JP2021086104A - Color filter coloring composition and color filter - Google Patents

Abstract

To provide a coloring composition which has superior robustness (heat resistance, solvent resistance), provides superior color characteristics (brightness) when used for color filters, generates no foreign matter and offers good stability, and to provide a color filter produced using the same.SOLUTION: The above challenge is cleared by a color filter coloring composition comprising a colorant (A), a binder resin, and an organic solvent, the colorant (A) comprising a specific salt-forming compound containing a triphenylmethane-based acidic dye.SELECTED DRAWING: None

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 imaging tube element, etc., and a color filter including a filter segment formed by using the coloring composition. is there.

A transparent electrode for driving a liquid crystal is generally formed on a color filter used in a color liquid crystal display device by vapor deposition or sputtering, and an alignment film for orienting the liquid crystal in a certain direction is formed on the transparent electrode. It is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to carry out the forming step at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher, and the color filter is required to have heat resistance.

Further, the voltage holding ratio can be mentioned as an index showing the display performance of the liquid crystal display device. Liquid crystal is a material with extremely high insulating properties, and when the polar compound remaining in the coloring composition for a color filter elutes into the liquid crystal cell, the voltage between the electrodes drops, causing a drop in the voltage retention rate, resulting in uneven display. Occurrence, misalignment, etc. may occur, which may reduce the performance of the liquid crystal display device. Therefore, the coloring composition for a color filter is required to be insoluble in liquid crystals.

Contrast ratio and lightness are important quality items required for color filters. If a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light leaks or when light must be transmitted (ON). Since the transmitted light is attenuated in the state), the screen becomes blurry. Therefore, in order to realize a high-quality liquid crystal display device, it is indispensable to increase the contrast ratio. Further, if a color filter having low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. However, from the viewpoint of suppressing power consumption, the trend is to increase the brightness of color filters.

Further, from the viewpoint of improving the image quality of color liquid crystal display devices and organic EL display devices, there is an increasing demand for color filters having higher color gamuts such as the Adobe RGB standard, the DCI standard, and the BT2020 standard. As a method for meeting the demand for higher color gamut, it is possible to increase the concentration of the colorant in the color filter or select a colorant having excellent coloring power. When the concentration of the colorant is increased, the photolithography suitability deteriorates such as the deterioration of the pattern linearity and the shape, and therefore it is desired to improve the coloring power of the colorant itself. Basically, there is a trade-off between high color gamut and optical characteristics (brightness / contrast ratio), and it is desired to develop a coloring composition that eliminates the trade-off. Therefore, in order to realize a high contrast ratio and high brightness that cannot be achieved with pigments, attention is being paid to dye-based coloring materials.

As the colorant used for forming the blue filter segment, a copper phthalocyanine pigment having excellent resistance and color tone is generally used, but the current situation is that the requirements for brightness and contrast ratio are not sufficiently met. It has also been proposed to use a triphenylmethane dye as a colorant for a color filter in order to achieve higher brightness and contrast ratio (Patent Documents 1 and 2). However, dyes are inferior in heat resistance, light resistance, and solvent resistance to pigments, and are not at a practical level.

As a method for improving heat resistance, Patent Document 3 proposes salt formation with phthalocyanine sulfonic acid or anthraquinone sulfonic acid as a counter for triphenylmethane dyes. However, even if a color filter is produced using such a dye, both heat resistance and light resistance are insufficient, and it has been confirmed that foreign matter is generated on the coating film. Further, Patent Document 4 proposes a triphenylmethane dye having good spectral characteristics and high solvent solubility, but the heat resistance is not satisfactory.

Japanese Unexamined Patent Publication No. 2001-81348 JP-A-2002-14222 Japanese Unexamined Patent Publication No. 2008-304766 Japanese Unexamined Patent Publication No. 2006-265438

The problem to be solved by the present invention is a coloring composition having excellent fastness (heat resistance, solvent resistance), excellent color characteristics (brightness) when used in a color filter, no foreign matter generation, and good stability. And to provide color filters.

As a result of diligent studies, the present inventors have made a coloring composition for a color filter composed of a coloring agent (A), a binder resin, and an organic solvent, wherein the coloring agent (A) has a general formula (1). A coloring composition for a color filter, which comprises a triphenylmethane acid dye (C) represented by a salt-forming compound (D) of a compound having a specific cationic group, solves the above-mentioned problems. We found that we could obtain it, and came up with the present invention.

〔式中Ｘ_１は、水素または置換基を有していても良い１価の炭素数１以上２０以下の脂肪族炭化水素基を表し、Ｘ_２は水素またはメチル基を表す。〕

一般式（２）

[一般式（２）中、Ｒ_１は水素原子、又は置換若しくは無置換のアルキル基を表す。Ｒ_２〜Ｒ_４は、それぞれ独立に、水素原子、置換されていてもよいアルキル基、置換されていてもよいアルケニル基、又は置換されていてもよいアリール基を表し、Ｒ_２〜Ｒ_４のうち２つは互いに結合して環を形成してもよい。Ｑ_１はアルキレン基、アリーレン基、−ＣＯＮＨ−Ｒ_５−、又は−ＣＯＯ−Ｒ_５−を表し、Ｒ_５はアルキレン基を表す。] That is, a coloring composition for a color filter containing a colorant (A), a binder resin, and an organic solvent, wherein the colorant (A) contains a salt-forming compound, and the salt-forming compound has a general formula ( The resin (E) contains a salt-forming compound (D) of a triphenylmethane-based acid dye (C) having a constituent unit represented by 1) and a resin (E) having a cationic group in a side chain. ) Shall have a structural unit represented by the following general formula (2), and the present invention relates to a coloring composition for a color filter.

General formula (1)

[In the formula, X ₁ represents an aliphatic hydrocarbon group having a monovalent carbon number of 1 or more and 20 or less, which may have a hydrogen or a substituent, and X ₂ represents a hydrogen or a methyl group. ]

General formula (2)

[In the general formula (2), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{2 to} R ₄ independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, respectively, of R _{2 to} R ₄ . Two of them may be combined with each other to form a ring. Q ₁ represents an alkylene group, an arylene group, -CONH-R _5- , or -COO-R _5- , and R ₅ represents an alkylene group. ]

Further, in the present invention, the resin (E) having a cationic group in the side chain contains at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, an oxetane group, and a t-butyl group. The present invention relates to the above-mentioned coloring composition for a color filter, which has a structural unit.

Further, in the present invention, the ratio of the salt-forming compound (D) to the theoretical value ((the salt-forming rate of the salt-forming compound (D)) / (the theoretical value of the salt-forming rate of the salt-forming compound (D)). ) Is 80% or more, the above-mentioned coloring composition for a color filter.

Further, the present invention is a coloring composition for a color filter containing a coloring agent (A), a binder resin, and an organic solvent, wherein the coloring agent (A) is triphenylmethane represented by the general formula (1). The present invention relates to the above-mentioned coloring composition for a color filter, which comprises a salt-forming compound of an acid dye (C) and a divalent or trivalent metal salt.

The present invention also relates to the above-mentioned coloring composition for a color filter, wherein the coloring agent (A) further contains a xanthene dye and / or a cyanine dye.

The present invention also relates to the above-mentioned coloring composition for a color filter, wherein the coloring agent (A) further contains a blue pigment having a copper phthalocyanine skeleton.

The present invention also relates to the above-mentioned coloring composition for a color filter, which further contains a photopolymerizable monomer and / or a photopolymerization initiator.

The present invention also relates to a color filter including a filter segment formed by the coloring composition for a color filter.

Hereinafter, the present invention will be described in detail.
In the present application, when "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", or "(meth) acrylate" is described, unless otherwise specified, "(meth) acrylate" is used. It shall represent "acryloyl and / or methacrylic acid", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", or "acrylate and / or methacrylate".
Further, "CI" mentioned in the present specification means a color index (CI).

The coloring composition for a color filter of the present invention is a coloring composition for a color filter composed of at least a coloring agent (A), a binder resin, and an organic solvent, and the coloring agent (A) is represented by the general formula (1). The present invention relates to a coloring composition for a color filter, which comprises a salt-forming compound (D) of a triphenylmethane-based acid dye (C) and a compound (B) having a cationic group.

