JP7484204B2 - Coloring composition for color filters and color filters - Google Patents

Description

The present invention relates to a color filter coloring composition used in the manufacture of color filters for use in color liquid crystal displays, color image pickup tube elements, etc., and to a color filter having filter segments formed using the same.

In recent years, dye-based coloring materials have been attracting attention in order to realize high contrast ratios and high brightness that cannot be achieved with pigments. Dyes generally tend to be inferior to pigments in terms of fastness, such as heat resistance and light resistance. Furthermore, some dyes exhibit fluorescent emission properties (Patent Document 1), which causes the problem of low contrast ratios.
In order to achieve these, the use of dyes as colorants has been studied. For example, Patent Documents 2 and 3 propose coloring compositions containing xanthene dyes. A technique for increasing heat resistance by using a xanthene dye in combination with a phthalocyanine amine compound (Patent Document 4) and a technique for improving heat resistance and brightness by using C.I. Acid Red 52 in combination with a phthalocyanine compound having a specific structure (Patent Document 5) have been proposed. However, even when such coloring compositions are used, the heat resistance is not satisfactory.

JP 2010-32999 A JP 2014-012814 A JP 2011-028236 A JP 2011-227491 A JP 2016-117799 A

The problem that the present invention aims to solve is to provide a coloring composition and a color filter that have excellent heat resistance, excellent color characteristics (brightness) when used in a color filter, no generation of foreign matter, and good stability.

As a result of intensive research by the inventors to solve the above problems, they discovered that a coloring composition for color filters containing at least a colorant (A), a binder resin, and an organic solvent, characterized in that the colorant (A) contains a copper phthalocyanine pigment, a dye derivative (B) having a copper phthalocyanine structure having an acidic substituent as a parent skeleton, and a salt-forming compound (E) of a resin (C) having a cationic group in the side chain and a xanthene acid dye, exhibits excellent filterability, and the present invention was made based on this finding.

That is, the present invention relates to a coloring composition for color filters that contains at least a colorant (A), a binder resin, and an organic solvent, characterized in that the colorant (A) contains a copper phthalocyanine pigment, a dye derivative (B) having a copper phthalocyanine structure having an acidic substituent as the parent skeleton, and a salt-forming compound (E) of a xanthene acid dye and a resin (C) having a cationic group in the side chain.

The present invention also relates to the above coloring composition for color filters, characterized in that the resin (E) having a cationic group on the side chain has a structural unit containing at least one type of 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 also relates to the above coloring composition for color filters, characterized in that the content of the dye derivative (B) is 5 to 45% by mass relative to 100% by mass of the salt-forming compound (E).

The present invention also relates to the above coloring composition for color filters, further comprising a photopolymerizable monomer and/or a photopolymerization initiator.

The present invention also relates to a color filter having filter segments formed from the above-mentioned coloring composition for color filters.

The present invention will be described in detail below.
In this application, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", and "(meth)acrylate" mean "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", and "acrylate and/or methacrylate", respectively.
In addition, "C.I." in this specification means Color Index (C.I.).

The coloring composition for color filters of the present invention is a coloring composition for color filters containing at least a colorant (A), a binder resin, and an organic solvent, characterized in that the colorant (A) contains a copper phthalocyanine pigment, a dye derivative (B) having a copper phthalocyanine structure having an acidic substituent as the parent skeleton, and a salt-forming compound (E) of a xanthene acid dye and a resin (C) having a cationic group in the side chain.

<Colorant (A)>
The colorant (A) of the present invention contains at least a copper phthalocyanine pigment, a dye derivative (B) having a copper phthalocyanine structure having an acidic substituent as a parent skeleton, and a salt-forming compound (E) of a resin (C) having a cationic group in a side chain and a xanthene acid dye.

<Copper phthalocyanine pigment>
The copper phthalocyanine pigment of the present invention is a blue pigment having a copper phthalocyanine skeleton, and examples of the blue pigment having a copper phthalocyanine skeleton include C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6. Among them, copper phthalocyanine blue pigments having an ε-type or α-type structure are preferred. Specifically, such preferred pigments are C.I. Pigment Blue 15:6 and C.I. Pigment Blue 15:1.

<Dye derivative (B) with a copper phthalocyanine structure having an acidic substituent as the main skeleton>

The colorant derivative (B) of the present invention having a copper phthalocyanine structure having an acidic substituent as a parent skeleton interacts well with the dye via the resin (C) having a cationic group in the colorant (A), and exhibits a large effect of preventing reagglomeration of the colorant (A) after dispersion.
In addition, since both the dye derivative (B) having a copper phthalocyanine structure as the parent skeleton and the xanthene acid dye have an acidic group, a coating film containing little foreign matter can be obtained.

The copper phthalocyanine structure can be produced by known methods. When copper phthalocyanine is used, it becomes a derivative with high clarity, excellent heat resistance and weather resistance, and is highly useful as a coloring material.

The dye derivative (B) may be any of the dye derivatives represented by general formulas (3) to (5). As the dye derivative having an acidic substituent, any of the dye derivatives having no counter ion represented by the following general formula (3), and the dye derivatives having a counter ion represented by the following general formulas (4) or (5) may be used.

General formula (3): CuPc-Z ¹
(In the general formula (3), ^Z1 of CuPc is _SO3H or COOH.)

General formula (4): (CuPc-Z ² ) [N ⁺ (R ¹ , R ² , R ³ , R ⁴ )]
(In general formula (4), CuPc represents a copper phthalocyanine residue, ^Z2 represents _SO3- ^{or COO-} , ^R1 represents an alkyl group having 5 to 20 carbon atoms, and ^R2 , ^R3 , and ^R4 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

General formula (5): (CuPc-Z ² ) x M y ⁺
(In the general formula (5), CuPc represents a copper phthalocyanine residue, My ⁺ represents a metal ion such as a lithium, sodium, potassium, magnesium, calcium, barium, iron, cobalt, nickel, copper, zinc, or aluminum ion, y represents the valence of the ion, x represents a value calculated by the formula x=y÷(number of ^Z2 ), and ^Z2 represents _SO3- ^{or COO-} .)

Z ¹ in the general formula (3) may be present in the range of 1 to 8 with respect to CuPc in the general formula (3).

^Z2 in the general formula (4) may be present in a range of 1 to 8 relative to CuPc in the general formula (4). At the same time, [N ⁺ (R ¹ , R ² , R ³ , R ⁴ )] may be present in the same number according to the number of ^Z2 .

Amines constituting the amine salt include lower amines such as ammonia, dimethylamine, trimethylamine, diethylamine, triethylamine, hydroxyethylamine, dihydroxyethylamine, 2-ethylhexylamine, N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, and N,N-dibutylaminopropylamine; long-chain alkylamines having an alkyl group with 12 or more carbon atoms such as laurylamine, oleylamine, palmitylamine, stearylamine, and dimethyllaurylamine; and long-chain alkyl quaternary ammonium ions having an alkyl group with 12 or more carbon atoms such as lauryltrimethylammonium, dilauryldimethylammonium, stearyltrimethylammonium, and distearyldimethylammonium. Among these, the use of salts of long-chain alkylamines having an alkyl group with 12 or more carbon atoms such as laurylammonium and stearylammonium provides a coloring composition with the most excellent dispersion stability and particularly high storage stability.

^Z2 in the general formula (5) may be present in the range of 1 to 8 with respect to CuPc in the general formula (5).
Examples of metal ions include various metals such as lithium, sodium, potassium, magnesium, calcium, barium, iron, cobalt, nickel, copper, zinc, aluminum, etc. Among these, aluminum is preferred in terms of heat resistance and brightness.

<Content of Dye Derivative (B)>
In the coloring composition of the present invention, the content of the dye derivative (B) is preferably 5 to 45% by mass relative to 100% by mass of the salt-forming compound (E). By containing the dye derivative in the above range in the colorant (A), the dye derivative and the salt-forming compound (E) interact efficiently, and the effect of preventing reagglomeration of the colorant (A) after dispersion is increased, resulting in very good viscosity stability. If the dye derivative (B) in the colorant (A) is less than 5% by mass relative to the salt-forming compound (E), it is difficult to obtain the effect of adding it, and if it exceeds 45% by mass, the brightness and heat resistance may be deteriorated. The dye derivative (B) may contain two or more kinds.

(Xanthene acid dyes)
Next, the xanthene acid dye for obtaining the salt-forming compound (E) will be described.
Xanthene acid dyes are dyes that exhibit red, purple, etc. Red and purple colors include acid dyes such as C.I. Acid Red and C.I. Acid Violet, and direct dyes such as C.I. Direct Red and C.I. Direct Violet. Here, direct dyes have a sulfonic acid group, and therefore are considered to be synonymous with acid dyes in the present invention.
The salt-forming compound (E) is a compound obtained by forming a salt and modifying it with these xanthene acid dyes (including direct dyes) and a resin (C) having a cationic group in the side chain which acts as a counter ion.

