KR20100029031A - Colored radiation-sensitive composition, color filter and color liquid crystal display device - Google Patents

Abstract

PURPOSE: A colored radiation-sensitive composition is provided to ensure high brightness and to form green pixels showing excellent resistance to solvents. CONSTITUTION: A colored radiation-sensitive composition comprises a colorant, an alkali-soluble resin, a multifunctional monomer, and a radiation-sensitive polymerization initiator. The colorant contains C I. pigment green 58. The content of the multifunctional monomer is 100 parts by mass or more and 400 parts by mass or less.

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, a green pixel formed using a pigment composition containing a polyhalogenated zinc phthalocyanine pigment is a C.I. Pigment Green 7 or C.I. Compared with pigment green 36, there was a problem that the solvent resistance was significantly lowered.

From the above background, development of the radiation sensitive composition which can form the green pixel which not only has high brightness but is excellent in solvent resistance is calculated | required strongly.

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 capable of forming a green pixel having not only high luminance but also excellent solvent resistance.

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 has been completed by finding that Pigment Green 58 can be solved by containing Pigment Green 58 together with an alkali-soluble resin and a polyfunctional monomer in a specific content ratio.

That is, this invention is a coloring radiation sensitive composition containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) radiation sensitive polymerization initiator, (A) As a coloring agent, it is C.I. It contains pigment green 58, and (C) provides the colored radiation-sensitive composition characterized by more than 100 mass parts and 400 mass parts or less with respect to 100 mass parts of (B) alkali-soluble resin. .

"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 a coloring radiation sensitive composition containing (A) coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) radiation sensitive polymerization initiator, (A) zinc bromide chloride as a coloring agent It provides a colored radiation-sensitive composition containing phthalocyanine and (C) content of a polyfunctional monomer is more than 100 mass parts and 400 mass parts or less with respect to 100 mass parts of (B) alkali-soluble resin.

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.

By using the colored radiation-sensitive composition of the present invention, a green pixel not only having high luminance but also having excellent solvent resistance can be formed.

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 of the present invention (hereinafter sometimes referred to simply as "radiation-sensitive composition"), the (A) colorant is a 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, CI. 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. Among them, it is preferable to contain a polymer having a carboxyl group, and in particular, an ethylenically unsaturated monomer (hereinafter referred to as "copolymerizable") which is copolymerizable with another ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as "carboxyl group-containing unsaturated monomer"). Preferred is a copolymer of "unsaturated monomer" (hereinafter referred to as "carboxyl group-containing copolymer").

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) acryloyloxyalkyl] 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.

The copolymerization ratio of a carboxyl group-containing unsaturated monomer in a carboxyl group-containing copolymer becomes like this. Preferably it is 5-50 mass%, More preferably, it is 10-40 mass%. In this case, when this 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, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, 2- Unsaturated carboxes such as hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, and ethylene oxide modified (meth) acrylate of p-cumylphenol 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 It is preferable to contain 1 or more types chosen from.

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 the 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, 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.It is the temperature of the reaction to usually from 0 to 150 ℃, preferably from can be prepared by living radical polymerization at 50 to 120 ℃.

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 the light-shielding layer of an unexposed part, and when too large, 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.

Although the (C) polyfunctional monomer in this invention is a monomer which has two or more polymerizable unsaturated bonds, in order to improve solvent resistance, it is preferable to contain the monomer which has four or more polymerizable unsaturated bonds, and it is 7 or more polymerization. It is more preferable to contain the monomer which has a sex unsaturated bond, and it is especially preferable to contain the monomer which has 7-10 polymerizable unsaturated bond.

As such a polyfunctional monomer, as a monomer which has 2-3 polymerizable unsaturated bonds (henceforth "a polyfunctional monomer (c1)"), for example, ethylene glycol di (meth) acrylate, propylene glycol di ( Meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylic And monoesters of pentaerythritol tri (meth) acrylate and succinic acid, tris [2- (meth) acryloyloxyethyl] phosphate, isocyanuric acid ethylene oxide modified triacrylate, and the like.

Further, as monomers having 4 to 6 polymerizable unsaturated bonds (hereinafter referred to as "multifunctional monomer (c2)"), for example, pentaerythritol tetra (meth) acrylate and dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate and succinic acid monoester, caprolactone modified dipentaerythritol hexa (meth) acrylate, pentaerythritol tree Acrylate hexamethylene diisocyanate (reactant of pentaerythritol triacrylate and hexamethylene diisocyanate), etc. are mentioned.

Further, as a monomer having seven or more polymerizable unsaturated bonds (hereinafter referred to as "multifunctional monomer (c3)"), for example, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) An acrylate, the compound represented by following formula (2), etc. are mentioned.

