JP2014194527A - Color filter coloring composition and color filters - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter coloring composition which offers good coatability and is superior in terms of storage stability, brightness, voltage retention rate, and heat resistance and to provide a color filter which is free from generation of foreign substances in a coated film.SOLUTION: A color filter coloring composition comprising at least a colorant, a resin, and an organic solvent contains a salt-forming compound obtained by having a resin containing a sulfate react with a cationic dye, which solves the above-mentioned problem.

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. Considered. Here, an 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.

  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 3). 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.

  In addition, a patent relating to a colored composition containing a triphenylmethane dye and a resin having a sulfo group or a phosphonooxy group has been reported (see Patent Document 4). However, in a colored composition characterized by a triphenylmethane dye and a resin having a sulfo group or a phosphonooxy group, a counter anion derived from a cationic dye and a counter cation derived from an anionic resin due to ionic interaction are included. It is presumed that the resulting salt is produced as a by-product, and therefore, the generation of foreign matters during film formation of the color filter and the decrease in heat resistance during baking are presumed. Therefore, none of the above dye compounds has been able to solve the solubility in the solvent used for the color filter, and the heat resistance and film-forming property that can be used as a color filter.

JP-A-6-75375 Japanese Patent Publication No.56-9557 JP 2000-162429 A JP 2012-252319 A

  The object of the present invention is a color composition for color filters having good coating properties, high storage stability, high brightness, high voltage holding ratio, heat resistance, storage stability, and generation of foreign matter on the coating film. There is no color filter to provide.

  As a result of intensive studies to solve the above problems, the present inventors have obtained an ethylenically unsaturated monomer containing an ethylenically unsaturated monomer (a-1) represented by the following general formula (1). The color filter coloring composition containing a salt-forming compound obtained by reacting a resin obtained by radical polymerization of (a) with a cationic dye has high storage stability, high brightness, high voltage holding ratio, high It has been found that it has contrast, heat resistance and coating properties, and that no foreign matter is generated on the coating film, and the present invention has been made based on this finding.

［一般式（１）中、Ｒ¹は水素原子、またはメチル基を表す。Ｒ²は、単結合または２価の連結基を表し、Ａは一般式（２）を表し、Ｙ⁺は無機または有機のカチオンを表す。］
一般式（２）

［一般式（２）中、Ｒ⁴は置換基を有しても良いアルキレン基を表し、ｎ＝１〜２０の整数である。］ That is, the present invention
A color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant contains an ethylenically unsaturated monomer (a-1) represented by the following general formula (1) The present invention relates to a color filter coloring composition comprising a salt-forming compound obtained by reacting a resin obtained by radical polymerization of a polymerizable unsaturated monomer (a) with a cationic dye.
General formula (1)

[In General Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a single bond or a divalent linking group, A represents the general formula (2), and Y ⁺ represents an inorganic or organic cation. ]
General formula (2)

[In General Formula (2), R ⁴ represents an alkylene group which may have a substituent, and n is an integer of 1 to 20. ]

In the present invention, in the general formula (1), the divalent linking group of R ² is —CH ₂ —O—CH ₂ CH (R ³ ) O—, and R ³ has 1 to 30 carbon atoms. The present invention relates to the color filter coloring composition, which represents a monovalent alkyl group.

  The present invention also relates to the colored composition for a color filter, wherein the cationic dye is a triarylmethane basic dye.

  The present invention also relates to the coloring composition for a color filter, wherein the triarylmethane basic dye is represented by the general formula (3).

［一般式（３）中、Ｒ１Ａ〜Ｒ１Ｆは、それぞれ独立に、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のアルケニル基、または、置換もしくは無置換のアリール基を表す。Ｒ１ＧおよびＲ１Ｈは、それぞれ独立に、水素原子、メチル基、または、エチル基を表す。］ General formula (3)

[In General Formula (3), R1A to R1F each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R1G and R1H each independently represent a hydrogen atom, a methyl group, or an ethyl group. ]

  In the present invention, the salt-forming compound is a radical of an ethylenically unsaturated monomer (a) containing the ethylenically unsaturated monomer (a-1) represented by the general formula (1) in an aqueous solution. A compound obtained by mixing a polymerized resin and a cationic dye and removing a salt composed of a counter cation of the resin containing the structural unit represented by the general formula (1) and a counter anion of the cationic dye. It is related with the said coloring composition for color filters characterized by the above-mentioned.

  The present invention also relates to the color filter coloring composition, wherein the colorant further contains a pigment.

