JP2016118619A - Colored composition for color filter, and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored composition for color filter which has good coating property and is excellent in high storage stability, high brightness, high voltage retention rate, and storage stability and heat resistance; and to provide a color filter which is free from generation of foreign substances in a coated film and is excellent in OC heat resistance.SOLUTION: A colored composition for color filter is constituted of at least a coloring agent, a binder resin and an organic solvent. The coloring agent contains a salt-forming compound obtained by reacting a resin having a sulfoimide structure with at least one kind of cationic dye selected from a methine dye, an azo dye, an auramine dye, an acridine dye, a setoflavine dye, a phenazine dye and a xanthene dye.SELECTED DRAWING: None

Description

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

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

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

As a technique for solving this problem, the practical application of a dye-based curable composition using a dye that can exist in a dissolved state in a medium of the curable composition as a colorant has been studied and proposed (for example, patents). Reference 1). However, a color filter using a dye as a colorant has the following problems. That is, the dye used for the color filter coloring composition is required to have heat resistance and light resistance and solubility in the resin and the organic solvent used for the resin.
If the solubility in the organic solvent is poor, it is necessary to drastically reduce the solid content in the color filter coloring composition. As a result, the coating properties become very poor, and the color filter coloring composition colorant. It becomes difficult to use as.

  The solubility of a cationic dye in an organic solvent is generally poor. Therefore, the solubility in an organic solvent is improved by salting an organic compound having a sulfonic acid group and a cationic dye to form a salt-forming dye. It has been studied (see Patent Document 2). Here, the organic compound having a sulfonic acid group can be expected to improve heat resistance and light resistance depending on the structure. However, since sufficient solubility cannot be obtained with respect to the solvent used at the time of producing the color filter and the compatibility with the resin to be added is poor, it should be used as a coloring material for the color filter coloring composition. It is the present condition that cannot be done. Moreover, since the solubility with respect to an organic solvent is insufficient, there also exists a malfunction that the cationic dye in the coloring composition for color filters precipitates with time. (Insufficient storage stability) In addition, when a colored composition for color filters prepared using a poorly soluble cationic dye is applied to a glass substrate, a large amount of foreign matter (undissolved cationic dye) is generated. There is also a problem such as.

Then, improvement examination of the heat resistance by salt-forming dye by the salt-forming of the organic compound which consists of sulfoimide groups with higher acidity than sulfonic acid and cationic dye is made (refer patent document 3). However, since the acidic compound that can be salified with the dye has a low molecular weight, a decrease in resistance in the baking process has been confirmed, and the coloring composition for color filters has a problem in practicality.

On the other hand, regarding the improvement of the film forming property of the color filter coloring composition using a cationic dye salt as a colorant, a color containing a polymer in which a triphenylmethane dye is covalently bonded in the molecule as a colorant. A filter has been proposed (see Patent Document 4). However, when a cationic dye having a polymerizable group is polymerized, since the cationic dye has a counter salt, the solubility in an organic solvent at the time of producing a color filter is insufficient. For this reason, there arises a problem that foreign matter is generated due to insufficient solubility.

Patents relating to a coloring composition containing a triphenylmethane dye and a resin having a sulfoimide group have been reported (see Patent Document 5). However, there is no detailed description about the solubility in the solvent used for the color filter, and the heat resistance and film-forming properties that can be used as a color filter.
In addition, the salt-forming compounds described in these documents have a problem that the lightness is likely to decrease due to poor heat resistance after the overcoat agent treatment, and the heat resistance after the overcoat agent treatment is excellent. There is a need for colored compositions.

JP-A-6-75375 Japanese Patent Publication No.56-9557 Japanese Patent Application Laid-Open No. 2012215686 JP 2000-162429 A JP 2012-194466 A

  The object of the present invention is a coloring composition for a color filter having good coating properties, high storage stability, high brightness, high voltage holding ratio, heat resistance, high contrast, and high OC (overcoat agent) heat resistance. The present invention also provides a color filter that does not generate foreign matter on the coating film.

The present invention is a color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant is an ethylenically unsaturated monomer represented by the following general formula (1) (a -1) a resin obtained by radical polymerization of an ethylenically unsaturated monomer, and a methine dye, an azo dye, an auramine dye, an acridine dye, a cetoflavin dye, a phenazine dye, and a xanthene dye. The present invention relates to a coloring composition for a color filter comprising a salt-forming compound obtained by reacting at least one selected cationic dye.
General formula (1)

[In general formula (1), X represents an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, or an aryl group, Y represents a divalent hydrocarbon group, and Z represents an ethylenic group. It is a group containing a saturated group. W ⁺ represents an inorganic or organic cation. ]

The present invention also relates to the colored composition for a color filter, wherein Z in the general formula (1) is a group represented by the general formula (2).
General formula (2)

  The present invention also relates to the color filter coloring composition, wherein the cationic dye is a methine dye and / or a xanthene dye.

  In addition, the present invention relates to the color filter coloring composition, wherein the colorant further contains a pigment and / or a dye.

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

  Moreover, this invention relates to the color filter formed with the said coloring composition for color filters.

  The coloring composition for a color filter of the present invention has high storage stability, high brightness, high voltage holding ratio, high contrast, heat resistance, and coating property, and does not generate foreign matters during coating film formation, and has a high OC ( Overcoat agent) A color filter having heat resistance can be obtained.

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

The colored composition for a color filter of the present invention is a resin and a cationic polymer obtained by radical polymerization of an ethylenically unsaturated monomer (a) containing at least a specific ethylenically unsaturated monomer (a-1). It contains a colorant containing a salt-forming compound obtained by reacting with a dye, a binder resin, and an organic solvent.

<Colorant>
(Resin formed by radical polymerization of ethylenically unsaturated monomer (a) containing ethylenically unsaturated monomer (a-1) represented by general formula (1))
A resin obtained by radical polymerization of an ethylenically unsaturated monomer (a) including the ethylenically unsaturated monomer (a-1) represented by the general formula (1) is an ethylenically unsaturated monomer represented by the general formula (1). It can be obtained by radical polymerization of the saturated monomer (a-1) and, if necessary, other ethylenically unsaturated monomers. From the viewpoint of compatibility with the binder resin in the color filter coloring composition, the ethylenically unsaturated monomer (a-1) represented by the general formula (1) and other ethylenically unsaturated monomers A vinyl resin obtained by radical polymerization of is preferably used.

  When preparing a coloring composition for a color filter containing the salt-forming compound of the present invention and exhibiting properties as a color filter, it is possible to use the same type of resin as the binder resin constituting the coloring composition for the color filter. desirable. Since a vinyl resin is preferably used as the binder resin, a vinyl resin is most preferable as a resin having a sulfoimide group for obtaining a salt-forming compound.

[Ethylenically unsaturated monomer (a-1) represented by general formula (1)]
The ethylenically unsaturated monomer (a-1) of the present invention is a monomer having a sulfoimide group represented by the following general formula (1).

General formula (1)

[In general formula (1), X represents an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, or an aryl group, Y represents a divalent hydrocarbon group, and Z represents an ethylenic group. It is a saturated group. W ⁺ represents an inorganic or organic cation. ]

  The alkyl group constituting X in the general formula (1) is a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms.

Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms of X include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and a heptyl group. Octyl group, nonyl group, decyl group, dodecyl group, octadecyl group, trifluoromethyl group, isopropyl group, isobutyl group, isopentyl group, 2-ethylhexyl group, sec-butyl group, tert-butyl group, sec-pentyl group, Examples include tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, 4-decylcyclohexyl group, and the like. It is not limited.

A part of hydrogen atoms in the alkyl group of X may be substituted with fluorine atoms. In particular, a fluorinated alkyl group having 1 to 3 carbon atoms and in which some or all of the hydrogen atoms are substituted with fluorine atoms is preferred. Among them, a perfluoroalkyl group in which all hydrogen atoms are substituted with fluorine atoms is a sulfoimide. This is particularly preferable in terms of increasing the acidity of the dye and improving the stability of the dye.

  Specifically, for example, trifluoromethyl group, difluoromethyl group, fluoromethyl group, pentafluoroethyl group, 2,2,2-trifluoroethyl group, 2-fluoroethyl group, 3,3,3-trifluoro A propyl group, a 3-fluoropropyl group, etc. can be mentioned.

In the general formula (1), the aryl group of X is a monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms, such as a phenyl group, a 1-naphthyl group, a 2-naphthyl group, p- Biphenyl group, m-biphenyl group, 2-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 2-fluorenyl group, 3-fluorenyl group, 9-fluorenyl group, 1- A pyrenyl group, a 2-pyrenyl group, a 3-perylenyl group and the like can be mentioned, but are not limited thereto.

A part of hydrogen atoms in the aryl group of X may be substituted with fluorine atoms. In particular, a fluorinated aryl group having 6 to 11 carbon atoms, in which some or all of the hydrogen atoms are substituted with fluorine atoms, and among them, a pentafluorophenyl group in which all the hydrogen atoms are substituted with fluorine atoms is a sulfoimide. This is particularly preferable in terms of increasing the acidity of the dye and improving the stability of the dye.

There is no restriction | limiting in particular as a bivalent hydrocarbon group of Y in General formula (1), For example, C1-C1
10 linear or branched alkylene groups, 6 to 20 arylene groups, 7 to 7 carbon atoms
And 20 arylalkylene groups.

