JP5659918B2 - 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 agent 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). Generally, it is known that the solubility of an anionic dye in an organic solvent is increased by changing the sodium sulfonate group (—SO ₃ Na) of the anionic dye into an organic amine salt. 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.

  In addition, as a salt-forming compound of an anionic dye, 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 because the amide structure acts as a dyeing point with the 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.

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

  An object of the present invention is to provide a color filter coloring composition having excellent storage stability, and a color filter having strong adhesion to a transparent substrate such as glass without occurrence of foreign matter on the coating film. That is.

  In addition, the present invention has good developability, and there is no residue (development residue) of the coloring composition on the non-pixel portion on the substrate after development, and no pattern chipping and / or peeling of the pixel portion. It is an object of the present invention to provide a productive color composition suitable as a color filter material and a color filter formed using the same.

  As a result of intensive studies to solve the above problems, the present inventors have obtained a structure obtained by reacting a resin (a1) having a cationic group in the side chain with an anionic dye (a2). The color filter coloring composition containing the salt compound (A1) as the colorant agent (A) and containing the polyfunctional monomer (C1) having an acid group has excellent storage stability and no foreign matter is generated on the coating film. , Having a strong adhesion with a transparent substrate such as glass, and having good developability, it can be found that the occurrence of a residue such as a colored composition on the non-pixel portion on the substrate after development can be suppressed; The present invention has been made based on this finding.

  That is, this invention is the coloring composition for color filters containing a coloring agent (A), binder resin (B), a monomer (C), and an organic solvent (D), Comprising: A coloring agent (A) is a side chain. Containing a salt-forming compound (A1) obtained by reacting a resin (a1) having a cationic group with an anionic dye (a2), and the polyfunctional monomer (C) having an acid group The present invention relates to a color filter coloring composition containing (C1).

Further, the present invention provides the colored composition for a color filter, wherein the resin (a1) having a cationic group in the side chain is a vinyl resin containing a structural unit represented by the following general formula (1): Related to things.
General formula (1):

[In General Formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{2 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{2 to} R ₄ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

The present invention also relates to the colored composition for color filters, wherein the acid group of the polyfunctional monomer (C1) having an acid group is a carboxylic acid.
In addition, the present invention relates to the colored composition for a color filter, which further contains a photopolymerization initiator (G).
In addition, the present invention relates to the coloring composition for a color filter, wherein the binder resin (B) contains an alkali-soluble photosensitive resin (B1).

  The present invention also relates to a color filter comprising a filter segment formed on the substrate by the color filter coloring composition.

  In the present invention, a salt-forming compound (A1) obtained by reacting a resin (a1) having a cationic group in the side chain with an anionic dye (a2), a polyfunctional monomer having an acid group (C1) ) Containing a coloring composition for a color filter having high storage stability, no generation of foreign matter during coating film formation, excellent adhesion, and good developability on a substrate after development. It is possible to obtain a color filter capable of suppressing the generation of a residue such as a colored composition in the non-pixel portion.

Hereinafter, the present invention will be described in detail.
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”.

The coloring composition for a color filter of the present invention is a coloring composition for a color filter containing a colorant (A), a binder resin (B), a monomer (C), and an organic solvent (D),
The colorant (A) contains a salt-forming compound (A1) obtained by reacting a resin (a1) having a cationic group in the side chain with an anionic dye (a2), and the monomer (C) The polyfunctional monomer (C1) having an acid group is contained.

The colored composition described above is obtained by first reacting a salt-forming compound (A1) contained as a colorant with a resin (a1) having a cationic group in the side chain and an anionic dye (a2). By forming a salt structure, the compatibility with the binder resin (B), the monomer (C) and the solvent is improved, so that the stability of the colored composition is improved and the generation of foreign substances is also suppressed. .
In addition, since the polyfunctional monomer (C1) having an acid group contained as the monomer (C) improves the alkali development performance, no residue is generated.

Moreover, it is thought that the adhesiveness to the glass surface improves by the influence of the acidic functional group of the polyfunctional monomer (C1) which has an acid group.
By combining these two, it is considered that the stability of the coloring composition is improved, the generation of foreign matter can be suppressed, no development residue is produced, and the adhesion to the substrate is enhanced.

[Colorant (A)]
The colorant (A) contains, as an essential component, a salt-forming compound (A1) obtained by reacting a resin (a1) having a cationic group in the side chain with an anionic dye (a2). Accordingly, pigments can be used in combination.

<Salt-forming compound (A1)>
The salt-forming compound (A1) is a salt-forming compound obtained by reacting a resin (a1) having a cationic group in the side chain with an anionic dye (a2).

(Resin (a1) having a cationic group in the side chain)
The resin (a1) 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 a preferable onium salt structure is from the viewpoint of availability and the like. Is preferably an ammonium salt, an iodonium salt, a sulfonium salt, a diazonium salt, and a phosphonium salt, and more preferably an ammonium salt, an iodonium salt, or a sulfonium salt in view of storage stability (thermal stability). . More preferred is an ammonium salt.

  When the coloring composition for color filters containing the salt-forming compound (A1) of the present invention is prepared and the characteristics as a color filter are expressed, it is the same kind as the binder resin (B) constituting the coloring composition for color filters. It is desirable to use a resin. In the present invention, since an acrylic resin is preferably used for the color filter coloring composition, the resin (a1) having a cationic group in the side chain for obtaining a salt-forming compound is preferably an acrylic resin. .

Moreover, as resin (a1) which has a cationic group in the side chain of this invention, the vinyl resin containing the structural unit represented by following General formula (1) is used preferably.
General formula (1)

[In General Formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{2 to} R ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group, and R _{2 to} R ₄ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

In general formula (1), R ₁ represents 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 has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

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

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

Here, as the alkyl group in R _{2 to} R ₄ , for example, 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 and cyclohexyl etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl and 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 to} R ₄ include linear or branched alkenyl groups (vinyl, aryl, 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 and the like) and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). 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 to} R ₄ include monocyclic aryl groups (such as phenyl), condensed polycyclic aryl groups (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and aromatic heterocyclic hydrocarbons. Groups (thienyl (group derived from thiophene)), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (from xanthone) Derived groups) and 9-oxothioxanthenyl (groups derived from thioxanthone) and the like.

When the alkyl group, alkenyl group, or aryl group represented by R _{2 to} R ₄ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from 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 to} R ₄ are preferably an alkyl group which may be substituted from the viewpoint of stability, and more preferably an unsubstituted alkyl group.

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

In general formula (1), the component of Q connecting the vinyl moiety and the ammonium base represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group, Among these, —CONH—R ₅ — and —COO—R ₅ — are preferable because of polymerizability and availability. R ₅ 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 (1) constituting the counter anion of the resin 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.

  In order to obtain a vinyl resin containing a structural unit represented by the general formula (1) which is a preferred embodiment of the present invention, only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component is used. Alternatively, after obtaining an acrylic resin having an amino group obtained by copolymerizing an ethylenically unsaturated monomer having an amino group as a monomer component, it may be obtained by a method in which an onium chlorinating agent is reacted and ammonium salified. good.

  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 (2).

General formula (2)

Z-R ₅ -COOR ₆

In general formula (2), Z is a halogen such as chlorine or bromine, preferably bromine, and R ₅ 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 ₆ 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, the polymer which has a carboxybetaine structure shown by General formula (2) Formula, and has an ammonium base can be obtained.

