JP2011232735A - Colored composition, color filter and color liquid crystal display element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for a color filter excellent in a chromaticity characteristic, alkali developability and storage stability.SOLUTION: The colored composition includes; (A) a coloring agent containing a pigment; (B) a block copolymer which has an amine number of 50-80 mgKOH/g and consists of an A block containing 60 mass% or more of repeating units arising from an ethylenic unsaturated monomer having an amino group and a B block containing repeating units arising from an ethylenic unsaturated monomer having an alkylene glycol chain; and (C) a solvent.

Description

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

  In producing a color filter using a colored radiation-sensitive composition, a pigment-dispersed colored radiation-sensitive composition is applied on a substrate and dried, and then the dried coating film is irradiated with radiation in a desired pattern shape. There is known a method (Patent Documents 1 and 2) for obtaining pixels of each color by irradiation (hereinafter referred to as “exposure”) and development. A method of forming a black matrix using a photopolymerizable composition in which carbon black is dispersed (Patent Document 3) is also known. Furthermore, a method of obtaining pixels of each color by an ink jet method using a pigment-dispersed colored resin composition is also known (Patent Document 4).

  By the way, in the field of color filters used for liquid crystal display elements and solid-state image sensors, pigments used tend to be increasingly atomized with the demand for higher brightness and higher contrast. In order to realize such a stable and good dispersibility of the atomized pigment, it is known that a dispersant is effective. And in patent document 5, in order to disperse | distribute the highly atomized pigment efficiently with a small addition amount, it is possible to use the block copolymer whose amine value is 80 mgKOH / g or more and 150 mgKOH / g as a dispersing agent. Proposed.

JP-A-2-144502 JP-A-3-53201 JP-A-6-35188 JP 2000-310706 A JP 2009-25813 A

  However, when a block copolymer having a high amine value proposed in Patent Document 5 is used as a dispersant, the alkali developability of the colored composition is deteriorated, which hinders mass production of color filters. In particular, when a pigment and a dye are used in combination as a colorant, the deterioration of alkali developability becomes remarkable. Therefore, there is a strong demand for the development of a coloring composition for a color filter that realizes the recent demands for high contrast and high brightness and is excellent in alkali developability.

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

  In view of this situation, the present inventors have conducted extensive research and found that the above-mentioned problems can be solved by using a specific block copolymer, thereby completing the present invention.

  That is, the present invention is represented by (A) a colorant containing a pigment, (B) an A block having 60% by mass or more of a repeating unit (1) represented by the following formula (1), and the following formula (2). A block copolymer (hereinafter also referred to as “(B) copolymer”) having an amine value of 50 mgKOH / g or more and less than 80 mgKOH / g, and (C) a solvent. It is intended to provide a coloring composition characterized by containing.

(In 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 have a hydrogen atom or a substituent. A chain or cyclic hydrocarbon group that may be present, and R ² and R ³ may be bonded to each other to form a cyclic structure.)

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

  The present invention also provides a color filter comprising a colored layer formed using the colored composition, and a color liquid crystal display device comprising the color filter. Here, the “colored layer” means each color pixel, black matrix, black spacer, etc. used in the color filter.

If the coloring composition of this invention is used, the color filter which has each color pixel which is excellent in chromaticity characteristic can be obtained. The colored composition of the present invention is also excellent in alkali developability and storage stability.
Therefore, the colored composition of the present invention has various colors including color filters for color liquid crystal display elements, color filters for color separation of solid-state imaging elements, color filters for organic EL display elements, and color filters for electronic paper. It can be used very suitably for producing a filter. Furthermore, the colored composition of the present invention can also be suitably used as a colored composition for electrophoresis used in an electrophoretic display element.

Hereinafter, the present invention will be described in detail.
Coloring composition will be described components of the colored composition of the present invention.

-(A) Colorant-
The coloring composition of the present invention contains a pigment as the colorant (A). The pigment is not particularly limited, and may be an organic pigment or an inorganic pigment. In this invention, a pigment can be used individually or in mixture of 2 or more types. Of course, a mixture of an organic pigment and an inorganic pigment can also be used.

Examples of the organic pigment include anthraquinone pigments, aminoanthraquinone pigments, quinacridone pigments, quinacridone quinone pigments, diketopyrrolopyrrole pigments, perylene pigments, perinone pigments, anthanthrone pigments, and benzimidazolone pigments. Examples thereof include pigments, disazo condensate pigments, azo pigments, thioindigo pigments, pyranthrone pigments, dioxazine pigments, quinophthalone pigments, isoindoline pigments, and phthalocyanine pigments.

Examples of the inorganic pigment include, for example, titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean curd (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.

Among these pigments, the (B) copolymer can disperse phthalocyanine pigments stably and satisfactorily. Among the phthalocyanine pigments, examples of the blue pigment include copper phthalocyanine. More specifically, compounds classified as pigments in the color index (CI; issued by The Society of Dyers and Colorists), that is, the color index (CI) name as shown below is attached. You can list what you have.

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

Among these phthalocyanine-based blue pigments, the (B) copolymer is C.I. I. It is preferably used to disperse Pigment Blue 15: 6.

Among the phthalocyanine pigments, the green pigment includes, for example, chlorinated and / or brominated metal phthalocyanines, more specifically copper phthalocyanine, zinc phthalocyanine, magnesium phthalocyanine, aluminum phthalocyanine, titanium phthalocyanine, vanadium phthalocyanine. Manganese phthalocyanine, iron phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine, tin phthalocyanine, germanium phthalocyanine, and the like.

Among these phthalocyanine-based green pigments, (B) the copolymer is chlorinated copper phthalocyanine, chlorinated brominated copper phthalocyanine, brominated copper phthalocyanine, chlorinated brominated zinc phthalocyanine, brominated zinc phthalocyanine, especially chlorine. It is preferably used to disperse brominated zinc phthalocyanine. The chlorinated brominated zinc phthalocyanine preferably has a structure represented by the following formula (I).

