JP2009223288A - 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 highly sensitive radiation-sensitive composition with superior dispersion stability, can form green pixels with high luminance. <P>SOLUTION: The radiation-sensitive composition for forming green pixels contains a colorant A, alkali-soluble polymer resin B, polyfunctional monomer C, and a radiation-sensitive polymerization initiator D. The colorant A contains C.I. pigment green 58, and the radiation-sensitive polymerization initiator D contains a compound represented by a formula 1. In the formula 1, R<SP>1</SP>-R<SP>4</SP>respectively independently indicates hydrogen atoms, alkyl groups of carbon numbers 1-18, and alkoxy groups of carbon numbers 1-18. <P>COPYRIGHT: (C)2010,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 device. The present invention relates to a suitably used radiation-sensitive composition, a color filter formed from the radiation-sensitive composition, and a color liquid crystal display device including the color filter.

  As a method for 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. A method of obtaining pixels of each color by irradiating radiation through a photomask having a pattern (hereinafter referred to as “exposure”), developing to dissolve and remove unexposed portions, and then post-baking (for example, patents) Documents 1 and 2) are known.

A liquid crystal display device having such a color filter is required to have high brightness and an expanded color reproduction region. For this reason, color filters having higher light transmittance and higher color purity are required in recent years. ing.
For green pixels, a pigment composition containing a polyhalogenated zinc phthalocyanine pigment is known as a material capable of providing a color filter having high luminance and a wide color reproduction range (for example, patents). Reference 3). However, since the pigment composition containing the polyhalogenated zinc phthalocyanine pigment has poor dispersion stability, it tends to generate foreign matter and is difficult to apply in mass production.

On the other hand, in the technical field of color filters in recent years, combined with the increase in the size of the substrate used for forming color filters, it has become the mainstream to reduce the exposure amount and shorten the tact time. The radiation-sensitive composition is required to have no pattern chipping or peeling at the time of development even at a low exposure amount, that is, high sensitivity.
In view of the above background, there is a strong demand for the development of a radiation-sensitive composition that can form green pixels with high brightness, is excellent in dispersion stability, and is highly sensitive.
JP-A-2-144502 JP-A-3-53201 JP 2007-284589 A

An object of the present invention is to provide a radiation-sensitive composition for forming a green pixel, which can form a green pixel with high luminance, is excellent in dispersion stability, and has high sensitivity.
Furthermore, the objective of this invention is providing the color liquid crystal display element which comprises the color filter provided with the pixel formed from the said radiation sensitive composition for green pixel formation, and the said color filter.

  In view of such circumstances, the present inventors have conducted extensive research and surprisingly found that C.I. which is a polyhalogenated zinc phthalocyanine pigment. I. It has been found that the above-mentioned problems can be solved by incorporating Pigment Green 58 in a radiation-sensitive composition in combination with a specific radiation-sensitive polymerization initiator, and the present invention has been completed.

  That is, the present invention relates to a radiation-sensitive composition for forming a green pixel, which comprises (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive polymerization initiator. Wherein (A) the colorant is C.I. I. Pigment Green 58 is provided, and (D) a radiation-sensitive composition for green pixel formation is provided, wherein the radiation-sensitive polymerization initiator contains a compound represented by the following formula (1) It is.

(Wherein, R ¹ to R ⁴ are, independently of one another hydrogen atom, an alkyl group or an alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms.)

  The present invention also provides a color filter including pixels formed using the radiation-sensitive composition, and a color liquid crystal display device including the color filter.

By using the radiation-sensitive composition of the present invention, a green pixel having high brightness, no foreign matter on the pixel, and no pattern chipping or peeling at the time of development is formed even at a low exposure amount. can do.
The color filter of the present invention is extremely useful for, for example, a transmissive or reflective color liquid crystal display device, a color image pickup tube element, a color sensor, and the like.

  In the radiation-sensitive composition for forming a green pixel of the present invention (hereinafter sometimes simply referred to as “radiation-sensitive composition”), (A) the colorant is C.I. I. Pigment Green 58 is contained. In this case, C.I. I. The content of Pigment Green 58 is preferably 20 to 100% by mass, and particularly preferably 35 to 75% by mass, based on the total colorant. And by using such a colorant, a green pixel having high luminance can be obtained.

