KR20100031457A - Colored radiation-sensitive composition, color filter and color liquid crystal display device - Google Patents

Abstract

PURPOSE: A colored radiation-sensitive composition, a color filter and a color liquid crystal display device using the same are provided to form green pixels with high brightness and contrast ratio, and to prevent the degradation of contrast ratio. CONSTITUTION: A colored radiation-sensitive composition comprises a coloring agent, an alkali soluble resin, a multifunctional monomer, a radiation-sensitive polymerization initiator and solvent. The coloring agent includes C I. pigment green 58. The solvent has two acetoxy groups. The colored radiation-sensitive composition further comprises a dispersing agent.

Description

Colored Radiation-Sensitive Composition, Color Filter and Color Liquid Crystal Display Device

The present invention relates to a colored radiation-sensitive composition, a color filter, and a color liquid crystal display device, and more particularly, a color filter used for a transmissive or reflective color liquid crystal display device, a color image tube device, an organic EL display device, an electronic paper, and the like. The radiation sensitive composition used for formation of the colored layer useful for the application, the color filter provided with the colored layer formed using this radiation sensitive composition, and the color liquid crystal display element provided with this color filter.

A method of forming a color filter using a colored radiation-sensitive composition, comprising: forming a coating film of a colored radiation-sensitive composition on a substrate or on a substrate on which a light shielding layer having a desired pattern is formed in advance, and radiation through a photomask having a predetermined pattern A method of obtaining pixels of each color by irradiating (hereinafter referred to as "exposure"), developing, dissolving and removing unexposed portions, and then post-baking is known (see, for example, Patent Documents 1 and 2). .

The liquid crystal display element provided with such a color filter is required to have high luminance and enlargement of the color reproduction area. Therefore, the color filter has also been required to have higher light transmittance and higher color purity in recent years.

As green materials, a pigment composition containing a polyhalogenated zinc phthalocyanine pigment is known and attracted attention as a material capable of providing a color filter having a high luminance and a wide color reproduction region (see Patent Document 3, for example). ). However, the pigment composition containing a polyhalogenated zinc phthalocyanine pigment has a problem that contrast ratio will fall with time, when trying to raise contrast ratio.

From the above background, development of the radiation sensitive composition which can form green pixel with high brightness | luminance and contrast ratio, and a contrast ratio does not fall with time is strongly requested | required.

Patent Document 1: Japanese Patent Application Laid-Open No. 2-144502

Patent Document 2: Japanese Patent Application Laid-Open No. 3-53201

Patent Document 3: Japanese Patent Application Laid-Open No. 2007-284589

An object of the present invention is to provide a radiation-sensitive composition which can form a green pixel having high luminance and contrast ratio, and in which the contrast ratio does not decrease with time.

Moreover, the objective of this invention is providing the color filter which comprises the green pixel formed from the said radiation sensitive composition, and the color liquid crystal display element provided with this color filter.

In view of such circumstances, the present inventors have made intensive studies, and surprisingly, the polyhalogenated zinc phthalocyanine pigment, C.I. The present invention was completed by discovering that the above-mentioned problems can be solved by dispersing pigment green 58 in combination with a specific solvent.

That is, this invention is colored radiation-sensitive composition containing (A) coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) radiation sensitive polymerization initiator, and (E) solvent, (A) CI as colorant Pigment Green 58 is contained and (E) it is providing the colored radiation-sensitive composition characterized by containing the solvent which has two acetoxy groups.

"Radiation" as used in the present invention means visible light, ultraviolet rays, far ultraviolet rays, electron beams, X-rays and the like.

Moreover, this invention is colored radiation-sensitive composition containing (A) coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) radiation sensitive polymerization initiator, and (E) solvent, (A) The coloring radiation sensitive composition containing zinc bromide chlorinated phthalocyanine as a coloring agent, and the solvent which has two acetoxy groups as (E) solvent are provided.

In addition, the present invention provides a C.I. It is providing the colorant dispersion liquid containing pigment green 58 and the solvent which has two acetoxy groups.

Moreover, this invention also provides the color filter which comprises the green pixel formed using the said colored radiation sensitive composition, and the color liquid crystal display element provided with the said color filter.

The colored radiation-sensitive composition of the present invention can form green pixels with high luminance and contrast ratio, and the contrast ratio does not decrease with time.

Therefore, the color filter which comprises the green pixel formed using the colored radiation-sensitive composition of this invention is a transmissive or reflective color liquid crystal display element, a color imaging tube element, a color sensor, an organic electroluminescence display element, an electron, for example. Very useful for paper.

In the colored radiation-sensitive composition (hereinafter, sometimes referred to simply as "radiation-sensitive composition") of the present invention, the (A) colorant is C.I. It contains Pigment Green 58. C.I. Pigment Green 58 is zinc chlorinated zinc phthalocyanine, and preferably has a structure represented by the following formula (1).

