JP6645335B2 - Coloring composition for color filter, and color filter - Google Patents

Description

The present invention relates to a color 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 have been rapidly spreading to television applications. For TV applications, it is required to further improve the performance such as brightness and contrast, and it is desired that color filters, which are components of a color liquid crystal display device, further improve transmittance and enhance contrast. ing.

As a method of manufacturing a color filter, after forming a pattern with a photoresist, a dyeing method for dyeing the pattern, or forming a transparent electrode of a predetermined pattern in advance, and applying a pigment-containing resin dissolved and dispersed in a solvent by applying a voltage. Electrodeposition method for patterning by ionization, printing method such as offset printing using ink containing thermosetting resin or ultraviolet curing resin, pigment dispersion using color resist agent in which colorant such as pigment is dispersed in photoresist material The pigment dispersion method has recently 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 and the like, and as a result, lowers the 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 use of a dye-based curable composition using a dye that can exist in a state of being dissolved in a medium of the curable composition as a coloring agent has been studied and proposed (for example, Patent Reference 1). However, dyes used for color resist agents have problems of heat resistance, light resistance, and solubility in resins and organic solvents used in resins.

Therefore, in order to increase solubility, color filters using a salt of an anionic dye and a cationic surfactant as a colorant have been proposed (for example, see Patent Documents 2 and 3). 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 a salt of an organic amine. In the above colorant, the solubility of the anionic dye in an organic solvent is increased by changing the sodium sulfonate group of the anionic dye into a base salt of the cationic surfactant. However, these methods cannot provide sufficient solubility in a solvent used for producing a color filter and have poor compatibility with a resin. It is difficult to provide strong adhesion between the film and a transparent substrate such as glass, and at the same time, it is not possible to solve important problems in color filters such as solvent resistance and alkali developability of the coating film. Was.

As salt forming compounds of anionic dyes, those using a cationic resin as a counter have been studied as crystalline water-based coloring materials (for example, see Patent Document 4). However, no detailed study has been made for color filter applications which require use in a dissolved state.

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 been proposed (for example, see 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, in the method disclosed herein, since the copolymer and the anionic dye are mixed in an organic solvent, there is a problem that a highly polar dye is not sufficiently dissolved, and foreign matter is generated.

On the other hand, in order to improve heat resistance and light resistance, a coloring composition in which a dye is chemically bonded to a polymer has been proposed (for example, see Patent Document 6). However, simply combining a polymer and a dye has insufficient solvent resistance and resistance, and has not been able to satisfy the recent required level of alkali developability.

JP-A-1994-75375 JP-A-1993-333207 JP 2004-307391 A JP 2005-350648 A JP 2000-352819 A JP 2000-162429 A JP 2011-242752 A JP 2013-33194 A

An object of the present invention is to provide a color composition for a color filter having excellent storage stability, and no generation of foreign matter in a coating film, having strong adhesion to a transparent substrate such as glass, heat resistance, An object of the present invention is to provide a color filter having high solvent resistance and excellent alkali solubility.

The present inventors have conducted intensive studies to solve the above problems, and as a result, an A block having a cationic group in the side chain and a B block having no heat-crosslinkable functional group without a cationic group. The coloring composition for a color filter containing a salt-forming compound (D) of an acrylic resin (B) and an anionic dye (C), which is a block resin comprising, has high storage stability; It has been found that there is no generation of foreign matter in the coating film, the adhesiveness is excellent, and high heat resistance is exhibited in a heat resistance test, and the present invention has been made based on this finding.
The use of a block resin for a salt forming dye is disclosed in JP-A-2011-242752, and a high-tg, salt-forming dye using a crosslinkable resin is exemplified in JP-A-2013-33194. .

That is, the present invention relates to a coloring composition for a color filter comprising at least a coloring agent (A), a binder resin, and an organic solvent,
The colorant (A) contains a salt-forming compound (D) of a resin (B) having a cationic group in a side chain and an anionic dye (C),
The resin (B) having a cationic group in the side chain is an acrylic resin containing a structural unit represented by the following general formula (1), wherein the acrylic resin is
A color filter characterized by being a block resin comprising an A block having a cationic group represented by the following general formula (1) and a B block having no cationic group and having a thermally crosslinkable functional group. It relates to a coloring composition.
(In the 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, Represents an optionally substituted alkenyl group or an optionally substituted aryl group, and _two of R _{2 to} R ₄ may combine with each other to form a ring, and Q represents an alkylene group, an arylene group, —CONH —R ₅ —, —COO—R ₅ —, R ₅ represents an alkylene group, and Y ⁻ represents an inorganic or organic anion.)

Further, the present invention relates to the coloring composition for a color filter, wherein the thermally crosslinkable functional group is at least one selected from the group consisting of a hydroxyl group and a carboxyl group.

Further, in the present invention, the block resin having a cationic group is an acrylic resin containing a structural unit represented by the general formula (1), and further, the structural unit represented by the general formula (1) is a resin composition. A block resin containing 3 to 90% by weight of the total of 100% by weight of the coloring composition for a color filter.

Further, the present invention relates to the coloring composition for a color filter, wherein the ammonium salt value of the acrylic resin containing the structural unit represented by the general formula (1) is 10 to 200 mgKOH / g.

Further, the present invention relates to the coloring composition for a color filter as described above, wherein the organic solvent contains propylene glycol monomethyl ether acetate as a main component.

Further, the present invention relates to the coloring composition for a color filter, wherein the coloring agent further contains a pigment.

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

General formula (2)

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

Furthermore, the present invention relates to the coloring composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

Further, the present invention relates to a method of mixing a resin (B) having a cationic group in a side chain and an anionic dye (C) in an aqueous solution to form a counter anion of the resin (B) having a cationic group in a side chain and an anionic dye. The method for producing a coloring composition for a color filter according to any one of claims 1 to 7, wherein a salt comprising a counter cation of the dye (C) is removed to obtain a salt forming compound (D).

Further, the present invention relates to a color filter formed by using the coloring composition for a color filter.

In the present invention, a block resin having a cationic group in the side chain, that is, a block resin including an A block having a cationic group and a B block having no cationic group and having a thermally crosslinkable functional group, The use of a coloring composition for a color filter containing a salt forming compound (D) of an acrylic resin (B) and an anionic dye (C) makes it possible to have high storage stability, It is possible to obtain a color filter which has no occurrence, has excellent adhesion, shows higher heat resistance and solvent resistance, and shows excellent alkali development.

Hereinafter, the present invention will be described in detail.
The color composition for a color filter of the present invention has a heat-crosslinkable functional group without having an A block having a cationic group in a side chain and a cationic group in a colorant carrier containing a binder resin and an organic solvent. A coloring composition for a color filter, comprising a salt-forming compound (D) of a resin (B) having a feature of being a block resin comprising a B block and an anionic dye (C).
First, the resin (B), which is a block resin composed of an A block having a cationic group in a side chain and a B block having no cationic group and having a thermally crosslinkable functional group, will be described.

<Resin having cationic group in side chain (B)>
The resin (B) having a cationic group in the side chain according to the present invention is a block resin comprising an A block having a cationic group in the side chain and a B block having no cationic group and having a thermally crosslinkable functional group. It is characterized by being.
When the cationic group forms a salt with the anionic group of the anionic dye (C), the salt forming compound (D) of the present invention can be obtained.

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

(In the 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, Represents an optionally substituted alkenyl group or an optionally substituted aryl group, and _two of R _{2 to} R ₄ may combine with each other to form a ring, and Q represents an alkylene group, an arylene group, —CONH _{-R 5 -, - COO-R} 5 - represents, .Y R ₅ is representative of the alkylene group ^- represents an inorganic or organic anion).

In the general formula (1), R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. Examples of the alkyl group 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 the alkyl group, an alkyl group having 1 to 12 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and an alkyl group having 1 to 4 carbon atoms is particularly preferable.

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

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

In the general formula (1), 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. No.

Here, as the alkyl group for 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-dodecyl) -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.). The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms.

Examples of the alkenyl group for R _{2 to} R ₄ include a linear or branched alkenyl group (vinyl, allyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1 -Propenyl, 1-methyl-2-propenyl, 2-methyl-1-propenyl and 2-methyl-2-propenyl and the like, and cycloalkenyl groups (such as 2-cyclohexenyl and 3-cyclohexenyl). The alkenyl group is preferably an alkenyl group having 2 to 18 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms.

Examples of the aryl group for R _{2 to} R ₄ include a monocyclic aryl group (such as phenyl), a condensed polycyclic aryl group (such as naphthyl, anthracenyl, phenanthrenyl, anthraquinolyl, fluorenyl, and naphthoquinolyl) and an aromatic heterocyclic hydrocarbon. Groups (thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxanthenyl (xanthone Derived groups) and 9-oxothioxanthenyl (a group 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, And a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. As the substituent, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

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

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

In the general formula (1), component of the Q connecting the acrylic sites and ammonium base is an alkylene group, an arylene _{group, -CONH-R 5 -, -} COO-R 5 - represents, but R ₅ represents an alkylene group, Among them, the polymerizable, for reasons of _{availability, -CONH-R 5 -, -} COO-R 5 - is preferably. Further, R ₅ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

Y in the general formula (1) which constitutes a counter anion of the resin ^- components may be any anion of an inorganic or organic. As the counter anion, known ones can be adopted without limitation, and specifically, hydroxide ion; halogen ion such as chloride ion, bromide ion and iodide ion; carboxylate ion such as formate ion and acetate ion; Such as carbonate, bicarbonate, nitrate, sulfate, sulfite, chromate, dichromate, phosphate, cyanide, permanganate, and even hexacyanoferrate (III) ions Complex ions and the like. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferred, and halogen ions are most preferred. When the counter anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded in the resin to form an inner salt.