(In Formula (I), Y shows a hydrogen atom, a chlorine atom, or a bromine atom mutually independently, and 10-15 pieces of all Y are a bromine atom, and 1-6 are a chlorine atom. )
In the color index (CI) name, chlorinated copper phthalocyanine is C.I. I. Pigment Green 7 is a pigment, and chlorinated brominated copper phthalocyanine is C.I. I. Pigment Green 36, a chlorinated brominated zinc phthalocyanine is C.I. I. Pigments classified as CI Pigment Green 58.

In the present invention, the pigment can be used after being purified by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method, or a combination thereof. Moreover, the pigment surface may be used by modifying the particle surface with a resin if desired. Examples of the resin that modifies the particle surface of the pigment include vehicle resins described in JP-A No. 2001-108817, and various commercially available resins for dispersing pigments. As a resin coating method on the carbon black surface, for example, methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment is preferably used by refining primary particles by so-called salt milling. As a salt milling method, for example, a method disclosed in Japanese Patent Application Laid-Open No. 08-179111 can be employed.

  By the way, in a coloring composition for a color filter, by using a dye as a colorant, it is possible to achieve high brightness and high contrast that cannot be achieved by a pigment alone. However, when a dye is used as the colorant, the alkali developability of the colored composition is significantly deteriorated. In the coloring composition of the present invention, by using the copolymer (B) as a pigment dispersant, a coloring composition having good alkali developability even when a pigment and a dye are used in combination as a coloring agent. You can get things. Examples of the dye include compounds having the following color index (CI) names.

C. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Direct Yellow 12, C.I. I. Direct Orange 26, C.I. I. Direct Green 28, C.I. I. Direct Green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Molded Red 7, C.I. I. Moldant Yellow 5, C.I. I. Azo dyes such as Moldant Black 7;
C. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Anthraquinone dyes such as Disperse Blue 60;
C. I. Phthalocyanine dyes such as Pad Blue 5;
C. I. Basic Blue 3, C.I. I. Quinone imine dyes such as Basic Blue 9;
C. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Quinoline dyes such as Disperse Yellow 64;
C. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Nitro dyes such as Disperse Yellow 42;
Methine dyes such as Disperse Yellow 201.

When using dye as a coloring agent in this invention, dye can be used individually or in mixture of 2 or more types.
(A) The content ratio of the colorant is usually 5 to 70% by mass in the solid content of the coloring composition, preferably from the point of forming a pixel having high luminance and excellent color purity, or a black matrix having excellent light shielding properties. 5 to 60% by mass. Here, solid content is components other than the solvent mentioned 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 60% by mass or more of the repeating unit (1) represented by the above formula (1), and the above formula (2). And a block copolymer having an amine value of 50 mgKOH / g or more and less than 80 mgKOH / g. “Having 60% by mass or more of repeating units (1)” means that the content of the repeating unit (1) in the A block is 60% by mass or more.

In the above formula (1), examples of the divalent linking group X include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R ⁷ — (*) group, —COO—R ⁸ —. (*) Group [wherein R ⁷ and R ⁸ are each independently a methylene group, an alkylene group having 2 to 10 carbon atoms, or an alkyleneoxyalkylene group having 2 to 10 carbon atoms, and (*) is N This indicates that the bond is a bond that joins with. ] Etc. are mentioned. Among them, X is preferably a —COO—R ⁸ — group, and R ⁸ is preferably an alkylene group having 2 to 6 carbon atoms.

Moreover, in —NR ² R ³ of the above formula (1), R ² and R ³ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, As a hydrocarbon group, a C1-C4 alkyl group is preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are especially preferable. Among the substituents on the hydrocarbon group, examples of the substituent on the chain hydrocarbon group include a halogen atom, an alkoxy group, and a benzoyl group. Examples of the substituent on the cyclic hydrocarbon group include a chain alkyl group, a halogen atom, and an alkoxy group. The chain hydrocarbon group represented by R ² and R ³ includes both linear and branched chains.

R ² and R ³ may be bonded to each other to form a cyclic structure. Examples of the cyclic structure include a 5- to 7-membered nitrogen-containing heterocyclic monocycle or a condensation of two of these. A condensed ring is mentioned. The nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specific examples include the following.

  These cyclic structures may further have a substituent.

In the above formula (2), R ⁴ is preferably an ethylene group or a methylethylene group. R ⁵ is preferably a methyl group, an ethyl group, a propyl group, or a butyl group. N is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and particularly preferably an integer of 1 to 5.

  (B) The A block of the copolymer may have a repeating unit other than the repeating unit (1) together with the repeating unit (1). Examples of such repeating units include ethylenically unsaturated monomers having a nitrogen-containing heterocyclic group such as pyridyl group, imidazolyl group, pyrazolyl group, triazolyl group, tetrazolyl group, imidazolinyl group, tetrahydropyrimidinyl group; Examples thereof include a repeating unit derived from an ethylenically unsaturated monomer having an ammonium base.

  (B) It is preferable that B block of a copolymer has the repeating unit (3) represented by following formula (3) with the said repeating unit (2).

(In Formula (3), R ⁹ is a chain or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl which may have a substituent. And R ¹⁰ represents a hydrogen atom or a methyl group.)

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, or an aralkyl group having 7 to 16 carbon atoms, such as a methyl group, an ethyl group, A propyl group, a butyl group, a 2-ethylhexyl group, a phenyl group, a benzyl group, and a phenylethyl group are particularly preferable. In addition, 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 aralkyl group include a chain alkyl group, a halogen atom, and an alkoxy group. In addition, the linear alkyl group represented by R ⁹ includes both linear and branched chains.

