JP6946681B2 - Coloring compositions and color filters for color filters - Google Patents

Description

The present invention relates to a coloring composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, etc., and a color filter including a filter segment formed by using the coloring composition. be.

Patent Document 1 discloses a coloring composition for a color filter containing a salt-forming compound obtained by reacting a cationic resin, which is a block resin having no t-butyl group and an oxetanyl group, with an anionic dye. Patent Document 2 discloses a coloring composition for a color filter containing a salt-forming compound obtained by reacting a cationic resin that is not a block resin having an oxetanyl group with an anionic dye. However, recent color filters are required to have higher heat resistance than conventional ones, and these methods have not been able to solve the problems of heat resistance these days.

Japanese Unexamined Patent Publication No. 2011-242752 Japanese Unexamined Patent Publication No. 2013-33194

An object of the present invention is to provide a coloring composition for a color filter and a color filter having excellent heat resistance.

That is, the present invention is a coloring composition for a color filter, which comprises at least a colorant (A), a binder resin, and an organic solvent.
The colorant (A) contains a salt-forming compound (D) of a resin (B) having a cationic group in the side chain and an anionic dye (C).
The resin (B) having a cationic group in the side chain is an acrylic resin containing a structural unit represented by the following general formula (1), and the acrylic resin is
It is a block resin composed of at least an A block having a cationic group represented by the following general formula (1) and a B block having at least a t-butyl group and an oxetanyl group (however, it does not have a cationic group).
The B block of the block resin may contain a carboxyl group.
The present invention relates to a coloring composition for a color filter in which the total number of moles of carbosilyl group and t-butyl group is 1.5 to 18.3 with respect to the number of moles of oxetanyl group of the block resin.

[In general formula (1),
R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R _{2 to} R ₄ independently represent a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an aryl group which may be substituted, and among _{R 2 to} R _{4, respectively.} The two may combine with each other to form a ring.
Q represents an alkylene group, an arylene group, —CONH-R ₅ −, —COO −R ₅ −, and R ₅ represents an alkylene group.
Y ^- is representative of an inorganic or organic anion. ]

The present invention also relates to the above-mentioned coloring composition for a color filter in which the resin (B) having a cationic group in the side chain is a copolymer of an ethylenically unsaturated monomer.

Further, the present invention is a precursor of a block having a cationic group represented by the general formula (1) in the side chain in the total amount of the ethylenically unsaturated monomer constituting the resin (B) having a cationic group in the side chain. The present invention relates to the coloring composition for a color filter, wherein the content of the monomer as a body is 3% by mass to 30% by mass.

The present invention also relates to the above-mentioned coloring composition for a color filter in which the ammonium salt value of the resin (B) having a cationic group in the side chain is 10 to 200 mgKOH / g.

The present invention also relates to the above-mentioned coloring composition for a color filter, in which the coloring agent further contains a pigment.

The present invention also relates to the above-mentioned coloring composition for a color filter, wherein the anionic dye (C) contains at least one selected from Acid Red 52, Acid Red 289 and a compound represented by the following general formula (2).

General formula (2)

[X1 and X3 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
X2 and X4 each independently represent a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group. ]

The present invention also relates to the above-mentioned coloring composition for a color filter, which further contains at least one selected from a photopolymerizable monomer and a photopolymerization initiator.

Furthermore, the present invention relates to a color filter formed by the above-mentioned coloring composition for a color filter.

In the present invention, the resin containing a salt-forming compound obtained by reacting a resin having a cationic group in the side chain with an anionic dye and further having a cationic group in the side chain is a cationic group. A composition for a color filter having excellent heat resistance and a composition for a color filter excellent in heat resistance because it is a block resin composed of an A block having You can get a color filter.

Hereinafter, the present invention will be described in detail.
<Resin (B) having a cationic group in the side chain>
The resin (B) having a cationic group in the side chain of the present invention has an A block having a cationic group in the side chain and a B block having at least a t-butyl group and an oxetanyl group without a cationic group. The B block of the block resin may contain a carboxyl group, and the total number of moles of the carbosyl group and the t-butyl group is 1. It is characterized by being 5 to 18.3. The salt-forming compound (D) of the present invention can be obtained by forming a salt of the cationic group with the anionic group of the anionic dye (C).

[A block having a cationic group]
The A block having a cationic group of the present invention is characterized by having a cationic group represented by the following general formula (1).

[In general formula (1),
R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R _{2 to} R ₄ independently represent a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an aryl group which may be substituted, and among _{R 2 to} R _{4, respectively.} The two may combine with each other to form a ring.
Q represents an alkylene group, an arylene group, —CONH-R ₅ −, —COO −R ₅ −, and R ₅ represents an alkylene group.
Y ^- is representative of an inorganic or organic anion. ]

In the general formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group in R ₁ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group and a cyclohexyl group. As the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

When the _{alkyl group represented by R 1} has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, _{as R 1} , a hydrogen atom or a methyl group is most preferable.

In the general formula (1), R _{2 to} R ₄ independently include a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an aryl group which may be substituted. Can be mentioned.

Here _{, examples of the alkyl group in R 2 to} R ₄ include linear alkyl groups (methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-octyl, n-decyl, n-dodecyl, n. -Tetradecyl, n-hexadecyl and n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3 -Tetramethylbutyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and crosslinked cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). As the alkyl group, an alkyl group having 1 to 18 carbon atoms is preferable, and an alkyl group having 1 to 8 carbon atoms is more preferable.

Examples of the alkenyl group in R _{2 to} R ₄ include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1. -Propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2-cyclohexenyl, 3-cyclohexenyl, etc.) can be mentioned. As the alkenyl group, an alkenyl group having 2 to 18 carbon atoms is preferable, and an alkenyl group having 2 to 8 carbon atoms is more preferable.

Examples of the aryl group in R _{2 to} R ₄ include a monocyclic aryl group (phenyl, etc.), a fused polycyclic aryl group (naphthyl, anthrasenyl, phenanthrenyl, anthraquinolyl, fluorenyl, naphthoquinolyl, etc.) and an aromatic heterocyclic hydrocarbon. Groups (thienyl (group derived from thiophene), frill (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (from xanthone) Induced groups) and 9-oxothioxanthenyl (groups derived from thioxanthone), etc.).

When the _{alkyl group, alkenyl group, and aryl group represented by R 2 to} R ₄ have a substituent, the substituent includes, for example, a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, and the like. Examples thereof include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group and the like. As the substituent, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

As R _{2 to} R ₄ , an alkyl group which may be substituted is preferable from the viewpoint of stability, and an unsubstituted alkyl group is more preferable.

Further, _{two of R 2 to} R ₄ may be bonded to each other to form a ring.

In the general formula (1), the component of Q that connects the acrylic moiety and the ammonium base represents an alkylene group, an arylene group, -CONH-R _5- , -COO-R _5- , and R ₅ represents an alkylene group. _{Of these, -CONH-R 5-} and -COO-R _5- are preferable for the reasons of polymerizability and availability. Further, it is more preferable that R ₅ is a methylene group, an ethylene group, a propylene group, or a butylene group, and it is particularly preferable that it is an ethylene group.

^{The component of Y −} in the general formula (1) constituting the counter anion of the resin may be an inorganic or organic anion. As the counter anion, known ones can be adopted without limitation, and specifically, hydroxide ion; halogen ion such as chloride ion, bromide ion and iodide ion; carboxylic acid ion such as formate ion and acetate ion; Like carbonate ion, bicarbonate ion, nitrate ion, sulfate ion, sulfite ion, chromate ion, dichromate ion, phosphate ion, cyanide ion, permanganate ion, and even hexacyanoferrate (III) acid ion. Examples include complex ions. From the viewpoint of synthetic suitability and stability, halogen ions and carboxylic acid ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylic acid ion, the organic acid ion may be covalently bonded to the resin to form an intramolecular salt.