(In Formula 2, R ¹ represents a hydrogen atom or a methyl group independently of each other, and R ² represents a divalent organic group.)

As a compound represented by the said Formula (1), the compound obtained by making dipentaerythritol penta (meth) acrylate and polyfunctional isocyanate react, for example, dipentaerythritol penta (meth) acrylate, and tetrabasic dianhydride are reacted, for example. The compound obtained, the compound obtained by making dipentaerythritol penta (meth) acrylate, and a polyfunctional epoxy compound react, etc. are mentioned.

As a specific example of the said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned.

Moreover, as a specific example of the said tetrabasic dianhydride, a pyromellitic dianhydride, a biphenyl tetracarboxylic dianhydride, a naphthalene tetracarboxylic dianhydride, a diphenyl ether tetracarboxylic dianhydride, butanetetracarboxylic dianhydride, , Cyclopentane tetracarboxylic dianhydride, oxydiphthalic anhydride, ethylene glycol bis anhydro trimellitate, glycerin bis (an hydro trimellitate monoacetate), benzophenone tetracarboxylic dianhydride, methylcyclohexete tetracar Acid dianhydride etc. are mentioned.

Moreover, as a specific example of the said polyfunctional epoxy compound, tris (glycidylphenyl) methane, triglycidyl isocyanurate, bis (3, 4- epoxycyclohexylmethyl) adipate, bis (3, 4- epoxy- 6-methylcyclohexylmethyl) adipate, methylenebis (3,4-epoxycyclohexane), bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, a novolak-type epoxy resin, etc. are mentioned.

In the present invention, as the multifunctional monomer (c3), a compound represented by the formula (2) is preferable, and a compound obtained by reacting dipentaerythritol penta (meth) acrylate with polyfunctional isocyanate is particularly preferable.

In this invention, a polyfunctional monomer can be used individually or in mixture of 2 or more types. Of course, also about polyfunctional monomer (c1)-(c3), it can respectively use individually or in mixture of 2 or more types.

Content of (C) polyfunctional monomer in this invention is more than 100 mass parts with respect to 100 mass parts of (B) alkali-soluble resin, 400 mass parts or less, Preferably it is 110-300 mass parts. In this case, if the content of the polyfunctional monomer is too small, the desired effect is not obtained. On the other hand, if the content is excessively large, for example, alkali developability is lowered, background contamination on the substrate or the light shielding layer of the unexposed portion, film residue, etc. It tends to be easy to occur.

In addition, the content ratio of the polyfunctional monomer (c3) is preferably 30 mass% or more, more preferably 50 mass% or more among all the polyfunctional monomers from the viewpoint of enhancing the desired effect.

In general, the more the polyfunctional monomer is contained in the radiation-sensitive composition, the higher the curability of the formed pixels and the better the solvent resistance. However, according to the present inventors, when the CI Pigment Green 58 is used, the polyfunctional simply Sufficient solvent resistance is not obtained only by containing more monomer. In other words, the content of the polyfunctional monomer is important to be adjusted in proportion to the alkali-soluble resin, and this is because the radiation-exposed portion where the pixel is formed is also subjected to erosion by the alkaline developer during development due to the presence of the alkali-soluble resin. do.

The radiation sensitive polymerization initiator (D) used in the present invention is an active species capable of initiating the polymerization of the polyfunctional monomer (C) by exposure to radiation such as visible light, ultraviolet ray, far ultraviolet ray, electron beam, or X-ray. It is a compound that occurs.

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 this invention, a radiation sensitive polymerization initiator can be used individually or in mixture of 2 or more types. As a radiation sensitive polymerization initiator, 1 or more types chosen from the group of a thioxanthone type compound, an acetophenone type compound, a biimidazole type compound, a triazine type compound, and an O-acyl oxime type compound are 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 agglomeration foreign material of the said pigment easily generate | occur | producing, and reducing this aggregation foreign material.

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, etc. are mentioned.

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, Preference is given to 4 ', 5,5'-tetraphenyl-1,2'-biimidazole.

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.

In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the content of the hydrogen donor is preferably 1 to 300 parts by mass, particularly 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-tetrahydropyranyl 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-tetrahydropyranylme Methoxybenzoyl) -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-dioxola Yl) 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 There exists a tendency for it to fall easily from a board | substrate at this time of image development.

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

As another 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-amino Ethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryl Adhesion promoters such as royloxypropyl trimethoxysilane and 3-mercaptopropyltrimethoxysilane; 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.

In the present invention, the radiation sensitive composition can be produced by a suitable method, for example, can be prepared by mixing the components (A) to (D) with a solvent or an additive. As a preferable manufacturing method of a radiation sensitive composition, C.I. In the presence of a dispersing agent and a dispersing aid which adds pigment green 58 containing pigment green 58 in a solvent, if necessary, it is grind | pulverized with a part of (B) component, for example using a bead mill, a roll mill, etc. The method of mixing and disperse | distributing to make a coloring agent dispersion liquid and adding and mixing a solvent and an additive with (B)-(D) component to this coloring agent dispersion liquid as needed, and the method are mentioned.