Moreover, the radiation sensitive composition of this invention is C.I. I. Other colorants other than CI Pigment Green 58 can be further contained. Other colorants are not particularly limited, but organic pigments are preferred because color filters are required to have high purity and high light-transmitting color development and heat resistance.
Examples of the other organic pigments include compounds classified as pigments in the color index, specifically, those having the following color index (CI) numbers.

C. I. Pigment green 7, C.I. I. Pigment green 36;
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 211, C.I. I. Pigment yellow 219;

  C. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 61, C.I. I. Pigment orange 64, C.I. I. Pigment orange 68, C.I. I. Pigment orange 70, C.I. I. Pigment orange 71, C.I. I. Pigment orange 72, C.I. I. Pigment orange 73, C.I. I. Pigment orange 74;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 5, C.I. I. Pigment red 17, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 41, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 149, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 209, C.I. I. Pigment red 214, C.I. I. Pigment red 220, C.I. I. Pigment red 221, C.I. I. Pigment red 224, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 262, C.I. I. Pigment red 264, C.I. I. Pigment Red 272.
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 7, C.I. I. Pigment green 36, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment Yellow 219 and the like are preferable.

  In the present invention, C.I. I. Pigment Green 58 and other pigments can be purified and used by recrystallization method, reprecipitation method, solvent washing method, sublimation method, vacuum heating method, or a combination thereof, if necessary. In addition, C.I. I. Pigment Green 58 and other pigments 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, (A) the colorant is preferably contained in an amount of 5 to 70% by mass, particularly preferably 5 to 60% by mass, based on the total solid content, from the viewpoint of forming a green pixel with high luminance. Here, solid content is components other than the solvent mentioned later.

  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 the alkali developer used in the development processing step when forming the colored layer. Although not intended, it is usually a polymer having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among these, those containing a polymer having a carboxyl group are preferred, 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 polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and 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.

  In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably 5 to 50% by mass, and more preferably 10 to 40% by mass. In this case, if the copolymerization ratio is less than 5% by mass, the solubility of the resulting radiation-sensitive composition in an alkali developer tends to decrease, whereas if it exceeds 50% by mass, the solubility in an alkali developer tends to be 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.

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 ] decane-8-
Unsaturation such as yl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol Carboxylic acid esters;

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. Those containing 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 Preferred are those containing at least one selected from the group consisting of ethylene oxide-modified (meth) acrylates, polystyrene macromonomers, and polymethyl methacrylate macromonomers, particularly N-phenylmaleimide, N-cyclohexylmaleimide, styrene, α -What contains at least 1 sort (s) chosen from the group which consists of methylstyrene, 2-ethylhexyl (meth) acrylate, and glycerol mono (meth) acrylate is preferable.

  In the present invention, for example, an alkali-soluble resin obtained by copolymerizing 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.

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 includes, for example, an unsaturated monomer such as (meth) acrylic acid, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2, 4-dimethylvaleronitrile) and 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) can be produced by polymerization in the presence of a radical polymerization initiator.

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) In the presence of a molecular weight regulator that acts as an iniferter such as sulfide, bis (3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bisthiobenzoyl disulfide In the inert solvent, the reaction temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C., and can be produced by living radical polymerization.
Furthermore, the alkali-soluble resin according to the present invention is a method in which each unsaturated monomer as a constituent component is radicalized in a suitable solvent in the presence of the radical polymerization initiator and a polyvalent thiol compound that acts as a chain transfer agent. It can be produced by polymerization. Here, the polyvalent thiol compound means a compound having two or more thiol groups in one molecule, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropio). Nate), tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3-mercaptobutyryl) Oxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), 1,3,5, -tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H , 5H) -trione and the like.

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.

  In the present invention, the content of the (B) alkali-soluble resin is usually preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the alkali-soluble resin is less than 10 parts by mass, for example, the alkali developability may be lowered, or a residue or background stain may occur on the substrate or the light shielding layer in the unexposed area. When the amount exceeds 1,000 parts by mass, the colorant concentration relatively decreases, and it may be difficult to achieve the target color density as a thin film.

The (C) 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 3 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.