  Other ethylenically unsaturated monomers that can be used in combination with an ethylenically unsaturated monomer that forms a structural unit having a cationic group in the side chain of the present invention include crotonic acid esters, vinyl Esters, maleic acid diesters, fumaric acid diesters, itaconic acid 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 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, as a method for obtaining a copolymer having a structural unit having a cationic group in the side chain, particularly a structural unit represented by the general formula (1), anionic polymerization, living anionic polymerization, cationic polymerization, living cation Known methods such as 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) Pamphlet of International Publication No. 96/030421 (Reference 6) Pamphlet of International Publication No. 97/018247 (Reference 7) JP-A-9-208616 (Reference 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 the ammonium base present in the vinyl resin containing the structural unit represented by the general formula (1) suitable for the present invention is not particularly limited, but the resin has an ammonium salt value of 10 to 200 mgKOH / It is preferable that it is g, and it is more preferable that it is 20-130 mgKOH / g.

  The molecular weight of the vinyl resin containing the structural unit represented by the general formula (1) suitable for the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is It is preferably 1,000 to 500,000, and more preferably 3,000 to 15,000.

  Moreover, it is preferable that the vinyl-type resin containing the structural unit represented by General formula (1) suitable for this invention has the 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.

  In the resin (a1) having a cationic group in the side chain, the total content of the structural unit represented by the general formula (1) is not particularly limited, but the resin (a1) having a cationic group in the side chain is not limited. When the total structural unit contained is 100% by weight, it is preferably 5% by weight or more, preferably 10 to 50% by weight from the viewpoint of solvent solubility and coloring power of the salt-forming compound (A1). Is more preferable.

(Anionic dye (a2))
The anionic dye (a2) may be a colored compound that is 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 (a2) include anthraquinone anionic dyes, monoazo anionic dyes, disazo anionic dyes, oxazine anionic dyes, aminoketone anionic dyes, xanthene anionic dyes, and quinoline anions. Dyes, triphenylmethane anionic dyes and the like. Moreover, as an aspect of an anionic dye (a2), it is preferable to use an acidic dye and a direct dye. Specific examples of the anionic dye (a2) that can be used for the synthesis of the salt-forming compound are shown below.

  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 Etc.

  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 used in the present invention is prepared by stirring or vibrating an aqueous solution in which the resin (a1) having a cationic group in the side chain and the anionic dye (a2) is dissolved, or having a cationic group in the side chain. It can be easily obtained by mixing an aqueous solution of the resin (a1) having an aqueous solution of the anionic dye (a2) with stirring or vibration. In the aqueous solution, the cationic group of the resin and the anionic group of the dye are ionized, these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, the salt composed of the counter anion of the resin and the counter cation of the acidic dye is water-soluble and can be removed by washing or the like. The resin (a1) and anionic dye (a2) each having a cationic group in the side chain to be used may be a single type or a plurality of types having different structures.

  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 resin (a1) having a cationic group in the side chain and the anionic dye (a2). 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 (a2) in the salt-forming compound (A1) used in the present invention can be adjusted to a range of 10 to 60% by weight in 100% by weight of the salt-forming compound (A1). In particular, the content is preferably in the range of 15 to 55% by weight. By controlling within this range, a salt-forming compound having excellent 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 (a2) contained in the salt-forming compound (A1) is adjusted to the same concentration. It can be calculated by measuring the spectral spectrum of the solution and the anionic dye (a2) solution and determining the spectral intensity ratio of the maximum absorption wavelength.

For example, using a solvent (such as N-methyl-2-pyrrolidone) that can well dissolve both the salt-forming compound (A1) and the anionic dye (a2), the salt-forming compound (A1) solution and the anionic dye (A2) A solution is prepared at a certain concentration, and the absorbance at the maximum absorption wavelength of the salt-forming compound (A1) solution and the anionic dye (a2) solution obtained by absorbance measurement is Xa and Xb, respectively. Many anionic dyes (a2) contain a counter ion such as an alkali metal ion. In that case, the number of counter ions present in one molecule is Na and the atomic weight of the counter ion is Ma. When the molecular weight of the dye is Mb, the weight% of the effective pigment component in the anionic dye (a2) 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 (a2) contained in the salt-forming compound (A1) can be calculated from the following formula.
(Xa / Xb) × (1-Ma × Na / Mb) × 100 [wt%]
The ratio of the resin (a1) having a cationic group in the side chain and the anionic dye (a2) is such that the molar ratio of the total cationic unit of the resin to the total anionic group of the anionic dye (a2) is 10/1. If it is in the range of ˜¼, the salt-forming compound of the present invention can be suitably adjusted, and it is more preferably in the range of 2/1 to ½.

<Pigment>
The coloring composition for a color filter of the present invention can further contain a pigment as the colorant (A).
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 the coloring composition for color filters is shown by a color index number.

  Examples of the red coloring composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 97, 122, 123, 146, 149, 166, 168, 176, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 221, 223, 224, 226, 227, 228, 240, Red pigments such as 242, 246, 254, 255, 264, and 272 can be used.

  In addition to these red pigments, the following yellow pigments and orange pigments can be used in combination.

  Examples of red coloring compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 17 , Such as 177,179,180,181,182,185,187,188,193,194,199,213,214 yellow pigment and / or C. I. Orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, 73 can be used in combination.

  Examples of the green coloring composition for forming the green filter segment include C.I. I. Green pigments such as CI Pigment Green 7, 10, 36, 37, and 58 can be used. The green coloring composition includes 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, 82,185,187,188,193,194,198,199,213,214,218,219,220, or a yellow pigment 221 and the like can be used in combination.

  Examples of the blue coloring composition 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. The blue coloring composition includes 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 the cyan coloring composition for forming the cyan filter segment include C.I. I. Blue pigments 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 magenta colored compositions for forming magenta color filter segments 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. A yellow pigment can be used in combination with the magenta composition.

  Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, 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.

(Miniaturization of pigment)
The pigment 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.

<Binder resin (B)>
The binder resin (B) serves to disperse the colorant (A), particularly the salt-forming compound (A1) and the pigment, or to dye and penetrate the salt-forming compound (A1). A resin having a transmittance of preferably 80% or more, more preferably 95% or more is preferable in the entire wavelength region of 400 to 700 nm. For example, there are a thermoplastic resin and a thermosetting resin, and these can be used alone or in combination of two or more. Moreover, when using the coloring 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 resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, a photosensitive resin having an ethylenically unsaturated double bond can be used.

  In particular, the alkali-soluble photosensitive resin (B1) having both alkali-soluble performance and photocuring performance in the binder resin (B) is preferable as having both performances.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

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

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group and a sulfone group.

  Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  The weight average molecular weight (Mw) of the binder resin (B) is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, still more preferably 5,000 to 30. , 000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  When the weight average molecular weight (Mw) of the binder resin (B) exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the color filter coloring composition is increased, which makes it difficult to handle. Further, if the weight average molecular weight (Mw) is less than 5,000, problems may occur in developability and adhesion to a substrate such as glass.

  The acid value of the binder resin (B) is preferably a resin having an acid value of 20 to 300 mgKOH / g from the viewpoints of dispersibility, penetrability, developability and resistance of the pigment. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern may not remain.

The binder resin (B) can be used in an amount of 20 to 400 parts by weight, preferably 50 to 250 parts by weight, with respect to 100 parts by weight of the colorant (A) in the coloring composition.
(Alkali-soluble photosensitive resin (B1))
It is preferable that binder resin (B) used for the coloring composition of this invention contains alkali-soluble photosensitive resin (B1).