<Triphenylmethane acid dye (C) represented by the general formula (1)>
First, the triphenylmethane acid dye (C) represented by the general formula (1) will be described.
General formula (1)

X ₁ represents an aliphatic hydrocarbon group having a monovalent carbon number of 1 to 20 and which may have hydrogen or a substituent. Aliphatic hydrocarbon groups are desirable from the viewpoint of heat resistance, and among them, aliphatic hydrocarbon groups of 2 or more and 6 or less are desirable.

Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by X _{1 include linear, branched, and cyclic aliphatic hydrocarbon groups.} Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group. , N-Undecyl group, n-dodecyl group and other linear saturated hydrocarbon groups, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, methylpentyl group, ethylbutyl group, methylhexyl group, Ethylpentyl group, propylbutyl group, (methylethyl) butyl group, (methylethyl) (methyl) propyl group, methylheptyl group, ethylhexyl group, propylpentyl group, (methylethyl) pentyl group, butylbutyl group, (butyl) ( (Methyl) butyl group, (dimethylethyl) (butyl) butyl group, dimethylpropyl group, dimethylbutyl group, (ethyl) (methyl) propyl group, dimethylpentyl group, (ethyl) (methyl) butyl group, dimethylhexyl group, ( Branched chain saturated hydrocarbon groups such as ethyl) (methyl) pentyl group, (propyl) (methyl) butyl group, (methylethyl) (methyl) butyl group, diethylbutyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group , Cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group and other alicyclic saturated hydrocarbon groups.
X ₁ may further have a substituent in the aliphatic hydrocarbon group. Specific examples thereof include an alkoxy group such as a methoxy group, an ethoxy group and a propoxy group, and a monovalent aromatic hydrocarbon group such as a phenyl group, a 1-naphthyl group and a 2-naphthyl group.

X ₂ represents a hydrogen atom or a methyl group. From the viewpoint of lightness, it is preferably a methyl group.

Examples of the triphenylmethane acid dye (C) represented by the general formula (1) include structures represented by the formulas (1-1) to (1-9).

Next, the resin (E) having a cationic group in the side chain will be described.

<Resin (E) having a cationic group in the side chain>
The resin (E) having a cationic group in the side chain of the present invention contains a structural unit represented by the following general formula (2), and the cationic group in the formula is the anionic group of the anionic dye (C). By forming a salt, the salt-forming compound (D) of the present invention can be obtained.

General formula (2)

In the general formula (2), R ₁ represents an alkyl group which may have a hydrogen atom or a substituent. R _{2 to} R ₄ independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or an aryl group which may have a substituent, and R ₂ two of to R ₄ may be bonded to each other to form a ring. Q ₁ is an alkylene group, an arylene group, _{-CONH-R 5} - or _{-COO-R 5} - represents, _{R 5} represents an alkylene group.

_{Examples of the alkyl group in R 1} in the general formula (2) 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. Be done. 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 alkoxy group.

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

_{Examples of the alkyl group in R 2 to} R ₄ in the general formula (2) 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 in the general formula (2) include a linear or branched alkenyl group (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 and 3-cyclo) Hexenyl, etc.). 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 in the general formula (2) include a monocyclic aryl group (phenyl, etc.) and a condensed polycyclic aryl group (naphthyl, anthracenyl, phenanthrenyl, anthracinolyl, fluorenyl, naphthoquinolyl, etc.). And 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 Examples thereof include −oxoxanthenyl (group derived from xanthone) and 9-oxothioxanthenyl (group derived from thioxanthone).

_{When the alkyl group, alkenyl group, or aryl group represented by R 2 to} R ₄ in the general formula (2) has a substituent, the substituent includes, for example, a halogen atom, a hydroxyl group, an alkoxy group, or an aryloxy group. , Alkenyl group, acyl group, alkoxycarbonyl group, carboxy group, phenyl group and the like. As the substituent, a halogen atom, a hydroxyl group, an alkoxy group and a phenyl group are particularly preferable.

_{As R 2 to} R ₄ in the general formula (2), 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 in} the general formula (2) may be bonded to each other to form a ring.

In the general formula (2), Q ₁ connecting 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. , polymerizable, for reasons of _{availability, -CONH-R 5 -, -} COO-R 5 - is preferably. 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 structural unit represented by the general formula (2) may have an inorganic or organic counter 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; and carboxylate 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 carboxylate 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 the resin (B) having a cationic group in the side chain containing the structural unit represented by the general formula (2), an ethylenically unsaturated monomer having an ammonium base is copolymerized as a monomer component. In addition to the method, an acrylic resin having an amino group copolymerized with an ethylenically unsaturated monomer having an amino group as a monomer component is obtained, and then an onium chloride agent is reacted to obtain ammonium chloride. You may.

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, methacrylic" 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".

<Ethylene unsaturated monomer having an ammonium base>
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) acryloylamino-based quaternary ammonium salts, dimethyldialylammonium methylsulfate, trimethylvinylphenylammonium chloride and the like can be mentioned.

<Ethylene unsaturated monomer having an amino group>
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.

<Onium Chloride>
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, and particularly when the vinyl monomer is ammonium chloride is ammonium chloride, the temperature is preferably about 30 ° C. or lower, 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 in 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 and an ammonium base can be obtained.

<Other monomers>
Examples of other ethylenically unsaturated monomers include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, and (meth) acrylamide. , Vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferred.

Specific examples of such ethylenically unsaturated monomers include the following compounds.

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- (meth) acrylic acid. Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2 (meth) acrylate -Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecil (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxy (meth) acrylate Ethyl, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene g (meth) acrylate Recall monoethyl ether, (meth) acrylate triethylene glycol monomethyl ether, (meth) acrylate triethylene glycol monoethyl ether, (meth) acrylate polyethylene glycol monomethyl ether, (meth) acrylate polyethylene glycol monoethyl ether, ( Β-Phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, ( Octafluoropentyl (meth) acrylate, perfluorooctyl ethyl acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, etc. Is done.

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, and dibutyl itaconic acid.

Examples of (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylic amide, N-isopropyl (meth) acrylamide, N- n-Butyl acrylic (meth) amide, N-t-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylic amide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) Examples thereof include acrylamide, N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholin, and diacetoneacrylamide.

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, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl. Examples include styrene, hydroxystyrene protected by a group that can be deprotected by an acidic substance (for example, t-Boc), methyl vinylbenzoate, and α-methylstyrene.

<Ethylene unsaturated monomer having a thermally crosslinkable group>
The resin (E) having a cationic group in the side chain of the present invention is selected from the group consisting of a hydroxy group, a carboxy group, an oxetane group, and a t-butyl group in addition to the structural unit represented by the general formula (2). It is preferable to contain at least one thermally crosslinkable group from the viewpoint of improving heat resistance and solvent resistance. In order to introduce these thermally crosslinkable groups into the resin (E) having a cationic group in the side chain, a method of copolymerizing an ethylenically unsaturated monomer having a thermally crosslinkable property as a monomer component can be mentioned. ..

(Ethylene unsaturated monomer having a hydroxy group)
Examples of the ethylenically unsaturated monomer having a hydroxy group include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, but if it has a hydroxy group, it can be used in addition to this. can do.

(Ethylene unsaturated monomer having a carboxy group)
Examples of ethylenically unsaturated monomers having a carboxy 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 and itaconic anhydride, but other unsaturated monomers can be used as long as they have a carboxy group.

(Ethylene unsaturated monomer having a t-butyl group)
As an example of the ethylenically unsaturated monomer having a t-butyl group, for example, if t-butyl acrylate, t-butyl methacrylate and the like have a t-butyl group, they may be used in addition to this. Can be done.

(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- (Methylmethacryloyloxymethyl) 3-hexyl oxetane and the like can be mentioned, but other than this can be used as long as it has an oxetanyl group.

The hydroxy group, carboxy group, oxetane group, and t-butyl group need to be contained at least one kind in the resin, and may be contained in two or more kinds.

(Method for synthesizing resin (E) having a cationic group in the side chain)
Known methods such as anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization are suitable methods for obtaining the resin (E) having a cationic group in the side chain in the present invention. Can be used. Of these, free radical polymerization or living radical polymerization is preferable.

The resin (E) having a cationic group in the side chain suitable for the present invention may be either a random type or a block type, but the block type is preferable from the viewpoint of heat resistance.

