JP5853731B2 - Coloring composition for color filter, and color filter - Google Patents

Description

  The present invention relates to a colored composition for a color filter used for manufacturing a color filter used for a color liquid crystal display device, a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. is there.

  In recent years, liquid crystal display devices have been evaluated for space saving, light weight, power saving, and the like due to their thinness, and recently they have been rapidly spread to television applications. For television applications, it is required to further improve the performance such as brightness and contrast, and further improvement of the transmittance and enhancement of the contrast are desired for the color filter which is a member of the color liquid crystal display device. ing.

  As a method for producing the color filter, after forming a pattern with a photoresist, a dyeing method for dyeing the pattern, or by forming a transparent electrode of a predetermined pattern in advance, and using a pigment-containing resin dissolved and dispersed in a solvent by voltage application Electrodeposition method for ionization and pattern formation, printing method such as offset printing using ink containing thermosetting resin or ultraviolet curable resin, pigment dispersion using color resist agent in which colorant such as pigment is dispersed in photoresist material Recently, the pigment dispersion method has become mainstream. However, a color filter using a pigment as a colorant disturbs the degree of polarization controlled by the liquid crystal due to light scattering by the pigment particles, resulting in a decrease in brightness and contrast of the color liquid crystal display device. There is a problem that it is easy.

  As a technique for solving this problem, the practical application of a dye-based curable composition using a dye that can exist in a dissolved state in a medium of the curable composition as a colorant has been studied and proposed (for example, patents). Reference 1). However, a color filter using a dye as a colorant has the following problems. That is, the dye used for the color resist material is required to have heat resistance, light resistance, and solubility in the resin and the organic solvent used for the resin.

Therefore, in order to increase solubility and improve heat resistance and light resistance, color filters using a salt of an anionic dye and a cationic surfactant as a colorant have been proposed (for example, Patent Documents 2 and 3). reference). In general, sodium sulfonate groups (—SO _{3) of} anionic dyes
It is known that the solubility of anionic dyes in organic solvents can be increased by changing Na) to organic amine salts. In the above colorants, by changing the sodium sulfonate group of the anionic dye to the base salt of the cationic surfactant, the solubility of the anionic dye in the organic solvent is increased and the molecular weight is increased to increase the heat resistance. , Improve light resistance. However, in these methods, sufficient solubility with respect to the solvent used at the time of color filter production cannot be obtained, and the compatibility with the resin is poor, so the long-term storage stability of the color filter coloring composition, It has been difficult to provide strong adhesion between the coating film and a transparent substrate such as glass.

  Further, as salt forming compounds of anionic dyes, those using a cationic resin as a counter have been studied as crystalline aqueous coloring materials (see, for example, Patent Document 4). In color filter applications that require use in a dissolved state, detailed studies have not been made.

On the other hand, a colored resin composition in which an anionic dye is added to a copolymer solution obtained by copolymerizing a monomer having an amide structure has also been proposed (see, for example, Patent Document 5). This is an amide structure

Acts as a dyeing point with an anionic dye, thereby stabilizing the dye in the coating film and improving the resistance. However, the method disclosed here has a problem in that since a copolymer and an anionic dye are mixed in an organic solvent, a highly polar dye is not sufficiently dissolved and foreign matter is generated.

  Further, it has been proposed to form a color filter with little development residue by using a photosensitive composition using a copolymer containing a specific acrylic component as a resin component. (For example, refer to Patent Documents 6 and 7, etc.) However, these methods are not sufficient at present.

JP-A-6-75375 JP-A-5-333207 JP 2004-307391 A JP-A-2005-350648 JP 2000-352819 A JP 2007-114604 A JP 2000-81508 A

  The object of the present invention is to provide a photosensitive coloring composition for a color filter that has excellent storage stability and no development residue, and no foreign matter is generated on the coating film, and is strong with a transparent substrate such as glass. It is to provide a color filter having adhesiveness.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a salt-forming compound obtained by reacting a copolymer having a specific structure with an anionic dye, and this copolymer. The photosensitive coloring composition for color filters containing a resin having the same structural unit as the above has excellent color characteristics, high storage stability, no development residue, and no foreign matter on the coating film It has been found that the adhesiveness is excellent, and the present invention has been made based on this finding.

That is, the present invention is a color filter coloring composition comprising a colorant (A), a resin (B), and an organic solvent (E),
A salt-formation in which the colorant (A) is formed from a copolymer containing the structural unit (a1) represented by the general formula (1) and the structural unit (a2) having a cationic group in the side chain and an anionic dye Containing compound (A1),
The resin (B) relates to a coloring composition for a color filter, wherein the resin (B) includes a structural unit (b1) represented by the general formula (4).
General formula (1)

[In General Formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ]
General formula (4)

[In the general formula (4), R ₅₁ are the same atom or group as R ₁ in the general formula (1), R ₅₂
Is the same atom or group as R ₂ in the general formula (1). ]
The present invention also relates to the photosensitive coloring composition for a color filter, wherein the structural unit (a2) having a cationic group in the side chain is a structural unit represented by the general formula (3).
General formula (2)

[In General Formula (2), R ₃ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{4 to} R ₆ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{4 to} R ₆ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₇ —, —COO—R ₇ —, and R ₇ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

Moreover, this invention relates to the coloring composition for color filters of Claim 1 or 2 whose weight average molecular weights of resin (B) are 5,000-25,000.
The present invention also relates to the color filter coloring composition, wherein the acid value of the resin (B) is 40 to 150 (KOH-mg / g).
In addition, the present invention relates to the coloring composition for a color filter, further comprising an antioxidant (F).
The present invention also relates to the color filter coloring composition, wherein the colorant (A) further contains a pigment.
The present invention also relates to the color composition for color filters, wherein the pigment is a blue pigment.
Further, the present invention relates to the color composition for color filters, further comprising a photopolymerizable monomer (C) and a photopolymerization initiator (D).
The present invention also relates to the coloring composition for a color filter, wherein the organic solvent (E) contains propylene glycol monomethyl ether acetate as a main component.
The present invention also relates to a color filter comprising a filter segment formed of the color filter coloring composition on a transparent substrate.

  In the present invention, a colored composition for a color filter comprising a salt-forming compound obtained by reacting a copolymer having a specific structural unit with an anionic dye, and a resin having the same structural unit as the copolymer. By using the color filter, it is possible to obtain a color filter having high storage stability, no development residue, no foreign matter when forming a coating film, and excellent adhesion.

Hereinafter, the present invention will be described in detail.
The color filter coloring composition of the present invention comprises a colorant (A) containing a salt-forming compound (A1) obtained by reacting a copolymer having a specific structure with an anionic dye, and a salt-forming compound ( A coloring composition for a color filter comprising a resin (B) containing the same structural unit (b1) as the structural unit (a1) constituting A1) and a colorant carrier containing an organic solvent (E).

<Colorant (A)>
The colorant (A) used in the photosensitive coloring composition for a color filter of the present invention contains a salt-forming compound (A1) formed from a copolymer and an anionic dye. Moreover, a pigment can also be used together for a coloring agent (A).

[Salt-forming compound (A1)]
(Copolymer)
The copolymer includes the structural unit (a1) represented by the general formula (1) and the structural unit (a2) having a cationic group in the side chain.

Especially, it is preferable that the copolymer of this invention is acrylic resin containing the structural unit represented by following General formula (1) and General formula (2).
General formula (1)

General formula (2)

In general formula (1) and general formula (2), R < ₁ > and R < ₃ > represent a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group for R ₁ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As this alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ₁ and R ₃ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

In General Formula (1) and General Formula (2), R ₂ and R _{4 to} R ₆ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or The aryl group which may be substituted is mentioned.

Here, examples of the alkyl group in R ₂ and R _{4 to} R ₆ include a linear alkyl group (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 and 1,1, 3,3-tetramethylbutyl, etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl, pinanyl, etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

Examples of the alkenyl group in R ₂ and R _{4 to} R ₆ 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, 2-methyl-2-propenyl, etc.), cycloalkenyl groups (2-cyclohexenyl, 3-cyclohexenyl, etc.) Can be mentioned. As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

Examples of the aryl group in R ₂ and R _{4 to} R ₆ include a monocyclic aryl group (such as phenyl), a condensed polycyclic aryl group (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and an aromatic complex. Ring hydrocarbon group (thienyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (Groups derived from xanthone) and 9-oxothioxanthenyl (groups derived from thioxanthone)).