Specific examples of acid dyes of xanthene dyes include C.I. Acid Red 51 (Erythrosine (Food Red No. 3)), C.I. Acid Red 52 (Acid Rhodamine), C.I. Acid Red 87 (Eosine G (Food Red No. 103)), C.I. Acid Red 92 (Acid Phloxine PB (Food Red No. 104)), C.I. Acid Red 289, C.I. Acid Red 388, Rose Bengal B (Food Red No. 5), Acid Rhodamine G, C.I. Acid Violet 9, C.I. Acid Violet 9, C.I. Acid Violet 30, and xanthene dyes represented by the following general formula (6) are preferably used.
Among them, it is preferable to use C.I. Acid 52, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 289, C.I. Acid Red 388, and xanthene dyes represented by the following general formula (6).

General formula (6)

[ _X1 and _X3 each independently represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
_X2 and _X4 each independently represent a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group.

The aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by _X1 and _X3 includes linear, branched and cyclic aliphatic hydrocarbon groups. Specific examples of such groups include linear saturated hydrocarbon groups such as methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl and n-dodecyl groups, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, methylpentyl, ethylbutyl, methylhexyl, ethylpentyl, propylbutyl, (methylethyl)butyl, (methylethyl)(methyl)propyl, methylheptyl, ethylhexyl, propylpentyl and (methylethyl)pentyl. branched-chain saturated hydrocarbon groups such as a butylbutyl group, a (butyl)(methyl)butyl group, a (dimethylethyl)(butyl)butyl group, a dimethylpropyl group, a dimethylbutyl group, an (ethyl)(methyl)propyl group, a dimethylpentyl group, an (ethyl)(methyl)butyl group, a dimethylhexyl group, an (ethyl)(methyl)pentyl group, a (propyl)(methyl)butyl group, a (methylethyl)(methyl)butyl group, or a diethylbutyl group; and alicyclic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, or a cyclodecyl group.
_X1 and _X3 may further have a substituent in the aliphatic hydrocarbon group, specifically, alkoxy groups such as methoxy, ethoxy, and propoxy groups, and monovalent aromatic hydrocarbon groups such as phenyl, 1-naphthyl, and 2-naphthyl groups.

Examples of the monovalent aromatic hydrocarbon group which may have a substituent and is represented by _X2 and _X4 include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

Examples of anionic dyes represented by general formula (6) include structures represented by formulas (6-1) to (6-4).

Formula (6-1)

Formula (6-2)

Formula (6-3)

Formula (6-4)

Next, we will explain resin (C) that has cationic groups on its side chains.

<Resin (C) Having Cationic Group in Side Chain>
The resin (C) having a cationic group in a side chain of the present invention preferably contains a structural unit represented by the following general formula (2): The cationic group in the formula forms a salt with the anionic group of the xanthene acid dye, thereby obtaining the salt-forming compound (E) of the present invention.

General formula (2)

In general formula (2), R ₁ represents a hydrogen atom or an alkyl group which may have a substituent. R ₂ to R ₄ each 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 two of R ₂ to R ₄ may be bonded to 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.

Examples of the alkyl group for 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. The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms.

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, R ₁ is most preferably a hydrogen atom or a methyl group.

Examples of the alkyl group in R ₂ to R ₄ in 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, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of the alkenyl group in R ₂ to R ₄ in general formula (2) include linear or branched alkenyl groups (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl, and 2-methyl-2-propenyl, etc.) and cycloalkenyl groups (2-cyclohexenyl, 3-cyclohexenyl, etc.). The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms.

Examples of the aryl group in R ₂ to R ₄ in general formula (2) include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl), and aromatic heterocyclic hydrocarbon groups (such as thienyl (a group derived from thiophene), furyl (a group derived from furan), pyranyl (a group derived from pyran), pyridyl (a group derived from pyridine), 9-oxoxanthenyl (a group derived from xanthone), and 9-oxothioxanthenyl (a group derived from thioxanthone)).

When the alkyl group, alkenyl group, or aryl group represented by _R2 to _R4 in general formula (2) has a substituent, the substituent may be, for example, a substituent selected from a halogen atom, a hydroxyl group, an alkoxy group, an aryloxy group, an alkenyl group, an acyl group, an alkoxycarbonyl group, a carboxy group, a phenyl group, etc. Among these, the halogen atom, the hydroxyl group, the alkoxy group, and the phenyl group are particularly preferred as the substituent.

In terms of stability, R ₂ to R ₄ in formula (2) are preferably alkyl groups which may be substituted, and more preferably unsubstituted alkyl groups.

In addition, two of R ₂ to R ₄ in formula (2) may be bonded to each other to form a ring.

In general formula (2), _Q1 linking the acrylic moiety and the ammonium salt group represents an alkylene group, an arylene group, -CONH- _R5- , or -COO- _R5- , and _R5 represents an alkylene group, of which -CONH- _R5- or -COO- _R5- is preferred from the standpoint of polymerizability and availability. Furthermore, _R5 is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The structural unit represented by the general formula (2) may have an inorganic or organic counter anion. Any known counter anion may be used without limitation, and specific examples thereof include hydroxide ions; halogen ions such as chloride ions, bromide ions, and iodide ions; carboxylate ions such as formate ions and acetate ions; carbonate ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and complex ions such as hexacyanoferrate (III) ions. From the viewpoints of synthesis suitability and stability, halogen ions and carboxylate ions are preferred, and halogen ions are most preferred. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded to the resin to form an intramolecular salt.

To obtain resin (C) having a cationic group in the side chain containing the structural unit represented by general formula (2), not only can an ethylenically unsaturated monomer having an ammonium salt group be copolymerized as a monomer component, but also an acrylic resin having an amino group can be obtained by copolymerizing an ethylenically unsaturated monomer having an amino group as a monomer component, and then reacting it with an onium chloride agent to form an ammonium chloride.

Specific examples of ethylenically unsaturated monomers having an ammonium base, ethylenically unsaturated monomers having an amino group, and onium chloride agents are shown below. In this specification, "(meth)acrylic" may be used to indicate either "acrylic" or "methacrylic", or both. Similarly, "(meth)acryloyl" may be used to indicate either "acryloyl" or "methacryloyl", or both.

<Ethylenically unsaturated monomer having an ammonium salt group>
Examples of the ethylenically unsaturated monomer having an ammonium salt group include alkyl (meth)acrylate-based quaternary ammonium salts such as (meth)acryloyloxyethyl trimethyl ammonium chloride, (meth)acryloyloxyethyl triethyl ammonium chloride, (meth)acryloyloxyethyl dimethyl benzyl ammonium chloride, and (meth)acryloyloxyethyl methyl morpholino ammonium chloride; alkyl (meth)acryloylamino-based quaternary ammonium salts such as (meth)acryloylaminopropyl trimethyl ammonium chloride, (meth)acryloylaminoethyl triethyl ammonium chloride, and (meth)acryloylaminoethyl dimethyl benzyl ammonium chloride; dimethyl diallyl ammonium methyl sulfate; and trimethyl vinyl phenyl ammonium chloride.

<Ethylenically unsaturated monomer having an amino group>
Examples of the ethylenically unsaturated monomer having an amino group include (meth)acrylic acid esters or (meth)acrylamides having a dialkylamino group such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dipropylaminoethyl (meth)acrylate, diisopropylaminoethyl (meth)acrylate, dibutylaminoethyl (meth)acrylate, diisobutylaminoethyl (meth)acrylate, di-t-butylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylamide, diethylaminopropyl (meth)acrylamide, dipropylaminopropyl (meth)acrylamide, diisopropylaminopropyl (meth)acrylamide, dibutylaminopropyl (meth)acrylamide, diisobutylaminopropyl (meth)acrylamide, and di-t-butylaminopropyl (meth)acrylamide; styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene; diallylamine compounds such as diallylmethylamine and diallylamine; and amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone, and N-vinylcarbazole.

<Onium chloride agent>
Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, and dipropyl sulfate; sulfonate esters such as methyl p-toluenesulfonate and methyl benzenesulfonate; alkyl chlorides such as methyl chloride, ethyl chloride, propyl chloride, and octyl chloride; alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chloride bromide; benzyl chloride; and benzyl bromide.

The reaction between the ethylenically unsaturated monomer having an amino group and the onium chloride agent can usually be carried out by dropping an equimolar or less amount of the onium chloride agent relative to the amino group into a solution of the ethylenically unsaturated monomer having an amino group. The temperature during the ammonium chloride reaction is about 90°C or less, and in particular when converting a vinyl monomer into an ammonium salt, about 30°C or less is preferred, 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 (7).

Z- ^R6 - ^COOR7 General formula (7)

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

The reaction of an ethylenically unsaturated monomer having an amino group with an alkoxycarbonylalkyl halide can be achieved by reacting an equimolar or less amount of alkoxycarbonylalkyl halide with respect to the amino group in the same manner as in the case of the onium chloride agent, and then hydrolyzing ^-COOR7 to convert it to a carboxylate ion ( ^-COO- ), thereby obtaining an ethylenically unsaturated monomer having a carboxybetaine structure and an ammonium salt group.

<Other monomers>
Preferred 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, (meth)acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, and (meth)acrylonitrile.