(Wherein X represents a hydrogen atom, a chlorine atom or a bromine atom independently of one another, 10 to 15 of all X are bromine atoms and 1 to 6 chlorine atoms)

The radiation sensitive composition of the present invention is C.I. It may further contain other coloring agents other than Pigment Green 58. Although it does not specifically limit as another coloring agent, Although all pigments, dyes, and a natural pigment can be used, an organic pigment is preferable because a color filter requires high purity, high permeability color development, and heat resistance.

In the present invention, C.I. The content ratio of Pigment Green 58 is preferably 20 to 100 mass%, particularly preferably 35 to 75 mass% in all colorants from the viewpoint of obtaining a green pixel having high luminance.

As said other coloring agent, the compound classified by the pigment in the color index, for example, the pigment to which the following color index (C.I.) name is given is mentioned.

C.I. Pigment Green 7, C.I. Pigment green 36;

C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, C.I. Pigment Yellow 17, C.I. Pigment Yellow 20, C.I. Pigment Yellow 24, C.I. Pigment Yellow 31, C.I. Pigment Yellow 55, C.I. Pigment Yellow 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 180, C.I. Pigment Yellow 211, C.I. Pigment yellow 219;

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

C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 5, C.I. Pigment Red 17, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 41, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 209, C.I. Pigment Red 214, C.I. Pigment Red 220, C.I. Pigment Red 221, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 262, C.I. Pigment Red 264, C.I. Pigment Red 272.

These other coloring agents can be used individually or in mixture of 2 or more types.

Among these other colorants, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 180, C.I. Pigment yellow 219 and the like are preferred.

In the present invention, C.I. Pigment Green 58 and other colorants can be purified by recrystallization, reprecipitation, solvent washing, sublimation, vacuum heating, combinations thereof, and the like, as necessary. In addition, C.I. Pigment Green 58 and other colorants can be used by modifying their particle surfaces with polymers as desired. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, the polymer for various pigment dispersions, or oligomer etc. which were marketed are mentioned, for example.

In the present invention, the content ratio of the colorant (A) is preferably 5 to 70% by mass and particularly preferably 5 to 60% by mass in the total solids from the viewpoint of forming a green pixel having high luminance and color purity. Solid content is components other than the solvent mentioned later here.

(B) Alkali-soluble resin contained in the radiation sensitive composition of this invention will not be specifically limited if it has solubility with respect to the alkaline developing solution used at the image development process at the time of forming a colored layer, Usually, it is a carboxyl group and phenolic It is a polymer which has acidic functional groups, such as a hydroxyl group. Especially, it is preferable to contain the polymer which has a carboxyl group, and especially the ethylenically unsaturated monomer copolymerizable with another ethylenically unsaturated monomer (Hereinafter, it may be called "carboxyl group-containing unsaturated monomer") which has one or more carboxyl groups (henceforth, The copolymer of the "copolymerizable unsaturated monomer" may be called) (hereinafter, may be called "carboxyl group-containing copolymer" hereafter).

As a carboxyl group-containing unsaturated monomer, for example,

Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid;

Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid;

Mono ((meth) acryloyloxy alkyl] of a divalent or higher polyhydric carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] ester;

and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as? -carboxypolycaprolactone mono (meth) acrylate.

The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

As the carboxyl group-containing unsaturated monomer in the present invention, (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl],? -Carboxypolycaprolactone mono (meth) acrylate, and the like are preferable, and in particular, (meth) Acrylic acid is preferred.

These carboxyl group-containing unsaturated monomers can be used individually or in mixture of 2 or more types.

In the carboxyl group-containing copolymer, the copolymerization ratio of the carboxyl group-containing unsaturated monomer is preferably 5 to 50 mass%, more preferably 10 to 40 mass%. In this case, when the said copolymerization ratio is too small, the solubility with respect to the alkaline developing solution of the radiation sensitive composition obtained tends to fall, while when too much, the solubility with respect to an alkaline developing solution will become excessive, and when developing with alkaline developing solution, It tends to be easy to drop off from the substrate and to cause film roughness of the pixel surface.

Moreover, as a copolymerizable unsaturated monomer, for example,

Maleimide:

N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-benzylmaleimide, N-cyclohexylmaleimide, N-succinimidyl-3 -Maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3-maleimide propionate, N- (acridy N-position substituted maleimide, such as nil) maleimide;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylphenol, m-vinylphenol, p-vinylphenol, p-hydroxy-α-methylstyrene, o-vinylbenzylmethyl ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzyl glycidyl ether, aromatic vinyl compounds such as m-vinylbenzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-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, methoxypropyl Lenglycol (meth) acrylate, methoxydipropyleneglycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, 2 Unsaturation such as hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of p-cumylphenol 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 and 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 and vinylidene cyanide;

Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;

Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene;

And macromonomers having a mono (meth) acryloyl group at the ends of polymer molecular chains such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.

These copolymerizable unsaturated monomers can be used individually or in mixture of 2 or more types.

In the present invention, the copolymerizable unsaturated monomer is selected from the group consisting of an N-position substituted maleimide, an aromatic vinyl compound, an unsaturated carboxylic acid ester, and a macromonomer having a mono (meth) acryloyl group at the terminal of the polymer molecular chain. It is preferable to contain species or more, and furthermore, N-phenylmaleimide, N-cyclohexyl maleimide, styrene, (alpha) -methylstyrene, p-hydroxy- (alpha) -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, Group consisting of 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of p-cumylphenol, polystyrene macromonomer, and polymethylmethacrylate macromonomer To contain at least one element selected from the preferred.

