TWI624505B - Coloring composition, color filter, and color liquid crystal display element - Google Patents

Abstract

An object of the present invention is to provide a coloring composition for a color filter having excellent chromaticity characteristics, alkaline developability, and storage stability.

The solution of the present invention is a coloring composition, which is characterized by containing: (A) a pigment-containing coloring agent, and (B) containing 60% by mass or more of a repeating unit derived from an ethylenically unsaturated monomer having an amine group. A block copolymer of a block A having a repeating unit derived from an ethylenically unsaturated monomer having an alkylene glycol chain and an amine value of 50 mgKOH / g or more and less than 80 mgKOH / g, and ( C) Solvent.

Description

Coloring composition, color filter and color liquid crystal display element

The present invention relates to a coloring composition, a color filter, and a color liquid crystal display element.

When a color filter is produced using a colored radiation-sensitive composition, it is known that a pigment-dispersed colored radiation-sensitive composition is coated on a substrate and dried, and then the dried coating film is formed in a desired pattern shape. A method of irradiating radiation (hereinafter, referred to as "exposure") to develop and obtain pixels of various colors (Patent Documents 1 to 2). A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed is also known (Patent Document 3). Furthermore, a method of obtaining pixels of various colors by an inkjet method using a pigment-dispersed colored resin composition is also known (Patent Document 4).

In the field of color filters used in liquid crystal display elements and solid-state imaging elements, pigments used tend to become more and more finer particles in accordance with requirements for higher brightness and higher control. The use of a dispersant is known to be effective in achieving stable micronized pigments and good dispersibility. In addition, Patent Document 5 has proposed that a block copolymer having an amine value of 80 mgKOH / g or more and 150 mgKOH / g can be used as a highly effective dispersion of a highly particulate pigment in a small amount of addition. Dispersant.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2-144502

[Patent Document 2] Japanese Unexamined Patent Publication No. 3-52201

[Patent Document 3] Japanese Unexamined Patent Publication No. 6-35188

[Patent Document 4] JP 2000-310706

[Patent Document 5] Japanese Patent Application Laid-Open No. 2009-25813

However, when a block copolymer having a high amine value as proposed in Patent Document 5 is used as a dispersant, the alkaline developability of the coloring composition is deteriorated, which causes a problem in mass production of color filters. obstacle. In particular, when a pigment and a dye are used as a colorant, the deterioration of the alkali developability becomes significant. For this reason, there has been a strong demand for the realization of high control and high brightness in recent years, and development of a coloring composition for a color filter that is also excellent in alkali developability.

Therefore, an object of the present invention is to provide a colored composition having excellent chromaticity characteristics, alkaline developability, and storage stability. Moreover, the subject of this invention is providing the color filter provided with the coloring layer formed from the said coloring composition, and the color liquid crystal display element provided with the same.

In view of this fact, when the present inventors conducted intensive studies, they found that the above-mentioned problems can be solved by using a specific block copolymer, and completed the present invention.

That is, the present invention provides a coloring composition characterized by containing: (A) a pigment-containing coloring agent, and (B) containing 60% by mass or more of A repeating units represented by the following formula (1) A block copolymer having a segment and a B block having a repeating unit (2) represented by the following formula (2) and having an amine value of 50 mgKOH / g or more and less than 80 mgKOH / g (hereinafter, also referred to as "(B ) Copolymer "), and (C) a solvent.

(In the formula (1), X represents a divalent linking group, R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or a chain or cyclic group which may have a substituent. Hydrocarbyl, R ² and R ³ may be bonded to each other to form a cyclic structure)

(In formula (2), R ⁴ represents an alkylene group having 2 to 4 carbon atoms independently, R ⁵ represents an alkyl group having 1 to 6 carbon atoms, R ⁶ represents a hydrogen atom or a methyl group, and n represents 1 to 150 Integer).

The present invention also provides a color filter including a coloring layer formed using the coloring composition, and a color liquid crystal display element including the color filter. Here, the "colored layer" means pixels of various colors, a black matrix, a black spacer, and the like used in a color filter.

By using the coloring composition of the present invention, a color filter having pixels of various colors having excellent chromaticity characteristics can be obtained. The coloring composition of the present invention is also excellent in alkali developability and storage stability.

Therefore, the coloring composition of the present invention is very suitable for use in the production of color filters for color liquid crystal display elements, color filters for color decomposition of solid-state imaging elements, color filters for organic EL display elements, and color for electronic newspapers. Various color filters led by filters. Furthermore, the coloring composition of the present invention is also suitably used as a coloring composition for electrophoresis for an electrophoretic display element.

[Mode for Carrying Out the Invention]

Hereinafter, the present invention will be described in detail.

[Coloring composition]

The constituents of the coloring composition of the present invention will be described below.

-(A) Colorant-

The coloring composition system of this invention contains a pigment as (A) colorant. The pigment system is not particularly limited, and may be any of an organic pigment and an inorganic pigment. In this invention, a pigment can be used individually or in mixture of 2 or more types. Of course, it is also possible to mix organic pigments and inorganic pigments.

Examples of the organic pigments include anthraquinone pigments, aminoanthraquinone pigments, quinacridone pigments, quinacridone quinone pigments, dioxopyrrolopyrrole pigments, perylene pigments, and violet Cyclic ketone pigments, anthracene anthraquinone pigments, benzimidazolone pigments, disazo condensate pigments, azo pigments, thioindigo pigments, dermatanthone pigments, dioxins Based pigments, quinoline yellow based pigments, isoindoline based pigments, phthalocyanine based pigments, and the like.

Examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, iron dan (red iron (III) oxide), cadmium red, ultramarine, Sapphire green, chrome oxide green, cobalt green, amber, titanium black, synthetic iron black, carbon black, etc.

The (B) copolymer system enables stable and good dispersion of these pigments, especially phthalocyanine-based pigments. Among the phthalocyanine pigments, examples of the blue pigment system include copper phthalocyanine. More specifically, in the color material index (C.I .; issued by The Society of Dyers and Colourists), for example, a compound classified as a pigment, that is, a person named as the color material index (C.I.) name as described below.

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6.

The copolymer (B) is particularly suitable for dispersing C.I. Pigment Blue 15: 6 among these phthalocyanine blue pigments.

Among the phthalocyanine-based pigments, as the green pigment-based chlorinated and / or brominated metal phthalocyanine, more specific examples include copper phthalocyanine, zinc phthalocyanine, and magnesium. Phthalocyanine, aluminum phthalocyanine, titanium phthalocyanine, vanadium phthalocyanine, manganese phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, tin phthalocyanine, germanium phthalocyanine, etc.

(B) Among these phthalocyanine-based green pigments, the copolymer is suitable for dispersing copper chloride phthalocyanine, copper bromide phthalocyanine, copper bromide phthalocyanine, and zinc bromide phthalate. Cyanine and zinc bromide phthalocyanine are especially suitable for dispersing zinc chloride bromide phthalocyanine. The zinc bromide phthalocyanine chloride preferably has a structure represented by the following formula (I).

(In the formula (I), Y represents a hydrogen atom, a chlorine atom, or a bromine atom independently of each other, and 10 to 15 of all Y are bromine atoms and 1 to 6 are chlorine atoms.) In addition, in the color material index ( In the name of CI), copper chloride phthalocyanine is classified as CI Pigment Green 7 pigment, copper chloride bromide phthalocyanine is classified as CI Pigment Green 36 pigment, and zinc chloride bromide phthalocyanine is classified as Pigment of CI Pigment Green 58.