Specific examples of the alkylene group include a methylene group, an ethylene group, an n-propylene group, an isopropylene group, and various butylene groups. Examples of the arylene group include a phenylene group and a naphthylene group. Examples of the arylalkylene group include an arylmethylene group, an arylethylene group, and an arylpropylene group. Of these, an arylalkylene group having 7 to 10 carbon atoms is preferable from the viewpoint of availability of raw materials and production, and an arylmethylene group, an arylethylene group, and an arylpropylene group are particularly preferable.
The arylalkylene group includes an ortho form, a meta form and a para form, but is preferably a para form from the viewpoint of no steric hindrance.

There is no restriction | limiting in particular as group containing the ethylenically unsaturated group of Z in General formula (1), For example, a (meth) acryloyl group, a vinyl group, etc. are mentioned, Preferably, it represents with General formula (2). It is a group.
General formula (2)

The W ⁺ component in the general formula (1) constituting the ethylenically unsaturated monomer represents an inorganic or organic cation, and any known one can be used without limitation. Specific examples of W include hydrogen, alkali metals, alkaline earth metals, and ammonium compounds. At that time, the alkali metal is preferably sodium or potassium, and the alkaline earth metal is preferably calcium or magnesium. An ammonium compound is a compound in which NH ₄ ⁺ or H thereof is substituted with a hydrocarbon group or the like.

Specific examples of the sulfoimide monomer include the following sulfoimide anion monomers, but the present invention is not limited thereto.

[Other ethylenically unsaturated monomers]
The other ethylenically unsaturated monomer is not particularly limited as long as it can be radically polymerized with the ethylenically unsaturated monomer (a-1) represented by the general formula (1). Can be selected as appropriate. For example,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, Linear or branched alkyl (meth) acrylates such as isomyristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;

Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;

Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;

Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;

(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) (Meth) acrylates having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate;

2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or (Meth) acrylates having a hydroxyl group such as caprolactone adducts of these monomers (immol number is 1 to 5);

Methoxy polyethylene glycol mono (meth) acrylate, octoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, lauroxy polyethylene glycol mono (meth) acrylate, stearoxy polyethylene glycol mono (meth) acrylate, phenoxy polyethylene glycol mono (meth) acrylate, Phenoxy polyethylene glycol polypropylene glycol mono (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, Lauroxy polyethylene glycol mono (meth) acrylate, Nonylphenoxy polyethylene glycol mono (meth) acrylate, Nonylphenoxy polypropylene glycol mono (meth) acrylate, Nonylphenoxy polyethylene glycol polypro Lenglycol mono (meth) acrylate, phenoxypolyethyleneglycol mono (meth) acrylate, methoxypolyethyleneglycol (meth) acrylate, n-butoxyethyl (meth) acrylate, n-butoxydiethylene glycol (meth) acrylate, 2-methoxyethyl (meth) (Meth) acrylates having an ether group such as acrylate and 2-ethoxyethyl (meth) acrylate;

3- (acryloyloxymethyl) 3-methyloxetane, 3- (methacryloyloxymethyl) 3-methyloxetane, 3- (acryloyloxymethyl) 3-ethyloxetane, 3- (methacryloyloxymethyl) 3-ethyloxetane, 3- Oxetanyl groups such as (acryloyloxymethyl) 3-butyloxetane, 3- (methacryloyloxymethyl) 3-butyloxetane, 3- (acryloyloxymethyl) 3-hexyloxetane and 3- (methacryloyloxymethyl) 3-hexyloxetane (Meth) acrylates having;

Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
N-substituted type (meta) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine ) Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile;
Antioxidant unit-containing (meth) acrylates having a hindered amine skeleton such as 1,2,2,6,6, -pentamethylpiperidyl (meth) acrylate and 2,2,6,6, tetramethylpiperidyl (meth) acrylate;
Alternatively, a mixture thereof can be mentioned.

Vinyl ethers having an ether group such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether can also be copolymerized with the monomer (a-1).

As other ethylenically unsaturated monomers, those having a thermally crosslinkable functional group or an alkyl group are preferred from the viewpoints of polymerizability with the monomer represented by formula (1) and the heat resistance of the colored composition.

The heat-crosslinkable functional group is not particularly limited as a suitable structure. For example, a hydroxyl group, a carboxyl group, a carboxylic acid anhydride, a primary or secondary amino group, an imino group, an oxetanyl group, a tertiary butyl group, an epoxy And ethylenically unsaturated monomers having a group, mercapto group, isocyanate group, allyl group, (meth) acryl, glycidyl group, and the like. Above all, from the viewpoint of storage stability and reactivity with other materials in the use of a coloring composition for a color filter, a hydroxyl group, a carboxyl group, an oxetanyl group, a tertiary butyl group, an isocyanate group, a (meth) acryl group, an epoxy group, A glycidyl group is preferable, and a hydroxyl group, a carboxyl group, an isocyanate group, and a glycidyl group are particularly preferable.

Of the ethylenically unsaturated monomers having a hydroxyl group, hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are most preferred from the viewpoint of heat resistance.

Of the ethylenically unsaturated monomers having a carboxyl group, (meth) acrylic acid is most preferable from the viewpoint of heat resistance.

  Of the ethylenically unsaturated monomers having an oxetanyl group, (3-ethyloxetane-3-yl) methyl (meth) acrylate is most preferable from the viewpoint of heat resistance.

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

The isocyanate group in the present invention includes a blocked isocyanate group and can be preferably used. Under normal conditions, the blocked isocyanate group can protect the isocyanate group with other functional groups to suppress the reactivity of the isocyanate group, and can be deprotected by heating to regenerate the active isocyanate group. The isocyanate block body is shown.

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

Examples of the ethylenically unsaturated monomer having a glycidyl group include a glycidyl (meth) acrylate group.

The structure suitable as the alkyl group is not particularly limited, but for example, a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group, a lauryl group, a dodecyl group, or an isostearyl group is preferable, and as the ethylenically unsaturated monomer, Is preferably methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, or isostearyl (meth) acrylate.

  As a method for obtaining a resin obtained by copolymerizing an ethylenically unsaturated monomer (a) containing an ethylenically unsaturated monomer (a-1) suitable for the present invention, free radical polymerization and living radical polymerization are used. A known method can be used.

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

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

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

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329 (reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

  It is preferable to use an organic solvent for the polymerization. Although it does not specifically limit as an organic solvent, For example, methanol, ethanol, normal propanol, isopropanol, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol Monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. Two or more kinds of these polymerization solvents may be mixed and used.

  The ethylenically unsaturated monomer (a-1) represented by the general formula (1) suitable for the present invention is 5% by weight to 95% by weight based on the total weight of the ethylenically unsaturated monomer (a). % Is preferable, more preferably 5% by weight to 40% by weight, and still more preferably 15% by weight to 35% by weight.

If the weight of the ethylenically unsaturated monomer (a-1) represented by the general formula (1) is less than 5% by weight, the amount of the unformulated cationic dye increases, so that the solvent solubility becomes low. In some cases, coating film foreign matter is likely to precipitate. On the other hand, if it exceeds 95% by weight, the amount of the cationic dye salted into the resin increases, and the heat resistance may deteriorate.

  The molecular weight of the resin obtained by radical polymerization of the ethylenically unsaturated monomer (a) including the ethylenically unsaturated monomer (a-1) represented by the general formula (1) used in the present invention is particularly Although not limited, it is preferable that the conversion weight average molecular weight measured by gel permeation chromatography (GPC) is 1,000-500,000, and it is more preferable that it is 3,000-15,000. More preferably, it is 3,000 to 8,000.

  In addition, a resin obtained by radical polymerization of an ethylenically unsaturated monomer (a) containing the ethylenically unsaturated monomer (a-1) represented by the general formula (1) suitable for the present invention is an organic solvent. A mixed solution may be used. As an organic solvent, methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol mono Chill ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol, Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone, and the like. Moreover, you may have the characteristic melt | dissolved in the propylene glycol monomethyl ether acetate etc. which are the solvent widely used for the coloring composition for color filters.

(Cationic dye)
Next, the cationic dye for obtaining the salt-forming compound of the present invention will be described. The cationic dye is ionically bonded to a resin obtained by radical polymerization of an ethylenically unsaturated monomer (a) including the ethylenically unsaturated monomer (a-1) represented by the general formula (1) described above. The cationic dye is at least one selected from methine dyes, azo dyes, auramine dyes, acridine dyes, cetoflavin dyes, phenazine dyes, and xanthene dyes. Among them, methine dyes and xanthene dyes are preferable because they have a high effect of improving heat resistance and solvent solubility by salt formation with a resin.

{Metin dyes}
The methine dye is not particularly limited as long as it is a dye having a methine group (—CH═) linked by a conjugated double bond in the molecular structure, but a dye represented by the following general formula (2) is preferable.

[In general formula (2),
X represents a carbon atom having a substituent or a hydrogen atom, a nitrogen atom having a substituent, or a sulfur atom,
R ^{3 to} R ⁶ are each independently a hydrogen atom, halogen atom, nitro group, substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted Represents a substituted aryl group or a substituted or unsubstituted acyl group;
R ⁷ represents a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ⁸ represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group,
A represents —CH═CH—, —CH═CH—NR ⁹ —,
R ⁹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ]

R ⁸ is preferably a group represented by the following general formulas (2a) to (2g).