In order to obtain an acrylic resin containing a structural unit represented by the general formula (1), not only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component but also an amino group is provided. An acrylic resin having an amino group copolymerized with an ethylenically unsaturated monomer as a monomer component may be obtained, and then an onium chloride agent is reacted to obtain ammonium chloride.

Specific examples of the ethylenically unsaturated monomer having an ammonium base, the ethylenically unsaturated monomer having an amino group, and the onium chloride agent are shown below. In the present specification, when either or both of "acrylic, methacryl" is indicated, it may be described as "(meth) acrylic". Similarly, when indicating either or both of "acryloyl and methacryloyl", it may be described as "(meth) acryloyl".

Examples of the ethylenically unsaturated monomer having an ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, and (meth) acryloyl. Alkyl (meth) acrylate-based quaternary ammonium salts such as oxyethylmethylmorpholinoammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride Alkyl (meth) acryloyl amide-based quaternary ammonium salt, dimethyldialylammonium methylsulfate, trimethylvinylphenylammonium chloride and the like can be mentioned.

Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, dit-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl A (meth) acrylic acid ester or (meth) having a dialkylamino group such as aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, dit-butylaminopropyl (meth) acrylamide, etc. Examples include acrylamide, styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylamine compounds such as diallylmethylamine and diallylamine, and amino such as N-vinylpyrrolidin, N-vinylpyrrolidone and N-vinylcarbazole. Group-containing aromatic vinyl-based monomers can be mentioned.

Examples of the onium chloride agent include alkyl sulphates such as dimethyl sulphate, diethyl sulphate, or dipropyl sulphate, sulfonic acid esters such as methyl p-toluene sulfonate, or methyl benzene sulfonate, methyl chloride, ethyl chloride, propyl chloride, or. Examples thereof include alkyl chlorides such as octyl chloride, methyl bromide, ethyl bromide, propyl bromide, alkyl bromides such as octyl chloride, benzyl chloride, benzyl bromide and the like.

In the reaction between an ethylenically unsaturated monomer having an amino group and an onium chloride agent, an onium chloride agent having an equimolar amount or less with respect to the amino group is usually added dropwise to an ethylenically unsaturated monomer solution having an amino group. Can be done by doing. The temperature during the ammonium chloride reaction is about 90 ° C. or lower, particularly preferably about 30 ° C. or lower when the vinyl monomer is ammonium chloride, and the reaction time is about 1 to 4 hours.

Alternatively, an alkoxycarbonylalkyl halide can be used as the onium chloride agent. The alkoxycarbonylalkyl halide is represented by the following general formula (3).

Z-R ^6- COOR ⁷ General formula (3)

[In the general formula (3), Z is a halogen such as chlorine or bromine, preferably bromine, and R ⁶ is an alkylene group having 1 to 6, preferably 1 to 5, and more preferably 1 to 3 carbon atoms. R ⁷ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms. ]

In the reaction of an ethylenically unsaturated monomer having an amino group with an alkoxycarbonylalkyl halide, an equimolar or less alkoxycarbonylalkyl halide is reacted with the amino group in the same manner as the above onium chloride agent, and then -COOR ⁷ is added. obtained by converting the - carboxylate ions by hydrolysis ^(-COO). As a result, an ethylenically unsaturated monomer having a carboxybetaine structure represented by the general formula (3) and having an ammonium base can be obtained.

[B block having a t-butyl group and an oxetanyl group]
The B block of the present invention is characterized by having at least a t-butyl group and an oxetanyl group. In order to introduce a t-butyl group and an oxetanyl group into the B block in the resin (B) having a cationic group in the side chain, an ethylenically unsaturated monomer having a t-butyl group and ethylene having an oxetanyl group are used. It is preferable to copolymerize the sex unsaturated monomer. Other monomers may be used in combination as appropriate. Further, after obtaining the acrylic resin, the functional group of the acrylic resin is reacted with a compound having a functional group capable of reacting with the functional group and a t-butyl group or an oxetanyl group to obtain a t-butyl group. An oxetanyl group may be introduced.

(Ethylene unsaturated monomer having a t-butyl group)
Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl acrylate and t-butyl methacrylate.

(Ethylene unsaturated monomer having an oxetanyl group)
Examples of the ethylenically unsaturated monomer having an oxetanyl group include 3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, and the like. 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (Methacryloxymethyl) 3-hexyloxetane and the like can be mentioned.

At least one type of each of the t-butyl group and the oxetanyl group needs to be contained in the resin, and two or more types may be contained.

The t-butyl group and the oxetanyl group react in a bake near 230 ° C., which is a heating step of the color filter, to crosslink the coating film. This makes it possible to impart heat resistance to the coating film. The oxetanyl group also reacts with the carboxyl group to crosslink the coating film, but the inclusion of a large amount of highly hydrophilic carboxyl groups means that the resin (B) having a cationic group in the side chain is soluble in the solvent. Until now, it has been difficult because the compatibility with other components deteriorates. However, due to the coexistence of t-butyl groups with strong hydrophobicity, the resin (B) having a cationic group in the side chain is soluble in a solvent even if it contains a large amount of highly hydrophilic carboxyl groups, and other substances. It is possible to suppress deterioration of compatibility with the components. As a result, the coating film can be crosslinked with a very high crosslink density, and high heat resistance can be imparted.

2 mol of carboxyl group and t-butyl group react with 1 mol of oxetanyl group. The quantitative relationship between the oxetanyl group, the t-butyl group, and the carboxyl group contained in the resin (B) having a cationic group in the side chain is the sum of the carboxyl group and the t-butyl group with respect to the number of moles of the oxetanyl group. The number of moles formed is preferably 1.5 to 3.5 times, more preferably 2.0 to 3.0 times.

Further, as for the ethylenically unsaturated monomer having an oxetanyl group, a carboxyl group and a t-butyl group, the acrylate-based monomer contains a resin (B) having a cationic group in the side chain containing the acrylate-based monomer, rather than the methacrylate-based monomer. This is preferable because the alkali developability of the coloring composition is improved.

Other ethylenically unsaturated monomers that can be used in addition to the above ethylenically unsaturated monomers include, for example, (meth) acrylic acid, (meth) acrylic acid anhydride, (meth) acrylic acid esters, and the like. Crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylic nitriles and the like are preferable.

Specific examples of such a vinyl monomer include the following compounds.

Examples of the ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid and the like, and are ethylenic having a carboxylic acid anhydride group. Examples of the unsaturated monomer include maleic anhydride, itaconic anhydride and the like.

Examples of (meth) acrylic acid esters include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n-butyl (meth) acrylic acid. , (Meta) acrylate isobutyl, (meth) acrylate t-butyl, (meth) acrylate n-hexyl, (meth) acrylate cyclohexyl, (meth) acrylate t-butylcyclohexyl, (meth) acrylate 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate , (Meta) Acrylic Acid Triethylene Glycol Monomethyl Ether, (Meta) Acrylic Acid Triethylene Glycol Monoethyl Ether, (Meta) Acrylic Acid Polyethylene Glycol Monomethyl Ether, (Meta) Acrylic Acid Polyethylene Glycol Monoethyl Ether, (Meta) Acrylic Acid β-Phenoxyethoxyethyl, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, (meth) acrylic acid Examples thereof include octafluoropentyl, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, and tribromophenyloxyethyl (meth) acrylate.

Examples of crotonic acid esters include butyl crotonic acid, hexyl crotonic acid and the like.

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate and the like. Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, dibutyl fumarate and the like.

Examples of itaconic acid diesters include dimethyl itaconic acid, diethyl itaconic acid, dibutyl itaconate and the like.

Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn. -Butylacryl (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N , N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholin, diacetone acrylamide and the like.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether and the like. Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, and chloromethyl. Examples thereof include styrene, hydroxystyrene protected by a group that can be deprotected by an acidic substance (for example, t-Boc), methyl vinyl benzoate, and α-methyl styrene.

[Block resin]
The block resin of the present invention can be obtained by copolymerizing an ethylenically unsaturated monomer. The block resin composed of the A block having a cationic group represented by the general formula (1) of the present invention and the B block having a specific group is AB block, BAB block, or A. -BA is preferable, and AB block and BAB block can be more preferably used. Such block copolymers are prepared, for example, by the living polymerization method shown below. Here, the living polymerization is a polymerization method for easily synthesizing a block polymer or a resin having a uniform molecular weight because side reactions that occur in general radical polymerization are suppressed and the growth of the polymerization occurs uniformly. The molecular weight of the polymer and the ratio of the monomer to be block copolymerized can be freely controlled by the charging ratio of the polymerization initiator added at the time of polymerization and the vinyl-based monomer, and the block polymer, gradient polymer, star-shaped polymer, comb polymer, and further Can be used in the production of terminal functional polymers and the like.

The block copolymer of the present invention can be synthesized by a known radical living polymerization method. As a specific example, the methods listed below have been developed and are being widely researched and developed. Nitroxide mediated polymerization (NMP method) utilizing the dissociation and binding of amine oxide radicals (see Reference 1). Atom transfer radical polymerization (ATRP method), which uses heavy metals such as copper, ruthenium, nickel, and iron, and a ligand that forms a complex with them, to polymerize a halogen compound as an initiating compound (Reference 2, Reference 2, See Reference 3 and Reference 4). Reversible addition-fragation chain transfer (RAFT method), which uses a dithiocarboxylic acid ester or xanthate compound as an initiator and polymerizes using an addition-polymerizable monomer and a radical initiator (references). 5) and Macromolecular Designvia Interchange of Xanthate (MADIX method) (see Reference 6). A method using heavy metals such as organic tellurium, organic bismuth, organic antimony, halogenated antimony, organic germanium, and halogenated germanium (Degenerative transfer: DT method) (see References 7 and 8).

(Reference 1) Chemical Review (2001) 101,3661
(Reference 2) Japanese Patent Application Laid-Open No. 2000-500516 (Reference 3) Japanese Patent Application Laid-Open No. 2000-514479 (Reference 4) Chemical Review (2001) 101,3689
(Reference 5) Japanese Patent Application Laid-Open No. 2000-515181 (Reference 6) International Publication No. 1999/05099 (Reference 7) Japanese Patent Application Laid-Open No. 2007-277533 (Reference 8) JournalofAmericanChemicalSociety (2002) 124,2874

Among these radical living polymerizations, the atom transfer radical polymerization method (ATRP method), in which an organic halide or a sulfonyl halide compound is used as an initiator and a metal complex having a transition metal as a central metal as a catalyst, is used. Not only from the viewpoint of controlling the molecular weight distribution, it is preferable in that it can be applied to a wide range of monomers and that a polymerization temperature applicable to existing equipment can be adopted.

In the atomic transfer radical polymerization method, a transition metal complex such as copper, ruthenium, iron, or nickel is used as a redox polymerization catalyst. Specific examples of the transition metal complex include low valence halogenated transition metals such as copper (I) chloride and copper (I) bromide.

An organic ligand is used for the fibrous metal complex. Organic ligands are used to allow solubility in polymerization solvents and reversible changes in redox polymerization catalysts. Examples of the coordination atom of the transition metal include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom.

As the initiator used in the atomic radical polymerization method, known ones can be used, but mainly organic halides having a highly reactive carbon halogen bond, sulfonyl halide compounds and the like are used. Specific examples thereof include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, chloride paratoluenesulfonic acid, 1-bromoethylbenzene, chloroethylbenzene and the like. These are used alone or in combination.

Among all the ethylenically unsaturated monomers constituting the block copolymer, the content of the monomer which is a precursor of the block having a cationic group represented by the general formula (1) in the side chain is 1 mass by mass. % To 50% by mass is preferable, 3% by mass to 30% by mass is preferable, and 5% by mass to 20% by mass is particularly preferable. By containing 1% by mass to 50% by mass of the A block, the remaining 50% by mass to 99% by mass constitutes the B block. Therefore, since the B block has an affinity for the solvent as the dispersion medium, the salt-forming compound can be stably present in the dispersion medium, and the stability with time is improved.

The content of the monomer which is a precursor of the block having a cationic group represented by the general formula (1) in the side chain is 80% by mass in the total amount of the ethylenically unsaturated monomer constituting the A block. It is preferably ~ 100% by mass, preferably 90% by mass to 100% by mass, and particularly preferably 100% by mass.

The block copolymer of the present invention preferably has an ammonium salt value of 10 to 200 mgKOH / g, and more preferably 20 to 130 mgKOH / g. In order for the ammonium salt value of the resin to satisfy the above range, the preferable content of the structural unit having a quaternary ammonium base is 4 to 74% by weight based on 100% by weight of the total structural units constituting the resin. A more preferable range is 8 to 48% by weight.

Further, in the block copolymer of the present invention, the dye that salt-forms in the A block having a cationic group is easier to form an aggregate between the dyes than the random body and the salt-forming dye, and as a result, the heat resistance of the dye Is expected to improve.

The molecular weight of the block copolymer of the present invention is usually preferably in the range of 1,000 or more and 100,000 or less on a polystyrene-equivalent weight average. Within the above range, both the stability over time and the solvent resistance of the salt-forming compound can be achieved.

In the step of producing the resin (B) having a cationic group in the side chain, a solvent-free or optionally a solvent can be used. Examples of the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, hexane, toluene, xylene, acetone, methyl ethyl ketone, methoxypropyl acetate, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, and ethylene glycol monoethyl. Ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and the like are used, but the present invention is not particularly limited thereto, and can be arbitrarily selected from the intended use, cost and the like. Two or more kinds of polymerization solvents may be mixed and used.

The amount of the solvent used is preferably 0 to 300 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. After the reaction is completed, the used solvent can be removed by an operation such as distillation, or can be used as it is as a part of the dispersant product.

<Anionic dye (C)>
Next, the anionic dye (C) for obtaining the salt-forming compound (D) of the present invention will be described. The anionic dye (C) may be any coloring compound having an anionic group that ionic bonds with the above-mentioned cationic group. The coloring compound is not particularly limited as long as it has a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, a phosphoric acid group, or a metal salt thereof in the molecule, and is not particularly limited, and is an organic solvent or a developing solution. It can be appropriately selected in consideration of all of the required performances such as solubility, salt forming property, absorbance, interaction with other components in the present composition, light resistance and heat resistance.

Examples of the anionic dye (C) include anthraquinone-based anionic dyes, monoazo-based anionic dyes, disazo-based anionic dyes, oxazine-based anionic dyes, aminoketone-based anionic dyes, xanthene-based anionic dyes, and quinoline-based anions. Examples include sex dyes and triphenylmethane-based anionic dyes. Specific examples of anionic dyes that can be used for the synthesis of the salt-forming compound (D) are shown below by color index numbers.

Examples of red dyes include C.I. I. Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25: 1, 26, 26: 1, 26: 2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76: 1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 249, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like can be mentioned.

In addition, C.I. I. Direct Red 1, 2, 2: 1, 4, 5, 6, 7, 8, 10, 10: 1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26: 1, 28, 29, 31, 33, 33: 1, 34, 35, 36, 37, 39, 42, 43, 43: 1, 44, 46, 49, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67: 1, 68, 72, 72: 1, 73, 74, 75, 77, 78, 79, 81, 81: 1, 85, 86, 88, 89, 90, 97, 100, 101, 101: 1, 107, 108, 110, 114, 116, 117, 120, 121, 122, 122: 1, 124, 125, 127, 127: 1, 127: 2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171 and 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238 and the like can also be used.