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

  Furthermore, 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 provides a color filter having high storage stability, high brightness, high voltage holding ratio, high contrast, heat resistance, and coating property, and no generation of foreign matters during coating film formation. be able to.

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 sulfate 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 represented by the following general formula (1).

［一般式（１）中、Ｒ¹は水素原子、またはメチル基を表す。Ｒ²は、単結合または２価の連結基を表し、Ａは一般式（２）を表し、Ｙ⁺は無機または有機のカチオンを表す。］ General formula (1)

[In General Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a single bond or a divalent linking group, A represents the general formula (2), and Y ⁺ represents an inorganic or organic cation. ]

［一般式（２）中、Ｒ⁴は置換基を有しても良いアルキレン基を表し、ｎ＝１〜２０の整数である。］ General formula (2)

[In General Formula (2), R ⁴ represents an alkylene group which may have a substituent, and n is an integer of 1 to 20. ]

The R ² of the general formula (1), an optionally substituted alkylene group, an optionally substituted oxyalkylene group, an arylene group which may have a substituent, -CH ₂ - O—CH ₂ CH (R ³ ) O—, —CONH—R ⁵ —, —COO—R ⁵ —, or —R ⁶ —O—, wherein R ³ is a monovalent alkyl having 1 to 30 carbon atoms. R ⁵ represents a single bond, an alkylene group which may have a substituent, an oxyalkylene group which may have a substituent, or an arylene group which may have a substituent, R ⁶ represents The arylene group which may have a substituent is represented.

In the general formula (1), specific examples of the alkylene group which may have a substituent of R ² include a methylene group, an ethylene group, a propylene group, a butylene group, a trimethylene group, a tetramethylene group, a hexamethylene group, or , Octamethylene group, etc .;
In the general formula (1), specific examples of the oxyalkylene group which may have a substituent of R ² include oxymethylene group, oxyethylene group, oxypropylene group, oxybutylene group, oxytetramethylene group, oxyhexa A methylene group or an oxyoctamethylene group;
In the general formula (1), specific examples of the arylene group which may have a substituent for R ² include a phenyl group, a nonylphenyl group, a paracumylphenyl group, and the like;
In the general formula (1), specific examples of the monovalent alkyl group having 1 to 30 carbon atoms of R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, and a nonyl group. Decyl group or dodecyl group, etc .;
However, it is not limited to these.

The monovalent alkyl group having 1 to 30 carbon atoms of R ³ is preferably a monovalent alkyl group having 1 to 18 carbon atoms, and more preferably a monovalent alkyl group having 8 to 18 carbon atoms. The reason is that an alkyl group having a small number of carbon atoms adversely affects heat resistance. Further, in the case of an alkyl group having a large number of carbon atoms, there is a concern that it may adversely affect the solubility in preparing a resin or a dye salt product.

In general formula (1), the alkylene group which may have a substituent of R ^5, an oxyalkylene group which may have a substituent, and an arylene group which may have a substituent include those represented by general formula (1) The alkylene group, the oxyalkylene group, and the arylene group described for R ² in () are included, but are not limited thereto.

In the general formula (1), examples of the arylene group which may have a substituent of R ⁶ include, but are not limited to, the arylene group described for R ² in the general formula (1).

  These general formulas (1) and (2) may have an alkyl group, an alkylene group, an oxyalkylene group or an arylene group substituent. Examples of such a substituent include an alkyl group, an alkenyl group, and an aryl group, and these are synonymous with the substituent described in the general formula (3) described later.

As R ² in the general formula (1), among them, —CH ₂ —O—CH ₂ CH (R ³ ) O— having a branch of a long-chain alkyl group having 8 to 18 carbon atoms is polymerizable, It is preferable for reasons of availability and heat resistance.

In general formula (1), A represents general formula (2). The ethylenically unsaturated monomer (a-1) of the present invention is characterized in that A next to the sulfo group (SO ₃ ) is an alkylene oxide represented by the general formula (2) and has a sulfate group structure. And Usually, a resin having a carboxylic acid group or a sulfonic acid group is used. In particular, it was thought that salt formation was caused by a strong interaction with a basic dye to improve the heat resistance of the colored composition, and the present invention was achieved.

In the general formula (2), specific examples of the alkylene group which may have a substituent of R ⁴ include the alkylene groups described for R ² in the general formula (1). The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and particularly preferably 2 or 3 carbon atoms.

  Moreover, n in General formula (2) is an integer of 1-20, it is preferable that n is an integer of 2-15, and it is more preferable that n is an integer of 5-10.