[In the general formulas (2a) to (2h)
X represents a carbon atom having a substituent or a hydrogen atom, a nitrogen atom having a substituent, or a sulfur atom,
R ¹⁰ and R ¹¹ each independently represent a C 1-6 alkyl group which may have a substituent,
R ^{12 to} R ¹⁸ each independently represent a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a nitro group,
R ^{19 to} R ²² are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms, substituted or unsubstituted Represents a substituted aryl group or a substituted or unsubstituted acyl group;
R ²³ represents a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms. ]

Specific examples of the general formula (2) include the following cationic dyes, but the present invention is not limited thereto. Examples of the counter of the cationic dye shown below include Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ SO ₄ ^— .

{Azo dyes}
The azo dye is not particularly limited as long as it is a dye having an azo group (RN = NR ′) in the dye structure and an aromatic ring in one of the organic groups, but the following general formula (3- Those represented by 1) to (3-3) are preferred.

[In the general formulas (3-1) to (3-3),
R ¹⁹ , R ²⁰ and R ²⁶ each independently represents a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ²¹ represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted heterocyclic group,
X represents a carbon atom having a substituent or a hydrogen atom, a nitrogen atom having a substituent, or a sulfur atom,
R ^{22 to} R ²⁵ and R ²⁷ are each independently a hydrogen atom, a halogen atom, a nitro group, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 4 carbon atoms. Represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted acyl group,
R ²⁸ represents a group that forms a quaternary ammonium salt. ]

Examples of the _{^{R 28, -NR 29 C m H}} 2m N + R 30 R 31 R 32 (m is an integer from 1 to 5, R ²⁹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ^{30 to} R ³² each independently represents an alkyl group having 1 to 6 carbon atoms), —COC _m H _2m N ⁺ R ³⁰ R ³¹ R ³² (m, R ³⁰ , R ³¹ and R ³² are as defined above). in _{a), - C m H 2m N} + (NH 2) is R ³³ R ³⁴ (m are as defined above, R ³³ and R ^34, independently of one another, represent an alkyl group having 1 to 6 carbon atoms ) Is preferred.

R ²¹ is preferably a group represented by the following general formulas (3a) to (3e).

[In the general formulas (3a) to (3e)
R ^{35 represents a} hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group or a benzyl group,
R ³⁶ and R ³⁷ each independently represents an alkyl group having 1 to 6 carbon atoms,
R ³⁸ and R ⁴³ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ³⁹ , R ⁴¹ , R ⁴⁴ and R ⁴⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Represents an alkyl group, an alkoxy group having 1 to 6 carbon atoms, a halogen atom, a nitro group, a hydroxyl group or a cyano group;
R ⁴⁰ and R ⁴² each independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group. ]

Specific examples of the general formula (3) include the following cationic dyes, but the present invention is not limited thereto. Examples of the counter of the cationic dye shown below include Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ SO ₄ ^— .

{Auramine dye}
As an auramine type | system | group pigment | dye, what is represented by following General formula (4) is preferable.


[In general formula (4),
R ^{46 to} R ⁵¹ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms,
R ⁵² and R ⁵³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a substituent. ]

Specific examples of the general formula (4) include the following cationic dyes, but the present invention is not limited thereto. Examples of the counter of the cationic dye shown below include Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ SO ₄ ^— .

{Acridine dyes}
As the acridine dye, those represented by the following general formula (5) are preferable.

[In general formula (5),
R ^{54 to} R ⁵⁸ each independently represent a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms,
R ⁵⁹ , R ⁶⁰ , and R ⁶¹ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 6 carbon atoms that may have a substituent. ]

Specific examples of the general formula (5) include the following cationic dyes, but the present invention is not limited thereto. Examples of the counter of the cationic dye shown below include Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ SO ₄ ^— .

{Cetoflavin dye}
As the cetoflavin dye, those represented by the following general formula (6) are preferable.

[In general formula (6),
Z represents a carbon atom having a substituent or a hydrogen atom, a nitrogen atom having a substituent, or a sulfur atom,
R ⁶² and R ⁶⁴ each independently represent a hydrogen atom, a halogen atom, an organic group having a polymerizable functional group, or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms,
R ⁶³ , R ⁶⁵ and R ⁶⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. ]

Specific examples of the general formula (6) include the following cationic dyes, but the present invention is not limited thereto. Examples of the counter of the cationic dye shown below include Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ SO ₄ ^— .

{Xanthene dyes}
The xanthene dye is not particularly limited as long as it is a dye having a three-membered structure condensed on a straight line having a pyran ring at the center, but those represented by the following general formula (7) are preferable.

[In general formula (7),
R ⁶⁷ , R ⁶⁸ , R ⁶⁹ and R ^{70 are} each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 6 carbon atoms, or an optionally substituted carbon number 1 Represents an aryl group of ˜6.
R ⁷¹ and R ⁷² each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
R ⁷³ represents —SO ₃ H, —SO ₃ M, —CO ₂ H, —CO ₂ R ⁷⁴ , —SO ₃ R ⁷⁴ , —SO ₂ NHR ⁷⁵ or —SO ₂ NR ⁷⁵ R ⁷⁶ .
m shows the integer of 0-5. When m is an integer of 2 or more, the plurality of R ⁷³ may be the same or different.
R ⁷⁴ represents an alkyl group having 1 to 10 carbon atoms which may have a substituent.
R ⁷⁵ and R ⁷⁶ each independently represent an optionally substituted alkyl group having 1 to 10 carbon atoms, or an optionally substituted aryl group having 1 to 6 carbon atoms. Or a heterocyclic group having 1 to 10 carbon atoms formed by bonding of R ⁷⁴ and R ⁷⁵ to each other. However, the hydrogen atom contained in the heterocyclic group is an alkyl group having 1 to 10 carbon atoms which may have a substituent, an aryl group having 1 to 6 carbon atoms which may have a substituent, -R ^74. Or may be substituted with -OH.
M represents a sodium atom or a potassium atom. ]

Specific examples of the general formula (7) include the following cationic dyes, but the present invention is not limited thereto. Examples of the counter of the cationic dye shown below include Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ SO ₄ ^— .

{Phenazine dye}
The phenazine dye is preferably represented by the following general formula (8).

[In general formula (8),
R ^{76 to} R ⁷⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms which may have a substituent.
R ⁸⁰ to R ⁸⁶ are independently of each other hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a substituent, or an aryl group having carbon atoms of 1-6 that may have a substituent Represent. ]

Specific examples of the general formula (8) include the following cationic dyes, but the present invention is not limited thereto. Examples of the counter of the cationic dye shown below include Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ SO ₄ ^— .

General formula (2), (2a)-(2g), (3-1)-(3-3), (3a)-(3e), (4), (5), (6), (7), In (8),
Examples of the “alkyl group” include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of the “alkoxy group” include methoxy group, ethoxy group, propoxy group, butoxy group, isopropoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, and the like.
As the “aryl group”, a phenyl group, a biphenylyl group, a terphenylyl group, a quarterphenylyl group, a pentarenyl group, an indenyl group, a naphthyl group, a binaphthalenyl group, a tannaphthalenyl group, a quarternaphthalenyl group, an azulenyl group, a heptaenyl group, a biphenylenyl group , Indacenyl group, fluoranthenyl group, acephenanthrenyl group, aceanthrylenyl group, phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, teranthracenyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group , Triphenylenyl group, pyrenyl group, chrycenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, Kisaseniru group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, ovalenyl group and the like,
Examples of the “halogen atom” include fluorine, chlorine, bromine and iodine.
Examples of the “acyl group” include acetyl group, ethanoyl group, propanoyl group, isopropanoyl group, butanoyl group, isobutanoyl group, sec-butanoyl group, tert-butanoyl group and the like.
Examples of the “aromatic hydrocarbon group” include a phenyl group, a biphenylyl group, a naphthyl group, and the like.
Examples of the “heterocyclic group” include indole ring, benzoindole ring, indolenine ring, benzoindolenin ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, benzimidazole ring, quinoline ring, and the like.

Moreover, general formula (2), (2a)-(2g), (3-1)-(3-3), (3a)-(3e), (4), (5), (6), (7 ), (8)
“Organic group having a polymerizable functional group” is a group composed of an atomic group that contains a polymerizable functional group, contains a carbon-hydrogen bond as a whole, and may contain atoms other than carbon if necessary. Indicates. Specifically, there are a case where it consists of only a polymerizable functional group and a case where it contains a polymerizable functional group and a linking group.
Here, examples of the polymerizable functional group include a (meth) acryloyl group, a vinyl group, an epoxy group, an isocyanate group, and the like (as viewed from the cyanine skeleton), an alkylene group (hereinafter referred to as -X- and -XO- group, -XNH- group, arylene group, aryleneoxy group, -XCONH- group, -XCOO- group, -XOCO- group, -XCOOX- group, -XOCOXX- group, -XCOOXCOO- group , -XOCOXCOO- group, and the like.