In the present invention, the pigment can also be purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. In addition, the pigment can also be used by modifying the surface of its particles with a resin as required. Examples of the resin system on the surface of the modified pigment particles include a toner resin described in Japanese Patent Application Laid-Open No. 2001-108817 or various commercially available resins for pigment dispersion. As the method for coating the resin on the surface of carbon black, for example, the methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969, and the like can be used. The organic pigment is preferably used by using a so-called salt milling method to refine primary particles. As a method of salt grinding, the method disclosed in Unexamined-Japanese-Patent No. 08-179111 can be used, for example.

In the coloring composition for color filters, by using a dye as a colorant, it is possible to achieve high brightness and high control that cannot be achieved by a pigment alone. However, when a dye is used as a colorant, the alkali developability of the coloring composition is significantly deteriorated. In the coloring composition of the present invention, by using the (B) copolymer as a pigment dispersant, even when a pigment and a dye are used in combination as a colorant, a coloring composition having good alkaline developability can be obtained. . Examples of the dye system include compounds named by the following colorant index (C.I.).

CI Acid Yellow 11, CI Acid Orange 7, CI Acid Red 37, CI Acid Red 180, CI Acid Blue 29, CI Direct Red 28, CI Direct Red 83, CI Direct Yellow 12, CI Direct Orange 26, CI Direct Green 28, CI Direct Green 59, CI Reactive Yellow 2, CI Reactive Red 17, CI Reactive Red 120, CI Reactive Black 5, CI Disperse Orange 5, CI Disperse Red 58, CI Disperse Blue 165, CI Basic Blue 41, Azo-based dyes such as CI Basic Red 18, CI Medium Red 7, CI Medium Yellow 5, CI Medium Black 7, etc .; CI Reduction Blue 4, CI Acid Blue 40, CI Acid Green 25, CI Reactive Blue 19, CI Anthraquinone dyes such as reactive blue 49, CI disperse red 60, CI disperse blue 56, CI disperse blue 60; phthalocyanine dyes such as CI reduction blue 5; CI basic blue 3, CI basic blue 9, etc. Quinoline dyes; CI solvent yellow 33, CI acid yellow 3, CI direct yellow 64 and other quinoline dyes; CI acid yellow 1, CI acid orange 3, CI direct yellow 42 and other nitro dyes; direct Yellow 201 and other methine dyes.

In the case where the dye is used as the colorant in the present invention, the dye may be used alone or in combination of two or more.

From the point of forming a pixel with high brightness and excellent color purity, or a black matrix with excellent light-shielding properties, the content ratio of the (A) colorant is usually 5 to 70% by mass of the solid content of the coloring composition, and is preferably 5 ~ 60 mass%. Here, the so-called solid content is a component other than a solvent described later.

-(B) Copolymer-

In the present invention, the (B) copolymer is a component that functions as a pigment dispersant, and includes an A block having a repeating unit (1) represented by the above formula (1) in an amount of 60% by mass or more, and 2) A block copolymer of the B block of the repeating unit (2) shown, and the amine value is 50 mgKOH / g or more and less than 80 mgKOH / g. The term “having a repeating unit (1) of 60% by mass or more” means that the content of the repeating unit (1) in the A block is 60% by mass or more.

Examples of the divalent linking group X in the formula (1) include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a -CONH-R ⁷ -(*) group, and -COO. -R ⁸ -(*) group [wherein R ⁷ and R ⁸ independently of each other represent a methylene group, an alkylene group having 2 to 10 carbon atoms, or an alkylene oxide group having 2 to 10 carbon atoms , (*) Represents a bonding bond with N] and the like. Wherein, as the line X is preferably -COO-R ⁸ - group, R ⁸ lines as is preferably an alkylene group having 2 to 6 carbon atoms.

Moreover, in -NR ² R ³ in the above formula (1), although R ² and R ³ independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, the hydrocarbon group is more suitable as the hydrocarbon group. It is preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably methyl, ethyl, propyl, or butyl. Among the substituents on the hydrocarbon group, examples of the substituents on the chain hydrocarbon group include a halogen atom, an alkoxy group, and a benzamidine group. Examples of the substituent on the cyclic hydrocarbon group include a chain alkyl group, a halogen atom, and an alkoxy group. The chain-like hydrocarbon group represented by R ² and R ³ includes any of linear and branched chains.

In addition, R ² and R ³ may be bonded to each other to form a cyclic structure. Examples of the cyclic structure include a nitrogen-containing heterocyclic monocyclic ring having 5 to 7 members or a fused structure formed by condensing two of these. ring. The non-nitrogen-containing heterocyclic ring is preferably an aromatic one, and more preferably a saturated ring. Specific examples include the following.

These cyclic structures may further contain a substituent.

In the above formula (2), R ⁴ is preferably ethylidene or methylethynyl. Further, as the R ⁵ system, methyl, ethyl, propyl, and butyl are preferred. In addition, n is preferably an integer of 1 to 20, an integer of 1 to 10 is more preferred, and an integer of 1 to 5 is particularly preferred.

The A block of the copolymer (B) may have a repeating unit (1) and a repeating unit other than the repeating unit (1). As an example of such a repeating unit, for example, a nitrogen-containing heterocyclic group derived from pyridyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, imidazoline, tetrahydropyrimidinyl, etc. may be mentioned. Ethylene unsaturated monomers; repeating units of ethylenically unsaturated monomers with a 4th level ammonium base, etc.

The B block system of the (B) copolymer may have the above-mentioned repeating unit (2) and the repeating unit (3) represented by the following formula (3).

(In formula (3), R ⁹ represents a linear or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may also have a substituent, and R ¹⁰ represents hydrogen Atom or methyl) in the above formula (3), R ^{9 is} preferably a chain alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms, and an aralkyl group having 7 to 16 carbon atoms. Preferred are methyl, ethyl, propyl, butyl, 2-ethylhexyl, phenyl, benzyl, phenylethyl. Examples of the substituent on the alkyl group represented by R ⁹ include a halogen atom and an alkoxy group. Examples of the substituent on the aryl group or the aralkyl group include a chain alkyl group, a halogen atom, and an alkoxy group. The linear alkyl group represented by R ⁹ may include either a linear or branched chain.

The B block of the copolymer (B) may have repeating units other than the repeating unit (2) and repeating unit (3). Examples of such repeating units include: styrene-based monomers such as styrene; (meth) acrylamide-based monomers such as (meth) acrylamide; vinyl acetate; propylene Repeating units of monomers such as nitrile.

(B) The structure of the copolymer is not particularly limited, but is preferably a block copolymer having an A block having a repeating unit (1) of 60% by mass or more and a B block having a repeating unit (2). It is an AB block copolymer or a BAB block copolymer.

The repeating unit (1) in the A block of (B) copolymer 1 may contain two or more kinds. In this case, the two or more kinds of the repeating unit (1) may include the aspect of either random copolymerization or block copolymerization. The content ratio of the repeating unit (1) in the A block is preferably 75% by mass or more, and particularly preferably 90% by mass or more.

In the B block of (B) copolymer 1, the repeating unit (2) may contain two or more kinds. In this case, the two or more types of repeating units (2) may include any one of random copolymerization and block copolymerization. When the B block has a repeating unit (3) and other repeating units, they may each contain two or more kinds in one B block. In this case, each of the repeating units may include an aspect of either random copolymerization or block copolymerization. The repeating unit (2) may include any of the repeating unit (3) and other repeating units, random copolymerization, and block copolymerization.

When the B block contains both the repeating unit (2) and the repeating unit (3), the copolymerization ratio (mass ratio) of the repeating unit (2) / repeating unit (3) in the B block is preferably 1/99 ~ 50/50, more preferably 1/99 ~ 30/70.

(B) The amine valence of the copolymer is 50 mgKOH / g or more and less than 80 mgKOH / g, but preferably 52 mgKOH / g or more and 79 mg KOH / g or less. The amine valence herein means the amount of alkali and the equivalent mg of KOH in mg of the solid content per dispersant.

