JP2018066778A - Coloring composition for color filter and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring composition for color filter excellent not only in dispersibility, storage stability and heat resistance but also in high definition.SOLUTION: A coloring composition for color filter contains a coloring agent, a dispersant (X), a binder resin and an organic solvent, where the dispersant (X) is a resin (S1) being a reaction product of a hydroxyl group of a polymer (A) having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride, and the polymer (S1) having the hydroxyl group has a constitutional unit derived a monomer (c1) represented by general formula (1), or is a resin (S2) being a polymer obtained by polymerization of an ethylenically unsaturated monomer containing the monomer (c1) represented by general formula (1) in the presence of a reaction product of a hydroxyl group of a compound (B) having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride.SELECTED DRAWING: None

Description

  TECHNICAL FIELD The present invention relates to a color filter coloring composition used for forming a filter segment constituting a color filter used in a color liquid crystal display device and a solid-state imaging device, and a color filter obtained using the color filter coloring composition. .

For the formation of the filter segment of the color filter, a color composition in which a colorant containing a pigment is dispersed in a dispersant, a resin, a monomer, an organic solvent, or the like is generally used to obtain a uniform coating film. Requires low viscosity and high fluidity. Therefore, many proposals have been made for pigment dispersion stabilization in a colored composition. Patent Documents 1 to 4 are excellent in dispersibility and storage stability by using a polyester dispersant having a specific structure, and A coloring composition for a color filter that achieves a high contrast ratio and heat resistance is disclosed. However, in recent years, the demand for high definition (high resolution) has been increasing, and the above-described coloring composition has not been able to meet these demands.
Patent Documents 5 to 6 disclose colored compositions having excellent heat resistance by using a polymer dispersant having a structural unit derived from a monomer that forms a specific ring structure. However, since the structure of the dispersant is not controlled, the obtained colored composition cannot achieve sufficient dispersibility (such as viscosity stability) in a field where high dispersibility is particularly required.
That is, the conventional coloring composition cannot satisfy all of the dispersant, the storage stability, the contrast ratio, the heat resistance, and the high definition (high resolution).

International Publication No. 2008/007776 JP 2008-298967 A JP 2009-155406 A Japanese Patent Application Laid-Open No. 2010-223988 JP 2010-168539 A JP 2011-45862 A

  An object of the present invention is to provide a color filter coloring composition and a color filter that are not only excellent in dispersibility, storage stability, and heat resistance, but also excellent in high definition (high resolution).

That is, the present invention is a color filter coloring composition comprising a colorant, a dispersant (X), a binder resin and an organic solvent, wherein the dispersant (X) is the following (S1) or (S2). A colored composition for a color filter.
(S1) A polymer which is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, and having the hydroxyl group (S1) has a structural unit derived from the monomer (c1) represented by the following general formula (1).
(S2) In the presence of the reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, the compound is represented by the following general formula (1). A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer containing the monomer (c1) to be produced.

General formula (1):

(In the general formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

  The present invention further relates to the above color filter coloring composition containing at least one selected from a photopolymerizable monomer and a photopolymerization initiator.

  Furthermore, this invention relates to the color filter which comprises the filter segment formed from the said coloring composition for color filters.

  With the color filter coloring composition of the present invention, it is possible to provide a color filter coloring composition that suppresses aggregation of pigments and is excellent in dispersion stability, and is also excellent in heat resistance and resolution.

<Coloring composition for color filter>
The coloring composition for a color filter of the present invention is a coloring composition for a color filter comprising a coloring agent, a dispersing agent (X), a binder resin and an organic solvent, and the dispersing agent (X) is the following ( It is the most characteristic that it is a coloring composition for color filters characterized by containing the resin of S1) or (S2).
(S1) A polymer which is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, and having the hydroxyl group (S1) has a structural unit derived from the monomer (c1) represented by the following general formula (1).
(S2) In the presence of the reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, the compound is represented by the following general formula (1). A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer containing the monomer (c1) to be produced.

General formula (1):

(In the general formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

  In the dispersant (X) of the present invention, a polycarboxylic acid moiety derived from a tricarboxylic anhydride and / or a tetracarboxylic dianhydride acts as a pigment adsorbing group. In addition, the polymer-derived polymer chain obtained by polymerizing an ethylenically unsaturated monomer acts as a pigment carrier affinity group, thereby suppressing pigment aggregation and excellent dispersion stability. Furthermore, the general formula (1 ) Represented by the monomer (c1), it is possible to exhibit aptitude excellent in heat resistance and high definition (high resolution).

<Dispersant (X)>
The resins (S1) and (S2) contained in the dispersant (X) of the present invention are mainly produced by two reactions, ie, an ethylenically unsaturated double bond polymerization reaction and an esterification reaction between a hydroxyl group and an acid anhydride group. Since it has a complex structure to be obtained and cannot be expressed by a general formula (structure) or is not practical, it is described by a manufacturing method. The pigment carrier in the present application represents a binder resin and / or a photopolymerizable monomer obtained by removing a pigment component and a dispersant from a solid content.

As described above, the dispersant (X) contains the following resin (S1) or (S2).
(S1) A polymer which is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, and having the hydroxyl group (S1) has a structural unit derived from the monomer (c1) represented by the following general formula (1).
(S2) In the presence of the reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, the compound is represented by the following general formula (1). A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer containing the monomer (c1) to be produced.

