JP2011117986A - Radiation-sensitive composition for forming green pixel, color filter and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition capable of forming a green pixel that has a high light transmittance in a bluish green region, can eliminate the need to increase the thickness of a coating film and to increase the content of a pigment component in the colored radiation-sensitive composition, and has high color purity. <P>SOLUTION: The radiation-sensitive composition for forming a colored layer is a radiation-sensitive composition for forming a green pixel which contains (A) a colorant containing C.I. Pigment Green 7, (B) an alkali soluble resin, (C) a multi-functional monomer, and (D) a photopolymerization initiator where a CIE chromaticity coordinate measured by a light source C in a visual field of 2 degrees is in a range of 0.140≤x≤0.270 and 0.500≤y≤0.630. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a radiation sensitive composition for forming a green pixel, a color filter, and a color liquid crystal display element. The present invention relates to a radiation-sensitive composition used in the present invention, a color filter including pixels formed from the radiation-sensitive composition, and a color liquid crystal display device including the color filter.

As a method of forming a color filter using a colored radiation-sensitive composition, a coating film of a colored radiation-sensitive composition is formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed, and a predetermined pattern is formed. A method of obtaining pixels of each color by irradiating radiation (hereinafter referred to as “exposure”) through a photomask having, developing and dissolving and removing unexposed portions, and then post-baking (for example, patent documents) 1 and Patent Document 2) are known.
A liquid crystal display device having such a color filter is required to have higher brightness and an expanded color reproduction region. For this reason, color filters are required to have higher light transmittance and higher color purity in recent years. ing.

  By the way, in forming a green pixel, C.I. I. Pigment Green 7 or C.I. I. It is known to use a colored radiation-sensitive composition containing CI Pigment Green 36, and the resulting green pixel has a higher luminance. I. The use of a colored radiation-sensitive composition containing Pigment Green 36 has become the mainstream. However, C.I. I. In the colored radiation-sensitive composition containing Pigment Green 36, sufficient light transmittance cannot be obtained in a bluish green region where x of the CIE chromaticity coordinate is 0.270 or less. There was a problem. Further, in the colored radiation-sensitive composition, in order to reproduce a region having high color purity such that y of the CIE chromaticity coordinate is 0.600 or more, the film thickness of the formed pixel is increased, It was necessary to increase the content of the pigment component in the colored radiation-sensitive composition, or both. For this reason, it is extremely difficult to make the coating film thickness constant within the substrate surface in the coating process of the colored radiation-sensitive composition, resulting in poor pixel curability, or generation of residues during development. There were various problems such as becoming.

JP-A-2-144502 JP-A-3-53201

The problem of the present invention is that the light transmittance is high in a bluish green region, and the coating film thickness is not increased and the content of the pigment component in the colored radiation-sensitive composition is not increased. The object is to provide a radiation-sensitive composition capable of forming a green pixel with high color purity.
Another object of the present invention is to provide a color filter having pixels formed from the radiation-sensitive composition, and a color liquid crystal display device including the color filter.

  As a result of intensive studies, the present inventors have surprisingly found that in the bluish green region, C.I. I. The present invention has been completed by finding that the above-mentioned problems can be solved by using Pigment Green 7.

The present invention, first,
(A) C.I. I. A radiation-sensitive composition for forming a green pixel, comprising a colorant comprising pigment green 7, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. , C light source, radiation sensitive composition for forming green pixels in which CIE chromaticity coordinates measured in a 2 degree visual field are in the range of 0.140 ≦ x ≦ 0.270 and 0.500 ≦ y ≦ 0.630 It consists of.
"Radiation" as used in the field of this invention means what contains visible light, an ultraviolet-ray, a far-ultraviolet, an electron beam, an X-ray, etc.

The present invention secondly,
It comprises a color filter comprising pixels formed using the radiation-sensitive composition.