In the (B) copolymer, the content ratio of the repeating unit (2) is preferably 1 to 30% by mass, and more preferably 1 to 25% by mass in all the repeating units.

By making the (B) copolymer into such a state, a colored composition having excellent dispersibility and basic developability can be obtained.

(B) The molecular weight of the copolymer is preferably a weight average molecular weight (hereinafter, also referred to as "Mw") in terms of polymethyl methacrylate measured by a gel permeation layer absorption method (GPC, elution solvent: DMF). 1,000 ~ 30,000, especially preferred is 5,000 ~ 15,000. The ratio (Mw / Mn) of the Mw of the (B) copolymer to the number-average molecular weight (hereinafter, also referred to as "Mn") in terms of polymethyl methacrylate measured by GPC (dissolution solvent: DMF). The range is preferably 1.0 to 2.0, and more preferably 1.0 to 1.8. By making the (B) copolymer into such a state, a colored composition having excellent dispersibility and basic developability can be obtained.

The copolymer (B) can be produced by a well-known method, for example, it can be produced by living polymerization of a monomer that provides each of the above-mentioned repeating units. As the living polymerization method, JP 9-62002, JP 2002-31713, P. Lutz, P. Masson et al, Polym. Bull., 12, 79 (1984); BC Anderson, GD Andrews et al, Macromolecules, 14,1601 (1981); K. Hatada, K. Ute, et al, Polym.J., 17,977 (1985); K. Hatada, K. Ute, et al, Polym.J. , 18, 1037 (1986), Right-hand Koichi, Putian Koichi, Polymer Processing, 36,366 (1987); Tomura Toshiyuki, Enomoto Masao, Polymer Essays, 46,189 (1989); M. Kuroki, T. Aida, J. Am.Chem.Soc., 109, 4737 (1987); Aida Takusan, Inoue Shoji, Organic Synthetic Chemistry, 43,300 (1985); DYSogoh, WHertler et al, Macromolecules, 20, 1473 (1987), etc. Well-known method.

Examples of the single system providing the repeating unit (1) include dimethylamine ethyl (meth) acrylate, diethylamine ethyl (meth) acrylate, and dimethylaminopropyl (meth) acrylate. Esters, diethylaminopropyl (meth) acrylate, and the like.

Examples of single systems that provide repeating units (2) include: polyethylene glycol (n = 1 to 5) methyl ether (meth) acrylate, polyethylene glycol (n = 1 to 5) ethyl ether (Meth) acrylate, polyethylene glycol (n = 1 to 5) propyl ether (meth) acrylate, polypropylene glycol (n = 1 to 5) methyl ether (meth) acrylate, polypropylene glycol ( n = 1 ~ 5) ethyl ether (meth) acrylate, polypropylene glycol (n = 1 ~ 5) propyl ether (meth) acrylate, etc.

Examples of the single system that provides the repeating unit (3) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, (formyl) Butyl acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentyl (meth) acrylate, isomethacrylate Bornyl ester, benzyl (meth) acrylate, phenethyl (meth) acrylate, and the like.

In addition, as the monomer capable of providing repeating unit (1) and the monomer capable of copolymerization in the A block, for example, (meth) acrylfluorenylaminopropyltrimethylammonium chloride, (Meth) acrylfluorenyloxyethyltrimethylammonium chloride, (meth) acrylfluorenyloxyethyltriethylammonium chloride, (meth) acrylfluorenyloxyethyltriethylammonium (4-benzene) Formamylbenzyl) dimethylammonium, (meth) acrylfluorenyloxyethylbenzyldimethylammonium, (meth) acrylfluorenyloxyethylbenzyldiethyl Other than ammonium, a monomer represented by the following formula is mentioned, for example.

(B) The copolymer can be used alone or in combination of two or more. The content of the copolymer (B) is usually 1 to 100 parts by mass, preferably 5 to 70 parts by mass, and more preferably 10 to 50 parts by mass based on 100 parts by mass of the pigment. (B) When there is too much content of a copolymer, there exists a possibility that a developing property may be impaired.

In order to improve dispersibility in the present invention, a well-known dispersant may be further contained. Examples of well-known dispersant systems include urethane-based dispersants, polyethyleneimine-based dispersants, polyoxyethylene alkyl ether-based dispersants, polyoxyethylene alkylphenyl ether-based dispersants, and polydisperses. Glycol diester-based dispersants, sorbitan fatty acid ester-based dispersants, fatty acid modified polyester-based dispersants, acrylic-based dispersants, pigment derivatives, and the like.

Specific examples of such a dispersant include, for example, the trade names EFKA (manufactured by EFKA CHEMICALS BV (EFKA)), Disperbyk (manufactured by BYK CHEMIE (BYK)), Disparlon (Nanmoto Chemicals Co., Ltd.), Solsperse (Made by Lubrizol), KP (made by Shin-Etsu Chemical Industry Co., Ltd.), POLYFLOW (made by Kyoeisha Chemical Co., Ltd.), F-TOP (made by Thochem Products), MEGAFAC (made by Dainippon Ink Chemical Industry (Stock)) ), Florado (Sumitomo 3M (stock) system), AsahiGuard, Surflon (above, Asahi Glass (stock) system), etc. Specific examples of the pigment derivative include copper phthalocyanine, dioxopyrrolopyrrole, and a sulfonic acid derivative of quinoline yellow.

-(C) Solvent-

First, the coloring composition of the present invention is usually pulverized and mixed with (B) a pigment-containing coloring agent together with (B) a copolymer and other components as necessary using a bead mill, a roll mill, or the like, and dispersed in (C) In a solvent, a pigment dispersion is prepared. In addition, in the case where the coloring composition of the present invention is imparted with hardenability and alkali developability, components (D) to (F) described below are added to the pigment dispersion, and (C) is further added as necessary. ) Solvents and additives. As the (C) solvent, as long as it disperses or dissolves the components (A), (B), and other components described below that constitute the coloring composition, and does not react with these components, it has moderate volatility. That's it, you can choose to use it appropriately.

Examples of such a solvent system include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, and diethylene glycol monomethyl ether. 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 (Poly) alkylene glycol monoalkyl ethers such as mono-n-butyl ether, tripropylene glycol monomethyl ether, and tripropylene glycol monoethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether Ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol (Poly) alkylene glycol monoalkyl ether acetates such as monomethyl ether acetate, 3-methoxybutyl acetate, and 3-methyl-3-methoxybutyl acetate ; Diethylene glycol dimethyl ether, Other ethers such as ethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran; ketones such as methyl ethyl ketone, cyclohexanone, 2-pentanone, and 3-pentanone; propylene glycol Diacetates such as diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, etc .; methyl 3-methoxypropionate, 3-methoxy Alkoxycarboxylates such as ethyl propionate, methyl 3-glycidyl propionate, ethyl 3-glycidyl propionate, ethyl acetate, 3-methyl-3-methoxybutyl propionate, etc. Acid esters; ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, ethyl butyrate, n-butyrate Propyl, isopropyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, ethyl acetoacetate, ethyl acetoacetate, 2-oxobutane Other esters such as ethyl acetate; aromatic hydrocarbons such as toluene and xylene; alkyl lactates such as methyl lactate and ethyl lactate; methanol, ethanol, propanol, butanol, isopropanol, isopropyl alcohol Butanol, tertiary butanol, octanol, 2-ethylhexanol, cyclohexanol (Cyclo) alkyl alcohols; keto alcohols such as diacetone alcohol; fluorene such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone Amines or lactams.

In this invention, a solvent can be used individually or in mixture of 2 or more types.