[Resin (S1)]
Resin (S1) can be manufactured by well-known methods, such as WO2008 / 007776, Unexamined-Japanese-Patent No. 2008-029901. The polymer (A) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, in the presence of the compound (B) having a hydroxyl group, the monomer represented by the general formula (1) ( It can be obtained as a polymer obtained by polymerizing the ethylenically unsaturated monomer (C) containing c1). The compound (B) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule as described later. Since the terminal hydroxyl group is preferably plural, among them, the compound (b1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

  That is, a polymer having two hydroxyl groups at one end, which is a more preferable example, includes the monomer (c1) in the presence of the compound (b1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (a1) obtained by polymerizing the ethylenically unsaturated monomer (C). The hydroxyl group of the polymer (A) having a hydroxyl group reacts with a tricarboxylic anhydride and / or an acid anhydride group of a tetracarboxylic dianhydride to form an ester bond, while the anhydrous ring is opened to give a carboxylic acid. Produce.

[Resin (S2)]
The resin (S2) can be produced by a known method such as JP 2010-185934 A, for example, a hydroxyl group of a compound (B) having a hydroxyl group, a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. It is obtained by polymerizing an ethylenically unsaturated monomer (C) containing the monomer (c1) represented by the general formula (1) in the presence of a reaction product with an acid anhydride group of the product. . In particular, in the presence of a reaction product of the hydroxyl group of the compound (b1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. And a polymer obtained by polymerizing the ethylenically unsaturated monomer (C) containing the monomer (c1).

  In (S1) and (S2), the introduction of the polymer site obtained by polymerizing the ethylenically unsaturated monomer (C) including the acidic group-containing ethylenically unsaturated monomer (c1) is performed first or later. That is the difference. The molecular weight may vary slightly depending on various conditions, but if the raw materials and reaction conditions are the same, the same can be theoretically produced.

[Synthesis of Resin (S1) (S2)]
(Production of polymer (A) having a hydroxyl group)
As described above, the polymer (A) having a hydroxyl group in the resin (S1) comprises an ethylenically unsaturated monomer (C) containing the monomer (c1) in the presence of the compound (B) having a hydroxyl group. It can be obtained as a polymerized polymer.

(Compound having a hydroxyl group (B))
The compound (B) having a hydroxyl group in the present invention preferably contains a compound having a hydroxyl group and a thiol group in the molecule, and the compound having a hydroxyl group and a thiol group in the molecule has a hydroxyl group and a thiol group. , Not limited. As such a compound, for example, in addition to a compound having two hydroxyl groups and one thiol group in the molecule described later,
Compounds having one hydroxyl group and one thiol group in the molecule, such as mercaptoethanol;
Compounds having one hydroxyl group and two thiol groups in the molecule, such as 1,2-dimercapto-3-propanol and 1,3-dimercapto-2-propanol;
Compounds having one hydroxyl group and three or more thiol groups in the molecule, such as pentaerythritol tris (3-mercaptoacetate) and dipentaerythritol pentakis (3-mercaptopropionate);
Compounds having two hydroxyl groups and two thiol groups in the molecule such as 1,2-dimercapto-1,2-ethanediol;
Compounds having three or more hydroxyl groups and two thiol groups in the molecule, such as dimercaptodipentaerythritol;
Compounds having two or more hydroxyl groups and three or more thiol groups in the molecule such as trimercaptodipentaerythritol;
And compounds having three or more hydroxyl groups and one thiol group in the molecule such as 1-mercapto-1,2,2′-ethanetriol. Especially, the compound (b1) which has two hydroxyl groups and one thiol group in a molecule | numerator is preferable.

(Compound (b1) having two hydroxyl groups and one thiol group in the molecule)
Examples of the compound having two hydroxyl groups and one thiol group in the molecule used in the present invention include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto- 1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propane Examples include diol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol. Of these, 3-mercapto-1,2-propanediol is preferred.

The compound (B) having a hydroxyl group may contain other than the compound having a hydroxyl group and a thiol group in the molecule. For example, polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, or hexanetriol;
Polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol;
Modified polyether polyols obtained by ring-opening polymerization of the polyhydric alcohols with (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, or allyl glycidyl ether;
Polyester polyols obtained by co-condensation with one or more of the above polyhydric alcohols and polycarboxylic acids, wherein the polycarboxylic acids are succinic acid, adipic acid, or 2,5,7-naphthalene Polyols such as tricarboxylic acid;
Lactone polyester polyols obtained by polycondensation reaction of one or more of the above polyhydric alcohols with lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone;
Lactone modified polyester polyols obtained by polycondensation reaction of the above polyhydric alcohols, polycarboxylic acids and various lactones;
Various epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids, polyesters Epoxy-modified polyester polyols obtained by combining one or more of the polyols during synthesis;
Examples include polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound or hydroxyl group-containing silicon resin. .

  The compound having a hydroxyl group and a thiol group is preferably subjected to bulk polymerization or solution polymerization using 1 to 10% by weight based on the total monomer weight of the ethylenically unsaturated monomer (C) described later. More preferably, it is 2 to 9% by weight, and further preferably 3 to 8% by weight. By setting it as the above range, a good balance as an affinity site for the pigment carrier and the solvent can be maintained, and both dispersibility and pigment aggregation suppression can be achieved.

(Ethylenically unsaturated monomer (C))
The ethylenically unsaturated monomer (C) of the present invention includes a monomer (c1) represented by the following general formula (1).

(Monomer (c1) represented by general formula (1))
General formula (1):

(In the general formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)

  For example, the monomer (c1) represented by the general formula (1) and the other copolymerizable ethylenically unsaturated monomer (c2) have two hydroxyl groups and one thiol group in the molecule. When the copolymer (a1) having two hydroxyl groups at one end is obtained by copolymerization in the presence of the compound (b1) having a monomer, the monomer (c1) represented by the general formula (1) simultaneously with the polymerization The cyclization reaction proceeds to form a tetrahydrofuran ring structure. It is considered that the formation of a tetrahydrofuran ring structure in the resin suppresses the movement of molecules, thereby making the resin rigid and improving heat resistance and fineness (resolution).