The Y ⁺ 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 Y 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 its H is substituted with a hydrocarbon group or the like.

As an ethylenically unsaturated monomer (a-1) shown by General formula (1), what is marketed may be used and what was synthesize | combined suitably, As a specific example,
A commercially available product of Daiichi Kogyo Seiyaku Co., Ltd., aqualon KH-10, KH-1025, or polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate such as KH-05;
Polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate such as HS-10, HS-1025, BC-10, BC-20;
A commercially available product manufactured by Sanyo Chemical Industries, Ltd., sodium polyoxyalkylene sulfate methacrylate such as Eleminol RS-3000;
Examples include commercially available products manufactured by Nippon Emulsifier Co., Ltd., bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate ester salts such as Antox MS-60, and the like.

  These ethylenically unsaturated monomers (a-1) represented by the general formula (1) may be used alone or in combination of two or more. Among these, Aqualon KH- 10, KH-05 can be preferably used.

[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;

Examples of the ethylenically unsaturated monomer having a hydroxyl group are not particularly limited. For example, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, glycerol (Meth) acrylates having a hydroxyl group such as mono (meth) acrylate, 4-hydroxyvinylbenzene, 2-hydroxy-3-phenoxypropyl acrylate or 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.

  As the ethylenically unsaturated monomer that can be used, those having a thermally crosslinkable functional group are preferable from the viewpoint of heat resistance. Although it is not particularly limited as a suitable structure, for example, hydroxyl group, carboxyl group, carboxylic anhydride, primary or secondary amino group, imino group, oxetanyl group, tertiary butyl group, epoxy group, mercapto group, isocyanate group, Examples thereof include ethylenically unsaturated monomers having an allyl group, (meth) acrylic group, 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.

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

  Examples of the ethylenically unsaturated monomer having 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.

  A structure suitable as an 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. , Methyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, dodecyl (meth) acrylate, and isostearyl (meth) acrylate are preferable.

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

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

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

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329 (reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference 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 10% by weight to 95% by weight based on the total weight of the ethylenically unsaturated monomer (a). % Is preferable, and more preferably 20% by weight to 60% by weight.

  When the weight of the ethylenically unsaturated monomer (a-1) represented by the general formula (1) is less than 10% by weight, the proportion of the cationic dye in which salt formation reaction occurs is low. Therefore, the amount of unformed salt cationic dye increases, and as a result, the solvent solubility is lowered and a phenomenon such as precipitation of foreign matters occurs. Further, in order to prevent the precipitation of foreign matters, it is necessary to increase the amount of solvent in the resist material, but this is not preferable because the coating property is remarkably deteriorated. On the other hand, when it exceeds 95% by weight, a salt is formed into a resin obtained by radical polymerization of the ethylenically unsaturated monomer (a) including the ethylenically unsaturated monomer (a-1) represented by the general formula (1). Since the amount of the cationic dye to be increased is too large, the heat resistance is deteriorated, which is not preferable.

  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. .

  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. As a cationic dye for obtaining the salt-forming compound of the present invention, an ethylenically unsaturated monomer (a) including the ethylenically unsaturated monomer (a-1) represented by the general formula (1) described above is used. Any colored compound that ionically bonds to a resin obtained by radical polymerization may be used.

Such a coloring compound is not particularly limited as long as it has at least one onium base or a broadly defined amino group (—NH ₂ , —NHR, —NR ₂ ) in the molecule. The salt structure is preferably an ammonium salt, iodonium salt, diazonium salt, and the like from the viewpoint of availability and the like, and in view of storage stability (thermal stability), it is an ammonium salt, iodonium salt, and It is more preferable. More preferred is an ammonium salt.

Examples of the cationic dye include anthraquinone cationic dyes, monoazo cationic dyes, disazo cationic dyes, oxazine cationic dyes, aminoketone cationic dyes, rhodamine cationic dyes among xanthene cationic dyes, Examples include quinoline cationic dyes, triarylmethane cationic dyes, diarylmethane cationic dyes, thiazine cationic dyes, acridine cationic dyes, azine cationic dyes, and methine cationic dyes. Specific examples of cationic dyes that can be used for the synthesis of salt-forming compounds are shown below by color index numbers.
Among these cationic dyes, the basic dye is preferable.

[Basic dye]
The basic dye used in the coloring composition for a color filter of the present invention includes a triarylmethane basic dye, a xanthene basic dye, preferably a rhodamine basic dye, a flavin basic dye, an auramine basic dye. And safranin basic dye, phloxine basic dye, thiazine basic dye, acridine basic dye, azine basic dye, methine basic dye, and methylene blue basic dye.