When the alkyl group, alkenyl group, or aryl group represented by R ₂ and R _{4 to} R ₆ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, Examples include a substituent selected from an acyl group, an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

R ₂ and R _{4 to} R ₆ are preferably an alkyl group which may be substituted from the viewpoint of stability, and more preferably an unsubstituted alkyl group.

Two of R _{4 to} R ₆ may be bonded to each other to form a ring.

  Below, the ethylenically unsaturated monomer which can be used in order to obtain the acrylic resin containing the structural unit represented by the general formula (1) and the cationic group, particularly the general formula (2), which is a preferred embodiment of the present invention. The example of a body is shown. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

  Examples of the ethylenically unsaturated monomer that can be used to form the structural unit represented by the general formula (1) include (meth) acrylic acid esters.

Specific examples of such an ethylenically unsaturated monomer include the following compounds.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

  The ethylenically unsaturated monomer that can be used in the structural unit represented by the general formula (1) may be used alone or in combination of two or more.

  The salt-forming compound (A1) forms a salt by an ionic bond between an anionic dye and a copolymer. Therefore, a copolymer contains the structural unit (a2) which has a cationic group in a side chain. The structural unit (a2) having a cationic group in the side chain is not particularly limited as long as it has at least one onium base in the side chain, but as a suitable onium salt structure, viewpoints such as availability Is preferably an ammonium salt, an iodonium salt, a sulfonium salt, a diazonium salt, and a phosphonium salt, and in view of storage stability (thermal stability), it is more preferably an ammonium salt, an iodonium salt, or a sulfonium salt. preferable. More preferred is an ammonium salt.

The structural unit (a2) having a cationic group in the side chain is preferably a structural unit represented by the general formula (2).
General formula (2)

In the general formula (2), in the structural unit, R ₃ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{4 to} R ₆ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{4 to} R ₆ Two of them may be bonded to each other to form a ring.

Q components is an alkylene group linking ammonium salt, an arylene _{group, -CONH-R 7 -, -} COO-R 7 - represents, but R ₇ is an alkylene group, among them, the polymerizable, for reasons of availability , —CONH—R ₇ —, —COO—R ₇ — are preferable. R ₇ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

The component Y ⁻ in the general formula (2) constituting the counter anion of the copolymer may be an inorganic or organic anion. As the counter anion, known ones can be used without limitation. Specifically, 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 even hexacyanoferrate (III) ions And complex ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

  The introduction of the structural unit (a2) having a cationic group in the side chain into the copolymer is not only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component, but also an amino acid. After obtaining an acrylic resin having an amino group obtained by copolymerizing an ethylenically unsaturated monomer having a group as a monomer component, it may be obtained by a method of reacting with an onium chlorinating agent and ammonium chloride.

  When copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component, examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, ( Alkyl (meth) acrylate quaternary ammonium salts such as (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxyethylmethylmorpholinoammonium chloride, (meth) acryloylaminopropyl Trimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammoni Alkyl (meth) acryloyl amide quaternary ammonium salts such as Mukuroraido, dimethyl diallyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  When an acrylic resin having an amino group is obtained and then reacted with an onium chlorinating agent to be ammonium chloride, examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl ( (Meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylaminoethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylamino Propyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropylaminopropyl (meth) acrylamide, dibutylaminopro (Meth) acrylic acid ester or (meth) acrylamide having a dialkylamino group such as ru (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butylaminopropyl (meth) acrylamide, and the like, dimethylaminostyrene, Styrenes having a dialkylamino group such as dimethylaminomethylstyrene, diallylamine compounds such as diallylmethylamine and diallylamine, and amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole Is mentioned.

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

  The reaction between the amino group and the onium chlorinating agent can usually be carried out by dropping an equimolar or less onium chlorinating agent with respect to the amino group into the polymer solution having the amino group. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

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

General formula (3)

Z-R ₈ -COOR ₉

In general formula (3), Z is a halogen such as chlorine or bromine, preferably bromine, and R ₈ is an alkylene group having 1 to 6 carbon atoms, preferably 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. And R ₉ is a lower alkyl group having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms.

The reaction between an amino group and an alkoxycarbonylalkyl halide is carried out by reacting an alkoxycarbonylalkyl halide with an equimolar amount or less with respect to the amino group in the same manner as the above onium chlorinating agent, then hydrolyzing -COOR ₉ to produce a carboxylate ion (- It is obtained by converting to COO ⁻ ). Thereby, a polymer having a carboxybetaine structure represented by the general formula (3) and having an ammonium base can be obtained.

  In addition, it can be used in combination with the ethylenically unsaturated monomer forming the structural unit (a1) represented by the general formula (1) and the structural unit (a2) having a cationic group in the side chain. Other ethylenically unsaturated monomers include crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, vinyl alcohol esters, (meth) acrylamides, vinyl ethers, Examples include vinyl alcohol esters, styrenes, (meth) acrylonitrile, and the like. Moreover, the copolymer unit derived from the monomer which has an acid group may be included.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

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

  Examples of itaconic acid 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, Nn -Butyl acryl (meth) amide, Nt-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, diacetone acrylamide and the like.

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

  Examples of the monomer having an acid group include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or anhydrides thereof; trivalent Unsaturated polyvalent carboxylic acids or anhydrides thereof; succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono (2-methacryloyloxyethyl) phthalate; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone Examples include mono (meth) acrylates of both terminal carboxy polymers such as monomethacrylate.

  In the present invention, a copolymer comprising the structural unit (a1) represented by the general formula (1) and the structural unit (a2) having a cationic group in the side chain, particularly a structural unit represented by the general formula (2) Known methods such as anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the following references 1 to 8 and the like.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference Document 7) JP-A-9-208616 (Reference Document 8) JP-A-8-41117 It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

  The amount of ammonium base present in the copolymer containing the structural unit (a1) represented by the general formula (1) and the structural unit (a2) having a cationic group in the side chain is particularly limited. However, the ammonium salt value is preferably 10 to 200 KOH-mg / g, more preferably 20 to 130 KOH-mg / g.

  The molecular weight of the copolymer used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 1,000 to 500,000. 3,000 to 15,000 is more preferable.

  Moreover, it is preferable that the copolymer used for this invention has the characteristic melt | dissolved in the solvent widely used for the photosensitive coloring composition for color filters. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

  In the copolymer, the total content of the structural unit (a2) having a cationic group in the side chain is not particularly limited. However, when the total structural unit contained in the copolymer is 100% by weight, the total content is not limited. From the viewpoint of solvent solubility and coloring power of the salt compound, the total content of structural units having a cationic group in the side chain is preferably 5% by weight or more, more preferably 10 to 50% by weight. .

(Anionic dye)
Any anionic dye may be used as long as it is a colored compound ionically bonded to the above-described copolymer. Such a coloring compound is not particularly limited as long as it has a carboxylic acid group, a sulfonic acid group, a phenolic hydroxyl group, a phosphoric acid group, or a metal salt thereof in the molecule, and an organic solvent or developer. Can be appropriately selected in consideration of all the required performance such as solubility in water, salt-forming property, absorbance, interaction with other components in the composition, light resistance, heat resistance and the like.

  Examples of the anionic dye include anthraquinone anionic dye, monoazo anionic dye, disazo anionic dye, oxazine anionic dye, aminoketone anionic dye, xanthene anionic dye, quinoline anionic dye, Examples include triphenylmethane anionic dyes. Moreover, as an aspect of an anionic dye, it is preferable to use an acid dye and a direct dye. Below, the specific example of the anionic dye which can be used for the synthesis | combination of a salt-forming compound is shown with a color index number.

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

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

Examples of yellow dyes include C.I. I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9

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

  In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134, etc. can also be used.

  Examples of orange dyes include C.I. I. Acid Orange 1, 1: 1, 4, 5, 6, 7, 8, 9, 10, 12, 14, 16, 17, 18, 19, 20, 20: 1, 22, 23, 24, 24: 1 25, 27, 28, 28: 1, 30, 31, 33, 35, 36, 37, 38, 41, 45, 49, 50, 51, 54, 55, 56, 59, 79, 83, 94, 95, 102, 106, 116, 117, 119, 128, 131, 132, 134, 136, 138 and the like.