  The monomer (c1) represented by the general formula (1) is preferably 0.5% by weight to 100% by weight, more preferably 2% by weight based on the weight of the total ethylenically unsaturated monomer (C). % To 50% by weight, more preferably 5 to 50% by weight. When it is 20% by weight or more, the heat resistance and resolution are remarkably improved.

  Examples of the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent in R in the general formula (1) include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t- Linear or branched alkyl groups such as butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl Alicyclic groups such as adamantyl and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl; Can be mentioned. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like and a hydrocarbon group which is difficult to be removed by heat are preferable from the viewpoint of heat resistance.

Specific examples of the monomer (c1) represented by the general formula (1) include, for example, α-allyloxymethyl acrylic acid, methyl α-allyloxymethyl acrylate, ethyl α-allyloxymethyl acrylate, α -N-propyl allyloxymethyl acrylate, i-propyl α-allyloxymethyl acrylate, n-butyl α-allyloxymethyl acrylate, s-butyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid t-butyl, α-allyloxymethyl acrylate n-amyl, α-allyloxymethyl acrylate s-amyl, α-allyloxymethyl acrylate t-amyl, α-allyloxymethyl acrylate neopentyl, α-allyloxy N-hexyl methyl acrylate, s-hexyl α-allyloxymethyl acrylate, α-a N-Heptyl ruoxymethyl acrylate, n-octyl α-allyloxymethyl acrylate, s-octyl α-allyloxymethyl acrylate, t-octyl α-allyloxymethyl acrylate, α-allyloxymethyl acrylic acid 2 -Ethylhexyl, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate, α-allyloxymethyl acrylate Tridecyl allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-allyloxyme Chain saturated hydrocarbon group-containing α- such as stearyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate (Allyloxymethyl) acrylate;
α- (allyloxymethyl) acrylates containing hydroxy-substituted chain saturated hydrocarbon groups such as hydroxyethyl α-allyloxymethyl acrylate, hydroxypropyl α-allyloxymethyl acrylate, hydroxybutyl α-allyloxymethyl acrylate;
Fluoroethyl α-allyloxymethyl acrylate, difluoroethyl α-allyloxymethyl acrylate, chloroethyl α-allyloxymethyl acrylate, dichloroethyl α-allyloxymethyl acrylate, bromoethyl α-allyloxymethyl acrylate, α- Halogen-substituted chain saturated hydrocarbon group-containing α- (allyloxymethyl) acrylate such as dibromoethyl allyloxymethyl acrylate;
α-allyloxymethyl acrylate cyclopentyl, α-allyloxymethyl acrylate cyclopentyl methyl, α-allyloxymethyl acrylate cyclohexyl, α-allyloxymethyl acrylate acrylate methyl, α-allyloxymethyl acrylate 4-methylcyclohexyl, α-allyloxymethyl acrylate 4-t-butylcyclohexyl, α-allyloxymethyl acrylate tricyclodecanyl, α-allyloxymethyl acrylate isobornyl, α-allyloxymethyl acrylate adamantyl, α-allyloxymethyl acryl Alicyclic hydrocarbon group-containing α- (allyloxymethyl) acrylates such as dicyclopentanyl acid and dicyclopentenyl α-allyloxymethyl acrylate;
α-Allyloxymethyl acrylate phenyl, α-allyloxymethyl acrylate methylphenyl, α-allyloxymethyl acrylate dimethylphenyl, α-allyloxymethyl acrylate trimethylphenyl, α-allyloxymethyl acrylate 4-t- Butylphenyl, α-allyloxymethyl acrylate, α-allyloxymethyl acrylate diphenylmethyl, α-allyloxymethyl acrylate diphenylethyl, α-allyloxymethyl acrylate triphenylmethyl, α-allyloxymethyl acrylate Aromatic hydrocarbon group-containing α- (allyloxymethyl) acrylates such as naphthyl and α-allyloxymethyl acrylate anthranyl;
methoxyethyl α-allyloxymethyl acrylate, methoxyethoxyethyl α-allyloxymethyl acrylate, methoxyethoxyethoxyethyl α-allyloxymethyl acrylate, 3-methoxybutyl α-allyloxymethyl acrylate, α-allyloxymethyl Chain ether group-based saturated hydrocarbon group-containing α- such as ethoxyethyl acrylate, ethoxyethoxyethyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, phenoxyethoxyethyl α-allyloxymethyl acrylate (Allyloxymethyl) acrylate;
α-allyloxymethyl acrylate cyclopentoxyethyl, α-allyloxymethyl acrylate cyclohexyloxyethyl, α-allyloxymethyl acrylate cyclopentoxyethoxyethyl, α-allyloxymethyl acrylate cyclohexyloxyethoxyethyl, α- Α- (allyloxymethyl) acrylate having both an alicyclic hydrocarbon group such as dicyclopentenyloxyethyl allyloxymethyl acrylate and a chain ether group;
α- (allyloxymethyl) acrylate having both an aromatic hydrocarbon group and a chain ether group such as phenoxyethyl α-allyloxymethyl acrylate and phenoxyethoxyethyl α-allyloxymethyl acrylate;
α-allyloxymethyl acrylate glycidyl, α-allyloxymethyl acrylate β-methyl glycidyl, α-allyloxymethyl acrylate β-ethyl glycidyl, α-allyloxymethyl acrylate 3,4-epoxycyclohexylmethyl, α- Allyloxymethyl acrylate 2-oxetanemethyl, α-allyloxymethyl acrylate 3-methyl-3-oxetanemethyl, α-allyloxymethyl acrylate 3-ethyl-3-oxetanemethyl, α-allyloxymethyl acrylate tetrahydrofura Cyclic esters such as Nyl, α-allyloxymethyl acrylate tetrahydrofurfuryl, α-allyloxymethyl acrylate tetrahydropyranyl, α-allyloxymethyl acrylate dioxazolanyl, α-allyloxymethyl acrylate dioxanyl, etc. -Ter group saturated hydrocarbon group-containing α- (allyloxymethyl) acrylate; and the like.
These monomers (c1) represented by the general formula (1) can be used singly or as a mixture of two or more at any ratio as required.