In order to obtain an acrylic resin containing a structural unit represented by the general formula (1), not only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium group as a monomer component but also an amino resin having an amino group After obtaining an acrylic resin having an amino group obtained by copolymerizing an ethylenically unsaturated monomer as a monomer component, it may be obtained by a method of reacting with an onium chloride and ammonium chloride.

Hereinafter, specific examples of the ethylenically unsaturated monomer having an ammonium group, the ethylenically unsaturated monomer having an amino group, and an onium chlorinating agent will be shown. In addition, in this specification, when either or both of “acryl and methacryl” are indicated, “(meth) acryl” may be described. Similarly, when any or both of “acryloyl and methacryloyl” are indicated, they may be described as “(meth) acryloyl”.

Examples of the ethylenically unsaturated monomer having an ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyl Alkyl (meth) acrylate-based quaternary ammonium salts such as oxyethylmethylmorpholinoammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride (Meth) acryloylamide quaternary ammonium salts such as Allyl ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

Examples of the ethylenically unsaturated monomer having an amino group include, for example, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, dibutylamino Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl (Meth) acrylic acid ester having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide; styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene; diallylmethylamine; diallylamine And amino-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

Examples of the onium chlorinating agent include, for example, alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonates such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or Examples include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl clobromide, and benzyl chloride or benzyl bromide.

The reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent is usually carried out by dropping an onium chlorinating agent in an equimolar amount or less with respect to the amino group into the ethylenically unsaturated monomer solution having the amino group. You can do this by doing The temperature during the ammonium salification reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium salified, the temperature is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

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

ZR ⁶ —COOR ⁷ General formula (3)

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

The reaction between an ethylenically unsaturated monomer having an amino group and an alkoxycarbonylalkyl halide is carried out by reacting an alkoxycarbonylalkyl halide in an equimolar amount or less with respect to the amino group in the same manner as the above onium chloride, and then -COOR ⁷ is added. It is obtained by hydrolysis and conversion to carboxylate ion (—COO ⁻ ). Thereby, an ethylenically unsaturated monomer having a carboxybetaine structure represented by the general formula (3) and having an ammonium base can be obtained.

[B block having a thermally crosslinkable functional group]
The B block of the present invention is characterized by containing a thermally crosslinkable functional group.

(Crosslinkable functional group)
The acrylic resin having a thermally crosslinked functional group of the present invention forms a crosslink between acrylic resins having a thermally crosslinked functional group or with a binder resin in a heating step in the production of a color filter. As a result, a strong film is formed, and the color change of the film can be prevented, that is, the heat resistance can be improved, and the solvent resistance can be improved.

The preferred structure of the heat-crosslinkable functional group is not particularly limited, and examples thereof include a hydroxyl group, a carboxyl group, a carboxylic anhydride, a primary or secondary amino group, an imino group, an oxetanyl group, a t-butyl group, Group, mercapto group, isocyanate group, allyl group, (meth) acryl group and the like.
Among them, a hydroxyl group, a carboxyl group, an oxetanyl group, a t-butyl group, an isocyanate group, and a (meth) acryl group are preferable from the viewpoint of storage stability and reactivity with other materials in the application of the coloring composition for a color filter. In particular, it is preferable to have a hydroxyl group.
Further, from the viewpoint of alkali developability, it preferably has a carboxyl group.

One method of introducing a thermally crosslinkable functional group into the B block in the resin (B) having a cationic group in the side chain used in the present invention is to prepare an ethylenically unsaturated monomer having a thermally crosslinkable functional group. And copolymerization.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include, but are not particularly limited to, for example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, Examples include glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate, and a caprolactone adduct of these monomers (the number of moles to be added is preferably 1 to 5).

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

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

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

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-isocyanate ethyl methacrylate, 2-isocyanate ethyl acrylate, 4-isocyanate butyl methacrylate, and 4-isocyanate butyl acrylate.

The isocyanate group in the present invention includes a blocked isocyanate group, and can be preferably used. A blocked isocyanate group means that, under normal conditions, the reactivity of the isocyanate group is suppressed by protecting the isocyanate group with another functional group, and the active isocyanate group can be regenerated by deprotection by heating. Indicates an isocyanate block.

Commercial products of such ethylenically unsaturated monomers having a blocked isocyanate group include, for example, 2-[(3,5-dimethylpyrazolyl) carboxyamino] ethyl methacrylate (Karenz MOI-BP, manufactured by Showa Denko); 2- (0- [1′-methylpropylideneamino] carboxyamino) ethyl methacrylate (Karenz MOI-BM, manufactured by Showa Denko).

As the ethylenically unsaturated monomer having a blocked isocyanate group, a commercially available product can be used, or it can be prepared and used by a known method. For example, an isocyanate compound having an ethylenically unsaturated bond and a blocking agent are stirred in a solvent at a temperature of about 0 to 200 ° C., and a known separation and purification means such as concentration, filtration, extraction, crystallization, or distillation is performed. And can be obtained by separation.

Another method of introducing a thermally crosslinkable functional group in the resin (B) having a cationic group in a side chain used in the present invention into an acrylic resin is as follows: This is a method of reacting a functional group capable of reacting with the functional group with a compound having a thermally crosslinkable functional group. For example, by reacting a glycidyl group of an ethylenically unsaturated monomer having a glycidyl group with a carboxyl group in an acrylic resin having a carboxyl group, an acrylic resin having a (meth) acryloyl group as a thermally crosslinkable functional group can be obtained. Obtainable.

The resin must contain at least one kind of the heat crosslinkable functional group, and may contain two or more kinds.

Furthermore, when two or more types of the thermally crosslinkable functional groups are contained, there is a preferable combination between the thermally crosslinkable functional groups. This is a combination in which the thermally crosslinkable functional groups are more likely to react with each other when heated, and in this case, the effect of crosslinking is improved. For example, it is effective to use an oxetanyl group and a carboxyl group simultaneously. Similarly, since the t-butyl group becomes a carboxyl group when heated, a combination of an oxetanyl group and a t-butyl group is also effective. Further, a combination of a hydroxyl group, a blocked isocyanate group and an isocyanate group is also effective. In particular, a combination of a hydroxyl group and a carboxyl group is most preferable because not only a strong film can be obtained by thermal crosslinking, but also in the alkali developing step before thermal crosslinking, the alkali developability is improved by the presence of the carboxyl group.

Next, the glass transition temperature of the resin (B) having a cationic group in a side chain used in the present invention will be described.

(Glass-transition temperature)
When synthesizing the resin (B) having a cationic group in a side chain used in the present invention, the glass transition temperature (hereinafter abbreviated as Tg) is 50 ° C. by selecting an ethylenically unsaturated monomer to be used. The above acrylic resin can be obtained. The Tg of the acrylic resin can be controlled by appropriately selecting the ethylenically unsaturated monomer to be used within a range that does not affect other physical properties. Since the Tg of the acrylic resin directly affects the heat resistance of the color filter, if the Tg is less than 50 ° C. and does not have a thermally crosslinkable functional group, a color change at a high temperature, that is, poor heat resistance occurs.

Considering use in the field of electronics such as a color filter having a heating step of 200 ° C. or more, the Tg of the acrylic portion is more preferably 70 ° C. or more. Although there is no particular upper limit for Tg, if it exceeds 150 ° C., there may be problems in workability and film forming properties in practical use.

The Tg of the acrylic resin of the present invention indicates a value calculated from the Tg of a homopolymer of each of the ethylenically unsaturated monomers to be copolymerized by the following Fox equation.
Fox equation 1 / Tg = W1 / Tg1 + W2 / Tg2 +... + Wn / Tgn
W1 to Wn indicate the weight fraction of the monomer used, and Tg1 to Tgn indicate the glass transition temperature (unit: absolute temperature “K”) of the homopolymer of the monomer.
The Tg (glass transition temperature) of the homopolymer of the main monomer used in the calculation is exemplified below.
Ethyl acrylate: -22 ° C (251K)
Butyl acrylate: -54 ° C (219K)
Benzyl methacrylate: 55 ° C (328K)
Acrylic acid: 106 ° C (379K)
Methyl methacrylate: 105 ° C (378K)
n-butyl methacrylate: 20 ° C (293K)
2-ethylhexyl methacrylate: -10 ° C (263K)
Hydroxyethyl methacrylate: 55 ° C (328K)
Methacrylic acid: 130 ° C (403K)
3- (methacryloyloxymethyl) 3-ethyloxetane: 105 ° C (378K)
2-isocyanate ethyl methacrylate: 60 ° C (333K)
t-butyl methacrylate: 107 ° C (380K)
Methacrylic acid dimethylaminoethyl methyl chloride salt: 58 ° C (331K)

For example, when calculated by the above method, the glass transition temperature of a vinyl polymer site obtained by radical polymerization of an ethylenically unsaturated monomer synthesized using 90 parts by weight of methyl methacrylate and 10 parts by weight of ethyl acrylate is 86.8. ° C.

In order to increase the Tg, it is necessary that the homopolymer contains an ethylenically unsaturated monomer having a high Tg in the copolymer composition. Among the ethylenically unsaturated monomers, the following are high in Tg, and are effective in increasing the Tg of the acrylic resin.
Monomers having a relatively high homopolymer Tg are listed.
Methyl methacrylate: 105 ° C (378K)
t-butyl methacrylate: 107 ° C (380K)
Methacrylic acid: 130 ° C (403K)
Acrylic acid: 106 ° C (379K)
3- (methacryloyloxymethyl) 3-ethyloxetane: 105 ° C (378K)
Isobornyl acrylate: 94 ° C (367K)
Isobornyl methacrylate: 180 ° C (453K)
Dicyclopentanyl acrylate: 120 ° C (393K)
Dicyclopentanyl methacrylate: 175 ° C (448K)
Adamantyl acrylate: 153 ° C (426K)
Adamantyl methacrylate: 250 ° C (523K)
Among them, t-butyl methacrylate and methacrylic acid are particularly preferable because they can increase Tg and can introduce a thermally crosslinkable functional group. In addition, methyl methacrylate is preferable from the viewpoint of versatility.