  Examples of the alkali-soluble photosensitive resin (B1) in the present invention include resins in which an ethylenically unsaturated double bond is introduced by the following methods (i) and (ii).

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

Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 2-glycidoxyethyl (meth).
An acrylate, 3,4 epoxy butyl (meth) acrylate, and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)
Acrylate is preferred.

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

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.
More than one type may be used together. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

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

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

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

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

  Examples of the alkali-soluble photosensitive resin (B1) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, or α-chloroacrylic acid, and carboxyls such as unsaturated dicarboxylic acids such as maleic acid or fumaric acid. And a resin containing a group and having an ethylenically unsaturated double bond. Other ethylenically unsaturated monomers that are precursors of the alkali-soluble photosensitive resin (B1) include methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth). Acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl ( (Meth) acrylate, 1-methylbutyl (meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) Examples include alkyl or alkenyl (meth) acrylates such as acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, cyclohexyl (meth) acrylate, allyl (meth) acrylate, or oleyl (meth) acrylate, depending on the purpose. In addition, other ethylenically unsaturated monomers can be selected without being limited to these, and two or more types can be used in combination. Of these, methyl (meth) acryl methacrylate or ethyl (meth) acrylate is preferred from the viewpoint of pigment dispersibility.

<Monomer (C)>
The monomer (C) in the present invention is characterized by containing a polyfunctional monomer (C1) having an acid group. In the present invention, the monomer (C) includes a monomer or oligomer that is cured by ultraviolet rays or heat to form a resin.

(Polyfunctional monomer having an acid group (C1))
As the polyfunctional monomer (C1) having an acid group, for example, an esterified product of a poly (meth) acrylate containing a free hydroxyl group of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polycarboxylic acid; Examples include esterified products with monohydroxyalkyl (meth) acrylates. Specific examples include monomethyl oligoacrylates or monohydroxy oligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. And monoesterified products containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids, such as benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid And a free carboxyl group-containing oligoester product of monohydroxy monoacrylate or monohydroxy monomethacrylate such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. be able to.

  These polyfunctional monomers (C1) can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  Moreover, the compound represented by following General formula (3) can also be used preferably.

General formula (3):
_{(H 2 C = C (R} 5) COO) m -X- (OCOCH (R 5) CH 2 S (R 6) COOH) n
[In General Formula (3), R ₅ is a hydrogen atom or a methyl group, R ₆ is a hydrocarbon group having 1 to 12 carbon atoms, and X is an (m + n) -valent carbon number 3 to 60 Organic group, m represents an integer of 2 to 18, and n represents an integer of 1 to 3. ]

Here, the compound represented by the general formula (3) can be easily obtained by, for example, the following method.
(1) A method of adding a mercapto compound to an obtained compound after esterifying the compound giving an organic group represented by X with acrylic acid to acrylate, and (2) a compound giving an organic group represented by X Is modified with a polyisocyanate compound, and then the resulting compound is acrylated with an acrylate compound having a hydroxyl group, and then a mercapto compound is added to the obtained compound. (3) An organic group represented by X is given. A method in which a compound is esterified with acrylic acid to be acrylated, then modified with a polyisocyanate compound, and a mercapto compound is added to the obtained compound.

  Examples of the compound giving an organic group represented by X include pentaerythritol, pentaerythritol modified caprolactone, pentaerythritol modified polyisocyanate, dipentaerythritol, dipentaerythritol caprolactone modified, dipentaerythritol polyisocyanate Denatured products can be mentioned.

  Examples of the mercapto compound include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, mercaptosuccinic acid, and the like.

  The content of the polyfunctional monomer (C1) having an acid group is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the binder resin (B). In this case, if the content of the polyfunctional monomer (C1) having an acid group is less than 5 parts by weight, the pixel strength or the smoothness of the pixel surface tends to decrease. There is a tendency that the soiling or film residue is likely to occur in the region other than the portion where the pixel is formed.

(Other polyfunctional monomers)
The monomer (C) in this invention can also contain other polyfunctional monomers other than the polyfunctional monomer (C1) which has an acid group.
Other polyfunctional monomers include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, EO-modified bisphenol A di (meth) acrylate, 1 , 4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyester (meth) acrylate, trimethylolpropane tri ( (Meth) acrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, dipentaerythritol penta (meth) acrylate, cap Lactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropane tetra (meth) acrylate, epoxy acrylate, and pentaerythritol tetra (meth) acrylate.
These other polyfunctional monomers can be used singly or in combination of two or more at any ratio as required.

(Monofunctional monomer)
The monomer (C) in the present invention can also contain a monofunctional monomer.
Examples of the monofunctional monomer include ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolactone monomethacrylate, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxypropyl succinic acid, 2 -Methacryloyloxypropyl succinic acid, methoxyethylene glycol acrylate, methoxyethylene glycol methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxydipropylene Glico Acrylate, methoxydipropylene glycol methacrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, and commercially available products such as 2-acryloyloxyethyl succinic acid (trade name M-5300) Can be mentioned.
These monofunctional monomers can be used singly or as a mixture of two or more at any ratio as required.

  When the polyfunctional monomer (C1) having an acid group and another polyfunctional monomer are used in combination, the content of the polyfunctional monomer (C1) having an acid group is based on the total amount of the monomer (C) ( 100% by weight) is 10% by weight or more, preferably 50% by weight or more. When the content of the polyfunctional monomer (C1) having an acid group is 10% by weight or more, an excellent filter segment can be obtained without adhesion to the substrate and development residue.

<Organic solvent (D)>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent can be included to facilitate formation.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 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- Methylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl 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, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  These solvents can be used singly or in combination of two or more at any ratio as required.

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

  When using 2 or more types of mixed solvents, it is preferable that said preferable organic solvent contains 65 to 95 weight%.

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

  In addition to the above-described components, the color composition for color filter of the present invention can use the following photopolymerization initiator, sensitizer, amine compound, leveling agent, curing agent, and curing accelerator.

<Photopolymerization initiator (G)>
The colored composition for a color filter of the present invention is a solvent development type or alkali development type colored resist material added with a photopolymerization initiator or the like 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

  As photopolymerization initiator (G), 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, Or benzoin compounds such as benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ' Benzophenone compounds such as 1,4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethyl Thioxanthone compounds such as thioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p Methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis ( Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl Triazine compounds such as-(4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl) Oxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.

  These photopolymerization initiators (G) can be used singly or as a mixture of two or more at any ratio as required.

  The content of the photopolymerization initiator (G) is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant (A), and 10 to 150 parts by weight from the viewpoint of photocurability and developability. It is more preferable.

<Sensitizer (H)>
The coloring composition for a color filter of the present invention can further contain a sensitizer (H).
Sensitizers (H) include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by 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 Body, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyrin derivative, annulene derivative, spiropyran derivative, Spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler 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) ben Examples include zophenone and 4,4′-diethylaminobenzophenone.

  These sensitizers (H) can be used singly or as a mixture of two or more at any ratio as required.

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

  The content of the sensitizer (H) is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (G), and 5 to 50 parts by weight from the viewpoint of photocurability and developability. More preferably.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 1.0 part by weight with respect to 100 parts by weight of the total weight of the coloring composition.

  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.

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

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. 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.