Third, the present invention
A color liquid crystal display device comprising the color filter;

Hereinafter, the present invention will be described in detail.
Radiation-sensitive composition for forming colored layer- (A) Colorant-
The radiation sensitive composition for forming a green pixel of the present invention (hereinafter sometimes simply referred to as “radiation sensitive composition”) is a color index (CI; The Society of Dyers) as a colorant. and the same as in the following). I. Pigment Green 7 is included.

The radiation-sensitive composition of the present invention is used for forming a green pixel. I. In addition to Pigment Green 7, other green or yellow colorants are included. Such a green or yellow colorant is not particularly limited, but an organic pigment is preferred because the color filter is required to have high purity and high light-transmitting color development and heat resistance.
C. I. Examples of green or yellow organic pigments other than CI Pigment Green 7 (hereinafter sometimes referred to as “other organic pigments”) include compounds classified as pigments in the color index, specifically, as described below. The color index (CI) number is attached.

C. I. Pigment green 36, C.I. I. Pigment green 58;
C. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 211, C.I. I. Pigment yellow 219;
These other organic pigments can be used alone or in admixture of two or more.

  Among these other organic pigments, C.I. I. Pigment green 36, C.I. I. Pigment green 58, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Preferably at least one selected from the group consisting of CI Pigment Yellow 150; I. Pigment Yellow 150 is particularly preferable.

  In the present invention, C.I. I. The content ratio of Pigment Green 7 is preferably 30% by weight or more, more preferably 30 to 60% by weight, based on the total colorant. At this rate, C.I. I. By using CI Pigment Green 7, the CIE chromaticity coordinates are preferably 0.120 ≦ x ≦ 0.270, 0.500 ≦ y ≦ 0.630, preferably 0.220 ≦ x ≦ 0.270, 0. In the range of 550 ≦ y ≦ 0.630, more preferably in the range of 0.230 ≦ x ≦ 0.260 and 0.580 ≦ y ≦ 0.620, a green pixel with high light transmittance can be obtained. .

  In the present invention, C.I. I. The pigment such as Green 7 can be used after purification by recrystallization method, reprecipitation method, solvent washing method, sublimation method, vacuum heating method, a combination thereof, or the like, if necessary. In addition, C.I. I. Green 7 and the like can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the particle surface of the pigment include the polymers described in JP-A-8-259876 and various commercially available polymers or oligomers for dispersing pigments.

  In the present invention, the radiation-sensitive composition can be prepared by an appropriate method, for example, by mixing the component (A) and the components (B) to (D) described later together with a solvent and additives. Although it can be prepared, the pigment is pulverized in a solvent, in the presence of a dispersing agent and, if necessary, a dispersing aid, optionally with a part of the component (B), for example, using a bead mill, a roll mill or the like. However, it is preferably prepared by mixing and dispersing to obtain a pigment dispersion, which is further mixed with components (B) to (D) and, if necessary, additional solvents and additives.

  As a dispersant used for the preparation of the pigment dispersion, for example, an appropriate dispersant such as a cationic, anionic, nonionic or amphoteric can be used, and a polymer dispersant is preferable. Specifically, a modified acrylic copolymer, an acrylic copolymer, polyurethane, polyester, a polymer copolymer alkylammonium salt or phosphate ester salt, a cationic comb graft polymer, and the like can be given. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branched polymers are grafted to one molecule of a trunk polymer having a plurality of basic groups (cationic functional groups). Examples thereof include a polymer composed of a ring-opening polymer in which the trunk polymer part is polyethyleneimine and the branch polymer part is ε-caprolactone. Among these dispersants, modified acrylic copolymers, polyurethane, and cationic comb graft polymers are preferable.

  Such a dispersant can be obtained commercially, for example, Disperbyk-2000, Disperbyk-2001 (above, manufactured by BYK Corporation) as a modified acrylic copolymer, Disperbyk-161 as polyurethane, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), and cationic comb-type graft polymer Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), Addisper PB821, Addisper PB822, Addispar PB823, Addisper PB824, Addisper PB827 (Ajinomoto PFA) Ntekuno Co., Ltd.), and the like.