In addition, examples of the ethylenically unsaturated monomer that can be used other than the above-mentioned ethylenically unsaturated monomer include, for example, (meth) acrylates, crotonic esters, vinyl esters, maleic diesters, Preferred are fumaric diesters, itaconic diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like.

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

Examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, 2- (meth) acrylate Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethyl) methacrylate (Xy) ethyl, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol mono (meth) acrylate Ethyl ether, polyethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monoethyl ether (meth) acrylate, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, (meth) acrylic acid Dicyclopentenyl, dicyclopentenyloxyethyl (meth) acrylate, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate , Perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, and the like.

Examples of crotonic esters include butyl crotonate and hexyl crotonate.

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

Examples of fumaric acid diesters include dimethyl fumarate, diethyl fumarate, 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, N-n -Butylacryl (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, diacetoneacrylamide 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, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, hydroxystyrene, methoxystyrene, butoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, and chloromethyl. Examples include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (such as t-Boc, etc.), methyl vinylbenzoate, and α-methylstyrene.

(Block resin)
The block resin of the present invention can be obtained by copolymerizing an ethylenically unsaturated monomer.
The block resin of the present invention comprising the A block having a cationic group represented by the general formula (1) and the B block having no cationic group represented by the general formula (1) is an AB block, BAB block or ABA is preferable, and AB block and BAB block can be more preferably used.
Such a block copolymer is prepared, for example, by the following living polymerization method. Here, the living polymerization is a polymerization method for easily synthesizing a block polymer or a resin having a uniform molecular weight since side reactions occurring in general radical polymerization are suppressed and furthermore, the growth of polymerization occurs uniformly. Depending on the charge ratio of the polymerization initiator and the vinyl monomer added during the polymerization, the molecular weight of the polymer and the ratio of the monomers to be block-copolymerized can be freely controlled, and the block polymer, gradient polymer, star polymer, comb polymer, Can be used for the production of terminal functional polymers and the like.

The block copolymer of the present invention can be synthesized by a known radical living polymerization method. As specific examples, the methods listed below have been developed and widely researched and developed. A nitroxide mediated polymerization (NMP) method utilizing dissociation and binding of an amine oxide radical (see Reference 1). Atom transfer radical polymerization (ATRP method) in which a heavy compound such as copper, ruthenium, nickel, and iron, and a ligand that forms a complex therewith are used as a starting compound to polymerize with a halogen compound (Reference 2, References 3 and 4). Reversible addition-fragmentation chain transfer (RAFT method) in which a dithiocarboxylic acid ester, a xanthate compound, or the like is used as an initiating compound and is polymerized using an addition-polymerizable monomer and a radical initiator. 5) and Macromolecular Designvia Interchange of Xanthate (MADIX method) (see reference document 6). A method using a heavy metal such as organic tellurium, organic bismuth, organic antimony, antimony halide, organic germanium, and germanium halide (Degenerative transfer: DT method) (see References 7 and 8).

(Reference 1) Chemical Review (2001) 101,3661.
(Reference Document 2) JP-T-2000-500516 (Reference Document 3) JP-T-2000-514479 (Reference Document 4) Chemical Review (2001) 101, 3689
(Reference 5) Japanese Patent Publication No. 2000-515181 (Reference 6) International Publication No. 1999-05099 pamphlet (Reference 7) JP 2007-277533 A (Reference 8) Journalnal American Chemical Society (2002) 124, 2874

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

The atom transfer radical polymerization method is performed using a transition metal complex such as copper, ruthenium, iron, or nickel as a redox polymerization catalyst. Specific examples of the transition metal complex include a low-valent halogenated transition metal such as copper (I) chloride and copper (I) bromide.

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

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

The content of the partial structure (A block) having a cationic group represented by the general formula (1) in the side chain with respect to the solid content of the block copolymer is preferably 1% by weight to 99% by weight, and more preferably 3% by weight. The content is preferably from 90% by weight to 90% by weight, particularly preferably from 5% by weight to 30% by weight. When the A block contains 20% to 30% by weight, the remaining 70% to 80% by weight constitutes the B block. Therefore, when the B block has affinity for the solvent as the dispersion medium, the salt forming compound can be stably present in the dispersion medium, and the stability over time is improved.

Regardless of whether the block copolymer used in the present invention is an AB block copolymer or a BAB block copolymer, the A block / B block ratio (weight) Ratio) is usually 1/99 or more, preferably 20/80 or more, more preferably 80/20 or less, especially preferably 60/40 or less. Outside this range, it may not be possible to achieve both good temporal stability and solvent resistance.

The block copolymer of the present invention preferably has an ammonium salt value of 10 to 200 mgKOH / g, more preferably 20 to 130 mgKOH / g. If the ammonium salt value is less than 10 mgKOH / g, the proportion of the anionic dye (C) to be reacted is reduced, so that the coloring power is reduced, and more salt forming compound (D) is required in the resist material. Therefore, the amount of the binder resin or the curable resin which is originally added to the resist material is reduced, so that the glass adhesion of the resist film and the coating resistance of the resist film may deteriorate. On the other hand, when it exceeds 200 mgKOH / g, the solubility of the salt forming compound (D) in the solvent is deteriorated, and the salt forming compound (D) is precipitated as a foreign substance in the resist material.
In order for the ammonium salt value of the resin to satisfy the above range, the preferred content of the structural unit having a quaternary ammonium salt group is 4 to 74% by weight based on 100% by weight of the total of the structural units constituting the resin, A more preferred range is from 8 to 48% by weight.

In addition, since the block copolymer of the present invention makes it easier to form an association between the dyes than the salt that forms a salt with the A block having a cationic group and the salt with a random form, the heat resistance of the dye is reduced as a result. It is thought to improve.

The molecular weight of the block copolymer of the present invention is preferably in the range of usually 1,000 or more and 100,000 or less in terms of weight average in terms of polystyrene. If the molecular weight of the block copolymer is less than 1,000, the stability over time of the salt-forming compound tends to decrease, and if it exceeds 100,000, the solvent resistance tends to decrease.

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

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

(Anionic dye (C))
Next, the anionic dye (C) for obtaining the salt forming compound (D) of the present invention will be described. The anionic dye (C) may be any colored compound having an anionic group that is ionically bonded to the above-mentioned cationic group. 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 a molecule. Can be appropriately selected in consideration of all required properties 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 (C) include an anthraquinone-based anionic dye, a monoazo-based anionic dye, a disazo-based anionic dye, an oxazine-based anionic dye, an aminoketone-based anionic dye, a xanthene-based anionic dye, and a quinoline-based anion. And a triphenylmethane-based anionic dye. Hereinafter, specific examples of the anionic dye that can be used for the synthesis of the salt forming compound (D) are shown by color index numbers.

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, 37, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177,181,229,231,237,239,240,241,242,249,252,253,255,257,260,263,264,266,267,274,276,280,286,289,299 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388 and the like.

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, 1 8, 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.

As yellow dyes, 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. And the like.

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.
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.

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, 8485, 86, 88, 89, 90, 90: 1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 110, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127: 1, 128, 129, 135, 137, 138, 143, 145, 147, 1 0, 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.

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

Examples of the purple dye 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.

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.

Green dyes 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.
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.

Further, a dye represented by the general formula (2) may be mentioned.

General formula (2)
[X1 and X3 represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
X2 and X4 represent a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group. ]

In particular, Acid Red 52, Acid 289, and the dye represented by Formula (2) are preferable.

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

As the aqueous solution used for salt formation, a mixed solution of water and a water-soluble organic solvent may be used to dissolve the resin (B) having a cationic group in the side chain and the anionic dye. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, and 2- (methoxymethoxy) ethanol. Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethylsulfoxide, 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, most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

The ratio of the resin (B) having a cationic group in the side chain to the anionic dye (C) is such that the molar ratio of all the cation units of the resin to all the anionic groups of the anionic dye (C) is 10/1. When it is in the range of 〜 to で き, the salt forming compound (D) of the present invention can be suitably adjusted, and in the range of 2/1 to 、 ２, it is more preferable.

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

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

The green coloring composition for forming the green filter segment includes, for example, 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, 182, 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.

The blue coloring composition for forming the blue filter segment includes, for example, C.I. I. Pigment Blue 1, 1: 2, 1: 3, 2: 1, 2: 2, 3, 8, 9, 10, 10: 1, 11, 12, 15, 15: 1, 15: 2, 15: Blue pigments such as 3, 15: 4, 15: 6, 16, 18, 19, 22, 24, 24: 1, 53, 56, 56: 1, 57, 58, 59, 60, 61, 62, 64, etc. Can be used. The blue coloring composition includes C.I. I. Violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50 can be used in combination. It is also preferable to use an aluminum phthalocyanine pigment, and it is also possible to use an aluminum phthalocyanine pigment described in JP-A-2004-333817, JP-A-4893859, and the like.

The cyan coloring composition for forming the cyan filter segment includes, for example, C.I. I. Blue pigments such as CI Pigment Blue 15: 1, 15: 2, 15: 4, 15: 3, 15: 6, 16, 81 and the like can be used alone or in combination.

The magenta coloring composition for forming the magenta color filter segment includes, for example, C.I. I. Pigment Violet 1, 19, C.I. I. A violet pigment and a red pigment such as CI Pigment Red 144, 146, 177, 169, and 81 can be used alone or in combination. A yellow pigment can be used in combination with the magenta color composition.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine, navy blue, chrome oxide green, cobalt green, and amber. And synthetic iron black. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between chroma and lightness.