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 and 192, 199 and the like can be mentioned.

In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 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 can also be used.

Examples of orange dyes include C.I. I. Acid Orange 1, 1: 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23, 24, 24: 1, 25, 27, 28, 28: 1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138 and the like can be mentioned.
In addition, C.I. I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29: 1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114 and the like can also be used.

As a blue dye, C.I. I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41: 1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203, 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261 and 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

In addition, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8: 1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21: 1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231 and 242, 243, 244, 253, 254, 260, 263 and the like can also be used.

As a purple dye, C.I. I. Acid Violet 1, 2, 3, 4, 5, 5: 1, 6, 7, 7: 1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc. Can be mentioned.

In addition, C.I. I. Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, 97 and the like can also be used.

As a green dye, C.I. I. Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25: 1, 27, 34, 36, Examples thereof include 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94 and 95.
In addition, C.I. I. Direct greens 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80 and the like can also be used.

In addition, a red dye represented by the general formula (2) can also be used.
General formula (2)

[In the general formula (2), X ₁ and X ₃ each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
X ₂ and X ₄ each independently represent a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group. ]

As the anionic dye (C), a red dye is preferable, and acid red 52, acid red 289, and a dye represented by the general formula (2) are particularly preferable.

<Salt formation>
The salt-forming compound (D) of the present invention is obtained by stirring or vibrating an aqueous solution prepared by dissolving a resin (B) having a cationic group in the side chain and an anionic dye (C), or making the side chain cationic. It can be easily obtained by mixing an aqueous solution of the resin (B) having a group and an aqueous solution of the anionic dye (C) with stirring or vibration. In the aqueous solution, the cationic group of the resin and the anionic group of the dye are ionized, and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, since the salt composed of the counter anion of the resin and the counter cation of the acid dye is water-soluble, it can be removed by washing with water or the like. As the resin (B) having a cationic group in the side chain to be used and the anionic dye (C), only one type may be used, or a plurality of types having different structures may be used.

As the aqueous solution used at the time of salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the resin (B) having a cationic group in the side chain and the anionic dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2-. Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone , Diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone , 1,2-Hexanediol, 2,4,6-hexanetriol, tetraflufuryl alcohol, 4-methoxy-4 methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

The ratio of the resin (B) having a cationic group in the side chain to the anionic dye (C) is such that the molar ratio of the total cationic unit of the resin to the total anionic group of the anionic dye (C) is 10/1. The salt-forming compound (D) of the present invention can be suitably adjusted in the range of ~ 1/4, and more preferably in the range of 2/1 to 1/2.

<Pigment>
The coloring composition for a color filter of the present invention can be used as a coloring composition for a color filter by further adding a pigment. As the pigment, an organic or inorganic pigment can be used alone or in combination of two or more. As the pigment, a pigment having high color development and high heat resistance, particularly a pigment having high heat resistance decomposition property is preferable, and an organic pigment is usually used. Specific examples of organic pigments that can be used in the coloring composition for color filters are shown below by color index numbers.

Examples of the red coloring composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 97, 122, 123, 146, 149, 150, 168, 169, 170, 176, 177, 178, 180, 184, 185, 187, 192, 200, 202, 208, 209, 210, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 246, 254, 255, 264, 268, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, Red pigments such as 285, 286, or 287 can be used. Further, the red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and other orange pigments and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1,37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, Yellow pigments such as 181 and 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination.

Examples of the green coloring composition for forming the green filter segment include C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63 and other green pigments can be used. Further, for the green coloring composition, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 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, Yellow pigments such as 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination.

The blue coloring composition for forming the blue filter segment includes, for example, C.I. I. Pigment Blue 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 15, 15: 1, 15: 2, 15: Blue pigments such as 3, 15: 4, 15: 6, 16, 18, 19, 22, 24, 24: 1, 53, 56, 56: 1, 57, 58, 59, 60, 61, 62, 64, etc. Can be used. Further, the blue coloring composition includes C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50 and other purple pigments can be used in combination. Further, it is also preferable to use an aluminum phthalocyanine pigment, and the aluminum phthalocyanine pigment and the like described in JP-A-2004-333817, Patent No. 4893859 and the like can also be used.

Cyan-colored compositions for forming cyan-colored filter segments include, for example, C.I. I. Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 and other blue pigments can be used alone or in combination.

Magenta coloring compositions for forming magenta filter segments include, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Purple pigments such as Pigment Red 144, 146, 177, 169, 81 and red pigments can be used alone or in combination. A yellow pigment can be used in combination with the magenta color composition.

Inorganic pigments include titanium oxide, barium sulfate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, and amber. , Synthetic iron black and the like. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while balancing saturation and lightness.

(Pigment miniaturization)
The pigment added to the coloring composition of the present invention is preferably finely divided by salt milling treatment or the like in order to correspond to high transmittance and high contrast. The primary particle size of the pigment is preferably 10 nm or more because it is well dispersed in the colorant carrier. Further, it is preferably 80 nm or less because a filter segment having high contrast can be formed. A particularly preferable range is the range of 20 to 60 nm.

Salt milling is a machine that heats a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a 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 acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

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 price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, most preferably 300 to 1000% by weight, based on the total weight of the pigment (100% by weight).

The water-soluble organic solvent has a function of wetting 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 used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. 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% by weight, most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

When the pigment is salt-milled, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200% by weight based on the total weight of the pigment (100% by weight).

<Binder resin>
The binder resin is a resin that disperses a colorant, particularly a salt-forming compound (D) and a pigment, or a resin that dyes and permeates a salt-forming compound, and examples thereof include a thermoplastic resin and a thermosetting resin.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. , Polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like.

Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

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. Further, since the coloring composition for a color filter of the present invention is in the form of an alkali-developing colored resist material, it is preferable to use an alkali-soluble vinyl-based resin copolymerized with an acidic group-containing ethylenically unsaturated monomer.

Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group and a sulfone group. Specifically, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Isobutylene / (maleic anhydride) maleic anhydride copolymer and the like can be mentioned. Among them, an acrylic resin having an acidic group and at least one resin selected from a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, are preferably used because of their high heat resistance and transparency.

In order to improve the photosensitivity of the alkali-soluble resin copolymerized with the acidic group-containing ethylenically unsaturated monomer, an energy ray-curable resin having an ethylenically unsaturated active double bond can also be used. Further, it is preferable to use an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain because it has an effect of improving the solvent resistance of the resist material.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an unsaturated ethylenically double bond is introduced by the methods (a) and (b) shown below.

[Method (a)]
As the method (a), for example, the side chain epoxy group of the copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group with one or more other types of monomers can be used. , The carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is added and reacted, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an unsaturated ethylenic double bond and a carboxyl group. There is a way to introduce it.

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

Examples of the unsaturated monobasic acid include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, and cyano-substituted products. Examples thereof include monocarboxylic acids, which may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic acid anhydride or a tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride may be used to obtain the remaining anhydride. The group can also be hydrolyzed. Further, when etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenically double bond is used as the polybasic acid anhydride, the unsaturated ethylenically double bond can be further increased.

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

[Method (b)]
As the method (b), 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 the side chain hydroxyl group of the obtained copolymer with the isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

Examples of the unsaturated ethylenic monomer 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 and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Further, a polyether mono (meth) acrylate obtained by superpolymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added can also be used. 2-Hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable from the viewpoint of suppressing foreign matter in the coating film.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited to these. However, two or more types can be used together.