(Method for synthesizing resin (E) having a cationic group in the block type side chain)
The resin (E) having a cationic group in the side chain of the block type is composed of an A block having a structural unit represented by the general formula (2) and a B block having a specific group. The BAB block or ABA is preferable, and the AB block and BAB block can be more preferably used. Such a block type resin is 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 and composition of the polymer can be freely controlled by the charge ratio of the polymerization initiator added at the time of polymerization and the ethylenically unsaturated monomer. It can be used in the production of terminal functional polymers and the like.

The block-type resin of the present invention can be synthesized by a known living radical 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 an addition-polymerizable monomer and a radical initiator to polymerize using a dithiocarboxylic acid ester or xanthate compound as an initiator compound (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) Refer to the pamphlet of International Publication No. 1999-05099 (Reference 7) Japanese Patent Application Laid-Open No. 2007-277533 (Reference 8) JournalofAmericanChemicalSociety (2002) 124,2874

Among these living radical 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 atom 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, p-toluenesulfonic acid chloride, 1-bromoethylbenzene, chloroethylbenzene and the like. These are used alone or in combination.

<Content of the structural unit represented by the general formula (2) in the resin (E) having a cationic group in the side chain>
In the resin (E) having a cationic group in the side chain of the present invention, the content of the structural unit represented by the general formula (2) is not particularly limited, but is in 100% by weight of the total structural units constituting the resin. It is preferably 4 to 74% by weight, more preferably 8 to 48% by weight. Within this range, the dye-derived coloring power of the salt-forming compound (D) is excellent, and the affinity for the solvent as the dispersion medium can be sufficiently secured, so that foreign substances are not generated and the mixture is stable over time. The sex becomes good.

In the resin (E) having a cationic group in the side chain of the block type, the content of the A block containing the structural unit represented by the general formula (2) is preferably 5% by mass to 74% by mass, preferably 10% by mass. ~ 48% by mass is preferable. Similarly, in the block type, when it is in this range, the A block contributes to the excellent coloring power when it is used as the salt-forming compound (D), and the B block functions as a part compatible with the solvent which is the dispersion medium. The salt-forming compound can be stably present in the dispersion medium, and the stability over time is improved.

The content of the structural unit represented by the general formula (2) in the A block is preferably 80% by mass to 100% by mass, preferably 90% by mass to 100% by mass, and particularly preferably 100% by mass.

<Weight average molecular weight of resin (E) having a cationic group in the side chain>
The molecular weight of the resin (E) having a cationic group in the side chain is not particularly limited, but in both the random type and the block type, the converted weight average molecular weight measured by gel permeation chromatography (GPC) is It is preferably 1,000 to 500,000, more preferably 3,000 to 15,000. Within the above range, both the stability over time and the solvent resistance of the salt-forming compound can be achieved.

Further, the resin (E) having a cationic group in the side chain preferably has a property of being soluble in a solvent widely used in a coloring composition for a color filter. As a result, a coating film that does not generate foreign matter can be obtained. In particular, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

<Polymerization solvent>
In the step of producing the resin (E) 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.

<Method for producing salt-forming compound (D) with resin (E) having a cationic group in the side chain>
The salt-forming compound (D) of the present invention is prepared by stirring or vibrating an aqueous solution in which a resin (E) having a cationic group in the side chain and a triphenylmethane acid dye (C) are dissolved, or the side chain. It can be easily obtained by mixing an aqueous solution of a resin (E) having a cationic group and an aqueous solution of a triphenylmethane acid dye (C) under stirring or vibration. In the aqueous solution, the cationic group of the compound 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 compound and the counter cation of the acid dye is water-soluble, it can be removed by washing with water or the like. As the compound (B) having a cationic group and the triphenylmethane-based acid dye (C) to be used, only one kind may be used, or a plurality of kinds having different structures may be used.

As an aqueous solution used for salt formation, a mixed solution of water and a water-soluble organic solvent is used to dissolve the resin (E) having a cationic group in the side chain and the triphenylmethane acid dye (C). May be good. 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).

<Divalent or trivalent metal salt>
The colorant (A) may be a salt-forming compound (D) of a triphenylmethane-based acid dye (C) represented by the general formula (1) and a divalent or trivalent metal. Examples of the divalent or trivalent metal include Ca, Ba, Al, Mn, Sr, Mg and Ni. Among these, when Al is used, a coloring composition having good heat resistance and high brightness can be obtained.

<Method for producing salt-forming compound (D) with divalent or trivalent metal>
A powder or aqueous solution of divalent or trivalent metal chloride, sulfate, nitrate, etc. is slowly added to the aqueous solution of the triphenylmethane acid dye (C) over 10 minutes to 5 hours to salt. Perform a forming reaction. The amount of the metal added is about equimolar to 5 times the valence of the acidic group of the triphenylmethane acid dye (C) until the bleeding is stopped. Then, the precipitated product is filtered off, washed thoroughly with water, and dried to obtain the desired product.

<Calculation of salt formation rate in salt formation compound (D)>
The salt-forming rate is the content (% by weight) of the active dye component derived from the triphenylmethane-based acid dye (C) in the salt-forming compound (D).
The salt production rate can be calculated by the following formula.
Salt production rate = A / B
A is an absorbance value at a wavelength at which the absorbance is maximized when the absorbance of a 10 ppm methanol solution of triphenylmethane acid dye (C) alone is measured using an ultraviolet-visible spectrophotometer. Further, B is an absorbance value at a wavelength at which the absorbance is maximized when the absorbance of the salt-forming compound (D) in a 10 ppm methanol solution is measured using an ultraviolet-visible spectrophotometer.
On the other hand, the theoretical value of the salt formation rate (theoretical salt formation rate) is the total cationic unit of the triphenylmethane acid dye (C) and the acrylic resin (E) having a cationic group in the side chain. It can be calculated from the weight ratio when the molar ratios of the above are set to be the same.

Ratio of salt-forming compound (D) to theoretical value = (salt-forming compound (D) salt-forming rate) / (salt-forming compound (D) salt-forming rate theoretical value)
And said.

When the salt-forming ratio derived from the triphenylmethane-based acid dye (C) in the salt-forming compound (D) is 80% or more with respect to the theoretical value, the heat resistance is excellent and the brightness is high. The reason why the salt formation rate dissociates from the theoretical value is that the counter anion of the resin (E) having a cationic group remains in the side chain during the synthesis of the salt formation compound (D), and the cation is contained in the salt formation compound (D) compound. The causes include the case where the resin (E) having a sex group is contained in a larger amount than the theoretical value, the triphenylmethane acid dye (C) is decomposed and the color is not developed, and the like. The salt formation rate of the salt-forming compound (D) is preferably 80% or more with respect to the theoretical value, and more preferably 90% or more from the viewpoint of heat resistance and lightness.

<Other colorants>

The coloring composition for a color filter of the present invention may contain pigments and dyes as long as the effects of the present invention are not impaired, in order to adjust the chromaticity and further improve the heat resistance.

As other colorants, pigments and dyes of various colors such as blue and purple can be used. Examples of the pigment include organic pigments such as phthalocyanine type, quinacridone type, benzimidazolone type, dioxazine type, indanthrone type, perylene type, rhodamine lake type, azo type and aminoketone type. In addition to this, various inorganic pigments and the like can also be used.

Examples of pigments used in combination are given below. "CI" means a color index (CI).

Examples of the blue pigment include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like can be mentioned.
Among these, C.I., which is preferably a blue pigment having a copper phthalocyanine skeleton. I. Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment Blue 15: 6.

As the purple pigment, C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Of these, C.I. I. Pigment Violet 19, 23, more preferably CI. Pigment Violet 23.

In order to maintain sufficient brightness as a coloring component for a color filter, the pigment component is preferably in the range of 500 parts by mass or less with respect to 100 parts by mass of the salt-forming compound (D) of the present invention.

The dye that can be used in combination is a dye that exhibits blue, red, or purple, and preferably has any form of an oil-soluble dye, an acid dye, a direct dye, and a basic dye. Among these, it is preferable to use a xanthene dye or a cyanine dye because of its excellent hue. In addition, rake pigments obtained by raked these dyes, inorganic salts of acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acid dyes and nitrogen-containing compounds, sulfonic acid amide compounds of acid dyes, and the like. It may be.