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

Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, t-octyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl (meth)acrylate, acetoxyethyl (meth)acrylate, phenyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, benzyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol (meth)acrylate Examples of such compounds include ricol monoethyl ether, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monoethyl ether (meth)acrylate, beta-phenoxyethoxyethyl (meth)acrylate, nonylphenoxy polyethylene glycol (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, dicyclopentanyl (meth)acrylate, tribromophenyl (meth)acrylate, and tribromophenyloxyethyl (meth)acrylate.

Examples of crotonate esters include butyl crotonate and hexyl crotonate.

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

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

Examples of itaconate diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

Examples of (meth)acrylamides include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-n-butylacryl(meth)amide, N-t-butyl(meth)acrylamide, N-cyclohexyl(meth)acrylamide, N-(2-methoxyethyl)(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-phenyl(meth)acrylamide, N-benzyl(meth)acrylamide, (meth)acryloylmorpholine, and diacetone acrylamide.

Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethylstyrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (e.g., t-Boc), methyl vinylbenzoate, and α-methylstyrene.

<Ethylenically unsaturated monomer having thermal crosslinkable group>
From the viewpoint of improving heat resistance and solvent resistance, it is preferable that the resin (C) having a cationic group in the side chain of the present invention contains at least one thermally crosslinkable group selected from the group consisting of a hydroxyl group, a carboxyl group, an oxetane group, and a t-butyl group in addition to the structural unit represented by formula (2). In order to introduce these thermally crosslinkable groups into the resin (C) having a cationic group in the side chain, there can be mentioned a method of copolymerizing an ethylenically unsaturated monomer having thermal crosslinkability as a monomer component.

(Ethylenically unsaturated monomer having a hydroxy group)
Examples of ethylenically unsaturated monomers having a hydroxy group include 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate, but other monomers can also be used as long as they have a hydroxy group.

(Ethylenically 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, and crotonic acid, and examples of ethylenically unsaturated monomers having a carboxylic acid anhydride group include maleic anhydride and itaconic anhydride, but other monomers can also be used as long as they have a carboxy group.

(Ethylenically unsaturated monomer having a t-butyl group)
Examples of ethylenically unsaturated monomers having a t-butyl group include t-butyl acrylate and t-butyl methacrylate, but other monomers can also be used as long as they have a t-butyl group.

(Ethylenically 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, 3-(methacryloyloxymethyl) 3-ethyloxetane, 3-(acryloyloxymethyl) 3-butyloxetane, 3-(methacryloyloxymethyl) 3-butyloxetane, 3-(acryloyloxymethyl) 3-hexyloxetane, and 3-(methacryloyloxymethyl) 3-hexyloxetane. However, other monomers may also be used as long as they have an oxetanyl group.

The above hydroxyl group, carboxyl group, oxetane group, and t-butyl group may be contained in two or more types in the resin.

(Method of synthesizing resin (C) having cationic groups in the side chains)
Suitable methods for obtaining the resin (C) having a cationic group in the side chain in the present invention include known methods such as anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Among these, free radical polymerization and living radical polymerization are preferred.

The resin (C) having a cationic group in the side chain suitable for use in the present invention may be either a random type or a block type, but is preferably a block type from the viewpoint of heat resistance.
(Method of synthesizing block type resin (C) having cationic groups in its side chains)
The block type resin (C) having a cationic group in the side chain is composed of an A block having a structural unit represented by the general formula (2) and a B block having a specific group, and is preferably an A-B block, a B-A-B block, or an A-B-A block, and more preferably an A-B block or a B-A-B block. Such a block type resin is prepared, for example, by the living polymerization method shown below. Here, living polymerization is a polymerization method in which side reactions occurring in general radical polymerization are suppressed and polymerization growth occurs uniformly, so that block polymers and resins with uniform molecular weights can be easily synthesized. The molecular weight and composition of the polymer can be freely controlled by the charging ratio of the polymerization initiator and the ethylenically unsaturated monomer added during polymerization, and the polymer can be used to produce block polymers, gradient polymers, star polymers, comb polymers, and even terminally functional polymers.

The block-type resin of the present invention can be synthesized by a known living radical polymerization method. As specific examples, the following methods have been developed and are being widely researched and developed. Nitroxide-mediated polymerization (NMP method) utilizes the dissociation and bonding of amine oxide radicals (see Reference 1). Atom transfer radical polymerization (ATRP method) uses heavy metals such as copper, ruthenium, nickel, and iron, and ligands that form complexes with them, and polymerizes halogen compounds as initiator compounds (see References 2, 3, and 4). Reversible addition-fragmentation chain transfer (RAFT method) uses dithiocarboxylic acid esters, xanthate compounds, and other initiator compounds to polymerize addition-polymerizable monomers and radical initiators (see Reference 5), and Macromolecular Designvia Interchange of Xanthate (MADIX method) (see Reference 6). A method that uses heavy metals such as organotellurium, organobismuth, organoantimony, antimony halides, organogermanium, and germanium halides (Degenerative transfer: DT method) (see References 7 and 8).

(Reference 1) Chemical Review (2001) 101, 3661
(Reference 2) JP-T-2000-500516 (Reference 3) JP-T-2000-514479 (Reference 4) Chemical Review (2001) 101, 3689
(Reference 5) JP-T-2000-515181 (Reference 6) WO-1999-05099 pamphlet (Reference 7) JP-A-2007-277533 (Reference 8) Journal of American Chemical Society (2002) 124, 2874

Among these living radical polymerizations, atom transfer radical polymerization (ATRP), which uses an organic halide or sulfonyl halide compound as an initiator and a metal complex with a transition metal as the central metal as a catalyst, is preferred not only from the standpoint of controlling the molecular weight and molecular weight distribution of the polymer, but also because it can be used with a wide range of monomers and can adopt a polymerization temperature that is compatible with existing equipment.

Atom transfer radical polymerization is carried out using a transition metal complex of copper, ruthenium, iron, nickel, or the like as a redox polymerization catalyst. Specific examples of transition metal complexes include low-valent transition metal halides such as copper(I) chloride and copper(I) bromide.

Organic ligands are used in the fiber metal complexes. The organic ligands are used to enable solubility in the polymerization solvent and reversible change of the redox polymerization catalyst. Coordinating atoms of transition metals include nitrogen atoms, oxygen atoms, phosphorus atoms, sulfur atoms, etc.

The initiator used in the atomic radical polymerization method can be any known one, but mainly, organic halides having highly reactive carbon-halogen bonds, halogenated sulfonyl compounds, etc. are used. Specific examples include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, paratoluenesulfonic acid chloride, 1-bromoethylbenzene, chloroethylbenzene, etc. These are used alone or in combination.

<Content of structural unit represented by general formula (2) in resin (C) having cationic group in its side chain>
In the resin (C) 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 preferably 4 to 74 mass%, more preferably 8 to 48 mass%, relative to 100 mass% of the total of the structural units constituting the resin. When it is in this range, the dye-derived coloring power when made into the salt-forming compound (E) is excellent, and affinity to the solvent, which is the dispersion medium, can be sufficiently secured, so that no foreign matter is generated and the stability over time is good.

In block type resin (C) having cationic groups in its side chains, the content of A block containing the structural unit represented by general formula (2) is preferably 5% by mass to 74% by mass, more preferably 10% by mass to 48% by mass. Similarly, in the block type, by being in this range, when the salt-forming compound (E) is formed, the A block contributes to excellent coloring power, and the B block functions as a site that has affinity for the solvent, which is the dispersion medium, and the salt-forming compound can be stably present in the dispersion medium, improving stability over time.

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

<Mass Average Molecular Weight of Resin (C) Having Cationic Groups on the Side Chains>
The molecular weight of the resin (C) having a cationic group in the side chain is not particularly limited, but in either the random type or the block type, the converted mass average molecular weight measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000, more preferably 3,000 to 15,000. By being in the above range, it is possible to achieve both the stability over time and the solvent resistance of the salt forming compound.

In addition, it is preferable that the resin (C) having a cationic group in the side chain has the property of being soluble in a solvent that is widely used in coloring compositions for color filters. This makes it possible to obtain a coating film that does not generate foreign matter. In particular, it is more preferable that it is soluble in propylene glycol monomethyl ether acetate.

<Polymerization Solvent>
In the step of producing the resin (C) having a cationic group in the side chain, no solvent or a solvent may be used in some cases. 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, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate, but are not particularly limited thereto and can be selected arbitrarily based on the application, cost, and the like. Two or more types of polymerization solvents may be mixed and used.

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

<Method for producing salt-forming compound (E) of resin (C) having a cationic group in the side chain and xanthene acid dye>
The salt-forming compound (E) of the present invention can be easily obtained by stirring or vibrating an aqueous solution in which a resin (C) having a cationic group in a side chain and a xanthene acid dye are dissolved, or by mixing an aqueous solution of a resin (C) having a cationic group in a side chain and an aqueous solution of a xanthene acid dye under stirring or vibration. In the aqueous solution, the cationic group of the compound and the anionic group of the dye are ionized, and they form an ionic bond, and the ionic bonded portion becomes water-insoluble and precipitates. On the other hand, the salt consisting of the counter anion of the compound and the counter cation of the acid dye is water-soluble, and can be removed by washing with water, etc. The resin (C) having a cationic group in a side chain and the xanthene acid dye may each be used alone or in combination with a plurality of different structures.