  In addition, C.I. I. Direct Orange 1, 2, 3, 4, 5, 6, 7, 8, 10, 13, 17, 19, 20, 21, 24, 25, 26, 29, 29: 1, 30, 31, 32, 33, 43, 49, 51, 56, 59, 69, 72, 73, 74, 75, 76, 79, 80, 83, 84, 85, 87, 88, 90, 91, 92, 95, 96, 97, 98, 101, 102, 102: 1, 104, 108, 112, 114, etc. can also be used.

  Examples of blue dyes include C.I. I. Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41: 1, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 62, 62: 1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 84, 85, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147 150,155,159,169,174,175,176,183,198,203,204,205,206,208,213,227,230,231,232,233,235,239,245,247,253 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280 and the like.

  In addition, C.I. I. Direct Blue 1, 2, 3, 4, 6, 7, 8, 8: 1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21: 1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98: 1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129, 130, 130: 1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158: 1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 2 13,215,225,226,229,230,231,242,243,244,253,254,260,263, etc. can also be used.

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

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

  Examples of the green dye include C.I. I. Acid Green 2, 3, 5, 6, 7, 8, 9, 10, 11, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 25: 1, 27, 34, 36, 37, 38, 40, 41, 42, 44, 54, 55, 59, 66, 69, 70, 71, 81, 84, 94, 95 and the like.

  In addition, C.I. I. Direct green 11, 13, 14, 24, 30, 34, 38, 42, 49, 55, 56, 57, 60, 78, 79, 80, etc. can also be used.

(Salt formation)
The salt-forming compound (A1) used in the present invention is prepared by stirring or vibrating an aqueous solution in which a copolymer and an anionic dye are dissolved, or stirring or vibrating an aqueous solution of a copolymer and an aqueous solution of an anionic dye. It can be easily obtained by mixing under. In the aqueous solution, the cationic group in the copolymer and the anionic group of the anionic dye are ionized, these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, since the salt composed of the counter anion of the copolymer and the counter cation of the anionic dye is water-soluble, it can be removed by washing or the like. As the copolymer and the anionic dye used, only a single type or a plurality of types having different structures may be used.

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

  The content of the pigment component derived from the anionic dye in the salt-forming compound (A1) can be adjusted to a range of 10 to 60% by weight, especially 15 to 15%, based on the salt-forming compound (A1) (100% by weight). A range of 55% by weight is preferred. By controlling in this range, a salt-forming compound (A1) excellent in solvent solubility can be obtained.

  The weight percentage of the effective pigment component (excluding counter ions such as alkali metal ions) in the anionic dye contained in the salt-forming compound (A1) is the same as the salt-forming compound (A1) solution and the anion adjusted to the same concentration. It can be calculated by measuring the spectral spectrum of the neutral dye solution and determining the spectral intensity ratio of the maximum absorption wavelength.

For example, a salt forming compound (A1) solution and an anionic dye solution are prepared using a solvent (such as N-methyl-2-pyrrolidone) that can dissolve both the salt forming compound (A1) and the anionic dye well. The absorbances at the maximum absorption wavelengths of the salt-forming compound (A1) solution and the anionic dye solution prepared at a constant concentration and obtained by absorbance measurement are Xa and Xb, respectively. Many anionic dyes contain a counter ion such as an alkali metal ion. In that case, the number of counter ions present in one molecule is Na, the atomic weight of the counter ion is Ma, and the molecular weight of the xanthene acid dye Is Mb, the weight% of the effective pigment component in the anionic dye is given by the following formula.
(1-Ma × Na / Mb) × 100 [wt%]
And using this formula, the weight% of the effective pigment component in the anionic dye contained in the salt-forming compound (A1) can be calculated from the following formula.
(Xa / Xb) × (1-Ma × Na / Mb) × 100 [wt%]

[Pigment]
In addition to the salt-forming compound (A1), the colorant (A) used in the photosensitive coloring composition for a color filter of the present invention is preferably added with a pigment and used in combination.
As the pigment, organic or inorganic pigments can be used alone or in admixture of two or more. The pigment is preferably a pigment having a high color developability and a high heat resistance, particularly a pigment having a high heat decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for a coloring agent (A) is shown by a color index number.

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

  Examples of the green pigment for forming the green filter segment include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, 37, 58 can be used. In addition to these green pigments, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 , 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination.

  Examples of the blue pigment for forming the blue filter segment include C.I. I. Pigment Blue 1, 1: 2, 1: 3, 2, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 18, 19, 22, 24, 24: 1, 53, 56, 56: 1, 57, 58, 59, 60, 61, 62, 64, etc. Can be used. In addition to these blue pigments, C.I. I. Purple violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination.

  Examples of cyan pigments for forming a cyan filter segment include C.I. I. Blue pigments for cyan such as CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, and 81 can be used alone or in combination.

  Examples of the magenta pigment for forming the magenta color filter segment include C.I. I. Pigment violet 1, 19, C.I. I. Purple pigments such as CI Pigment Red 144, 146, 177, 169, 81, and red pigments can be used alone or in combination. As these magenta pigments, yellow pigments can be used in combination with the magenta red and purple pigments.

  In addition, inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, chromium oxide green, cobalt green, amber And synthetic iron black. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.

  The use ratio of the pigment and the salt-forming compound (A) is preferably 1 to 800 parts by weight of the salt-forming compound (A) with respect to 100 parts by weight of the pigment. More preferably, it is 5 to 400 parts by weight. If the addition amount of the salt-forming compound (A) is less than 1 part by weight, the reproducible chromaticity region becomes narrow, and if it exceeds 800 parts by weight, the hue changes, which is not preferable.

  When converted in consideration of the color composition, the blending ratio of the pigment and the content of the effective pigment component in the anionic dye in the salt-forming compound (A) is 100 parts by weight of the pigment and the effective pigment in the dye. The component is preferably 1 to 400 parts by weight. More preferably, the effective pigment component in the dye is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the pigment.

(Miniaturization of pigment)
The pigment added to the colorant (A) used in the present invention is preferably refined by a salt milling process or the like in order to correspond to high transmittance and high contrast. The primary particle diameter of the pigment is preferably 10 nm or more because of good dispersion in the colorant carrier. Moreover, since a filter segment with high contrast can be formed, it is preferable that it is 80 nm or less. A 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 heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

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

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

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

<Resin (B)>
As a structural unit constituting the resin (B), a photosensitive coloring composition for a color filter containing the salt-forming compound (A1) of the present invention is prepared and the characteristics as a color filter having no development residue are expressed. It is necessary to have the same structural unit (b1) as the structural unit (a1) contained in the copolymer constituting the salt-forming compound (A1). That is, the resin (B) is R ₅₁ which is the same atom or group as R ₁ in the structural unit (a1) of the copolymer constituting the salt-forming compound (A1), and R which is the same atom or group as R _{2. When the} structural unit (b1) represented by the general formula (4) having ₅₂ is included, the intermolecular interaction is increased, and the salt-forming compound (A1) is formed during development of the photosensitive coloring composition for a color filter. A photosensitive coloring composition for a color filter that is easily developed with the resin (B) and has no development residue can be obtained. Further, the copolymer must contain a structure having a cationic group in the side chain as a reactive site with the anionic dye, preferably a structure represented by the general formula (2). The role of B) is to disperse the colorant (A), particularly the salt-forming compound and the pigment, or to dye and penetrate the salt-forming compound.

  The resin (B) is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using the photosensitive resin composition of this invention with the form of an alkali image development type | mold coloring resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  In addition to the structural unit represented by the general formula (4), the energy ray curable resin having an ethylenically unsaturated active double bond is a highly functional group having a reactive substituent such as a hydroxyl group, a carboxyl group, and an amino group. By reacting a molecule with a (meth) acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group or an epoxy group or cinnamic acid, a photocrosslinkable group such as a (meth) acryloyl group or a styryl group is added to the polymer. The introduced resin is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  Further, the resin (B) is not only used as a binder resin, but when the colorant (A) further contains a pigment, it may be used in the form of a resin-type dispersant when the pigment is dispersed. Well, the final colored composition for a color filter comprises a copolymer composed of a structural unit (a1) represented by the general formula (1) and a structural unit (a2) having a cationic group in the side chain, an anionic dye, The salt-forming compound (A1) formed from the above and the resin (B) containing the structural unit (b1) represented by the general formula (4) may be included.