  These dispersants can be used alone or in admixture of two or more. The content of the dispersant is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, and particularly preferably 10 to 100 parts by weight with respect to 100 parts by weight of the (A) colorant. 50 parts by weight. In this case, when the content of the dispersant exceeds 100 parts by weight, developability and the like may be impaired.

  Examples of the dispersion aid include a blue pigment derivative and a yellow pigment derivative. Specific examples include a copper phthalocyanine derivative.

-(B) Alkali-soluble resin-
The (B) alkali-soluble resin contained in the radiation-sensitive composition of the present invention is particularly limited as long as it is soluble in an alkali developer used in the development processing step when forming pixels. Although it is not a thing, it is a polymer which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group normally. Among them, it is preferable to contain a polymer having a carboxyl group, and in particular, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “carboxyl group-containing unsaturated monomer”). Copolymers (hereinafter referred to as “carboxyl group-containing copolymers”) with other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as “copolymerizable unsaturated monomers”) are preferred. .

As the carboxyl group-containing unsaturated monomer, for example,
Unsaturated carboxylic 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 anhydrides thereof;
Mono [(meth) acryloyloxyalkyl] of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl] ester;
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.
The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.
In the present invention, the carboxyl group-containing unsaturated monomer is preferably (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, Particularly preferred is (meth) acrylic acid.
These carboxyl group-containing unsaturated monomers can be used alone or in admixture of two or more.

Examples of the copolymerizable unsaturated monomer include:
Maleimide;
N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3-maleimidobenzoate, N- N-substituted maleimides such as succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N- (acridinyl) maleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinyl Phenol, p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether , Aromatic vinyl compounds such as p-vinylbenzyl 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-ethylhexyl (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, methoxydi Propylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, Unsaturated carboxylic acid esters such as glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate;
Other unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, 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;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include a macromonomer 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.

  In the present invention, as the copolymerizable unsaturated monomer, an N-substituted maleimide, an aromatic vinyl compound, an unsaturated carboxylic acid ester, or a macromonomer having a mono (meth) acryloyl group at the end of the polymer molecular chain. It is preferable to contain at least one selected from the group consisting of N-phenylmaleimide, N-cyclohexylmaleimide, styrene, α-methylstyrene, p-hydroxy-α-methylstyrene, methyl (meth) acrylate, n -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) Acrylate, paracumylfe It is preferable to contain at least one selected from the group consisting of an ethylene oxide-modified (meth) acrylate of a polyol, a polystyrene macromonomer, and a polymethylmethacrylate macromonomer.

In the present invention, for example, an alkali-soluble resin obtained by copolymerization of a copolymerizable unsaturated monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate is added to an alkali-soluble resin such as 2- (meth) acryloyloxyethyl isocyanate. By reacting the saturated isocyanate compound, a polymerizable unsaturated bond can be introduced into the side chain of the alkali-soluble resin.

  In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. In this case, when 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 when it exceeds 50% by weight, the solubility in an alkali developer is low. When the development is performed with an alkaline developer, the pixel tends to drop off from the substrate or the surface of the pixel becomes rough.

The weight average molecular weight in terms of polystyrene (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 1,000 to 45,000. Preferably it is 3,000-20,000. If the Mw is less than 1,000, the residual film rate of the resulting coating may be reduced, the pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated, while exceeding 45,000. Then, the resolution may be reduced, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.
Further, the number average molecular weight in terms of polystyrene (hereinafter also referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is usually 1,000 to 45, 000, preferably 3,000 to 20,000.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin in the present invention is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

  The alkali-soluble resin in the present invention comprises an unsaturated monomer as a constituent component in a suitable solvent, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvalero). Nitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like, and can be produced by polymerization in the presence of a radical polymerization initiator.