  Among these, chain saturated hydrocarbon group-containing α- (allyloxymethyl) acrylate is preferable, and α-allyloxymethylacrylic acid and α-allyloxymethylacrylate methyl are particularly preferable.

(Other monomer (c2))
Examples of the ethylenically unsaturated monomer (c2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) ) Acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, isomyristyl (meth) acrylate, stearyl (meth) acrylate, or straight chain such as isostearyl (meth) acrylate The branched alkyl (meth) acrylates;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) (Meth) acrylates having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
N-substituted type (meta) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine ) Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile;
Methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol polypropylene glycol (meth) acrylate, ethyl vinyl ether, n-propyl vinyl ether Ethylenically unsaturated monomers having an ether group, such as vinyl ethers such as isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; or a mixture thereof.

  In the polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (C). As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

  In the case of solution polymerization, the polymerization solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like are used, but are not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more. After completion of the reaction, the solvent used in the polymerization reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

  The reaction temperature is preferably 40 to 150 ° C, more preferably 50 to 110 ° C. The polymerization reaction in the resin (S2) is the same as described above.

  The weight average molecular weight of the polymer (A) is preferably 1,000 to 15,000, more preferably 2000 to 13,000, and still more preferably 3,000 to 12,000. This site becomes an affinity site for the pigment carrier and the solvent. The polymer (A) can be easily adjusted in molecular weight within the above range, and the polymer (A) within the above range also has good affinity for the solvent.

(Reaction of polymer (A) having acid group with acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride (polyester synthesis))
(Tricarboxylic anhydride)
Examples of the tricarboxylic acid anhydride include an aliphatic tricarboxylic acid anhydride or an aromatic tricarboxylic acid anhydride. Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned. Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, or 3,4,4'-biphenylsulfo Tricarboxylic anhydride and the like.
In the present invention, it is preferable to use an aromatic tricarboxylic acid anhydride from the viewpoint of adsorptivity to the pigment.

(Tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydride used in the present invention include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3- Dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 3 , 5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3 -Aliphatic tetracarbo such as cyclohexene-1,2-dicarboxylic dianhydride or bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Acid dianhydride, or
Pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride Anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4 '-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarboxyl) Phenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (Triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, Alternatively, aromatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride may be used.
In the present invention, it is preferable to use an aromatic tetracarboxylic dianhydride from the viewpoint of adsorptivity to the pigment.

  The tricarboxylic acid anhydride and tetracarboxylic acid dianhydride in the resins (S1) and (S2) are preferably tetracarboxylic acid dianhydrides and more preferably aromatic tetracarboxylic acid dianhydrides from the viewpoint of adsorptivity to the pigment. . Of these, pyromellitic dianhydride is preferable. Aromatic carboxylic acids have higher pigment adsorption capacity than aliphatic carboxylic acids. The tricarboxylic acid anhydride and tetracarboxylic dianhydride used in the present invention are not limited to the compounds exemplified above, and may have any structure as long as they have two carboxylic acid anhydride groups. These may be used alone or in combination.

(Reaction solvent)
Polyester synthesis can be produced using only the raw materials listed so far, but it is preferable to use a solvent in order to avoid problems such as high viscosity and non-uniform reaction. There is no limitation in particular as a solvent used, A well-known thing can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile and the like can be mentioned. After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent for the next step or as part of a product.

(Reaction catalyst)
As a catalyst used for polyester synthesis, a known catalyst can be used. The catalyst is preferably a tertiary amine compound such as triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, 5-diazabicyclo- [4.3.0] -5-nonene and the like.

(Reaction temperature)
The reaction temperature for polyester synthesis is 50 ° C to 180 ° C, preferably 80 ° C to 140 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the carboxyl group and the hydroxyl group may undergo an esterification reaction, resulting in a decrease in acid value or gelation. Ideally, the reaction is stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but when the acid value of the polyester is in the range of 5 to 200, or the hydroxyl value is 20 to 200. The reaction may be stopped when entering the range.

(Molecular weight)
The weight average molecular weight of the resins (S1) and (S2) is preferably 2,000 to 35,000, more preferably 4,000 to 30,000, and still more preferably 6,000 to 20,000. If the weight average molecular weight is less than 2000, the stability of the pigment composition may be reduced, and if it exceeds 35,000, the interaction between the resins becomes strong and the viscosity of the color composition for color filter may increase. is there.

(Acid value)
As for the acid value of resin (S1) and (S2), 5-200 are preferable. More preferably, it is 10-150, More preferably, it is 20-100. If the acid value is less than 5, the pigment adsorbing ability may be reduced and the pigment dispersibility may be problematic, and if it exceeds 200, the interaction between the resins may become strong and the viscosity of the pigment dispersion composition may be increased.

  The reaction between the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride in the resin (S2) is the same as described above.

  The content of the dispersant (X) in the color filter coloring composition is preferably 0.01 to 100% by weight, more preferably 0.01 to 60% by weight, still more preferably 5 based on the weight of the pigment. -40% by weight. When the content of the dispersant (X) is less than 0.01% by weight, the dispersion effect is insufficient, and when it exceeds 100% by weight, the dispersibility may be deteriorated.