Further, in the present invention, as disclosed in, for example, Japanese Patent Application Laid-Open No. Hei 5-19467, Japanese Patent Application Laid-Open No. 6-230212, Japanese Patent Application Laid-Open No. 2008-181095, etc. A carboxyl group-containing copolymer which has a polymerizable unsaturated bond, such as an (meth) acryloyl group, can be used as alkali-soluble resin.

The polystyrene reduced weight average molecular weight (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 3,000 to 20,000. If Mw is too small, the remaining film ratio of the resulting film may be reduced, the pattern shape and heat resistance may be impaired, or the electrical properties may be deteriorated. There exists a possibility that a dry foreign material may arise easily at the time of application | coating.

In addition, the ratio (Mw / Mn) of Mw of alkali-soluble resin and polystyrene conversion number average molecular weight (henceforth "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) in this invention. Is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0.

Alkali-soluble resin in this invention is a 2,2'- azobisisobutyronitrile and 2,2'- azobis (2, 4- dimethylvalle), for example, unsaturated monomers, such as (meth) acrylic acid, in a suitable solvent. It can manufacture by polymerizing in presence of radical polymerization initiators, such as a ronitrile) and 2,2'- azobis (4-methoxy-2, 4- dimethylvaleronitrile).

As mentioned above, alkali-soluble resin in this invention can be refine | purified via the reprecipitation method which uses two or more types of organic solvents from which polarity differs, after radically polymerizing an unsaturated monomer. That is, the solution in the good solvent after polymerization is removed, if necessary, by infiltration, centrifugation, or the like, and then poured into a large amount (usually 5 to 10 times the volume of the polymer solution) in a precipitant (poor solvent) and the copolymer. Purify by reprecipitation. At this time, among 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.

As a good solvent / precipitator combination used for this reprecipitation method, for example, diethylene glycol monomethyl ether acetate / n-hexane, methyl ethyl ketone / n-hexane, diethylene glycol monomethyl ether acetate / n-heptane, methyl Ethyl ketone / n-heptane; and the like.

In addition, the alkali-soluble resin in this invention is a 2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), each unsaturated monomer used as the copolymerization component, Radical polymerization initiators such as 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, pyrazole- 1-dithiocarboxylic acid 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) disulfide, bis (3,4,5-trimethyl-pyra Inert solvent in the presence of a molecular weight controlling agent that acts as an iniferter such as sol-1-ylthiocarbonyl) disulfide, bis (pyrrole-1-ylthiocarbonyl) disulfide, bisthiobenzoyldisulfide, etc. medium It can be prepared by living radical polymerization at a reaction temperature of usually 0 to 150 ° C, preferably 50 to 120 ° C.

Moreover, alkali-soluble resin in this invention can be manufactured by radically polymerizing each unsaturated monomer used as the copolymerization component in a suitable solvent in presence of the said radical polymerization initiator and the polyhydric thiol compound which acts as a chain transfer agent. Here, a polyvalent thiol compound means the compound which has two or more thiol groups in 1 molecule, For example, trimethylol propane tris (3-mercapto propionate) and pentaerythritol tetrakis (3-mercapto propionate) , Tetraethylene glycol bis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), 1,4-bis (3- Mercaptobutyryloxy) 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.

In this invention, content of (B) alkali-soluble resin is 10-1,000 mass parts normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 20-500 mass parts. In this case, when there is too little content of alkali-soluble resin, alkali developability may fall, for example, residue or ground contamination may arise on the board | substrate or light-shielding layer of an unexposed part, and when too much, a coloring agent concentration will be comparatively high. Since it falls, it may become difficult to attain 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, or dicarboxylic acid modified substances thereof;

Oligo (meth) acrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins, and spiran resins;

Di (meth) acrylates of both terminal hydroxyl polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactones;

Tris [2- (meth) acryloyloxyethyl] phosphate, isocyanuric acid ethylene oxide modified triacrylate, poly (meth) acrylate having urethane structure, poly (meth) acrylate having caprolactone structure

Etc. can be mentioned.

Among these polyfunctional monomers, poly (meth) acrylates of trivalent or higher polyhydric alcohols, their dicarboxylic acid modified substances, poly (meth) acrylates having a urethane structure, and poly (meth) acryls having a caprolactone structure Rate is preferred. As poly (meth) acrylates of trivalent or more polyhydric alcohols, and these dicarboxylic acid modified substances, trimethylol propane triacrylate, trimethylol propane trimethacrylate, pentaerythritol triacrylate, pentaerythritol tri Methacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexametha Acrylates, monoesters of pentaerythritol triacrylate and succinic acid, monoesters of pentaerythritol trimethacrylate and succinic acid, monoesters of dipentaerythritol pentaacrylate and succinic acid, dipentaerythritol pentametha Monoesters of Acrylate and Succinic Acid Especially, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol triacrylate and succinic acid monoesterate and dipenta The monoesters of erythritol pentaacrylate and succinic acid have high strength of the colored layer, excellent surface smoothness of the colored layer, and low surface contamination and film residue on the substrate and the light-shielding layer of the unexposed portion. desirable.