Among these solvents, when preparing the pigment dispersion liquid, it is preferable to use (poly) alkylene glycol monoalkyl ethers, (poly) alkylene glycol monoalkyl ether acetates, and diacetic acid. The esters and alkoxycarboxylic acid esters constitute at least one selected from the group. Its content ratio is in all solvents contained in the pigment dispersion liquid, and is preferably 80% by mass or more, and more preferably 90% by mass or more.

Among the (poly) alkylene glycol monoalkyl ethers, (poly) alkylene glycol monoalkyl ether acetates, diacetates, and alkoxycarboxylic acid esters, propylene glycol is particularly preferred. Monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methyl Oxybutyl acetate, dipropylene glycol monomethyl ether acetate, propylene glycol diacetate, 1,3-butanediol diacetate, 1,6-hexanediol diacetate, 3- Ethyl methoxypropionate, methyl 3-epoxypropionate, ethyl 3-epoxypropionate.

The content of the solvent is not particularly limited, but the total concentration of each component of the solvent from which the coloring composition is removed is preferably an amount of 5 to 50% by mass, and particularly preferably an amount of 10 to 40% by mass. By being in such a state, a colored composition having good dispersibility, stability, and coatability can be obtained.

-(D) Crosslinking agent-

(D) A crosslinking agent may be contained in the coloring composition of this invention. Thereby, a thermosetting property or a radiation hardening property can be provided to a coloring composition. Here, the (D) crosslinking agent refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an ethylene oxide group, a propylene oxide group, and an N-alkoxymethylamino group. In the present invention, as the (D) crosslinking agent, a compound having two or more (meth) acrylfluorenyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

Specific examples of the compound having two or more (meth) acrylfluorenyl groups include, for example, a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound with (meth) acrylic acid, Polyfunctional (meth) acrylate modified by lactone, polyfunctional (meth) acrylate modified by alkylene oxide, polyfunctional amine obtained by reacting (meth) acrylate having hydroxyl group with polyfunctional isocyanate Carbamate (meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, and the like obtained by reacting a (meth) acrylate having a hydroxyl group with an acid anhydride.

Here, examples of the above-mentioned aliphatic polyhydroxy compounds include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol; such as glycerol, trimethylolpropane, and pentaerythritol. , 3-pentaerythritol, tripentaerythritol, trivalent or higher aliphatic polyhydroxy compounds. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, and Pentaerythritol penta (meth) acrylate, glyceryl dimethacrylate and the like. Examples of the polyfunctional isocyanate include toluene diisocyanate, cyclohexane diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and the like. Examples of the acid anhydride system include: anhydrous anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, and hexahydrophthalic anhydride; such as pyromellitic anhydride, biphenyl Tetracarboxylic dianhydride of tetracarboxylic dianhydride and benzophenone tetracarboxylic dianhydride.

Examples of the polyfunctional (meth) acrylate modified with caprolactone include compounds described in paragraphs [0015] to [0018] of Japanese Patent Application Laid-Open No. 11-44955. As the polyfunctional (meth) acrylate modified by the alkylene oxide, for example, bisphenol A modified ethylene oxide and / or propylene oxide modified di (meth) acrylate, isotricyanic acid Ethylene oxide and / or propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide and / or propylene oxide modified tri (meth) acrylate, pentaerythritol ethylene oxide and / or propylene oxide modified Modified tri (meth) acrylate, pentaerythritol ethylene oxide and / or propylene oxide modified tetra (meth) acrylate, dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, dipentaerythritol Of ethylene oxide and / or propylene oxide modified hexa (meth) acrylate.

Examples of the compound system having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, the so-called melamine structure and benzoguanamine structure refer to those having 1 or more amines. Ring or phenyl substituted tri The ring as the basic structure of the chemical structure also includes the concept of melamine compounds, benzoguanamine compounds or their condensates. Specific examples of the compound having two or more N-alkoxymethylamino groups include, for example, N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetrakis (alkoxymethyl) benzoguanamine, N, N, N, N-tetrakis (alkoxymethyl) acetylene urea and the like.

Among these polyfunctional monomers, polyfunctional (meth) acrylates obtained by reacting a trivalent or more aliphatic polyhydroxy compound with (meth) acrylic acid, and polyfunctional modified with caprolactone are preferred. (Meth) acrylate, polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate with carboxyl group, N, N, N, N, N, N-hexa (alkoxy) (Meth) melamine, N, N, N, N-tetrakis (alkoxymethyl) benzoguanamine. From the point that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and scum and residual film are hardly generated on the substrate of the unexposed portion and the light-shielding layer, the trivalent or higher aliphatic polyhydroxy compound is used. Among the polyfunctional (meth) acrylates obtained by reacting with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are particularly preferred. Among the carboxyl polyfunctional (meth) acrylates, particularly preferred are compounds obtained by the reaction of pentaerythritol triacrylate and succinic anhydride, and compounds obtained by the reaction of dipentaerythritol pentaacrylate and succinic anhydride.

In the present invention, the (D) crosslinking agent can be used alone or in combination of two or more.

The content of the (D) crosslinking agent in the present invention is preferably 10 to 1,000 parts by mass, and particularly preferably 20 to 500 parts by mass, with respect to 100 parts by mass of the colorant (A). In this case, when there is too little content of a crosslinking agent, there exists a possibility that sufficient hardenability may not be acquired. On the other hand, when the content of the cross-linking agent is too large, in the case where an alkali developability is imparted to the colored composition of the present invention, the alkali developability is lowered, and the substrate is easily exposed on a substrate or a light-shielding layer in an unexposed area. There is a tendency for scum, residual film, and the like.

-(E) Adhesive resin-

(E) An adhesive resin may be contained in the coloring composition of this invention. This makes it possible to impart basic developability to the coloring composition and adhesion to the substrate. Although it does not specifically limit as such an adhesive resin, It is preferable that it is an acidic functional group which has a carboxyl group, a phenolic hydroxyl group, etc. Among them, a polymer having a carboxyl group (hereinafter, referred to as a "carboxyl-containing polymer") is preferable, and examples thereof include an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, referred to as an "unsaturated monomer" Copolymer (e1) ") and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as" unsaturated monomers (e2) ").

Examples of the unsaturated monomer (e1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloxyethyl ester], and ω-carboxy poly Caprolactone mono (meth) acrylate, p-vinyl benzoic acid, etc.

These unsaturated monomers (e1) can be used individually or in mixture of 2 or more types.

Examples of the unsaturated monomer (e2) include, for example, N-substituted maleimide of N-phenylmaleimide and N-cyclohexylmaleimide; for example, styrene , Α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, aromatic vinyl compounds of naphthalene; such as methyl (meth) acrylate, N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, Polyethylene glycol (n = 2 ~ 10) methyl ether (meth) acrylate, polypropylene glycol (n = 2 ~ 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 ~ 10 ) Mono (meth) acrylate, polypropylene glycol (n = 2 ~ 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclic [5.2.1.0 ^2,6 ] dec-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, p-isopropyl Phenylphenol modified ethylene oxide (meth) acrylate, glycidyl (meth) acrylate, (formaldehyde) ) 3,4-epoxycyclohexyl methyl acrylate, 3-[(meth) propenyloxymethyl] oxetane, 3-[(meth) propenyloxymethyl] -3- (Meth) acrylates of ethyloxetane; such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] dec-8-yl vinyl ether, pentacyclopentadecane Vinyl ethers, vinyl ethers of 3- (vinyloxymethyl) -3-ethyloxetane; such as polystyrene, polymethyl (meth) acrylate, n-butyl (meth) acrylate Ester and polysiloxane are macromonomers having a mono (meth) acrylfluorene group at the end of the polymer molecular chain.

These unsaturated monomers (e2) can be used alone or in combination of two or more.