  Specifically, triarylmethane basic dyes include C.I. I. Basic Violet 1 (Methyl Violet), 3 (Crystal Violet), 14 (Magenta), C.I. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 26 (Victoria Blue B conc.), C.I. I. Basic green 1 (brilliant green GX), 4 (malachite green), dyes represented by general formula (3) described later, and the like. Among them, C.I. I. It is preferable to use a dye represented by basic blue 7, green 4, violet 1, violet 3, and general formula (3).

  Examples of rhodamine-based basic dyes include C.I. I. Basic Red 1 (Rhodamine 6G, 6GCP), 3 and 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among them, C.I. I. Basic Red 1 and Violet 10 are preferably used.

Examples of flavin basic dyes include C.I. I. Basic Yellow 1,
Examples of auramine basic dyes include C.I. I. Basic Yellow 2, 3,
Examples of the safranine basic dye include C.I. I. Basic Red 2,
Phloxine basic dyes include C.I. I. Basic Red 12,
Examples of the acridine basic dye include C.I. I. Basic Yellow 5,
Examples of the oxazine-based basic dye include C.I. I. Basic Blue 3,
Examples of thiazine-based basic dyes include C.I. I. Basic Blue 24,
Examples of methine basic dyes include C.I. I. Basic Red 12, C.I. I. Basic Yellow 11, 21, 21, 28
Examples of methylene blue basic dyes include C.I. I. Basic Blue 9 (Methylene Blue FZ, Methylene Blue B), 25 (Basic Blue GO), 24 (New Methylene Blue NX) and the like. Among them, C.I. I. Basic Yellow 1, Blue 9, Blue 24 and Blue 25 are preferably used.

In forming a red pixel, a flavin basic dye as a complementary color is an effective material. Methylene blue basic dye is a preferable material in that it exhibits a clear blue color and is excellent in heat resistance when used as a salt-forming dye. A flavin basic dye is a preferable material because it exhibits a clear yellowish color and is excellent in heat resistance when used as a salt-forming dye.
Among these, triarylmethane basic dyes, rhodamine basic dyes, and methylene blue basic dyes are preferably used in terms of good color developability, and triarylmethane basic dyes and rhodamine basic dyes are more preferable. Triarylmethane basic dyes are preferred and particularly preferred.
The triarylmethane basic dye and rhodamine basic dye will be described in detail below.

[Triarylmethane basic dye]
The triarylmethane basic dye develops color when the NH ₂ or OH group located in the para position with respect to the central carbon takes a quinone structure by oxidation.
Depending on the number of NH ₂ and OH groups, it can be divided into the following three types. Among them, a triaminotriphenylmethane-based basic dye is preferable in terms of good blue, red and green coloring. .
a) Diaminotriphenylmethane basic dye b) Triaminotriphenylmethane basic dye c) Rosolic acid basic dye having OH group Triaminotriphenylmethane basic dye, diaminotriphenylmethane basic dye The dye has a clear color tone and is excellent in sunlight fastness than the other dyes and is preferable. Further, diphenylnaphthylmethane basic dye and / or triphenylmethane basic dye are preferable.

  The blue triarylmethane basic dye has spectral characteristics having a high transmittance at 400 to 440 nm. Among these, a dye having a structure represented by the following general formula (3) is particularly preferable from the viewpoint of heat resistance.

General formula (3)

  In General Formula (3), R1A to R1F each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R1G and R1H each independently represent a hydrogen atom, a methyl group, or an ethyl group.

  As the alkyl group for R 1A to R 1F, a linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms, or one or more ester bonds (—COO— ) And / or a linear, branched, monocyclic or condensed polycyclic alkyl group containing an ether bond (—O—).

  Specific examples of the linear, branched, monocyclic or condensed polycyclic alkyl group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. 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, tert- A pentyl group, a tert-octyl group, a neopentyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a 4-decylcyclohexyl group, and the like can be mentioned. It is not something.

Specific examples of the linear or branched alkyl group having 2 to 30 carbon atoms and containing one or more ester bonds include —CH ₂ —CH ₂ —CH ₂ —COO—CH ₂ —CH ₃ , —CH _{2 -CH (-CH 3) -CH 2} -COO-CH 2 -CH 3, -CH 2 -CH 2 -CH 2 -OCO-CH 2 -CH 3, -CH 2 -CH 2 -CH 2 -CH 2 _{-COO-CH 2 -CH (CH 2} -CH 3) -CH 2 -CH 2 -CH 2 -CH 3, - (CH 2) 5 -COO- (CH 2) 11 -CH 3, -CH 2 -CH _{2 -CH 2 -CH- (COO-CH} 2 -CH 3) can be exemplified _2, etc., but is not limited thereto.

