. be able to.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.
When the liquid composition is applied to the substrate, application using a slit die coater is employed.
The prebaking condition is usually about 2 to 4 minutes at 70 to 110 ° C.
The coating thickness is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after removal of the solvent.

(2) Exposure step Thereafter, the formed coating film is exposed through, for example, a photomask having an appropriate pattern.
As the radiation used in this step, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
The exposure dose of radiation is usually 10 to 10,000 J / m2.

(3) Development step Thereafter, development is preferably performed using an alkaline developer to dissolve and remove the unexposed portions of the coating film.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- An aqueous solution of diazabicyclo- [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
The development conditions are preferably 5 to 300 seconds at room temperature.

(4) Heat treatment step After the post-baking, a substrate on which pixel patterns are arranged in a predetermined arrangement can be obtained.
The heat treatment is preferably performed at 180 to 230 ° C. for about 20 to 40 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.5 to 3.0 μm.

By repeating the steps (1) to (4) using each radiation sensitive composition in which red, green or blue pigments are dispersed, red, green and blue pixel patterns are formed on the same substrate. Accordingly, a colored layer in which pixel patterns of the three primary colors of red, green, and blue are arranged in a predetermined arrangement can be formed on the substrate.
In the present invention, the order of forming the pixel patterns of the respective colors is not limited to the order described above.

Color filter The color filter of this invention has a colored layer formed from the radiation sensitive composition for color filters of this invention.
The color filter of the present invention is extremely useful for color imaging tube elements, color sensors, etc., in addition to transmissive or reflective color liquid crystal display devices.

Color liquid crystal display device The color liquid crystal display device of the present invention comprises a color filter formed from the radiation-sensitive composition for a color filter of the present invention.
The color liquid crystal display device of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other through the liquid crystal layer. Furthermore, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed include a liquid crystal layer. It is also possible to adopt a structure facing each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

  Hereinafter, the embodiments of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

Reference example 1
(A) 100 parts by weight of a 5/95 (weight ratio) mixture of CI Pigment Red 177 and CI Pigment Red 254 as a colorant, and 62 weights of EFKA-47 (solid content concentration 37.6%) manufactured by Efcar Chemicals as a dispersant Part, (B) methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene copolymer (copolymerization weight ratio = 15/25/35/10/15, Mw = 10,000, 70 parts by weight of (Mn = 5,000), (C) 80 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, and (D) 2-benzyl-2-dimethylamino-1- (4) as a photopolymerization initiator. -Morpholinophenyl) butanone-1 in 50 parts by weight and (E) 3-methoxybutyl acetate as solvent 200 parts by weight of a salt, 700 parts by weight of ethyl 3-ethoxypropionate and 500 parts by weight of propylene glycol monomethyl ether acetate were mixed to prepare a liquid composition (R1) of a radiation sensitive composition.
<Formation and evaluation of pixel array>
After applying the liquid composition (R1) on the surface of a soda glass substrate (550 mm × 650 mm) on which a SiO ₂ film that prevents elution of sodium ions is formed on the surface using a spin coater, clean at 90 ° C. Pre-baking was performed in an oven for 10 minutes to form a coating film having a film thickness of 1.7 μm. When the surface of the coating film was observed by irradiating with sodium lamp light, no coating unevenness such as stripe unevenness and drying unevenness was observed in all areas.
Then, after cooling the substrate to room temperature, the coating film was exposed to ultraviolet rays containing wavelengths of 365 nm, 405 nm, and 436 nm through a photomask at an exposure amount of 2,000 J / m 2 using a high-pressure mercury lamp. Thereafter, the substrate was developed by being immersed in a 0.1 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 1 minute, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 25 minutes to form a red stripe pixel array on the substrate.
When the obtained pixel array was observed using an optical microscope, no development residue was observed on the unexposed substrate. Further, the adhesion of the obtained pixel to the substrate was also excellent.

Reference example 2
(A) 100 parts by weight of a 95/5 (weight ratio) mixture of CI Pigment Blue 15: 6 and CI Pigment Violet 23 as a colorant, BYK163 (solid content concentration 45%) 55 parts by weight as a dispersant, (B ) Methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymerization weight ratio = 15/15/70, Mw = 25,000, Mn = 10,000) as an alkali-soluble resin, 70 parts by weight, (C) 80 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1 as a photopolymerization initiator , 2'-biimidazole, 6 parts by weight of 4,4'-bis (diethylamino) benzopheno as an amine-based hydrogen donor and mel Mixing 3 parts by weight of 2-mercaptobenzothiazole as a pentane hydrogen donor and 600 parts by weight of 3-methoxybutyl acetate, 400 parts by weight of ethyl 3-ethoxypropionate and 300 parts by weight of propylene glycol monomethyl ether acetate as the solvent (E) Then, a liquid composition (B1) of a radiation sensitive composition was prepared.
<Formation and evaluation of pixel array>
A coating film is formed on the substrate and a blue stripe pixel array is formed in the same manner as in Reference Example 1 except that the liquid composition (B1) is used instead of the liquid composition (R1). Evaluation was performed.
When the surface of the obtained coating film was observed by irradiating with sodium lamp light, coating unevenness was not observed in all regions. When the coated surface of the obtained coating film was observed, no unevenness was found. Further, when the pixel array was observed using an optical microscope, no development residue was observed on the unexposed portion of the substrate. The resulting pixel had excellent adhesion to the substrate.