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

From the viewpoints of dispersibility, permeability, developability, and heat resistance of pigments and salt-forming compounds, the binder resin has an affinity for a carboxyl group that acts as a colorant adsorbent group and an alkali-soluble group during development, a colorant carrier, and a solvent. The balance of aliphatic groups and aromatic groups acting as sex groups is important for the dispersibility, permeability, developability, and durability of pigments and salt-forming compounds, and a resin having an acid value of 20 to 300 mgKOH / g is used. Is preferable. If the acid value is less than 20 mgKOH / g, the solubility in a developing solution is poor and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, no fine pattern remains.

Since the binder resin has good film forming properties and various resistances, it is preferable to use the binder resin in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight), and the colorant concentration is high and good. Since it can exhibit color characteristics, it is preferably used in an amount of 500% by weight or less.

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated into the colorant carrier, and the filter segment 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 can be included to facilitate the formation.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, and the like. 2-Heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-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, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-Dichlorobenzene, p-chlorotoluene, 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 monotersial 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 monomethyl 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 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 cyclo Hexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like can be mentioned.

Among them, since the pigment and the salt-forming compound (D) of the present invention are well dispersed and dissolved, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether are good. It is preferable to use glycol acetates such as acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone. In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety and hygiene and low viscosity.

These organic solvents may be used alone or in admixture of two or more. When two or more kinds of mixed solvents are used, it is preferable that the above-mentioned preferable organic solvent is contained in an amount of 65 to 95% by weight.

Further, since the organic solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness, 800 to 4000 weight based on the total weight of the colorant (100% by weight). It is preferable to use it in an amount of%.

<Dispersion>
The coloring composition of the present invention comprises a salt-forming compound (D) obtained by reacting a resin (B) having a cationic group in a side chain with an anionic dye (C), the binder resin and a solvent. When the pigment is further contained in the colorant carrier, it is finely dispersed by using various dispersion means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor, preferably together with a dispersion aid such as a dye derivative. Can be manufactured. Further, the coloring composition of the present invention can also be produced by mixing a pigment, a salt-forming compound (D), another coloring agent and the like separately dispersed in a coloring agent carrier.

(Dispersion aid)
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a dye derivative, a resin-type dispersant, or a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersing the colorant and has a great effect of preventing the reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid is used. When used, a color filter having high spectral transmittance can be obtained. In the present description, the salt-forming compound (D) is also expected to play a role as a dispersant aid for pigments.

<< Dye derivative >>
Examples of the dye derivative include compounds in which an organic pigment, anthraquinone, acridone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimide methyl group which may have a substituent. Those described in Japanese Patent Publication No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469, etc. can be used, and these can be used. It can be used alone or in combination of two or more.

From the viewpoint of improving the dispersibility of the added pigment, the blending amount of the dye derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 1% by weight or more, based on the total amount of the added pigment (100% by weight). 3% by weight or more. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40% by weight or less, more preferably 35% by weight or less, based on the total amount of the added pigment (100% by weight).

<< Resin type dispersant >>
The resin-type dispersant has a pigment-affinitive moiety having a property of adsorbing to the additive pigment and a moiety compatible with the colorant carrier, and adsorbs to the additive pigment to stabilize the dispersion on the colorant carrier. It works. Specifically, as the resin type dispersant, 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 of these, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oil-based dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone Resins, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds, phosphate esters, etc. are used, and these can be used alone or in admixture of two or more. It is not necessarily limited to these.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by BASF Japan Limited. , 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykuman, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, manufactured by Lubrizol Japan, Inc. 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, manufactured by BASF Japan Ltd. 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451 and 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. And so on.

《Sea surface activator》
Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When the resin type dispersant and the surfactant are added, the blending amount is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the added pigment (100% by weight). Is. When the blending amount of the resin type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the effect of addition, and when the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

<Photopolymerizable monomer>
The coloring composition of the present invention can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator. The photopolymerizable monomer of the present invention contains a monomer or oligomer that is cured by ultraviolet rays, heat, or the like to produce a transparent resin, and these can be used alone or in combination of two or more. The blending amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

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 ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Etherdi (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

<Photopolymerization initiator>
The coloring composition for a color filter of the present invention is a solvent-developed or alkali-developed colored resist material to which a photopolymerization initiator or the like is added when the composition is cured by ultraviolet irradiation to form a filter segment by a photolithography method. It can be prepared in the form of. When the photopolymerization initiator is used, the blending amount is preferably 5 to 200% by weight, and 10 to 150% by weight from the viewpoint of photocurability and developability, based on the total amount of the colorant. More preferred.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetphenone compounds such as − [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Methyldiphenyl sulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 Thioxanthone compounds such as −diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoy) Luoxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; A carbazole-based compound; an imidazole-based compound; or a titanosen-based compound or the like is used.

These photopolymerization initiators can be used alone or in admixture of two or more at any ratio, if necessary. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorants in the color filter coloring composition (100% by weight), and are 10 from the viewpoint of photocurability and developability. More preferably, it is ~ 150% by weight.

<Sensitizer>
Further, the coloring composition for a color filter of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azulenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anuren derivative, Spiropyran derivative, Spiroxazine derivative, Thiospyropyrane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglycolate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4,4'- Examples thereof include tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-diethylaminobenzophenone.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " The sensitizers described in "Special Functional Materials" (1986, CMC) can be mentioned, but are not limited thereto. In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

Two or more sensitizers may be used at an arbitrary ratio, if necessary. When the sensitizer is used, the blending amount is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the coloring composition (100% by weight), and is photocurable. From the viewpoint of developability, it is more preferably 5 to 50% by weight.

<Amine compounds>
Further, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to a glass plate despite having low surface tension lowering ability, and in an addition amount in which defects of the coating film due to foaming do not appear. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes 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 polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane 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 to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.

Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Esther and the like can be mentioned.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. Phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective as the curing agent, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (eg, 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 amidin compounds and salts thereof (eg, eg, dimethylamine). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6, etc.) -Methacryloxyethyl-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.) and the like can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15% by weight based on the total amount of the thermosetting resin.

<Other additive ingredients>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate.

Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphoric acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

Adhesion improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and 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-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).

<Removal of coarse particles>
The coloring composition of the present invention was mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more of coarse particles by means of centrifugation, sintering filter, membrane filter, or the like. It is preferable to remove dust. As described above, it is preferable that the coloring composition does not substantially contain particles having a size of 0.5 μm or more. 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 comprises a filter segment formed by using the coloring composition for a color filter of the present invention. Color filters include those comprising a red filter segment, a green filter segment, and a blue filter segment, or those comprising a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment.

As the transparent substrate, a glass plate such as soda-lime glass, low-alkali borosilicate glass, or non-alkali aluminum borosilicate glass, or a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate is used. Further, on the surface of the glass plate or the resin plate, a transparent electrode made of indium oxide, tin oxide or the like may be formed for driving the liquid crystal display after paneling.

<Manufacturing method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of filter segments by the printing method can be patterned simply by repeating printing and drying of the coloring composition prepared as the printing ink, so that the color filter manufacturing method is low cost and excellent in mass productivity. There is. Furthermore, with the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted by using a dispersant or an extender pigment.

When the filter segment is formed by the photolithography method, the coloring composition prepared as the solvent-developable or alkali-developable colored resist material is applied onto a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By the method, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. Then, after immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to manufacture a color filter. be able to. Further, in order to promote the polymerization of the colored resist material, heating can be applied as needed. According to the photolithography method, a color filter having higher accuracy than the above printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. In order to increase the UV exposure sensitivity, the colored resist material is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above methods, but the coloring composition of the present invention can be used in any of the methods. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. Further, the transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and the filter segment is transferred to a desired substrate.