The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

20-500 mass parts is preferable with respect to 100 mass parts of (B) alkali-soluble resin, and, as for content of (C) polyfunctional monomer in this invention, 100-300 mass parts is especially preferable. In this case, when there is too little content of a polyfunctional monomer, there exists a tendency for the intensity | strength, surface smoothness, and solvent resistance of a pixel to fall, and when too much, alkali developability falls, for example, on the board | substrate of an unexposed part, or light-shielding. Background contamination, film residues, etc. tend to occur on the layer.

In the present invention, a part of the polyfunctional monomer may be substituted with a monofunctional monomer having one polymerizable unsaturated bond.

As said monofunctional monomer, the mono [of bivalent or more polyvalent carboxylic acid, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl], for example, Mono (meth) acrylate or N- (meth) acryl of a polymer having a carboxyl group and a hydroxyl group at both terminals such as (meth) acryloyloxyalkyl] ester and ω-carboxypolycaprolactone mono (meth) acrylate In addition to morpholine, N-vinylpyrrolidone, and N-vinyl- epsilon caprolactam, M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item.

These monofunctional monomers can be used individually or in mixture of 2 or more types.

The content rate of the monofunctional monomer in this invention becomes like this. Preferably it is 90 mass% or less, More preferably, it is 50 mass% or less with respect to the sum total of a polyfunctional monomer and a monofunctional monomer. In this case, when there is too much use ratio of a monofunctional monomer, there exists a tendency for the intensity | strength and surface smoothness of a pixel to fall.

The (D) radiation sensitive polymerization initiator used for this invention is said (C) polyfunctional monomer and monofunctional monomer used by the said (C) polyfunctional monomer by exposure of radiation, such as a visible ray, an ultraviolet-ray, an ultraviolet ray, an electron beam, X-rays, etc. It is a compound which generates the active species which can start superposition | polymerization of.

Examples of such radiation-sensitive polymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, and benzophenone compounds. A compound, the (alpha)-diketone type compound, a multinuclear quinone type compound, a diazo type compound, an imide sulfonate type compound, etc. are mentioned.

In the present invention, the radiation-sensitive polymerization initiator may be used alone or in combination of two or more thereof. Examples of the radiation-sensitive polymerization initiator include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, At least one selected from the group of O-acyl oxime compounds is preferable. In addition, C.I. It is preferable that the radiation sensitive composition containing pigment green 58 contains a thioxanthone type compound from a viewpoint of agglomerated foreign matter of the said pigment easily generate | occur | producing, and reducing this aggregated foreign matter.

In this invention, it is more preferable to use combining the said thioxanthone type compound and another radiation sensitive polymerization initiator. In this case, the content rate of a thioxanthone type compound is 1-75 mass% in all the radiation sensitive polymerization initiators, Especially preferably, it is 5-50 mass%. By using such a radiation sensitive polymerization initiator, the radiation sensitive composition which is not only high sensitivity but excellent in dispersion stability can be obtained.

As a specific example of a thioxanthone type compound in the preferable radiation sensitive polymerization initiator in this invention, thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2-dode Silthioxanthone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthone, 2-chloro thioxanthone, and the like.

Among these thioxanthone compounds, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, and 2,4-diethyl thioxanthone are preferable.

The thioxanthone compound may be used alone or in combination of two or more thereof.

Moreover, as a specific example of the said acetophenone type compound, 2-hydroxy-2- methyl-1- phenyl propane- 1-one, 2-methyl-1- [4- (methylthio) phenyl] -2- morpholino Propane-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 phenyl ketone, 2,2-dimethoxy- 1,2-diphenylethan-1-one, etc. are mentioned.

Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholine Nophenyl) butan-1-one and 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one are preferred.

The acetophenone compounds may be used alone or in combination of two or more thereof.

Moreover, as a specific example of the said biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1,2 '-Biimidazole, 2,2'-bis (2-bromophenyl) -4,4', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5 ' -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 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, etc. are 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.

The said biimidazole type compound can be used individually or in mixture of 2 or more types.

Moreover, when using a biimidazole type compound as a radiation sensitive polymerization initiator, using a hydrogen donor together is preferable at the point which can raise a sensitivity. The "hydrogen donor" as used here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, and 4,4'-bis (di Amine hydrogen donors, such as ethylamino) benzophenone, are mentioned. In the present invention, the hydrogen donor may be used alone or in combination of two or more, but it is preferable to use a mercaptan-based hydrogen donor.

When the hydrogen donor is used in combination with the biimidazole compound in the present invention, the content of the hydrogen donor is preferably 1 to 300 parts by mass, more preferably 5 to 200 parts by mass, based on 100 parts by mass of the biimidazole compound, More preferably, it is 10-150 mass parts. In this case, when there is too little content of a hydrogen donor, there exists a tendency for the improvement effect of a sensitivity to fall, and when too much, the formed colored layer tends to fall off from a board | substrate at the time of image development.