The alkali-soluble resin in the present invention can be purified through a reprecipitation method using two or more kinds of organic solvents having different polarities after radical polymerization of the polymerizable unsaturated compound as described above. That is, after removing insoluble impurities from the solution in a good solvent after polymerization by filtration or centrifugation as necessary, a large amount (usually 5 to 10 times the volume of the polymer solution) of a precipitant (poor) Purification by pouring into the solvent) and reprecipitation of the copolymer. At that time, of the impurities remaining in the polymer solution, impurities soluble in the precipitant remain in the liquid phase and are separated from the purified alkali-soluble resin.
Examples of the good solvent / precipitant combination used in this reprecipitation method include diethylene glycol monomethyl ether acetate / n-hexane, methyl ethyl ketone / n-hexane, diethylene glycol monomethyl ether acetate / n-heptane, and methyl ethyl ketone / n-heptane. Can be mentioned.

  Moreover, the alkali-soluble resin in the present invention includes, for example, 2,2′-azobisisobutyronitrile and 2,2′-azobis (2,4-dimethylvaleronitrile) as unsaturated compounds as constituent components. , Radical polymerization initiators such as 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, pyrazole-1-dithiocarboxylate benzyl Ester, tetraethylthiuram disulfide, bis (pyrazol-1-ylthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4-methyl-pyrazol-1-ylthiocarbonyl) disulfide, Bis (5-methyl-pyrazol-1-ylthiocarbonyl ) Presence of molecular weight regulators acting as iniferters such as disulfide, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bisthiobenzoyl disulfide Below, it can manufacture by carrying out living radical polymerization by making reaction temperature into 0-150 degreeC normally in an inert solvent, Preferably it is 50-120 degreeC.

  In this invention, content of alkali-soluble resin is 10-1,000 weight part normally with respect to 100 weight part of (A) coloring agents, Preferably it is 20-500 weight part. In this case, if the content of the alkali-soluble resin is less than 10 parts by weight, for example, the alkali developability may be reduced, or a residue or background stain may occur on the unexposed part of the substrate or the light shielding layer. When the amount exceeds 1,000 parts by weight, the colorant concentration relatively decreases, and it may be difficult to achieve the target color density 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 such a polyfunctional 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 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 end hydroxyl polymers such as both end hydroxypoly-1,3-butadiene, both end hydroxypolyisoprene, both end hydroxypolycaprolactone;
Tris [2- (meth) acryloyloxyethyl] phosphate,
Examples include isocyanuric acid ethylene oxide-modified triacrylate.

Among these polyfunctional monomers, poly (meth) acrylates of polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, pentaerythritol triacrylate and amber Monoesterified product with acid, monoester with pentaerythritol trimethacrylate and succinic acid Preferred are monoesterified products of dipentaerythritol pentaacrylate and succinic acid, and monoesterified products of dipentaerythritol pentamethacrylate and succinic acid, particularly trimethylolpropane triacrylate, pentaerythritol triacrylate, dipenta Erythritol pentaacrylate, dipentaerythritol hexaacrylate, monoesterified product of pentaerythritol triacrylate and succinic acid and monoesterified product of dipentaerythritol pentaacrylate and succinic acid have high strength of the colored layer, and the surface of the colored layer is smooth. It is preferable in that it has excellent properties and hardly causes scumming or 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 content of the polyfunctional 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. 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 pixel tend to be reduced. On the other hand, if it exceeds 500 parts by weight, for example, alkali developability is reduced. In addition, background stains, film residue, etc. tend to occur on the unexposed portion of the substrate or on 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 divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl]. Mono [(meth) acryloyloxyalkyl] ester of acid; mono (meth) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate; N-vinylsuccinimide, N-vinylpyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinyl Indole, N-vinylindoline, N-vinylbenzimidazole, N-vinylcarbazo N-vinyl nitrogen-containing heterocyclic compounds such as alcohol, N-vinyl piperidine, N-vinyl piperazine, N-vinyl morpholine, N-vinyl phenoxazine; N- (meth) acryloyl morpholine and other commercially available products , M-5300, M-5400, M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like.
These monofunctional monomers can be used alone or in admixture of two or more.