In the copolymer of the unsaturated monomer (e1) and the unsaturated monomer (e2), the copolymerization ratio of the unsaturated monomer (e1) in the copolymer is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. When the unsaturated monomer (e1) is copolymerized in such a range, a colored composition having excellent alkali developability and storage stability can be obtained.

Specific examples of the copolymer of the unsaturated monomer (e1) and the unsaturated monomer (e2) include, for example, JP-A No. 7-140654, JP-A No. 8-259876, and JP-A No. 10-31308. The copolymers disclosed in JP 10-300922, JP 11-174224, JP 11-258415, JP 2000-56118, and JP 2004-101728.

In the present invention, for example, Japanese Patent Application Laid-Open No. 5-19467, Japanese Patent Application Laid-Open No. 6-230212, Japanese Patent Application Laid-Open No. 7-207211, Japanese Patent Application Laid-Open No. 09-325494, and Japanese Patent Application Laid-Open No. 11-140144 can also be used. A carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acrylfluorenyl group in a side chain disclosed in the gazette, Japanese Patent Application Laid-Open No. 2008-181095, and the like is used as an adhesive resin.

The weight average molecular weight in terms of polystyrene measured by GPC (eluting solvent: tetrahydrofuran) in the adhesive resin of the present invention is generally 1,000 to 100,000, preferably 3,000 to 50,000. When the weight average molecular weight is too small, the residual film rate of the obtained film is reduced, the pattern shape, heat resistance, and the like are deteriorated, and the electrical characteristics may be deteriorated. On the other hand, when it is too large, the resolution is reduced and the pattern shape is affected. Otherwise, there is a possibility that dry foreign matter may be easily generated during coating by the slit nozzle method.

The ratio of the weight average molecular weight of the adhesive resin of the present invention to the number average molecular weight in terms of polystyrene measured by GPC (eluting solvent: tetrahydrofuran) is preferably 1.0 to 5.0, and more preferably 1.0 to 3.0. .

The adhesive resin system of the present invention can be produced by a well-known method, and methods such as those disclosed in JP 2003-222717, JP 2006-259680, and International Publication No. 07/029871 can be used. To control its structure, molecular weight, and molecular weight distribution.

In this invention, an adhesive resin can be used individually or in mixture of 2 or more types.

In the present invention, the content of the adhesive resin is usually 10 to 1,000 parts by mass, and preferably 20 to 500 parts by mass based on 100 parts by mass of the (A) colorant. When the content of the adhesive resin is too small, there is a fear that, for example, the alkali developability is lowered and the storage stability of the obtained colored composition is lowered. On the other hand, when the content of the adhesive resin is too large, the colorant concentration may be relatively reduced, which may make it difficult. The goal is to achieve the color density of the film.

-(F) Photopolymerization initiator-

The coloring composition of the present invention contains (F) a photopolymerization initiator. This makes it possible to impart a sense of radiation to the colored composition. The (F) photopolymerization initiator used in the present invention generates the activity for starting the polymerization of the (D) crosslinking agent by exposing radiation such as visible light, ultraviolet rays, far ultraviolet rays, electron beams, and X-rays. The source of the compound.

Examples of such photopolymerization initiator systems include 9-oxysulfur Compounds, acetophenone compounds, biimidazole compounds, three Based compounds, O-fluorenyl oxime based compounds, onium salt based compounds, benzoin based compounds, benzophenone based compounds, α-diketone based compounds, polynuclear quinone based compounds, diazonium based compounds, pyrimidine Ester-based compounds and the like.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. As a photopolymerization initiator, preferably 9-oxysulfur Compounds, acetophenone compounds, biimidazole compounds, three At least one selected from the group consisting of a system compound and an O-fluorenyl oxime system compound.

Among the preferred photopolymerization initiators of the present invention, as 9-oxysulfur Specific examples of the compound are, for example, 9-oxysulfur , 2-chloro9-oxysulfur 2-methyl 9-oxysulfur , 2-isopropyl 9-oxysulfur , 4-isopropyl 9-oxysulfur , 2,4-dichloro 9-oxysulfur Ketone, 2,4-dimethyl 9-oxosulfur , 2,4-diethyl 9-oxysulfur 2,4-diisopropyl 9-oxysulfur Wait.

Specific examples of the acetophenone-based compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzene. Methyl-2-dimethylamino-1- (4-morpholinyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1 -(4-morpholinylphenyl) butan-1-one and the like.

Moreover, as a specific example of the above-mentioned biimidazole-based compound, for example, 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.

In the case where a biimidazole-based compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor in combination in terms of improving sensitivity. The "hydrogen donor" here refers to a compound that can provide a hydrogen atom to a radical generated from a biimidazole-based compound by exposure. Examples of the hydrogen supply system include thiol-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4'-bis (dimethylamino) benzophenone, 4 , 4'-bis (diethylamino) benzophenone and other amine-based hydrogen donors. In the present invention, hydrogen donors can be used alone or in combination of two or more. From the viewpoint of further improving the sensitivity, it is preferable to use one or more thiol-based hydrogen donors and one or more amines in combination. Hydrogen donor.

Again, the above three Specific examples of the compound are, for example, 2,4,6-tris (trichloromethyl) -s-tri , 2-methyl-4,6-bis (trichloromethyl) -s-tri , 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (4-Diethylamino-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- [2- (3,4-dimethoxyphenyl) vinyl] -4,6-bis (trichloromethyl) -s-tri , 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-epoxystyryl) -4,6-bis (trichloromethyl) -s-tri , 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-tri Halomethyl Department of compounds.

Specific examples of the O-fluorenyl oxime-based compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzylhydrazone). Oxime), ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime), ethyl Ketone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofurylmethoxybenzyl) -9H-carbazol-3-yl]-, 1- (O-ethylfluorenyl Oxime), ethyl ketone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolyl) methoxybenzidine Group} -9H-carbazol-3-yl]-, 1- (O-ethylamidoxime) and the like.

In the present invention, when a photopolymerization initiator other than a biimidazole-based compound such as an acetophenone-based compound is used, a sensitizer may be used. Examples of such sensitizers include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4- Diethylaminoacetophenone, 4-dimethylaminophenylacetone, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, 2,5- Bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzyl) coumarin, 4- (diethyl Aminoamino) chalcone and the like.

In the present invention, the content of the photopolymerization initiator is preferably 0.01 to 120 parts by mass, and particularly preferably 1 to 100 parts by mass, with respect to 100 parts by mass of the (D) crosslinking agent. In this case, when the content of the photopolymerization initiator is too small, there is a fear that the hardening due to exposure may be insufficient; on the other hand, when the content is too large, the colored layer formed may be easily removed during development. The tendency of the substrate to come off.

-additive-

The coloring composition of the present invention may contain various additives as necessary.

Examples of the additive system include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); and interfacial activities such as fluorine-based surfactants and silicon-based surfactants. Agent; vinyltrimethoxysilane, vinyltrioxidesilane, vinyltri (2-methoxyepoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethyl Oxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrioxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3 -Adhesion promoters such as chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc .; 2,2-thiobis (4-methyl -6-tert-butylphenol), 2,6-di-tert-butylphenol and other antioxidants; 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5 -Ultraviolet absorbers such as chlorobenzotriazole and alkoxybenzophenones; aggregation inhibitors such as sodium polyacrylate Malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, Residue improving agents such as 3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol; succinic acid mono [2- (methyl) Developability improvers such as acryloxyethyl], fumaric acid mono [2- (meth) acryloxyethyl], ω-carboxy polycaprolactone mono (meth) acrylate, and the like.

[Color filter and manufacturing method thereof]

The color filter of the present invention includes a coloring layer formed using the coloring composition of the present invention.