In addition, specific examples of the triazine-based 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 (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine , 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl)- Triazine type compounds which have halomethyl groups, such as 4, 6-bis (trichloromethyl) -s-triazine, are mentioned.

The said triazine type compound can be used individually or in mixture of 2 or more types.

In addition, specific examples of the O-acyl oxime-based compound include 1,2-heptanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1,2-octanedione, 1 -[4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 1,2-octanedione, 1- [4- (benzoyl) phenyl]-, 2- (O-benzoyloxime), eta Non, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (3-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyl Oxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), eta Paddy, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbene Crude) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1 , 3-dioxolanyl) benzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetra Hydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyra Nylmethoxybenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl ) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9H -Carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-diox Solanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime), and the like.

Among these O-acyl oxime compounds, 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyl oxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylme Methoxybenzoyl) -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) is preferred.

The O-acyl oxime compounds may be used alone or in combination of two or more thereof.

Content of a radiation sensitive polymerization initiator in this invention is 0.01-120 mass parts normally with respect to 100 mass parts of (C) polyfunctional monomers, Preferably it is 1-100 mass parts, More preferably, it is 1-70 mass parts. . In this case, when there is too little content of a radiation sensitive polymerization initiator, hardening by exposure may become inadequate, and it may become difficult to obtain the color filter by which the pixel pattern was arrange | positioned according to the predetermined | prescribed arrangement, and when too large, the formed pixel pattern It tends to be easy to fall off from the substrate during this development.

The solvent (E) used for this invention contains the solvent which has two acetoxy groups. As a specific example of the solvent which has two acetoxy groups, propylene glycol diacetate, 1, 3- butylene glycol diacetate, 1, 6- hexanediol diacetate, etc. are mentioned.

The solvent having two acetoxy groups may be used alone or in combination of two or more thereof.

In the present invention, other solvents can be used together with the solvent having two acetoxy groups. As such another 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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, tripropylene glycol monomethyl ether, tri (Poly) alkylene glycol monoalkyl ethers such as propylene glycol monoethyl 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-methoxy (Poly) alkylene glycol monoalkyl ether acetates such as butyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutyl propionate;

Ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone;

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-3-methylbutyrate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, butyric acid Other esters such as ethyl, butyric acid n-propyl, butyric acid i-propyl, butyric acid n-butyl, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxobutanoate;

Aromatic hydrocarbons such as toluene and xylene;

Amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these other solvents, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethyl 3-methoxypropionate and methyl 3-ethoxypropionate from the viewpoints of pigment dispersibility, solubility of components other than pigments, and coating properties. Ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutylpropionate are preferred.

The said other solvent can be used individually or in mixture of 2 or more types.

It is preferable that the solvent used for this invention is a mixture of the solvent which has two acetoxy groups, and another solvent, It is preferable that the content rate of the solvent which has two acetoxy groups is 1-60 mass% in all the solvents, It is especially preferable that it is 1-45 mass%. In this case, when there are too few content ratios of the solvent which has two acetoxy groups, there exists a possibility that a desired effect may not be acquired. On the other hand, when too much, a solvent component will become difficult to evaporate and it may become difficult to form a coating film.

Although content of a solvent is not specifically limited, From the viewpoint of the applicability | paintability, stability, etc. of the radiation sensitive composition obtained, the quantity by which the total concentration of each component except the solvent of the said composition becomes 5-50 mass% is preferable, Especially 10-10- The amount which becomes 40 mass% is preferable.

In this invention, a radiation sensitive composition can be manufactured by a suitable method, for example, can be manufactured by mixing (A)-(E) component with the additive mentioned later. As a preferable manufacturing method of a radiation sensitive composition, C.I. In the presence of the dispersing agent which adds the coloring agent which consists of pigment green 58 containing the solvent which has two acetoxy groups, and (F) dispersing agent and if necessary, if necessary, The mixture is dispersed and dispersed with a part, for example, using a bead mill, a roll mill, or the like to form a colorant dispersion, and the components (B) to (D) are added to the colorant dispersion and, if necessary, a solvent or an additive is further added. The method of manufacturing by mixing is mentioned.

In this case, it is preferable that the content rate of the solvent which has two acetoxy groups in all the solvent used for manufacture of a coloring agent dispersion liquid is 2 mass% or more, and it is especially preferable that it is 5 mass% or more.

As the dispersant (F) used in the preparation of the colorant dispersion, suitable dispersants such as cationic, anionic, nonionic, amphoteric and the like can be used, but a polymer dispersant is preferable, and in particular, a block and a side chain having a pigment adsorbing group in the side chain are used. A block copolymer (hereinafter sometimes referred to as "block copolymer type dispersant") containing a block having no pigment adsorbing group is preferable.

As a pigment adsorption group in a block copolymer type dispersing agent, basic groups, such as an amino group, a carboxyl group, a phosphono group, a quaternary ammonium base group, a carboxylate group, a phosphate group, etc. are mentioned, for example. The block which has a pigment adsorption group in a side chain is comprised by the repeating unit derived from the (meth) acrylic acid ester which has these pigment adsorption groups, for example.