<Colorant>
The colorant that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments and dyes. The following are typical pigments and dyes that can be used in the present invention.

  Examples of red pigments that can be used in the present invention include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208,209,210,216,220,221,224,226,242,246,254,255,264,270,272,273,274,276,277,278,279,280,281,2 2,283,284,285,286,287 or diketopyrrolopyrrole pigment described in JP-T 2011-523433 discloses the like, but not particularly limited thereto. Also, red dyes such as xanthene, azo, disazo, and anthraquinone can be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  Examples of the orange pigment that can be used in the present invention include C.I. I. Pigment Orange 38, 43, 71, 73, etc. are mentioned, but it is not particularly limited to these.

  Yellow dyes include azo dyes, azo metal complex dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, quinoline dyes , Naphthoquinone dyes and oxazine dyes.

  Therefore, specific examples of yellow dyes include C.I. I. Acid Yellow 2,3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199 Etc.

In addition, C.I. I. Direct yellow 1, 2, 4, 5, 12, 13, 15, 20, 2
4, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like.

In addition, C.I. I. Basic yellow 1, 2, 5, 11, 13, 14, 15, 19,
21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like.

In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13
, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186 187, 188, 190, 191, 192, 194, 195 and the like.

  In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

  As the yellow pigment, organic or inorganic pigments can be used alone or in admixture of two or more, and pigments having high color development properties and high heat resistance, particularly pigments having high heat decomposition resistance are preferred. Organic pigments are used. As the organic pigment, commercially available ones can be used, and natural pigments and inorganic pigments can be used in combination according to the desired hue of the filter segment.

Below, the specific example of the yellow organic pigment which can be used for the said coloring composition is shown. Examples of yellow pigments include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 1
5, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 19 It can be used yellow pigments such as 199,213,214. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150, and 185 are preferable.
These yellow pigments can be used alone or in combination of two or more depending on the desired color characteristics.

  Examples of the green pigment that can be used in the present invention include C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63, and the like are exemplified, but not limited thereto.

  Examples of blue pigments that can be used in the present invention include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Examples include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but are not limited thereto.

  The preferred colorant content in all the non-volatile components of the colored composition according to the present invention is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of sufficient color reproducibility and stability. Most preferably, it is 20 to 80% by weight.

<Dye derivative>
The coloring composition of the present invention can optionally contain various conventionally known pigment derivatives. Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP2003-167112, JP2004-091497, JP2004-307854, JP2007-156395, JP2008-094773, JP2008-094986 JP, 2009-095007, JP 2008-19591 JP, it may be used those described in Japanese Patent No. 4585781 Patent Publication.

  Examples of the pigment derivative having a basic group of the present invention are shown below, but are not limited thereto.

Compound 1:

Compound 2:

Compound 3:

Compound 4:

Compound 5:

(Miniaturization of pigment)
When the colorant used in the coloring composition of the present invention is a pigment, it can be refined by a salt milling process or the like. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

<Binder resin>
The binder resin used in the coloring composition of the present invention is one that disperses, dyes, or penetrates a colorant, and includes a thermoplastic resin. Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali development type colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. As a result, the colorant is fixed, heat resistance is improved, and fading (deterioration of spectral characteristics) due to heat of the colorant can be suppressed. In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

  The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 7,000 to 80,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the binder resin is used as a photosensitive coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, and it may be difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The binder resin is preferably used in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

  Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, the side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group to There is a way to introduce.

  Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4 epoxybutyl (meth) acrylate, And 3,4 epoxy cyclohexyl (meth) acrylates, and these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an unsaturated ethylenic monomer having a hydroxyl group is used, and a monomer of an unsaturated monobasic acid having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

  Examples of unsaturated ethylenic monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with the thermoplastic resin which is a binder resin. Examples of the thermosetting compound include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, phenol compounds and / or resins, but the present invention is not limited thereto.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated in the coloring agent carrier, and is applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl- 1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butyl Benzene, n-propyl acetate, o-xylene, o-diethylbenzene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol Monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl Ether, ethylene glycol Dimonomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene Glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl Chill ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol Monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, Acetic acid Propyl, and dibasic acid esters. These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the coloring agent, the penetrability, and the coating property of the coloring composition are good, so that ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a desired colored film having a uniform thickness. Is preferred.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin. Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate and other acrylic acid esters and methacrylic acid esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, ru (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight based on the total weight of the colorant (100 parts by weight), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used. These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, biimidazole derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, or 4,4′-tetra (t-butylperoxyca Rubonyl) benzophenone, 4,4′-diethylaminobenzophenone and the like. These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercap -s- triazine, 2- (N, N- dibutylamino) -4,6-dimercapto -s- triazine. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

  The content of the polyfunctional thiol is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight based on the weight (100% by weight) of the total solid content of the color filter coloring composition. . When the polyfunctional thiol content is less than 0.1% by weight, the effect of adding the polyfunctional thiol is insufficient, and when it exceeds 30% by weight, the sensitivity is too high and the resolution may be lowered.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant increases the transmittance of the coating film in order to prevent the photopolymerization initiator and thermosetting compound contained in the colored composition from being oxidized and yellowing due to a thermal process during thermal curing or ITO annealing. be able to. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants. These antioxidants can be used singly or in combination of two or more at any ratio as required.

  When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition (100% by weight), brightness and sensitivity are more preferable.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen. Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Of these, compounds having two or more phenolic hydroxyl groups in one molecule and amine curing agents are preferred. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention comprises a coloring agent in a coloring agent carrier such as a binder resin and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, It can be produced by finely dispersing (colorant dispersion) using various dispersing means such as a vertical sand mill, an annular bead mill, or an attritor. At this time, two or more kinds of colorants or the like may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. When the solubility of the colorant such as a dye is high, specifically, it is highly soluble in the solvent to be used, and if it is dissolved and no foreign matter is confirmed by stirring, it is finely dispersed as described above. There is no need.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Dispersing aid>
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good. The dye derivative is as described above.