Specific examples of the linear or branched alkyl group having 2 to 30 carbon atoms and containing one or more ether bonds include —CH ₂ —O—CH ₃ , —CH ₂ —CH ₂ —O—. CH ₂ —CH ₃ , —CH ₂ —CH ₂ —CH ₂ —O—CH ₂ —CH ₃ , — (CH ₂ —CH ₂ —O) _n —CH ₃ (where n is 1 to 8), _{- (CH 2 -CH 2 -CH 2} -O) m -CH 3 ( here m is 5 _{1), - CH 2 -CH (} CH 3) -O-CH 2 -CH 3 -, - CH _2- CH- (OCH ₃ ) _{2 and the} like can be mentioned, but are not limited thereto.

  Specific examples of the monocyclic or condensed polycyclic alkyl group having 2 to 30 carbon atoms and optionally including one or more ether bonds include the following, but are not limited thereto. Absent.

Furthermore, specific examples of linear, branched, and alkyl groups having 3 to 30 carbon atoms and including one or more ester bonds (—COO—) and ether bonds (—O—) include —CH ₂ — _{CH 2 -COO-CH 2 -CH 2} -O-CH 2 -CH (CH 2 -CH 3) -CH 2 -CH 2 -CH 2 -CH 3, -CH 2 -CH 2 -COO-CH 2 -CH _{2 -O-CH 2 -CH 2 -O} -CH 2 -CH (CH 2 -CH 3) can be exemplified _{-CH 2 -CH 2 -CH 2 -CH 3} , but the invention is not limited to .

  Examples of the alkenyl group in R1A to R1F include linear, branched, monocyclic or condensed polycyclic alkenyl groups having 1 to 18 carbon atoms. They may have a plurality of carbon-carbon double bonds in the structure. Specific examples include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 4- Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclohexadienyl group, cyclopenta Although a dienyl group etc. can be mentioned, it is not limited to these.

  The aryl group in R1A to R1F is a monocyclic or condensed polycyclic aromatic group having 6 to 18 carbon atoms, and examples thereof include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 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-pyrenyl group, 2- Although a pyrenyl group, 3-perylenyl group, etc. can be mentioned, it is not limited to these.

  The alkyl group, alkenyl group, and aryl group in R1A to R1F may have a substituent. Examples of such a substituent include an alkyl group, an alkenyl group, and an aryl group, and these are as defined above.

  R1G and R1H each independently represent a hydrogen atom, a methyl group, or an ethyl group. A methyl group or an ethyl group is preferred, and either R1G or R1H is more preferably a methyl group or an ethyl group.

  The position of the cation of the triarylmethane dye may be anywhere as long as a stable resonance structure can be obtained, and may be any nitrogen portion of the amine portion or the central carbon portion of the triarylmethane.

  For example, the triarylmethane dye represented by the general formula (5) can be obtained by salt exchange between a corresponding triarylmethane basic dye and a specific sodium sulfate, potassium salt, ammonium salt or the like.

General formula (5)

(Salt exchange)

[Rhodamine basic dye]
Next, the rhodamine-based basic dye will be described.
The rhodamine-based basic dye that can be preferably used in the present invention exhibits a red color and a violet color. To exhibit red and violet color, C.I. I. Basic Red, C.I. I. Basic belongs to basic dyes such as violet.

The rhodamine-based basic dye has spectral characteristics having a high transmittance at 400 to 430 nm.
The rhodamine basic dye used in the present invention has a transmittance of 90% or more in the region of 650 nm in the transmission spectrum, a transmittance of 75% or more in the region of 600 nm, and a transmittance of 5% or less in the region of 500 to 550 nm. In the region of 400 nm, the transmittance is preferably 70% or more. More preferably, the transmittance is 95% or more in the region of 650 nm, the transmittance is 80% or more in the region of 600 nm, the transmittance is 10% or less in the region of 500 to 550 nm, and the transmittance is 75% in the region of 400 nm. That's it.