As the aqueous solution used for salt formation, a mixed solution of water and a water-soluble organic solvent may be used to dissolve the resin (C) having a cationic group in the side chain and the xanthene acid dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2-(methoxymethoxy)ethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, propylene glycol monomethyl ether acetate, di ... Examples of the water-soluble organic solvent include ethanol, 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, tetrafurfuryl alcohol, and 4-methoxy-4-methylpentanone. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by mass, and most preferably 5 to 20% by mass, based on the total mass of the aqueous solution (100% by mass).

＜Other colorants＞

The coloring composition for color filters of the present invention may contain pigments and dyes to adjust the chromaticity and further improve the heat resistance, etc., within the range that does not impair the effects of the present invention.

As other colorants, pigments and dyes of various colors such as blue and purple can be used. In addition, examples of pigments include organic pigments such as phthalocyanine, quinacridone, benzimidazolone, dioxazine, indanthrene, perylene, rhodamine lake, azo, and aminoketone. In addition, various inorganic pigments can also be used.

Below are examples of pigments that can be used in combination. "C.I." stands for Color Index (C.I.).

Blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, and 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, etc.
Among these, preferred are C.I. Pigment Blue 1, 15, 15:1, 15:2, 15:3, 15:4, and 15:6, which are blue pigments having a copper phthalocyanine skeleton, and more preferred is C.I. Pigment Blue 15:6.

Examples of purple pigments include C.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, and 50. Among these, C.I. Pigment Violet 19 and 23 are preferred, and C.I. Pigment Violet 23 is more preferred.

In order to maintain sufficient brightness as a coloring component for color filters, it is preferable that the pigment component be in the range of 500 parts by mass or less per 100 parts by mass of the salt-forming compound (E) of the present invention.

Dyes that can be used in combination are preferably blue, red, or purple and are in the form of oil-soluble dyes, acid dyes, direct dyes, or basic dyes. Of these, triphenylmethane dyes and cyanine dyes are preferred because they have excellent hues. These dyes may also be in the form of lake pigments, 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, etc.

(Micronization of pigments)
The pigment to be added to the coloring composition of the present invention is preferably pulverized by salt milling or the like in order to achieve high transmittance and high contrast. The primary particle size of the pigment is preferably 10 nm or more in order to provide good dispersion in the colorant carrier. In addition, the primary particle size is preferably 80 nm or less in order to form a filter segment with high contrast. The particularly preferred range is 20 to 60 nm.

Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while being heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment with a very fine primary particle diameter, a narrow distribution range, and a sharp particle size distribution.

Sodium chloride, potassium chloride, sodium sulfate, etc. can be used as the water-soluble inorganic salt, but sodium chloride (table salt) is preferred from the viewpoint of cost. From the viewpoints of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by mass, and most preferably 300 to 1000% by mass, based on the total mass of the pigment (100% by mass).

The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, dissolves (is miscible with) water, and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporate, a high-boiling point solvent with a boiling point of 120°C or higher is preferred from the standpoint 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, etc. may be used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, and most preferably 50 to 500% by mass, based on the total mass of the pigment (100% by mass).

When the pigment is subjected to salt milling, a resin may be added as necessary. There are no particular limitations on the type of resin used, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvents. The amount of resin used is preferably in the range of 5 to 200% by mass, based on the total mass of the pigment (100% by mass).

<Binder resin>
The coloring composition of the present invention contains a binder resin. The binder resin is a resin that disperses a colorant or a resin that dyes or impregnates a salt-forming compound, and examples of the binder resin include thermoplastic resins and thermosetting resins.

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

Examples of thermosetting resins include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenolic resins.

The binder resin is preferably a resin having a spectral transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region. In addition, since the coloring composition for color filters of the present invention is in the form of an alkali-developable color resist material, it is preferable to use an alkali-soluble vinyl resin copolymerized with an acidic group-containing ethylenically unsaturated monomer.

Examples of alkali-soluble resins copolymerized with acidic group-containing ethylenically unsaturated monomers include resins having acidic groups such as carboxyl groups and sulfonic groups. Specific examples of alkali-soluble resins include acrylic resins having acidic groups, α-olefin/maleic acid (anhydride) copolymers, styrene/styrene sulfonic acid copolymers, ethylene/(meth)acrylic acid copolymers, and isobutylene/maleic acid (anhydride) copolymers. Among these, at least one resin selected from acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers, particularly acrylic resins having acidic groups, are preferably used because of their high heat resistance and transparency.

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

Examples of active energy ray-curable resins having ethylenically unsaturated double bonds include resins into which unsaturated ethylenically double bonds have been introduced by the methods (a) to (c) shown below.

[Method (a)]
Method (a) can be exemplified by a method in which an unsaturated ethylenic monomer having an epoxy group is copolymerized with one or more other monomers to obtain a copolymer, and a carboxy group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction with the side-chain epoxy group of the copolymer, and then a polybasic acid anhydride is reacted with the resulting hydroxyl group to introduce an unsaturated ethylenic double bond and a carboxy group.

Examples of unsaturated ethylenic monomers having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, and 3,4 epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxy, halogen, nitro, or cyano at the α-position. These may be used alone or in combination of two or more.

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., which may be used alone or in combination of two or more. If necessary, for example to increase the number of carboxy groups, it is also possible to use a tricarboxylic acid anhydride such as trimellitic anhydride, or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride, which has an unsaturated ethylenic double bond, is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

[Method (b)]
As a method similar to the method (a), for example, there is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the side chain carboxy groups of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxy group with one or more other monomers, thereby introducing an unsaturated ethylenic double bond and a carboxy group.
In this method, a larger amount of hydroxyl groups derived from the unsaturated ethylenic monomer having an epoxy group is generated compared to the method (a). When the resin having a cationic group in the side chain used for obtaining the salt forming compound of the present invention contains an oxetanyl group or a t-butyl group as a thermally crosslinkable functional group, it is preferable to use the resin obtained by the method (b) as the binder resin because it exhibits higher heat resistance.

[Method (c)]
Method (c) includes a method in which an unsaturated ethylenic monomer having a hydroxyl group is used and copolymerized with another monomer of an unsaturated monobasic acid having a carboxyl group or with another monomer, and the side chain hydroxyl group of the copolymer is reacted with an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

The unsaturated ethylenic monomer having a hydroxyl group includes hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate, which may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to the above hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly)12-hydroxystearic acid, etc., may also be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl (meth)acrylate or glycerol (meth)acrylate is preferred.

Examples of unsaturated ethylenic monomers having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but are not limited to these and two or more types can be used in combination.

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

When the binder resin is used as a photosensitive composition, it is preferable to use a resin with an acid value of 20 to 300 mgKOH/g from the viewpoints of dispersibility, penetration, developability, and heat resistance of the pigment and salt-forming compound. If the acid value is less than 20 mgKOH/g, the solubility in the developer is poor, making it difficult to form a fine pattern. If the acid value exceeds 300 mgKOH/g, the fine pattern may not remain.

Because the binder resin has good film-forming properties and various resistances, it is preferably used in an amount of 30% by mass or more, based on the total mass of the colorant (100% by mass), and because the colorant concentration is high and good color characteristics can be expressed, 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 the thermoplastic resin, which is a binder resin. When a color filter is produced using the coloring composition for color filters of the present invention, the thermosetting compound reacts during baking of the filter segment to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segment, suppressing pigment aggregation during baking of the filter segment, and improving the contrast ratio.

Examples of thermosetting compounds include epoxy compounds and/or resins, benzoguanamine compounds and/or resins, rosin-modified maleic acid compounds and/or resins, rosin-modified fumaric acid compounds and/or resins, melamine compounds and/or resins, urea compounds and/or resins, and phenolic compounds and/or resins, but the present invention is not limited thereto. 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.), polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyls ...vinylbenzene, divinylbiphenyls, etc.), polycondensates of phenols and various diene compounds (divinylbenzene, divinylbiphenyls, etc.), polycondensates of phenols and various diene compounds (divinylbenzene, divinylbiphenyls, etc.), polycondensates of phenols and various diene compounds (divinylbenzene, divinylbiphenyl Examples of epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α',α'-benzene dimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, glycidyl amine epoxy resins, and glycidyl ester epoxy resins, but are not limited to these, so long as they are commonly used epoxy compounds. These may be used alone, or two or more of them may be used.

Commercially available products include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (all trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (all trade names; manufactured by Japan Epoxy Resins Co., Ltd.), TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade names; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; manufactured by Japan Epoxy Resins Co., Ltd.), JER
157S65, 157S70 (trade name; manufactured by Japan Epoxy Resins Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (all trade names; manufactured by Japan Epoxy Resins Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all trade names; manufactured by Nippon Kayaku Co., Ltd.), Celoxide 2021, EHPE-3150 (all trade names; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-810, EX-830, EX-851, EX-512, EX-421, EX-313, EX-201, EX-111 (all trade names; manufactured by Nagase ChemteX Co., Ltd.), and the like, but are not limited thereto.