  (B) The B block of the copolymer may have other repeating units other than the repeating unit (2) and the repeating unit (3). Examples of such repeating units include styrene monomers such as styrene; (meth) acrylamide monomers such as (meth) acrylamide; vinyl acetate; repeating units derived from monomers such as acrylonitrile. It is done.

  The structure of the (B) copolymer is not particularly limited as long as it is a block copolymer including an A block having 60% by mass or more of the repeating unit (1) and a B block having the repeating unit (2). Is preferably an A-B block copolymer or a B-A-B block copolymer.

  (B) In one A block of the copolymer, two or more repeating units (1) may be contained. In that case, 2 or more types of repeating units (1) may be contained in any of random copolymerization and block copolymerization. The content of the repeating unit (1) in the A block is preferably 75% by mass or more, particularly preferably 90% by mass or more.

  (B) In one B block of the copolymer, two or more repeating units (2) may be contained. In that case, 2 or more types of repeating units (2) may be contained in any mode of random copolymerization and block copolymerization. Moreover, when it has a repeating unit (3) and still another repeating unit in B block, they may be contained 2 or more types in one B block, respectively. In that case, each repeating unit may be contained in either mode of random copolymerization or block copolymerization. The repeating unit (2), the repeating unit (3) and other repeating units may also be contained in any mode of random copolymerization and block copolymerization.

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

The amine value of the (B) copolymer is 50 mgKOH / g or more and less than 80 mgKOH / g, preferably 52 mgKOH / g or more and 79 mgKOH / g or less. Here, the amine value represents the number of mg of KOH equivalent to the amount of base per gram of the solid content of the dispersant.
In the copolymer (B), the content of the repeating unit (2) is preferably 1 to 30% by mass, more preferably 1 to 25% by mass in all repeating units.
(B) By making a copolymer into such an aspect, the coloring composition excellent in the dispersibility and alkali developability can be obtained.

The molecular weight of the copolymer (B) is preferably 1,000 in terms of weight average molecular weight in terms of polymethyl methacrylate (hereinafter also referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: DMF). ˜30,000, particularly preferably 5,000 to 15,000. Further, the ratio (Mw / Mn) between the Mw of the copolymer (B) and the number average molecular weight in terms of polymethyl methacrylate (hereinafter referred to as “Mn”) measured by GPC (elution solvent: DMF) is preferably Is 1.0 to 2.0, more preferably 1.0 to 1.8. (B) By making a copolymer into such an aspect, the coloring composition excellent in the dispersibility and alkali developability can be obtained.

(B) A copolymer can be manufactured by a well-known method, For example, it can manufacture by carrying out living polymerization of the monomer which gives each said repeating unit. Examples of the living polymerization method include JP-A-9-62002, JP-A-2002-31713, and P.I. Lutz, P.M. Masson et al, Polym. Bull. , 12, 79 (1984); C. Anderson, G.M. D. Andrews et al, Macromolecules, 14, 1601 (1981); Hatada, K .; Ute, et al, Polym. J. et al. 17, 977 (1985); Hatada, K .; Ute, et al, Polym. J. et al. , 18, 1037 (1986), Koichi right hand, Koichi Hatada, polymer processing, 36, 366 (1987); Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989); Kuroki, T .; Aida, J .; Am. Chem. Soc. 109, 4737 (1987); Takuzo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985); Y. Sogoh, W .; R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) and the like can be employed.

Examples of the monomer that gives the repeating unit (1) include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth) acrylate, and the like. .

Examples of the monomer that gives the repeating unit (2) include polyethylene glycol (n = 1-5) methyl ether (meth) acrylate, polyethylene glycol (n = 1-5) ethyl ether (meth) acrylate, polyethylene glycol ( n = 1-5) propyl ether (meth) acrylate, polypropylene glycol (n = 1-5) methyl ether (meth) acrylate, polypropylene glycol (n = 1-5) ethyl ether (meth) acrylate, polypropylene glycol (n = 1-5) propyl ether (meth) acrylate and the like.

Examples of the monomer that gives the repeating unit (3) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) ) Acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, isobornyl (meth) acrylate, benzyl (meth) acrylate, phenylethyl (meth) acrylate, and the like.

  Examples of the monomer that may be copolymerized with the monomer that gives the repeating unit (1) in the A block include (meth) acryloylaminopropyltrimethylammonium chloride and (meth) acryloyloxyethyltrimethylammonium. Chloride, (meth) acryloyloxyethyl triethylammonium chloride, (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide, (meth) acryloyloxyethylbenzyldimethylammonium chloride, (meth) acryloyloxyethylbenzyldiethylammonium chloride Other examples include monomers represented by the following formula.

  (B) A copolymer can be used individually or in mixture of 2 or more types. (B) Content of a copolymer is 1-100 mass parts normally with respect to 100 mass parts of pigments, Preferably it is 5-70 mass parts, More preferably, it is 10-50 mass parts. (B) When there is too much content of a copolymer, there exists a possibility that developability may be impaired.

In the present invention, a known dispersing agent may be further contained in order to improve dispersibility. Known dispersants include, for example, urethane dispersants, polyethylene imine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkyl phenyl ether dispersants, polyethylene glycol diester dispersants, sorbitan fatty acid ester dispersants. Examples thereof include a dispersant, a fatty acid-modified polyester dispersant, an acrylic dispersant, and a pigment derivative.
Specific examples of such a dispersant include trade names of EFKA (manufactured by EFKA Chemicals BV (EFKA)), Disperbyk (manufactured by BYK (BYK)), Disparon (manufactured by Enomoto Kasei Co., Ltd.), Solsperse ( Lubrizol Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), F-Top (Tochem Products Co., Ltd.), MegaFuck (Dainippon Ink Chemical Co., Ltd.) , Florard (manufactured by Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), and the like. Specific examples of the pigment derivative include copper phthalocyanine, diketopyrrolopyrrole, and sulfonic acid derivative of quinophthalone.