<Method for producing colored composition>
The coloring composition for a color filter of the present invention is prepared by mixing a salt-forming compound (A1) in a salt-forming compound solution obtained by stirring and dissolving in a binder resin (B) and / or an organic solvent (D). A functional monomer (C), a photopolymerization initiator (G), and, if necessary, further mixed with an organic solvent (D), other additives, etc., and a solvent developing type or alkali developing type photosensitive coloring composition (resist Material).

  Further, when a pigment is further included as the colorant (A), the pigment is mixed with a three-roll mill, two in a binder resin (B) and / or an organic solvent (D) together with a pigment dispersant shown below as required. A pigment dispersion obtained by finely dispersing using various dispersing means such as the present roll mill, sand mill, kneader, attritor and the like, a salt-forming compound solution, a polyfunctional monomer (C), a photopolymerization initiator (G), A color filter coloring composition can be prepared by mixing with an organic solvent (D) or the like.

  In addition, the colorant solution and the pigment dispersion can be produced separately and mixed, and the salt-forming compound (A1) and the pigment can be mixed and dispersed together before use.

  When the pigment is dispersed in the binder resin (B) and / or the organic solvent (D), a dispersion aid such as a resin-type pigment dispersant, a surfactant, or a pigment derivative can be appropriately contained. The dispersion aid is excellent in dispersion of the pigment and has a great effect of preventing re-aggregation of the pigment after dispersion. Therefore, the color composition for a color filter is obtained by dispersing the pigment in a resin and / or solvent using the dispersion aid. When an object is used, a color filter excellent in transparency can be obtained.

<Dispersing aid>
When the pigment is dispersed in a colorant carrier such as a binder resin or an organic solvent, a dispersion aid such as a dye derivative, a resin-type dispersant, or a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion. When used, a color filter having a high spectral transmittance can be obtained.

  In the present invention, the salt-forming compound (A1) is also expected to play a role as a dispersion aid for the pigment used in combination.

(Dye derivative)
Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. can be used. These can be used alone or in combination of two or more.

  The content of the pigment derivative is preferably 0.01 parts by weight or more, more preferably 0.5 parts by weight or more, and most preferably 1 part 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, it is preferably 200 parts by weight or less, and more preferably 100 parts by weight or less.

  In particular, when the coloring composition for a color filter of the present invention contains a blue pigment, a basic compound of copper phthalocyanine in which a basic substituent is introduced into the phthalocyanine pigment, in particular, as a dye derivative for dispersing the blue pigment. It is preferable to use it. As the basic compound of copper phthalocyanine, an amine compound of copper phthalocyanine is preferable, and examples thereof include a copper phthalocyanine sulfonic acid ammonium salt compound, a copper phthalocyanine tertiary amine compound, and a copper phthalocyanine sulfonic acid amide compound.

  Specifically, an amine compound of copper phthalocyanine represented by the following general formula (3), preferably an amine compound of copper phthalocyanine having basic groups represented by the following general formulas (4) to (6): Can be used.

By using a basic compound of copper phthalocyanine, particularly an amine compound of copper phthalocyanine, in the blue coloring composition of the present invention, high brightness and a high contrast ratio can be achieved when a blue color filter is used. This is because the basic compound of copper phthalocyanine suppresses the generation of fluorescence derived from the salt-forming compound (A1) while improving the dispersion of the blue pigment. In particular, the significance of the coexistence of the salt-forming compound (A1) and the basic compound of copper phthalocyanine in the blue coloring composition is significant.
Formula (50):
P-Lm
[In general formula (50),
P: organic pigment residue, anthraquinone residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group m: an integer of 1 to 4 is there]
Examples of the dye derivative are described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, or JP-B-5-9469. What is currently used can be used, These can be used individually or in mixture of 2 or more types.

  In the general formula (50), examples of the organic pigment constituting the organic pigment residue of P include the following.

  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; copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine, Phthalocyanine pigments such as metal-free phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigment; dioxazine pigment; perinone pigment; Thioindigo pigments; isoindoline pigments; isoindolinone pigments; selenium pigments; quinophthalone pigments; dioxazine pigments; metal complex pigments.

  Especially, the pigment derivative which has a basic substituent whose L in General formula (50) is a basic substituent can be used preferably.

  By including a dye derivative having a basic substituent, a pigment composition having excellent dispersibility, fluidity, and storage stability can be obtained even in the case of a pigment that is difficult to disperse without a dye derivative having a basic substituent. This is preferable. The pigment can be effectively dispersed by the synergistic effect of the acidic resin type dispersant and the dye derivative having a basic substituent, and a pigment composition having excellent fluidity and storage stability can be obtained.

Among the basic substituents, L is preferably a substituent selected from the group represented by the general formulas (51), (52), and (53).
General formula (51):

Formula (52):

Formula (53):

[In the general formulas (51) to (53),
X _{is, -SO 2 -, - CO -} , - CH 2 -, - CH 2 NHCOCH 2 -, - CH 2 NHSO 2 CH 2 -, or a direct bond,
Y is —NH—, —O—, or a direct bond;
k is an integer of 1 to 10,
Y ¹ is —NH—, —NR ⁵⁸ —Z—NR ⁵⁹ —, or a direct bond;
R ⁵⁸ and R ⁵⁹ are each independently a hydrogen bond, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or A phenyl group which may have a substituent,
Z is an alkylene group which may have a substituent, or an arylene group which may have a substituent,
R ⁵⁰ and R ⁵¹ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 30 carbon atoms, an optionally substituted alkenyl group having 2 to 30 carbon atoms, or R ⁵⁰ and R ⁵¹ together are a heterocyclic ring which may further have a substituent containing a further nitrogen, oxygen or sulfur atom,
R ⁵² , R ⁵³ , R ⁵⁴ , and R ⁵⁵ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms that may have a substituent, or 2 to carbon atoms that may have a substituent. 20 alkenyl group, an arylene group having 6 to 20 carbon atoms which may have a substituent,
R ⁵⁶ is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms,
R ⁵⁷ is a substituent represented by the general formula (51) or a substituent represented by the general formula (52);
Q is a hydroxyl group, an alkoxyl group, a substituent represented by the above general formula (51), or a substituent represented by the above general formula (52). ]

  Examples of the amine component used for forming the substituents represented by the general formulas (51) to (53) include dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethyl. Propylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine , Dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methylocta Silamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylamino Ethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N , N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylamino Nthylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic acid, Isonipecotic acid, Methyl isonipecotate, Isonipecotic acid Ethyl, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoly N-aminopropyl-4-pipecholine, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine Etc.

The dye derivative having a basic substituent of the present invention can be synthesized by various synthetic routes. For example, after introducing a substituent represented by formulas (54) to (57) into an organic dye, the amine component reacts with the substituent to form a substituent represented by formulas (51) to (53), For example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine, or 4- [4-hydroxy-6- [3- (dibutylamino) propylamino] -1,3,5-triazin-2-ylamino It can be obtained by reacting aniline or the like.
Equation (54): -SO ₂ Cl
Formula (55): -COCl
Equation _{(56): -CH 2 NHCOCH 2} Cl
Equation (57): -CH ₂ Cl
During the reaction of the substituents of formulas (54) to (56) with the amine component, some of the substituents of formulas (54) to (57) are hydrolyzed, and chlorine is substituted with a hydroxyl group. It may be. In that case, the formula (54) and the formula (55) are a sulfonic acid group and a carboxylic acid group, respectively, but both may be a free acid, or a 1-3 valent metal or the above monoamine. Or a salt thereof.