(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, since it is possible to form a filter segment having high contrast, it is preferably 80 nm or less. 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 salt milling 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, 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 subjected to salt milling treatment, 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 coloring composition of the present invention contains a binder resin. The binder resin is one that disperses a colorant or 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 carboxy 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, is preferably used because of its 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 resins in which an unsaturated ethylenically double bond is introduced by the methods (a) to (c) shown below.

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group with one or more other types of monomers can be used. , An unsaturated monobasic acid having a unsaturated ethylenic double bond is subjected to an addition reaction, and a polybasic acid anhydride is reacted with the generated hydroxyl group to form an unsaturated ethylenic double bond and a carboxy 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 unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxy, halogen, nitro, and cyano substituents. 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 carboxy groups, a tricarboxylic dianhydride such as trimellitic hydride is used, or a tetracarboxylic dianhydride such as pyromellitic dianhydride is used to obtain the remaining anhydride. The group can also be hydrolyzed. Further, when tetrahydrophthalic 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.

[Method (b)]
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 carboxy group with one or more other monomers. There is a method of introducing an unsaturated ethylenically double bond and a carboxy group by adding an unsaturated ethylenic monomer having an epoxy group to a part of the carboxy group.
In this method, more hydroxyl groups derived from unsaturated ethylenic monomers having an epoxy group are generated as compared with the method (a). When the resin having a cationic group in the side chain used to obtain the salt-forming compound of the present invention contains an oxetanyl group and a t-butyl group as thermally crosslinkable functional groups, the method as a binder resin ( It is preferable to use the resin obtained in b) because it exhibits higher heat resistance.

[Method (c)]
As the method (c), an unsaturated ethylenic monomer having a hydroxyl group is used, and by copolymerizing with an unsaturated monobasic acid monomer having another carboxy group or another monomer. There is a method of reacting the side chain hydroxyl group of the obtained copolymer with the isocyanate group of the 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 addition-polymerizing 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.

When the binder resin is used as the photosensitive composition, it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g from the viewpoint of dispersibility, permeability, developability and heat resistance of the pigment and the salt-forming compound. 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, fine patterns may not remain.

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 mass or more based on the total weight of the colorant (100% by mass), and the colorant concentration is high and good. Since it can exhibit color characteristics, it is preferably used in an amount of 500% by mass or less.

<Thermosetting compound>
The coloring composition of the present invention can further contain a thermosetting compound in combination with a thermoplastic resin which is a binder resin. When a color filter is produced using the coloring composition for a color filter of the present invention, the inclusion of a thermosetting compound causes a reaction during firing of the filter segment to increase the crosslink density of the coating film, and thus the heat resistance of the filter segment is increased. It is improved, pigment aggregation at the time of firing the filter segment is suppressed, and the effect of improving the contrast ratio can be obtained.

Thermosetting compounds include, for example, epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins. Examples include, but are not limited to, urea compounds and / or resins, and phenolic compounds and / or resins. Epoxy compounds and / or resins are preferably used in the coloring composition for color filters of the present invention.

The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxy). Weight of benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and polymers of various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadien, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), phenol Polycondensate of class and ketones (acetone, methylethyl ketone, methylisobutylketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol , Biphenyldimethanol, α, α, α', α'-biphenyldimethanol, etc.) and phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) Examples thereof include polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylizing alcohols, alicyclic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like. However, the epoxy compound is not limited to these as long as it is a commonly used epoxy compound. These may be used alone or two or more kinds may be used.

Examples of commercially available products include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (or more). Is a product name: Japan Epoxy Resin Co., Ltd., TECHMORE VG3101L (Product name: Mitsui Chemicals Co., Ltd.), EPPN-501H, 502H (Product name: Nippon Kayaku Co., Ltd.), JER 1032H60 (Product name) ; Made by Japan Epoxy Resin Co., Ltd., JER
157S65, 157S70 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (trade name; manufactured by Nippon Kayaku Co., Ltd.), Serokiside 2021, EHPE-3150 (trade name; manufactured by Daicel Chemical Industry Co., Ltd.), Examples thereof include Denacol EX-810, EX-830, EX-851, EX-512, EX-421, EX-313, EX-201, EX-111 (the above are trade names; manufactured by Nagase ChemteX Corporation). However, it is not limited to these.

The blending amount of the epoxy compound is preferably 0.5 to 300 parts by mass, and more preferably 1.0 to 50 parts by mass with respect to 100 parts by weight of the colorant. If it is less than 0.5 parts by mass, the effect of improving heat resistance is small, and if it is more than 300 parts by mass, a problem may occur when forming a filter segment by photolithography.

Further, the coloring composition for a color filter 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 compound. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but the curing agent is not particularly limited thereto and can react with thermosetting compounds. Any curing agent may be used as long as it is used. 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). 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.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4) -Diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) Can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound.

<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 (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic amidin compounds and salts thereof (eg, eg). 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.

<Organic solvent>
The coloring composition of the present invention contains an organic solvent. The organic solvent makes it easy to sufficiently disperse and permeate the colorant in the colorant carrier and apply it on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a filter segment. Can be.

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-Butanol, 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 Examples thereof include hexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester.

Among them, ethyl lactate and propylene glycol monomethyl are excellent in dispersion and dissolution of the salt-forming compound of the fluorescent dye used in the present invention, the salt-forming compound of the metal complex salt dye, the pigment used as an option and other dyes that can be used in combination. It is preferable to use glycol acetates such as ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and 3-methoxybutanol, and ketones such as cyclohexanone. .. In particular, it is most preferable to use 3-methoxybutanol from the viewpoint of the solubility of the fluorescent dye used in the present invention in the salt-forming compound and the metal complex salt-forming dye in the salt-forming compound.

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 mass.

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, it should be used in an amount of 500 to 4000 parts by mass with respect to 100 parts by mass of the colorant. Is preferable.

<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.

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.
These photopolymerizable monomers may be used alone or in admixture of two or more at any ratio as required.

The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 to 300 parts by mass from the viewpoint of photocurability and developability. ..

<Photopolymerization initiator>
To the coloring composition of the present invention, a photopolymerization initiator is added to cure the composition by ultraviolet irradiation and to form a filter segment by a photolithography method, and a solvent-developed or alkali-developing photosensitive coloring composition is added. Can be prepared in the form of.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 -Acetophenone compounds such as 4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -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-benzoyloxime) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxyamine; 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; carbazole A system compound; an imidazole system compound; or a titanosen system compound or the like is used.
These photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required. The content of the photopolymerization initiator is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 3 to 150 parts by mass from the viewpoint of photocurability and developability.

<Sensitizer>
Further, a sensitizer can be added to the coloring composition for a color filter of the present invention.
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, azurenium 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, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, α-Acyloxy ester , Acylphosphine oxide, methylphenylglioxylate, 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.
These sensitizers can be used alone or in admixture of two or more at any ratio, if necessary.

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

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

<Multifunctional thiol>
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol that acts as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene. Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropanthithioglycolate, trimethylolpropanthithiopropionate, trimethylolpropanthris (3-mercaptobutyrate), pentaerythritol tetraxthioglycolate, Pentaerythritol tetraxthiopropionate, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-) Dibutylamino) -4,6-dimercapto-s-triazine and the like can be mentioned. These polyfunctional thiols can be used alone or in admixture of two or more at any ratio as required.

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

<Antioxidant>
The coloring composition for a color filter of the present invention may contain an antioxidant. The antioxidant is a transmittance of the coating film in order to prevent the photopolymerization initiator and the thermosetting compound contained in the coloring composition for the color filter from being oxidized and yellowed by the thermal process at the time of thermosetting or ITO annealing. Can be raised. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorbing function, a radical catching function, or a peroxide decomposition function. Specifically, the antioxidant is a hindered phenol-based or a hindered amine-based compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxyamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the preferred ones are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Agents can be mentioned. Further, more preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant.

These antioxidants may be used alone or in admixture of two or more at any ratio as required. The content of the antioxidant is more preferably 0.5 to 5.0% by mass based on the solid content weight of the coloring composition for a color filter because the brightness and sensitivity are good.

<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 mass based on the total weight of the coloring composition (100% by mass).

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 the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. 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 Examples include ester.

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.