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

Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is heated using a kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, and a sand mill. This is a process of removing the water-soluble inorganic salt and the water-soluble organic solvent by rinsing with water. The water-soluble inorganic salt functions as a crushing aid, and the pigment is crushed by utilizing the hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution range, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used in terms of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000% by weight, and most preferably 300 to 1000% by weight, based on the total weight of the pigment (100% by weight) in terms 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) with water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high boiling solvent having a boiling point of 120 ° C. or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

When the pigment is subjected to the salt milling treatment, a resin may be added as necessary. The type of the resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, 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% by weight based on the total weight of the pigment (100% by weight).

<Binder resin>
The binder resin disperses a coloring agent, particularly the salt forming compound (D) and the pigment, or dyes and penetrates the salt forming compound, and examples thereof include a thermoplastic resin and a thermosetting resin.

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

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

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Since the coloring composition for a color filter of the present invention is in the form of an alkali-developing colored resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an ethylenically unsaturated monomer having an acidic group.

Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydride) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Isobutylene / (anhydride) maleic acid copolymer; Above all, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrenesulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and high transparency.

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

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin into which an unsaturated ethylenic double bond has been introduced by the following method (a) or (b).

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

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

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

Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. I don't care. Increasing the number of carboxyl groups, etc., if necessary, using a tricarboxylic anhydride such as trimellitic anhydride, or using a tetracarboxylic dianhydride such as pyromellitic dianhydride, the remaining anhydride Hydrolysis of the group is also possible. In addition, when an ethahydrophthalic anhydride or a maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

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

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or by copolymerizing with another monomer. There is a method in which an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group is reacted with a side chain hydroxyl group of the obtained copolymer.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate and cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. Also, polyether mono (meth) acrylate obtained by addition-polymerizing ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like has been added. From the viewpoint of suppressing paint film foreign matter, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferred.

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

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. 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.

From the viewpoints of dispersibility, permeability, developability, and heat resistance of the pigment and the salt forming compound, the binder resin has a carboxyl group serving as a colorant-adsorbing group and an alkali-soluble group during development, an affinity for a colorant carrier and a solvent. The balance between the aliphatic group and the aromatic group serving as a functional group is important for the dispersibility, permeability, developability, and durability of the pigment and the salt forming compound, and a resin having an acid value of 20 to 300 mgKOH / g is used. Is preferred. When the acid value is less than 20 mgKOH / g, the solubility in a developer is poor, and it is difficult to form a fine pattern. If it exceeds 300 mgKOH / g, no fine pattern remains.

The binder resin is preferably used in an amount of 30% by weight or more based on the total weight of the colorant (100% by weight) because of its good film formability and various resistances. It is preferable to use it in an amount of 500% by weight or less because color characteristics can be exhibited.

<Organic solvent>
In the coloring composition of the present invention, a coloring agent is sufficiently dispersed and penetrated in a coloring agent carrier, and applied on a substrate such as a glass substrate so that a dry film thickness becomes 0.2 to 5 μm to form a filter segment. 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.

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

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

In addition, the organic solvent can adjust the coloring composition to an appropriate viscosity and form a filter segment having a desired uniform film thickness. Therefore, the organic solvent is 800 to 4000 weight based on the total weight of the coloring agent (100% by weight). % Is preferably used.

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

(Dispersion aid)
When dispersing the colorant in the colorant carrier, a dispersing aid such as a dye derivative, a resin-type dispersant, or a surfactant can be appropriately used. The dispersing agent is excellent in dispersing the colorant and has a large effect of preventing re-aggregation of the colorant after the dispersion. When used, a color filter having a high spectral transmittance is obtained.
In the present invention, the salt forming compound (D) is also expected to play a role as a pigment dispersion aid.

Examples of the dye derivative include a compound in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced 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 and the like can be used. They can be used alone or in combination of two or more.

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

The resin-type dispersant has a pigment affinity site having a property of adsorbing to the additive pigment, and a site compatible with the colorant carrier, and stabilizes dispersion to the colorant carrier by adsorbing to the additive pigment. It works. Specific examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt, and polycarboxylic acid alkylamine salt. , Polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylic esters, modified products thereof, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with a polyester having a free carboxyl group Such as oil-based dispersants, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone, etc. Resins, water-soluble polymer compounds, polyesters, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, 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, 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 LACTIMON, LACTIMON-WS, or BYKUMEN, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Lubrizol Japan, Ltd. , 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500 EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320 , 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

As the surfactant, sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphate, 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 alkyl betaines such as betaine acetate and alkyl imidazolines, and these can be used alone or as a mixture of two or more, but are not necessarily limited thereto.

When the resin-type dispersant and the surfactant are added, the amount is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the added pigment (100% by weight). It is. When the amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, the effect of the addition is difficult to be obtained. May be exerted.

<Photopolymerizable monomer>
The coloring composition of the present invention can be used as a photosensitive coloring composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

The photopolymerizable monomer of the present invention includes a monomer or an oligomer that is cured by ultraviolet light or heat to form a transparent resin, and these can be used alone or in combination of two or more. The amount of the monomer is preferably from 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably from 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

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

<Photopolymerization initiator>
The coloring composition for a color filter of the present invention is a solvent-developable or alkali-developable colored resist material which is obtained by curing the composition by ultraviolet irradiation and forming a filter segment by a photolithographic method by adding a photopolymerization initiator or the like. Can be prepared. The amount of the photopolymerization initiator used is preferably from 5 to 200% by weight, based on the total amount of the colorant, and from 10 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 − [4
Acetophenone-based compounds such as-(4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin methyl ether, Benzoin-based compounds such as benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl Benzophenone-based compounds such as sulfide or 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methyl Thioxanthone compounds such as thioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6- Bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (tric Triazine-based compounds such as (romethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; -Octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy- Oxime ester compounds such as naphthyl) ethylidene) hydroxylamine; phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Quinone compounds such as phenanthrenequinone, camphorquinone and ethylanthraquinone Products; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.

These photopolymerization initiators can be used singly or as a mixture of two or more at any ratio as needed. These photopolymerization initiators are preferably from 5 to 200% by weight based on the total amount of the colorant in the coloring composition for color filter (100% by weight), and from the viewpoint of photocurability and developability are preferably 10 to 200% by weight. It is more preferable that the content is about 150% by weight.

<Sensitizer>
Further, the coloring composition for a color filter of the present invention may contain a sensitizer.

Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxanol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivative, azulhenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, Trapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxaliloporphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyllin derivative, annulene derivative, spiropyran derivative, spirooxazine Derivative, thiospiropyran derivative, metal arene complex, organic ruthenium complex, or Michler's ketone derivative, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophene And non-, 4,4'-diethylaminobenzophenone.

More specifically, edited by Shin Okawara et al., "Dye Handbook" (1986, Kodansha), edited by Shin Okawara et al., "Chemistry of Functional Dyes" (1981, CMC), edited by Chusaburo Ikemori, and others. Sensitizers described in "Specially Functional Materials" (1986, CMC), but are not limited thereto. In addition, a sensitizer that absorbs light in the ultraviolet to near infrared region can be contained.

Two or more sensitizers may be used at any ratio as needed. The compounding amount when the sensitizer is used is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the coloring composition (100% by weight). From the viewpoint of developability, the content is more preferably 5 to 50% by weight.

<Amine compound>
Further, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen.

Examples of such an amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylamino benzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
It is preferable to add a leveling agent to the coloring composition of the present invention in order to improve the leveling property of the composition on the transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray and 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. Usually, the content of the leveling agent is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

Particularly preferred as a leveling agent is a kind of a so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when added to a coloring composition, It has the feature that surface tension lowering ability is low, and even though the surface tension lowering ability is low, it is useful that the wettability to the glass plate is good, and at the amount of addition that does not cause defects in the coating film due to foaming Those which can sufficiently suppress the charging property can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

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

Anionic, cationic, nonionic, or amphoteric surfactants can also be added to the leveling agent. Two or more surfactants may be used as a mixture.

Examples of anionic surfactants to be added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymer, sodium alkylnaphthalenesulfonate, alkyldiphenyletherdisulfonate Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, styrene-acrylic acid copolymer monoethanolamine, polyoxyethylene alkyl ether phosphate Esters and the like.

Examples of the chaotic surfactant supplementally added to the leveling agent include an alkyl quaternary ammonium salt and an ethylene oxide adduct thereof. Nonionic surfactants to be added to the leveling agent supplementally include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkylbetaines such as alkyldimethylaminoacetate betaines and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, and the like, if necessary, to assist the curing of the thermosetting resin. As the curing agent, a phenolic resin, an amine compound, an acid anhydride, an active ester, a carboxylic acid compound, a sulfonic acid compound and the like are effective, but not particularly limited thereto, and a thermosetting resin Any curing agent may be used as long as it can react with the curing agent. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably exemplified. Examples of the curing accelerator include amine compounds (eg, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl) —N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (eg, dimethylamine, etc.), imidazole derivative bicyclic 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 Le-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) and the like. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15% by weight based on the total amount of the thermosetting resin.

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

As the storage stabilizer, for example, benzyltrimethyl chloride, quaternary ammonium chloride such as diethylhydroxyamine, lactic acid, organic acids such as oxalic acid and its methyl ether, t-butyl pyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

Examples of the adhesion improver include vinylsilanes 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 Xysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).

<Removal of coarse particles>
The coloring composition of the present invention was mixed with coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, a sintered filter, a membrane filter or the like. It is preferable to remove dust. As described above, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

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

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

<Production method of color filter>
The color filter of the present invention can be manufactured by a printing method or a photolithography method.

The formation of the filter segment by the printing method can be patterned by simply repeating the printing and drying of the coloring composition prepared as a printing ink. Therefore, as a method of manufacturing a color filter, the cost is low, and the mass production is excellent. I have. Further, fine patterns having high dimensional accuracy and smoothness can be printed by the development of printing technology. In order to perform printing, it is preferable that the composition be such that the ink does not dry and solidify on a printing plate or on a blanket. In addition, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted by a dispersant or extender.