Reference example 3
(A) 100 parts by weight of a 65/35 (weight ratio) mixture of CI Pigment Green 36 and CI Pigment Yellow 150 as a colorant, and BYK-161 (solid content concentration 30%) 100 parts by weight (B ) Methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate copolymer (copolymerization weight ratio = 15/15/70, Mw = 25,000, Mn = 10,000) 75 parts by weight as alkali-soluble resin, (C) 75 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl)-as a photopolymerization initiator 10 parts by weight of s-triazine and (E) 700 parts by weight of 3-methoxybutyl acetate as a solvent, propylene A liquid composition (G1) of a radiation sensitive composition was prepared by mixing 600 parts by weight of lenglycol monomethyl ether acetate and 300 parts by weight of cyclohexanone.
<Formation and evaluation of pixel array>
A coating film is formed on the substrate and a green stripe pixel array is formed in the same manner as in Reference Example 1 except that the liquid composition (G1) is used instead of the liquid composition (R1). Evaluation was performed.
When the surface of the obtained coating film was observed by irradiating with sodium lamp light, coating unevenness was not observed in all regions. Further, when the pixel array was observed using an optical microscope, no development residue was observed on the unexposed portion of the substrate. The resulting pixel had excellent adhesion to the substrate.

Example 1
<Formation and evaluation of pixel array>
A coating film is formed on the substrate in the same manner as in Reference Example 1 except that the liquid composition (B1) is used instead of the liquid composition (R1) and the slit die coater is used instead of the spin coater. Then, a blue stripe pixel array was formed and evaluated.
When the pixel array was observed using an optical microscope, no development residue was observed on the unexposed substrate. The resulting pixel had excellent adhesion to the substrate.

Reference example 4
The liquid composition (R2) of the radiation sensitive composition was prepared by replacing the (E) solvent of the liquid composition (R1) with 1400 parts by weight of 3-methoxybutyl acetate and mixing.
<Formation and evaluation of pixel array>
A coating film was formed on the substrate and evaluated in the same manner as in Reference Example 1 except that the liquid composition (R2) was used instead of the liquid composition (R1).
When the surface of the obtained coating film was irradiated with a sodium lamp and observed, partial coating unevenness was observed.

Reference Example 5
The liquid composition (B2) was prepared by replacing the (E) solvent of the liquid composition (B1) with 330 parts by weight of 3-methoxybutyl acetate and mixing.
<Formation and evaluation of pixel array>
A coating film was formed on the substrate and evaluated in the same manner as in Reference Example 1 except that the liquid composition (B2) was used instead of the liquid composition (R1).
When the obtained coating film surface was observed by irradiating with sodium lamp light, coating unevenness was observed.
Reference Example 6
A liquid composition (G2) of a radiation sensitive composition was prepared by replacing the (E) solvent of the liquid composition (G1) with 300 parts by weight of 3-methoxybutyl acetate and 250 parts by weight of propylene glycol monomethyl ether acetate. did.
<Formation and evaluation of pixel array>
A coating film was formed on the substrate and evaluated in the same manner as in Reference Example 1 except that the liquid composition (G2) was used instead of the liquid composition (R1).
When the surface of the obtained coating film was irradiated with a sodium lamp and observed, partial coating unevenness was observed.
Reference Example 7
The liquid composition (G3) was prepared by replacing the solvent (E) in the liquid composition (G1) with 1600 parts by weight of propylene glycol monomethyl ether acetate and mixing.
<Formation and evaluation of pixel array>
A coating film was formed on the substrate and evaluated in the same manner as in Reference Example 1 except that the liquid composition (G3) was used instead of the liquid composition (R1).
When the surface of the obtained coating film was irradiated with a sodium lamp and observed, partial coating unevenness was observed.
Comparative Example 1
<Formation and evaluation of pixel array>
A coating film was formed on the substrate and evaluated in the same manner as in Example 1 except that the liquid composition (B2) was used instead of the liquid composition (B1).
When the surface of the obtained coating film was irradiated with a sodium lamp and observed, coating unevenness was observed over the entire surface.

Claims (4)

It comprises a radiation sensitive composition containing (A) a pigment, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a photoradical generator, and (E) a solvent. , 3-methoxybutyl acetate and 3-ethoxypropionate are those containing at least one selected from ethyl and propylene glycol monomethyl ether acetate tape preparative O Li Cheng group 15 3-methoxybutyl acetate of the total solvent A radiation-sensitive composition for a color filter, characterized in that it has a solid content concentration of 10 to 30% by weight and is used for coating with a slit die coater. (B) As an alkali-soluble resin, a carboxyl group-containing unsaturated monomer component containing (meth) acrylic acid, styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, N- phenylmaleimide, using a copolymer of at least one selected from the group consisting of polystyrene macromonomer and polymethyl methacrylate macromonomer, of claim 1 A radiation-sensitive composition for color filters. Claim 1 or 2 color filter formed from the color filter radiation-sensitive composition according to. A color liquid crystal display device comprising the color filter according to claim 3 .