<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 chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass with respect to 100 parts by mass of the colorant.

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 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition.

<Manufacturing method of coloring composition for color filter>
The coloring composition of the present invention can be produced by dispersing the coloring agent (A) in a coloring agent carrier such as a binder resin and / or a solvent using a dispersion aid (coloring agent dispersion). As the dispersing means, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, an attritor, or the like is appropriately selected and dispersed as necessary. At this time, two or more kinds of colorants (A) may be dispersed in the colorant carrier at the same time, or those dispersed separately in the colorant carrier may be mixed.
The active energy ray-curable resin having an ethylenically unsaturated double bond may be added at the stage of preparing the colorant dispersion, or the same effect can be obtained by adding it to the prepared colorant dispersion later. From the viewpoint of stability of the coloring composition, it is preferable to add the photosensitive coloring composition at the stage of preparation.
If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need. In this case, the dispersion aid can be used only by adding and mixing with a colorant solution in which a dye or the like is dissolved.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkaline-developed coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a resin-type dispersant, a dye derivative, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has high brightness and viscosity stability. Become good.

(Dye derivative)

As the dye derivative used in the present invention, a known dye derivative having an acidic group, a basic group, a neutral group or the like in the organic dye residue can be used. For example, a compound having an acidic substituent such as a sulfo group, a carboxy group or a phosphate group, an amine salt thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, a phenyl group or a phthalimide. Examples thereof include compounds having a neutral substituent such as an alkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzo. Indole pigments such as isoindole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, etc. Be done.

Specifically, as the diketopyrrolopyrrole dye derivative, JP-A-2001-22520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine. Examples of the dye derivative are JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, Patent No. 5735266, and as an anthraquinone-based dye derivative, JP-A-63-264674. Japanese Patent Application Laid-Open No. 09-272812, Japanese Patent Application Laid-Open No. 10-245501, Japanese Patent Application Laid-Open No. 10-265697, Japanese Patent Application Laid-Open No. 2007-079094, WO2009 / 025325 pamphlet, as a quinacridone-based dye derivative, JP-A-48- 54128, 03-9961 and 2000-273383, the dioxazine dye derivative is 2011-162662, and the thiazineindigo dye derivative is 2007-314785. Examples of JP, Triazine-based dye derivatives include JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, and JP-A-2004-217842. JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, JP-A-2003-167112, JP-A-2006-291194, and JP-A as quinophthalone-based dye derivatives. 2008-31281, 2012-226110, naphthol dye derivatives are 2012-208329, 2014-5439, and azo dye derivatives are 2001-172520. Japanese Unexamined Patent Publication No. 2012-172092, JP-A-2004-307854 as acidic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005 as basic substituents. Examples thereof include known dye derivatives described in Japanese Patent Application Laid-Open No. -181383, Japanese Patent Application Laid-Open No. 2005-213404, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a sex group is synonymous with a dye derivative.

These dye derivatives 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 colorant-affinitive portion having a property of adsorbing to the additive colorant and a portion compatible with the colorant carrier, and is adsorbed on the additive colorant and dispersed on the colorant carrier. It works to stabilize. 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 carboxy group. Oily dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Water-soluble resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphate ester-based, etc. are used, and these can be used alone or in admixture of two or more. However, it is not necessarily limited to these.

The resin type dispersant is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the colorant.

Examples of commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, manufactured by Big Chemi Japan. 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykuman, etc. 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, manufactured by BASF. 4,300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajinomoto Fine-Techno's Ajispa-PA111, PB711, PB821, PB822, PB824 and the like are preferable.

Further, the resin type dispersant used in the present invention preferably contains the following (S1) or (S2) as a resin type dispersant having a carboxy group.
(S1) A resin-type dispersant which is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic dianhydride.
(S2) A weight obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. A resin-type dispersant that is a coalescence.

≪Resin type dispersant (S1) ≫
The resin-type dispersant (S1) can be produced by a known method such as WO2008 / 007776, Japanese Patent Application Laid-Open No. 2008-029901, and Japanese Patent Application Laid-Open No. 2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal. For example, the ethylenically unsaturated monomer (r) is polymerized in the presence of the compound (q) having a hydroxyl group. It can be obtained as a polymer. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since the number of terminal hydroxyl groups is preferably plural, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferable example, a polymer having two hydroxyl groups at one end contains a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (p1) obtained by polymerizing the ethylenically unsaturated monomer (r) contained therein. The hydroxyl group of the polymer (p) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydrous ring is opened and the carboxylic acid. Produces.

≪Resin type dispersant (S2) ≫
The resin-type dispersant (S2) can be produced by a known method such as JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, and for example, a compound having a hydroxyl group. By polymerizing the ethylenically unsaturated monomer (r) in the presence of a reaction product of the hydroxyl group of (q) and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. can get. Above all, in the presence of a reaction product of the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. It is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing the monomer (r1).

The difference between (S1) and (S2) is whether the introduction of the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is performed first or later. The molecular weight and the like may differ slightly depending on various conditions, but theoretically the same can be obtained if the reaction conditions are the same as those of the raw material.

(Surfactant)
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 alkylimidazolin, 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 a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass with respect to 100 parts by mass of the colorant. If the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by mass, the dispersion may be affected by the excess dispersant. ..

<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, a sintered filter, a 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. Examples of the color filter include those including a red filter segment, a green filter segment, and a blue filter segment, or those including 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, a transparent electrode made of indium oxide, tin oxide or the like may be formed on the surface of the glass plate or the resin plate for driving the liquid crystal after the panelization.

<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. Further, with the development of printing technology, it is possible to print a fine pattern 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-developing type or alkali-developing type 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.

The color filter is bonded to the opposite substrate using a sealing agent, liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. A liquid crystal display panel is manufactured by laminating.

Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optical convencend bend (OCB). It can be used in the liquid crystal display mode in which colorization is performed using a color filter such as.

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".

(Average molecular weight of acidic dispersant and binder resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the acidic dispersant and the binder resin are GPC (Tosoh, HLC-8120GPC) equipped with an RI detector using a TSKgel column (manufactured by Tosoh). , The polystyrene-equivalent number average molecular weight (Mn) and the weight average molecular weight (Mw) measured using THF as a developing solvent.

(Acid value of acid dispersant and binder resin)
The acid value of the acidic dispersant and the resin (E) resin having a cationic group in the side chain is a value obtained by converting the measured acid value (mgKOH / g) into a solid content in accordance with the potentiometric titration method of JIS K 0070. is there.

(Average molecular weight of the resin (E) having a cationic group in the side chain)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin (E) having a cationic group in the side chain were measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Ammonium salt value of resin (E) having a cationic group in the side chain)
The ammonium value of the resin (E) 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 converted to an equivalent amount of potassium hydroxide. It is a value (mgKOH / g) obtained by converting the measured total ammonium salt value into the solid content of the resin.

<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.

<Manufacture of resin (E) having a cationic group in the side chain>
(Resin (E-1) solution having a cationic group in the side chain)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 33.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, and 27.3 parts of 2-ethylhexyl methacrylate, and nitrogen was poured. While stirring at 50 ° C. for 1 hour, the inside of the system was replaced 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. did. 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 12.2 parts of dimethylaminoethyl methyl chloride salt methacrylate as a second block monomer were added to this reactor, and the mixture was stirred while maintaining a nitrogen atmosphere at 100 ° C. , The reaction continued. Two hours after the addition of the dimethylaminoethylmethyl chloride salt methacrylic acid, 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 temperature was 50 ° C. Cooled to. Then, methanol was added to obtain a resin (E-1) having a cationic group in the side chain having a resin component of 40% by mass. The weight average molecular weight (Mw) of the resin (E-1) was 7300.

(Solutions of resins (E-2) to (E-6) having a cationic group in the side chain)
Hereinafter, the same as the resin (E-1) except that the type and blending amount of the monomer were changed as shown in Table 1, the resins (E-2) to (E-6) having a cationic group in the side chain. ) Was obtained.