-(C) Solvent-
The colored composition of the present invention is usually first pulverized by using, for example, a bead mill, a roll mill, etc. together with a colorant containing a pigment in (C) a solvent, together with (B) a copolymer and other components as necessary. However, it is mixed and dispersed to prepare a pigment dispersion. And when giving sclerosis | hardenability and alkali developability to the coloring composition of this invention, (D) solvent (C) which is further added to this pigment dispersion liquid as needed, and (C) solvent further added as needed. Add additives and mix. (C) As a solvent, the components (A) and (B) constituting the colored composition, and other components described later are dispersed or dissolved, and do not react with these components and have appropriate volatility. As long as it has, it can be appropriately selected and used.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as 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, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, 3-methyl-3-methoxybutylpropionate ;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyric acid Other esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol, cyclohexanol;
Keto alcohols such as diacetone alcohol;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

In this invention, a solvent can be used individually or in mixture of 2 or more types.
Among these solvents, in preparing the pigment dispersion, the (poly) alkylene glycol monoalkyl ethers, (poly) alkylene glycol monoalkyl ether acetates, diacetates, and alkoxycarboxylic acid esters are used. It is preferable to use at least one selected. The content is preferably 80% by mass or more, more preferably 90% by mass or more in the total solvent contained in the pigment dispersion.

Among the (poly) alkylene glycol monoalkyl ethers, (poly) alkylene glycol monoalkyl ether acetates, diacetates and alkoxycarboxylic acid esters, in particular, propylene glycol 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-methoxybutyl acetate, dipropylene glycol monomethyl ether acetate, propylene glycol diacetate, 1,3-butylene glycol Diacetate, 1,6-hexanediol diacetate, 3-methoxy Propionic acid ethyl, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate are preferred.

  The content of the solvent is not particularly limited, but the total concentration of each component excluding the solvent of the coloring composition is preferably 5 to 50% by mass, and particularly 10 to 40% by mass. An amount is preferred. By setting it as such an aspect, the coloring composition with favorable dispersibility, stability, and applicability | paintability can be obtained.

-(D) Crosslinking agent-
The coloring composition of the present invention can contain (D) a crosslinking agent. Thereby, thermosetting or radiation sclerosis | hardenability 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 oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, the (D) crosslinking agent is preferably a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate obtained by reacting an aliphatic polyhydroxy compound and (meth) acrylic acid, a caprolactone-modified polyfunctional ( (Meth) acrylate, alkylene oxide-modified polyfunctional (meth) acrylate, hydroxyl-functional (meth) acrylate and polyfunctional isocyanate obtained by reacting with polyfunctional isocyanate, hydroxyl-functional (meth) acrylate and acid The polyfunctional (meth) acrylate which has a carboxyl group obtained by making an anhydride react can be mentioned.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol, and polypropylene glycol, glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and triglyceride. Mention may be made of trivalent or higher aliphatic polyhydroxy compounds such as pentaerythritol. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diester. A methacrylate etc. can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. Examples of acid anhydrides include succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid. Examples thereof include dianhydrides and tetrabasic acid dianhydrides such as benzophenone tetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A No. 11-44955. Examples of the alkylene oxide-modified polyfunctional (meth) acrylate include ethylene oxide of bisphenol A and / or propylene oxide modified di (meth) acrylate, ethylene oxide of isocyanuric acid and / or propylene oxide modified tri (meth) acrylate, tri Ethylene oxide and / or propylene oxide modified tri (meth) acrylate of methylolpropane, ethylene oxide and / or propylene oxide modified tri (meth) acrylate of pentaerythritol, ethylene oxide and / or propylene oxide modified tetra (meth) acrylate of pentaerythritol Dipentaerythritol ethylene oxide and / or propylene oxide modified penta (meth) acrylate, di It can be mentioned pointer ethylene oxide erythritol and / or propylene oxide-modified hexa (meth) acrylate.

  Examples of the compound having two or more N-alkoxymethylamino groups include compounds having a melamine structure, a benzoguanamine structure, and a urea structure. In addition, a melamine structure and a benzoguanamine structure refer to a chemical structure having one or more triazine rings or phenyl-substituted triazine rings as a basic skeleton, and are a concept including a melamine compound, a benzoguanamine compound, or a condensate thereof. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl). ) Benzoguanamine, N, N, N, N-tetra (alkoxymethyl) glycoluril and the like.

Of these polyfunctional monomers, polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, polyfunctional (meth) acrylates modified with caprolactone, Polyfunctional urethane (meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N, N, N, N-hexa (alkoxymethyl) melamine, N, N, N, N-tetra (alkoxymethyl) ) Benzoguanamine is preferred. Among the polyfunctional (meth) acrylates obtained by reacting trivalent or higher aliphatic polyhydroxy compounds with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Erythritol hexaacrylate is a compound obtained by reacting pentaerythritol triacrylate and succinic anhydride, among polyfunctional (meth) acrylates having a carboxyl group, obtained by reacting dipentaerythritol pentaacrylate and succinic anhydride. The compound is particularly preferable in that the strength of the colored layer is high, the surface smoothness of the colored layer is excellent, and background stains and film residues are hardly generated on the unexposed substrate and the light shielding layer.
In the present invention, the (D) crosslinking agent can be used alone or in admixture of two or more.

  In the present invention, the content of the (D) crosslinking agent is preferably 10 to 1,000 parts by mass, particularly preferably 20 to 500 parts by mass with respect to 100 parts by mass of the (A) colorant. In this case, if the content of the crosslinking agent is too small, sufficient curability may not be obtained. On the other hand, if the content of the crosslinking agent is too large, when the coloring composition of the present invention is imparted with alkali developability, the alkali developability is deteriorated, and the soil or film on the unexposed portion of the substrate or on the light shielding layer is deteriorated. There is a tendency for the rest to occur easily.