<Resin type dispersant>
The resin-type dispersant has a colorant-affinity part that has the property of adsorbing to the additive colorant and a part that is compatible with the colorant carrier, and is adsorbed to the additive colorant and dispersed in the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Among the above-mentioned dispersants, a polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion is lowered and a high contrast is exhibited with a small addition amount, and a nitrogen atom-containing graft copolymer or side chain is preferable. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having functional groups containing tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, and the like are preferred. The resin type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the colorant, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or LACTIMON, LACTIMON-WS or BYKUMEN et al., SOLPERSE-3000, 9000, manufactured by Lubrizol Japan 3000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4 00,5010,5065,5066,5070,7500,7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

<Surfactant>
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When the surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion may be affected by an excessive dispersant. .

<Removal of coarse particles>
The colored composition of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention is provided with a filter segment or a black matrix formed from the coloring composition of the present invention on a transparent substrate, and a general color filter includes at least one red filter segment and at least one red filter segment. It comprises a green filter segment and at least one blue filter segment, or comprises at least one magenta filter segment, at least one cyan filter segment and at least one yellow filter segment.

  As the transparent substrate, glass plates such as soda lime glass, low alkali borosilicate glass and non-alkali alumino borosilicate glass, and resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate are used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

  The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

  Formation of each color filter segment and black matrix by photolithography is performed by the following method. That is, the photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material has a dry film thickness of 0. 0 on a transparent substrate by a coating method such as spray coating, spin coating, slit coating or roll coating. It apply | coats so that it may become 2-10 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film.

  Thereafter, the filter segment and the black matrix can be formed by immersing in a solvent or an alkali developer or spraying the developer by spraying or the like to remove the uncured portion and forming a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment and the black matrix formed by development, heating can be performed as necessary. According to the photolithography method, it is possible to form a filter segment and a black matrix with higher accuracy than the printing method.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. 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.

  In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. After forming, UV exposure can also be performed.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. “Parts” and “%” mean “parts by mass” and “% by mass”. PGMAc represents propylene glycol monomethyl ether acetate.

<Manufacture of finer pigments>
(Production of refined pigment (G-1))
120 parts of halogenated copper phthalocyanine-based green pigment PG36 (“Lionol Green 6YK” manufactured by Toyocolor Co., Ltd.), 1500 parts of crushed salt and 250 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. Kneaded for 15 hours. The mixture was poured into 5000 parts of warm water, stirred at a high-speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts refined pigment (G-1).

(Production of refined pigment (Y-1))
100 parts of quinophthalone yellow pigment PY138 (“Pariol Yellow K0961HD” manufactured by BASF), 3 parts of a pigment derivative (the above-mentioned compound 1), 800 parts of crushed salt, and 180 parts of diethylene glycol are made of 1 gallon kneader made of stainless steel (Inoue Seisakusho). And kneaded at 70 ° C. for 4 hours. The mixture was added to 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts refined pigment (Y-1).

(Production of refined pigment (Y-2))
500 parts of a metal complex yellow pigment PY150 (“E4GN” manufactured by LANXESS), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. Next, the kneaded product is put into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of micronized pigment (Y-2).

(Production of refined pigment (R-1))
100 parts of diketopyrrolopyrrole red pigment PR254 ("Irgaphore Red B-CF" manufactured by BASF), 10 parts of a pigment derivative (previously compound 2), 1000 parts of crushed salt, and 120 parts of diethylene glycol, 1 gallon made of stainless steel A kneader (manufactured by Inoue Seisakusho) was charged and kneaded at 70 ° C. for 8 hours. The mixture was poured into 2000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts refined pigment (R-1).

(Production of refined pigment (R-2))
100 parts of anthraquinone red pigment PR177 (“chromophthaled red A2B” manufactured by BASF), 5 parts of a pigment derivative (the above-mentioned compound 3), 800 parts of crushed salt and 180 parts of diethylene glycol are made of 1 gallon kneader made of stainless steel (manufactured by Inoue Seisakusho). And kneaded at 70 ° C. for 5 hours. The mixture was poured into 4000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 100 parts refined pigment (R-2).

(Production of refined pigment (B-1))
100 parts of copper phthalocyanine-based blue pigment PB15: 6 (“Lionol Blue ES” manufactured by Toyocolor Co., Ltd.), 5 parts of a pigment derivative (the above-mentioned compound 4), 1000 parts of crushed salt, and 100 parts of diethylene glycol, 1 gallon kneader made of stainless steel (Made by Inoue Seisakusho) and kneaded at 50 ° C. for 12 hours. The mixture was poured into 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed with water to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts refined pigment (B-1).

(Production of refined pigment (V-1))
300 parts of dioxazine-based purple pigment PV23 (“Rionogen Violet RL” manufactured by Toyocolor Co., Ltd.) was added to 3000 parts of 96% sulfuric acid, and the mixture was stirred for 1 hour and poured into 5 ° C. water. After stirring for 1 hour, it was filtered, washed with warm water until the washing solution became neutral, and dried at 70 ° C. 120 parts of the obtained acid pasting pigment, 5 parts of a dye derivative (the above-mentioned compound 5), 1500 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 20 ° C. Kneaded for hours. The mixture was poured into 5000 parts of warm water, stirred at a high-speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts refined pigment (V-1).