  In the present invention, the content of the (C) polyfunctional monomer is usually preferably 5 to 500 parts by mass, particularly preferably 20 to 300 parts by mass with respect to 100 parts by mass of the (B) alkali-soluble resin. In this case, when the content of the polyfunctional monomer is less than 5 parts by mass, the strength and surface smoothness of the pixel tend to be reduced. On the other hand, when the content exceeds 500 parts by mass, 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) acrylate of a polymer having a carboxy group and a hydroxyl group at both ends, such as mono [(meth) acryloyloxyalkyl] ester of acid, ω-carboxypolycaprolactone mono (meth) acrylate, and N- (meth) In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, examples of commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
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 mass or less, more preferably 50% by mass or less, with respect to the total of the polyfunctional monomer and the monofunctional monomer. In this case, when the use ratio of the monofunctional monomer exceeds 90% by mass, the strength and surface smoothness of the pixel tend to be lowered.

The (D) radiation-sensitive polymerization initiator used in the present invention is used by the (C) polyfunctional monomer and optionally by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound that generates an active species capable of initiating polymerization of a monofunctional monomer.
In the present invention, (D) a radiation sensitive composition having high sensitivity and excellent dispersion stability can be obtained by incorporating the compound represented by the above formula (1) as a radiation sensitive polymerization initiator. it can.
That is, a radiation-sensitive polymerization initiator such as a (diamino) benzophenone compound generally has a plurality of amino groups in the molecule, and the present inventors have found that the plurality of amino groups are C.I. I. As a result of earnest examination considering that foreign substances are generated by interacting with Pigment Green 58 and destroying the dispersed state, the compound represented by the above formula (1) is C.I. I. It has been found that it is optimal in combination with Pigment Green 58.

In the above formula (1), R ¹ and R ³ are preferably hydrogen atoms, and R ² and R ⁴ are preferably hydrogen atoms or alkyl groups having 1 to 12 carbon atoms. Furthermore, R ² and R ⁴ are preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Specific examples of the thioxanthone compound represented by the above formula (1) include thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-dodecylthioxanthone, 2,4-dimethylthioxanthone, 2,4 -Diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. can be mentioned.
Of these thioxanthone compounds, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone are preferable.
In the present invention, the thioxanthone compounds can be used alone or in admixture of two or more.

  In the present invention, it is preferable to use another radiation-sensitive polymerization initiator together with the thioxanthone compound. In this case, the content of the thioxanthone compound is preferably 1 to 75% by mass and more preferably 5 to 50% by mass in the radiation-sensitive polymerization initiator from the viewpoint of dispersion stability. By using such a radiation-sensitive polymerization initiator initiator, a radiation-sensitive composition having high sensitivity and excellent dispersion stability can be obtained.

  Other radiation sensitive polymerization initiators include, for example, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketones Examples include compounds, polynuclear quinone compounds, xanthone compounds, diazo compounds, imide sulfonate compounds, and the like.

  In the present invention, the other radiation-sensitive polymerization initiator can be used alone or in admixture of two or more, but the other radiation-sensitive polymerization initiator in the present invention includes an acetophenone compound, At least one selected from the group consisting of biimidazole compounds and O-acyloxime compounds is preferred.

Among other preferable radiation-sensitive polymerization initiators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2 -(Dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenylketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1,2- And 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, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, 1,2-octanedione and the like are preferable.
The acetophenone compounds can be used alone or in admixture of two or more.

  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.
The biimidazole compounds can be used alone or in admixture of two or more.

In the present invention, when a biimidazole compound is used as another radiation-sensitive polymerization initiator, 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.
The hydrogen donor in the present invention is preferably a mercaptan compound defined below.

  The mercaptan-based compound includes 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.

A mercaptan-based compound 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, a condensed ring is formed. However, it may not be formed.
Further, when the mercaptan compound has two or more mercapto groups, one or more of the remaining mercapto groups may be substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. In addition, 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 disulfide. It can have structural units joined in form.
Furthermore, the mercaptan-based compound 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 compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto-2, 5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan compounds, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.
In the present invention, the mercaptan compounds can be used alone or in admixture of two or more.

  In the present invention, when a mercaptan compound is used in combination with a biimidazole compound, the content of the mercaptan compound is preferably 1 to 300 parts by mass, particularly preferably 5 to 100 parts by mass of the biimidazole compound. It is 200 mass parts or less, More preferably, it is 10-150. In this case, if the content of the hydrogen donor is less than 1 part by mass, the effect of improving the sensitivity tends to decrease. On the other hand, if the content exceeds 300 parts by mass, the formed colored layer tends to fall off from the substrate during development. Tend to be.