  At this time, the resin used as the binder resin may be a conventionally used thermoplastic resin or thermosetting resin.

That is, the resin (B) of the present invention comprises R ₅₁ and R ₂ which are the same atoms or groups as R ₁ in the structural unit (a1) represented by the general formula (1) constituting the salt-forming compound (A1). It includes a structural unit (b1) represented by the general formula (4) having R ₅₂ which is the same atom or group. Here, having R ₅₁ which is the same atom or group as R ₁ and R ₅₂ being the same atom or group as R ₂ means that, for example, when R ₁ is a hydrogen atom and R ₂ is a methyl group, It means that R ₅₁ is a hydrogen atom and R ₅₂ is a methyl group.

As long as at least one type of the same structural unit is the same structural unit, two or more types may have the same structural unit.
General formula (4)

[In General Formula (4), R ₅₁ is the same atom or group as R ₁ in General Formula (1), and R ₅₂ is the same atom or group as R ₂ in General Formula (1). ]
Therefore, in the general formula (4), R ₅₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group as in R ₁ . R ₅₂ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, as in R ₂ .

  Examples of the ethylenically unsaturated monomer that can be used to form the structural unit represented by the general formula (4) include the same as the structural unit represented by the general formula (1), for example, (meth) acrylic Acid esters are preferred.

  Specific examples of such an ethylenically unsaturated monomer include the following compounds.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

  Other ethylenically unsaturated monomers that can be used in combination with the ethylenically unsaturated monomer that forms the structural unit (b1) represented by the general formula (4) of the present invention include crotonic acid. Esters, vinyl esters, maleic diesters, fumaric diesters, itaconic diesters, vinyl alcohol esters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile Etc. Moreover, the copolymer unit derived from the monomer which has an acid group may be included.

  Examples of the monomer having an acid group include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid.

  Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.

  Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

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

  Examples of itaconic acid 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, Nn -Butyl acryl (meth) amide, Nt-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, diacetone acrylamide and the like.

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

Examples of the monomer having an acid group include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid and other unsaturated dicarboxylic acids or anhydrides thereof; trivalent Unsaturated polyvalent carboxylic acids or anhydrides thereof; succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as mono (2-methacryloyloxyethyl) phthalate; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone Mono (meth) acrylate of carboxy polymer at both ends such as monomethacrylate

Examples include related substances.

  Examples of the method for obtaining the resin (B) containing the structural unit represented by the general formula (4) suitable for the present invention include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. A known method can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

  Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the above-mentioned References 1 to 8 as in the copolymer synthesis method.

  It is preferable to use an organic solvent during the polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

  When used as a binder resin, the resin (B) is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the colorant (A) because the film-forming property and various resistances are good. Is preferably used in an amount of 500 parts by weight or less because it is high and can exhibit good color characteristics.

  Further, the blending amount when used as a resin-type dispersant when dispersing the pigment is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant (A). Part. When the blending amount of the resin (B) is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the occurrence of development residue can be suppressed, but an excess resin ( The presence of B) can adversely affect the dispersion.

  The acid value of the resin (B) containing the structural unit (b1) represented by the general formula (4) suitable for the present invention is preferably 40 to 200 (KOH-mg / g), more preferably 40 to 150 (KOH-mg / g), more preferably 60 to 150 (KOH-mg / g). When the acid value is less than 40 (KOH-mg / g), development is slow and development residues are likely to occur. Moreover, when an acid value becomes larger than 200 (KOH-mg / g), image development will be too quick and adhesiveness with a base material will worsen.

  The molecular weight of the resin (B) in the present invention is preferably a converted weight average molecular weight measured by gel permeation chromatography (GPC) of 1,000 to 500,000, preferably 5,000 to 25,000. Is more preferable. It is preferable that the weight average molecular weight of the resin (B) is 1,000 to 500,000, because film loss is unlikely to occur during development, and the non-pixel portion is liable to be easily removed during development. Further, if the weight average molecular weight is less than 5,000, the adhesion may be deteriorated, and if it exceeds 25,000, a problem may occur in the development residue.

  Moreover, it is preferable that resin (B) containing the structural unit represented by suitable General formula (4) has a characteristic melt | dissolved in the solvent widely used for the coloring composition for color filters. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

  The content of the structural unit (b1) that is the same as the structural unit (a1) in the resin (B) is 100 parts by weight of the structural unit (a1) in the copolymer constituting the salt-forming compound (A). The amount is preferably 1 to 10,000 parts by weight, and more preferably 10 to 1000 parts by weight. When the amount is less than 1 part by weight, the contribution of the resin (B) is reduced, and a development residue tends to remain. When the amount is 10,000 parts by weight or more, the development residue disappears, but the development adhesion tends to deteriorate.

  Furthermore, the coloring composition for color filters of this invention adds a photopolymerizable monomer (C) and a photoinitiator (D), and uses it as a photosensitive coloring composition (resist material) for color filters. can do.

<Photopolymerizable monomer (C)>
The photopolymerizable monomer (C) includes a monomer or an oligomer that is cured by ultraviolet rays or heat to generate a transparent resin, and these can be used alone or in combination of two or more. The blending amount of the photopolymerizable monomer (C) is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant (A), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

<Photopolymerization initiator (D)>
The colored composition for a color filter of the present invention is a solvent development type or alkali development type by adding a photopolymerization initiator (D) when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method. It can be prepared in the form of a colored resist material. The blending amount when using the photopolymerization initiator (D) is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant (A). More preferred are parts by weight.

  As photopolymerization initiator (D), 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 Acetophenone compounds such as 1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether Benzoin compounds such as tereline or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 Benzophenone compounds such as', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4- Thioxanthone compounds such as diethyl thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, -(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) -6-triazine, or 2, Triazine compounds such as 4-trichloromethyl- (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzene) Nzoyloxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4 , 6-trimethylbenzoyl) phenylphosphine oxide or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; A compound; a carbazole compound; an imidazole compound; or a titanocene compound is used.

  These photopolymerization initiators (D) can be used alone or in combination of two or more at any ratio as required.

<Sensitizer>
Furthermore, the photosensitive coloring composition for a color filter of the present invention can contain a sensitizer.

  Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzo Phenone, 4,4'-diethylaminobenzophenone, etc. are mentioned.

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

  Two or more kinds of sensitizers may be used in any ratio as required. It is preferable that the compounding quantity at the time of using a sensitizer is 3-60 weight part with respect to 100 weight part of photoinitiators contained in a coloring composition, and 5 from a viewpoint of photocurability and developability. More preferably, it is -50 weight part.

<Organic solvent (E)>
In the photosensitive color composition for color filter of the present invention, the colorant (A) is sufficiently dispersed and penetrated in the colorant carrier, and the dry film thickness becomes 0.2 to 5 μm on a substrate such as a glass substrate. In order to make it easy to apply and form a filter segment, an organic solvent (E) can be included.

  Examples of the organic solvent (E) 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, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butyl Benzene, 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 Cole monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Ter, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol , Methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like because of good dispersion and dissolution of the colorant (A) It is preferable to use aromatic alcohols such as benzyl alcohol and ketones such as cyclohexanone.

  These organic solvents (E) can be used individually by 1 type or in mixture of 2 or more types. When using it as a 2 or more types of mixed solvent, it is preferable that said preferable organic solvent contains 65 to 95 weight% on the basis (100 weight%) of organic solvent (E) whole quantity.

  Among these, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of safety and health and low viscosity, and it is preferable that propylene glycol monomethyl ether acetate is a main component. In the present invention, the main component is a solvent having the largest percentage by weight in the total solvent.

  Moreover, since the organic solvent (E) can adjust a coloring composition to appropriate viscosity and can form the filter segment of the target uniform film thickness, it is 800-4000 weight part with respect to 100 weight part of coloring agents (A). It is preferable to use it in the quantity.