-(E) Binder resin-
The coloring composition of the present invention can contain (E) a binder resin. Thereby, alkali developability and the binding property to a board | substrate can be provided to a coloring composition. Such a binder resin is not particularly limited, but is preferably a resin having an acidic functional group such as a carboxyl group or a phenolic hydroxyl group. Among them, a polymer having a carboxyl group (hereinafter referred to as “carboxyl group-containing polymer”) is preferable. For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter referred to as “unsaturated monomer”). (E1) ”) and other copolymerizable ethylenically unsaturated monomers (hereinafter referred to as“ unsaturated monomer (e2) ”).

Examples of the unsaturated monomer (e1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meta ) Acrylate, p-vinylbenzoic acid and the like.
These unsaturated monomers (e1) can be used alone or in admixture of two or more.

Moreover, as said unsaturated monomer (e2), for example,
N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzylglycidyl ether, acenaphthylene;

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 to 10) methyl ether (meth) acrylate, polyethylene glycol (n = 2 to 10) mono (meth) acrylate, polypropylene glycol (n = 2 to 10) ) Mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate, G Serol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[(meta ) (Meth) acrylic acid esters such as acryloyloxymethyl] oxetane, 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane ;
Examples thereof include a macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane.
These unsaturated monomers (e2) can be used alone or in admixture 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, it is 10 to 40% by mass. By copolymerizing the unsaturated monomer (e1) within such a range, a colored composition excellent in 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-7-140654, JP-A-8-259876, and JP-A-10-31308. Copolymers disclosed in JP-A-10, JP-A-10-300902, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like. Can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Kaikai 2008-181095 and the like, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in the side chain can also be used as a binder resin.

  The binder resin in the present invention has a polystyrene-reduced weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) of usually 1,000 to 100,000, preferably 3,000 to 50,000. If the weight average molecular weight is too small, the residual film ratio of the resulting coating may decrease, the pattern shape, heat resistance, etc. may be impaired, and electrical characteristics may be deteriorated. There is a risk that the pattern may be lowered, the pattern shape may be impaired, and dry foreign matter may be easily generated during application by the slit nozzle method.

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

  The binder resin in the present invention can be produced by a known method. For example, it is disclosed in Japanese Patent Application Laid-Open No. 2003-222717, Japanese Patent Application Laid-Open No. 2006-259680, International Publication No. 07/029871, etc. The structure, molecular weight, and molecular weight distribution can be controlled by the method.

In this invention, binder resin can be used individually or in mixture of 2 or more types.
In this invention, content of binder 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. If the content of the binder resin is too small, for example, the alkali developability may be decreased, or the storage stability of the resulting colored composition may be decreased. On the other hand, if the content is too large, the colorant concentration is relatively high. Therefore, it may be difficult to achieve the target color density as a thin film.

-(F) Photopolymerization initiator-
The coloring composition of the present invention can contain (F) a photopolymerization initiator. Thereby, radiation sensitivity can be provided to a coloring composition. The photopolymerization initiator (F) used in the present invention generates an active species capable of initiating polymerization of the above (D) crosslinking agent by exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. A compound.

  Examples of such photopolymerization initiators include thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α -A diketone type compound, a polynuclear quinone type compound, a diazo type compound, an imide sulfonate type compound etc. can be mentioned.

  In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. The photopolymerization initiator is preferably at least one selected from the group consisting of thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, and O-acyloxime compounds.

  Among preferred photopolymerization initiators in the present invention, specific examples of thioxanthone compounds include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, 2 , 4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone and the like.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4 -Morpholinophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

  Specific examples of the biimidazole compound include 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, Examples thereof include 4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

  In addition, when using a biimidazole-type compound as a photoinitiator, it is preferable at the point which can improve a sensitivity to use a hydrogen donor together. The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan-based hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, and the like. And an amine-based hydrogen donor. In the present invention, hydrogen donors can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2 -(5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Specific examples of the O-acyloxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), ethanone and 1- [9-ethyl. -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime), ethanone, 1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3) -Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.

  In this invention, when using photoinitiators other than biimidazole type compounds, such as an acetophenone type compound, a sensitizer can also be used together. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl. Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

  In this invention, 0.01-120 mass parts is preferable with respect to 100 mass parts of (D) crosslinking agents, and, as for content of a photoinitiator, 1-100 mass parts is especially preferable. In this case, if the content of the photopolymerization initiator is too small, curing by exposure may be insufficient. On the other hand, if the content is too large, the formed colored layer tends to be detached from the substrate during development.

-Additives-
The coloring composition of this invention can also contain a various additive as needed.
Examples of additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylates); surfactants such as fluorosurfactants and silicon surfactants; vinyl Trimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxy Silane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyl Dimethoxysilane, 3-chloropropi Adhesion promoters such as trimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-di- Antioxidants such as t-butylphenol; UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Aggregation such as sodium polyacrylate Inhibitor: malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2 -Propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanedio Residue improving agents such as succinic acid; development of succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, etc. And the like, and the like.

Color filter and method for producing the same The color filter of the present invention includes a colored layer formed using the colored composition of the present invention.

  As a method for producing a color filter, first, the following method may be mentioned. First, a light shielding layer (black matrix) is formed on the surface of the substrate so as to divide a portion where pixels are formed, if necessary. Next, for example, after applying a liquid composition of the radiation-sensitive composition of the present invention in which a red colorant is dispersed on the substrate, pre-baking is performed to evaporate the solvent, thereby forming a coating film. Subsequently, after exposing this coating film through a photomask, it develops using an alkali developing solution, and the unexposed part of a coating film is dissolved and removed. Thereafter, post-baking is performed to form a pixel array in which red pixel patterns are arranged in a predetermined arrangement.