Summarizing the basic dyes by color,
Those that can be preferably used for blue pixels are triarylmethane basic dyes, methylene blue basic dyes, and the like. I. Basic Blue 1 (Basic Cyanine 6G), 5 (Basic Cyanine EX), 7 (Victoria Pure Blue BO), 9 (Methylene Blue FZ, Methylene Blue B), 24 (New Methylene Blue NX), 25 (Basic) Blue GO), 26 (Victoria Blue B conc.), Dyes represented by the general formula (3), and the like. Of these, C.I. I. Basic Violet 10, C.I. I. Basic Blue 7, a dye represented by the general formula (3) is preferred, and C.I. I. Basic Blue 7, the dye represented by the general formula (3) is more preferable, and the dye represented by the general formula (3) is most preferable as described above.
In addition, rhodamine-based basic dyes, safranin-based basic dyes, phloxine-based basic dyes, and the like that exhibit red as described later are also effective as complementary colors of blue pixels. For example, a blue pixel with high brightness can be obtained by using a copper phthalocyanine pigment (CI Pigment Blue 15: 6) and a salt-forming compound derived from a basic dye exhibiting red. In particular, a combination of a copper phthalocyanine pigment (CI Pigment Blue 15: 6) and one using a rhodamine-based basic dye is preferable because high brightness is obtained.

  Those that can be preferably used for red pixels are rhodamine-based basic dyes, safranine-based basic dyes, phloxine-based basic dyes, and the like. I. Basic Red 1 (Rhodamine 6G, 6GCP), 2 (Safranin basic dye), 8 (Rhodamine G), 12 (Phloxine basic dye), C.I. I. Basic violet 10 (Rhodamine B) and the like. Further, a flavin-based basic dye exhibiting yellow as a complementary color of a red pixel is preferable.

  What can be preferably used for the green pixel is a triarylmethane basic dye. I. Basic Green 1 (Brilliant Green GX), 4 (Malachite Green) and the like.

  As an aspect of the cationic dye, in addition to the aspect of the basic dye, it can be used in the form of an oil-soluble dye. For example, C.I. I. Solvent Red 49 and the like are preferable.

(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 sulfate-derived anionic group in the resin and the cationic group of the dye are ionized, and these are ionically bonded, and the ion-bonded portion is insolubilized and precipitated in water. Conversely, a salt formed by reacting a counter cation of a resin with a counter anion of a basic dye is water-soluble and can be removed by washing with water.

  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, Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like can be mentioned. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight (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. 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.

<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. If the amount is more than 300 parts by weight, a problem may occur when forming a filter segment by photolithography.

  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. In the case of using two or more kinds of mixed solvents, it is preferable that the above-mentioned preferable organic solvent is contained in an amount of 65 to 95% by weight.

  In addition, the organic solvent can 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 great effect of preventing reaggregation of the colorant after dispersion. When used, a color filter having a high spectral transmittance can be obtained.
In the present invention, the salt-forming compound 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, 21116 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 1394 manufactured by Nihon Lubrizol Corporation, Lactimon, Lactimon-WS, or Bykumen et al. 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by BASF 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500 7554,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these 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. When the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. 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 Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
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, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) 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 for a liquid crystal display mode in which colorization is performed using a color filter such as.

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

(Purple refined pigment (P-2))
Dioxazine-based purple pigment C.I. I. 120 parts of Pigment Violet 23 (“Fast Violet RL” manufactured by Clariant), 1600 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 90 ° C. for 18 hours. The mixture was put into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 118 parts purple refinement | purification pigment (P-2). The average primary particle diameter of the obtained pigment was 26.4 nm.

(Red fine pigment (P-3))
Diketopyrrolopyrrole red pigment C.I. I. 120 parts of Pigment Red 254 ("IRGAZIN RED 2030" manufactured by 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.

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

(Green fine pigment (P-5))
Phthalocyanine green pigment C.I. I. 120 parts of Pigment Green 58 (“Fastgen Green A110” manufactured by DIC Corporation), 1600 parts of sodium chloride, and 270 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 12 hours. The mixture was poured into 5000 parts of warm water, stirred at a high speed mixer for about 1 hour while being heated to about 70 ° C. to form a slurry, filtered and washed repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It dried and obtained 117 parts of green refined pigment (P-5). The average primary particle diameter of the obtained pigment was 32.6 nm.

<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 RS-3000 (manufactured by Sanyo Chemical Industries), 45.0 parts methyl methacrylate, 15.0 parts n-butyl methacrylate, 10.0 parts 2-ethylhexyl methacrylate, 10.0 parts hydroxyethyl methacrylate, 7.02 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) and 23.0 parts of methyl ethyl ketone were homogenized and charged into a dropping funnel and attached to a four-necked separable flask over 2 hours. And dripped. Three hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 4730, 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 19))
(Resin not polymerizing monomer (a-1) (Resin 20 to Resin 22))
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 1 were used. After completion of the reaction, the resin was diluted with methanol, the resin 2 to the resin 19 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 20 to 22 not containing 1) were synthesized. Table 1 shows the weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the obtained resins 2 to 22.