As a method for manufacturing a color filter, the first method is, for example, the following method. First, a light-shielding layer (black matrix) is formed on the surface of the substrate in such a manner that the pixel portions are formed in a divided manner as needed. Next, after the liquid composition of the radiation-sensitive composition of the present invention in which a red colorant is dispersed is applied on the substrate, pre-baking is performed to evaporate the solvent to form a coating film. Next, after exposing the coating film through a photomask, development is performed using an alkaline developing solution, and an unexposed portion of the coating film is dissolved and removed. Then, a post-baking process is performed to form a pixel array in which red pixel patterns are arranged in a specific arrangement.

Next, coating, pre-baking, exposing, developing, and post-baking of each of the colored radiation-sensitive compositions are performed in the same manner as described above using each of the colored radiation-sensitive compositions in green or blue, and the same are applied on the same substrate In order to form a green pixel array and a blue pixel array. Thereby, a color filter with pixel arrays of three primary colors of red, green and blue arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of various colors is not limited to the above.

In addition, the black matrix can be formed by forming a desired pattern on a metal thin film such as chromium formed by sputtering or vapor deposition using a photo-etching method, and a coloring composition having a black colorant dispersed can be used to form a radial composition. And is formed in the same manner as in the case where the above-mentioned pixels are formed.

Examples of the substrate system used when forming a color filter include glass, silicon, polycarbonate, polyester, aromatic polyimide, polyimide, imine, and polyimide.

In addition, appropriate pretreatments such as chemical treatment with a silane coupling agent, plasma treatment, ion plating, sputtering, vapor phase reaction method, and vacuum evaporation may be performed on these substrates as required.

When the colored radiation-sensitive composition is applied to the substrate, a suitable coating method such as a spray coating method, a roll coating method, a spin coating method (spin coating method), a slot die coating method, or a bar coating method may be used. Spin coating method and slot die coating method are used.

Pre-baking is usually performed by combining reduced pressure drying and heat drying. Drying under reduced pressure is usually carried out to 50 to 200 Pa. The conditions for heating and drying are usually 70 to 110 ° C and about 1 to 10 minutes.

The coating thickness is usually 0.6 to 8.0 μm, preferably 1.2 to 5.0 μm after drying.

Examples of the radiation source used when forming the pixels and / or black matrix include xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide mercury lamps, medium-pressure mercury lamps, and low-pressure mercury lamps Lamp light sources and laser light sources such as argon ion lasers, YAG lasers, XeCl excimer lasers, nitrogen lasers, etc. are preferably radiation with a wavelength in the range of 190 to 450 nm.

The radiation exposure is generally preferably 10 to 10,000 J / m ² .

In addition, as the above-mentioned basic developing solution, preferred examples are sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0 ] -7-Undecylcarbamate, 1,5-diazabicyclo- [4.3.0] -5-nonene and other aqueous solutions.

An appropriate amount of a water-soluble organic solvent such as methanol and ethanol, a surfactant, and the like may be added to the alkaline developing solution. In addition, after alkaline development, water washing is usually performed.

As the imaging processing system, a spray imaging method, a spray imaging method, an immersion bath (immersion) imaging method, an immersion (liquid pool) imaging method, and the like can be applied. The imaging conditions are preferably 5 to 300 seconds at room temperature.

Post-baking conditions are usually 180 to 280 ° C, about 10 to 60 minutes.

The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, and preferably 1.0 to 3.0 μm.

As a second method for manufacturing a color filter, a method of obtaining pixels of various colors by an inkjet method disclosed in Japanese Patent Application Laid-Open No. 7-318723, Japanese Patent Application Laid-Open No. 2000-310706, and the like can be used. In this method, first, a partition wall that also has a light shielding function is formed on the surface of the substrate. Next, a liquid composition such as the colored composition of the present invention in which a red colorant is dispersed is ejected into the formed partition wall using an inkjet device, and then pre-baked to evaporate the solvent. Next, after exposing the coating film as required, it is cured by post-baking to form a red pixel pattern.

Next, a green pixel pattern and a blue pixel pattern are sequentially formed on the same substrate in the same manner as described above using each of the green or blue colored compositions. Thereby, a color filter in which pixel patterns of three primary colors of red, green, and blue are arranged on a substrate can be obtained. However, in the present invention, the order of forming pixels of various colors is not limited to the above.

In addition, since the above-mentioned partition wall can not only realize the light-shielding function, but also the function of not mixing the colored composition of various colors discharged into the section, the film is compared with the black matrix used in the first method described above. Thicker. Therefore, the partition wall is usually formed using a black radiation-sensitive composition.

The substrate and the radiation light source used in forming the color filter, and the methods and conditions for pre-baking and post-baking are the same as the first method described above. In this way, the film thickness of the pixel formed by the inkjet method is about the same as the height of the partition wall.

After forming a protective film on the pixel pattern thus obtained, a transparent conductive film is formed by sputtering. After the transparent conductive film is formed, a spacer may be further formed as a color filter. The spacer is usually formed using a radiation-sensitive composition, and a spacer (black spacer) having a light-shielding property may be formed. In this case, a color-sensitive radiation composition in which a black coloring agent is dispersed is used, and the coloring composition of the present invention is also suitable for forming the black spacer.

Since the color filter of the present invention thus obtained has extremely high brightness and color purity, it is extremely useful in color liquid crystal display elements, color photographic tube elements, color sensors, organic EL display elements, and electronic newspapers.

[Color LCD display element]

The color liquid crystal display element of the present invention is provided with the color filter of the present invention.

The color liquid crystal display element of the present invention can have a suitable structure. For example, a color filter is formed on another substrate different from a driving substrate on which a thin film transistor (TFT) is arranged, and the substrate forming the driving substrate and the color filter are formed to be opposed to each other through a liquid crystal layer. Structure, and a substrate on which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is arranged, and a substrate on which an ITO (tin-doped indium oxide) electrode is formed, can also be formed through a liquid crystal layer Contrasting structure. The latter structure has the advantage that the aperture ratio can be increased particularly, and a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display device of the present invention may include a backlight unit with a white LED as a light source in addition to a cold cathode fluorescent tube (CCFL: Cold Cathode Fluorescent Lamp). Examples of the white LED system include: a white LED that uses a red LED, a green LED, and a blue LED with independent spectrums to obtain white light; and a combination of red LED, green LED, and blue LED to obtain white light White LED; white LED by combining blue LED, red LED and green phosphor to obtain white light; white LED by combining blue LED, red emitting phosphor and green phosphor to combine White LEDs with white light are obtained; white LEDs with white light are obtained by mixing blue LEDs with YAG-based phosphors; blue LEDs, orange light-emitting phosphors, and green light-emitting phosphors are combined and mixed to obtain White LEDs with white light; white LEDs, etc. by combining ultraviolet LEDs, red light-emitting phosphors, green light-emitting phosphors, and blue light-emitting phosphors to mix colors to obtain white light.

The color liquid crystal display element of the present invention can be applied to TN (Twisted Nematic, Twisted Nematic) type, STN (Super Twisted Nematic, Super Twisted Nematic) type, IPS (In-Planes Switching) type, VA (Vertical Suitable liquid crystal modes, such as an Alignment (vertical alignment) type and an OCB (Optically Compensated Birefringence) type.

[Example]

Hereinafter, examples will be given to further specifically describe the embodiments of the present invention. However, the present invention is not limited to the following examples.