  Next, each colored radiation-sensitive composition of green or blue is used, and each colored radiation-sensitive composition is applied, pre-baked, exposed, developed, and post-baked in the same manner as described above, so that the green pixel array and blue Are sequentially formed on the same substrate. Thereby, a color filter in which pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming pixels of each color is not limited to the above.

  A black matrix can be formed by forming a metal thin film such as chromium formed by sputtering or vapor deposition into a desired pattern using a photolithography method. Using the radiation-sensitive composition, it can be formed in the same manner as in the case of forming the pixel.

Examples of the substrate used when forming the color filter include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired.

  When the colored radiation-sensitive composition is applied to the substrate, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed. In particular, it is preferable to employ a spin coating method or a slit die coating method.

  Pre-baking is usually performed by combining vacuum drying and heat drying. The drying under reduced pressure is usually performed until the pressure reaches 50 to 200 Pa. Moreover, the conditions of heat drying are 70-110 degreeC normally for about 1 to 10 minutes.

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

  Examples of radiation light sources used in forming pixels and / or black matrices include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultrahigh pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, and low pressure mercury lamps. Examples of the light source include a laser light source such as an argon ion laser, a YAG laser, a XeCl excimer laser, and a nitrogen laser. Radiation having a wavelength in the range of 190 to 450 nm is preferable.

In general, the exposure dose of radiation is preferably 10 to 10,000 J / m ² .
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.

An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied. The development conditions are preferably 5 to 300 seconds at room temperature.

The post-baking conditions are usually 180 to 280 ° C. and about 10 to 60 minutes.
The film thickness of the pixel thus formed is usually 0.5 to 5.0 μm, preferably 1.0 to 3.0 μm.

  Further, as a second method for producing a color filter, a method of obtaining pixels of each color by an ink jet method disclosed in JP-A-7-318723 and JP-A-2000-310706 can be employed. . In this method, first, a partition having a light shielding function is formed on the surface of the substrate. Next, after the liquid composition of the colored composition of the present invention in which, for example, a red colorant is dispersed in the formed partition wall is discharged by an ink jet apparatus, pre-baking is performed to evaporate the solvent. Next, this coating film is exposed as necessary and then cured by post-baking to form a red pixel pattern.

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

In addition, the partition has not only a light shielding function but also a function for preventing the color composition of each color discharged in the section from being mixed, so that the film is a film compared to the black matrix used in the first method described above. Thick. Therefore, a partition is normally formed using a black radiation sensitive composition.
The substrate used when forming the color filter, the light source of radiation, and the pre-baking and post-baking methods and conditions are the same as in the first method described above. In this way, the film thickness of the pixel formed by the ink jet method is approximately the same as the height of the partition wall.

A protective film is formed on the pixel pattern thus obtained as necessary, and then a transparent conductive film is formed by sputtering. After forming the transparent conductive film, a spacer can be further formed to form a color filter. The spacer is usually formed using a radiation-sensitive composition, but may be a light-shielding spacer (black spacer). In this case, a colored radiation-sensitive composition in which a black colorant is dispersed is used, but the colored composition of the present invention can also be suitably used for forming such a black spacer.
Since the color filter of the present invention thus obtained has extremely high luminance and color purity, it is extremely useful for color liquid crystal surface elements, color imaging tube elements, color sensors, organic EL display elements, electronic paper, and the like.

Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
The color liquid crystal display element of the present invention can have an appropriate structure. For example, the color filter is formed on a substrate different from the driving substrate on which the thin film transistor (TFT) is arranged, and the driving substrate and the substrate on which the color filter is formed are opposed to each other with a liquid crystal layer interposed therebetween. In addition, a substrate in which a color filter is formed on the surface of a driving substrate on which a thin film transistor (TFT) is disposed, and a substrate in which an ITO (indium oxide doped with tin) electrode is formed are a liquid crystal layer. It is also possible to adopt a structure that is opposed to each other. The latter structure has the advantage that the aperture ratio can be remarkably improved, and a bright and high-definition liquid crystal display element can be obtained.

The color liquid crystal display element of the present invention may include a backlight unit using a white LED as a light source in addition to a cold cathode fluorescent lamp (CCFL). As the white LED, for example, a white LED that obtains white light using a red LED, a green LED, and a blue LED having independent spectra, a white LED that obtains white light by mixing colors by combining the red LED, the green LED, and the blue LED, White LED that obtains white light by color mixing by combining blue LED, red LED and green phosphor, White LED that obtains white light by color mixing by combining blue LED, red light emitting phosphor and green light emitting phosphor, Blue LED and YAG system White LED that obtains white light by mixing phosphors, white LED that obtains white light by mixing blue LED, orange light emitting phosphor and green light emitting phosphor, UV LED, red light emitting phosphor, green light emitting phosphor and blue A white LED that obtains white light by mixing colors by combining light emitting phosphors can be exemplified.