  Further, when the organic dye is an azo dye, the substituent represented by the general formulas (51) to (53) is introduced into the diazo component or the coupling component in advance, and then a coupling reaction is performed, thereby performing the azo pigment. Derivatives can also be produced.

  Among the amine compounds of copper phthalocyanine, the substituent represented by the general formula (53) can be synthesized by various synthetic routes. For example, an amine component starting from cyanuric chloride and forming a substituent represented by formulas (51) and (52) on at least one chlorine of cyanuric chloride, such as N, N-dimethylaminopropylamine or N-methyl It is obtained by reacting piperazine or the like and then reacting the remaining chlorine of cyanuric chloride with various amines or alcohols.

  Among the amine compounds of copper phthalocyanine used in the present invention, the most preferred form is a copper phthalocyanine sulfonic acid amide compound.

The copper phthalocyanine sulfonic acid amide compound is a copper phthalocyanine compound having the above basic substituent, wherein X in the general formulas (51) to (53) is —SO ₂ —, —CH ₂ NHSO ₂ CH ₂ —. ,
Y ⁰ is —NH— or a direct bond;
k is an integer of 1 to 10,
Y ¹ is a compound which is —NH— or —NR ⁵⁸ —Z—NR ⁵⁹ —.
[Wherein R ⁵⁸ and R ⁵⁹ are each independently a hydrogen atom, an alkyl group having 1 to 36 carbon atoms, an alkenyl group having 2 to 36 carbon atoms, or a phenyl group, and Z is a group having 1 to 20 alkylene groups, preferably an alkylene group having 1 to 10 carbon atoms, or an arylene group having 1 to 20 carbon atoms, preferably an arylene group having 1 to 10 carbon atoms. Examples include a methylene group, an ethylene group, and propylene. Group and phenylene group. ]

  The amine compound of copper phthalocyanine can be used alone, but two or more kinds may be used in combination. The compounding amount of the copper phthalocyanine amine compound is preferably 0.01 to 200 parts by weight and more preferably 1 to 100 parts by weight with respect to 100 parts by weight of the total amount of the blue pigment.

  Moreover, in the blue coloring composition of this invention, the compounding quantity of the amine compound of copper phthalocyanine is 0.3-1 for the weight ratio (Amine compound of copper phthalocyanine / Salt formation compound (A1)) with a salt formation compound (A1). .5 is preferable.

  A blue coloring composition that can suppress the fluorescence generated from the salt-forming compound (A) while improving the dispersion of the blue pigment by satisfying this range, and as a result, can achieve high brightness and high contrast ratio as a color filter. It can be.

  If it is less than 0.3, the contrast is lowered due to insufficient suppression of fluorescence and dispersibility of the amine compound of copper phthalocyanine, and if it exceeds 1.5, the color characteristics may be affected, resulting in low brightness. The more preferred weight ratio (a copper phthalocyanine amine compound / salt-forming compound (A)) is 0.4 to 1.2, and the most preferred weight ratio (copper phthalocyanine amine compound / salt-forming compound (A1)) is 0.00. 5 to 1.1.

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

  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.

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

  The amount of the resin-type dispersant and the surfactant added 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 caused by an excessive dispersant. May have adverse effects.

<Other additive components>
The colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned.

  The content of 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 content of 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).

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

<Color filter>
Next, the color filter of the present invention will be described. The color filter of this invention comprises the filter segment formed with the 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.

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

<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 filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. 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 the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. 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 UV exposure sensitivity, after applying 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, etc. in addition to the above method, but the colored composition 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.

  The colored composition of the present invention can be used in any of the methods described above, but is most suitable for the photolithography method.

  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. On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

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

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

  Moreover, the polymerization average molecular weight (Mw) of the resin, the acid value of the resin, the ammonium salt value of the resin, the amine value of the resin, the specific surface area of the pigment, and the average primary particle diameter of the pigment are as follows.

<Resin polymerization average molecular weight (Mw)>
It is a weight average molecular weight (Mw) in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and using GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector using THF as a developing solvent.

<Resin acid value>
It is the acid value (mgKOH / g) measured according to the potentiometric titration method of JIS K 0070.

<Ammonium salt value of resin>
This is a value converted to an equivalent of potassium hydroxide after titration with a 0.1N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as an indicator, and indicates the ammonium salt value of the solid content.

<Amine number of resin>
After obtaining by a potentiometric titration method using a 0.1N hydrochloric acid aqueous solution, it was converted to an equivalent of potassium hydroxide.

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

<Average primary particle diameter of pigment>
Measurement was performed by directly measuring the size of primary particles from an electron micrograph. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size. The electron microscope used was a transmission type (TEM).

  Subsequently, the binder resin (B) used in the examples and comparative examples, the refined pigment, the resin (a1) having a cationic group in the side chain, the salt-forming compound, the polyfunctional monomer (C1) having an acid group, The production method of the pigment dispersion and the salt-forming compound solution will be described.

<Method for producing binder resin (B)>
(Method for producing alkali-soluble photosensitive resin (B1))
[Binder resin solution (B1-1)]
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. A mixture of 5.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was dropped over 2.5 hours from the dropping tube at a temperature to polymerize. Reaction was performed.
Next, the inside of the flask was purged with air, and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added to 17.0 parts of acrylic acid, and the reaction was continued at 120 ° C. for 5 hours. The reaction was terminated when the value reached 0.8, and a resin solution having a weight average molecular weight of about 12000 (measured by GPC) was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours. Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40%, and a binder resin solution (B1-1 )

[Binder resin solution (B1-2)]
The binder resin solution (B1-2) is synthesized by the same method as the binder resin solution (B1-1) except that dicyclopentanyl methacrylate in the binder resin solution (B1-1) is changed to dicyclopentenyl methacrylate. Got. The weight average molecular weight was 12500.

[Binder resin solution (B1-3)]
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of propylene glycol monomethyl ether acetate, heated to 80 ° C., and the flask was purged with nitrogen, and then dropped. From the tube, 18 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyro A mixture of 2.0 parts of nitrile was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container was replaced with air, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (equivalent of glycidyl group), and 6 parts at 120 ° C. The reaction was continued for a while, and the reaction was terminated when the acid value of the solid content reached 0.5 to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (equivalent of generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
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 obtain a binder resin solution (B1-3). The weight average molecular weight (Mw) was 19000.

(Method for producing alkali-soluble non-photosensitive resin solution)
[Binder resin solution (B2-1)]
70.0 parts of propylene glycol monomethyl ether acetate was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer, the temperature was raised to 80 ° C., and the inside of the reaction vessel was purged with nitrogen After that, 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) ) A mixture of 7.4 parts and 0.4 part of 2,2′-azobisisobutyronitrile 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 solid content of 30% by weight and a weight average molecular weight of 26000.
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 obtain a binder resin solution (B2-1).

<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.

[Purple refined pigment (P-2)]
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 put 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 purple refinement | purification pigment (P-2). The average primary particle diameter of the obtained pigment was 26.4 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 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 115 parts of red refined pigment (P-3). The average primary particle diameter of the obtained pigment was 24.8 nm.

[Yellow fine pigment (P-4)]
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 refined pigments (P-4). The average primary particle diameter of the obtained pigment was 39.2 nm.

[Green refined pigment (P-5)]
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-5). The average primary particle diameter of the obtained pigment was 32.6 nm.