  The O-acyloxime compound is a compound having an oxime ester structure (> C═N—O—CO—), and specific examples thereof include, for example, 1,2-octanedione-1- [4 -(Phenylthio) phenyl] -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] -octa -1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -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- Carbazole-3-yl] -, 1- (O- acetyloxime) and the like.

Among these O-acyloxime compounds, in particular, 1,2-octanedione-1- [4- (phenylthio) phenyl] -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 of the (D) radiation-sensitive polymerization initiator is usually preferably 0.01 to 120 parts by mass, particularly preferably 1 to 100 parts by mass with respect to 100 parts by mass of the (C) polyfunctional monomer. 100 parts by mass, more preferably 1 to 70 parts by mass. In this case, if the content of the radiation-sensitive polymerization initiator is less than 0.01 parts by mass, curing by exposure becomes insufficient, and it becomes difficult to obtain a color filter in which pixel patterns are arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 120 parts by mass, the formed pixel pattern tends to be detached from the substrate during development.

Although the radiation sensitive composition of this invention contains the said (A)-(D) component, it can also contain another additive as needed.
Examples of other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); nonionic surfactants, cationic surfactants, and anionic surfactants. Surfactants such as surfactants; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-chloropropylmethyl Adhesion promoters such as methoxysilane, 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-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Anticoagulants such as sodium polyacrylate; alkali solubility improvers such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

  In the present invention, the radiation-sensitive composition can be prepared by an appropriate method. For example, the component (A) and the components (B) to (D) are mixed together with the solvent and additives described below. (A) In the presence of a dispersing agent and, if necessary, a dispersion aid to which a colorant is added in a solvent, optionally together with a part of the component (B), for example, a bead mill, a roll mill, etc. , Mixed and dispersed while pulverizing to obtain a pigment dispersion, which is prepared by adding (B) to (D) components and, if necessary, additional solvents and additives and mixing. It is preferable to do.

  As the 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, an alkyl ammonium salt or a phosphate ester salt of a high molecular copolymer, 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, polyurethanes, and cationic comb graft polymers are preferable.

  Such a dispersant is commercially available. For example, as a modified acrylic copolymer, Disperbyk-2000, Disperbyk-2001, BYK-LPN21116, BYK-LPN21324 (above, manufactured by BYK Corporation (BYK)) Dispersbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by BYK Chemy (BYK)), Solsperse 76500 (manufactured by Lubrizol Corp.) As a cationic comb-shaped graft polymer, Solsperse 24000 (manufactured by Lubrizol Co., Ltd.), Azisper PB821, Azisper PB822, Azisper PB823, A Spar PB824, mention may be made of Ajisper PB827 (Ajinomoto Fine-Techno Co., Ltd.), and the like.

  These dispersants can be used alone or in admixture of two or more. Content of a dispersing agent is 100 mass parts or less normally with respect to 100 weight part of (A) coloring agents, Preferably it is 0.5-100 mass parts, More preferably, it is 1-70 mass parts, Most preferably, it is 10-10. 50 parts by mass. In this case, when the content of the dispersant exceeds 100 parts by mass, developability and the like may be impaired.

The radiation-sensitive composition for forming a colored layer according to the present invention comprises the components (A) to (D) as essential components and, if necessary, the additive component, but is prepared as a liquid composition by adding a solvent. You can also
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

As such a solvent, for example,
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, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, such as tripropylene glycol monoethyl ether (poly) alkylene glycol monoalkyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxy (Poly) alkylene glycol monoalkyl ether acetates such as butyl acetate, 3-methyl-3-methoxybutylpropionate;
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;

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 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl 3-methylbutanoate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, Other esters such as n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Mention may be made of amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone.

Of these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol from the viewpoints of pigment dispersibility, solubility of components other than pigment, and coating properties. Dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethyl lactate, ethyl 3-methoxypropionate, Methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxy Preferred are butyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate and ethyl pyruvate. .
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high boiling point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can 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 from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition, the total concentration of each component excluding the solvent of the composition is usually An amount of 5 to 50% by mass is preferable, and an amount of 10 to 40% by mass is particularly desirable.