On the other hand, in the block which does not have a pigment adsorption group in a side chain, it is preferable to have a linear or cyclic alkyl group, an aryl group, an aralkyl group, a polycaprolactone structure, a polyether structure, etc. in the side chain. The block which does not have a pigment adsorption group in a side chain is comprised by the repeating unit derived from the (meth) acrylic acid ester which has these functional groups and structures, for example.

Such block copolymer-type dispersants are commercially available and include, for example, Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116 (BYK Corporation), and the like.

The said block copolymer dispersing agent can be used individually or in mixture of 2 or more types.

In the present invention, other dispersants may be used together with the block copolymer type dispersant. Specific examples of such other dispersants include polyurethanes, polyesters, cationic graft polymers, and the like. Here, the cationic comb graft polymer refers to a polymer having a structure in which two or more branched polymers are graft-bonded to one molecule of a stem polymer having a plurality of basic groups (cationic functional groups). The polymer comprised from the ring-opened polymer of addition (epsilon) -caprolactone is mentioned.

Such dispersants are commercially available and include, for example, Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, and Disperbyk-182 (above, manufactured by BYK) as polyurethanes. Solsperpers 76500 (manufactured by Lubrizol Co., Ltd.), cationic graft polymer, Solsperth 24000 (manufactured by Lubrizol Co., Ltd.), Azisper PB821, Azisper PB822, Azisper PB823, Azisper PB824, Ajisper PB827 (made by Ajino Moto Fine Techno Co., Ltd.), etc. are mentioned.

These dispersants can be used individually or in mixture of 2 or more types.

Content of a dispersing agent is 100 mass parts or less normally with respect to 100 mass parts of (A) coloring agents, Preferably it is 0.5-100 mass parts, More preferably, it is 1-70 mass parts, Especially preferably, it is 10-50 mass parts. . In this case, when content of a dispersing agent exceeds 100 mass parts, there exists a possibility that developability may be impaired.

Although the radiation sensitive composition of this invention contains the said (A)-(E) component, it may further contain an additive as needed.

As an additive here, For example, fillers, such as glass and an alumina; Polymer compounds such as polyvinyl alcohol and poly (fluoroalkylacrylate) s; Surfactants such as nonionic surfactants, cationic surfactants, and anionic 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-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation inhibitors such as sodium polyacrylate; And developing residue improving agents such as malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, and mesaconic acid.

The color filter of this invention is equipped with the green pixel formed from the radiation sensitive composition of this invention.

Hereinafter, the method of forming the color filter of this invention is demonstrated.

First, a light shielding layer is formed on the surface of the substrate so as to partition a portion forming a pixel as necessary, and after applying the liquid composition of the radiation-sensitive composition in which the green pigment of the present invention is dispersed on the substrate, preliminary baking is performed. The solvent is evaporated to form a coating film. Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, melt | dissolves and removes the unexposed part of a coating film, and then post-bakes to form the pixel array in which the green pixel pattern was arrange | positioned in the predetermined | prescribed arrangement. .

Thereafter, using the liquid composition of each radiation-sensitive composition in which red or blue pigments are dispersed, the liquid composition is applied, prebaked, exposed, developed and postbaked in the same manner as described above, and the red pixel array And a blue pixel array are sequentially formed on the same substrate, thereby obtaining a color filter in which pixel arrays of three primary colors of red, green, and blue are disposed on the substrate. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

As a board | substrate used when forming a pixel, glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example.

Moreover, according to the objective, these board | substrates can be suitably pretreated, such as chemical | medical processing, plasma processing, ion plating, sputtering, vapor phase reaction method, and vacuum deposition.

When applying the liquid composition of a radiation sensitive composition to a board | substrate, although the appropriate coating methods, such as spraying method, the roll coating method, the spin coating method (spin coating method), the slit die coating method, the bar coating method, the inkjet method, can be used, Spin coating and slit die coating are particularly preferred.

The coating thickness is usually 0.1 to 10 탆, preferably 0.2 to 8.0 탆, particularly preferably 0.2 to 6.0 탆 as the film thickness after drying.

As the radiation used when forming the pixel, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable.

In general, the exposure dose of the radiation is preferably 10 to 10,000 J / m 2.

As the alkaline developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- Aqueous solutions, such as diazabicyclo- [4.3.0] -5-nonene, are preferable.

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. In addition, after alkali image development, it washes with water normally.

As the developing treatment method, a shower developing method, a spray developing method, an immersion developing method, a puddle developing method and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

Since the color filter of this invention obtained in this way has high brightness and contrast ratio, it is very useful for a color liquid crystal display element, a color image tube element, a color sensor, an organic EL display element, an electronic paper, etc.

<Example>

Hereinafter, an Example is shown and embodiment of this invention is described more concretely. However, the present invention is not limited to the following examples.