General formula (2), (2a)-(2g), (3-1)-(3-3), (3a)-(3e), (4), (5), (6), (7), In (8),
Examples of the “substituent” include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, and tert-pentyl group. Aliphatic hydrocarbon groups such as; polymerizable functional groups such as (meth) acryloyl groups, vinylaryl groups, vinyloxy groups, allyl groups, epoxy groups; phenyl groups, o-tolyl groups, m-tolyl groups, p-tolyl groups , Xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group and other aromatic hydrocarbon groups; methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec- Alkoxy groups such as butoxy group, tert-butoxy group and pentyloxy group; aryloxy groups such as phenoxy group An aralkyloxy group such as a benzyloxy group; a group having an ester bond such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an acetoxy group, or a benzoyloxy group; a methylsulfamoyl group, a dimethylsulfamoyl group, an ethylsulfuryl group; Famoyl group, diethylsulfamoyl group, n-propylsulfamoyl group, di-n-propylsulfamoyl group, isopropylsulfamoyl group, diisopropylsulfamoyl group, n-butylsulfamoyl group, di- alkylsulfamoyl groups such as n-butylsulfamoyl group; methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, isobutylsulfonyl group, sec-butylsulfonyl group, tert- Alkylsulfonyl groups such as Chirusuruhoniru group; fluorine atom, a chlorine atom, a bromine atom, a halogen atom such as iodine atom; a nitro group, can be a cyano group.

(Salt making)
The salt-forming compound of the present invention comprises a resin obtained by radical polymerization of an ethylenically unsaturated monomer (a) containing the ethylenically unsaturated monomer (a-1) represented by the general formula (1), a cation An ethylenically unsaturated monomer (a) containing an ethylenically unsaturated monomer (a-1) represented by the general formula (1): ) Can be easily obtained by mixing an aqueous solution or organic solvent of a resin obtained by radical polymerization with a cationic dye under stirring or vibration.
In the solution, the anionic group derived from the ethylenically unsaturated monomer (a) in the resin and the cationic group of the dye are ionized, these are ionically bonded, and the ionic bond portion is insolubilized and precipitated in water. To do. On the contrary, the salt formed by reacting the counter cation derived from the ethylenically unsaturated monomer (a) and the counter anion of the dye in the resin is water-soluble and can be removed by washing or the like.

The resin obtained by radical polymerization of the ethylenically unsaturated monomer (a) including the ethylenically unsaturated monomer (a-1) represented by the general formula (1) to be used and the cationic dye are each a simple substance. Only one type may be used, or a plurality of types having different structures may be used.

  Moreover, the salt-forming compound of the present invention radically polymerizes an ethylenically unsaturated monomer (a) containing the ethylenically unsaturated monomer (a-1) represented by the general formula (1) in an aqueous solution. And a radical dye polymerization of the ethylenically unsaturated monomer (a) including the ethylenically unsaturated monomer (a-1) represented by the general formula (1). A compound formed by removing a salt composed of a counter cation of a resin and a counter anion of a cationic dye with water is preferable.

  As an aqueous solution used at the time of salt formation, a mixed solution of water and an organic solvent may be used in order to dissolve the resin having sulfate ions and the cationic dye. As an organic solvent, methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol, Propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol mono Chill ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone, N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol, Examples include tetrafurfuryl alcohol and 4-methoxy-4-methylpentanone. 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 (100% by weight) of the aqueous solution.

  The ratio of the resin obtained by radical polymerization of the ethylenically unsaturated monomer (a) containing the ethylenically unsaturated monomer (a-1) represented by the general formula (1) and the cationic dye is the resin The salt-forming compound of the present invention can be suitably adjusted so long as the molar ratio of the total anion unit of the cationic dye to the total cationic group of the cationic dye is in the range of 10/1 to 1/4. If it is a range, it is more preferable.

(Pigment)
The colorant of the present invention may further contain a pigment.
As the pigment, organic or inorganic pigments can be used alone or in admixture of two or more. The pigment is preferably a pigment having a high color developability and a high heat resistance, particularly a pigment having a high heat decomposition resistance, and an organic pigment is usually used. Below, the specific example of the organic pigment which can be used for the coloring composition for color filters is shown by a color index number.

  Examples of the red coloring composition for forming the red filter segment include C.I. I. Pigment Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 123, 146, 150, 166, 168, 169, 176, 177, 178, 179, 180, 184, 185, 187, 192, 200, 202, 208, 210, 215, 216, 217, 220, 221, 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, Red pigments such as 286 or 287 can be used. The red coloring composition includes C.I. I. Pigment Orange 36, 38, 43, 71, or 73, and / or C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181 , 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221 can be used in combination.

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

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

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

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

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

[Miniaturization of pigment]
When the colorant used in the coloring composition of the present invention contains a pigment, it is preferably used after being refined. There are no particular limitations on the method of miniaturization. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As exemplified in the present invention, salt milling treatment by a kneader method, which is one type of wet grinding. Etc. can be made finer. It is preferable that the average primary particle diameter calculated | required by TEM (transmission electron microscope) of a pigment is the range of 5-90 nm. When the thickness is smaller than 5 nm, dispersion in an organic solvent becomes difficult. When the thickness is larger than 90 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 10 to 70 nm.

  Salt milling is a batch or continuous type of mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, such as a kneader, 2-roll mill, 3-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. In this process, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water after mechanically kneading while heating using a kneader. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

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

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

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

(dye)
The colorant of the present invention may further contain a dye.
As the dye, organic or inorganic dyes can be used alone or in admixture of two or more. Below, the specific example of the organic pigment which can be used for the coloring composition for color filters is shown.

Anthraquinone dye, acridine dye, azo dye, azamethine dye, hydrazomethine dye, triphenylmethane dye, benzodifuranone dye, coumarin dye, diketopyrrolopyrrole dye, dioxazine dye, diphenylmethane dye, formazan dye, indigoid indophenol dye, naphthalimide dye , Naphthoquinone dye, nitroaryl dye, merocyanine dye, methine oxazine dye, perinone dye, perylene dye, pyrenequinone dye, phthalocyanine dye, phenazine dye, quinoneimine dye, quinacridone dye, quinophthalone dye, styryl dye, stilbene dye, xanthene dye, thiazine dye And thioxanthene dyes can be used.

<Binder resin>
The binder resin is one that disperses a colorant, particularly a salt-forming compound and a pigment, or one that dyes and permeates the salt-forming compound, and examples thereof include a thermoplastic resin. In the present invention, the colorant is composed of the salt-forming compound or the salt-forming compound and a pigment.

  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. Moreover, when using with the form of an alkali image development type color resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

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

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

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. Further, a polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferred as the color filter coloring composition.

  The molecular weight of the binder resin used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC) is preferably 5,000 to 100,000. More preferably, it is 7,000-50,000. It is preferable that the converted weight average molecular weight of the binder resin is 5,000 to 100,000, because film loss is unlikely to occur during development, and the non-pixel portion is liable to be easily removed during development. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are HLC-8220GPC (manufactured by Tosoh Corporation) as a device, and TSK-GEL SUPER HZM-N is connected in series as a column. Is a molecular weight in terms of polystyrene measured using THF.

  When the binder resin is used as a coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that acts as an alkali-soluble group during development, an aliphatic group that acts as an affinity group for the colorant carrier and solvent, and an aromatic group The balance of groups is important for the dispersibility, penetrability, developability, and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

  The binder resin is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant. If it is less than 20 parts by weight, the film formability and various resistances will be insufficient, and if it is more than 500 parts by weight, the concentration of the colorant will be low and color characteristics may not be exhibited.

<Thermosetting compound>
In the present invention, it is preferable to further include a thermosetting compound in combination with the thermoplastic resin which is a binder resin. When producing a color filter using the coloring composition for a color filter of the present invention, by including a thermosetting compound, it reacts at the time of firing the filter segment to increase the crosslinking density of the coating film, so that the heat resistance of the filter segment is increased. This improves the effect of suppressing pigment aggregation during firing of the filter segment and improving the contrast ratio.

  Examples of thermosetting compounds include epoxy compounds and / or resins, benzoguanamine compounds and / or resins, rosin-modified maleic acid compounds and / or resins, rosin-modified fumaric acid compounds and / or resins, melamine compounds and / or resins, Examples include urea compounds and / or resins, and phenol compounds and / or resins, but the present invention is not limited thereto. In the coloring composition for a color filter of the present invention, an epoxy compound and / or a resin are preferably used.

The epoxy compound may be a low molecular compound or a high molecular weight compound such as a resin.
Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxy Benzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Condensates, phenols and various diene compounds (dicyclopentadiene, terpenes, Polymers with nylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.) ), Polyphenols and aromatic dimethanols (benzenedimethanol, α, α, α ′, α′-benzenedimethanol, biphenyldimethanol, α, α, α ′, α′-biphenyldimene) Methanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, alcohols Etc. glycidylated Glycidyl ether epoxy resins, alicyclic epoxy resins, glycidyl amine-based epoxy resin, glycidyl ester type epoxy resins, but are not limited to these would normally epoxy compound used. These may be used alone or in combination of two or more.

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

  The compounding amount of the epoxy compound is preferably 0.5 to 300 parts by weight, and more preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the colorant. If the amount is less than 0.5 part by weight, the effect of improving heat resistance is small.

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

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. Contains an organic solvent 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, since the salt-forming compound used in the present invention and the optional pigment are well dispersed and dissolved, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether 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 health and safety and low viscosity.