<Antioxidant (F)>
In order to increase the transmittance of the coating film, it is preferable that the photosensitive coloring composition for a color filter of this embodiment further contains an antioxidant (F).
The antioxidant (F) is oxidized by a heat treatment performed in the photocuring step and the annealing step of ITO (indium tin oxide) by the photopolymerization initiator and the thermosetting resin contained in the photosensitive coloring composition, As a result, yellowing can be prevented. Therefore, when the antioxidant (F) is contained in the coloring composition, the transmittance of the coating film can be increased.

  As the antioxidant (F), for example, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, or a sulfide-based antioxidant is preferably used, and the hindered phenol-based antioxidant is used. It is more preferable to use a hindered amine antioxidant or a phosphorus antioxidant. These may be used alone or in combination of two or more.

  Examples of the hindered phenol antioxidant include pentaerythritol-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(laurylthio) methyl]- o-cresol, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl), 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6- Dimethylbenzyl), and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine.

  Examples of the hindered amine antioxidant include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl). Sebacate, N, N′-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl) -4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2, 3,4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6 , 6-Tetramethyl-4- Peridyl) imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2 , 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl) Polycondensates with -4-hydroxy-2,2,6,6-tetramethylpiperidine, and N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2 , 2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine.

  Examples of the phosphorus-based antioxidant include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphine. Pin-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphine- 2-yl) oxy] ethyl] amine, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like.

  Examples of sulfide antioxidants include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl. ] -O-cresol and 2,4-bis [(laurylthio) methyl] -o-cresol.

  The antioxidant (F) is preferably used in an amount of 0.1 to 5% by weight in a total of 100% by weight of the solid content of the photosensitive coloring composition for color filter.

<Amine compound>
Moreover, the photosensitive coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

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

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

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

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

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

<Other additive components>
The photosensitive coloring composition for color filters of the present invention is used to stabilize the viscosity over time of the composition.

Storage stabilizers can be included for this purpose. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant (A).

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

<Method for producing colored composition for color filter>
The colored composition for a color filter of the present invention is prepared by stirring and dissolving the salt-forming compound (A1) in an organic solvent (E) (colorant solution), resin (B), photopolymerizable monomer (C), The photopolymerization initiator (D), if necessary, can be further mixed with an organic solvent (E), other additives, etc. to prepare a solvent development type or alkali development type coloring composition (resist material). .
Further, after the salt-forming compound (A1) is stirred and dissolved in the organic solvent (E) (colorant solution), the resin (B) is added and mixed, and then the photopolymerizable monomer (C) and photopolymerization start. The solvent development type or alkali development type coloring composition (resist material) can be obtained by mixing with the agent (D) and, if necessary, the organic solvent (E) and other additives. .

  Moreover, when using a pigment further as a coloring agent (A), the process which knead | mixes the mixture containing the component of at least resin (B) and a coloring agent (A) with a 2 roll mill etc. to make a sheet-like substance in multiple times. After being performed, the chips obtained by pulverization are dissolved in an organic solvent (E) with stirring and dispersed with a media dispersing machine such as a bead mill, or the above mixture is directly dispersed with a media dispersing machine such as a bead mill. It can prepare by mix | blending a photopolymerizable monomer (C), a photoinitiator (D), an organic solvent (E), etc. with the intermediate body (pigment dispersion) of a thing.

  The photosensitive coloring composition for a color filter can be prepared by mixing the salt-forming compound (A1) and the pigment and dispersing them together, and separately preparing the colorant solution and the pigment dispersion and using them. You can also.

  It is preferable that a coloring agent (A) is contained in the photosensitive coloring composition for color filters in the ratio of 0.5 to 10 weight%. Further, the colorant (A) is finally contained in the filter segment in a proportion of preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and the remainder is the resin (B) or photopolymerizable monomer. It consists essentially of a monomer (C), a photopolymerization initiator (D), and the like.

(Dispersing aid)
When dispersing the pigment further contained in the colorant (A) in the colorant carrier, in addition to using the resin (B) in the form of a resin-type dispersant, a pigment derivative, other resin-type dispersant, A dispersion aid such as a surfactant can be further used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the pigment carrier using the dispersion aid is used. If so, a color filter with high spectral transmittance can be obtained.

Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.
Of these, pigment derivatives are preferable, and the structure thereof is a compound represented by the following general formula (5). P-Ln Formula (5)
(However,
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group n: an integer of 1 to 4 is there)
Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigments; dioxazine pigments; perinone pigments; perylene pigments; thioindigo pigments; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

  Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and the like. What is currently used can be used, These can be used individually or in mixture of 2 or more types.

  The blending amount of the dye derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight or more with respect to 100 parts by weight of the pigment from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 40% by weight or less, and most preferably 35% by weight or less with respect to 100 parts by weight of the pigment.

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

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 75 4,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

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

  When a resin type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the pigment. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the blending amount is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The photosensitive coloring composition for color filter of the present invention is 5 μm or more coarse particles, preferably 1 μm or more coarse particles, more preferably 0.5 μm or more by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove coarse particles and mixed dust.
Thus, it is preferable that the photosensitive coloring composition for color filters does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

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

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

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the photosensitive coloring composition for a color filter prepared as a printing ink. Excellent mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

  When forming a filter segment by a photolithography method, the photosensitive coloring composition for a color filter prepared as the solvent developing type or alkali developing type coloring resist material is applied to a transparent substrate by spray coating, spin coating, slit coating, It applies so that a dry film thickness may be 0.2-5 micrometers by application | coating methods, such as a roll coat. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

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

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

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” means “parts by weight”.

  Further, the weight average molecular weight (Mw) of the resin was measured by using TSKgel column (manufactured by Tosoh Corp.) and GPC equipped with RI detector (manufactured by Tosoh Corp., HLC-8120GPC) using polystyrene as a developing solvent. It is a weight average molecular weight (Mw) in terms of conversion.

  The acid value of the resin is the acid value (KOH-mg / g) measured according to the potentiometric titration method of JIS K 0070.

  The weight average molecular weight (Mw) of the copolymer was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The ammonium salt value is a value converted to the equivalent of potassium hydroxide after titration with a 0.1N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as an indicator. Show.

  The specific surface area of the pigment particles was determined by the BET method using nitrogen adsorption. For the measurement, an automatic vapor adsorption amount measuring device (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) was used.

  The average primary particle diameter of the pigment is determined by measuring the primary particle diameter of all pigment particles in the observation sample at 50,000 times using a transmission electron microscope (“JEM-1200EX” manufactured by JEOL Ltd.), and calculating the average value. Using. In addition, when the particle shape was not spherical, the major axis and the minor axis were measured, and the value obtained by (major axis + minor axis) / 2 was defined as the particle diameter.

  First, the production method of the resin (B), copolymer, salt-forming compound, fine pigment, pigment dispersion, and colorant solution used in Examples and Comparative Examples will be described.

<Method for Producing Resin (B) Solution>
(Resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of dicyclopentanyl methacrylate, 10.0 parts of methyl methacrylate, 12.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. Aronix M110 ") 38.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 parts were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 30000 and an acid value of 78 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare Resin Solution 1.

(Resin solution 2)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 13.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 37.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 part was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 11300 and an acid value of 88 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare Resin Solution 2.

(Resin solution 3)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of ethyl methacrylate, 13.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 37.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 part was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 10900 and an acid value of 87 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare Resin Solution 3.

(Resin solution 4)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of benzyl methacrylate, 13.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 37.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 part was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 10400 and an acid value of 84 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare Resin Solution 4.

(Resin solution 5)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of cyclohexyl methacrylate, 13.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 37.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 part was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 11100 and an acid value of 86 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution 5.

(Resin solution 6)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of acrylate n-butyl, 10.0 parts of t-butyl methacrylate, 13.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd. Aronix M110 ") 37.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 parts were added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 10600 and an acid value of 88 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution 6.

(Resin solution 7)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 13.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 37.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.8 part was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 5200 and an acid value of 82 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare Resin Solution 7.

(Resin solution 8)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 13.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 37.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.2 part was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 25300 and an acid value of 83 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution 8.

(Resin solution 9)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 5.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 45.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 parts was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 11100 and an acid value of 34 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Acetate was added to prepare a resin solution 9.