A black matrix can be formed in advance before each color filter segment is formed on the transparent substrate or the reflective substrate. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but the black matrix is not limited thereto. It is also possible to form a thin film transistor (TFT) on the transparent substrate or the reflective substrate in advance, and then form each color filter segment. Further, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention, if necessary.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass".

<Preparation method of binder resin solution>
(Preparation of binder resin solution 1)
70.0 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then a dropping tube was used. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toa Synthetic Co., Ltd.), A mixture of 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and methoxypropyl acetate is added to the previously synthesized resin solution so that the non-volatile content is 20% by weight. It was added to prepare a binder resin solution 1. Here, the weight average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Preparation of binder resin solution 2)
207 parts of cyclohexanone was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C., the inside of the flask was replaced with nitrogen, and then methacrylic acid was added from the dropping tube. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobisisobutyronitrile. 1.33 parts of the mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Showa Denko's Karenz). A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. Approximately 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight to obtain the binder resin solution 2. Prepared. The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin solution 3)
123 g of cyclohexanone was introduced into a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the atmosphere inside the flask was changed from air to nitrogen, the temperature was raised to 100 ° C., and then benzyl methacrylate was used. 72.6 g (0.41 mol), 42.0 g (0.49 mol) of methacrylic acid, 23.0 g (0.10 mol) of monomethacrylate of tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) and A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture consisting of 137 g of cyclohexanone was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was further stirred at 100 ° C. for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 21.3 g of glycidyl methacrylate [0.15 mol, (31 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were placed in the flask and the reaction was continued at 110 ° C. for 6 hours. Approximately 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight to prepare the binder resin solution 3. Prepared. The weight average molecular weight (Mw) was 10,500.

(Preparation of binder resin solution 4)
370 parts of cyclohexanone was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, the temperature was raised to 80 ° C. Milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.) 18 parts, benzyl methacrylate 10 parts, glycidyl methacrylate 18.2 parts, methyl methacrylate 25 parts, and 2,2'-azobisisobutyronitrile 2.0 The mixture of parts was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100 ° C. for 3 hours, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container at 120 ° C. The reaction was continued for 6 hours, and when the solid content acid value reached 0.5, the reaction was terminated to obtain a copolymer solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently added and reacted at 120 ° C. for 3.5 hours to obtain a carboxyl group and a copolymer solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the previously synthesized resin solution so that the non-volatile content was 20% by weight. Binder resin solution 4 was prepared. The weight average molecular weight (Mw) was 19000.

<Manufacturing method of finely divided pigments>
(Blue refined pigment (P-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyo Color's "Rionol Blue ES"), 800 parts of crushed salt, and 100 parts of diethylene glycol are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. bottom. This mixture is poured into 3000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 98 parts of a blue fine pigment (P-1). The average primary particle size of the obtained pigment was 28.3 nm.

Here, the average primary particle size of the pigment is measured by measuring the primary particle size of all the pigment particles in the observation sample at a magnification of 50,000 using a transmission electron microscope (“JEM-1200EX” manufactured by JEOL Ltd.). The average value was used. When the particle shape was not spherical, the major axis and the minor axis were measured, and the value obtained by (major axis + minor axis) / 2 was taken as the particle diameter.

(Purple refined pigment (P-2))
Dioxazine-based purple pigment C.I. I. Pigment Violet 23 (“FastViolet RL” manufactured by Clariant), 1600 parts of crushed salt, and 100 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. This mixture is poured into 5000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 118 parts of a purple finely divided pigment (P-2). The average primary particle size of the obtained pigment was 26.4 nm.

(Red refined pigment (P-3))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 (“IRGAZINRED2030” manufactured by BASF Japan Ltd.), 1400 parts of crushed salt, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. This mixture is put into 8000 parts of warm water, stirred with a high speed mixer for about 2 hours while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 85 ° C. for 24 hours. The mixture was dried to obtain 190 parts of a red fine pigment (P-3). The average primary particle size of the obtained pigment was 24.8 nm.

(Red refined pigment (P-4))
Red pigment C.I. I. 200 parts of Pigment Red 242 (“NOVOPERMSCARLET4RF” manufactured by Clariant), 1400 parts of crushed salt, and 360 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. This mixture is put into 8000 parts of warm water, stirred with a high speed mixer for 2 hours while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 85 ° C. for 24 hours. Then, 190 parts of red fine pigment (P-4) was obtained. The average primary particle size of the obtained pigment was 28.5 nm.

<Manufacture of resin (B) having a cationic group in the side chain>
(Resin B-1 solution having a cationic group in the side chain)
25.0 parts of (3-ethyloxetane-3-yl) methyl acrylate, 40.0 parts of t-butyl acrylate, 5.0 parts of methacrylic acid in a reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer. 15.0 parts of methyl methacrylate, 15.0 parts of dimethylaminoethylmethyl chloride salt methacrylate, and 1.6 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to replace the inside of the system with nitrogen. .. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was raised to 100 ° C. under a nitrogen stream to start the polymerization of the first block. bottom. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content. Next, 8.1 parts of propylene glycol monomethyl ether and 15.0 parts of dimethylaminoethyl methyl chloride salt methacrylate as a second block monomer were added to this reactor, and the mixture was stirred while maintaining the atmosphere of 100 ° C. and nitrogen. , The reaction continued. Two hours after the addition of the dimethylaminoethylmethyl chloride salt methacrylate, the polymerization solution was sampled and the solid content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more in terms of the non-volatile content, and the reaction was carried out. The solution was cooled to room temperature to terminate the polymerization. As a result of GPC measurement, the polymer was Mw9200 and Mw / Mn = 1.5, and the reaction conversion rate was 98.5%. In this way, a block resin (B-1) having a quaternary ammonium salt value of 40 mgKOH / g per solid content was obtained. After cooling to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether is added so that the non-volatile content becomes 40% by weight to block resin (block resin ( B-1) A solution was obtained.

Here, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The ammonium salt value of the resin (B) having a cationic group in the side chain was determined by titrating with a 0.1 N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then determining the equivalent amount of potassium hydroxide. It is a converted value and indicates the ammonium salt value of the solid content.

(Resin B-2 to B-12 solutions having a cationic group in the side chain)
Block resin (B-2 to B-12) solutions were obtained in the same manner as in B-1, except that the type and blending amount of the monomers were changed as shown in Table 1.

(Resin B-13 solution having a cationic group in the side chain)
75.1 parts of isopropyl alcohol was placed in a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised to 75 ° C. under a nitrogen stream. Separately, 25.0 parts of (3-ethyloxetane-3-yl) methyl methacrylate, 40.0 parts of t-butyl methacrylate, 5.0 parts of methacrylic acid, 15.0 parts of methyl methacrylate, dimethylaminoethyl methyl chloride salt of dimethyl methacrylate. After homogenizing 15.0 parts and 7.0 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) separately dissolved in 23.4 parts of methyl ethyl ketone, it was charged into a dropping funnel and four-mouth separa. It was attached to a bull flask and added dropwise over 2 hours. Two hours after the completion of the dropping, it was confirmed from the solid content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 8330, and the mixture was cooled to 50 ° C. Then, 14.3 parts of methanol was added to obtain a resin (B-13) solution having a weight average molecular weight of 8500 and a non-volatile content of 40% by weight in the side chain having a cationic group. The ammonium salt value of the obtained resin was 40 mgKOH / g.