  These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When two or more kinds of mixed solvents are used, it is preferable that 65 to 95% by weight of the above-mentioned preferable organic solvent is contained.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

<Dispersion>
The coloring composition of the present invention reacts a resin obtained by radical polymerization of an ethylenically unsaturated monomer (а-1) containing an ethylenically unsaturated monomer represented by the general formula (1) with a cationic dye. When a pigment is further included in the colorant carrier comprising the salt-forming compound obtained above, the binder resin and the solvent, preferably a three-roll mill, a two-roll mill, a sand mill together with a dispersion aid such as a pigment derivative. It can be manufactured by finely dispersing using various dispersing means such as a kneader or an attritor. The colored composition of the present invention can also be produced by mixing pigments, salt-forming compounds, other colorants and the like separately dispersed in a colorant carrier.

《Dispersing aid》
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.
In the present invention, the salt-forming compound is also expected to play a role as a pigment dispersion aid.

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

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

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

   Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., BASF Manufactured by 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, 7554, 101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

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

  The amount of the resin-type dispersant and surfactant added 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 blending amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. May affect.

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

  The photopolymerizable monomer of the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these can be used alone or in combination of two or more.

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

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

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy) Enyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime) Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) ) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds An imidazole compound; or a titanocene compound.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Other additive components>
(Sensitizer)
Furthermore, the coloring composition for a color filter of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophen Non, 4,4′-diethylaminobenzophenone and the like.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

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

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

(Multifunctional thiol)
The coloring composition for a color filter of the present invention can contain a polyfunctional thiol that functions as a chain transfer agent.
The polyfunctional thiol may be a compound having two or more thiol groups. For example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, Pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene,
2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine and the like. These polyfunctional thiols can be used singly or in combination of two or more in any ratio as necessary.

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

(Antioxidant)
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

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

  When the content of the antioxidant is 0.5 to 5.0% by weight based on the solid content weight of the color filter coloring composition (100% by weight), brightness and sensitivity are more preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

  The formation of filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink can be adjusted with a dispersant or extender pigment.

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

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

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

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

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

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

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” means “parts by weight”. Moreover, the measuring method of the average primary particle diameter of a pigment and the weight average molecular weight (Mw) of resin is as follows.

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

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

  First, radical polymerization was performed on the ethylenically unsaturated monomer including the binder resin, the refined pigment, and the ethylenically unsaturated monomer (a-1) represented by the general formula (1) used in Examples and Comparative Examples. The production method of the resin, the salt-forming compound, and the mixture of the binder resin and the cationic dye will be described.

<Binder resin production method>
(Preparation of binder resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 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 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. The binder resin solution 1 was obtained by addition.

(Preparation of binder resin solution 2)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 30.0 parts of methyl methacrylate, 40.0 parts of n-butyl methacrylate, 20.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile ) And 25.1 parts of methyl ethyl ketone were made uniform, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of the dropping, it was confirmed that the polymerization yield was 98% or more from the solid content, and the weight average molecular weight (Mw) was 7140, and the mixture was cooled to room temperature. Thereafter, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. A resin solution 2 was obtained.

<Production method of fine pigment>
(Red fine pigment (P-1): PR254)
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 ("IRGAZIN RED 2030" manufactured by BASF), 1000 parts of ground sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 60 ° C for 10 hours. The mixture was added to 2000 parts of warm water, heated to about 80 ° C. and stirred with a high speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 115 parts of red refined pigment (P-3). The average primary particle diameter of the obtained pigment was 24.8 nm.

(Blue refined pigment (P-2): PB15: 6)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyocolor Co., Ltd. “Lionol Blue ES”) 100 parts, 800 parts of ground salt and 100 parts of diethylene glycol were 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 at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 98 parts of blue refinement | purification pigments (P-1). The average primary particle diameter of the obtained pigment was 28.3 nm.

(Blue refined pigment (P-3): aluminum phthalocyanine pigment)
In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of anhydrous aluminum chloride were added to 1250 parts of n-amyl alcohol and stirred. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Further, 100 parts of chloroaluminum phthalocyanine was slowly added to 1200 parts of concentrated sulfuric acid at room temperature in a reaction vessel. The mixture was stirred at 40 ° C. for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The blue precipitate was filtered, washed with water and dried to obtain 102 parts of an aluminum phthalocyanine pigment represented by the following formula (9).

  Subsequently, 100 parts of an aluminum phthalocyanine pigment represented by the formula (9), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. . The kneaded product was poured into 3000 parts of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. all day and night. A fine pigment (P-7 intermediate) was obtained. The average primary particle size was 30.4 nm.

Formula (9)

Subsequently, 100 parts of methanol phthalocyanine pigment represented by the formula (9) and 49.5 parts of diphenyl phosphate were added to 1000 parts of methanol in a reaction vessel, heated to 40 ° C., and reacted for 8 hours. . After cooling this to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of an aluminum phthalocyanine pigment represented by the following formula (10).
The obtained aluminum phthalocyanine pigment represented by the formula (10) was subjected to a salt milling treatment similar to that for the blue fine pigment (P-7 intermediate) to obtain a blue fine pigment (P-7). The average primary particle size was 31.2 nm.

Formula (10)

<Method for producing pigment paste>
(Preparation of pigment paste PP-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition (PP-1) was produced by filtration using a filter.
Finer pigment (P-1): 10.0 parts Binder resin solution 1: 35.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts Resin-type dispersant: 15.0 parts (Ajinomoto Fine (20% PGMAc solution of “Ajisper PB821” manufactured by Techno)

(Preparation of pigment paste PP-2 to 3)
A pigment paste (PP-2 to 3) was obtained in the same manner as the pigment paste (PP-1) except that the type of fine pigment described in Table 1 was changed.

<Cationic dye>

(Synthesis of Cationic Dye DC-1)
The following cyanine dyes that are methine dyes are J. Org. Chem., 1995, 60 (8), pp 2411-2422, J. Am. Chem. Soc., 2011, 133 (40), pp 15870- I referred to 15873.

To a 100 ml four-necked flask equipped with a thermometer, a dropping funnel and a condenser, 5 g of 5-chloro-2,3,3-trimethylindolenine, 7.35 g of iodobutane, and 10 ml of acetonitrile were added and heated to reflux for 24 hours. After cooling to room temperature, the solvent was distilled off with an evaporator to precipitate a solid. Thereto, 40 ml of diethyl ether was added, washed and filtered with suction. 8.61 g of product (Intermediate 1) was obtained. The yield was 87%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 250.28 (molecular weight 250.14).

8.61 g of Intermediate 1 and 15 ml of acetic anhydride were added to a 100 ml four-necked flask equipped with a thermometer, a dripping funnel, a condenser tube, and a nitrogen flow tube, and 4.05 g of triethyl orthoformate was added thereto using the dripping funnel. The solution was added dropwise and heated to reflux. After 1 hour, the mixture was cooled to room temperature to precipitate a solid. The precipitated solid was filtered off with suction and washed with 30 ml of ethyl acetate and 30 ml of ion-exchanged water. The mixture was heated and dried overnight at 40 ° C. with a hot air dryer to obtain 6.44 g of the product (DC-1). The yield was 89%. The compound was identified with a mass spectrometer (TOF-MS: autoflex II manufactured by Bruker Daltonics). It was confirmed that the product was a target product with a cationic component m / z = 509.38 (molecular weight 509.25).

The cationic dyes DC-2 to DC-9 described in Table 2 are manufactured by Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich Co.

<Production of monomer represented by general formula (1)>
(Synthesis of sulfoimide monomer IC-1)
Synthesis of intermediate IC-1-1

After adding 6.33 g (1.1 equivalent) of trifluoromethanesulfonamide, 5.53 g (2 equivalent) of potassium carbonate, and 160 ml of acetonitrile to a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser tube, 9.00 g (1.0 equivalent) of 4-acetamidobenzenesulfonyl chloride was added in portions and heated to reflux for 5 hours. After cooling to room temperature, 400 ml of acetonitrile was added and stirred well, and then the filtrate obtained by suction filtration was concentrated to obtain 13.01 g of product. It was confirmed by ¹ H, ¹³ C-NMR spectrum (solvent: deuterated chloroform) that the obtained compound was the target compound (intermediate IC-1-1).

Synthesis of intermediate IC-1-2

To a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser tube, 12.76 g (1.1 equivalent) of the intermediate IC-1-1 and 50 g of 5% hydrochloric acid aqueous solution were added, followed by heating for 2 hours 90 The mixture was heated and stirred at ° C. After cooling to room temperature, a saturated aqueous sodium hydrogen carbonate solution was added to bring the pH of the system to 7 or higher. Thereafter, the solvent was concentrated under reduced pressure to obtain the target compound (synthesis of intermediate IC-1-2).

Synthesis of intermediate IC-1-3
In a four-necked separable flask equipped with a thermometer, a stirrer, and a condenser, 11.37 g (1.1 equivalents) of intermediate IC-1-2 and 3.90 g (1.2 equivalents) of maleic anhydride In addition, 50 g of tetrahydrofuran and 50 g of 1,4-dioxane were added, and the mixture was stirred at room temperature for 12 hours. The precipitate produced by the reaction was collected by suction filtration to obtain 10.5 g of the target compound (intermediate IC-1-3).