The following monomers were used as the monomers in Table 1.
DMC78: Dimethylaminoethyl methyl methacrylate salt MMA: Methyl methacrylate,
n-BMA: n-butyl methacrylate,
2-EHMA: 2-ethylhexyl methacrylate,
HEMA: hydroxyethyl methacrylate,
MAA: Methacrylic acid,
OXMA: 3- (methacryloyloxymethyl) 3-ethyloxetane,
t-BuMA: Tashari Butyl Methacrylate,

（トリフェニルメタン系酸性染料（Ｃ−２）の合成）
Ｃ．Ｉ．アシッド ブルー ９０を４５．０部と、１−ヨードメタン２９．９部および炭酸カリウム３６．８部をＮ−メチルピロリドン２８０部中に加え、４０℃で６時間攪拌した。得られた反応液を室温まで冷却後、酢酸エチル３０００部に添加し室温下、１時間攪拌したところ、結晶が析出した。析出した結晶を濾別して取得後、酢酸エチル２５００部で洗浄後、1晩６０℃減圧乾燥し、下記構造式で表わされるトリフェニルメタン系酸性染料（Ｃ−２）４４．６部を得た。

（トリフェニルメタン系酸性染料（Ｃ−３）の合成）
Ｃ．Ｉ．アシッド ブルー ９０を４５．０部と、１−ブロモ−ｎ−オクタン４０．２部および炭酸カリウム３６．８部をＮ−メチルピロリドン２８０部中に加え、４０℃で６時間攪拌した。得られた反応液を室温まで冷却後、酢酸エチル３０００部に添加し室温下、１時間攪拌したところ、結晶が析出した。析出した結晶を濾別して取得後、酢酸エチル２５００部で洗浄後、1晩６０℃減圧乾燥し、下記構造式で表わされるトリフェニルメタン系酸性染料（Ｃ−３）４７．３部を得た。

（トリフェニルメタン系酸性染料（Ｃ−４）の合成）
Ｃ．Ｉ．アシッド ブルー ９０を４５．０部と、２−ブロモジエチルエーテル３２．３部および炭酸カリウム３６．８部をＮ−メチルピロリドン２８０部中に加え、１００℃で６時間攪拌した。得られた反応液を室温まで冷却後、酢酸エチル３０００部に添加し室温下、１時間攪拌したところ、結晶が析出した。析出した結晶を濾別して取得後、酢酸エチル２５００部で洗浄後、1晩６０℃減圧乾燥し、下記構造式で表わされるトリフェニルメタン系酸性染料（Ｃ−４）４５．１部を得た。

（トリフェニルメタン系酸性染料（Ｃ−５））
Ｃ．Ｉ．アシッド ブルー ９０を４５．０部と、α−ブロモトルエン３４．５部および炭酸カリウム３６．８部をＮ−メチルピロリドン２８０部中に加え、１００℃で６時間攪拌した。得られた反応液を室温まで冷却後、酢酸エチル３０００部に添加し室温下、１時間攪拌したところ、結晶が析出した。析出した結晶を濾別して取得後、酢酸エチル２５００部で洗浄後、1晩６０℃減圧乾燥し、下記構造式で表わされるトリフェニルメタン系酸性染料（Ｃ−５）４９．０部を得た。

<Manufacturing of triphenylmethane acid dye (C)>
(Synthesis of triphenylmethane acid dye (C-1))
C. I. 45.0 parts of Acid Blue 90, 35.8 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 40 ° 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 46.2 parts of a triphenylmethane-based acid dye (C-1) represented by the following structural formula.

(Synthesis of triphenylmethane acid dye (C-2))
C. I. 45.0 parts of Acid Blue 90, 29.9 parts of 1-iodomethane and 36.8 parts of potassium carbonate were added to 280 parts of N-methylpyrrolidone, and the mixture was stirred at 40 ° 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 44.6 parts of a triphenylmethane-based acid dye (C-2) represented by the following structural formula.

(Synthesis of triphenylmethane acid dye (C-3))
C. I. 45.0 parts of Acid Blue 90, 40.2 parts of 1-bromo-n-octane and 36.8 parts of potassium carbonate were added to 280 parts of N-methylpyrrolidone, and the mixture was stirred at 40 ° 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 47.3 parts of a triphenylmethane-based acid dye (C-3) represented by the following structural formula.

(Synthesis of triphenylmethane acid dye (C-4))
C. I. 45.0 parts of Acid Blue 90, 32.3 parts of 2-bromodiethyl ether and 36.8 parts of potassium carbonate were added to 280 parts of N-methylpyrrolidone, and the mixture was stirred at 100 ° 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 45.1 parts of a triphenylmethane-based acid dye (C-4) represented by the following structural formula.

(Triphenylmethane acid dye (C-5))
C. I. 45.0 parts of Acid Blue 90, 34.5 parts of α-bromotoluene and 36.8 parts of potassium carbonate were added to 280 parts of N-methylpyrrolidone, and the mixture was stirred at 100 ° 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 49.0 parts of a triphenylmethane-based acid dye (C-5) represented by the following structural formula.

(Triphenylmethane acid dye (C-6))
C. I. Acid Blue 90 was used.

(Triphenylmethane acid dye (C-7))
C. I. 45.0 parts of Acid Blue 83, 37.0 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 100 ° 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 47.5 parts of a triphenylmethane-based acid dye (C-7) represented by the following structural formula.

(Triphenylmethane acid dye (C-8))
C. I. Acid Blue 93 was used.

<Manufacturing of xanthene dyes>

(Xanthene dye (X-1))
C. I. Acid Red 52 was used.

(Xanthene dye (X-2))
C. I. Acid Red 289 was used.

＜シアニン染料の製造＞ (Synthesis of xanthene dye (X-3))
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 a xanthene dye (X-3) represented by the following structural formula.

<Manufacturing of cyanine dye>

(Cyanine dye (X-4))
A cyanine dye manufactured by Tokyo Chemical Industry Co., Ltd., which has the following structure, was used.

(Cyanine dye (X-5))
C. I. Basic Red 12 was used.

(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. did. 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).

<Manufacturing method of salt-forming compound (D)>
(Preparation of salt-forming compound (D-1))
A salt-forming compound (D-1) composed of a triphenylmethane-based acid dye (C-1) and a resin (E-1) was produced by the following procedure.
A resin (E-1) having a cationic group in the side chain of 42 parts is added to 2000 parts of water, and the mixture is sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, an aqueous solution prepared by dissolving 10 parts of a triphenylmethane-based acid dye (C-1) in 90 parts of water is prepared at pH 4, and is gradually added dropwise to the above 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 salt consisting of the counter anion of the resin having a cationic group in the side chain and the counter cation of the triphenylmethane acid dye (C-1) is removed by suction filtration and washing with water. The salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 32 parts of the triphenylmethane-based acid dye (C-1) and the resin (E-1) were combined with the salt-forming compound (D). -1) was obtained. The salt-forming rate of the salt-forming compound (D-1) was 75% with respect to the theoretical value.

(Preparation of salt-forming compound (D-2))
A resin (E-1) having a cationic group on the side chain of 42 parts was added to 2000 parts of water, and the mixture was stirred at 20 ° C. for 30 minutes. On the other hand, an aqueous solution prepared by dissolving 10 parts of a triphenylmethane-based acid dye (C-1) in 90 parts of water is prepared at pH 4, and is gradually added dropwise to the above resin solution. After the dropping, the mixture is stirred at 20 ° 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 salt consisting of the counter anion of the resin having a cationic group in the side chain and the counter cation of the triphenylmethane acid dye (C-1) is removed by suction filtration and washing with water. The salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 34 parts of the triphenylmethane-based acid dye (C-1) and the resin (E-1) were combined with the salt-forming compound (D). -2) was obtained. The salt-forming rate of the salt-forming compound (D-2) was 97% with respect to the theoretical value.

(Preparation of salt-forming compound (D-3))
A resin (E-1) having a cationic group in the side chain of 42 parts was added to 2000 parts of water, and the mixture was stirred at 5 ° C. for 30 minutes. On the other hand, an aqueous solution prepared by dissolving 10 parts of a triphenylmethane-based acid dye (C-1) in 90 parts of water is prepared at pH 4, and is gradually added dropwise to the above resin solution. After the dropping, the mixture is stirred at 5 ° 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 salt consisting of the counter anion of the resin having a cationic group in the side chain and the counter cation of the triphenylmethane acid dye (C-1) is removed by suction filtration and washing with water. The salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 31 parts of the triphenylmethane-based acid dye (C-1) and the resin (E-1) were combined with the salt-forming compound (D). -3) was obtained. The salt-forming rate of the salt-forming compound (D-3) was 90% with respect to the theoretical value.