<Method for Producing Resin (a1) Having Cationic Group in Side Chain>
[Resin having a cationic group in the side chain (a1-1)]
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 methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) ) And 25.1 parts of methyl ethyl ketone were made uniform, charged 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 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, resin (a1-1) which has a cationic group in the side chain whose resin component is 47% by weight was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

[Resin having a cationic group in a side chain (a1-2)]
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, 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-dimethylvaleronitrile 5.7) and 15.6 parts of methyl ethyl ketone were made uniform, 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 resin (a1-2) having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 45 mgKOH / g.

[Resin having a cationic group in the side chain (a1-3)]
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 (2,4-dimethyl) 6.7 parts of valeronitrile) 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, resin (a1-3) which has a cationic group in the side chain whose resin component is 50% by weight was obtained. The ammonium salt value of the obtained resin was 60 mgKOH / g.

[Resin having a cationic group in the side chain (a1-4)]
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, 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), 20.0 parts of N-vinylpyrrolidone, After homogenizing 4.7 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 15.6 parts of isopropyl alcohol, the mixture was charged into a dropping funnel and attached to a four-necked separable flask for 2 hours. It was dripped over. 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 resin (a1-4) having a cationic group in the side chain of 44% by weight of the resin component. The ammonium salt value of the obtained resin was 92 mgKOH / g.

[Resin having a cationic group in side chain (a1-5)]
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, Kayamer PM-21 (manufactured by Nippon Kayaku Co., Ltd., 1 mol of ε-caprolaclone 1-hydroxyethyl methacrylate phosphate 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, and then a dropping funnel Was 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, resin (a1-5) having a cationic group in the side chain of 48% by weight of the resin component was obtained. The amine salt value of the obtained resin was 49 mgKOH / 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 a resin (a1-1) having a cationic group in the side chain was produced.
The resin (a1-1) having a cationic group in the side chain of 51 parts is added to 2000 parts of water, 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 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 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) between Acid Red 289 and a resin (a1-1) having a cationic group in the side chain 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) consisting of Acid Red 289 and a resin (a1-2) having a cationic group in the side chain was produced.
88 parts of the resin (a1-2) having a cationic group 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 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, and 43 parts of C.I. I. A salt-forming compound (A1-2) of Acid Red 289 and a resin having a cationic group (a1-2) 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 a resin (a1-3) having a cationic group in the side chain was produced.
Add 46.7 parts of a resin (a1-3) having a cationic group in the side chain to 2000 parts of a 10% aqueous N, N-dimethylformamide solution, thoroughly stir and mix, and then heat 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 the resulting solution is dropped little by little into the resin (a1-3) solution having a cationic group in the side chain. 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) between Acid Red 289 and a resin (a1-3) having a cationic group in the side chain 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 a resin (a1-4) having a cationic group in the side chain was produced.
A solution in which 20.0 parts of the cationic group-containing resin (a1-4) is dissolved 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 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 (A1-4) of Acid Red 289 and a resin having a cationic group (a1-4) 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) consisting of Acid Red 289 and a resin (a1-5) having a cationic group in the side chain was produced.
The resin (a1-5) having a cationic group in the side chain was added to 2000 parts of 20% acetic acid in 63.2 parts of the side chain, sufficiently stirred and mixed, and then heated to 60 ° C. Ammonium chloride of tertiary amino group is performed. 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) between Acid Red 289 and a resin (a1-5) having a cationic group in the side chain 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. Acid Blue 112 and a resin having a cationic group in the side chain (a
A salt-forming compound (A1-6) consisting of 1-1) was produced.
88 parts of a resin (a1-1) having a cationic group in the side chain is added to 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 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, and 43 parts of C.I. I. A salt-forming compound (A1-6) of Acid Blue 112 and a resin (a1-1) having a cationic group in the side chain 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 Blue 112 was 22% by weight.

[Salt-forming compound (A1-7)]
In the following procedure, C.I. I. Acid Blue 93 and a resin having a cationic group in the side chain (a1
-1) and a salt-forming compound (A1-7).
Add 46.7 parts of the resin (a1-1) having a cationic group in the side chain to 2000 parts of an aqueous 10% N, N-dimethylformamide solution, thoroughly stir and mix, and then heat to 70 ° C. . On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Blue 93 is dissolved is prepared and added dropwise little by little to the previous 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 (A1-7) between Acid Red 93 and a resin (a1-1) having a cationic group in the side chain was obtained. At this time, C.I. in the salt-forming compound (A-3). I. The content of the effective pigment component derived from Acid Blue 93 was 30% by weight.

[Salt-forming compound (A1-8)]
In the following procedure, C.I. I. A salt-forming compound (A1-8) comprising Acid Red 249 and a resin (a1-1) having a cationic group in the side chain was produced.
The resin (a1-1) having a cationic group in the side chain of 63.2 parts was added to 2000 parts of 20% acetic acid, and after sufficiently stirring and mixing, the mixture was heated to 60 ° C. Perform group ammonium chloride. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which Acid Red 249 is dissolved is prepared, and the solution is gradually added dropwise 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. Acid Red 2
A salt-forming compound (A1-8) of 49 and a resin (a1-1) having a cationic group 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 Red 249 was 23% by weight.

[Salt-forming compound (A1-9)]
In the following procedure, C.I. I. Acid Yellow 5 and a salt-forming compound (A1-9) composed of a resin (a1-1) having a cationic group in the side chain was prepared.
The resin (a1-1) having a cationic group in the side chain of 51 parts is added to 2000 parts of water, sufficiently stirred and mixed, and then 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 side chains are cations. A salt-forming compound (A1-9) with a resin (a1-1) having a functional group was obtained. At this time, C.I. in the salt-forming compound (A1-9). The content of the effective pigment component derived from I. Acid Yellow 5 was 33% by weight.

[Salt-forming compound (A1-10)]
In the following procedure, C.I. I. A salt-forming compound (A1-10) composed of Direct Blue 86 and Disperbyk-2000 (manufactured by Big Chemie Japan, modified acrylic block copolymer, ammonium salt value 61 mgKOH / g) was produced.
Add 50.9 parts Disperbyk-2000 to 2000 parts water, stir and mix thoroughly, and then heat to 60 ° C. On the other hand, 10 parts of C.I. in 90 parts of water. I. An aqueous solution in which direct blue 86 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 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 31 parts of C.I. I. A salt-forming compound (A1-10) between Direct Blue 86 and Disperbyk-2000 was obtained. At this time, C.I. in the salt-forming compound (A1-10). I. The content of the effective pigment component derived from Direct Blue 86 was 33% 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. At this time, C.I. I. The content of the effective pigment component derived from Acid Red 289 was 42% by weight.

<Method for Producing Polyfunctional Monomer (C1) Having Acid Group>
[Polyfunctional monomer having acid group (C1-1)]
In a 1 L four-necked flask, 578 g of dipentaerythritol hexaacrylate, 20 g of mercaptoacetic acid, 0.5 g of N, N-dimethylbenzylamine, and 0.6 g of 4-methoxyphenol are charged at a temperature of 50 to 60 ° C. The reaction was performed for 6 hours to obtain a polyfunctional monomer having an acid group. This acid value was 20, and the content of the polyfunctional monomer having an acid group was 25% in terms of area by gel permeation chromatography. Moreover, the acid value of the polyfunctional monomer (C1-1) was 20 KOH-mg / g.