Synthesis of sulfoimide monomer IC-1
To a four-necked separable flask equipped with a thermometer, a stirrer, and a cooling tube, a mixed liquid consisting of 10.2 g of intermediate IC-1-3, 51.04 g of acetic anhydride and 4.10 g of sodium acetate was added, Stirring was performed at 70 ° C. for 3 hours. Diethyl ether was added to the reaction product, the precipitated solid was suction filtered, acetonitrile was added, and the precipitate was removed by filtration. Diethyl ether was added to the filtrate to cause precipitation, followed by filtration to obtain 9.2 g of the target sulfoimide monomer IC-1.

The sulfoimide monomers (IC-2 to IC-10) as exemplified in Table 1 can also be obtained by the same synthesis method as IC-1.

(Synthesis of sulfoimide monomer IC-11)
Synthesis of Intermediate IC-11-1

In a three-necked flask equipped with a thermometer, stirrer, and condenser, p-vinylbenzenesulfonic acid sodium salt 10.3 g (50.0 mmol), N, N-dimethylformamide (DMF) manufactured by Wako Pure Chemical Industries, Ltd. 3 ml and n-heptane 50 ml were added, and 8.92 g (75.0 mmol) of thionyl chloride was added dropwise at room temperature. After completion of the dropwise addition, the mixture was reacted at 70 ° C. for 2 hours. The n-heptane layer was separated and washed with a saturated aqueous sodium hydrogen carbonate solution. The organic layer was dehydrated with sodium sulfate and concentrated to obtain 2.73 g of the target compound, p-vinylbenzenesulfonyl chloride.

Synthesis of sulfoimide monomer IC-11

Next, 1.49 g (10.0 mmol) of trifluoromethanesulfonamide manufactured by Tokyo Chemical Industry Co., Ltd. and 25 ml of chloroform were added to a three-necked flask equipped with a thermometer, a stirrer, and a condenser tube while cooling to 5 ° C. or lower. . Further, 2.02 g (20.0 mmol) of triethylamine manufactured by Wako Pure Chemical Industries, Ltd. was dropped, and 2.18 g (10.0 mmol) of the synthesized intermediate IC-11-1 was added after completion of the dropping. After stirring for 1 hour while controlling the temperature below 5 ° C., the mixture was further stirred at room temperature for 5 hours, and quenched by adding 100 ml of water to the reaction solution. The separated reaction solution was separated, the organic layer was washed with water, and the organic layer was concentrated under reduced pressure to obtain 3.74 g of the desired compound.

The sulfoimide monomers (IC-12 to IC-13) as exemplified in Table 1 can also be obtained by the same synthesis method as IC-11.

(Synthesis of sulfoimide monomer IC-14)
Synthesis of intermediate IC-14-1

To a three-necked flask equipped with a thermometer, a stirrer, and a condenser tube, 12.3 g (50.0 mmol) of 3-sulfopropyl potassium methacrylate manufactured by Tokyo Chemical Industry Co., Ltd., 10 ml of N, N-dimethylformamide (DMF), While cooling to 0 ° C., 7.15 g (60.0 mmol) of thionyl chloride was added dropwise. After completion of dropping, the reaction was allowed to proceed for 5 hours while controlling at 0 ° C. The reaction solution was concentrated, methyl ethyl ketone was added thereto, the salt was removed by filtration, and the obtained filtrate was concentrated to obtain 3.39 g of 3-sulfonyl chloride methacrylate as the target compound.

Synthesis of sulfoimide monomer IC-14

Next, 1.49 g (10.0 mmol) of trifluoromethanesulfonamide manufactured by Tokyo Chemical Industry Co., Ltd. and 25 ml of chloroform were added to a three-necked flask equipped with a thermometer, a stirrer, and a condenser tube while cooling to 5 ° C. or lower. . Further, 2.02 g (20.0 mmol) of triethylamine manufactured by Wako Pure Chemical Industries, Ltd. was dropped, and 2.26 g (10.0 mmol) of the synthesized intermediate IC-14-1 was added after completion of the dropping. After stirring for 1 hour while controlling the temperature below 5 ° C., the mixture was further stirred at room temperature for 5 hours, and quenched by adding 100 ml of water to the reaction solution. The separated reaction solution was separated, the organic layer was washed with water, and the organic layer was concentrated under reduced pressure to obtain 3.04 g of the desired compound.

The sulfoimide monomers (IC-15 to IC-16) as exemplified in Table 1 can also be obtained by the same synthesis method as IC-14.

<Manufacture of resin formed by radical polymerization of monomer (a-1) represented by general formula (1)>
(Resin formed by polymerizing monomer (a-1) (Resin 1))
75.0 parts of methanol was charged into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, and the temperature was raised to 68 ° C. under a nitrogen stream. Separately, 20.0 parts of sulfoimide anion IC-1, 45.0 parts of methyl methacrylate, 15.0 parts of n-butyl methacrylate, 10.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of hydroxyethyl methacrylate, 2, 2 After 7.0 parts of '-azobis (2,4-dimethylvaleronitrile) and 23.0 parts of methyl ethyl ketone were made uniform, they were charged into a dropping funnel, attached to a four-necked separable flask and dropped over 2 hours. . Three hours after the completion of the dropwise addition, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 4860, and the mixture was cooled to 50 ° C. To this, 61.0 parts of ethanol was added, reacted at 50 ° C. for 2 hours, then heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 containing the monomer (a-1) represented by the general formula (1) having a resin component of 39.0% by weight was obtained.

(Resin formed by polymerizing monomer (a-1) (resin 2 to resin 18))
(Resin not polymerizing monomer (a-1) (Resin 19 to Resin 20))
The reaction was carried out under the same synthesis conditions as for Resin 1 except that the raw materials and preparation amounts shown in Table 3 were used. After completion of the reaction, the resin was diluted with methanol, and the resin component 2 to resin 16 containing the monomer (a-1) represented by the general formula (1) having a resin component of 39.0% by weight, and the monomer (a- Resins 17 to 18 containing 1) were synthesized. Table 3 shows the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained resins 1 to 18.

The structure for abbreviations in Table 3 is shown below.

<Method for producing salt-forming compound>
(Production Example 1: Salt-forming compound (A-1))
A salt-forming compound (A-1) comprising a cationic dye (DC-1) and resin 1 was produced by the following procedure.
At 25 ° C., 48 parts of Resin 1 was added to 2000 parts of water and mixed thoroughly. On the other hand, an aqueous solution in which 10 parts of DC-1 is dissolved in 190 parts of water is prepared and added dropwise to the resin solution. After the dropping, the mixture is stirred at 50 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, the reaction solution was dropped onto the filter paper, and it was judged that the salt-forming compound was obtained with the point where the bleeding disappeared as the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 29 parts of DC-1 and Resin 1 The salt-forming compound (A-1) was obtained.

(Production Examples 2 to 55, 58 to 62: Salt-forming compounds (A-2 to 55, 58 to 62))
Except for using the dyes and resins described in Table 5, the same salt-forming reaction as that of the salt-forming compound (A-1) was performed to obtain the salt-forming compounds (A-2 to 55, 58 to 62) of the dye. It was.

(Production Example 56: Salt-forming compound (A-56))
A salt-forming compound (A-56) comprising DC-1 and resin 1 was produced by the following procedure.
At 25 ° C., 48 parts of Resin 1 was added to 2000 parts of water and mixed thoroughly with stirring to prepare a resin solution. Meanwhile, 10 parts of DC-1 solution was prepared in 190 parts of water. The resin solution is dripped little by little into the dye solution. After the dropping, the mixture is stirred at 50 ° C. for 120 minutes to sufficiently react. In order to confirm the end point of the reaction, the reaction solution was dropped onto the filter paper, and it was judged that the salt-forming compound was obtained with the point where the bleeding disappeared as the end point. The mixture was allowed to cool to room temperature while stirring, and then suction filtration was performed to obtain a salt-forming compound on the filter paper. Thereafter, the salt-forming compound was further added to 500 parts of water, followed by stirring for 30 minutes and washing with water. Thereafter, filtration was performed again, and the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, to obtain 29 parts of a salt-forming compound (A-56) of DC-1 and resin 1. .

(Production Example 57: Salt-forming compound (A-57))
A salt-forming compound (A-57) comprising DC-1 and resin 1 was produced by the following procedure.
At 25 ° C., 10 parts of DC-1 was added little by little into 48 parts of resin 1. After the addition, the mixture was stirred at 25 ° C. for 120 minutes to sufficiently react to obtain a dye solution. Thereafter, suction filtration was performed to obtain 31 parts of a salt-forming compound of DC-10 and resin 1 (a mixture in which the salt of the counter ion was not removed) (A-57).

(Production Example 63: Salt-forming compound (A-63))
A salt-forming compound (A-63) composed of DC-1 and binder resin solution 2 was prepared by the following procedure.
A stainless steel 1 gallon kneader (Inoue Seisakusho) was charged with 46.7 parts of binder resin solution 2 and 10 parts of DC-1, and kneaded at 60 ° C. for 10 hours. The obtained mixture was heated to about 80 ° C. with a high speed mixer for about 2 hours, dried, then taken out, cooled to room temperature, and pulverized with a sample mill (KIIW-1 type, 5 mm mesh). A salt-forming compound consisting of DC-1 and binder resin 2 (a mixture in which the salt of the counter ion was not removed) (A-63) was obtained.

(Production Example 64: Salt-forming compound (A-64))
Except for changing from DC-1 to DC-2, a salt-forming reaction is performed under the same conditions as the salt-forming compound (A-63), and the salt-forming compound of the dye (a mixture in which the salt of the counter ion is not removed) ( A-64) was obtained.