(Preparation of salt-forming compound (D-4))
A resin (E-1) having a cationic group on the side chain of 42 parts was added to 2000 parts of water, and the mixture was stirred at 20 ° C. for 30 minutes. On the other hand, an aqueous solution prepared by dissolving 10 parts of a triphenylmethane-based acid dye (C-1) in 90 parts of water is prepared at pH 7, and is gradually added dropwise to the above resin solution. After the dropping, the mixture is stirred at 20 ° 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 salt consisting of the counter anion of the resin having a cationic group in the side chain and the counter cation of the triphenylmethane acid dye (C-1) is removed by suction filtration and washing with water. The salt-forming compound remaining on the filter paper was dried by removing water with a dryer, and 32 parts of the triphenylmethane-based acid dye (C-1) and the resin (E-1) were combined with the salt-forming compound (D). -4) was obtained. The salt-forming rate of the salt-forming compound (D-4) was 82% with respect to the theoretical value.

(Preparation of salt-forming compound (D-16))
10 parts of triphenylmethane acid dye (C-1) was dissolved in 1000 parts of water, and a 25% aqueous sodium hydroxide solution was added with stirring to adjust the pH to 11.5. Further, the mixture was heated to 60 ° C. at pH 11.5 and stirred for 2 hours. An aqueous solution in which 8.0 parts of aluminum chloride (hexahydrate) was dissolved was gradually added dropwise to this solution to obtain a blue precipitate. To confirm the end point of the reaction, it was determined that the aluminum salt of the triphenylmethane acid dye (C-1) was obtained by dropping the reaction solution onto the filter paper and using the point where the bleeding disappeared as the end point. The pH after the total addition was 3.5. The blue precipitate was filtered off, washed with water, and dried to obtain 40 parts of a salt-forming compound (D-16) which is an aluminum salt of a triphenylmethane acid dye (C-1).

(Preparation of salt-forming compound (D-17))
10 parts of triphenylmethane acid dye (C-1) was dissolved in 1000 parts of water, and a 25% aqueous sodium hydroxide solution was added with stirring to adjust the pH to 11.5. Further, the mixture was heated to 60 ° C. at pH 11.5 and stirred for 2 hours. An aqueous solution in which 5.2 parts of nickel chloride (hexahydrate) was dissolved was gradually added dropwise to this solution to obtain a blue precipitate. To confirm the end point of the reaction, it was determined that the nickel salt of the triphenylmethane acid dye (C-1) was obtained by dropping the reaction solution onto the filter paper and using the point where the bleeding disappeared as the end point. The pH after the total addition was 3.8. The blue precipitate was filtered off, washed with water, and dried to obtain 40 parts of a salt-forming compound (D-17) which is a nickel salt of a triphenylmethane acid dye (C-1).

(Preparation of salt-forming compounds D-5 to 15, 18 to 23)
Hereinafter, the salt-forming compounds (D-5) to (D-15), (D-) are the same as in (D-2) except that the resin having a cationic group in the side chain is changed to the one shown in Table 2. 18) to (D-23) were prepared.

<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 a 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. It was.

<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 coloring composition (DP-1) was prepared by filtering with a filter.

Salt compound (D-1) 10.0 parts Dispersant 1 4.0 parts Binder resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC)
46.0 copies

[Examples 2 to 25, Comparative Examples 1 to 4]
The coloring composition (salt-forming compound (D), other colorants, binder resin solution, dispersant, and propylene glycol monomethyl ether acetate were changed to the compositions and blending ratios shown in Table 3 in the same manner as in Example 1 (s). DP-2) to (DP-29) were prepared.

<Evaluation of coloring composition for color filter>
The obtained coloring composition (DP-1 to 29) was tested for brightness, heat resistance, foreign matter in the coating film, and viscosity by the following method. The results are shown in Table 4.

(Brightness evaluation)

(Method of evaluating the brightness of the coating film)
The coloring composition was applied to a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm with a spin coater so that y = 0.100, then dried at 60 ° C. for 5 minutes, and then dried at 230 ° C. for 20 minutes. A coated substrate was produced by heating and allowing to cool. Brightness (spectral transmittance) was measured using the obtained coated substrate. The brightness (spectral transmittance) in the XYZ colorimetric chromaticity diagram was measured using a spectrophotometer (OTSUKALCF-1100M). The judgment criteria are as follows. X is a level that is difficult to use.
⊚: 12.0 or more ○: 11.5 or more and less than 12.0 Δ: 11.0 or more and less than 11.5 ×: less than 11.0

(Heat resistance evaluation)
The coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dry film thickness was 2.0 μm, then dried at 70 ° C. for 20 minutes, and then at 230 ° C. A coated substrate (one aspect of a color filter) was prepared by heating and allowing to cool for 60 minutes. Use a microspectrophotometer (“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 250 ° 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. , Color difference ΔEab ^* was determined and evaluated in the following four stages.

ΔEab ^* = √ ((L ^* (2) -L ^* (1)) ² + (a ^* (2) -a ^* (1)) ² + (b ^* (2) -b ^* (1)) ² )

⊚: ΔEab ^* is less than 1.0 (extremely good)
◯: ΔEab ^* is 1.0 or more and less than 2.5 (good)
Δ: ΔEab ^* is 2.5 or more and less than 5.0 (defective)
×: ΔEab ^* is 5.0 or more (extremely defective)

(Evaluation of foreign matter on the coating film)
The coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dry film thickness was 2.0 μm, then dried at 70 ° C. for 20 minutes, and then 230. A coated substrate was prepared by heating and allowing to cool at ° C. for 60 minutes. The evaluation was performed by observing the surface using a metallurgical microscope "BX60" manufactured by Olympus System Corporation. The magnification was set to 500 times, and the number of particles that could be observed in any five fields of view by transmission was counted. It was evaluated on the following four stages.

⊚: The number of foreign substances is less than 5 (extremely good)
◯: The number of foreign substances is 5 or more and less than 10 (good)
Δ: The number of foreign substances is 10 or more and less than 60 (defective)
X: The number of foreign substances is 60 or more (extremely defective)

(Viscosity evaluation)
The viscosity of the coloring composition was measured at 25 ° C. on the day of adjustment using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.) at a rotation speed of 20 rpm (initial viscosity). In the evaluation results below, ⊚ is very good, ◯ is good, Δ is a level with high viscosity but no problem in use, and × is a level with problem in use.
⊚: Less than 10.0 [mPa · s]
◯: 10.0 or more and less than 15.0 [mPa · s]
Δ: 15.0 or more and less than 20.0 [mPa · s]
X: 20.0 or more [mPa · s]

In Examples 1 to 25 of the present invention, the results were excellent in brightness, heat resistance, foreign matter in the coating film, and viscosity. In Examples 1 to 4, when the salt formation rate is 80% or more with respect to the theoretical value, the viscosity is good, and among them, Example 2 having the highest salt formation rate with respect to the theoretical value is lightness and coating. The results of membrane foreign matter were also excellent. Further, as in Examples 2 and 5-8, those in which X1 of the triphenylmethane acid dye (C) was alkyl and X2 was methyl had good brightness.
Further, as can be seen from Examples 13 to 15, the resin (E) having a cationic group in the side chain containing 3- (methacryloyloxymethyl) 3-ethyloxetane has a lightness and a foreign matter in the coating film. And the viscosity was excellent.
On the other hand, as in Comparative Examples 1 to 4, a coloring composition using the triphenylmethane acid dye (C) alone, or a structure other than the triphenylmethane acid dye (C) represented by the general formula (1). In the salt-forming product of the triphenylmethane-based acid dye, the heat resistance and foreign matter in the coating film were inferior.