The color filter of the present invention includes a green pixel formed from the radiation-sensitive composition of the present invention.
The method for forming the color filter of the present invention will be described below.
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 preferred 10~10,000J / m ^2. The radiation-sensitive composition of the present invention does not cause chipping or peeling of the pixel pattern during development even at an exposure amount of 400 J / m ² or less.
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.

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.

  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 58 and C.I. I. 40 parts by mass of 60/40 (mass ratio) mixture with Pigment Yellow 150, Disperbyk-2 as a dispersant
A mixture of 24 parts by mass of 001 (BYK) (solid content concentration: 45.1% by mass) and 136 parts by mass of propylene glycol methyl ether acetate as a solvent was mixed and dispersed by a bead mill for 12 hours to obtain a pigment. A dispersion (A-1) was prepared.

Preparation Example 2
(A) C.I. I. Pigment Green 58 and C.I. I. 40 parts by weight of a 40/60 (mass ratio) mixture with Pigment Yellow 138, Disperbyk-2 as a dispersant
A mixed liquid consisting of 24 parts by weight of 001 (BYK) (solid content concentration: 45.1% by mass) and 136 parts by weight of propylene glycol methyl ether acetate as a solvent was mixed and dispersed for 12 hours by a bead mill to obtain a pigment. A dispersion (A-2) was prepared.

Preparation Example 3
(A) C.I. I. Pigment green 58, C.I. I. Pigment green 36 and C.I. I. 40 parts by weight of a 19/41/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by weight of Disperbyk-2001 (BYK) as a dispersant, solid content concentration 45.1% by weight, and propylene glycol as a solvent A mixed liquid consisting of 136 parts by mass of methyl ether acetate was mixed and dispersed by a bead mill for 12 hours to prepare a pigment dispersion (A-3).

Preparation Example 4
(A) C.I. I. Pigment Green 36 and C.I. I. 40 parts by weight of 55/45 (mass ratio) mixture with CI Pigment Yellow 150, Disperbyk-2 as a dispersant
A mixed liquid consisting of 24 parts by weight of 001 (BYK) (solid content concentration: 45.1% by mass) and 136 parts by weight of propylene glycol methyl ether acetate as a solvent was mixed and dispersed by a bead mill for 12 hours to obtain a pigment. A dispersion (A-4) was prepared.

Synthesis example 1
(B) Synthesis of alkali-soluble resin A flask equipped with a condenser and a stirrer was charged with 2.5 parts by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of ethylene glycol monomethyl ether acetate. Subsequently, 15 parts by weight of methacrylic acid, 10 parts by weight of ω-carboxydicaprolactone monoacrylate, 15 parts by weight of N-phenylmaleimide, 33 parts by weight of 2-ethylhexyl methacrylate, 12 parts by weight of styrene, 15 parts by weight of glycerol monomethacrylate and α-methylstyrene After charging 5.0 parts by weight of a dimer (chain transfer agent) and purging with nitrogen, the reaction solution was heated to 80 ° C. while gently stirring and polymerized for 3 hours while maintaining this temperature. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 0.5 part by mass of 2,2′-azobis (2,4-dimethylvaleronitrile) was added, and polymerization was continued for another hour, whereby a resin solution ( Solid content concentration = 30% by mass) was obtained. The obtained resin was Mw = 14,000 and Mn = 5,700. This resin solution is referred to as “resin solution (B-1)”.

Example 1
Preparation of liquid composition Pigment dispersion (A-1) 400 parts by mass, (B) 200 parts by mass of resin solution (B-1) as alkali-soluble resin, (C) Dipentaerythritol hexaacrylate as polyfunctional monomer 60 parts by mass, (D) 6 parts by mass of 2,4-diethylthioxanthone as a radiation-sensitive polymerization initiator, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -, 1- (O-acetyloxime) (Ciba Specialty Chemicals make, brand name IRGACURE OX02) 5 parts by mass, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5' -2 parts by mass of tetraphenyl-1,2'-biimidazole and 2 parts by mass of 2-mercaptobenzothiazole and propylene glycol monomethyl ether as solvent It was mixed so that the solid content concentration of 20.0% by using the acetate, liquid composition (G1) was prepared.
The liquid composition (G1) was evaluated according to the following procedure. The evaluation results are shown in Table 2.