In order to confirm the solubility of each salt-forming compound, a solubility test with cyclohexanone and propylene glycol monomethyl ether acetate (PGMAC) was performed.
The evaluation criteria are as follows.
AA: 10 wt% or more A: 5 Wt% or more, less than 10 wt% B: 1 Wt% or more, less than 5 Wt% C: less than 1 Wt%

<Method for producing dye paste and coloring composition>
[Example 1]
(Preparation of dye paste DP-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A dye paste (DP-1) was prepared by filtration using a filter.
Salt-forming compound (A-1): 10.0 parts Binder resin solution 1: 50.0 parts Cyclohexanone: 20.0 parts Propylene glycol monomethyl ether acetate: 20.0 parts

(Preparation of colored composition (DB-1))
Next, when the pigment paste (PP-3) and the dye paste (DP-1) are dried, the chromaticity of the coating film is x = 0 in the microspectrophotometer ("OSP-SP100" C light source manufactured by Olympus Optical Co., Ltd.). .661, y = 0.323, and a red colored composition (DB-1) was obtained by stirring and mixing with a disper for 1 hour.

[Examples 2-52, 72, 73, Comparative Examples 1-3, 8, 9]
(Dye paste (DP-2 to DP-52, DP-72 to DP-76, DP-81 to DP-82) and red coloring composition (DB-2 to DB-52, DB-72 to DB-76 , DB-81 to DB-82)
Dye pastes were prepared in the same manner as dye paste DP-1, except that the types of salt-forming compounds shown in Tables 6 and 7 were changed.
Next, a red colored composition was produced in the same manner as the red colored composition DB-1, except that the types of pigment paste and dye paste shown in Tables 6 and 7 were changed.

[Examples 53 to 68, Comparative Examples 5 to 6]
(Preparation of dye paste (DP-53 to DP-68, DP-77 to DP-78) and blue colored composition (DB-53 to 68, DB-77 to DB-78))
A dye paste was prepared in the same manner as the dye paste DP-1, except that the type of salt-forming compound shown in Table 6 was changed.
Next, similar to the red colored composition DB-1, except that the pigment paste and the dye paste shown in Table 6 were changed and the chromaticity of the dried coating film was adjusted to x = 0.090 and y = 0.139. Thus, a blue colored composition was produced.

[Examples 69 to 71, Comparative Examples 7 to 8]
(Preparation of dye paste (DP-69 to DP-71, DP-79 to DP-80) and coloring composition (DB-69 to 71, DB-79 to DB-80))
A dye paste was prepared in the same manner as the dye paste DP-1, except that the type of salt-forming compound shown in Table 6 was changed.
Next, similar to the red coloring composition DB-1, except that the pigment paste and the dye paste shown in Table 6 were changed and the chromaticity of the dried coating film was adjusted to x = 0.290 and y = 0.600. Thus, a green coloring composition was produced.

<Evaluation of coloring composition>
About the obtained coloring composition (DB-1 to 82), the test regarding heat resistance, coating property, a coating-film foreign material, and storage stability was done with the following method. The test results are shown in Table 7.

(Evaluation of heat resistance of coating film)
The coloring composition (DB-1 to 82) is applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 230 ° C. for 1 hour. The coated substrate was prepared by heating and allowing to cool. The prepared coated substrate was heat-treated at 230 ° C., and the film thickness measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)” was about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. After that, as a heat resistance test, it was heated at 240 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated according to the following criteria. C is a difficult level to use.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
S: ΔEab * is less than 1.5 AA: ΔEab * is 1.5 or more and less than 3.0
A: ΔEab * is 3.0 or more and less than 5.0 B: ΔEab * is 5.0 or more and less than 10.0 C: ΔEab * is 10.0 or more

(Coating test method)
The coloring composition (DB-1 to 82) was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater at 500 rpm, and then dried at 70 ° C. for 20 minutes to form a coated substrate. Was made. The film thickness (referred to as t1) at the center of the glass substrate was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. Next, 10 concentric places 25 mm from the center of the glass substrate were measured, and the average value was calculated. (It is set as t2.) Next, the measured t1 and t2 were applied to the following formula to determine the film uniformity, and the coatability was evaluated based on the value. C is a difficult level to use.
Film uniformity = t1 / t2 × 100 (%)
S: 99.0% or more and less than 100.5% AA: 98.5% or more and less than 99.0%, or 100.5% or more and less than 101.5% A: 97.5% or more and less than 98.5%, or 101.5% or more and less than 102.5% B: 95.0% or more and less than 97.5%, or 102.5% or more and less than 105.0% C: Less than 95.0% or 105.0% or more

(Coating foreign material test method)
A test substrate was prepared with the colored composition (DB-1 to 82) immediately after preparation, and the evaluation was performed by counting the number of particles. First, a colored composition was applied on a transparent substrate so that the dry coating film was about 2.0 μm, and heated at 230 ° C. for 20 minutes to obtain a test substrate. Then, surface observation was performed using a metal microscope “BX60” manufactured by Olympus System (magnification is 500 times), and the number of particles that can be observed in any five visual fields by transmission was counted and evaluated according to the following criteria. did.
S: Less than 3 (very good)
AA: 3 or more and less than 5 (good)
A: 5 or more and less than 20 (a level with no problem in use)
B: 20 or more and less than 100 (a level at which there are many foreign objects but no problem in use)
C: 100 or more (unusable level due to coating unevenness due to foreign matter)

(Storage stability test method)
The produced colored composition (DB-1 to 82) is stored in a thermostatic chamber at 40 ° C. for 7 days, and then a foreign matter test is performed by the same method as the coating foreign matter test method described above. C is a difficult level to use.
S: Less than 3 (very good)
AA: 3 or more and less than 5 (good)
A: 5 or more and less than 20 (a level with no problem in use)
B: 20 or more and less than 100 (a level at which there are many foreign objects but no problem in use)
C: 100 or more (unusable level due to coating unevenness due to foreign matter)

Colored compositions (DB-1 to 73) containing salt-forming compounds (A-1 to 57) using a resin copolymerized with a sulfoimide monomer are generally excellent in heat resistance, coating property and storage stability. As a result, almost no foreign matter was generated on the film. In particular, the heat resistance of the resin having the sulfonesulfimide group of the present application is higher than that of the resin (A-58) made of a phosphate group-containing monomer or the resin (A-5, A-61) made of a sulfonic acid group-containing monomer. However, the result was much better.
In addition, as a difference of the sulfoimide-containing counter compound that can interact with the dye, the salt formation compounds (DB-1 to DB-73) using the resin copolymerized with the sulfoimide monomer of the present invention are similar to the sulfoimide. As a result, it was found that the coating film foreign matter was improved as compared with the colored composition (DB-76, 78, 80) composed of the low molecular weight compound and the salt forming compound of the dye. It is inferred that this is because salt formation with a low molecular weight compound causes aggregation between molecules to promote fading between the dyes and the generation of foreign matter.
Further, the coating film foreign matter of the colored composition (DB-7) composed of a resin composed of a sulfoimide-containing vinyl monomer and a salt forming compound (A-7) of a dye is a colored composition (DB-1) of a sulfoimide-containing maleimide monomer. However, as a heat resistance, the maleimide group-containing resin and the salt-forming compound of the dye were slightly superior. This is presumably due to the fact that the heat resistance of the resin comprising N-phenylmaleimide or N-cyclohexylmaleimide group is higher than that of the styrene resin comprising vinyl group.
Furthermore, the coloring composition (DB-81, 82) containing the mixture (A-63, 64) of the binder resin solution 2 and the cationic dye generally has heat resistance, coating properties, and storage stability when heated for a long time. When the coating film was prepared with a colored composition stored over time, a large amount of foreign matter was deposited.

[Example 74]
(Resist material (R-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to prepare an alkali developing resist material (R-1).
Coloring composition (DB-1): 60.0 parts Binder resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (“NK Ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.)
Photopolymerization initiator ("Irgacure 907" manufactured by BASF): 1.2 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts Cyclohexanone: 5.2 parts Propylene glycol monomethyl ether acetate: 18.0 parts

[Examples 75 to 145, 149, Comparative Examples 10 to 18]
(Resist material (R-2 to 72, 76 to 85))
Hereinafter, alkali-developable resist materials (R-2 to 72, 76 to 85) were produced in the same manner as in Example 74 except that the colored composition (DB-1) was changed to the colored composition shown in Table 8. .

[Example 146]
(Resist material (R-73))
An alkali developing resist material (R-73) was prepared in the same manner as the resist material (R-1) except that the binder resin solution 1 was replaced with a 20% PGMAC solution of “EHPE3150” manufactured by Daicel Chemical Industries, Ltd. .

[Example 147]
(Resist material (R-74)
An alkali-developable resist material (R-74) was prepared in the same manner as the resist material (R-53) except that the binder resin solution 1 was replaced with a 20% PGMAC solution of “EHPE3150” manufactured by Daicel Chemical Industries, Ltd. .

[Example 148]
(Resist material (R-75))
An alkali-developable resist material (R-75) was prepared in the same manner as the resist material (R-69) except that the binder resin solution 1 was replaced with a 20% PGMAC solution of “EHPE3150” manufactured by Daicel Chemical Industries, Ltd. .