The abbreviations in Table 1 are shown below.
DMCMA: Dimethylaminoethyl methyl chloride salt DMCA: Dimethylaminoethyl methyl chloride salt MMA: Methyl methacrylate tBA: t-butyl acrylate tBMA: t-butyl methacrylate MAA: AA methacrylate: MMA acrylate: Methyl methacrylate BMA: Butyl methacrylate

<Manufacturing of anionic dye (C)>
(Synthesis of anionic dye 1)
C. I. 45.0 parts of Acid Red 289, 45.3 parts of 1-iodopropane and 36.8 parts of potassium carbonate were added to 280 parts of N-methylpyrrolidone, and the mixture was stirred at 90 ° C. for 6 hours. The obtained reaction solution was cooled to room temperature, added to 3000 parts of ethyl acetate, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were separated by filtration, washed with 2500 parts of ethyl acetate, and dried under reduced pressure at 60 ° C. overnight to obtain 47.6 parts of anionic dye.

(Synthesis of anionic dye 2)
C. I. 45.0 parts of Acid Red 289, 56.6 parts of 2-iodopropane and 46.0 parts of potassium carbonate were added to 360 parts of N-methylpyrrolidone, and the mixture was stirred at 85 ° C. for 12 hours. The obtained reaction solution was cooled to room temperature, added to 3600 parts of ethyl acetate, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were separated by filtration, washed with 3000 parts of ethyl acetate, and dried under reduced pressure at 60 ° C. overnight to obtain 243.0 parts of anionic dye.

(Synthesis of anionic dye 3)
The same operation as for the synthesis method of the anionic dye 1 was carried out except that 45.3 parts of 1-iodopropane was changed to 71.4 parts of 1-iododecane, and 53.2 parts of the anionic dye was obtained.

(Synthesis of anionic dye 4)
20.0 parts of the compound represented by the formula (20) and 8.5 parts of sulfanilic acid were added to 180 parts of N-methylpyrrolidone, and the mixture was stirred at 100 ° C. for 2 hours. Then 10.0 parts of aniline was added and stirred at 120 ° C. for 4 hours. The obtained reaction solution was cooled to room temperature, 2000 parts of ethyl acetate was added, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were separated by filtration and dried under reduced pressure overnight to obtain 25.7 parts of Intermediate 1. 25.0 parts of Intermediate 1, 28.2 parts of 1-iodopropane and 23.0 parts of potassium carbonate were added to 200 parts of N-methylpyrrolidone, and the mixture was stirred at 90 ° C. for 4 hours. The obtained reaction solution was cooled to room temperature, added to 2000 parts of ethyl acetate, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were separated by filtration, washed with 1500 parts of ethyl acetate, and dried under reduced pressure at 60 ° C. overnight to obtain 26.7 parts of anionic dye 4.

Equation (20)

The obtained anion dyes 1 to 4 are shown below. The anion dyes 1 to 4 are compounds represented by the following general formula (2) and further having a substituent in Table 2. In Table 2, * indicates a bond with N.
General formula (2)

<Manufacturing method of salt-forming compound (D)>
(Preparation of salt-forming compound D-1)
Follow the procedure below to C.I. I. A salt-forming compound (D-1) composed of Acid Red 52 and resin B-1 was produced.
Resin B-1 having a cationic group in the side chain of 42 parts is added to 2000 parts of water, and after sufficient stirring and mixing, the mixture is heated to 60 ° C. On the other hand, 90 parts of water and 10 parts of C.I. I. An aqueous solution in which Acid Red 52 is dissolved is prepared, and the solution is gradually added dropwise to the resin solution. After the dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, it was determined that the salt-forming compound was obtained by dropping the reaction solution onto the filter paper and using the point where the bleeding disappeared as the end point. After allowing to cool to room temperature with stirring, the counter anion of the resin having a cationic group in the side chain and C.I. I. After removing the salt consisting of the counter cation of Acid Red 52, the salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 32 parts of C.I. I. A salt-forming compound D-1 of Acid Red 52 and resin B-1 was obtained.

(Preparation of salt-forming compounds D-2 to 21)
Hereinafter, salt-forming compounds D-2 to 21 were prepared in the same manner as D-1 except that the resins and dyes having a cationic group in the side chain were changed to those shown in Table 3.

The abbreviations in Table 3 are shown below.
BYK2000: Disperbyk-2000 manufactured by Big Chemie Japan Co., Ltd. (Quaternary ammonium salt-containing block resin, which does not have t-butyl group and oxetanyl group)

<Manufacturing method of dispersant>
(Dispersant 1)
70 parts of methyl methacrylate, 20 parts of t-butyl methacrylate and 10 parts of methacrylic acid were charged in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., 6.0 parts of 1-thioglycerol was added, and the reaction was carried out for 12 hours. It was confirmed by solid content measurement that 95% had reacted. Next, 8.5 parts of pyromellitic anhydride, 115 parts of propylene glycol monomethyl ether acetate (PGMAc), and 0.20 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene (DBU) as a catalyst. Was added and reacted at 100 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated to obtain Dispersant 1 having a non-volatile content of 50% by weight, an acid value of 100 mgKOH / g, and a weight average molecular weight of 9000. rice field.

(Dispersant 2)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 25 parts of (3-ethyloxetane-3-yl) methyl methacrylate acrylate, 45 parts of t-butyl methacrylate, 20 parts of methyl methacrylate, and 10 parts of methacrylic acid were placed. It was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., 6.0 parts of 1-thioglycerol was added, and the reaction was carried out for 12 hours. It was confirmed by solid content measurement that 95% had reacted. Next, 8.5 parts of pyromellitic anhydride, 115 parts of propylene glycol monomethyl ether acetate (PGMAc), 1,8-diazabicyclo- [5. 4. 0] -7-Undesen (DBU) 0. 20 parts were added and the reaction was carried out at 100 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. The non-volatile content was 50% by weight, the acid value was 101 mg KOH / g, and the weight average molecular weight was 90. A dispersant 2 of 0 was obtained.

<Manufacturing of coloring compositions for color filters>
[Example 1]
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion (DB-1) was prepared by filtering with a filter.
Salt compound (D-1) 4.0 parts Fine pigment (P-1) 7.0 parts Binder resin solution 1 40.0 parts Cyclohexanone 10.0 parts Propylene glycol monomethyl ether acetate (PGMAC)
38.0 parts Dispersant (BASF Japan "EFKA4300")
1.0 copy

[Examples 2 to 21, 24 to 27, Comparative Examples 1 to 4]
Coloring compositions (DB-2 to 21, 24-31) were prepared in the same manner as in Example 1 except that the salt-forming compound, the refined pigment, and the binder resin solution were changed to the compositions shown in Table 4.
However, Example 9 is a reference example.

[Example 22]
The following mixture is stirred and mixed so as to be uniform, and then dispersed for 5 hours with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A pigment dispersion (DB-22) was prepared by filtering with a filter.
Salt compound (D-1) 4.0 parts Fine pigment (P-1) 7.0 parts Binder resin solution 1 40.0 parts Cyclohexanone 10.0 parts Propylene glycol monomethyl ether acetate (PGMAC)
37.0 parts Dispersant 1 2.0 parts

[Example 23]
A coloring composition (DB-23) was prepared in the same manner as in Example 22 except that the dispersant was changed to the composition shown in Table 4.

<Evaluation of coloring composition for color filter>
The obtained coloring composition (DB-13 to 31) was subjected to a test for storage stability over time by the following method. The results are shown in Table 4.