As a solvent used for manufacture of the said coloring agent dispersion liquid, the solvent mentioned later is mentioned.

Moreover, as a dispersing agent used for manufacture of the said coloring agent dispersion liquid, suitable dispersing agents, such as cationic, anionic, nonionic, and amphoteric, can be used, for example, A polymer dispersing agent 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 graft polymer, etc. are mentioned. Herein, the cationic 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). For example, the stem polymer moiety is a polyethyleneimine or branched polymer. The polymer comprised from the ring-opened polymer of addition (epsilon) -caprolactone is mentioned. Of these dispersants, modified acrylic copolymers, polyurethanes, and cationic graft polymers are preferred.

Such dispersants are commercially available, for example, Disperbyk-2000, Disperbyk-2001 (above, manufactured by BYK) as a modified acrylic copolymer, Disperbyk-161, Disperbyk-162, Disperbyk- as polyurethanes 165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above, manufactured by Big Chemie (BYK)), Solsperth 76500 (manufactured by Lubrizol Co., Ltd.), Solsper 24000 (Lubric) Sol, Ajisper PB821, Ajisper PB822, Ajisper PB823, Ajisper PB824, Ajisper PB827 (manufactured by Ajinomoto Fine Techno Co., Ltd.).

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 etc. may be impaired.

Although the radiation sensitive composition of this invention makes the said (A)-(D) component an essential component, and contains the said additive component as needed, it can also manufacture a liquid composition by mix | blending a solvent.

As said solvent, as long as it disperse | distributes or melt | dissolves or dissolves the components (A)-(D) and the additive component which comprise a radiation sensitive composition, and does not react with these components, it can select suitably and can use.

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, 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-methoxybutyl acetate (Poly) alkylene glycol monoalkyl ether acetates such as 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;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate and 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-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 solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, di, etc., from the viewpoint of pigment dispersibility, solubility of components other than pigment, coating property, and the like. Ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, propylene glycol diacetate, 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-methoxybutylpropionate , 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 is preferable.

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

In addition, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, together with the solvent High boiling point solvents, such as diethyl oxalate, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate, can also be used together.

The said high boiling point solvent can be used individually or in mixture of 2 or more types.

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 which the total concentration of each component except the solvent of the said composition normally becomes 5-50 mass% is preferable, In particular, the amount which becomes 10-40 mass% is preferable.

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 a substrate so as to partition a portion forming a pixel, if necessary, and a liquid composition of a radiation sensitive composition in which the green pigment of the present invention is dispersed on the substrate is subjected to prebaking. To evaporate the solvent 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, In particular, the spin coating method and the slit die coating method are preferable.

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 luminance and a wide color reproduction area | region, 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 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).

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, 22 parts by mass of Solsper's 76500 (manufactured by Lubrizol Co., Ltd., 50% solid content) as a dispersant, and 138 parts by mass of propylene glycol methyl ether acetate The mixed solution containing was 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 40/60 (mass ratio) mixture of Pigment Yellow 138, 24 parts by mass of Disperbyk-2001 (by BYK Co., Ltd., solid content concentration 45.1 mass%) 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-3).

Preparation Example 4

(A) As a coloring agent, C.I. Pigment Green 36 and C.I. 40 parts by mass of 55/45 (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-4).

(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 Liquid Composition

500 mass parts of pigment dispersion liquid (A-1), (B) 50 mass parts (solid content conversion) of resin solution (B-1) as alkali-soluble resin, (C) 100 mass parts of dipentaerythritol hexaacrylate as a polyfunctional monomer (D) 10 parts by mass of 2,4-diethyl thioxanthone, ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl as a radiation sensitive polymerization initiator ]-, 1- (O-acetyl oxime) (Siba Specialty Chemicals make, brand name IRGACURE OX02) 10 mass parts and it mixes so that solid content concentration may be 20% using propylene glycol monomethyl ether acetate as a solvent, and liquid phase Composition (G-1) was prepared.

The liquid composition (G-1) was evaluated according to the following procedure. The evaluation results are shown in Table 2.

phenomenon Residue  And Solvent resistance  evaluation

After coating using a spin coater on the liquid composition of a soda glass substrate, SiO ₂ film is formed to prevent the elution of sodium ions on the surface of the (G-1), by performing the pre-baking on a hot plate at 90 ℃ 4 minutes, and after pre-baking Four coating films with a film thickness of 2.5 mu m were formed.