<Evaluation of resist material>
About the obtained resist material (R-1 to 85), the test regarding heat resistance, coating property, coating-film foreign material, storage stability, coating-film foreign material, and voltage holding ratio was done by the following method. The test results are shown in Table 8.

(Evaluation of heat resistance of coating film)
The obtained resist material is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, then heated at 230 ° C. for 1 hour and allowed to cool. Thus, a coated substrate was produced. The prepared coated substrate was heat-treated at 230 ° C., and the film thickness measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)” was about 2.0 μm. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. After that, as a heat resistance test, it was heated at 240 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated according to the following criteria. C is a difficult level to use.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
SS: ΔEab * is less than 1.0 S: ΔEab * is 1.0 or more and less than 1.5 AA: ΔEab * is 1.5 or more and less than 3.0 A: ΔEab * is 3.0 or more, 5.0 Less than B: ΔEab * is 5.0 or more and less than 10.0 C: ΔEab * is 10.0 or more

(Coating test method)
The obtained resist material was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater at 500 rpm, and then dried at 70 ° C. for 20 minutes to prepare a coated substrate. The film thickness (referred to as t1) at the center of the glass substrate was measured using a surface shape measuring device “Dektak 8 (manufactured by Veeco)”. Next, 10 concentric places 2.5 mm from the center of the glass substrate were measured, and the average value was calculated. (It is set as t2.) Next, the measured t1 and t2 were applied to the following formula to determine the film uniformity, and the coatability was evaluated based on the value. C is a difficult level to use.
Film uniformity = t1 / t2 × 100 (%)
S: 99.0% or more and less than 100.5% AA: 98.5% or more and less than 99.0%, or 100.5% or more and less than 101.5% A: 97.5% or more and less than 98.5% Or 101.5% or more and less than 102.5% B: 95.0% or more and less than 97.5%, or 102.5% or more and less than 105.0% C: less than 95.0% or 105.0% or more

(Coating foreign material test method)
The obtained resist material was spin-coated on a 100 mm × 100 mm, 1.1 mm thick glass substrate at a rotational speed of 2.5 μm after drying, dried at 70 ° C. for 20 minutes, and then 100 μm wide. UV exposure was performed with an integrated light quantity of 150 mJ / cm ² using an ultrahigh pressure mercury lamp through a photomask having a stripe-shaped opening, and the unexposed area was washed away with a 5% aqueous sodium carbonate solution. Then, the substrate was baked in a hot air oven to form a stripe pattern having a width of 100 μm on the substrate. Thereafter, the surface of the fabricated substrate was observed using a metal microscope “BX60” manufactured by Olympus System (magnification is 500 times), and the number of particles that can be observed in any five fields of view by counting was counted. Evaluation was based on criteria.
S: Less than 3 (very good)
AA: 3 or more and less than 5 (good)
A: 5 or more and less than 20 (a level with no problem in use)
B: 20 or more and less than 100 (a level at which there are many foreign objects but no problem in use)
C: 100 or more (unusable level due to coating unevenness due to foreign matter)

(Storage stability test method)
After the resist material thus obtained was stored in a constant temperature room at 40 ° C. for 7 days, a foreign matter test was performed by the same method as the coating foreign matter test method described above. C is a difficult level to use.
S: Less than 3 (very good)
AA: 3 or more and less than 5 (good)
A: 5 or more and less than 20 (a level with no problem in use)
B: 20 or more and less than 100 (a level at which there are many foreign objects but no problem in use)
C: 100 or more (unusable level due to coating unevenness due to foreign matter)

(Voltage holding ratio measurement method)
The obtained resist material was applied to a glass substrate (10 cm × 10 cm) with a spin coater so that the film thickness of the dry film was 2.0 μm. Next, the coating film was exposed at an exposure amount of 40 mJ / cm ² , spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 40 seconds, and baked at 230 ° C. in an oven. A resist-coated substrate was obtained. 0.05 g of the coated film was scraped off from the obtained coated substrate, immersed in 2.0 g of liquid crystal (MJ971189, manufactured by Merck & Co.), aged for 65 minutes in a 120 ° C. clean oven, and centrifuged at 5000 rpm for 20 minutes. After separation, the supernatant liquid was collected to prepare a contamination source boiled liquid into the liquid crystal.
After completion of contamination source boiling, the liquid crystal is taken out and sealed in a glass cell with an ITO electrode, and the voltage holding ratio (holding ratio after 16.7 milliseconds at an applied voltage of 5 V) using a liquid crystal property evaluation machine (6254, manufactured by Toyo Technica). Was measured and evaluated according to the following criteria. C is a difficult level to use.
S: 97% or more AA: 95% or more and less than 97% A: 90% or more and less than 95% B: 85% or more and less than 90% C: less than 85%

(OC heat resistance measurement method)
The obtained resist material was applied to a glass substrate (10 cm × 10 cm) with a spin coater so that the dry film thickness was 2.0 μm, exposed at an exposure amount of 40 mJ / cm ² , and then at 24 ° C. The resist coating substrate was obtained by spray development with 0.2 wt% sodium carbonate aqueous solution for 40 seconds and baking at 230 ° C. in an oven. It was obtained by applying an overcoat solution (a solution obtained by dissolving a monomer such as a thermosetting resin or methacrylic acid in diethylene glycol dimethyl ether in diethylene glycol dimethyl ether) to the resulting coated substrate and treating it in an oven at 230 ° C. for 15 minutes. . The film thickness of the overcoat layer was measured by using a non-contact film thickness meter.
The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. After that, as a heat resistance test, it was heated at 240 ° C. for 1 hour, and the chromaticity with a C light source ([L * (2), a * (2), b * (
2)]) was measured, the color difference ΔEab * was determined by the following formula, and evaluated according to the following criteria. C
Is a difficult level to use.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2) -a * (1)) ² + (b * (2) -b * (1)) ² )
SS: ΔEab * is less than 1.0 S: ΔEab * is 1.0 or more and less than 1.5 AA: ΔEab * is 1.5 or more and less than 3.0 A: ΔEab * is 3.0 or more, 5.0 Less than
B: ΔEab * is 5.0 or more and less than 10.0 C: ΔEab * is 10.0 or more

In the resist materials (R-1 to 76) of Examples 74 to 149, the coating film foreign matter was in a range that can be used as a color filter, and the voltage holding ratio and OC heat resistance were also good. Moreover, the resist material (R-73 to 75) using an epoxy resin was more excellent in terms of heat resistance and coatability.
On the other hand, the resist materials (R-77 to R-85) of Comparative Examples 10 to 18 had poor OC heat resistance, and did not reach a grade usable as a color filter. In particular, the voltage holding ratio of the resist material (R-79, 81,) using bistrifluoromethanesulfonamide, which is a low molecular weight as an anionic species, decreased.
In addition, the resist material (R-76) using a salt-formation product obtained by reacting a dye and a resin and not removing a salt made of counter ions is made of the same resin and dye, and the salt made of counter ions is removed. Compared to the resist material (R-1) using a salt product, the heat resistance, coating film foreign matter, and voltage holding ratio decreased. Probably derived from a salt consisting of counter-ion of dye and resin, which is probably a by-product. From these results, it is desirable that a salt-forming compound formed by salting a dye and a resin is washed with water to remove a salt derived from a counter ion as a by-product.
It became clear that the resists (R-1 to 76) used in the examples had good heat resistance even after heat treatment after the overcoat agent treatment. In addition, there was almost no decrease in transmittance in the transmission spectrum of these resists. From these, the resist (R-1 to 76) used in the examples can create a coating film with high brightness. However, since the resists (R-77 to R-85) used in the comparative examples have poor OC heat resistance, transmittance reduction and fading occurred in the transmission spectrum of these resists. Therefore, the brightness was inferior compared to the resists (R-1 to 76) used in the examples.

In addition, thereby, a colored composition containing a salt-forming compound using a resin having a sulfoimide structure is excellent in heat resistance, coating property, and storage stability, has no coating film foreign matter, and has high OC heat resistance. Obviously, an excellent color filter can be provided.

Claims (6)

A color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant comprises an ethylenically unsaturated monomer (a-1) represented by the following general formula (1): A resin obtained by radical polymerization of an ethylenically unsaturated monomer, and at least one selected from methine dyes, azo dyes, auramine dyes, acridine dyes, cetoflavine dyes, phenazine dyes, and xanthene dyes A coloring composition for a color filter, comprising a salt-forming compound obtained by reacting with a cationic dye.
General formula (1)

[In general formula (1), X represents an alkyl group in which at least a part of hydrogen atoms may be substituted with fluorine atoms, or an aryl group, Y represents a divalent hydrocarbon group, and Z represents an ethylenic group. It is a saturated group. W ⁺ represents an inorganic or organic cation. ] The colored composition for a color filter according to claim 1, wherein Z in the general formula (1) is a group represented by the general formula (2).
General formula (2)
  The coloring composition for a color filter according to claim 1 or 2, wherein the cationic dye is a methine dye and / or a xanthene dye.   The coloring composition for a color filter according to any one of claims 1 to 3, wherein the colorant further contains a pigment and / or a dye.   Furthermore, the coloring composition for color filters in any one of Claims 1-4 containing a photopolymerizable monomer and / or a photoinitiator. A color filter formed from the coloring composition for a color filter according to claim 1.