Preparation of Colorant Dispersion

Preparation Example 1

(A) As a coloring agent, C.I. Pigment Green 58 (manufactured by DIC Corporation) and C.I. 40 parts by mass of 60/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1% by mass) as a dispersant and 116 parts by mass of propylene glycol methyl ether acetate And a mixed liquid containing 20 parts by mass of 1,3-butylene glycol diacetate were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (A-1).

Preparation Example 2

(A) As a coloring agent, C.I. Pigment Green 58 (manufactured by DIC Corporation) and C.I. 40 parts by mass of 60/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1% by mass) as a dispersant and 116 parts by mass of propylene glycol methyl ether acetate And a mixed liquid containing 20 parts by mass of propylene glycol diacetate were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (A-2).

Preparation Example 3

(A) As a coloring agent, C.I. Pigment Green 58 (manufactured by DIC Corporation) and C.I. 40 parts by mass of 60/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1% by mass) as a dispersant and 96 parts by mass of propylene glycol methyl ether acetate And a mixed liquid containing 40 parts by mass of 1,3-butylene glycol diacetate were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (A-3).

Preparation Example 4

(A) As a coloring agent, C.I. Pigment Green 58 (manufactured by DIC Corporation) and C.I. 40 parts by mass of 60/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1% by mass) as dispersant and 76 parts by mass of 3-ethoxypropionate as solvent A mixed liquid containing 60 parts by mass of 1,3-butylene glycol diacetate was mixed and dispersed for 12 hours with a bead mill to prepare a pigment dispersion (A-4).

Preparation Example 5

(A) As a coloring agent, C.I. Pigment Green 58 (manufactured by DIC Corporation) and C.I. 40 parts by mass of 60/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1% by mass) as a dispersant and 76 parts of 3-methoxybutyl acetate as a solvent A mixed solution containing 60 parts by mass of 1,3-butylene glycol diacetate was mixed and dispersed for 12 hours with a bead mill to prepare a pigment dispersion (A-5).

Preparation Example 6

(A) As a coloring agent, C.I. Pigment Green 58 (manufactured by DIC Corporation) and C.I. 40 parts by mass of 60/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1% by mass) as a dispersant and 1,3-butylene glycol di as a solvent A mixed liquid containing 136 parts by mass of acetate was mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (A-6).

Comparative Production Example 1

(A) As a coloring agent, C.I. Pigment Green 58 (manufactured by DIC Corporation) and C.I. 40 parts by mass of 60/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1% by mass) as a dispersant and 136 parts by mass of propylene glycol methyl ether acetate as a solvent. The mixed solution containing was mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (a-1).

Comparative Production Example 2

(A) As a coloring agent, C.I. Pigment Green 58 (manufactured by DIC Corporation) and C.I. 40 parts by mass of 60/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1% by mass) as a dispersant and triacetin (three acetoxy groups as a solvent) Solvent) and a mixed liquid containing 136 parts by mass was mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (a-2).

Comparative Production Example 3

(A) As a coloring agent, C.I. Pigment Green 58 (manufactured by DIC Corporation) and C.I. 40 parts by mass of 60/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1% by mass) as a dispersant and 116 parts by mass of propylene glycol methyl ether acetate And the mixed liquid containing 20 mass parts of cyclohexanone were mixed and dispersed for 12 hours by the bead mill, and the pigment dispersion liquid (a-3) was produced.

Comparative Production Example 4

(A) As a coloring agent, C.I. Pigment Green 58 (manufactured by DIC Corporation) and C.I. 40 parts by mass of 60/40 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1% by mass) as a dispersant and 116 parts by mass of propylene glycol methyl ether acetate And a mixed liquid containing 20 parts by mass of propylene glycol monomethyl ether were mixed and dispersed for 12 hours by a bead mill to prepare a pigment dispersion (a-4).

Comparative Production Example 5

(A) As a coloring agent, C.I. Pigment Green 36 and C.I. 40 parts by mass of 53/47 (mass ratio) mixture of Pigment Yellow 150, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1 mass%) as a dispersant and 116 parts by mass of propylene glycol methyl ether acetate And the mixed liquid containing 20 mass parts of cyclohexanone were mixed and dispersed for 12 hours by the bead mill, and the pigment dispersion liquid (a-5) was produced.

(B) Synthesis of Alkali-Soluble Resin

Synthesis Example 1

2.5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) and 200 parts by mass of ethylene glycol monomethyl ether acetate were charged into a flask equipped with a cooling tube and a stirrer, followed by 15 parts by mass of methacrylic acid, 10 parts by mass of ω-carboxydicaprolactone monoacrylate, 15 parts by mass of N-phenylmaleimide, 33 parts by mass of 2-ethylhexyl methacrylate, 12 parts by mass of styrene, 15 parts by mass of glycerol monomethacrylate and α-methyl 5.0 mass parts of styrene dimers (chain transfer agent) were added, nitrogen-substituted, and the reaction solution was heated up to 80 degreeC, stirring slowly, and it superposed | polymerized for 3 hours, maintaining this temperature. Thereafter, the reaction solution was heated to 100 ° C, 0.5 parts by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the polymerization was continued for 1 hour to further increase the resin solution (solid content concentration = 30). Mass%) was obtained. 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 radiation sensitive composition

400 mass parts of pigment dispersion liquid (A-1), (B) 200 mass parts of resin solution (B-1) as alkali-soluble resin, (C) 60 mass parts of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 6 parts by mass of 2,4-diethyl thioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1 as a radiation-sensitive polymerization initiator -(O-acetyl oxime) (Ciba Specialty Chemicals make, brand name IRGACURE OX02) 5 mass parts, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl- 2 mass parts of 1,2'-biimidazole and 2 mass parts of 2-mercaptobenzothiazoles, and propylene glycol monomethyl ether acetate as a solvent are mixed so that solid content concentration may be set to 20.0%, and a liquid composition (G1) Was prepared.