Abbreviations in Table 1 are shown below.
KH-10: Polyoxyethylene-1- (allyloxymethyl) alkyl ether ammonium sulfate (commercially available product, product name: Aqualon KH-10, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
KH-05: ammonium polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate (Daiichi Kogyo Seiyaku Co., Ltd., commercial name: Aqualon KH-05)
HS-10: Polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate (commercially available from Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon HS-10)
BC-10: Polyoxyethylene nonylpropenyl phenyl ether ammonium sulfate (commercially available from Daiichi Kogyo Seiyaku Co., Ltd., trade name: Aqualon BC-10)
RS-3000: Sodium polyoxyalkylene sulfate methacrylate (commercially available product, product name: Eleminol RS-3000 manufactured by Sanyo Chemical Industries)
MS-60: Bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate (commercially available from Nippon Emulsifier Co., Ltd., trade name: Antox MS-60)

<Manufacture of cationic dyes>
(Cationic dye represented by formula (3) (Dye 1))
[Synthesis of Dye Intermediate 1]
To a mixture of 25 parts of 4-diethylaminobenzoic acid (Tokyo Chemicals) and 90 parts of toluene, 23 parts of thionyl chloride was added and stirred at 80 ° C. for 1 hour, followed by concentration under reduced pressure to obtain acid chloride. In a separate container, 20.4 parts of anhydrous aluminum chloride and 130 parts of 1,2-dichloroethane were added. After cooling in an ice bath, a solution having acid chloride dissolved in 60 parts of 1,2-dichloroethane was added dropwise. After the dropping, the mixture was stirred for 15 minutes, 21 parts of N, N-diethyl-m-toluidine (Tokyo Chemicals) was added dropwise, returned to room temperature, and stirred for 2 hours. Thereafter, the mixture was poured into ice water, adjusted to pH 11 or higher with 4N sodium hydroxide, and extracted with chloroform. This was washed with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (hexane / ethyl acetate = 4/1). The purified product was further dissolved in THF and reprecipitated with hexane. After drying at 60 ° C. under reduced pressure, 15.4 parts of dye intermediate 1 were obtained. The yield was 35.0%.

[Synthesis of Dye 1]
10 parts of dye intermediate 1 and 5.0 parts of N-ethyl-1-naphthylamine (Tokyo Chemicals) were dissolved in 40 parts of toluene, 6.8 parts of phosphorus oxychloride was added, and the mixture was refluxed for 3 hours. Then, it returned to room temperature, 1N hydrochloric acid was added, and chloroform extracted. This was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The concentrate was purified by silica gel chromatography (chloroform / methanol = 4/1). After drying under reduced pressure at 60 ° C., 13.8 parts of Dye 1 was obtained. The yield was 88.8%.

<Method for producing salt-forming compound>
(Production Example 1: Salt-forming compound (A-1))
In the following procedure, C.I. I. A salt-forming compound (A-1) comprising basic violet 10 and resin 2 was produced.
At 25 ° C., 48 parts of Resin 2 was added to 2000 parts of water and sufficiently stirred and mixed. On the other hand, 10 parts of C.I. I. An aqueous solution in which Basic Violet 10 was dissolved was prepared and added dropwise little by little to the previous 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. The mixture was allowed to cool to room temperature with stirring, suction filtered, washed with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer, and 29 parts of C.I. I. A salt-forming compound (A-1) of basic violet 10 and resin 2 was obtained.

(Production Examples 2 to 13, 15 to 31, 45 to 49: salt-forming compounds (A-2 to 13, 15 to 31, 45 to 49))
Except for using the dyes and resins described in Table 2, the same salt-forming reaction as that of the salt-forming compound (A-1) was performed, and the salt-forming compound of the dye (A-2 to 13, 15 to 31, 45 to 45) 49) was obtained.

(Production Example 14: Salt-forming compound (A-14))
In the following procedure, C.I. I. A salt-forming compound (A-14) comprising Basic Blue 7 and Resin 2 was produced.
At 25 ° C., 48 parts of resin 2 was added to 2000 parts of water and mixed thoroughly with stirring to prepare a resin solution. On the other hand, 10 parts of C.I. I. A dye aqueous solution in which Basic Blue 7 was dissolved was prepared, and the resin solution was added dropwise to the dye aqueous solution little by little. 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. I. A salt-forming compound (A-14) of Basic Blue 7 and Resin 2 was obtained.