The amount of epoxy compound blended is preferably 0.5 to 300 parts by mass, and more preferably 1.0 to 50 parts by mass, per 100 parts by mass of 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, problems may occur when forming filter segments by photolithography.

In addition, the coloring composition for color filters of the present invention may contain a curing agent, a curing accelerator, etc., as necessary, to assist the curing of the thermosetting compound. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. are effective, but are not particularly limited to these, and any curing agent may be used as long as it can react with the thermosetting compound. Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, etc.), and the like. , 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 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 relative to 100 parts by mass of the thermosetting compound.

<Curing agent, curing accelerator>
In addition, the coloring composition of the present invention may contain a curing agent, a curing accelerator, etc., as necessary, in order to assist the curing of the thermosetting resin. As the curing agent, a phenolic resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound, etc. are effective, but are not particularly limited thereto, and any curing agent may be used as long as it can react with the thermosetting resin. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferably mentioned. Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, etc.), and the like. dazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), guanamine compounds (e.g., melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g., 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% by mass with respect to the total amount of the thermosetting resin.

<Organic Solvent>
The coloring composition of the present invention contains an organic solvent, which allows the coloring agent to be sufficiently dispersed and penetrated into the coloring agent carrier, and makes it easy to form a filter segment by applying the coloring agent to a substrate such as a glass substrate so as to give a dry film thickness of 0.2 to 5 μm.

Examples of organic solvents include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol. butyl ether, 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 monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol 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, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.

Among these, it is preferable to use glycol acetates such as ethyl lactate, propylene glycol monomethyl 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, because they provide good dispersion and dissolution of the fluorescent dye salt-forming compound used in the present invention, the metal complex dye salt-forming compound, the optional pigment, and other dyes that can be used in combination. In particular, it is most preferable to use 3-methoxybutanol from the viewpoint of solubility in the fluorescent dye salt-forming compound used in the present invention and the metal complex dye salt-forming compound.

These organic solvents can be used alone or in combination of two or more. When using a mixed solvent of two or more, it is preferable that the above preferred organic solvents are contained in an amount of 65 to 95% by mass.

The organic solvent is preferably used in an amount of 500 to 4,000 parts by weight per 100 parts by weight of the colorant, since it adjusts the viscosity of the coloring composition to an appropriate level and enables the formation of filter segments with the desired uniform thickness.

<Photopolymerizable Monomer>
The colored composition of the present invention can be used as a photosensitive colored composition for color filters by further adding a photopolymerizable monomer and/or a photopolymerization initiator.
The photopolymerizable monomer of the present invention includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin, and these can be used alone or in combination of two or more kinds.

Examples of monomers and oligomers that are cured by ultraviolet light or heat to produce a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, and the like. Examples of the acrylic acid esters and methacrylic acid esters include, but are not limited to, diethyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylol melamine, epoxy (meth)acrylate, and urethane acrylate; (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.
These photopolymerizable monomers may be used alone or in combination of two or more kinds in any ratio as required.

The amount of photopolymerizable monomer is preferably 5 to 400 parts by weight per 100 parts by weight of colorant, and more preferably 10 to 300 parts by weight from the viewpoints of photocurability and developability.

<Photopolymerization initiator>
The coloring composition of the present invention can be prepared in the form of a solvent-developable or alkali-developable photosensitive coloring composition by adding a photopolymerization initiator to cure the composition by ultraviolet irradiation and form a filter segment by a photolithography method.

Examples of the photopolymerization initiator include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin, benzoin methyl ether, etc. benzoin compounds such as benzoin ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone. Ton-based compounds: 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-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl) triazine-based compounds such as 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine, 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; phosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, or ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; or titanocene-based compounds.
These photopolymerization initiators may be used alone or in combination of two or more at any ratio as required. The content of the photopolymerization initiator is preferably 2 to 200 parts by mass, and more preferably 3 to 150 parts by mass, relative to 100 parts by mass of the colorant, from the viewpoints of photocurability and developability.

<Sensitizer>
Furthermore, a sensitizer can be added to the coloring composition for color filters of the present invention.
Examples of the sensitizer include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. Examples of the compound include conductors, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-diethylaminobenzophenone.
These sensitizers may be used alone or in combination of two or more kinds in any desired ratio, as required.

More specifically, examples of sensitizers include those described in "Dye Handbook" edited by Okawara Makoto et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Okawara Makoto et al. (CMC, 1981), "Tokushu No Futon Zairyo" edited by Ikemori Chuzaburo et al., and "Tokushu No Futon Zairyo" (CMC, 1986), but are not limited to these. In addition, sensitizers that absorb light from the ultraviolet to near infrared regions can also be included.

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

<Multifunctional thiol>
The coloring composition for color filters of the present invention may contain a polyfunctional thiol that acts as a chain transfer agent.
The polyfunctional thiol may be any compound having two or more thiol groups, and examples thereof include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. These polyfunctional thiols can be used alone or in combination of two or more kinds in any ratio as required.

The content of the polyfunctional thiol is preferably 0.1 to 30% by mass, and more preferably 1 to 20% by mass, based on the mass of the total solid content of the coloring composition for color filters (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 becomes too high, and the resolution decreases.

<Antioxidants>
The coloring composition for color filters of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the coloring composition for color filters from being oxidized and yellowed by the thermal process during heat curing or ITO annealing, and can increase the transmittance of the coating film. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be any compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specific examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic 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 sensitivity of the coating film, preferred ones include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Furthermore, hindered phenol-based antioxidants, hindered amine-based antioxidants, and phosphorus-based antioxidants are more preferred.

These antioxidants can be used alone or in a mixture of two or more in any ratio as necessary. The content of the antioxidant is preferably 0.5 to 5.0% by mass based on the solid content mass of the coloring composition for color filters (100% by mass) because this provides good brightness and sensitivity.

<Amine compounds>
The coloring composition of the present invention may contain an amine compound that has the function of reducing dissolved oxygen.
Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

<Leveling Agent>
It is preferable to add a leveling agent to the colored composition of the present invention in order to improve the leveling property of the composition on a transparent substrate.
As the leveling agent, dimethylsiloxane having a polyether structure or polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK-Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie Co., Ltd. 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 mass of the colored composition (100% by mass).

Particularly preferred leveling agents are those that have hydrophobic and hydrophilic groups in the molecule, and are characterized by low solubility in water despite having hydrophilic groups, and low surface tension reducing ability when added to a coloring composition. Furthermore, those that have good wettability to glass plates despite their low surface tension reducing ability are useful, and those that can sufficiently suppress electrostatic charging in an amount added that does not cause defects in the coating film due to foaming are preferably used. Dimethylpolysiloxanes having polyalkylene oxide units are preferably used as leveling agents having such preferred properties. Examples of polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxanes may have both polyethylene oxide units and polypropylene oxide units.

The bonding form of the polyalkylene oxide unit with the dimethylpolysiloxane may be any of a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a terminal modified type in which the polyalkylene oxide unit is bonded to the terminal of the dimethylpolysiloxane, and a linear block copolymer type in which the polyalkylene oxide unit is bonded alternately and repeatedly to the dimethylpolysiloxane. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., and examples thereof include, but are not limited to, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

The leveling agent may be supplemented with an anionic, cationic, nonionic, or amphoteric surfactant. Two or more types of surfactants may be mixed together.

Examples of anionic surfactants that can be added to the leveling agent as an auxiliary include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, 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, etc.

Examples of cationic surfactants that can be added to the leveling agent as supplementary agents include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants that can be added to the leveling agent as supplementary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; alkyl betaines such as alkyl dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

<Other additives>
The colored composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Also, an adhesion improver such as a silane coupling agent may be contained to improve adhesion to a transparent substrate.

Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, organic phosphines such as tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by mass per 100 parts by mass of the colorant.

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

<Method of producing coloring composition for color filter>
The coloring composition of the present invention can be produced by dispersing the colorant (A) in a colorant carrier such as a binder resin and/or a solvent using a dispersing aid (colorant dispersion). As a dispersion means, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, or the like is appropriately selected as necessary to disperse the colorant. At this time, two or more types of colorants (A) may be dispersed simultaneously in the colorant carrier, or they may be mixed after being separately dispersed in the colorant carrier.
The active energy ray curable resin having an ethylenically unsaturated double bond may be added at the stage of preparing the colorant dispersion, and the same effect can be obtained by adding it to the prepared colorant dispersion later. However, from the viewpoint of the stability of the colorant composition, it is preferable to add it at the stage of preparing the photosensitive colorant composition.
When the colorant such as a dye has high solubility, specifically when it is highly soluble in the solvent used and dissolves by stirring without any foreign matter being found, there is no need to produce it by finely dispersing it as described above. In this case, the dispersion aid can be used by simply adding and mixing it with the colorant solution in which the dye or the like has been dissolved.