[Polyfunctional monomer having acid group (C1-2)]
In a 1 L four-necked flask, 515 g of dipentaerythritol hexaacrylate, 50 g of tetrahydrophthalic anhydride, and 0.5 g of N, N-dimethylbenzylamine are charged and reacted at a temperature of 80 to 100 ° C. for 10 hours. The polyfunctional monomer C containing the polyfunctional monomer which has a group was obtained. The acid value was 38, and the content of the polyfunctional monomer having an acid group by gel permeation chromatography was 40% in terms of area. The acid value of the polyfunctional monomer (C1- 2) was 38KOH-mg / g.

<Method for producing pigment dispersion>
[Blue pigment dispersion (Q-B)]
The mixture having the composition shown below was uniformly stirred and mixed, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 1 mm, and then with a 5 μm filter. Filtration gave a blue pigment dispersion (Q-B).

Blue refined pigment (P-1): 18.0 parts Copper phthalocyanine derivative: 2.0 parts
Resin type pigment dispersant: 8.0 parts (BYK-111 manufactured by BYK Japan)
Binder resin solution (B1-1): 60.0 parts cyclohexanone: 12.0 parts

[Purple pigment dispersion (Q-V)]
A purple pigment dispersion (QV) was obtained in the same manner as the blue pigment dispersion (QB) using a mixture having the following composition.

Purple refined pigment (P-2): 20.0 parts Resin-type pigment dispersant: 8.0 parts (BYK-111 manufactured by Big Chemie Japan)
Binder resin solution (B1-1): 60.0 parts cyclohexanone: 12.0 parts

[Red pigment dispersion (QR)]
A red pigment dispersion (QR) was obtained in the same manner as the blue pigment dispersion (QB) using a mixture having the following composition.

Red refined pigment (P-3): 10.0 parts anthraquinone pigment (CI Pigment Red 177): 2.0 parts ("Chromophthal Red A2B" manufactured by Ciba Japan)
Yellow refined pigment (P-4): 4.0 parts Diketopyrrolopyrrole pigment derivative: 4.0 parts
Resin-type pigment dispersant: 8.0 parts (“Solsperse 20000” manufactured by Nippon Lubrizol)
Binder resin solution (B1-1): 60.0 parts cyclohexanone: 12.0 parts

[Green pigment dispersion (QG)]
A green pigment dispersion (QG) was obtained in the same manner as the blue pigment dispersion (QB) using a mixture having the following composition.

Green refined pigment (P-5): 13.5 parts Yellow refined pigment (P-4): 6.5 parts Resin-type pigment dispersant: 8.0 parts ("EFKA4300" manufactured by Ciba Japan)
Binder resin solution (B1-1): 60.0 parts cyclohexanone: 12.0 parts

<Method for producing salt-forming compound solution>
[Salt-forming compound solution (Z-1)]
The following mixture was stirred and mixed with a disper so as to be uniform, and then filtered through a 5.0 μm filter to obtain a salt-forming compound solution (Z-1).

Salt-forming compound (A1-1): 10.0 parts propylene glycol monomethyl ether acetate (PGMEA): 90.0 parts

[Salt-forming compound solution (Z-2 to 11)]
Hereinafter, salt-forming compound solutions (Z-2 to 11) were prepared in the same manner as the salt-forming compound solution (Z-1) except that the salt-forming compounds shown in Table 1 were changed.
The content of the pigment component at this time is also shown in Table 2.
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 salt-forming compound solution. Is expressed.

[Example 1]
(Photosensitive coloring composition (resist material R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered and mixed with a 5.0 μm filter to obtain a photosensitive coloring composition (resist material R-1).

Salt-forming compound solution (Z-1): 30.0 parts Binder resin solution (B1-1): 22.8 parts Binder resin solution (B2-1): 5.7 parts Monomer (C1-1): 4.5 Part photopolymerization initiator (G-1): 1.6 parts Sensitizer (H-1): 0.2 parts Propylene glycol monomethyl ether acetate (PGMEA): 35.2 parts Leveling agent (M-1): 0 .005 copies

[Examples 2-34, Comparative Examples 1-4]
(Photosensitive coloring composition (resist materials R-2 to 34, 36 to 39))
Table 2-4 salt-forming compound solution, pigment dispersion, binder resin solution, monomer (C), photopolymerization initiator, sensitizer, polyfunctional thiol, storage stabilizer, ultraviolet absorber, polymerization inhibitor, leveling Photosensitive coloring compositions (resist materials R-2 to 34, 36 to 39) were obtained in the same manner as the photosensitive coloring composition (resist material R-1) except that the type and amount of the agent were changed. .

[Example 35]
(Photosensitive coloring composition (resist material R-35))
Photosensitive coloring in the same manner as the photosensitive coloring composition (resist material R-6) except that 35.2 parts of propylene glycol monomethyl ether acetate (PGMEA) as a solvent to be added were all changed to cyclohexanone to give a total of 53.2 parts. A composition (resist material R-35) was obtained.

Abbreviations in Tables 2 to 4 are shown below.
<Polyfunctional monomer (C1) having an acid group>
-Polyfunctional monomer having an acid group (C1-3): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and a succinic acid derivative of dipentaerythritol pentaacrylate TO-1382 (manufactured by Toagosei Co., Ltd.) Acid value: 29)
-Polyfunctional monomer having an acid group (C1-4): a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate and a succinic acid derivative of dipentaerythritol pentaacrylate TO-2349 (manufactured by Toagosei Co., Ltd.) Acid value: 68)
<Polyfunctional monomer having no acid group>
Polyfunctional monomer having no acid group (C2-1): Dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
Polyfunctional monomer having no acid group (C2-2): trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)

<Photopolymerization initiator (G)>
Photopolymerization initiator (G-1): 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (Ciba Japan) “Irgacure 379”)
Photopolymerization initiator (G-2): 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (“Irgacure 907” manufactured by Ciba Japan)
Photopolymerization initiator (G-3): ethane-1-one, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl], 1- (O-acetyloxime)
("Irgacure OXE02" manufactured by Ciba Japan)
<Sensitizer (H)>
Sensitizer (H-1): 2,4-diethylthioxanthone (“Kayacure DETX-S” manufactured by Nippon Kayaku Co., Ltd.)
Sensitizer (H-2): 4,4′-bis (diethylamino) benzophenone (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.)

<Multifunctional thiol>
Polyfunctional thiol (I-1): trimethylol ethane tris (3-mercaptobutyrate)
("TEMB" manufactured by Showa Denko KK)
Polyfunctional thiol (I-2): trimethylolpropane tri (3-mercaptobutyrate)
("TPMB" manufactured by Showa Denko KK)
<Storage stabilizer>
Storage stabilizer (J-1): 2,6-bis (1,1-dimethylethyl) -4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
-Storage stabilizer (J-2): Triphenylphosphine ("TPP" manufactured by Hokuko Chemical Co., Ltd.)
<Ultraviolet absorber>
UV absorber (K-1): 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4- Dimethylphenyl) -1,3,5-triazine (“TINUVIN400” manufactured by Ciba Japan)
Ultraviolet absorber (K-2): 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol (“TINUVIN900” manufactured by Ciba Japan)

<Polymerization inhibitor>
Polymerization inhibitor (L-1): N-nitrosophenylhydroxylamine aluminum salt (“Q-1301” manufactured by Wako Pure Chemical Industries, Ltd.)
Polymerization inhibitor (L-2): Methylhydroquinone (“MH” manufactured by Seiko Chemical Co., Ltd.)
<Leveling agent>
Leveling agent (M-1): Dimethylsiloxane (“BYK-333” manufactured by Big Chemie)
Leveling agent (M-2): Dimethylsiloxane (“FZ-2” manufactured by Toray Dow Corning)

<Evaluation of coloring composition>
About the obtained photosensitive coloring composition (resist material R-1 to 39), the test regarding storage stability and a coating-film foreign material was done with the following method. The test results are shown in Table 5. In the evaluation results, ◎ is a very good level, ◯ is a good level, Δ is a level that does not interfere with use, and x is a level that is not preferable for use.