When the filter segment is formed by a photolithography method, the coloring composition prepared as the solvent-developable or alkali-developable colored resist material is coated on a transparent substrate by spray coating, spin coating, slit coating, roll coating, or the like. According to the method, coating is performed so that the dry film thickness becomes 0.2 to 5 μm. The film dried as required 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 an alkaline developer or spraying the developer with a spray or the like to remove an uncured portion and form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Further, in order to promote 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 printing method can be manufactured.

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

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

Before forming each color filter segment on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Alternatively, 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 transparent conductive film or the like is formed as necessary.

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

First, the method for producing the binder resin, the finely divided pigment, the resin (B) having a cationic group in the side chain, and the salt forming compound (D) used in Examples and Comparative Examples will be described.

<Preparation method of binder resin solution>
(Preparation of binder resin solution 1)
A reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, and a stirrer in a separable four-necked flask was charged with 70.0 parts of cyclohexanone, the temperature was raised to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin having a weight average molecular weight of 26,000. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. This was added to prepare a binder resin solution 1.
Here, the weight average molecular weight (Mw) of the binder resin was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance.

(Preparation of binder resin solution 2)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas inlet pipe, a dropping pipe, and a stirrer, the temperature was raised to 80 ° C., and the flask was purged with nitrogen. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobisisobutyronitrile 1.33 parts of the mixture were added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer solution.
Next, nitrogen gas was stopped with respect to the whole amount of the obtained copolymer solution, and the mixture was stirred while injecting dry air for 1 hour, then cooled to room temperature, and then cooled to 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). (MOI) 6.5 parts, a mixture of 0.08 parts of dibutyltin laurate and 26 parts of cyclohexanone were added dropwise at 70 ° C. over 3 hours.
Approximately 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Prepared. The weight average molecular weight (Mw) was 18,000.

(Preparation of binder resin solution 3)
207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas inlet pipe, a dropping pipe, and a stirrer. 20 parts of acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of glycerol monomethacrylate, and 1.3 parts of 2,2′-azobisisobutyronitrile.
Three parts of the mixture were added dropwise over 2 hours. After the completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer solution.
Next, nitrogen gas was stopped with respect to the total amount of the obtained copolymer solution, and the mixture was stirred while injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours.
Approximately 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. Prepared. The weight average molecular weight (Mw) was 19000.

(Preparation of binder resin solution 4)
370 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas inlet pipe, a dropping pipe, and a stirrer. 18 parts of millphenol 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′-azobisisobutyronitrile 2.0 Parts of the mixture were added dropwise over 2 hours. After dropping, the mixture was further reacted at 100 ° C. for 3 hours. Then, a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Then, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the container, and the mixture was heated at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain a copolymer solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 part of triethylamine were successively added and reacted at 120 ° C. for 3.5 hours to obtain a carboxyl group and a copolymer solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Thus, a binder resin solution 4 was prepared. The weight average molecular weight (Mw) was 19000.

<Production method of micronized pigment>
(Blue refined pigment (P-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor “Lionol Blue ES”) 100 parts, ground salt 800 parts and diethylene glycol 100 parts are charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. did. The mixture was poured into 3000 parts of warm water, stirred for about 1 hour with a high-speed mixer while heating to about 70 ° C. to form a slurry. It dried and obtained 98 parts of blue refined pigments (P-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

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

(Violet fine pigment (P-2))
Dioxazine purple pigment C.I. I. Pigment Violet 23 (“FastViolet RL” manufactured by Clariant), 120 parts, ground salt 1600 parts, and diethylene glycol 100 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was poured into 5000 parts of warm water, stirred for about 1 hour with a high-speed mixer while heating 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 was dried to obtain 118 parts of a violet fine 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. Pigment Red 254 (“IRGAZINRED2030” manufactured by BASF Japan), 200 parts of ground salt, and 1400 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. The mixture was poured into 8000 parts of warm water, and stirred at about 80 ° C. for about 2 hours while being heated to about 80 ° C. to form a slurry. It dried and 190 parts of red fine pigments (P-3) were obtained. The average primary particle diameter of the obtained pigment was 24.8 nm.

(Red fine pigment (P-4))
Red pigment C.I. I. Pigment Red 242 (Clariant “NOVOPERMS”
200 parts of CARLET4RF), 1400 parts of ground salt and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. This mixture was poured into 8000 parts of warm water, and stirred at a high speed mixer for 2 hours while being heated to about 80 ° C to form a slurry. Filtration and washing were repeated to remove salt and solvent, followed by drying at 85 ° C for 24 hours. Thus, 190 parts of a red fine pigment (P-4) was obtained. The average primary particle diameter of the obtained pigment was 28.5 nm.

<Method for preparing resin (B) having a cationic group in the side chain>
(Production Example 1: Preparation of resin B-1 having a cationic group in a side chain)

A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 18.2 parts of methyl methacrylate, 27.3 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, and 15 parts of 2-hydroxyethyl methacrylate. And 1.6 parts of tetramethylethylenediamine, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to purge the system with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was increased to 100 ° C. under a nitrogen stream to start polymerization of the first block. did. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methacrylate methyl chloride salt as a second block monomer were charged into this reactor, and the mixture was stirred while maintaining a temperature of 100 ° C. and a nitrogen atmosphere. The reaction was continued. Two hours after the addition of dimethylaminoethylmethyl methacrylate chloride, the polymerization solution was sampled and the solid content was measured. The conversion of the second block, which was calculated from the non-volatile content, was 98% or more. The solution was cooled to room temperature to terminate the polymerization.
As a result of GPC measurement, Mw of the polymer was 9200, Mw / Mn was 1.5, and the reaction conversion was 98.5%. Thus, a block resin (B-1) having a quaternary ammonium salt value of 33 mgKOH / g per solid was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by weight, and quaternary ammonium was added. A block resin solution having a salt was obtained.

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

(Production Example 2: Preparation of resin B-2 having a cationic group in a side chain)

A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 8.2 parts of methyl methacrylate, 25.3 parts of n-butyl methacrylate, 25.3 parts of 2-ethylhexyl methacrylate, and 15 parts of 2-hydroxyethyl methacrylate. And 1.6 parts of tetramethylethylenediamine, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to purge the system with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was increased to 100 ° C. under a nitrogen stream to start polymerization of the first block. did. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 8.1 parts of propylene glycol monomethyl ether and 26.2 parts of dimethylaminoethyl methyl methacrylate chloride as a second block monomer were charged into this reactor, and the mixture was stirred while maintaining the temperature in a nitrogen atmosphere at 100 ° C. The reaction was continued. Two hours after the addition of dimethylaminoethylmethyl methacrylate chloride, the polymerization solution was sampled and the solid content was measured. The conversion of the second block, which was calculated from the non-volatile content, was 98% or more. The solution was cooled to room temperature to terminate the polymerization.
As a result of GPC measurement, Mw of the polymer was 9000, Mw / Mn was 1.5, and the reaction conversion was 98.5%. Thus, a block resin (B-2) having a quaternary ammonium salt value of 71 mgKOH / g per solid was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by weight, and quaternary ammonium was added. A block resin solution having a salt was obtained.

(Production Example 3: Preparation of resin B-3 having a cationic group in a side chain)

In a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 35.5 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 12.3 parts of 2-ethylhexyl methacrylate, 10 parts of 2-hydroxyethyl methacrylate, 1.6 parts of tetramethylethylenediamine was charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to purge the system with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was increased to 100 ° C. under a nitrogen stream to start polymerization of the first block. did. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content. Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methacrylate methyl chloride salt as a second block monomer were charged into this reactor, and the mixture was stirred while maintaining a temperature of 100 ° C. and a nitrogen atmosphere. The reaction was continued. Two hours after the addition of dimethylaminoethylmethyl methacrylate chloride, the polymerization solution was sampled and the solid content was measured. The conversion of the second block, which was calculated from the non-volatile content, was 98% or more. The solution was cooled to room temperature to terminate the polymerization.
As a result of GPC measurement, Mw of the polymer was 9,500 and Mw / Mn was 1.5, and the reaction conversion was 98.5%. Thus, a block resin (B-3) having a quaternary ammonium salt value of 33 mgKOH / g per solid was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by weight, and quaternary ammonium was added. A block resin solution having a salt was obtained.

(Production Example 4: Preparation of resin B-4 having a cationic group in a side chain)

A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 22.4 parts of methyl methacrylate, 16.7 parts of n-butyl methacrylate, 27.3 parts of 2-ethylhexyl methacrylate, and 15.0 parts of hydroxyethyl methacrylate. Parts, 2.5 parts of methacrylic acid, 1.3 parts of t-butyl methacrylate, 1.3 parts of isobutyl methacrylate, 1.3 parts of cyclohexyl methacrylate, and 1.6 parts of tetramethylethylenediamine, and charged at 50 ° C. while flowing nitrogen. After stirring for an hour, the inside of the system was replaced with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was increased to 100 ° C. under a nitrogen stream to start polymerization of the first block. did. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methacrylate methyl chloride salt as a second block monomer were charged into this reactor, and the mixture was stirred while maintaining a temperature of 100 ° C. and a nitrogen atmosphere. The reaction was continued. Two hours after the addition of dimethylaminoethylmethyl methacrylate chloride, the polymerization solution was sampled and the solid content was measured. The conversion of the second block, which was calculated from the non-volatile content, was 98% or more. The solution was cooled to room temperature to terminate the polymerization.
As a result of GPC measurement, Mw of the polymer was 9000, Mw / Mn was 1.5, and the reaction conversion was 98.5%. Thus, a block resin (B-4) having a quaternary ammonium salt value of 33 mgKOH / g per solid was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by weight, and quaternary ammonium was added. A block resin solution having a salt was obtained.