(Resin solution 10)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 7.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 43.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 part was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 10800 and an acid value of 44 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution 10.

(Resin solution 11)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 22.5 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 27.5 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 part was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 10700 and an acid value of 145 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution 11.

(Resin solution 12)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 25.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 25.0 parts and a mixture of 2,2'-azobisisobutyronitrile 0.4 parts was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 11300 and an acid value of 161 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution 12.

(Resin solution 13)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 13.0 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 37.0 parts and a mixture of 0.9 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 3300 and an acid value of 83 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution 13.

(Resin solution 14)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 25 parts of n-butyl acrylate, 10.0 parts of methyl methacrylate, 14.8 parts of methacrylic acid, 15.0 parts of 2-hydroxyethyl methacrylate, paracumylphenol ethylene oxide modified acrylate (“Aronix” manufactured by Toagosei Co., Ltd.) M110 ") 35.2 parts and a mixture of 2,2'-azobisisobutyronitrile 0.2 part was added dropwise over 2 hours. After completion of the dropping, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 26800 and an acid value of 87 KOH-mg / g. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution 14.

(Resin solution 15)
10. A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a stirring device, 60 parts of ethyl methacrylate, 40 parts of n-butyl acrylate, 90.0 parts of methyl methacrylate, 10. 0 parts were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 30 parts of pyromellitic anhydride, 242 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and an acrylic resin solution having a weight average molecular weight (Mw) of 10,000 and an acid value of 74 KOH-mg / g was obtained. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution 15.

(Resin solution 16)
Reaction vessel equipped with a separable four-necked flask equipped with a thermometer, cooling tube, nitrogen gas introduction tube, stirring device, 48 parts of n-butyl acrylate, 30.0 parts of methyl methacrylate, 10.0 parts of methacrylic acid, dimethacrylate 112.0 parts of cyclopentanyl was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 12 parts of 3-mercapto-1,2-propanediol was added. Reacted for hours. It was confirmed that 95% had reacted by solid content measurement. 30 parts of pyromellitic anhydride, 242 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added and reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and an acrylic resin solution having a weight average molecular weight (Mw) of 10,000 and an acid value of 75 KOH-mg / g was obtained. After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. The resin solution 16 was prepared by adding acetate.

Abbreviations in Table 1 are shown below.
EMA: ethyl methacrylate BA: n-butyl acrylate CHMA: cyclohexyl methacrylate MMA: methyl methacrylate t-BMA: t-butyl methacrylate DCPMA: dicyclopentanyl methacrylate BzMA: benzyl methacrylate MAA: methacrylate HEMA: 2-hydroxyethyl methacrylate M110: Aronix M110 (manufactured by Toagosei Co., Ltd.)

<Method for producing copolymer>
(Copolymer 1)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl acrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4 -Dimethylvaleronitrile) 6.5 parts and 21.5 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50 ° C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, a copolymer 1 having a resin component of 47% by weight was obtained. The ammonium salt value of the obtained copolymer was 34 KOH-mg / g.

(Copolymer 2)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 62.4 parts of isopropyl alcohol and heated to 75 ° C. under a nitrogen stream. Separately, 32.1 parts of ethyl methacrylate, 25.1 parts of n-propyl methacrylate, 25.1 parts of lauryl methacrylate, 17.7 parts of methacryloylaminopropyltrimethylammonium chloride, 2,2′-azobis (2,4- After 5.7 parts of dimethylvaleronitrile) and 15.6 parts of methyl ethyl ketone were made uniform, they were charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and the mixture was cooled to 50 ° C. Thereafter, 72 parts of isopropyl alcohol was added to obtain a copolymer 2 having a resin component of 40% by weight. The ammonium salt value of the obtained copolymer was 45 KOH-mg / g.

(Copolymer 3)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 27.5 parts of isopropyl methacrylate, 25.0 parts of benzyl methacrylate, 27.5 parts of 2-ethylhexyl methacrylate, 20.0 parts of N, N-dimethylaminomethylstyrene, 2,2′-azobis (2, 6.7 parts of 4-dimethylvaleronitrile) and 25.1 parts of methyl ethyl ketone were homogenized, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6770, and the mixture was cooled to 50 ° C. To this, 15.7 parts of benzyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, a copolymer 3 having a resin component of 50% by weight was obtained. The ammonium salt value of the obtained copolymer was 60 KOH-mg / g.

(Copolymer 4)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 62.4 parts of isopropyl alcohol was charged and heated to 75 ° C. under a nitrogen stream. Separately, 25.0 parts of methyl methacrylate, 25.0 parts of stearyl methacrylate, 20.0 parts of cyclohexyl methacrylate, 15.0 parts of Bremer PE90 (manufactured by NOF Corporation, diethylene glycol monomethacrylate), N-vinylpyrrolidone 20. After 0 parts, 4.7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 15.6 parts of isopropyl alcohol were made uniform, charged into a dropping funnel and attached to a four-necked separable flask. It was dripped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7550, and the mixture was cooled to 50 ° C. To this, 9.0 parts of methyl chloride and 22.0 parts of isopropyl alcohol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thereafter, 50 parts of isopropyl alcohol was added to obtain a copolymer 4 having a resin component of 44% by weight. The ammonium salt value of the obtained copolymer was 92 KOH-mg / g.

(Copolymer 5)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 82.0 parts of methyl ethyl ketone and heated to 75 ° C. under a nitrogen stream. Separately, 23.5 parts of ethyl methacrylate, 26.0 parts of t-butyl methacrylate, 25.0 parts of lauryl methacrylate, Kayamar PM-21 (manufactured by Nippon Kayaku Co., Ltd., 1 mol of ε-caprolaclone 1-hydroxyethyl methacrylate) Of phosphoric acid ester) 10.0 parts, diethylaminopropyl methacrylate 17.5 parts, 2,2'-azobis (2,4-dimethylvaleronitrile) 6.0 parts, and methyl ethyl ketone 25.6 parts. Thereafter, the mixture was placed in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7010, and the mixture was cooled to 50 ° C. Thus, copolymer 5 having a resin component of 48% by weight was obtained. The copolymer obtained had an ammonium salt value of 49 KOH-mg / g.

<Method for producing salt-forming compound>
(Salt-forming compound (A1-1))
In the following procedure, C.I. I. A salt-forming compound (A1-1) composed of Acid Red 289 and Copolymer 1 was produced.
51 parts of copolymer 1 is added to 2000 parts of water, and after sufficient stirring and mixing, the mixture is heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 is dissolved is prepared and added dropwise little by little to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (A1-1) of Acid Red 289 and Copolymer 1 was obtained. At this time, C.I. in the salt-forming compound (A1-1). I. The content of the effective pigment component derived from Acid Red 289 was 29% by weight.

(Salt-forming compound (A1-2))
In the following procedure, C.I. I. A salt-forming compound (A1-2) composed of Acid Red 289 and Copolymer 2 was produced.
The copolymer 2 is added to 88 parts of a side chain in 2000 parts of a 10% aqueous methanol solution, and the mixture is sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 is dissolved is prepared and added dropwise little by little to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound (A1-2) of Acid Red 289 and Copolymer 2 was obtained. At this time, C.I. in the salt-forming compound (A1-2). I. The content of the effective pigment component derived from Acid Red 289 was 22% by weight.

(Salt-forming compound (A1-3))
In the following procedure, C.I. I. A salt-forming compound (A1-3) composed of Acid Red 289 and Copolymer 3 was produced.
46.7 parts of the copolymer 3 is added to 2000 parts of a 10% N, N-dimethylformamide aqueous solution, and the mixture is sufficiently stirred and mixed, and then heated to 70 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 is dissolved is prepared and added dropwise little by little to the resin solution. After dropping, the mixture is stirred at 70 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 29 parts of C.I. I. A salt-forming compound (A1-3) of Acid Red 289 and Copolymer 3 was obtained. At this time, C.I. in the salt-forming compound (A1-3). I. The content of the effective pigment component derived from Acid Red 289 was 30% by weight.