Subsequently, after cooling these board | substrates to room temperature, it exposed to the coating film with the exposure amount of the radiation of 2,000 J / m <2> containing each wavelength of 365 nm, 405 nm, and 436 nm through a photomask using a high pressure mercury lamp. Subsequently, after developing a shower by discharging the developer containing 23.degree. C. aqueous solution of 0.04% by weight potassium hydroxide at a developing pressure of 1 kgf / cm 2 (nozzle diameter 1 mm) for 1 minute, the substrate was subjected to shower development. Post-baking was carried out for a minute to form a 200 × 200 μm green dot pattern on the substrate.

The obtained dot pattern was observed with an optical microscope, and when the development residue was not observed at all on the glass substrate of an unexposed part, (circle) and the case where the development residue was observed slightly, (triangle | delta) and the case where the development residue was remarkably evaluated as x. .

Furthermore, the board | substrate with the said dot pattern was immersed in 60 degreeC N-methylpyrrolidone for 10, 20, 30, 40 minutes. As a result, when the dot pattern is maintained after immersion and N-methylpyrrolidone is not colored at all after immersion, the dot pattern is maintained after immersion, but N-methylpyrrolidone is slightly colored after immersion. ?, The case where the dot pattern which peeled from the board | substrate after immersion was observed and N-methylpyrrolidone was colored after immersion was evaluated as x.

Evaluation of Chromaticity Characteristics

The liquid composition (G-1) was applied onto a soda glass substrate on which a SiO ₂ film was formed to prevent elution of sodium ions on the surface using a spin coater, followed by preliminary baking for 4 minutes on a hot plate at 90 ° C. Three different coating films were formed.

About the obtained dot pattern, the chromaticity coordinate value (x, y) and the stimulus value (Y) in a CIE colorimeter were measured by C light source and 2 degree visual field using a color analyzer (MCPD2000, Otsuka Denshi Co., Ltd.). . From the measurement results, the chromaticity coordinate value x and the stimulus value (Y) at the 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 (luminance).

Examples 2-18 and Comparative Examples 1-10

In Example 1, liquid compositions (G-2) to (G-28) were prepared in the same manner as in Example 1, except that the kind and amount of the containing component were changed as shown in Table 1.

Next, it evaluated similarly to Example 1 except having used liquid compositions (G-2)-(G-28) instead of liquid composition (G-1), respectively. The results are shown in Table 2.

In Table 1, each component is as follows.

C-1: dipentaerythritol hexaacrylate

C-2: pentaerythritol tetraacrylate

C-3: pentaerythritol triacrylate hexamethylene diisocyanate

C-4: dipentaerythritol pentaacrylate hexamethylene diisocyanate (reactant of dipentaerythritol pentaacrylate with hexamethylene diisocyanate)

C-5: biscoat # 802 (mixture of tripentaerythritol octaacrylate and tripentaerythritol hepacrylate)

D-1: ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (brand name IRGACURE OX02, Ciba specialty ㆍ Manufactured by Chemicals

D-2: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals, Inc.)

D-3: 2,4-diethyl thioxanthone

As is apparent from Tables 1 and 2, C.I. By containing Pigment Green 58 together with the alkali-soluble resin and the polyfunctional monomer in a specific content ratio, a green pixel having high brightness and excellent solvent resistance can be formed and a radiation-sensitive composition having no developing residue is obtained. It can be seen that. As is clear from Comparative Examples 1 and 3, simply containing more polyfunctional monomers cannot achieve sufficient solvent resistance.

Claims (7)

It is a coloring radiation sensitive composition containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) radiation sensitive polymerization initiator, (A) contains CI pigment green 58 as a coloring agent, And (C) content of a polyfunctional monomer is more than 100 mass parts with respect to 100 mass parts of (B) alkali-soluble resin, and it is 400 mass parts or less, The colored radiation-sensitive composition characterized by the above-mentioned. It is a coloring radiation sensitive composition containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) radiation sensitive polymerization initiator, (A) contains a brominated zinc chlorinated zinc phthalocyanine as a coloring agent, (C) Content of a polyfunctional monomer is more than 100 mass parts with respect to 100 mass parts of (B) alkali-soluble resins, The colored radiation-sensitive composition characterized by the above-mentioned. The colored radiation-sensitive composition of Claim 1 or 2 containing the compound which has 7 or more polymerizable unsaturated bonds as a polyfunctional monomer. The colored radiation-sensitive composition according to claim 3, wherein the compound having seven or more polymerizable unsaturated bonds is a compound represented by the following general formula (2). <Formula 2>

(In Formula 2, R ¹ represents a hydrogen atom or a methyl group independently of each other, and R ² represents a divalent organic group.) The colored radiation-sensitive composition of Claim 1 or 2 containing a thioxanthone type compound as a radiation sensitive polymerization initiator. 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 6.