(Production Example 5: Preparation of resin B-5 having a cationic group in a side chain)

A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 34.7 parts of isobornyl methacrylate, 1.7 parts of n-butyl methacrylate, 30.0 parts of hydroxyethyl methacrylate, and 2.5 parts of methacrylic acid. Parts, 16.3 parts of t-butyl methacrylate, 1.3 parts of isobutyl methacrylate, 1.3 parts of cyclohexyl methacrylate, and 1.6 parts of tetramethylethylenediamine, and stirred at 50 ° C. for 1 hour while flowing nitrogen. It was replaced with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was increased to 100 ° C. under a nitrogen stream to start polymerization of the first block. did. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methacrylate methyl chloride salt as a second block monomer were charged into this reactor, and the mixture was stirred while maintaining a temperature of 100 ° C. and a nitrogen atmosphere. The reaction was continued. Two hours after the addition of dimethylaminoethylmethyl methacrylate chloride, the polymerization solution was sampled and the solid content was measured. The conversion of the second block, which was calculated from the non-volatile content, was 98% or more. The solution was cooled to room temperature to terminate the polymerization.
As a result of GPC measurement, Mw of the polymer was 9200, Mw / Mn was 1.5, and the reaction conversion was 98.5%. Thus, a block resin (B-5) having a quaternary ammonium salt value of 33 mgKOH / g per solid was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by weight, and quaternary ammonium was added. A block resin solution having a salt was obtained.

(Production Example 6: Preparation of resin B-6 having a cationic group in a side chain)

A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 22.5 parts of isobornyl methacrylate, 1.7 parts of n-butyl methacrylate, 30.0 parts of hydroxyethyl methacrylate, and 2.5 parts of methacrylic acid. Parts, 16.3 parts of t-butyl methacrylate, 1.3 parts of isobutyl methacrylate, 1.3 parts of cyclohexyl methacrylate, and 1.6 parts of tetramethylethylenediamine, and stirred at 50 ° C. for 1 hour while flowing nitrogen. It was replaced with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was increased to 100 ° C. under a nitrogen stream to start polymerization of the first block. did. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 8.1 parts of propylene glycol monomethyl ether and 24.4 parts of dimethylaminoethyl methacrylate methyl chloride salt as a second block monomer were charged into the reactor, and the mixture was stirred while maintaining a temperature of 100 ° C. and a nitrogen atmosphere. The reaction was continued. Two hours after the addition of dimethylaminoethylmethyl methacrylate chloride, the polymerization solution was sampled and the solid content was measured. The conversion of the second block, which was calculated from the non-volatile content, was 98% or more. The solution was cooled to room temperature to terminate the polymerization.
As a result of GPC measurement, Mw of the polymer was 9200, Mw / Mn was 1.5, and the reaction conversion was 98.5%. Thus, a block resin (B-6) having a quaternary ammonium salt value of 66 mgKOH / g per solid was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by weight, and quaternary ammonium was added. A block resin solution having a salt was obtained.

(Production Example 7; Preparation of resin B-7 having a cationic group in a side chain)

In a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 50.0 parts of methyl methacrylate, 30.0 parts of n-butyl methacrylate, 15 parts of 2-hydroxyethyl methacrylate, 2.5 parts of methacrylic acid, 1.6 parts of tetramethylethylenediamine was charged, and the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen to purge the inside of the system with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was increased to 100 ° C. under a nitrogen stream to start polymerization of the first block. did. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 8.1 parts of propylene glycol monomethyl ether and 2.5 parts of dimethylaminoethyl methyl methacrylate chloride as a second block monomer were charged into the reactor, and the mixture was stirred while maintaining a temperature of 100 ° C. and a nitrogen atmosphere. The reaction was continued. Two hours after the addition of dimethylaminoethylmethyl methacrylate chloride, the polymerization solution was sampled and the solid content was measured. The conversion of the second block, which was calculated from the non-volatile content, was 98% or more. The solution was cooled to room temperature to terminate the polymerization.
As a result of GPC measurement, Mw of the polymer was 9100 and Mw / Mn was 1.5, and the reaction conversion was 98.8%. Thus, a block resin (B-7) having a quaternary ammonium salt value per solid of 7 mgKOH / g was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by weight, and quaternary ammonium was added. A block resin solution having a salt was obtained.

(Production Example 8: Preparation of resin B-8 having a cationic group in a side chain)

A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 60.0 parts of methyl methacrylate, 17.8 parts of n-butyl methacrylate, 10.0 parts of 2-isocyanatoethyl methacrylate, and 1 part of tetramethylethylenediamine. Then, the mixture was stirred at 50 ° C. for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was increased to 100 ° C. under a nitrogen stream to start polymerization of the first block. did. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methacrylate methyl chloride salt as a second block monomer were charged into this reactor, and the mixture was stirred while maintaining a temperature of 100 ° C. and a nitrogen atmosphere. The reaction was continued. Two hours after the addition of dimethylaminoethylmethyl methacrylate chloride, the polymerization solution was sampled and the solid content was measured. The conversion of the second block, which was calculated from the non-volatile content, was 98% or more. The solution was cooled to room temperature to terminate the polymerization.
As a result of GPC measurement, Mw of the polymer was 9,800 and Mw / Mn was 1.6, and the reaction conversion was 98.3%. Thus, a block resin (B-8) having a quaternary ammonium salt value of 33 mgKOH / g per solid was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by weight, and quaternary ammonium was added. A block resin solution having a salt was obtained.

(Production Example 9: Preparation of resin BC-1 having a cationic group in a side chain)
75.1 parts of isopropyl alcohol was charged into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and heated to 75 ° C. under a nitrogen stream. Separately, it is dissolved in 17.8 parts of methyl methacrylate, 60.0 parts of n-butyl methacrylate, 10.0 parts of 2-hydroxyethyl methacrylate, 12.2 parts of dimethylaminoethyl methyl methacrylate, and 23.4 parts of methyl ethyl ketone. 2,2'-azobis (2,4-
After uniformizing 7.0 parts of dimethylvaleronitrile, the mixture was charged into a dropping funnel, attached to a four-neck separable flask, and dropped over 2 hours. Two hours after completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content, and that the weight average molecular weight (Mw) was 8330, and the mixture was cooled to 50 ° C. Thereafter, 14.3 parts of methanol was added to obtain a resin BC-1 having a resin component of 40% by weight and a Tg of 40 ° C. having a cationic group in a side chain. The ammonium salt value of the obtained resin was 33 mgKOH / g.

(Production Example 10: Preparation of resin BC-2 having a cationic group in a side chain)
A reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 17.8 parts of methyl methacrylate, 70.0 parts of n-butyl methacrylate, and 1.6 parts of tetramethylethylenediamine. The mixture was stirred at ℃ for 1 hour, and the inside of the system was replaced with nitrogen. Next, 2.1 parts of ethyl bromoisobutyrate, 1.9 parts of cuprous chloride, and 62.3 parts of propylene glycol monomethyl ether were charged, and the temperature was increased to 100 ° C. under a nitrogen stream to start polymerization of the first block. did. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 8.1 parts of propylene glycol monomethyl ether and 12.2 parts of dimethylaminoethyl methacrylate methyl chloride salt as a second block monomer were charged into this reactor, and the mixture was stirred while maintaining a temperature of 100 ° C. and a nitrogen atmosphere. The reaction was continued. Two hours after the addition of dimethylaminoethylmethyl methacrylate chloride, the polymerization solution was sampled and the solid content was measured. The conversion of the second block, which was calculated from the non-volatile content, was 98% or more. The solution was cooled to room temperature to terminate the polymerization.
As a result of GPC measurement, Mw of the polymer was 9100, Mw / Mn was 1.5, and the reaction conversion was 98.4%. Thus, a block resin (BC-2) having a quaternary ammonium salt value of 33 mgKOH / g per solid was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and propylene glycol monomethyl ether was added so that the nonvolatile content was 40% by weight, and quaternary ammonium was added. A block resin solution having a salt was obtained.

The following monomers were used in Table 1. Shown together with the glass transition temperature.
Methacrylic acid dimethylaminoethyl methyl chloride salt:
Light ester DQ-100 (manufactured by Kyoeisha Chemical Co.) (58 ° C)
MMA: methyl methacrylate (105 ° C)
n-BMA: n-butyl methacrylate (20 ° C.)
2-EHMA: 2-ethylhexyl methacrylate (-10 ° C)
2-EHA: 2-ethylhexyl acrylate (-85 ° C)
HEMA: hydroxyethyl methacrylate (55 ° C)
MAA: methacrylic acid (130 ° C)
t-BMA: t-butyl methacrylate (107 ° C.)
IBMA: isobutyl methacrylate (67 ° C.)
CHMA: cyclohexyl methacrylate (66 ° C)
IBX: isobornyl methacrylate (180 ° C)
MOI: 2-isocyanatoethyl methacrylate (60 ° C)

The value of Tg in Table 1 is a value calculated using the above equation.

<Production of anionic dye (C)>
(Anionic dye 1)
The anionic dyes 1 to 4 are compounds represented by the following general formula (2).

General formula (2)
Table 2 shows X _{1 to} X ₄ in the general formula (2).

Here, * indicates a bond with N.

Anionic dyes 1 to 4 were synthesized by the following method.
(Synthesis of Anionic Dye 1)
C. I. 45.0 parts of Acid Red 289, 45.3 parts of 1-iodopropane and 36.8 parts of potassium carbonate were added to 280 parts of N-methylpyrrolidone, and the mixture was stirred at 90 ° C for 6 hours. After the obtained reaction solution was cooled to room temperature, it was added to 3000 parts of ethyl acetate, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were collected by filtration, washed with 2500 parts of ethyl acetate, and dried under reduced pressure at 60 ° C. overnight to obtain 147.6 parts of an anionic dye.

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

(Synthesis of anionic dye 3)
Except that 45.3 parts of 1-iodopropane was changed to 71.4 parts of 1-iododecane, the same operation as in the synthesis of anionic dye 1 was carried out to obtain 353.2 parts of anionic dye.