When used as a photosensitive coloring composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable coloring composition. The solvent-developable or alkali-developable coloring composition can be prepared by mixing the colorant dispersion, the photopolymerizable monomer and/or the photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. 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 dispersing the colorant in the colorant carrier, a dispersing aid such as a resin-type dispersing agent, a dye derivative, a surfactant, etc. may be appropriately contained. The dispersing aid has a large effect of preventing reagglomeration of the colorant after dispersion, so that the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has good brightness and viscosity stability.

(Dye Derivatives)
As the dye derivative used in the present invention, in addition to the copper phthalocyanine pigment and the dye derivative (B) having a copper phthalocyanine structure having an acidic substituent as a parent skeleton, known dye derivatives having an acidic group, a basic group, a neutral group, etc. in an organic dye residue can be used. Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, a phosphoric acid group, etc., and amine salts thereof, compounds having a sulfonamide group or a basic substituent such as a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo, and polyazo, and the like.

Specifically, diketopyrrolopyrrole dye derivatives are described in JP 2001-220520 A, WO 2009/081930 pamphlet, WO 2011/052617 pamphlet, WO 2012/102399 pamphlet, and JP 2017-156397 A; phthalocyanine dye derivatives are described in JP 2007-226161 A, W2016/163351 pamphlet, JP 2017-165820 A, and Japanese Patent No. 5753266 A; anthraquinone dye derivatives are described in JP JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325 pamphlet; quinacridone dye derivatives are shown in JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383; dioxazine dye derivatives are shown in JP-A-2011-162662; thiazine indigo dye derivatives are shown in JP-A-2007-314785 As triazine-based dye derivatives, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, as benzisoindole-based dye derivatives, JP-A-2009-57478, as quinophthalone-based dye derivatives, JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-2 Examples of known dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439 as naphthol dye derivatives, JP-A-2001-172520 and JP-A-2012-172092 as azo dye derivatives, JP-A-2004-307854 as acidic substituents, and JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, and JP-A-2005-213404 as basic substituents. In these documents, the dye derivative may be referred to as a derivative, pigment derivative, dispersant, pigment dispersant, or simply a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

These dye derivatives can be used alone or in combination of two or more types.

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

(Resin-type dispersant)
A resin-type dispersant has a colorant affinity site that has the property of adsorbing to an added colorant, and a site that is compatible with the colorant carrier, and functions to adsorb to the added colorant and stabilize the dispersion in the colorant carrier. Specifically, the resin-type dispersant includes polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylate esters, and modified products thereof, poly(lower alkylene imines) and free carboxyl groups formed by reaction with polyesters, and their salts, oil-based dispersants, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, water-soluble resins and water-soluble polymer compounds such as polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters, which can be used alone or in a mixture of two or more, but are not necessarily limited to these.

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

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2010, 2011, 2012, 2013, 2014, 2015, 2016, 2017, 2018, 2019, 2020, 2025, 2050, 2070, 2095, 2018, 2020, 2025, 2050, 2070, 2095, 2019, 2020, 2025, 2050, 2070, 2095, 2020, 2025 ... 150, 2155, 2163, 2164, Anti-Terra-U, 203, 204, BYK-P104, P104S, 220S, 6919, Lactimon, Lactimon-WS, Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000 manufactured by Nippon Lubrizol Co., Ltd. , 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 manufactured by BASF, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajispar PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd. are preferred.

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 between a hydroxyl group of a hydroxyl group-containing polymer and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride.
(S2) A resin-type dispersant which is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between 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.

<Resin-type dispersant (S1)>
The resin-type dispersant (S1) can be produced by known methods such as those described in WO2008/007776, JP2008-029901A, and JP2009-155406A. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the end, and can be obtained, for example, as a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) in the presence of a compound (q) having a hydroxyl group. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that the terminal hydroxyl group is a plurality of hydroxyl groups, among them, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferred example of a polymer having two hydroxyl groups at one end can be obtained as a polymer (p1) by polymerizing an ethylenically unsaturated monomer (r) including a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. The hydroxyl groups of the polymer (p) having hydroxyl groups react with the acid anhydride groups of the tricarboxylic acid anhydride and/or tetracarboxylic acid dianhydride to form ester bonds, while the anhydride ring opens to produce a carboxylic acid.

<Resin-type dispersant (S2)>
The resin-type dispersant (S2) can be produced by known methods such as those described in JP-A-2009-155406, JP-A-2010-185934, and JP-A-2011-157416, and is obtained, for example, by polymerizing an ethylenically unsaturated monomer (r) in the presence of a reaction product between a hydroxyl group of a compound (q) having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride. Among them, a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) containing a monomer (r1) in the presence of a reaction product between a hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride is preferred.

The difference between (S1) and (S2) is whether the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is introduced first or later. The molecular weight and other factors may differ slightly depending on various conditions, but in theory, the same product can be produced if the raw materials and reaction conditions are the same.

(Surfactant)
Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyl dimethylaminoacetate betaine, and amphoteric surfactants such as alkyl imidazolines. These can be used alone or in combination of two or more, but are not necessarily limited to these.

When a surfactant is added, the amount is preferably 0.1 to 55 parts by weight, and more preferably 0.1 to 45 parts by weight, per 100 parts by weight of colorant. If the amount of surfactant is less than 0.1 parts by weight, it is difficult to obtain the effect of adding it, and if the amount is more than 55 parts by weight, the excess dispersant may affect the dispersion.

<Removal of coarse particles>
The coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, sintered filter, membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention is provided with a filter segment formed using the coloring composition for color filters of the present invention. Examples of the color filter include a filter provided with a red filter segment, a green filter segment, and a blue filter segment, or a filter provided with a magenta filter segment, a cyan filter segment, and a yellow filter segment.

Transparent substrates include glass plates such as soda-lime glass, low-alkali borosilicate glass, and non-alkali aluminoborosilicate glass, and resin plates such as polycarbonate, polymethylmethacrylate, and polyethylene terephthalate. Transparent electrodes made of indium oxide, tin oxide, etc. may be formed on the surface of the glass or resin plate to drive the liquid crystal after panelization.

<Manufacturing method of color filter>
The color filter of the present invention can be produced by a printing method or a photolithography method.
The formation of filter segments by the printing method can be patterned simply by repeatedly printing and drying a colored composition prepared as a printing ink, and is therefore a low-cost and mass-productive method for producing color filters. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to print, it is preferable to use a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, control of the ink flowability on the printing machine is also important, and the ink viscosity can be adjusted by using a dispersant or an extender pigment.

When forming filter segments by photolithography, the coloring composition prepared as the above-mentioned solvent-developable or alkali-developable colored resist material is applied to a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern that is in contact with or not in contact with the film. Thereafter, the uncured parts are removed by immersing the film in a solvent or alkali developing solution or spraying the developing solution by a spray or the like to form a desired pattern, and the same operation is repeated for other colors to produce a color filter. Furthermore, heating can be performed as necessary to promote polymerization of the colored resist material. According to the photolithography method, a color filter with higher accuracy than the above-mentioned printing method can be produced.

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

The color filter of the present invention can be manufactured by the above-mentioned method, as well as by an electrodeposition method, a transfer method, etc., and the coloring composition of the present invention can be used in any of these methods. The electrodeposition method is a method of manufacturing a color filter by using a transparent conductive film formed on a substrate to electrodeposit each color filter segment onto the transparent conductive film by electrophoresis of colloidal particles. The transfer method is a method in which filter segments are formed in advance on the surface of a peelable transfer base sheet, and the filter segments are then transferred to the desired substrate.

Before forming each color filter segment on the transparent substrate or reflective substrate, a black matrix can be formed in advance. Examples of black matrices that can be used include, but are not limited to, multilayer films of chromium or chromium/chromium oxide, inorganic films such as titanium nitride, and resin films with light-shielding agents dispersed therein. Thin film transistors (TFTs) can also be formed in advance on the transparent substrate or reflective substrate, and then each color filter segment can be formed. In addition, an overcoat film, a transparent conductive film, etc. can be formed on the color filter of the present invention as necessary.

The color filter is attached to the opposing substrate using a sealant, liquid crystal is injected through an injection port provided in the seal, the injection port is then sealed, and a polarizing film or retardation film is attached to the outside of the substrate as required, to produce a liquid crystal display panel.

Such liquid crystal display panels can be used in liquid crystal display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically concentric bend (OCB).

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

(Acid value of acidic dispersant and binder resin)
The acid value of the acidic dispersant and the resin (C) having a cationic group on the side chain is the acid value (mgKOH/g) measured according to the potentiometric titration method of JIS K 0070 and converted into a solid content.

(Average Molecular Weight of Resin (C) Having Cationic Groups on Side Chains)
The number average molecular weight (Mn) and mass average molecular weight (Mw) of the resin (C) having a cationic group on the side chain were measured by gel permeation chromatography (GPC) using polystyrene as the standard substance.

(Ammonium Salt Value of Resin (C) Having Cationic Groups on Side Chains)
The ammonium value of the resin (C) having a cationic group in the side chain is determined by titrating with a 0.1 N aqueous solution of silver nitrate using a 5% aqueous solution of potassium chromate as an indicator, and then converting the value into the equivalent amount of potassium hydroxide. The measured total ammonium salt value is converted into the solid content of the resin (mg KOH/g).