<Synthesis of (B) copolymer> Synthesis Example 1

In a flask equipped with a stir bar, 0.6 g of methoxypolyethylene glycol monomethacrylate (PME-200 Nippon Oil Co., Ltd.) (hereinafter, referred to as "PME-200") and 12.9 g of N-butyl methacrylate (hereinafter referred to as "nBMA"), 10.5 g of methyl methacrylate (hereinafter referred to as "MMA"), 323 mg of 2,2'-azobisisobutyronitrile (hereinafter (Referred to as "AIBN") and 833 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene and subjected to nitrogen bubble treatment for 30 minutes. Then, the temperature of the reaction solution was raised to 57 ° C. by slowly stirring, and the temperature was maintained for 34 hours to perform living radical polymerization.

Next, a solution of 211 mg of AIBN and 4.1 g of dimethylamine ethyl methacrylate (hereinafter, referred to as "DAMA") was dissolved in 20 mL of toluene, and nitrogen substitution was performed for 30 minutes, and added to the above reaction solution, and Living radical polymerization was performed at 57 ° C for 34 hours. Then, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile matter was set to 40% by mass. In this way, a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200, nBMA, and MMA was obtained. The obtained copolymer was referred to as "copolymer (B-1)".

Synthesis Example 2

In a flask equipped with a stir bar, 1.4 g of PME-200, 10.6 g of nBMA, 2.8 g of 2-ethylhexyl methacrylate (hereinafter, referred to as "EHMA"), 7.0 g of MMA, and 295 mg of AIBN and 726 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene and subjected to a nitrogen bubble treatment for 30 minutes. Then, the temperature of the reaction solution was raised to 60 ° C. by slowly stirring, and the temperature was maintained for 24 hours to perform living radical polymerization.

Next, a solution of 352 mg of AIBN and 6.2 g of DAMA in 20 mL of toluene and nitrogen substitution for 30 minutes was added to the above reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile matter was set to 40% by mass. In this way, a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200, nBMA, EHMA, and MMA is obtained. The obtained copolymer was referred to as "copolymer (B-2)".

Synthesis Example 3

In a flask equipped with a stir bar, 1.4 g of PME-200, 5.0 g of nBMA, 6.7 g of EHMA, 1.7 g of benzyl methacrylate (hereinafter referred to as "BzMA"), 7.0 g of MMA, 352 mg of AIBN and 649 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene and subjected to a nitrogen bubble treatment for 30 minutes. Then, the temperature of the reaction solution was raised to 62 ° C. by slowly stirring, and the temperature was maintained for 20 hours to perform living radical polymerization.

Next, a solution in which 448 mg of AIBN and 6.2 g of DAMA were dissolved in 20 mL of toluene and nitrogen substitution was performed for 30 minutes was added to the above reaction solution, and living radical polymerization was performed at 62 ° C for 20 hours. Then, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile matter was set to 40% by mass. In this way, a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200, nBMA, EHMA, BzMA, and MMA is obtained. The obtained copolymer was referred to as "copolymer (B-3)".

Comparative Synthesis Example 1

In a flask equipped with a stir bar, 5.6 g of PME-200, 6.4 g of nBMA, 5.0 g of EHMA, 1.7 g of BzMA, 5.6 g of MMA, 256 mg of AIBN, and 660 mg of pyrazole-1-dithioxo The cyano (dimethyl) methyl carboxylate was dissolved in 30 mL of toluene and subjected to a nitrogen bubble treatment for 30 minutes. Then, the temperature of the reaction solution was raised to 60 ° C. by slowly stirring, and the temperature was maintained for 24 hours to perform living radical polymerization.

Next, a solution in which 189 mg of AIBN and 3.6 g of DAMA were dissolved in 20 mL of toluene and nitrogen substitution was performed for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile matter was set to 40% by mass. In this way, a block copolymer solution composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200, nBMA, EHMA, BzMA, and MMA is obtained. The obtained copolymer was referred to as "copolymer (b-1)".

Comparative Synthesis Example 2

In a flask equipped with a stir bar, 7.8 g of PME-200, 6.6 g of nBMA, 7.0 g of MMA, 236 mg of AIBN, and 610 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) formaldehyde The base ester was dissolved in 30 mL of toluene and subjected to a nitrogen bubble treatment for 30 minutes. Then, the temperature of the reaction solution was raised to 60 ° C. by slowly stirring, and the temperature was maintained for 24 hours to perform living radical polymerization.

Next, a solution in which 342 mg of AIBN and 6.6 g of DAMA were dissolved in 20 mL of toluene and nitrogen substitution was performed for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Then, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile matter was set to 40% by mass. In this way, a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from PME-200, nBMA, and MMA was obtained. The obtained copolymer was referred to as "copolymer (b-2)".

Comparative Synthesis Example 3

In a flask equipped with a stir bar, 7.0 g of nBMA, 6.7 g of EHMA, 1.7 g of BzMA, 7.0 g of MMA, 240 mg of AIBN, and 690 mg of pyrazole-1-diluocarboxylic acid cyano (dimethylformamide (Methyl) methyl ester was dissolved in 30 mL of toluene and subjected to a nitrogen bubble treatment for 30 minutes. Then, the temperature of the reaction solution was raised to 62 ° C. by slowly stirring, and the temperature was maintained for 20 hours to perform living radical polymerization.

Next, a solution in which 290 mg of AIBN and 5.6 g of DAMA were dissolved in 20 mL of toluene and nitrogen substitution was performed for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 62 ° C. for 20 hours. Then, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile matter was set to 40% by mass. In this way, a block copolymer composed of an A block having a repeating unit derived from DAMA and a B block having a repeating unit derived from nBMA, EHMA, BzMA, and MMA is obtained. The obtained copolymer was referred to as "copolymer (b-3)".

<Measurement of Mw and Mw / Mn>

The Mw and Mn of the (B) copolymer obtained in each of the above Synthesis Examples were measured by GPC of the following specifications. Table 1 shows the measurement results together with the copolymerization ratio (% by mass) of each monomer in the (B) copolymer.

Device: GPC-104 (manufactured by Showa Denko Corporation).

Tubular column: Used in combination with KD-G, KF-603, KF-602, KF-601.

Mobile phase: DMF.

<Determination of Amine Value>

The amine value of the (B) copolymer obtained in each of the above Synthesis Examples was measured in the following manner. The measurement results are shown in Table 1.

0.5g of the copolymer solution was accurately weighed to a unit of 1mg, and the solution was placed in a glass container. 20 ml of dissolved acetic anhydride / acetic acid = 9/1 (volume ratio) was added, and it was left at room temperature for 3 hours. Then, after adding 30 ml of acetic acid, a potentiometric measurement device AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.) was used, and titration was performed with a 0.1 mol / l perchloric acid‧acetic acid solution. Control experiments were also performed. The amine value (unit: mgKOH / g) was calculated from the dripping amount of the 0.1 mol / l perchloric acid · acetic acid solution of the copolymer (B) and the control experiment.

<Preparation and Evaluation of Pigment Dispersion> Example 1

7.2 parts by mass of CI Pigment Green 58 (manufactured by DIC Corporation), 4.8 parts by mass of CI Pigment Yellow 150, and 10 parts by mass of the copolymer (B-1) solution (nonvolatile content = 40% by mass) were used as colorants. 70 parts by mass of propylene glycol monomethyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether were used as solvents, and they were processed with a bead mill to prepare a pigment dispersion liquid (A-1).

The viscosity of the obtained pigment dispersion liquid was measured using an E-type viscosity meter (manufactured by Tokyo Keiki Co., Ltd.). The obtained pigment dispersion liquid was filled in a light-shielding glass container, and left to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscosity meter (manufactured by Tokyo Keiki Co., Ltd.). Then, the increase rate of the viscosity after storage for 14 days to the viscosity after the preparation was calculated, and the evaluation rate was "A" when the increase rate was 10% or less, and "B" when the increase rate was 10% or more. The evaluation results are shown in Table 2.