(Salt-forming compound (A1-4))
In the following procedure, C.I. I. A salt-forming compound (A1-4) composed of Acid Red 289 and Copolymer 4 was produced.
A solution in which the copolymer 4 is dissolved in 20.0 parts of a side chain in 1000 parts of water is prepared, sufficiently stirred and mixed, and then heated to 70 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 is dissolved is prepared and added dropwise little by little to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 19 parts of C.I. I. A salt-forming compound (A1-4) of Acid Red 289 and Copolymer 4 was obtained. At this time, C.I. in the salt-forming compound (A1-4). I. The content of the effective pigment component derived from Acid Red 289 was 53% by weight.

(Salt-forming compound (A1-5))
In the following procedure, C.I. I. A salt-forming compound (A1-5) composed of Acid Red 289 and Copolymer 5 was produced.
Copolymer 5 is added to 63.2 parts of the side chain in 2000 parts of 20% acetic acid, sufficiently stirred and mixed, and then heated to 60 ° C. to carry out ammonium chloride of the tertiary amino group of the side chain. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 is dissolved is prepared and added dropwise little by little to the ammonium chloride resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound (A1-5) of acid red 289 and copolymer 5 was obtained. At this time, C.I. in the salt-forming compound (A1-5). I. The content of the effective pigment component derived from Acid Red 289 was 23% by weight.

(Salt-forming compound (A1-6))
In the following procedure, C.I. I. A salt-forming compound (A1-6) composed of Acid Red 52 and Copolymer 1 was produced.
51 parts of copolymer 1 is added to 2000 parts of water, and after sufficient stirring and mixing, the mixture is heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 52 is dissolved is prepared and added dropwise to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (A1-6) of acid red 52 and copolymer 1 was obtained. At this time, C.I. in the salt-forming compound (A1-6). I. The content of the effective pigment component derived from Acid Red 52 was 30% by weight.

(Salt Forming Compound (A1-7))
In the following procedure, C.I. I. A salt-forming compound (A1-7) composed of Acid Red 92 and Copolymer 1 was produced.
51 parts of copolymer 1 is added to 2000 parts of water, and after sufficient stirring and mixing, the mixture is heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 92 is dissolved is prepared and added dropwise to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 32 parts of C.I. I. A salt-forming compound (A1-7) of Acid Red 92 and Copolymer 1 was obtained. At this time, C.I. in the salt-forming compound (A1-7). I. The content of the effective pigment component derived from Acid Red 92 was 29% by weight.

(Salt-forming compound (A1-8))
In the following procedure, C.I. I. A salt-forming compound (A1-8) consisting of Acid Yellow 5 and Copolymer 1 was produced.
The resin 1 having a cationic group in the side chain of 51 parts is added to 2000 parts of water, and after sufficiently stirring and mixing, the mixture is heated to 60 ° C. On the other hand, an aqueous solution in which 10 parts of Acid Yellow 5 is dissolved in 90 parts of water is prepared and added dropwise to the resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 32 parts of Acid Yellow 5 and Copolymer 1 The salt-forming compound (A1-8) was obtained. At this time, C.I. in the salt-forming compound (A1-8). I. The content of the effective pigment component derived from Acid Yellow 5 was 33% by weight.

(Salt Forming Compound (A1-9))
In the following procedure, C.I. I. A salt-forming compound (A1-9) composed of Acid Blue 112 and Copolymer 1 was produced.
88 parts of the copolymer 1 is added to 2000 parts of a 10% aqueous methanol solution, and after sufficient stirring and mixing, the mixture is heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Blue 112 is dissolved is prepared and added dropwise little by little to the previous resin solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound (A1-9) of Acid Blue 112 and Copolymer 1 was obtained. At this time, C.I. in the salt-forming compound (A1-9). I. The content of the effective pigment component derived from Acid Blue 112 was 35% by weight.

(Salt Forming Compound (AC-1))
In the following procedure, C.I. I. A salt-forming compound (AC-1) consisting of Acid Red 289 and distearyldimethylammonium chloride (Coatamine D86P) was produced.
11.5 parts of Cotamine D86P is added to 2000 parts of a 10% aqueous sodium hydroxide solution, sufficiently stirred and mixed, and then heated to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 289 is dissolved is prepared and added dropwise to the previous solution. After dropping, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 17 parts of C.I. I. A salt-forming compound (AC-1) of Acid Red 289 and Cotamine D86P was obtained.

(Salt-forming compound (AC-2))
In the following procedure, C.I. I. A salt-forming compound (AC-2) composed of Acid Blue 112 and monolauryltrimethylammonium chloride (Coatamine 24P) was produced.
8.1 parts of Cotamine 24P is added to 2000 parts of a 7% aqueous sodium hydroxide solution, and after sufficient stirring and mixing, the mixture is heated to 50 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Blue 112 is dissolved is prepared and added dropwise little by little to the previous solution. After the dropping, the mixture is stirred at 50 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, it was judged that a salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer. I. A salt-forming compound (AC-2) of Acid Blue 112 and Cotamin 24P was obtained.

<Production method of fine pigment>
(Blue refined pigment (P-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“Lionol Blue ES” manufactured by Toyo Ink Mfg. Co., Ltd.), 800 parts of crushed salt and 100 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) at 70 ° C. for 12 hours. Kneaded. The mixture was added to 3000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of blue refinement | purification pigments (P-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

(Green refined pigment (P-2))
Phthalocyanine green pigment C.I. I. 120 parts of Pigment Green 36 (“Lionol Green 6YK” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. . The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts of green refined pigment (P-2). The average primary particle diameter of the obtained pigment was 32.6 nm.

(Red fine pigment (P-3))
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 (“IRGAZIN RED 2030” manufactured by Ciba Japan Co., Ltd.), 1000 parts of crushed salt and 120 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 10 hours. The mixture was poured into 2000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 80 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts of red refined pigment (P-3). The average primary particle diameter of the obtained pigment was 24.8 nm.

(Purple refined pigment (P-4))
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 118 parts of purple refinement | purification pigment (P-4). The average primary particle diameter of the obtained pigment was 26.4 nm.

(Yellow fine pigment (P-5))
Nickel complex yellow pigment C.I. I. 100 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 95 parts of yellow refinement | purification pigments (P-5). The average primary particle diameter of the obtained pigment was 39.2 nm.

<Method for producing pigment dispersion>
(Preparation of pigment dispersion (DP-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (DP-1) was produced.

Blue refined pigment (P-1): 12.0 parts (CI Pigment Blue 15: 6)
Resin solution 1: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts (Preparation of pigment dispersion (DP-2 to 5))
Hereinafter, pigment dispersions (DP-2 to DP-5) were produced in the same manner as the pigment dispersion (DP-1) except that the pigments were changed to the pigments shown in Table 2.

<Method for producing colorant solution>
(Preparation of colorant solution (DA-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a colorant solution (DA-1).

Salt-forming compound (A1-1): 5.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 95.0 parts

(Preparation of colorant solution (DA-2 to 9, DC-1, 2))
Hereinafter, a colorant solution (DA-2 to 9, DC-1 to 2)) was prepared in the same manner as the colorant solution (DA-1) except that the salt formation compound shown in Table 3 was changed. .
Table 3 shows the content of the pigment component at this time.
Here, the pigment content A represents the effective pigment component content (% by weight) in the salt-forming compound (A1), and the pigment content B represents the effective pigment component content (% by weight) in the colorant solution. Show.

* 1 Dye component content A: Effective dye component content (wt%) of salt-forming compounds
* 2 Dye component content B: Effective dye component content (% by weight) in the colorant solution

<Examples 1 to 26, Comparative Examples 1 to 5; Resist material (R-1 to 31)>
(Example 1; Preparation of photosensitive coloring composition (resist material (R-1)))
The following mixture was stirred and mixed to be uniform, and then filtered and mixed with a 5.0 μm filter to prepare a photosensitive coloring composition (resist material (R-1)).
Colorant solution (DA-1): 60.0 parts Resin solution 2: 26.6 parts Dipentaerythritol penta and hexaacrylate: 4.9 parts (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator (“Irgacure-379” manufactured by Ciba Japan): 1.8 parts Propylene glycol monomethyl ether acetate (PGMAC): 6.7 parts

(Examples 2 to 5; resist material (R-2 to 5))
Hereinafter, as shown in Table 4, a photosensitive coloring composition (resist material (R-2 to 5)) was obtained in the same manner as the resist material (R-1) except that the type of the colorant solution was changed.