<Manufacture of binder resin solution>
370 parts of propylene glycol monomethyl ether acetate (PGMAc) is put in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator is dropped at the same temperature over 1 hour. The polymerization reaction was carried out.
Methacrylic acid: 13.0 parts 2-hydroxyethyl methacrylate: 14.0 parts Glycerol monomethacrylate: 25.0 parts Benzyl methacrylate: 25.0 parts Butyl methacrylate: 23.0 parts 2,2′-azobisisobutyronitrile : 4.0 parts

  After completion of the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of propylene glycol monomethyl ether acetate (PGMAc) was added. The reaction was continued for a time to obtain a copolymer solution. After cooling to room temperature, about 2 g of the alkali-soluble resin solution is sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate (PGMAc) was added. The obtained non-photosensitive transparent resin had a weight average molecular weight of 32,000 and an acid value of 78.

<Production of dispersant (X1)>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.0 parts of 3-mercapto-1,2-propanediol and 9.7 mol of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.) Part and 31.7 parts of PGMAc were charged and replaced with nitrogen gas. As a catalyst, 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene was added and reacted at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. Next, 50.0 parts of methyl methacrylate and 50.0 parts of methyl α-allyloxymethyl acrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 45.4 parts of propylene glycol monomethyl ether acetate was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. After completion of the reaction, the mixture was prepared by adding propylene glycol monomethyl ether acetate so that the nonvolatile content was 60% by weight, and a solution of a polyester dispersant (X1) having an acid value of 43 mgKOH / g and a weight average molecular weight of 9,500 was obtained.

(Production of dispersant (X2))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is charged with 40.0 parts of methyl methacrylate, 50.0 parts of methyl α-allyloxymethyl acrylate, and 10.0 parts of t-butyl methacrylate, and nitrogen gas. Replaced with. The inside of the reaction vessel was heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2′-azobisisobutyronitrile were added to propylene glycol monomethyl ether acetate 45. The solution dissolved in 4 parts was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 31.7 parts of PGMAc, and 1,8-diazabicyclo- [5.4.0] -7-undecene 0.2 as a catalyst An additional portion was added and reacted at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After completion of the reaction, propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 60% by weight to obtain a solution of polyester dispersant (X2) having an acid value of 43 mgKOH / g and a weight average molecular weight of 9,500.

(Production of dispersant (X3 to X8))
Synthesis was carried out in the same manner as the dispersant (X2) except that the raw materials and preparation amounts shown in Table 1 were used to obtain propylene glycol monomethyl ether acetate solutions of the dispersants (X3) to (X8).

(Production of dispersant (X9))
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 50.0 parts of benzyl methacrylate and 50.0 parts of n-butyl methacrylate and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., 6 parts of 3-mercapto-1,2-propanediol, 0.1 part of 2,2′-azobisisobutyronitrile, 45.4 parts of propylene glycol monomethyl ether acetate The solution dissolved in was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic dianhydride, 31.7 parts of propylene glycol monomethyl ether acetate and 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. And reacted at 120 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After completion of the reaction, propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 60% by weight, and a solution of a dispersant (X9) having an acid value of 43 mgKOH / g and a weight average molecular weight of 9,500 was obtained.

(Production of dispersant (X10))
Synthesis was carried out in the same manner as the dispersant (X9) except that the raw materials and preparation amounts shown in Table 1 were used to obtain a propylene glycol monomethyl ether acetate solution of the dispersant (X10).

The abbreviations in Table 1 are shown below.
MMA: methyl methacrylate EA: ethyl acrylate MAA: methacrylic acid n-BMA: n-butyl acrylate BzMA: benzyl methacrylate t-BMA: t-butyl acrylate Thioglycerol: 3-mercapto-1,2- Propanediol, AIBN: 2,2′-azobisisobutyronitrile, PGMAc: propylene glycol monomethyl ether acetate, PMA: pyromellitic dianhydride, TMA: trimellitic acid anhydride, DBU: 1,8-diazabicyclo- [5.4.0] -7-Undecene M-402; Aronix M-402: Dipenter erythritol pentaacrylate / dipentaerythritol hexaacrylate (manufactured by Toagosei Co., Ltd.)
Irgacure 907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF)
EAB-F: 4,4′-bis (diethylamino) benzophenone (Hodogaya Chemical Co., Ltd.)

<Adjustment of photosensitive coloring composition>
[Example 1]
(Adjustment of photosensitive coloring composition (C1))
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A green pigment dispersion (D1) was prepared.

Refined pigment (G-1) 8.0 parts Refined pigment (Y-1) 6.0 parts Polyester dispersant (X1) solution 6.0 parts Binder resin solution 16.0 parts PGMac 64.0 parts

  Next, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive coloring composition (C1) for a green color filter.

Green pigment dispersion (D1) 54.0 parts Binder resin solution 6.0 parts Photopolymerizable monomer (M-402) 2.0 parts Photopolymerization initiator (Irgacure 907) 1.8 parts Sensitizer ( EAB-F) 0.2 part PGMAc 37.0 parts

[Examples 2-8, Comparative Examples 1-2]
(Adjustment of photosensitive coloring composition (C2 to C10))
A green color filter photosensitive coloring composition was prepared in the same manner as in Example 1 except that the polyester dispersant solution was changed to the dispersant shown in Table 2 to prepare a green pigment dispersion (D2 to 10). (C2-10) were obtained.

[Example 9]
(Adjustment of photosensitive coloring composition (C11))
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A red pigment dispersion (D11) was prepared.

Refined pigment (R-1) 5.0 parts Refined pigment (R-2) 4.0 parts Refined pigment (Y-2) 2.0 parts Polyester dispersant (X2) 5.0 parts Binder resin solution 28 .0 part PGMAc 55.0 parts

  Next, the mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive colored composition for a red color filter.