Examples 2 to 4 and Comparative Examples 1 to 5

A colorant dispersion liquid (A-2) to (A-) was prepared in the same manner as in Example 1, except that the amounts of the colorant, (B) copolymer, and solvent in Preparation Example 1 were changed to those shown in Table 2. 9) to evaluate. The evaluation results are shown in Table 2.

In Table 2, the so-called "G58" refers to CI Pigment Green 58, the so-called "Y150" refers to CI Pigment Yellow 150, the so-called "Y179" refers to CI Solvent Yellow 179 for organic dyes, and the so-called "PGMEA" It refers to propylene glycol monomethyl ether acetate. The so-called "PGME" refers to propylene glycol monomethyl ether. The so-called "BYK6919" refers to BYK-LPN6919 (manufactured by BYK CHEMIE (BYK)), which is a commercially available dispersant. In addition, BYK-LPN6919 is a dispersant solution of a block copolymer having repeating units (1) and repeating units (2), and having an amine value = 120 mgKOH / g (nonvolatile content conversion), nonvolatile content = 60% by mass .

<Synthesis of Adhesive Resin> Synthesis Example 4

In a flask equipped with a cooling tube and a stirrer, 25.0 g of BzMA, 20.0 g of nBMA, 15.0 g of hydroxyethyl methacrylate, 20.0 g of styrene, and 20.0 g of methacrylic acid were dissolved in 200 g of propylene glycol monoformate To the ether ether acetate, 3.0 g of AIBN and 5.0 g of 2,4-diphenyl-4-methyl-1-pentene were added, followed by purging with nitrogen for 15 minutes. After purging with nitrogen, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubble treatment, and polymerization was performed for 5 hours to obtain a solution containing 33% by mass of the adhesive resin (E-1). The weight average molecular weight of this adhesive resin (E-1) in terms of polystyrene equivalent measured by GPC (dissolution solvent: tetrahydrofuran) = 10,500, and the weight average molecular weight in terms of polystyrene equivalent measured by GPC (elution solvent: tetrahydrofuran). Ratio to number average molecular weight = 2.5.

<Preparation and evaluation of colored radiation-sensitive composition> [Modulation of colored radiation-sensitive composition] Example 5

100 parts by mass of a pigment dispersion liquid (A-1), 33.5 parts by mass of an adhesive resin (E-1) solution as an adhesive resin, and 9.7 parts by mass of a cross-linking agent manufactured by Toa Synthetic Co., Ltd. 402 (dipentaerythritol hexaacrylate as a main component) and 4.3 parts by mass of 2-benzyl-2-dimethylamino-1- (4-morpholinyl) butane-1 as a photopolymerization initiator -Ketone (trade name: Irgacure 369, manufactured by Ciba‧Speciality Chemicals), and ethyl 3-epoxypropionate as a solvent, to prepare a coloring radioactive composition having a solid content concentration of 20% by mass.

[Evaluation of dropout time]

After applying the obtained colored radiation-sensitive composition to a glass substrate using a spin coater, pre-baking was performed on a hot plate at 100 ° C. for 2 minutes to form a coating film having a film thickness of 2.5 μm. Next, after the substrate was cooled to room temperature, the coating film on the substrate was exposed using a high-pressure mercury lamp, and radiation containing 365 nm, 405 nm, and 436 nm wavelengths was transmitted through a photomask and exposed at 1,000 J / m ² . Coating film. Then, a 0.04% by weight potassium hydroxide aqueous solution at 23 ° C. was sprayed onto the coating film on the substrate to perform shower development. At this time, the time until the coating film of the unexposed part was completely peeled off (falling time) was measured. In addition, the case where the fall-off time is 60 seconds or less is evaluated as "A", the case where the fall time is 60 seconds or more, the case which is 120 seconds or less is evaluated as "B", the case where the time is 120 seconds or more, and the time is less than 180 seconds is evaluated as "C". The situation was evaluated as "D". The shorter the time, the faster the development speed, which has the advantage of shortening the tact time for manufacturing a color filter. The evaluation results are shown in Table 3.

[Evaluation of chromaticity characteristics]

After applying the obtained colored radiation-sensitive composition to a glass substrate using a spin coater, pre-baking was performed on a hot plate at 100 ° C. for 2 minutes to form three coating films with different film thicknesses. Next, after their substrates were cooled to room temperature, the coating film on the substrates was exposed using a high-pressure mercury lamp, and radiation containing 365 nm, 405 nm, and 436 nm wavelengths was transmitted through a photomask without exposure to 1,000 J / m ² . Each coating film was exposed. Then, post-baking was performed at 180 ° C for 20 minutes to form a cured film on the substrate. Using the color analyzer (MCPD2000, manufactured by Otsuka Electronics Co., Ltd.), the obtained three cured films were measured for chromaticity coordinates (x, y) and stimuli in the CIE color system under a C light source and a 2 degree field of view. Value (Y). From the measurement results, the chromaticity coordinate value x and the stimulus value (Y) when the chromaticity coordinate value y = 0.590 were obtained. The evaluation results are shown in Table 3.

Examples 6 to 8 and Comparative Examples 5 to 9

A colored radioactive composition was prepared and evaluated in the same manner as in Example 5 except that the type of the pigment dispersion liquid in Example 5 was changed to those shown in Table 3. The evaluation results are shown in Table 3.

Claims (10)

A coloring composition comprising: (A) a pigment-containing coloring agent; (B) an A block having a repeating unit (1) having a repeating unit represented by the following formula (1) of 60% by mass or more; A block copolymer having a repeating unit (2) represented by formula (2), an amine value of 50 mgKOH / g or more and less than 80 mgKOH / g, and (C) a solvent; and (A) is colored The content of the agent is 5 to 70% by mass in the solid content of the coloring composition; (In the formula (1), X is a -COO-R ⁸ -(*) group (where, R ⁸ represents a methylene group, an alkylene group having 2 to 10 carbon atoms, or an alkylene group having 2 to 10 carbon atoms (*) Represents a bonding bond with N), R ¹ represents a hydrogen atom or a methyl group, and R ² and R ³ each independently represent a hydrogen atom or a chain having a substituent Or a cyclic hydrocarbon group, R ² and R ³ may be bonded to each other to form a cyclic structure), (In formula (2), R ⁴ represents an alkylene group having 2 to 4 carbon atoms independently, R ⁵ represents an alkyl group having 1 to 6 carbon atoms, R ⁶ represents a hydrogen atom or a methyl group, and n represents 1 to 150 Integer). For example, the colored composition of the first patent application range, wherein the B block of the aforementioned (B) block copolymer has a repeating unit (3) represented by the following formula (3), and the repeating unit in the B block ( 2) The copolymerization ratio (repeating unit (2) / repeating unit (3), mass ratio) with the repeating unit (3) is 1/99 ~ 30/70, (In formula (3), R ⁹ represents a linear or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may also have a substituent, and R ¹⁰ represents hydrogen Atom or methyl). For example, the colored composition according to item 1 or 2 of the patent application range, wherein the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn of the aforementioned (B) block copolymer is 1.0 to 1.8. For example, the coloring composition of the scope of application for item 1 or 2 contains a phthalocyanine pigment as a colorant. For example, the coloring composition of item 1 or 2 of the patent application scope contains C.I. Pigment Green 58 as a pigment. For example, the coloring composition of the scope of patent application No. 1 further contains (D) a crosslinking agent and (E) an adhesive resin. For example, the coloring composition in the sixth item of the patent application scope further contains a dye as a colorant. For example, the coloring composition in the scope of the patent application No. 6 further contains (F) a photopolymerization initiator. A color filter includes a coloring layer formed using the coloring composition according to any one of claims 6 to 8 of the scope of patent application. A color liquid crystal display element is provided with a color filter as in item 9 of the scope of patent application.