(Synthesis of Anionic Dye 4)
20.0 parts of the compound represented by the formula (20) and 8.5 parts of sulfanilic acid were added in 180 parts of N-methylpyrrolidone, and the mixture was stirred at 100 ° C for 2 hours. Next, 10.0 parts of aniline was added, and the mixture was stirred at 120 degrees for 4 hours. After cooling the obtained reaction solution to room temperature, 2,000 parts of ethyl acetate was added and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were separated by filtration and dried under reduced pressure overnight to obtain 25.7 parts of Intermediate 1.
25.0 parts of Intermediate 1, 28.2 parts of 1-iodopropane and 23.0 parts of potassium carbonate were added to 200 parts of N-methylpyrrolidone, and the mixture was stirred at 90 ° C for 4 hours. After the obtained reaction solution was cooled to room temperature, it was added to 2,000 parts of ethyl acetate, and the mixture was stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were collected by filtration, washed with 1500 parts of ethyl acetate, and dried under reduced pressure overnight at 60 ° C. to obtain 26.7 parts of anionic dye 4.

Equation (20)

<Method for producing salt-forming compound (D)>
(Production Example 11: Preparation of salt-forming compound D-1) C.I. I. Acid Red 289 and Resin B-1 Having a Cationic Group in the Side Chain
A salt-forming compound (D-1) consisting of

To 2000 parts of water, 51 parts of resin B-1 having a cationic group in a side chain are added, and after sufficiently stirring and mixing, the mixture is heated to 60 ° C. On the other hand, 90 parts of water and 10 parts of C.I. I. An aqueous solution in which Acid Red 289 is dissolved is prepared, and is gradually added dropwise to the resin solution. After the dropwise addition, the mixture is stirred at 60 ° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was dropped on filter paper, and the point where no bleeding was observed was regarded as the end point, and it was judged that a salt forming compound was obtained. After allowing to cool to room temperature with stirring, suction filtration and washing with water were performed, and the counter anion of the resin having a cationic group in the side chain and C.I. I. After removing the salt comprising the counter cation of Acid Red 289, the salt-forming compound remaining on the filter paper was dried by removing the water with a drier, and dried in 32 parts of C.I. I. Thus, a salt-forming compound D-1 comprising Acid Red 289 and a resin B-1 having a cationic group in a side chain was obtained.

(Production Examples 13-15, 18-19, 21-23, 26-27, 29-31, 34-43; Salt-forming compounds D-3-5, 8-9, 11-13, 16-17, 19- 21, 24 to 33)
Hereinafter, the salt-forming compounds D-3 to 5, 8 to 9, 11 to 13, and 16 were prepared in the same manner as in Production Example 11 except that the resin and the dye having a cationic group in the side chain were changed to those shown in Table 3. To 17, 19 to 21, and 24 to 30 were produced.
(Production Examples 12, 20, 28; Preparation of salt-forming compounds D-2, 10, 18)
Hereinafter, salt-forming compounds D-2, 10, and 18 were produced in the same manner as in Production Example 11 except that 24 parts of resin B-2 having a cationic group in the side chain was used.
(Production Examples 16, 24, 32; Preparation of salt-forming compounds D-6, 14, 22)
Hereinafter, salt-forming compounds D-6, 14, and 32 were produced in the same manner as in Production Example 11, except that 25.5 parts of resin B-6 having a cationic group in the side chain was used.
(Production Examples 17, 25, 33; Preparation of salt-forming compounds D-7, 15, 23)
Hereinafter, salt-forming compounds D-7, 15, and 23 were produced in the same manner as in Production Example 11, except that 249.4 parts of resin B-7 having a cationic group in the side chain was used.

[Examples 1 to 34, Comparative Examples 1 to 16]
[Example 1]
(Preparation of Blue Coloring Composition (DB-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. The mixture was filtered through a filter to prepare a pigment dispersion (DB-1). 4.0 parts of salt forming compound (D-1) 7.0 parts of finely divided pigment (P-1) 14 parts of binder resin solution 10.0 parts of cyclohexanone 10.0 parts of propylene glycol monomethyl ether acetate (PGMAC) 38.0 parts of resin type 1.0 part of dispersant (“EFKA4300” manufactured by BASF Japan)

[Examples 2 to 34, Comparative Examples 1 to 16]
(Blue colored composition (DB-2 to 25, DB-35 to 41), purple colored composition (DB-26 to 28, DB-42 to 44), red colored composition (DB-29 to 34, DB- Creation of 45-50)
Colored compositions (DB-2 to 50) were prepared in the same manner as in Example 1 except that the salt forming compound and the finely divided pigment were changed to the compositions shown in Table 4.

About the obtained coloring composition (DB-1-50), the heat resistance evaluation of a coating film, a foreign substance test, and the test regarding the storage stability with time of the coloring composition were performed by the following methods. Table 4 shows the test results.

(Evaluation of heat resistance of coating film)
The coloring composition (DB-1 to 50) is applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 30 minutes. The coated substrate was prepared by heating and cooling. After the heat treatment at 220 ° C., the coating rotation speed of the spin coater was adjusted so that the film thickness of the prepared coated substrate became 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). It measured using. Further, after that, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. And the color difference ΔEab *.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
If ΔEab * is less than 2.0, there is no practical problem as a color filter, and if ΔEab is 1.5 or less, it is more preferred, and most preferably 1.0 or less.

(Test for storage stability over time)
The colored composition (DB-1 to 50) stored for 6 months under the condition of 10 ° C. was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater. After drying for 30 minutes, and then heating and cooling at 220 ° C. for 30 minutes, a coated substrate was prepared, and the coated substrate was observed at 500 × using an optical microscope.
<Evaluation criteria>
：: No foreign matter was observed at all. ○: Foreign matter was observed but was within the allowable range.

(Test method for paint foreign matter)
A test substrate was prepared using the coloring composition (DB-1 to 50) immediately after the preparation, and the evaluation was performed by counting the number of particles. First, a colored composition is applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate by a spin coater so that the film thickness after drying is about 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes. A test substrate was obtained. Then, the surface is observed using a metal microscope “BX60” manufactured by Olympus System (magnification: 500 times), the number of particles observable in any five visual fields by transmission is counted, and evaluated according to the following criteria. did. In the evaluation results, ◎ and ○ indicate that the number of foreign substances was small and good, and △ indicates that the number of foreign substances was large but no problem in use. Equivalent to.
◎: up to less than 5 ：: 5 or more, less than 20 △: 20 or more, less than 100 ×: 100 or more

AR289: C.I. I. Acid Red 289
AR52: C.I. I. Acid Red 52

Examples 1 to 34 contain a salt-forming compound (D) of a resin (B) having a cationic group in a side chain and an anionic dye (C), and the resin having a cationic group is a cationic group. Since the block resin was composed of an A block having the following formula and a B block having no cationic group and having a thermally crosslinkable functional group, all had good heat resistance, and ΔEab was 1.0 or less. In addition, the storage stability was excellent, and the foreign matter of the coating film was in a range usable as a color filter, which was a good result.
On the other hand, in Comparative Example 1, the resin having a cationic group did not have a block structure, and in Comparative Examples 2 to 16, the resin having a cationic group did not have a thermally crosslinkable functional group. Unfortunately, ΔEab exceeded 2.5.

[Example 35]
(Preparation of blue photosensitive coloring composition (R-1))
After stirring and mixing the following mixture to be uniform, the mixture was filtered through a 1.0 μm filter,
An alkali developable resist material R-1 was prepared.
60.0 parts of a blue coloring composition (DB-1) 111.0 parts of a binder resin solution 4.2 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
1.2 parts of photopolymerization initiator (“IRGACURE 907” manufactured by BASF Japan) 0.4 parts of sensitizer (“EAB-F” manufactured by Hodogaya Chemical) 5.2 parts of cyclohexanone 5.2 parts of propylene glycol monomethyl ether acetate (PGMAC) 18.0 copies

[Examples 36 to 60, Comparative Examples 17 to 32]
(Blue photosensitive coloring composition (R-2-17, R-27-33), purple photosensitive coloring composition (R-18-20, R-34-36), red photosensitive coloring composition (R- Production of 21-26, R-37-42)
Except that the coloring composition and the binder resin solution were changed to the coloring compositions shown in Table 5, alkali-developing photosensitive coloring compositions (R-2-36) were prepared in the same manner as in Example 35.

(Evaluation of photosensitive coloring composition)
About the obtained photosensitive coloring composition (R-1 to 42), evaluation of heat resistance of coating film, foreign matter test, storage stability over time, test for adhesion to transparent substrate such as glass, test for solvent resistance And an alkali developability test. The following methods were used for the foreign matter test, the test for adhesion to a transparent substrate such as glass, the solvent resistance test, and the test for alkali developability. Other evaluation and test methods were performed in the same manner as described in Examples 1 to 34 and Comparative Examples 1 to 16.