<Manufacturing method of photosensitive coloring composition>
[Example 19]
(Manufacture of Photosensitive Coloring Composition (DR-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive coloring composition (DR-1).
Coloring composition (DP-1) 60.0 parts Binder resin solution 1 11.0 parts Epoxy compound (thermosetting compound)
("EHPE-3150" manufactured by Daicel) 0.10 part photopolymerizable monomer ("Aronix M400" manufactured by Toa Synthetic Co., Ltd.) 2.8 parts Photopolymerizable monomer ("Aronix M350" manufactured by Toa Synthetic Co., Ltd.) 1 . 4-part photopolymerization initiator (BASF Japan's "Irgacure OXE01") 0.6-part photopolymerization initiator (BASF's "Irgacure 369") 0.6-part thiol compound (pentaerythritol tetraxthiopropionate) ) 0.20 part Leveling agent ("BYK-330" manufactured by Big Chemie) 0.05 part Antioxidant ("IRGANOX1010" manufactured by BASF) 0.05 part Cyclohexanone 5.2 part propylene glycol monomethyl ether acetate (PGMAC) ) 18.0 copies

[Examples 101-125, Comparative Examples 101-104]
(Manufacture of Photosensitive Coloring Compositions (DR-2-29))
Photosensitive coloring compositions (DR-2 to 29) were prepared in the same manner as in Example 101 except that the coloring composition was changed to the coloring composition shown in Table 5.

<Evaluation of photosensitive coloring composition>
The brightness, heat resistance, foreign matter of the coating film, solvent resistance, viscosity, and storage stability of the photosensitive coloring compositions of Examples 101 to 125 and Comparative Examples 101 to 104 were evaluated by the following methods.
The results are shown in Table 5.

(Method of evaluating the brightness of the coating film)
The photosensitive coloring composition (DR-1 to 29) was applied to a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm with a spin coater so that y = 0.100, and then at 60 ° C. for 5 minutes. A coated substrate was prepared by drying, then heating at 230 ° C. for 20 minutes, and allowing to cool. Brightness (spectral transmittance) was measured using the obtained coated substrate. The brightness (spectral transmittance) in the XYZ colorimetric chromaticity diagram was measured using a spectrophotometer (OTSUKALCF-1100M). The judgment criteria are as follows. X is a level that is difficult to use.
⊚: 12.0 or more ○: 11.5 or more and less than 12.0 Δ: 11.0 or more and less than 11.5 ×: less than 11.0

(Evaluation of heat resistance of coating film)
The photosensitive coloring composition (DR-1 to 29) is applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and is fired in an oven at 230 ° C. for 30 minutes to obtain a coating film after heat treatment. The film thickness was measured using a surface shape measuring device "Dektak8 (manufactured by Veeco)", and three coated substrates were prepared so that the film thickness was about 2.0 μm. Use a microspectrophotometer (“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. , Color difference ΔEab * was obtained and evaluated according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
⊚: ΔEab * is less than 1.0 〇: ΔEab * is 1.0 or more and less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Evaluation of foreign matter on the coating film)
The photosensitive coloring composition (DR-1 to 29) is rotationally coated on a glass substrate using a spin coater so that the dry film thickness is 1.2 μm, and prebaked at 120 ° C. for 120 seconds for testing. A sample substrate was prepared. The evaluation was carried out by observing the surface using a metallurgical microscope "BX60" manufactured by Olympus System Corporation. The magnification is set to 500 times, and the number of particles that can be observed in any five fields of view by transmission is counted. 3 or more was set as a practical level.

5: Foreign matter less than 20 4: Foreign matter 20 or more, less than 50 3: Foreign matter 50 or more and less than 100 2: Foreign matter 100 or more 1: Foreign matter 100 or more, uneven coating surface

(Evaluation of solvent resistance of coating film)
The photosensitive coloring composition (DR-1 to 29) is applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, and is fired in an oven at 230 ° C. for 30 minutes to obtain a coating film after heat treatment. The film thickness was measured using a surface shape measuring device "Dektak8 (manufactured by Veeco)", and three coated substrates were prepared so that the film thickness was about 2.0 μm. Use a microspectrophotometer (“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, the coating film obtained as a chemical resistance test was immersed in 1-methyl-2-pyrrolidone for 30 minutes, and then 1-methyl-2-pyrrolidone was washed with pure water, and then the chromaticity with a C light source ( [L * (2), a * (2), b * (2)]) was measured, the color difference ΔEab * was obtained by the following formula, and evaluated according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
⊚: ΔEab * is less than 1.0 〇: ΔEab * is 1.0 or more and less than 1.5 Δ: ΔEab * is 1.5 or more and less than 3.0 ×: ΔEab * is 3.0 or more

(Viscosity evaluation of coloring composition)
The viscosity of the photosensitive coloring composition (DR-1 to 29) was measured using an E-type viscometer. Evaluation was made according to the following criteria. ⊚ is a very good level, ◯ is a good level, Δ is a practical level, and × is a level unsuitable for practical use.

⊚: Viscosity is less than 5.0 〇: Viscosity is 5.0 or more and less than 10.0 Δ: Viscosity is 10.0 or more and less than 20.0 ×: Viscosity is 20.0 or more

(Evaluation of storage stability)
From the initial viscosity on the day of preparation of the photosensitive coloring composition (DR-1 to 29) and the viscosity measured after storage in a constant temperature chamber at 40 ° C. for 7 days, the viscosity change rate (%) = (after storage at 40 ° C. for 7 days). Viscosity-initial viscosity) / initial viscosity x 100) was calculated, and the storage stability was evaluated according to the following criteria. 3 or more was set as a practical level.
Both the initial and post-storage viscosities were measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd .: ELD-type viscometer) under the conditions of a temperature of 25 ° C. and a rotation speed of 50 rpm.

⊚: Viscosity change rate is less than 5% 〇: Viscosity change rate is 5% or more and less than 10%
Δ: Viscosity change rate is 10% or more and less than 15% ×: Viscosity change rate is 15% or more

The results of the photosensitive coloring composition were similar to those of the coloring compositions shown in Examples 1 to 25 and Comparative Examples 1 to 4. In Examples 101 to 125 of the present invention, the solvent resistance and the stability over time were also excellent.

<Making color filters>
By using the photosensitive coloring composition of the present invention, a color filter exhibiting good performance could be produced.

Claims (8)

A coloring composition for a color filter containing a colorant (A), a binder resin, and an organic solvent, wherein the colorant (A) contains a salt-forming compound, and the salt-forming compound is a general formula (1). The resin (E) contains a salt-forming compound (D) of a triphenylmethane-based acid dye (C) having a structural unit represented by, and a resin (E) having a cationic group in a side chain. A coloring composition for a color filter, which has a structural unit represented by the following general formula (2).

General formula (1)

[In the formula, X ₁ represents an aliphatic hydrocarbon group having a monovalent carbon number of 1 or more and 20 or less, which may have a hydrogen or a substituent, and X ₂ represents a hydrogen or a methyl group. ]

General formula (2)

[In the formula, R ₁ represents a hydrogen atom or an optionally substituted alkyl group. R _{2 to} R ₄ independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, respectively, of R _{2 to} R ₄ . Two of them may be combined with each other to form a ring. Q ₁ represents an alkylene group, an arylene group, -CONH-R _5- , or -COO-R _5- , and R ₅ represents an alkylene group. ] The resin (E) having a cationic group in the side chain has a structural unit containing at least one thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, an oxetane group, and a t-butyl group. The coloring composition for a color filter according to claim 1. The ratio of the content of the structural unit derived from the acidic dye (C) in the salt-forming compound (D) to the theoretical value (the salt-forming rate of the salt-forming compound (D)) (the production of (salt-forming compound (D)). The coloring composition for a color filter according to claim 1 or 2, wherein the salt ratio) / (theoretical value of the salt formation ratio of the salt-forming compound (D)) is 80% or more. A coloring composition for a color filter containing a coloring agent (A), a binder resin, and an organic solvent, wherein the coloring agent (A) has a triphenylmethane-based acid having a structural unit represented by the general formula (1). A coloring composition for a color filter, which comprises a salt-forming compound of a dye (C) and a divalent or trivalent metal salt. The coloring composition for a color filter according to any one of claims 1 to 4, wherein the colorant (A) further contains a xanthene dye and / or a cyanine dye. The coloring composition for a color filter according to any one of claims 1 to 5, wherein the coloring agent (A) further contains a blue pigment having a copper phthalocyanine skeleton. The coloring composition for a color filter according to any one of claims 1 to 6, further containing a photopolymerizable monomer and / or a photopolymerization initiator. A color filter comprising a filter segment formed by the coloring composition for a color filter according to any one of claims 1 to 7.