Evaluation of foreign matter and sensitivity The liquid composition (G1) was applied on a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface using a spin coater, and then on a hot plate at 90 ° C. Pre-baking was performed for 100 seconds to form a coating film having a thickness of 2.5 μm.
Next, after cooling this substrate to room temperature, a high-pressure mercury lamp is used, and the exposure dose of 400 J / m ² is applied to the coating film through the photomask (slit width 90 μm). And exposed. Thereafter, a developer at 30 ° C. composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. is discharged over 90 seconds under the conditions of a development pressure of 110 kPa and a developer flow rate of 1.2 liters / minute. As a result, shower development was performed. Thereafter, the substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 220 ° C. for 30 minutes to form a pixel array in which green stripe pixel patterns were arranged on the substrate. .

  When the pixel pattern on the obtained substrate was observed with an optical microscope, no foreign matter was observed on the pixel pattern, and no chipping was observed on the pattern edge.

Evaluation of Chromaticity After coating the liquid composition (G1) on a soda glass substrate on which a SiO ₂ film that prevents elution of sodium ions is formed on the surface using a spin coater, the number of rotations is varied. Then, pre-baking was performed for 4 minutes on a hot plate at 90 ° C. to form three coating films having different film thicknesses.
Next, after these substrates were cooled to room temperature, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at a dose of 400 J / m ² through a photomask using a high-pressure mercury lamp. After that, shower development was performed by discharging a developer composed of a 0.04 mass% potassium hydroxide aqueous solution at 23 ° C. at a development pressure of 1 kgf / cm ² (nozzle diameter 1 mm). Thereafter, this substrate was washed with ultrapure water, air-dried, and then post-baked in a clean oven at 220 ° C. for 30 minutes to form a 200 × 200 μm dot pattern on the substrate.

  About the obtained dot pattern, using a color analyzer (MCPD2000 manufactured by Otsuka Electronics Co., Ltd.), a C light source, a chromaticity coordinate value (x, y) and a stimulus value (Y) in the CIE color system with a 2-degree field of view. Was measured. From the measurement results, a chromaticity coordinate value x and a stimulus value (Y) at a constant chromaticity coordinate value y were obtained. The evaluation results are shown in Table 2. The larger the Y value, the higher the light transmittance (brightness).

Examples 2-6 and Comparative Examples 1-8
In Example 1, liquid compositions (G2) to (G14) were prepared in the same manner as in Example 1 except that the types and amounts of the constituent components were changed as shown in Table 2.
Next, evaluation was performed in the same manner as in Example 1 except that the liquid compositions (G2) to (G14) were used instead of the liquid composition (G1). The results are shown in Table 2.

C-1: Dipentaerythritol hexaacrylate D-1: 2,4-diethylthioxanthone D-2: Mixture of 2-isopropylthioxanthone and 4-isopropylthioxanthone (trade name DAROCURE IDX, manufactured by Ciba Specialty Chemicals)
D-3: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (trade name IRGACURE OX02, Ciba Specialty・ Made by Chemicals
D-4: 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole D-5: 2-mercaptobenzothiazole D-6: 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
D-7: Benzophenone D-8: 2,4-Diethylaminobenzophenone D-9: 2,4-Dimethylaminobenzophenone

  From Tables 1 and 2, C.I. I. When CI Pigment Green 58 is used and a thioxanthone compound is used as a polymerization initiator, the light transmittance (Y value), which is an index of luminance, is high, no foreign matter is generated on the pixel, and the pattern is not chipped. I couldn't.

Claims (4)

A radiation-sensitive composition for forming a green pixel, comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a radiation-sensitive polymerization initiator, A) The colorant is C.I. I. A radiation-sensitive composition for forming a green pixel, which contains CI Pigment Green 58, and (D) the radiation-sensitive polymerization initiator contains a compound represented by the following formula (1).

(Wherein, R ¹ to R ⁴ are, independently of one another hydrogen atom, an alkyl group or an alkoxy group having 1 to 18 carbon atoms having 1 to 18 carbon atoms.)   (D) The sensation according to claim 1, wherein the radiation-sensitive polymerization initiator further contains at least one compound selected from the group consisting of acetophenone compounds, biimidazole compounds and O-acyloxime compounds. Radiation composition.   A color filter comprising a pixel formed using the radiation-sensitive composition according to claim 1.     A color liquid crystal display device comprising the color filter according to claim 3.