(Test method for paint foreign matter)
A test substrate was prepared using the photosensitive coloring composition (R-1 to 42) immediately after preparation, and the evaluation was performed by counting the number of particles. First, a photosensitive coloring composition is applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate with a spin coater so that the film thickness after drying is about 2.0 μm, and dried at 70 ° C. for 20 minutes. Using a super-high pressure mercury lamp through a photomask having a stripe-shaped opening having a width of 100 μm, ultraviolet exposure was performed at an integrated light amount of 150 mJ / cm ² , and no exposure was performed using a 0.05% aqueous potassium hydroxide solution containing a surfactant. The portion was washed away and developed, and then placed in a hot air oven at 230 ° C. for 20 minutes to form a 100 μm-wide striped pattern on the substrate to obtain a test substrate. Then, the surface is observed using a metal microscope “BX60” manufactured by Olympus System (magnification: 500 times), the number of particles observable in any five visual fields by transmission is counted, and evaluated according to the following criteria. did. In the evaluation results, ◎ and ○ indicate that the number of foreign substances was small and good, and △ indicates that the number of foreign substances was large but no problem in use. Equivalent to.
◎: up to less than 5 ：: 5 or more, less than 20 △: 20 or more, less than 100 ×: 100 or more

(Glass adhesion test method)
A test substrate was formed in the same procedure as in the above-described coating film foreign matter test, and evaluated by confirming chemical resistance. The obtained test substrate was immersed in a 5% aqueous sodium hydroxide solution at 25 ° C. for 30 minutes, and the adhesion to glass before and after immersion was evaluated by visual observation in three steps.
〇: No peeling is observed at all △: Slight peeling is observed ×: Peeling is observed

(Solvent resistance test)
After immersing the test substrate obtained in the same procedure as the above coating film foreign matter test in an N-methylpyrrolidone solution for 30 minutes, washing with ion-exchanged water and air-drying, using a light microscope for the pattern in the 100 μm photomask portion. It was observed and evaluated. The ranking of the evaluation is as follows.
◎: good appearance and color without change ○: wrinkles and the like are partially generated, but color is good without change △: slight discoloration occurs ×: peeling and discoloration occur

(Alkali developability test)
The photosensitive coloring composition (R-1 to 27) is applied on a 100 mm × 100 mm, 1.1 mm thick transparent glass substrate by a spin coater so that the film thickness after drying is about 2.0 μm, After drying for 20 minutes, the substrate was exposed to ultraviolet light through a photomask having a stripe-shaped opening having a width of 100 μm using an ultra-high pressure mercury lamp at an integrated light amount of 150 mJ / cm ² . When developing by washing away the unexposed area with a 0.05% aqueous solution of potassium hydroxide containing a surfactant, development is performed for an appropriate development time of +10 seconds and +20 seconds, and the developed glass surface is subjected to a microspectrophotometer ( This was measured using Olympus Optical Co., Ltd. “OSP-SP200”), and the alkali developability was determined based on the presence or absence of the residue.
◎: No residue at appropriate development time ○: No residue at appropriate development time +10 seconds 秒: No residue at appropriate development time +20 seconds ×: Residue at appropriate development time +20 seconds

As in Examples 35 to 60, the resin containing a salt-forming compound (D) of a resin (B) having a cationic group in a side chain and an anionic dye (C), wherein the resin having a cationic group is a cation Since it is a block resin composed of an A block having a functional group and a B block having no cationic group and having a thermally crosslinkable functional group, all have good heat resistance and have a ΔEab of 1.0 or less. Was. Further, the storage stability was excellent, the foreign matter of the coating film was in a range usable as a color filter, and the glass adhesion, solvent resistance, and alkali developability were also good.
On the other hand, Comparative Example 17 resulted in poor heat resistance because the resin having a cationic group did not have a block structure. Further, Comparative Examples 18 to 32 did not have a thermally crosslinkable functional group, so that the heat resistance ΔEab exceeded 2.5 and the solvent resistance was poor.

<Preparation of color filter>
A red photosensitive coloring composition, a blue photosensitive coloring composition, and a green photosensitive coloring composition, which are used in producing a color filter in combination with the photosensitive coloring composition of the present invention, were produced.

(Preparation of red photosensitive coloring composition (RR-1))
After the mixture having the following composition was stirred and mixed so as to be uniform, using a zirconia bead having a diameter of 0.5 mm, an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) was used.
), And filtered through a 5.0 μm filter to prepare a red colored composition (DR-1).
9.6 parts of red pigment (CI Pigment Red 254) 2.4 parts of red pigment (CI Pigment Red 177) 1.0 part of resin-type dispersant (“EFKA4300” manufactured by BASF Japan) 1.0 part of binder resin solution 135.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

Subsequently, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a red photosensitive coloring composition (RR-1).

42.0 parts of a red coloring composition (DR-1) 113.2 parts of a binder resin solution 113.2 parts of a photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 2.8 parts of a photopolymerization initiator (manufactured by BASF Japan) Irgacure 907 ") 2.0 parts Sensitizer (" EAB-F "manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of blue photosensitive coloring composition (RB-1))
After the mixture having the following composition was stirred and mixed so as to be uniform, using a zirconia bead having a diameter of 0.5 mm, an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) was used.
) For 5 hours, and then filtered through a 5.0 μm filter to prepare a blue colored composition (DB-100).

7.2 parts of blue pigment (CI Pigment Blue 15: 6) 4.8 parts of violet pigment (CI Pigment Violet 23) 1.0 part of resin-type dispersant (“EFKA4300” manufactured by BASF Japan) Binder 117.5 parts of a resin solution 69.5 parts of propylene glycol monomethyl ether acetate

Subsequently, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered with a 1.0 μm filter to prepare a blue photosensitive coloring composition (RB-1).

Blue colored composition (DB-100) 34.0 parts Binder resin solution 17.6 parts Photopolymerizable monomer (Toagosei Co., Ltd. "Aronix M400") 3.3 parts Photopolymerization initiator (BASF Japan Co., Ltd.) Irgacure 907 ”) 2.0 parts Sensitizer (“ EAB-F ”manufactured by Hodogaya Chemical Industry Co., Ltd.) 0.4 parts Ethylene glycol monomethyl ether acetate 52.7 parts

(Preparation of green photosensitive coloring composition (RG-1))
After the mixture having the following composition was stirred and mixed so as to be uniform, using a zirconia bead having a diameter of 0.5 mm, an Eiger mill (“Mini Model M-250MKII” manufactured by Eiger Japan Co., Ltd.) was used.
), And filtered through a 5.0 μm filter to prepare a green colored composition (DG-1).

12.0 parts of a green pigment (CI Pigment Green 58) 1.0 part of a resin-type dispersant (“EFKA4300” manufactured by BASF Japan) 135.0 parts of a binder resin solution 55.0 parts of propylene glycol monomethyl ether acetate

Subsequently, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare a green photosensitive coloring composition (RG-1).
Green coloring composition (DG-1) 34.0 parts Binder resin solution 115.2 parts Photopolymerizable monomer ("Aronix M400" manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (manufactured by BASF Japan) 2.0 parts of Irgacure 907 "0.4 parts of sensitizer (" EAB-F "manufactured by Hodogaya Chemical Co., Ltd.) 45.1 parts of ethylene glycol monomethyl ether acetate

A black matrix was patterned on a glass substrate, and a red photosensitive coloring composition (RR-1) was applied on the substrate by a spin coater to a thickness such that x = 0.640 to form a colored film. The coating was irradiated with ultraviolet rays at 300 mJ / cm2 using a super high pressure mercury lamp through a photomask. Next, the unexposed portions were removed by spray development with an alkali developing solution composed of a 0.2% by weight aqueous sodium carbonate solution, and the substrate was washed with ion-exchanged water. Was formed. According to the same method, the blue photosensitive coloring composition (R-2) of the present invention is formed to have a thickness of 2.0 μm to form a blue filter segment, and then the green photosensitive coloring composition (RG-1) ) Was applied to a film thickness such that y = 0.600, and a green filter segment was formed to obtain a color filter.

Similarly, using the red photosensitive coloring composition (R-15), the blue photosensitive coloring composition (RB-1) and the green photosensitive coloring composition (RG-1) of the present invention, a color filter I got

By using the photosensitive coloring composition of the present invention, the heat resistance of the color filter, the foreign substance test, the adhesion to a transparent substrate such as glass, the solvent resistance, the alkali developability are improved, and the color filter is preferably used. Was completed.

Claims (10)

A color filter coloring composition comprising at least a coloring agent (A), a binder resin, and an organic solvent,
The colorant (A) contains a salt-forming compound (D) of a resin (B) having a cationic group in a side chain and an anionic dye (C),
The resin (B) having a cationic group in the side chain is an acrylic resin containing a structural unit represented by the following general formula (1), wherein the acrylic resin is
A color resin characterized by being a block resin comprising an A block having a cationic group represented by the following general formula (1) and a B block having no cationic group and having a thermally crosslinkable functional group. Coloring composition.

(In the general formula (1), R ₁ .R ₂ to R ₄ represents a hydrogen atom or a methyl group, represents an alkyl group having 1 to 8 carbon atoms, Q is - COO-R ₅ - represents, R ₅ represents a methylene group, an ethylene group, a propylene group, or a butylene group, and Y ⁻ represents an inorganic or organic anion.)   The coloring composition for a color filter according to claim 1, wherein the thermally crosslinkable functional group is at least one selected from the group consisting of a hydroxyl group and a carboxyl group.   The resin (B) having a cationic group in the side chain is a block resin further containing 3 to 90% by weight of a total of 100% by weight of the resin composition of the general formula (1). The coloring composition for a color filter according to claim 1.   The colored composition for a color filter according to any one of claims 1 to 3, wherein the acrylic resin containing the structural unit represented by the general formula (1) has an ammonium salt value of 10 to 200 mgKOH / g. .   The coloring composition for a color filter according to any one of claims 1 to 4, wherein the organic solvent contains propylene glycol monomethyl ether acetate as a main component.   The coloring composition for a color filter according to any one of claims 1 to 5, wherein the coloring agent further contains a pigment. The anionic dye (C) contains at least one selected from Acid Red 52, Acid Red 289, and a compound represented by the following general formula (2). Coloring composition for color filters.
General formula (2)


[X1 and X3 represent a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
X2 and X4 represent a monovalent aromatic hydrocarbon group which may have a substituent, and at least one of them has a sulfo group. ]   The coloring composition for a color filter according to any one of claims 1 to 7, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.   In an aqueous solution, a resin (B) having a cationic group in the side chain and an anionic dye (C) are mixed, and a pair of the anion and the anionic dye (C) of the resin (B) having a cationic group in the side chain is mixed. The method for producing a colored composition for a color filter according to any one of claims 1 to 8, wherein a salt comprising a cation is removed to obtain a salt forming compound (D). A color filter formed of the coloring composition for a color filter according to claim 1.