  The content ratio of the monofunctional monomer in the present invention is preferably 90% by weight or less, more preferably 50% by weight or less based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the pixel tend to be lowered.

-(D) Photopolymerization initiator-
The photopolymerization initiator in the present invention is the above-mentioned (C) polyfunctional monomer and a monofunctional monomer used in some cases upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates active species capable of initiating polymerization of the body.

  Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, α-diketone compounds, and polynuclear quinone compounds. Examples include compounds, xanthone compounds, diazo compounds, imide sulfonate compounds, and the like. These compounds are components that generate active radicals or active acids or both active radicals and active acids upon exposure.

  In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, an acetophenone compound, a biimidazole compound, a triazine compound, At least one selected from the group of O-acyloxime compounds is preferred.

  In the present invention, the general content of the photopolymerization initiator is usually 0.01 to 120 parts by weight, preferably 1 to 100 parts by weight, per 100 parts by weight of the (C) polyfunctional monomer. is there. In this case, if the content of the photopolymerization initiator is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the pixel pattern is arranged according to a predetermined arrangement, On the other hand, if it exceeds 120 parts by weight, the formed pixels tend to fall off the substrate during development.

Among preferred photopolymerization initiators 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-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- Examples include 1,2-diphenylethane-1-one and 1,2-octanedione.
Among these acetophenone compounds, in particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) butan-1-one, 1,2-octanedione and the like are preferred.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, the content in the case of using an acetophenone-based compound as a photopolymerization initiator is usually 0.01 to 80 parts by weight, preferably 1 with respect to 100 parts by weight of the (C) polyfunctional monomer. -70 weight part, More preferably, it is 1-60 weight part. In this case, if the content of the acetophenone compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which pixel patterns are arranged according to a predetermined arrangement, If it exceeds 80 parts by weight, the formed pixels tend to fall off 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′-bi Imidazole, 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'-tetra Phenyl-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 preferable, and in particular, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole is preferred.

These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and sufficiently advance the curing reaction by exposure with a small amount of energy. Since no curing reaction occurs in the exposed area, the coated film after exposure is clearly divided into a cured area that is insoluble in the developer and an uncured area that has high solubility in the developer, Thereby, a high-definition color filter in which pixel patterns without undercuts are arranged according to a predetermined arrangement can be formed.
The biimidazole compounds can be used alone or in admixture of two or more.

  In the present invention, the content in the case of using a biimidazole compound as a photopolymerization initiator is usually 0.01 to 40 parts by weight, preferably 100 parts by weight of (C) polyfunctional monomer, 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the content of the biimidazole compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which a pixel pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 40 parts by weight, there is a tendency that the formed pixels are easily detached from the substrate and the surface of the colored layer is likely to come off.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor described below 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 “ Amine-based hydrogen donor ").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor 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 and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

In addition, the amine hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. A 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.
Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone 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 from 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, and more preferred combinations 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / , 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, the content when the hydrogen donor is used in combination with the biimidazole compound is preferably 0.01 to 40 parts by weight, more preferably 100 parts by weight of (C) polyfunctional monomer. 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, if the content of the hydrogen donor is less than 0.01 parts by weight, the effect of improving the sensitivity tends to be reduced. On the other hand, if the content exceeds 40 parts by weight, the formed pixels are detached from the substrate during development. It tends to be easier.

The amine-based hydrogen donor can function as a sensitizer when used in combination with a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound. When an amine-based hydrogen donor is used as a sensitizer, the content thereof is usually 300 parts by weight or less, preferably 200 parts by weight or less, based on 100 parts by weight of a photopolymerization initiator other than a biimidazole compound. The amount is preferably 100 parts by weight or less, but if the content is too small, it is difficult to obtain a sufficient effect. Therefore, the lower limit of the content is preferably 2 parts by weight, more preferably 5 parts by weight.

  Specific examples of the triazine compound 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 (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -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, the content when using a triazine compound as a photopolymerization initiator is preferably 0.01 to 40 parts by weight, more preferably 100 parts by weight of (C) polyfunctional monomer. 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, if the content of the triazine compound is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the formed pixels tend to drop off from the substrate during development.