The color liquid crystal display element of the present invention includes a TN (twisted nematic) type, a STN (super twisted nematic) type, an IPS (in-plane switching) type, a VA (vertical aligned type) type, and an OCB (optically conjugated type). An appropriate liquid crystal mode can be applied.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of (B) copolymer>
Synthesis example 1
In a flask equipped with a stirrer, 0.6 g of methoxypolyethylene glycol monomethacrylate (PME-200 manufactured by NOF Corporation) (hereinafter referred to as “PME-200”), normal butyl methacrylate (hereinafter referred to as “nBMA”). 12.9 g, methyl methacrylate (hereinafter referred to as “MMA”) 10.5 g, 2,2′-azobisisobutyronitrile (hereinafter referred to as “AIBN”) 323 mg and 833 mg of pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester was dissolved in 30 mL of toluene and subjected to nitrogen bubbling for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 57 ° C., and this temperature was maintained for 34 hours to perform living radical polymerization.
Subsequently, 211 mg of AIBN and 4.1 g of dimethylaminoethyl methacrylate (hereinafter referred to as “DAMA”) were dissolved in 20 mL of toluene, and a solution purged with nitrogen for 30 minutes was added to the above reaction solution. Polymerization was performed. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, nBMA, and MMA was obtained. The obtained copolymer is 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”), MMA 7.0 g, AIBN 295 mg and pyrazole-1-di 726 mg of cyanocarboxylic acid cyano (dimethyl) methyl ester was dissolved in 30 mL of toluene and subjected to nitrogen bubbling for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution obtained by dissolving 352 mg of AIBN and 6.2 g of DAMA in 20 mL of toluene and performing nitrogen replacement for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, nBMA, EHMA, and MMA was obtained. The obtained copolymer is 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 pyrazole-1 -649 mg of dithiocarboxylic acid cyano (dimethyl) methyl ester was dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 62 ° C., and this temperature was maintained for 20 hours to carry out living radical polymerization.
Next, a solution obtained by dissolving 448 mg of AIBN and 6.2 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 62 ° C. for 20 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, nBMA, EHMA, BzMA, and MMA was obtained. The obtained copolymer is 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-dithiocarboxylic acid cyano (dimethyl) methyl ester were added. And dissolved in 30 mL of toluene, and nitrogen bubbling was performed for 30 minutes. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution obtained by dissolving 189 mg of AIBN and 3.6 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer solution which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, nBMA, EHMA, BzMA, and MMA was obtained. Let the obtained copolymer be "copolymer (b-1)."

Comparative Synthesis Example 2
In a flask equipped with a stirrer, 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) methyl ester were dissolved in 30 mL of toluene, Nitrogen bubbling was performed for a minute. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 60 ° C., and this temperature was maintained for 24 hours to perform living radical polymerization.
Next, a solution obtained by dissolving 342 mg of AIBN and 6.6 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 60 ° C. for 24 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from PME-200, nBMA, and MMA was obtained. The obtained copolymer is 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-dithiocarboxylic acid cyano (dimethyl) methyl ester were dissolved in 30 mL of toluene, Nitrogen bubbling was performed for a minute. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 62 ° C., and this temperature was maintained for 20 hours to carry out living radical polymerization.
Next, a solution obtained by dissolving 290 mg of AIBN and 5.6 g of DAMA in 20 mL of toluene and performing nitrogen substitution for 30 minutes was added to the reaction solution, and living radical polymerization was performed at 62 ° C. for 20 hours. Thereafter, the solvent was replaced with propylene glycol monomethyl ether acetate by concentration under reduced pressure, and the nonvolatile content was adjusted to 40% by mass. Thus, the block copolymer which consists of A block which has a repeating unit derived from DAMA, and B block which has a repeating unit derived from nBMA, EHMA, BzMA, and MMA was obtained. The obtained copolymer is referred to as “copolymer (b-3)”.

<Measurement of Mw and Mw / Mn>
Mw and Mn of the (B) copolymer obtained in each of the above synthesis examples were measured by GPC having the following specifications. In Table 1, a measurement result is shown with the copolymerization ratio (mass%) of each monomer in (B) copolymer.
Apparatus: GPC-104 (made by Showa Denko KK).
Column: KD-G, KF-603, KF-602, KF-601 were used in combination.
Mobile phase: DMF.

<Measurement of amine value>
The amine value of the (B) copolymer obtained in each of the above synthesis examples was measured as follows. Table 1 shows the measurement results.
0.5 g of the copolymer solution was precisely weighed to a unit of 1 mg and separated into a glass container. Acetic anhydride / acetic acid = 9/1 (volume ratio) 20 ml was added and dissolved, and left at room temperature for 3 hours. Thereafter, 30 ml of acetic acid was further added, and titration was performed with a 0.1 mol / l perchloric acid / acetic acid solution using a potentiometer AT-510 (manufactured by Kyoto Electronics Industry Co., Ltd.). Similarly, a blank test was performed. (B) The amine value (unit: mg KOH / g) was calculated from the amount of the copolymer and the 0.1 mol / l perchloric acid / acetic acid solution dropped in the blank test.

<Preparation and evaluation of pigment dispersion>
Example 1
As a coloring agent, C.I. I. Pigment green 58 (manufactured by DIC) 7.2 parts by mass and C.I. I. 4.8 parts by mass of Pigment Yellow 150, 10 parts by mass of the copolymer (B-1) solution (nonvolatile component = 40% by mass), and 70 parts by mass of propylene glycol monomethyl ether acetate and 8 parts by mass of propylene glycol monomethyl ether as a solvent. The pigment dispersion (A-1) was prepared by using a bead mill.
The viscosity of the obtained pigment dispersion was measured using an E-type viscometer (manufactured by Tokyo Keiki). The obtained pigment dispersion was filled in a light-shielding glass container and allowed to stand at 23 ° C. for 14 days in a sealed state, and then the viscosity was measured again using an E-type viscometer (manufactured by Tokyo Keiki). And the increase rate of the viscosity after 14 days storage with respect to the viscosity immediately after preparation was calculated, and the case where the increase rate was less than 10% was evaluated as "A", and the case where it was 10% or more was evaluated as "B". The evaluation results are shown in Table 2.

Examples 2-4 and Comparative Examples 1-5
In Preparation Example 1, the colorant dispersions (A-2) to (A-) were prepared in the same manner as in Example 1 except that the amounts of the colorant, (B) copolymer and solvent were changed as shown in Table 2. 9) was prepared and evaluated. The evaluation results are shown in Table 2.
In Table 2, “G58” means C.I. I. Pigment Green 58, “Y150” is C.I. I. Pigment Yellow 150 and “Y179” are organic dyes such as C.I. I. Solvent Yellow 179, “PGMEA” is propylene glycol monomethyl ether acetate, “PGME” is propylene glycol monomethyl ether, “BYK6919” is a commercially available dispersant BYK-LPN6919 (manufactured by BYK Corporation) Means each. BYK-LPN6919 is a dispersant solution containing a block copolymer having a repeating unit (1) and a repeating unit (2) and an amine value of 120 mgKOH / g (in terms of non-volatile content). 60% by mass.