Example 6 Photosensitive Coloring Composition (Preparation of Resist Material (R-6))
The following mixture was stirred and mixed so as to be uniform, and then filtered and mixed with a 5.0 μm filter to prepare a photosensitive coloring composition (resist material (R-6)).
Colorant solution (DA-1): 13.0 parts Pigment dispersion (DP-1): 19.6 parts Resin solution 2: 18.8 parts Dipentaerythritol penta- and hexaacrylate: 4.9 parts (Toagosei Co., Ltd.) "Aronix M-402")
Photopolymerization initiator (“Irgacure-379” manufactured by Ciba Japan): 1.8 parts Propylene glycol monomethyl ether acetate (PGMAC): 41.9 parts

(Examples 7 to 26, Comparative Examples 1 to 5; Resist material (R-7 to 31))
Hereinafter, as shown in Table 4, the colored composition (resist material (R-7 to 31) was the same as the resist material (R-6) except that the types of the colorant solution, the pigment dispersion, and the resin solution were changed. )
Got.

  About the obtained resist material (R-1 to 31), the test regarding storage stability, a coating-film foreign material, glass adhesiveness, and a development residue was done with the following method. The results are shown in Table 5.

(Storage stability test method)
The viscosity at 25 ° C. of the resist material (R-1 to 31) was measured at a rotation speed of 20 rpm using an E-type viscometer (TUE-20L type manufactured by Toki Sangyo Co., Ltd.). The rate of change with time in viscosity was calculated from the initial viscosity on the day of preparation of the resist material and the accelerated time-lapse viscosity after storage for 7 days in a thermostatic chamber at 40 ° C., and the storage stability was evaluated according to the following criteria.
(Change in viscosity over time) = | [(initial viscosity) − (viscosity over time)] / (initial viscosity) | × 100 (%)
◎: Less than 10% ○: 10% or more, less than 20% △: 20% or more, less than 50% ×: 50% or more

(Coating foreign material test method)
The resist material (R-1 to 31) was spin-coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate at a rotation speed of 2.5 μm after drying, and dried at 70 ° C. for 20 minutes. Then, UV exposure was performed with an integrated light amount of 150 mJ / cm ² using an ultrahigh pressure mercury lamp through a photomask having a stripe-shaped opening having a width of 100 μm, and the unexposed portion was washed away with a 5% sodium carbonate aqueous solution. The substrate was baked in a hot air oven at 230 ° C. for 20 minutes to form a stripe pattern having a width of 100 μm on the substrate. Thereafter, the surface of the fabricated substrate was observed using a metal microscope “BX60” manufactured by Olympus System (magnification is 500 times), and the number of particles that can be observed in any five fields of view by counting was counted. Evaluation was based on criteria. In the evaluation results, ◎ and ○ are good with a small number of foreign matters, △ is a level where there is a large number of foreign matters, but there is no problem in use, and × is a state where it cannot be used because uneven coating due to foreign matters occurs Equivalent to.
◎: Less than 5 ○: 5 or more, less than 20 △: 20 or more, less than 100 ×: 100 or more

(Glass adhesion test method)
As a test for adhesion to glass, the coating film was formed in the same procedure as the coating film foreign matter test, and the chemical resistance of the obtained coating film was confirmed. As a test method, it was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C. for 30 minutes, and the adhesion to the glass before and after immersion was evaluated in three stages by visual observation.
◯: No peeling at all Δ: Slight peeling is observed ×: Peeling is recognized

(Development residue test method)
The resist material (R-1 to 31) was spin-coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate at a rotation speed of 2.5 μm after drying, and dried at 70 ° C. for 20 minutes. Then, UV exposure was performed with an integrated light amount of 150 mJ / cm ² using an ultrahigh pressure mercury lamp through a photomask having a stripe-shaped opening having a width of 100 μm, and the unexposed portion was washed away with a 5% sodium carbonate aqueous solution. The developed glass surface was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.), and the presence or absence of a residue was determined.
○: No residue △: There is a slight residue ×: There is a residue

  The resist material of the present invention comprising a resin (B) containing the salt-forming compound (A1) and having the same structural unit (b1) as the structural unit (a1) of the copolymer constituting the salt-forming compound (A1), , Both were excellent in storage stability, had few coating film foreign matters, and were in a range that could be preferably used as a color filter.

  On the other hand, the resist material (R-27 to 31) of the comparative example had many development residues, and did not reach the grade that can be used as a color filter.

  When the resin (B) having the same structural unit (b1) as the structural unit (a1) of the copolymer constituting the salt-forming compound (A1) is contained in the pigment dispersion to be used in combination even when added during resist adjustment In addition, all showed excellent characteristics as a color filter, and in both cases, excellent effects as a resist material could be confirmed.

  Further, when resist materials (R-19 to 22) that differ only in the type of the resin (B) are compared, the resist materials (R-19 and 20) in which the weight average molecular weight of the resin (B) is in the range of 5,000 to 25,000. ) Was more excellent in adhesion to glass and free from development residue.

<Examples 27 and 28; resist material (R-32 and 33)>
(Example 27: Production of colored composition (resist material (R-32)))
The following mixture was stirred and mixed to be uniform, and then filtered and mixed with a 5.0 μm filter to prepare a colored composition (resist material (R-32)).
Colorant solution (DA-1): 12.6 parts Pigment dispersion (DP-1): 20.0 parts Resin solution 2: 18.0 parts Antioxidant a: 0.2 parts (1, 3, 5- Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)) dipentaerythritol penta and hexaacrylate: 4.9 parts (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Photopolymerization initiator ("Irgacure-379" manufactured by Ciba Japan): 1.8 parts Propylene glycol monomethyl ether acetate (PGMAC): 42.5 parts

(Example 28; resist material (R-33))
The resist material (R A colored composition (resist material (R-33)) was obtained in the same manner as in -32).

(Evaluation of color characteristics)
A resist material was applied on a glass substrate so that x = 0.138 and y = 0.085 in a C light source, and this substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).
The results are shown in Table 6 below.

The resist material (R-32, 33) containing the antioxidant (F) has high brightness and can provide a more excellent color filter.

Claims (9)

A color filter coloring composition comprising a colorant (A), a resin (B), and an organic solvent (E),
Copolymer and anionic colorant (A) comprising a structural unit (a1) represented by general formula (1) and a structural unit (a2) having a cationic group in the side chain represented by general formula (2) A salt-forming compound (A1) formed from a dye and
The resin (B) includes the structural unit (b1) represented by the general formula (4), and the content of (b1) is 140 to 10,000 parts by weight with respect to 100 parts by weight of (a1). A colored composition for a color filter.

General formula (1)

[In General Formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂ represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group. ]

General formula (2)


[In General Formula (2), R ₃ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₄ to R ₆ are each independently a hydrogen atom, an optionally substituted alkyl group, an alkenyl group which may be substituted or an optionally substituted aryl group, the R ₄ to R ₆ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₇ —, —COO—R ₇ —, and R ₇ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

General formula (4)

[In General Formula (4), R ₅₁ is the same atom or group as R ₁ in General Formula (1), and R ₅₂ is the same atom or group as R ₂ in General Formula (1). ]
The weight average molecular weight of the resin (B) is a color filter for coloring composition according to claim 1, characterized in that the 5,000 to 25,000. The coloring composition for a color filter according to claim 1 or 2 , wherein the acid value of the resin (B) is 40 to 150 (KOH-mg / g). Furthermore, antioxidant (F) is contained, The coloring composition for color filters of any one of Claims 1-3 characterized by the above-mentioned. The coloring composition for a color filter according to any one of claims 1 to 4 , wherein the colorant (A) further contains a pigment. The coloring composition for a color filter according to claim 5 , wherein the pigment is a blue pigment. Furthermore, the coloring composition for color filters of any one of Claims 1-6 containing a photopolymerizable monomer (C) and a photoinitiator (D). The coloring composition for a color filter according to any one of claims 1 to 7 , wherein the organic solvent (E) contains propylene glycol monomethyl ether acetate as a main component. A color filter comprising a filter segment formed on the transparent substrate by the colored composition for color filter according to any one of claims 1 to 8 .