  Specific examples of the O-acyloxime compound include, for example, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl. -6-benzoyl-9H-carbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -Nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -pentane-1,2-pentane-2-oxime-O -Acetate, 1- [9-ethyl-6-benzoyl-9H-carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) -9H-carbazol-3-yl ] -Ethane-1-one oxime-O-benzoate, 1- [9-butyl-6- (2-ethylbenzoyl) -9H-carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone , 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- [2- Methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like. it can.

Among these O-acyloxime compounds, in particular, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6 -(2-Methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- [2-methyl-4- (2,2- Dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like are preferable.
The O-acyloxime compounds can be used alone or in admixture of two or more.

  In the present invention, the content when an O-acyloxime compound is used as the photopolymerization initiator is preferably 0.01 to 80 parts by weight with respect to 100 parts by weight of the (C) polyfunctional monomer, More preferably, it is 1-70 weight part, Most preferably, it is 1-60 weight part. In this case, if the content of the O-acyloxime compound is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it is difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if the amount exceeds 80 parts by weight, the formed pixels tend to drop off from the substrate during development.

-Other additives-
Examples of the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, anionic interfaces Surfactants such as activators; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, 3-chloropropylmethyldi Adhesion promoters such as toxisilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), Antioxidants such as 2,6-di-t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; poly Anticoagulation agents such as sodium acrylate; alkali solubility improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

Solvent The radiation-sensitive composition for forming a colored layer of the present invention contains the components (A) to (D) and other additives that are optionally added. Prepared as a liquid composition.
As the solvent, components (A) to (D) constituting the radiation-sensitive composition and other additive components are dispersed or dissolved, and do not react with these components and have appropriate volatility. As long as it is, it can be selected and used as appropriate.

As such a solvent, for example,
Alcohols such as methanol, ethanol, benzyl alcohol;
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, 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 monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, di Propylene glycol mono- - butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol (poly) alkylene glycol monoalkyl ethers such as monoethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-propyl ether acetate, ethylene glycol mono-n-butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-propyl ether Acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate (Poly) alkylene glyco Monoalkyl ether acetates;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, diacetone alcohol (4-hydroxy-4-methylpentan-2-one), 4-hydroxy-4-methylhexane-2-one;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, N-butyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, ethyl hydroxyacetate, ethyl ethoxyacetate, Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, Ethyl 2-hydroxy-2-methylpropionate, 2 Hydroxy-3-methyl-butyric acid methyl, other esters such as ethyl 2-oxo-butyric acid;
Aromatic hydrocarbons such as toluene and xylene;
Examples thereof include amides such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.

Among these solvents, from the viewpoint of solubility, pigment dispersibility, coatability, etc., ethylene glycol mono-n-butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol mono-n -Butyl ether acetate, diethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether , Cyclohexanone, 2-heptanone, 3-heptanone, 1,3-butylene Cole diacetate, 1,6-hexanediol diacetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyrate Preferred are -butyl, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl pyruvate and the like.
The said solvent can be used individually or in mixture of 2 or more types.

Further, together with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl acetate, ethyl benzoate, diethyl oxalate, maleic acid A high boiling point solvent such as diethyl, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate may be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the composition is preferable from the viewpoints of applicability, storage stability, and the like of the resulting radiation-sensitive composition. Is preferably 5 to 50% by weight, more preferably 10 to 40% by weight.