(Storage stability test method)
The viscosity at 25 ° C. of the produced colored composition was measured at a rotation speed of 20 rpm using an E-type viscometer (TUE-20L type manufactured by Toki Sangyo Co., Ltd.). The viscosity change rate was calculated from the initial viscosity on the day of preparation of the colored composition and the accelerated aging 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 with time) = | [(initial viscosity) − (viscosity with 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)
A test substrate was prepared from the colored composition immediately after preparation and evaluated by counting the number of particles. First, a resist material was applied on a 100 mm × 100 mm, 1.1 mm transparent glass substrate with a spin coater so that the film thickness after drying was about 2.0 μm, dried at 70 ° C. for 20 minutes, and then a width of 100 μm. UV exposure is performed with an integrated light quantity of 150 mJ / cm ² using a super high pressure mercury lamp through a photomask having a stripe-shaped opening, and the unexposed area is washed away with a 0.05% aqueous potassium hydroxide solution containing a surfactant. Development was performed, and the plate was placed 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 to obtain a test substrate. Then, surface observation was performed 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 visual fields by transmission was counted and evaluated according to the following criteria. did. 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 Δ: 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 obtained photosensitive coloring composition was spin-coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate at a rotation speed of 2.0 μm after drying, and dried at 70 ° C. for 20 minutes. UV exposure is performed with an integrated light quantity of 150 mJ / cm ² using a super high pressure mercury lamp through a photomask having a stripe-shaped opening having a width of 100 μm, and the unexposed area is washed away with a 5% sodium carbonate aqueous solution, and then developed. The obtained 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 residue

  The colorant (A) contains a salt-forming compound (A1) obtained by reacting a resin (a1) having a cationic group in the side chain with an anionic dye (a2), and the monomer (C) The coloring composition for a color filter of the present invention containing the polyfunctional monomer (C1) having an acid group is excellent in storage stability, has few coating film foreign matters, has good glass adhesion, and has no development residue. The color filter was in a range that can be preferably used.

  By reacting a resin (a1) having a cationic group in the side chain with an anionic dye (a2), which is a colorant used in these photosensitive coloring compositions (resist materials R-1 to 35). It is considered that the obtained salt-forming compound has extremely good compatibility with the components constituting other resists, and thus the resist material exhibits stable coating liquid characteristics. Thus, it is considered that the storage stability of the resist material can be obtained, and as a result, no coating film foreign matter is generated mainly due to aggregation of coloring components and the like.

  In these photosensitive coloring compositions (resist materials R-1 to 35), a salt-forming compound obtained by reacting a resin having a cationic group in the side chain with an anionic dye (a2) is used as a colorant. In addition, the development characteristics are extremely good by using a polyfunctional monomer having an acid group as a resist material composition, and the pattern peeling from the glass substrate during the development and chipping of the pattern edge are not possible. Is suppressed.

  Further, it is considered that the use of the above-mentioned polyfunctional monomer having an acid group improves the solubility of the resist material coating film in the developer and greatly reduces the residue in the unexposed areas.

  On the other hand, the photosensitive coloring composition of Comparative Example 1 (resist material R-36) was poor in stability and the viscosity of the composition was significantly increased. Moreover, the generation | occurrence | production of the foreign material on a coating film was very much. Moreover, there were many development residues and it did not reach the grade which can be used as a color filter.

  This is because the coloring component used in the resist material is not a salt-forming compound obtained by reacting a resin having a cationic group in the side chain with an anionic dye (a2), but a component constituting the resist material. Therefore, it can be judged that the color components are agglomerated and various properties are inferior.

  The photosensitive coloring compositions of Comparative Examples 2 and 3 (resist materials R-37 and 38) had good stability and generation of coating film foreign matter, but had problems with development residues. From this, it can be seen that the inclusion of the polyfunctional monomer (C1) having an acid group as the monomer enables the colored composition to reduce residues during development and to provide an excellent color filter.

  The resist material (R-38) of Comparative Example 4 does not contain a salt-forming compound obtained by reacting a resin having a cationic group in the side chain with an anionic dye (a2), and has a polyfunctionality having an acid group As a result, the various properties were greatly inferior.

<Manufacture of color filters>
The total amount of 21.0 parts of the salt-forming compound solution (Z-1) and the blue pigment dispersion (QB) in the resist material R-6 is changed to the red pigment dispersion (QR) in the case of the red resist material. In the material, except that the green pigment dispersion (QG) was replaced, the salt-forming compound solution (Z-1) and the blue pigment dispersion (Q-B) of the resist material R-6 were replaced with the respective color pigment dispersions, A red colored composition for a color filter and a green colored composition for a color filter were obtained.

The red coloring composition was applied on a 100 mm × 100 mm glass substrate with a die coater to a thickness of about 2 μm, and the solvent was removed and dried in an oven at 70 ° C. for 20 minutes. Subsequently, stripe pattern exposure was performed with ultraviolet rays using an exposure apparatus. The exposure amount was 100 mJ / cm ² . Furthermore, after spray development with a developer composed of an aqueous sodium carbonate solution to remove unexposed portions, the substrate is washed with ion-exchanged water, and this substrate is heated at 230 ° C. for 30 minutes to form a red filter segment having a line width of about 50 μm. did. Next, in the same manner, a green filter segment is formed using the green coloring composition next to the red filter segment, and then a blue filter segment is formed using the resist material R-6. Three color filters are formed on the same glass substrate. A color filter having segments was obtained.

  When the coloring composition for a color filter in the present invention is used, a color filter having a filter segment having excellent color characteristics and excellent heat resistance in a wide chromaticity range can be produced.

Claims (5)

A color filter coloring composition comprising a colorant (A), a binder resin (B), a monomer (C), and an organic solvent (D),
The colorant (A) contains a salt-forming compound (A1) obtained by reacting a resin (a1) having a cationic group in the side chain with an anionic dye (a2), and
When the resin (a1) having a cationic group in the side chain is 100% by weight of the total structural units contained in the resin (a1), the structural unit represented by the following general formula (1) is 10 to 50. It is a vinyl resin containing
The coloring composition for a color filter, wherein the monomer (C) contains a polyfunctional monomer (C1) having an acid group.
General formula (1):
[In General Formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂ to R ₄ 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 ₂ to R ₄ Two of them may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₅ —, —COO—R ₅ —, and R ₅ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ] The coloring composition for a color filter according to claim 1, wherein the acid group of the polyfunctional monomer (C1) having an acid group is a carboxylic acid. Furthermore, a photoinitiator (G) is contained, The coloring composition for color filters of Claim 1 or 2 characterized by the above-mentioned. The colored composition for a color filter according to any one of claims 1 to 3 , wherein the binder resin (B) contains an alkali-soluble photosensitive resin (B1). A color filter comprising a filter segment formed on the substrate by the color filter coloring composition according to any one of claims 1 to 4 .