Red pigment dispersion (D11) 44.0 parts Binder resin solution 13.0 parts Photopolymerizable monomer (M402) 2.0 parts Photopolymerization initiator (Irgacure 907) 1.8 parts Sensitizer (EAB- F) 0.2 part PGMac 40.0 parts

[Examples 10 to 12, Comparative Example 3]
(Adjustment of photosensitive coloring composition (C12 to C15))
The polyester dispersing agent solution was changed to the dispersing agent shown in Table 2 and blended. Otherwise, a photosensitive coloring composition for a red color filter was obtained in the same manner as in Example 9. The red pigment dispersion (D12-15) was prepared by changing the polyester dispersant solution to the dispersant shown in Table 2, and a photosensitive coloring composition for red color filter was used in the same manner as in Example 9 except that it was used. (C12-15) was obtained.

[Example 13]
(Adjustment of photosensitive coloring composition (C16))
After the mixture having the following composition is uniformly stirred and mixed, the mixture is dispersed for 2 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. A blue pigment dispersion (D16) was prepared.

Refined pigment (B-1) 13.0 parts Refined pigment (V-1) 1.0 part Polyester dispersant (X2) solution 6.0 parts Binder resin solution 16.0 parts PGMAc 64.0 parts

  Next, a mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive colored composition for a blue color filter.

Blue pigment dispersion (D16) 32.0 parts Binder resin solution 13.0 parts Photopolymerizable monomer (M402) 5.0 parts Photopolymerization initiator (Irgacure 907) 1.8 parts Sensitizer (EAB- F) 0.2 part PGMAc 49.0 parts

[Examples 14 to 16, Comparative Example 4]
(Adjustment of photosensitive coloring composition (C17 to C20))
A blue pigment dispersion (D17 to 20) was prepared by changing the polyester dispersant solution to the dispersant shown in Table 2, and a photosensitive coloring composition for red color filter was used in the same manner as in Example 9 except that it was used. (C17-20) was obtained.

<Evaluation of photosensitive coloring composition>
(Contrast ratio)
The obtained colored composition for color filter was applied on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 0.7 mm using a spin coater at 500 rpm, 1000 rpm, and 1500 rpm, and three types of coatings having different film thicknesses. A substrate was obtained. The coloring composition coated substrate for color filter was dried at 70 ° C. for 20 minutes, then exposed to ultraviolet light with an integrated light amount of 150 mJ using an ultra high pressure mercury lamp, heated at 230 ° C. for 1 hour, allowed to cool, and then measured for contrast ratio. . Next, the chromaticity (Y, x, y) of the coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the three sets of contrast ratio and chromaticity measurement results, the color coating colored composition-coated substrate is y = 0.14 for the blue coating, y = 0.60 for the green coating, and x = for the red coating. The contrast ratio at 0.64 was determined using an approximation method.

(Viscosity stability)
About the obtained coloring composition for color filters, the viscosity stability was evaluated by the following method. Using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.), the initial viscosity of the next day after preparing the color filter coloring composition and the time-lapse viscosity accelerated at 40 ° C. for 1 week, The measurement was performed at 25 ° C. under the condition of a rotation speed of 50 rpm. From the values of the initial viscosity and the viscosity with time, the change rate with time was calculated by the following formula, and the viscosity stability was evaluated in three stages.

[Change in viscosity with time] = | ([initial viscosity] − [viscosity with time]) / [initial viscosity] | × 100
○: Change rate of less than 5% △: Change rate of 5% or more and less than 10% ×: Change rate of 10% or more

(Evaluation of heat resistance (weight loss) of coating film)
After coating the obtained colored composition for color filter on glass and removing the solvent, weight loss (%) before and after heating at 200 ° C. for 1 hour was calculated and evaluated according to the above criteria.
○: Weight loss within 5% ×: Weight loss greater than 5%

(Resolution evaluation)
After coating the obtained photosensitive coloring composition on a 100 mm × 100 mm, 1.1 mm thick glass substrate, the solvent was removed by heating at 70 ° C. for 20 minutes in a clean oven to obtain a coating film of about 2 μm. Got. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 330 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive coloring composition, and this was set as an appropriate development time. The alkali developer is 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used. The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

The pattern in the 25 μm photomask portion of the filter segment formed by the above method was evaluated by observing with an optical microscope. The rank of evaluation is as follows. The poor resolution means that adjacent stripe patterns are connected or chipped. The resolution evaluation was determined according to the following criteria.
◎: Good resolution and linearity ○: Slightly inferior in linearity but good resolution ×: Partially poor resolution

  The above results are shown in Table 3.

  As shown in Table 3, the color filter of the present invention using dispersants X1 to 8 containing resin (S1) or (S2) having a structural unit derived from monomer (c1) represented by general formula (1) The coloring composition for use was superior in heat resistance and resolution while maintaining a high contrast ratio as compared with those using dispersants X9 to 10.

Claims (3)

A color filter coloring composition comprising a colorant, a dispersant (X), a binder resin and an organic solvent, wherein the dispersant (X) contains a resin of the following (S1) or (S2) A colored composition for a color filter.
(S1) A polymer which is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, and having the hydroxyl group (S1) has a structural unit derived from the monomer (c1) represented by the following general formula (1).
(S2) In the presence of the reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, the compound is represented by the following general formula (1). A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer containing the monomer (c1) to be produced.
General formula (1):

(In the general formula (1), R represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)   Furthermore, the coloring composition for color filters of Claim 1 containing at least 1 sort (s) chosen from a photopolymerizable monomer and a photoinitiator.   The color filter which comprises the filter segment formed from the coloring composition for color filters of Claim 1 or 2.