Color filter The color filter of the present invention comprises a green pixel formed from the radiation-sensitive composition of the present invention.
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming a pixel, and a liquid of the radiation sensitive composition in which the green pigment of the present invention is dispersed on the substrate. After applying the composition, pre-baking is performed to evaporate the solvent and form a coating film. Next, this coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked, whereby a green pixel pattern is formed in a predetermined pattern. A pixel array arranged in an array is formed.
Then, using the liquid composition of each radiation-sensitive composition in which a red or blue pigment is dispersed, each liquid composition is coated, pre-baked, exposed, developed and post-baked in the same manner as described above, and then red. By sequentially forming the pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

Examples of the substrate used when forming the pixel include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
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 applying a liquid composition of a radiation sensitive composition to a substrate, an appropriate application such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, etc. Although a method can be employed, a spin coating method and a slit die coating method are particularly preferable.
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 drying.

For example, visible rays, ultraviolet rays, far ultraviolet rays, electron beams, X-rays, and the like can be used as the radiation used when forming the pixels, but radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of the radiation is generally a 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-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.

The color filter of the present invention thus obtained is extremely useful for color liquid crystal surface elements, color image pickup tube elements, color sensors and the like because of its high luminance and wide color reproduction range.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
Further, as one embodiment of the color liquid crystal display element of the present invention, by using the radiation-sensitive composition for forming a colored layer of the present invention, pixels are formed as described above on a thin film transistor substrate array. In particular, a color liquid crystal display element having high luminance and a wide color reproduction range can be produced.

The radiation-sensitive composition of the present invention has a high light transmittance in a bluish green region, and increasing the coating film thickness also increases the content of the pigment component in the radiation-sensitive composition. Without any problem, a green pixel with high color purity can be formed.
Therefore, the synthetic radiation-sensitive composition of the present invention is very suitably used for the production of various color filters including color filters for color liquid crystal display devices and color filters for color separation of solid-state image sensors in the electronic industry. be able to.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. Pigment Green 7 and C.I. I. 30 parts by weight of a 60/40 (weight ratio) mixture with CI Pigment Yellow 150, 15 parts by weight of Disperbyk-2001 (BYK) (solid content concentration 45.1% by weight) as a dispersant, and 3-ethoxy as a solvent A mixed liquid consisting of 155 parts by weight of ethyl propionate was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (A-1).

Preparation Examples 2-11
In Preparation Example 1, pigment dispersions (A-2) to (A-11) were prepared in the same manner as in Example 1 except that the type and weight ratio of the colorant were changed as shown in Table 1.

In Table 1, “G7” means C.I. I. Pigment Green 7, “G36” is C.I. I. Pigment Green 36, “Y150” is C.I. I. Each means CI Pigment Yellow 150.

(B) Synthesis of alkali-soluble resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobisisobutyronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 15 parts by weight of methacrylic acid and ω-carboxydicaprolactone monoacrylate. 10 parts by weight, N-phenylmaleimide 20 parts by weight, benzyl methacrylate 35 parts by weight, styrene 10 parts by weight, glycerol monomethacrylate 10 parts by weight and α-methylstyrene dimer (chain transfer agent) 2.5 parts by weight were charged with nitrogen. After the substitution, the reaction solution was heated to 80 ° C. while gently stirring, and polymerization was carried out for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by weight of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was continued for another 1 hour, whereby a resin solution ( Solid content concentration = 30 wt%) was obtained. The obtained resin was Mw = 6,000 and Mn = 3,000. This resin solution is referred to as “resin solution (B-1)”.

Example 1
Preparation of liquid composition Pigment dispersion (A-1) 1000 parts by weight, (B) Resin solution (B-1) 150 parts by weight as alkali-soluble resin, (C) Dipentaerythritol hexaacrylate as polyfunctional monomer 70 parts by weight, (D) 30 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator, and 250 parts by weight of propylene glycol monomethyl ether acetate as a solvent By mixing, a liquid composition (G1) was prepared.
The liquid composition (G1) was evaluated according to the following procedure. The evaluation results are shown in Table 2.

After applying the liquid composition (G1) for forming the pixel pattern on the soda glass substrate on which the SiO2 film that prevents elution of sodium ions is formed on the surface, the number of rotations is varied using a spin coater, Pre-baking was performed for 10 minutes in a clean oven at 90 ° C. to form five coating films with different film thicknesses.
Next, after these substrates are cooled to room temperature, the coating film is exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 5,000 J / m ² through a photomask using a high-pressure mercury lamp. did. After that, these substrates were immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-treated at 230 ° C. for 30 minutes. Baking was performed to form a green stripe pixel pattern on the substrate.