The liquid composition (G1) was evaluated in the following order. The evaluation results are shown in Table 1.

Chromaticity characteristics and Contrast  evaluation

Day subjected to manufacture, after the liquid composition (G1) a, using a spin coater on a soda glass substrate formed film is SiO ₂ for preventing the elution of sodium ions on the surface of variance with more than three sheets of applying the number of revolutions, the 90 ℃ hot Preliminary baking was performed for 4 minutes on the plate, and three coating films from which film thickness differs were formed.

Subsequently, after cooling these board | substrates to room temperature, the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was exposed to the coating film by the high pressure mercury lamp at the exposure amount of 400 J / m <2>. Thereafter, the developer was discharged at a developing pressure of 1 kgf / cm 2 (nozzle diameter of 1 mm) at a developing pressure of 23 ° C. containing 0.04% by mass of potassium hydroxide aqueous solution to perform the shower development for 1 minute. Then, after wash | cleaning this board | substrate with ultrapure water and air drying, it post-baked for 30 minutes in the 220 degreeC clean oven, and formed the cured film for evaluation.

About three obtained cured films, chromaticity coordinate value (x, y) and stimulus value (Y) in a CIE colorimeter with a C light source and a 2-degree field of view using a color analyzer (MCPD2000, manufactured by Otsuka Denshi Co., Ltd.). Was measured. From the measurement result, chromaticity coordinate value x and stimulus value (Y) in chromaticity coordinate value y = 0.600 were calculated | required.

In addition, about the obtained three cured films, contrast ratio was measured using the contrast system (TSUBO Corporation Denki Co., Ltd. CT-1, blank 5000), and the contrast ratio in chromaticity coordinate value y = 0.600 was calculated | required.

Similarly, the liquid composition (G1) was stored at room temperature for one month, and chromaticity characteristics and contrast ratios were measured, and chromaticity coordinate values x, stimulus values (Y) and contrast ratios at chromaticity coordinate values y = 0.600 were obtained. The evaluation results are shown in Table 1.

Examples 2-6 and Comparative Examples 1-5

In Example 1, except having changed the kind of pigment dispersion liquid as shown in Table 1, it carried out similarly to Example 1, and prepared liquid compositions (G2)-(G11).

Next, it evaluated similarly to Example 1 except having used liquid compositions (G2)-(G11) instead of liquid composition (G1), respectively. The evaluation results are shown in Table 1.

As is apparent from Table 1, C.I. It can be seen that the radiation-sensitive composition containing pigment green 58 and a solvent having two acetoxy groups can form a green pixel having high brightness and contrast ratio, and the contrast ratio does not decrease with time. In contrast, when a solvent having one acetoxy group is used (Comparative Example 1), when a solvent having three acetoxy groups is used (Comparative Example 2), when a solvent having two acetoxy groups is used. The contrast ratio is low.

Claims (8)

It is a colored radiation-sensitive composition containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) radiation sensitive polymerization initiator, and (E) solvent, (A) As a coloring agent, it is C.I. Pigment Green 58 is contained, (E) The colored radiation-sensitive composition characterized by containing the solvent which has two acetoxy groups as a solvent. It is a colored radiation-sensitive composition containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) radiation sensitive polymerization initiator, and (E) solvent, (A) zinc bromide chloride as a coloring agent A colored radiation-sensitive composition comprising phthalocyanine and (E) a solvent having two acetoxy groups as a solvent. (E) A solvent is a mixture of the solvent which has two acetoxy groups, and the other solvent, The content rate of the solvent which has two acetoxy groups is 1-60 mass% in all the solvent. Phosphorus colored radiation-sensitive composition. The colored radiation-sensitive composition according to claim 3, further comprising (F) a dispersant. The colored radiation-sensitive composition according to claim 4, comprising (F) a dispersant comprising a block copolymer comprising a block having a pigment adsorbing group in the side chain and a block having no pigment adsorbing group in the side chain. C.I. Pigment Green 58, The blocker containing the solvent which has two acetoxy groups, and the block copolymer containing the block which has a pigment adsorption group in a side chain, and the block which does not have a pigment adsorption group in a side chain, The coloring agent dispersion liquid characterized by the above-mentioned. The color filter provided with the green pixel formed using the colored radiation-sensitive composition of Claim 1 or 2. The color liquid crystal display element provided with the color filter of Claim 7.