<Synthesis of binder resin>
Synthesis example 4
In a flask equipped with a condenser and a stirrer, BzMA 25.0 g, nBMA 20.0 g, hydroxyethyl methacrylate 15.0 g, styrene 20.0 g and methacrylic acid 20.0 g were dissolved in propylene glycol monomethyl ether acetate 200 g, and AIBN 3.0 g And 5.0 g of 2,4-diphenyl-4-methyl-1-pentene were added, and then purged with nitrogen for 15 minutes. After the nitrogen purge, the reaction solution was heated to 80 ° C. with stirring and nitrogen bubbling and polymerized for 5 hours to obtain a solution containing 33% by mass of the binder resin (E-1). This binder resin (E-1) has a polystyrene-equivalent weight average molecular weight measured by GPC (elution solvent: tetrahydrofuran) = 10,500 and a polystyrene-equivalent weight average molecular weight and number average measured by GPC (elution solvent: tetrahydrofuran). Ratio to molecular weight = 2.5.

<Preparation and evaluation of colored radiation-sensitive composition>
Preparation of colored radiation-sensitive composition Example 5
100 parts by weight of pigment dispersion (A-1), 33.5 parts by weight of binder resin (E-1) solution as binder resin, and M-402 manufactured by Toagosei Co., Ltd. as a crosslinking agent (mainly dipentaerythritol hexaacrylate) 9.7 parts by mass, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name: Irgacure 369, manufactured by Ciba Specialty Chemicals) as a photopolymerization initiator 4 .3 parts by mass and ethyl 3-ethoxypropionate as a solvent were mixed to prepare a colored radiation-sensitive composition having a solid content concentration of 20% by mass.

Evaluation of removal time After the obtained colored radiation-sensitive composition was applied on a glass substrate using a spin coater, it was pre-baked on a hot plate at 100C for 2 minutes to obtain a film thickness of 2. A 5 μm coating film was formed. Next, after cooling the substrate to room temperature, a high-pressure mercury lamp was used for the coating film on the substrate, and radiation containing each wavelength of 365 nm, 405 nm, and 436 nm was applied to each coating film through a photomask at 1,000 J It exposed with an exposure amount of / ^{m 2.} Thereafter, shower development was performed by discharging a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. onto the coating film on the substrate. Under the present circumstances, the time (missing time) until the coating film of an unexposed part peeled completely was measured. Then, “A” when the missing time is less than 60 seconds, “B” when 60 seconds or more and less than 120 seconds, “C” when 120 seconds or more and less than 180 seconds, and “D” when 180 seconds or more. As evaluated. The shorter this time is, the faster the development speed is, and there is an advantage that the tact time for manufacturing the color filter can be shortened. The evaluation results are shown in Table 3.

Evaluation of chromaticity characteristics The obtained colored radiation-sensitive composition was applied onto a glass substrate using a spin coater, and then pre-baked on a hot plate at 100 ° C. for 2 minutes to obtain three sheets having different film thicknesses. A coating film was formed. Next, after these substrates are cooled to room temperature, a high-pressure mercury lamp is used for the coating film on the substrate, and radiation including each wavelength of 365 nm, 405 nm, and 436 nm is applied to each coating film without passing through a photomask. The exposure was performed at an exposure amount of 1,000 J / m ² . Thereafter, 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 chromaticity coordinate value (x, y) and the stimulus value in the CIE color system with a C light source and a 2-degree visual field for the three cured films obtained. (Y) was measured. 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 6-8 and Comparative Examples 5-9
In Example 5, the colored radiation composition was prepared and evaluated in the same manner as in Example 5 except that the type of the pigment dispersion was changed as shown in Table 3. The evaluation results are shown in Table 3.

Claims (8)

(A) Colorant containing a pigment, (B) A block having 60% by mass or more of a repeating unit (1) represented by the following formula (1), and a repeating unit (2) represented by the following formula (2) A colored composition comprising a block copolymer having a B block having an amine value of 50 mgKOH / g or more and less than 80 mgKOH / g, and (C) a solvent.

(In 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 have a hydrogen atom or a substituent. A chain or cyclic hydrocarbon group that may be present, and R ² and R ³ may be bonded to each other to form a cyclic structure.)

(In Formula (2), R ⁴ independently represents an alkylene group having 2 to 4 carbon atoms, R ⁵ represents an alkyl group having 1 to 6 carbon atoms, and R ⁶ represents a hydrogen atom or a methyl group. N represents an integer of 1 to 150.) In the formula (1), X represents a —COO—R ⁸ — (*) group (where R ⁸ represents a methylene group, an alkylene group having 2 to 10 carbon atoms, or an alkyleneoxyalkylene group having 2 to 10 carbon atoms). The coloring composition according to claim 1, wherein (*) represents a bond that binds to N. The coloring composition of Claim 1 or 2 whose ratio Mw / Mn of the weight average molecular weight Mw of the said (B) block copolymer and number average molecular weight Mn is 1.0-1.8.   The coloring composition according to any one of claims 1 to 3, further comprising (D) a crosslinking agent and (E) a binder resin.   The coloring composition of any one of Claims 1-4 which further contains dye as a coloring agent.   (F) The coloring composition of Claim 4 or 5 which further contains a photoinitiator.   The color filter provided with the colored layer formed using the coloring composition of any one of Claims 4-6.   A color liquid crystal display device comprising the color filter according to claim 7.