Evaluation of Chromaticity Characteristics For the obtained striped pixel pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a chromaticity coordinate value (x, y) in the CIE color system with a C light source and a 2-degree field of view. ) And stimulation value (Y) were measured. Further, the thickness of the obtained stripe pixel pattern was measured using an alpha step IQ manufactured by KLA-Tencor. From the measurement results, the chromaticity coordinate value x, the stimulus value (Y), and the film thickness at which the chromaticity coordinate value y becomes 0.615, 0.600, and 0.580 were obtained. The evaluation results are shown in Table 2. The larger the stimulus value (Y), the higher the light transmittance (brightness), and the thinner the film thickness, the higher the coloring power.

Examples 2-5 and Comparative Examples 1-6
Liquid compositions (G2) to (G11) were prepared in the same manner as in Example 1, except that the pigment dispersion was changed as shown in Table 1 in Example 1.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (G2) to (G11) were used instead of the liquid composition (G1). The results are shown in Table 1.

As is clear from Tables 1 and 2, for example, when Example 1 and Comparative Example 1 are compared, the chromaticity coordinate value (x, y) = (0.240, 0.580) I. When CI Pigment Green 7 is used, C.I. I. It can be seen that the stimulation value (Y) is improved by 2.4 points and the coating film thickness can be reduced by 0.7 μm as compared with the case of using Pigment Green 36. Further, when Example 2 and Comparative Example 2 are contrasted, C.I. is obtained when chromaticity coordinate values (x, y) = (0.239 to 0.240, 0.615). I. When CI Pigment Green 7 is used, C.I. I. It can be seen that the stimulation value (Y) is improved by 1.3 points as compared with the case of using Pigment Green 36, and the coating film thickness can be reduced by 1.0 μm. Further, when Example 3 and Comparative Example 3 are compared, C.I. is obtained at chromaticity coordinate value (x, y) = (0.250, 0.615). I. When CI Pigment Green 7 is used, C.I. I. It can be seen that the stimulation value (Y) is improved by 0.4 points and the coating film thickness can be reduced by 1.0 μm as compared with the case of using Pigment Green 36. Further, when Example 3 and Comparative Example 4 are compared, C.I. is obtained when chromaticity coordinate values (x, y) = (0.260 to 0.261, 0.600). I. When CI Pigment Green 7 is used, C.I. I. It can be seen that the stimulation value (Y) is improved by 1.4 points and the coating film thickness can be reduced by 0.7 μm as compared with the case of using Pigment Green 36.
On the other hand, when Example 5 and Comparative Example 6 are compared, when the chromaticity coordinate value (x, y) = (0.278 to 0.280, 0.600), C.I. I. When CI Pigment Green 7 is used, C.I. I. It can be seen that the stimulation value (Y) is reduced by 0.5 points as compared with the case where the pigment green 36 is used.

Claims (5)

(A) C.I. I. A radiation-sensitive composition for forming a green pixel, comprising a colorant comprising pigment green 7, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. , C light source, radiation sensitive composition for forming green pixels in which CIE chromaticity coordinates measured in a 2 degree visual field are in the range of 0.140 ≦ x ≦ 0.270 and 0.500 ≦ y ≦ 0.630 . C. I. The radiation-sensitive composition according to claim 1, wherein the content ratio of Pigment Green 7 is 30% by weight or more based on the total colorant. A color filter comprising pixels formed using the radiation-sensitive composition according to claim 1. A color liquid crystal display device comprising the color filter according to claim 3.   C. C light source, CIE chromaticity coordinates measured in a two-degree field of view are used for green pixels in the range of 0.140 ≦ x ≦ 0.270 and 0.500 ≦ y ≦ 0.630. I. Pigment Green 7.