<Method of preparing binder resin solution>
(Preparation of binder resin solution 1)
A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. 70.0 parts of cyclohexanone was charged in the reaction vessel, which was then heated to 80°C. The atmosphere in the reaction vessel was replaced with nitrogen, and a mixture of 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 Toagosei Co., Ltd.), and 0.4 parts of 2,2'-azobisisobutyronitrile was dripped over 2 hours from the drip tube. After dripping was completed, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin with a mass average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the resin solution previously synthesized so that the nonvolatile content was 20% by mass to prepare binder resin solution 1.

<Production of dye derivative>
[Production of dye derivative (B)]
The dye derivative (B) having the copper phthalocyanine structure shown in Table 1 as the parent skeleton can be produced by, for example, the methods described in JP-A-2001-356210, JP-A-2011-057910, etc. Table 2 shows dye derivatives (B-1) to (B-5) having the copper phthalocyanine structure as the parent skeleton.

Meanings of Abbreviations in Table 1 (Dye Derivative (B-1))
"SOLSPERSE 5000" (manufactured by Lubrizol Japan); copper phthalocyanine sulfonate ammonium salt

[Production of other dye derivatives (F-1)]
(Production of copper phthalocyanine amine compound (F-1); copper phthalocyanine sulfonic acid amide compound)
According to the method for producing the phthalocyanine amine compound (C-3) described in JP-A-2011-227491, the following copper phthalocyanine sulfonic acid amide compound (F-1) was obtained.

Copper phthalocyanine sulfonic acid amide compound (F-1)

(Blue Micronized Pigment (Copper Phthalocyanine Pigment) (P-1))
100 parts of a phthalocyanine blue pigment C.I. Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70° C. This mixture was added to 3,000 parts of hot water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly with water to remove salt and solvent, and then dried at 80° C. for 24 hours to obtain 98 parts of a blue fine pigment (P-1).

(Blue Micronized Pigment (Copper Phthalocyanine Pigment) (P-2))
Phthalocyanine blue pigment C.I. Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.) 97 parts, dye derivative (B-2) 3 parts, ground salt 800 parts, and diethylene glycol 100 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 70 ° C. This mixture was added to 3000 parts of hot water, heated to about 70 ° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 ° C. for 24 hours to obtain 98 parts of blue fine pigment (P-2).

(Blue Micronized Pigment (Copper Phthalocyanine Pigment) (P-3))
100 parts of crude β-type copper phthalocyanine was added to 600 parts of 98% sulfuric acid, and the mixture was stirred at 40° C. for 2 hours to completely dissolve it, and then poured into 1,000 parts of water with stirring. After stirring for 30 minutes, the mixture was filtered, washed with water, dried, and pulverized to obtain 95 parts of crude α-type phthalocyanine.
92 parts of the obtained crude α-type copper phthalocyanine, 8 parts of the dye derivative (B-1), 800 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 12 hours at 70° C. The mixture was poured into 3,000 parts of warm water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain 97 parts of a finely divided blue pigment (P-3) which is an α-type copper phthalocyanine.

<Production of Resin (C) Having Cationic Groups on the Side Chains>
(Solution of Resin (C-1) Having Cationic Groups on the Side Chains)
A reaction apparatus equipped with a gas inlet tube, a condenser, an agitator 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 the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and 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 initiate polymerization of the first block. 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 based on the non-volatile content. Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methacrylate methyl chloride salt as a second block monomer were charged into the reaction apparatus, and the mixture was stirred while maintaining a nitrogen atmosphere at 100°C, and the reaction was continued. Two hours after the addition of dimethylaminoethyl methacrylate methyl chloride salt, 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 calculated from the non-volatile content, and the solution was cooled to 50° C. Methanol was then added to obtain a resin (C-1) having a cationic group in the side chain and a resin component of 40% by mass. The mass average molecular weight (Mw) of the resin (C-1) was 7,300.

(Solution of Resins (C-2) to (C-6) Having Cationic Groups on the Side Chains)
Resins (C-2) to (C-6) having cationic groups on the side chains were obtained in the same manner as for Resin (C-1), except that the types and amounts of monomers used were changed as shown in Table 2.

The monomers in Table 2 used were as follows:
DMC78: dimethylaminoethyl methacrylate methyl chloride 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: tertiary butyl methacrylate,

<Production of anionic dye (D)>
(Synthesis of anionic dye (D-1))
45.0 parts of C.I. Acid Red 289, 56.6 parts of 2-iodopropane, and 46.0 parts of potassium carbonate were added to 360 parts of N-methylpyrrolidone, and the mixture was stirred at 85°C for 12 hours. The resulting reaction solution was cooled to room temperature, and then added to 3600 parts of ethyl acetate and stirred at room temperature for 1 hour, resulting in precipitation of crystals. The precipitated crystals were collected by filtration, washed with 3000 parts of ethyl acetate, and dried overnight at 60°C under reduced pressure to obtain 43.0 parts of anionic dye (D-1) represented by the following structural formula.

Anionic dye (D-1)

(Synthesis of anionic dye (D-2))
45.0 parts of C.I. 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 resulting reaction solution was cooled to room temperature, and then added to 3,000 parts of ethyl acetate and stirred at room temperature for 1 hour, resulting in the precipitation of crystals. The precipitated crystals were collected by filtration, washed with 2,500 parts of ethyl acetate, and dried overnight at 60°C under reduced pressure to obtain 47.6 parts of anionic dye (D-2) represented by the following structural formula.

Anionic dye (D-2)

(Synthesis of anionic dye (D-3))
45.0 parts of C.I. Acid Red 289, 71.4 parts of 1-iododecane, and 46.0 parts of potassium carbonate were added to 360 parts of N-methylpyrrolidone, and the mixture was stirred at 85°C for 12 hours. The resulting reaction solution was cooled to room temperature, and then added to 3600 parts of ethyl acetate and stirred at room temperature for 1 hour, resulting in precipitation of crystals. The precipitated crystals were collected by filtration, washed with 3000 parts of ethyl acetate, and dried overnight at 60°C under reduced pressure to obtain 53.0 parts of anionic dye (D-3) represented by the following structural formula.

Anionic dye (D-3)

<Method for producing salt-forming compound (E)>
(Preparation of Salt-Forming Compound (E-1))
A salt-forming compound (E-1) consisting of C.I. Acid Red 289 and resin (C-1) was produced according to the following procedure.
42 parts of resin (C-1) having a cationic group in the side chain is added to 2000 parts of water, and the mixture is thoroughly stirred and mixed, and then heated to 60 ° C. Meanwhile, an aqueous solution of 10 parts of C.I. Acid Red 289 dissolved in 90 parts of water is prepared, and the solution is gradually dropped into the resin solution. After the dropwise addition, the mixture is stirred at 60 ° C for 120 minutes to thoroughly react. To confirm the end point of the reaction, the reaction solution is dropped onto a filter paper, and the end point is when the bleeding disappears, and it is determined that a salt-forming compound has been obtained. After cooling to room temperature while 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 anionic dye (C-1) is removed by suction filtration and washing with water, and the salt-forming compound remaining on the filter paper is dried by removing moisture in a dryer, and 32 parts of C.I. Acid Red 289 and resin (C-1) are used to obtain a salt-forming compound (E-1).

(Preparation of salt-forming compounds (E-2) to (E-13))
Thereafter, salt-forming compounds (E-2) to (E-13) were prepared in the same manner as in (E-1), except that the resin having a cationic group in the side chain and the dye were changed to those shown in Table 3.

<Method of producing dispersant>
(Dispersant 1)
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 70 parts of methyl methacrylate, 20 parts of t-butyl methacrylate, and 10 parts of methacrylic acid, and substituted with nitrogen gas. The reaction vessel was heated to 80 ° C., 6.0 parts of 1-thioglycerol was added, and the mixture was reacted for 12 hours. It was confirmed that 95% had reacted by measuring the solid content. 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 were added, and the mixture was reacted at 100 ° C. for 7 hours. It was confirmed by measuring the acid value that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated, and a dispersant 1 having a non-volatile content of 50% by mass, an acid value of 100 mgKOH / g, and a mass average molecular weight of 9000 was obtained.

<Production of Color Composition for Color Filter>
[Example 1]
The mixture below was stirred and mixed to be homogeneous, and then dispersed for 5 hours in an Eiger mill (Eiger Japan Co., Ltd. "Mini Model M-250MKII") using zirconia beads having a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to prepare a colored composition (EP-1).

Salt forming compound (E-1) 5.0 parts Dye derivative (B-1) 1.0 parts Blue fine pigment (P-1) 4.0 parts Dispersant 1 4.0 parts Binder resin solution 1 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC)
46.0 parts
However, Example 1 is a reference example.

[Examples 2 to 22, Comparative Examples 1 to 4]
Colored compositions (EP-2) to (EP-26) were prepared in the same manner as in Example 1, except that the blue pigment, salt-forming compound, dye derivative, finely divided pigment, dispersant, binder resin solution, and propylene glycol monomethyl ether acetate were changed to the compositions and blending ratios shown in Table 4.
However, Examples 7 and 14 to 22 are reference examples.