(Test on storage stability over time)
The coloring composition (DB-13 to 31) stored at 10 ° C. for half a year was applied onto a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm using a spin coater, and then 20 at 70 ° C. A coating film substrate was prepared by drying for a minute, then heating at 220 ° C. for 30 minutes, and allowing to cool, and the coated film substrate was observed at a magnification of 500 using an optical microscope.
<Evaluation criteria>
⊚: No foreign matter was found ○: Foreign matter was found but acceptable range ×: Foreign matter was generated frequently and was out of the allowable range

<Manufacturing of photosensitive coloring compositions for color filters>
[Example 28]
(Preparation of Blue Photosensitive Coloring Composition (R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare an alkali-developable resist material R-1.
Coloring composition (DB-1) 60.0 parts Binder resin solution 1 11.0 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.)
4.2 Part Photopolymerization Initiator (BASF Japan "Irgacure OXE01")
1.2 parts Cyclohexanone 5.2 parts Propylene glycol monomethyl ether acetate (PGMAC)
18.0 copies

[Examples 29 to 54, Comparative Examples 5 to 8]
Alkali-developed photosensitive coloring compositions (R-2 to 31) were prepared in the same manner as in Example 28 except that the coloring composition and the binder resin solution were changed to the coloring compositions shown in Table 5.
However, Example 36 is a reference example.

<Evaluation of photosensitive coloring composition for color filters>
The obtained photosensitive coloring composition (R-1 to 31) was evaluated for heat resistance of the coating film and subjected to an alkali developability test. The test method was as follows.

(Evaluation of heat resistance of coating film)
The coloring composition (R-1 to 31) was applied onto a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm using a spin coater, then dried at 70 ° C. for 20 minutes, and then dried at 220 ° C. for 30 minutes. A coating film substrate was produced by heating and allowing to cool. After the heat treatment at 220 ° C., the coating rotation speed of the spin coater was adjusted so that the film thickness of the produced coating film substrate was 2.0 μm. Use a microspectroscopy (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) to measure the chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source. Measured using. After that, as a heat resistance test, the mixture was heated at 230 ° C. for 1 hour, the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured, and the following formula was used. , The color difference ΔEab * was calculated. If it is less than Δ3.0, there is no problem in practical use.
ΔEab * ＝ √ ((L * (2) -L * (1)) 2+ (a * (2) -a * (1)) 2+ (b * (2) -b * (1)) 2)
◯: ΔEab * is less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Alkaline developability test)
The photosensitive coloring composition (R-1 to 31) is applied on a transparent glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm with a spin coater so that the film thickness after drying is about 2.0 μm, and at 70 ° C. After drying for 20 minutes, ultraviolet exposure was performed with an ^{integrated light intensity of 150 mJ / cm 2} using an ultrahigh pressure mercury lamp through a photomask having a striped opening having a width of 100 μm. When developing by rinsing the unexposed part with a 0.05% potassium hydroxide aqueous solution containing a surfactant, the development is performed with an appropriate development time of +10 seconds and +20 seconds, and the developed glass surface is subjected to a microdifferential photophotometer ( The measurement was carried out using "OSP-SP200" manufactured by Olympus Optical Co., Ltd., and the alkali developability was determined by the presence or absence of a residue.
〇: No residue at proper development time △: No residue at proper development time + 20 seconds ×: Residual at proper development time + 20 seconds

As in Examples 28 to 54, the resin containing the salt-forming compound (D) of the resin (B) having a cationic group in the side chain and the anionic dye (C) and having the cationic group is cationic. Since it is a block resin composed of an A block having a group and a B block having an oxetanyl group and a t-butyl group without having a cationic group, both have good heat resistance, and ΔEab is 3.0 or less. there were. In addition, the storage stability was excellent, foreign matter in the coating film was in the range where it could be used as a color filter, and the alkali developability was also good. On the other hand, in Comparative Example 7, since the resin having a cationic group did not have a block structure, the heat resistance was poor. Further, since Comparative Examples 5, 6 and 8 did not have an oxetanyl group and a t-butyl group at the same time, the heat resistance of ΔEab exceeded 3.0.

<Making color filters>
A red photosensitive coloring composition, a blue photosensitive coloring composition, and a green photosensitive coloring composition used for producing a color filter in combination with the photosensitive coloring composition of the present invention were prepared.

(Preparation of Green Photosensitive Coloring Composition (RG-1))
After stirring and mixing the mixture having the following composition so as to be uniform, the mixture was dispersed for 5 hours on an Eiger mill (“Mini model M-250MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then 5. The mixture was filtered through a 0 μm filter to prepare a green coloring composition (DG-1).
Green pigment (CI Pigment Green 58) 12.0 parts Resin type dispersant (BASF Japan "EFKA4300") 1.0 part Binder resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a green photosensitive coloring composition (RG-1).
Green coloring composition (DG-1) 34.0 parts Binder resin solution 1 15.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF Japan Ltd.) "Irgacure 907" 2.0 parts Sensitizer ("EAB-F" manufactured by Hodoya Chemical Industry Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 45.1 parts

A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (R-11) was applied onto the substrate with a spin coater to a film thickness such that x = 0.640 to form a colored film. The coating film was irradiated with ultraviolet rays of ^{300 mJ / cm 2} using an ultrahigh pressure mercury lamp via a photomask. Next, the unexposed portion was removed by spray development with an alkaline developer consisting of a 0.2 wt% sodium carbonate aqueous solution, washed with ion-exchanged water, and the substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Was formed. By the same method, the green photosensitive coloring composition (RG-1) is used to form a green filter segment having a thickness of y = 0.600, and then the blue photosensitive coloring composition (R) of the present invention is formed. -1) was formed into blue filter segments having a film thickness such that y = 0.060, and each of them was applied to obtain a color filter.

By using the photosensitive coloring composition of the present invention, the heat resistance and alkali developability of the color filter were improved, and the color filter could be suitably used.

Claims (8)

A coloring composition for a color filter, which comprises at least a colorant (A), a binder resin, and an organic solvent.
The colorant (A) contains a salt-forming compound (D) of a resin (B) having a cationic group in the side chain and an anionic dye (C).
The resin (B) having a cationic group in the side chain is an acrylic resin containing a structural unit represented by the following general formula (1), and the acrylic resin is
It is a block resin composed of at least an A block having a cationic group represented by the following general formula (1) and a B block having at least a t-butyl group and an oxetanyl group (however, it does not have a cationic group).
The B block of the block resin may contain a carboxyl group.
A coloring composition for a color filter in which the total number of moles of carbosilyl group and t-butyl group is 1.5 to 18.3 with respect to the number of moles of oxetanyl group of the block resin.

[In general formula (1),
R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group.
R _{2 to} R ₄ independently represent a hydrogen atom, an alkyl group which may be substituted, an alkenyl group which may be substituted, or an aryl group which may be substituted, and among _{R 2 to} R _{4, respectively.} The two may combine with each other to form a ring.
Q represents an alkylene group, an arylene group, —CONH-R ₅ −, —COO −R ₅ −, and R ₅ represents an alkylene group.
Y ^- is representative of an inorganic or organic anion. ]
The coloring composition for a color filter according to claim 1, wherein the resin (B) having a cationic group in the side chain is a copolymer of an ethylenically unsaturated monomer. Among all the ethylenically unsaturated monomers constituting the resin (B) having a cationic group in the side chain, a single amount which is a precursor of a block having a cationic group represented by the general formula (1) in the side chain. The coloring composition for a color filter according to claim 2, wherein the content of the body is 3% by mass to 30% by mass. The coloring composition for a color filter according to any one of claims 1 to 3, wherein the resin (B) having a cationic group in the side chain has an ammonium salt value of 10 to 200 mgKOH / g. The coloring composition for a color filter according to any one of claims 1 to 4, wherein the coloring agent further contains a pigment. The color filter according to any one of claims 1 to 5, wherein the anionic dye (C) contains at least one selected from Acid Red 52, Acid Red 289 and a compound represented by the following general formula (2). Coloring composition for.
General formula (2)

[X1 and X3 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
X2 and X4 each independently represent a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group. ] The coloring composition for a color filter according to any one of claims 1 to 6, further comprising at least one selected from a photopolymerizable monomer and a photopolymerization initiator. A color filter formed by the coloring composition for a color filter according to any one of claims 1 to 7.