(Lightness Evaluation)
The colored composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater so that y = 0.100, then dried at 60°C for 5 minutes, and then heated at 230°C for 20 minutes and allowed to cool to produce a coated substrate. The lightness (spectral transmittance) was measured using the obtained coated substrate. The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKALCF-1100M). The evaluation criteria are as follows. × is a level that is difficult to use.
◎: 11.5 or more ○: 10.8 or more and less than 11.5 △: 10.0 or more and less than 10.8 ×: Less than 10.0

(Heat resistance evaluation)
The colored composition was applied to a glass substrate of 100 mm x 100 mm and 1.1 mm thickness using a spin coater so that the dry film thickness was 2.0 μm, then dried at 70 ° C for 20 minutes, and then heated at 230 ° C for 60 minutes and allowed to cool to produce a coating film substrate (one embodiment of a color filter). The chromaticity ([L ^* (1), a ^* (1), b ^* (1)]) of the obtained coating film under C light source was measured using a microspectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"). Thereafter, as a heat resistance test, the coating film was heated at 250 ° C for 1 hour, and the chromaticity ([L ^* (2), a ^* (2), b ^* (2)]) under C light source was measured, and the color difference ΔEab ^* was calculated using the following formula and evaluated on the following four-level scale.

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

◎: ΔEab ^* is less than 2.0 (very good)
○: ΔEab ^* is 2.0 or more and less than 3.5 (good)
△: ΔEab ^* is 3.5 or more and less than 6.0 (poor)
×: ΔEab ^* is 6.0 or more (very poor)

(Paint film foreign matter evaluation)
The colored composition was applied to a 100 mm x 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 heated at 230° C. for 60 minutes and allowed to cool to produce a coated substrate. Evaluation was performed by observing the surface using a metal microscope "BX60" manufactured by Olympus Systems Co., Ltd. The magnification was set to 500 times, and the number of particles observable in any five visual fields in transmission was counted. Evaluation was performed using the following four-level scale.

◎: The number of foreign objects is less than 5 (very good)
○: The number of foreign objects is 5 or more and less than 10 (good)
△: The number of foreign objects is 10 or more and less than 60 (defective)
×: The number of foreign objects is 60 or more (extremely poor)

(Viscosity Evaluation)
The viscosity of the colored composition was measured at 25° C. on the day of preparation 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, △ is a level where the viscosity is high but does not cause problems in use, and × is a level where there are problems in use.
◎: Less than 10.0 [mPa·s]
○: 10.0 or more and less than 15.0 [mPa·s]
△: 15.0 or more and less than 20.0 [mPa·s]
×: 20.0 or more [mPa·s]

In Examples 1 to 22 of the present invention, the lightness, heat resistance, coating foreign matter, and viscosity were excellent. On the other hand, in Comparative Examples 1 and 2, which used a dye derivative having a base skeleton of a copper phthalocyanine structure having a basic substituent, and Comparative Examples 3 and 4, which are coloring compositions using a xanthene acid dye alone, the coating foreign matter and viscosity were poor.
In Examples 4 to 6, in which the resin (C) having a cationic group had a structural unit containing an oxetane group or a t-butyl group, the heat resistance was excellent.

<Production of photosensitive coloring composition for color filter>
[Example 101]
(Preparation of Photosensitive Coloring Composition (ER-1))
The following mixture was stirred and mixed to a uniform consistency, and then filtered through a 1.0 μm filter to prepare an alkali development type resist material R-1.
Colored composition (EP-1) 60.0 parts Binder resin solution 11.0 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.)
4.2 parts photopolymerization initiator (BASF Japan "Irgacure OXE01")
1.2 parts cyclohexanone 5.2 parts propylene glycol monomethyl ether acetate (PGMAC)
18.0 parts
However, Example 101 is a reference example.

[Examples 101 to 122, Comparative Examples 101 to 104]
The coloring compositions were prepared in the same manner as in Example 101 to prepare alkali-developable photosensitive coloring compositions (ER-2 to ER-26).
However, Examples 107 and 114 to 122 are reference examples.

<Evaluation of Photosensitive Coloring Composition>
The lightness, heat resistance, foreign matter in the coating film, solvent resistance, viscosity, and storage stability of the photosensitive coloring compositions of Examples 101 to 122 and Comparative Examples 101 to 104 were evaluated by the following methods. The results are shown in Table 6.

(Lightness Evaluation)
The photosensitive coloring compositions (ER-1 to 26) were applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate with a spin coater so that y = 0.100, then dried at 60°C for 5 minutes, and then heated at 230°C for 20 minutes and allowed to cool to produce a coated substrate. The lightness (spectral transmittance) was measured using the obtained coated substrate. The lightness (spectral transmittance) in the XYZ color system chromaticity diagram was measured using a spectrophotometer (OTSUKALCF-1100M). The evaluation criteria are as follows. × is a level that is difficult to use.
◎: 11.5 or more ○: 10.8 or more and less than 11.5 △: 10.0 or more and less than 10.8 ×: Less than 10.0

(Heat resistance evaluation)
The photosensitive coloring composition (ER-1 to 26) was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater, baked in an oven at 230 ° C for 30 minutes, and the film thickness of the coating film after heat treatment was measured using a surface profiler "Dektak8 (Veeco)". Three coated substrates were prepared so that the film thickness was about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film under C light source was measured using a microspectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"). After that, the heat resistance test was performed by heating at 230 ° C for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) under C light source was measured, and the color difference ΔEab * was calculated using the following calculation formula and evaluated according to the following criteria. Here, ⊚ indicates a very good level, ◯ indicates a good level, Δ indicates a practically usable level, and × indicates a level not suitable 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. ○: ΔEab* is 1.0 or more and less than 1.5. △: ΔEab* is 1.5 or more and less than 3.0. ×: ΔEab* is 3.0 or more.

(Foreign matter evaluation)
The photosensitive coloring compositions (ER-1 to 26) were spin-coated on a glass substrate using a spin coater so that the dry film thickness was 1.2 μm, and the substrate was pre-baked at 120° C. for 120 seconds to prepare a test sample substrate. The surface was observed using a metal microscope (BX60) manufactured by Olympus Systems Co., Ltd. The magnification was 500 times, and the number of particles observable in any five visual fields in transmission was counted. ◎ is a very good level, ○ is a good level, △ is a practical level, and × is a level not suitable for practical use.


◎: Less than 20 foreign objects. ◯: 20 or more but less than 50 foreign objects. △: 50 or more but less than 100 foreign objects. ×: 100 or more foreign objects.

(Evaluation of Viscosity of Colored Composition)
The viscosity of the photosensitive coloring compositions (ER-1 to 26) was measured using an E-type viscometer. Evaluation was performed according to the following criteria. In addition, ◎ is a very good level, ○ is a good level, △ is a practical level, and × is a level not suitable for practical use.

◎: Viscosity less than 5.0 ○: Viscosity 5.0 or more and less than 10.0 △: Viscosity 10.0 or more and less than 20.0 ×: Viscosity 20.0 or more

(Evaluation of storage stability)
From the initial viscosity on the day of preparation of the photosensitive coloring compositions (ER-1 to 26) and the viscosity measured after storage for 7 days in a thermostatic chamber at 40°C, the viscosity change rate (%) = (viscosity after storage for 7 days at 40°C - initial viscosity) / initial viscosity x 100) was calculated, and the storage stability was evaluated according to the following criteria: ◎ is a very good level, ○ is a good level, △ is a practical level, and × is a level not suitable for practical use.
Both the initial viscosity and the viscosity after storage were measured using an E-type viscometer (ELD type viscometer manufactured by Toki Sangyo Co., Ltd.) at a temperature of 25° C. and a rotation speed of 50 rpm.

◎: Viscosity change rate is less than 5%. ◯: Viscosity change rate is 5% or more but less than 10%.
△: Viscosity change rate is 10% or more but less than 15% ×: Viscosity change rate is 15% or more

The photosensitive coloring composition also gave results similar to those of the coloring compositions shown in Examples 1 to 22 and Comparative Examples 1 to 4.

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

Claims (4)

A coloring composition for color filters containing at least a colorant (A), a binder resin, and an organic solvent, wherein the colorant (A) contains a copper phthalocyanine pigment, a dye derivative (B) having a copper phthalocyanine structure having an acidic substituent as a parent skeleton, and a salt-forming compound (E) of a xanthene acid dye and a resin (C) having a cationic group in a side chain ;
A coloring composition for color filters, characterized in that a resin (C) having a cationic group in a side chain has a structural unit containing at least one type of thermally crosslinkable group selected from the group consisting of a hydroxy group, a carboxy group, an oxetane group, and a t-butyl group. 2. The coloring composition for color filters according to claim 1 , wherein the content of the dye derivative (B) is 5 to 45% by mass relative to 100% by mass of the salt-forming compound (E). The coloring composition for color filters according to claim 1 or 2, further comprising a photopolymerizable monomer and/or a photopolymerization initiator. A color filter formed from the coloring composition for color filters according to any one of claims 1 to 3 .