(Production Example 32: Salt-forming compound (A-32))
In the following procedure, C.I. I. A salt-forming compound (A-32) comprising Basic Blue 7 and Resin 2 was produced.
At 25 ° C., 10 parts of C.I. I. Basic Blue 7 was added little by little. 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, and 31 parts of C.I. I. A salt-forming compound (A-32) of Basic Blue 7 and Resin 2 was obtained.

(Production Example 33: Salt-forming compound (A-33))
A salt-forming compound (A-33) comprising dye 1 and resin 1 was produced by the following procedure.
At 25 ° C., 7.21 parts of Resin 2 was added to 2000 parts of water and mixed thoroughly with stirring. On the other hand, an aqueous solution in which 12 parts of dye 1 is dissolved in 190 parts of water is prepared and added dropwise little by little 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 13.7 parts of dye 1 and resin The salt-forming compound (A-33) with 1 was obtained. The yield was 79.7%.

(Production Examples 34 to 44: Salt-forming compound (A-34 to 44))
Except having used the resin described in Table 2, salt-formation reaction was performed on the same conditions as salt-formation compound (A-33), and the salt-formation compound (A-34-44) of dye was obtained.

(Production Example 50: Mixture (A-50))
In the following procedure, C.I. I. A mixture (A-50) composed of Basic Blue 7 and binder resin solution 2 was prepared.
26.7 parts of binder resin solution 2 and 10 parts of C.I. I. Basic Blue 7 was charged and kneaded at 60 ° C. for 10 hours. The resulting mixture was stirred at a high speed mixer for about 2 hours while being heated to about 80 ° C., dried, then taken out, cooled to room temperature, and pulverized with a sample mill (KIIW-1 type, 5 mm mesh). C. I. A mixture (A-50) composed of Basic Blue 7 and Binder Resin 2 was obtained.

(Production Example 51: Salt-forming compound (A-51))
Except having used the dye described in Table 2, salt-formation reaction was performed on the same conditions as salt-formation compound (A-50), and the salt-formation compound (A-51) of dye was obtained.

[Example 1]
(Preparation of colored composition (DB-1))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. A colored composition (DB-1) was produced by filtration using a filter.
Salt-forming compound (A-1): 4.0 parts Fine pigment (P-1): 7.0 parts Binder resin solution 1: 40.0 parts Cyclohexanone: 10.0 parts Propylene glycol monomethyl ether acetate: 38.0 Part Resin type dispersant: 1.0 part ("EFKA4300" manufactured by BASF)

[Examples 2-44, Comparative Examples 1-7]
(Coloring composition (DB-2 to 51))
Hereinafter, a colored composition (DB-2 to 51) was prepared in the same manner as in Example 1 (colored composition (DB-1)) except that the salt-forming compound and the refined pigment were changed to the compositions shown in Table 3. did.

<Evaluation of coloring composition>
About the obtained coloring composition (DB-1 to 51), the test regarding heat resistance, coating property, a coating-film foreign material, and storage stability was done with the following method. The results of the test are shown in Table 3.

(Evaluation of heat resistance of coating film)
The coloring composition (DB-1 to 51) 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. X is a difficult level to use.
ΔEab * = √ ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
A: ΔEab * is less than 1.5 A: ΔEab * is 1.5 or more and less than 3.0 B: ΔEab * is 3.0 or more and less than 5.0 Δ: ΔEab * is 5.0 or more, 10.0 Less than ×: ΔEab * is 10.0 or more

(Coating test method)
The coloring composition (DB-1 to 51) 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. X is a difficult level to use.
Film uniformity = t1 / t2 × 100 (%)
◎: 99.0% or more and less than 100.5% ◎: 98.5% or more and less than 99.0%, or 100.5% or more and less than 101.5% ○: 97.5% or more and less than 98.5% Or 101.5% or more and less than 102.5% Δ: 95.0% or more and less than 97.5%, or 102.5% or more and less than 105.0% ×: 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 51) immediately after preparation, and evaluation was performed by counting the number of particles. First, a coloring composition was applied on a transparent substrate so that the dried coating film was about 2.0 μm, and heated in an oven 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.
◎◎: Less than 3 (very good)
A: 3 or more and less than 5 (good)
○: 5 or more and less than 20 (a level that causes no problem in use)
Δ: 20 or more and less than 100 (a level at which there is a large number of foreign matters but no problem in use)
×: 100 or more (unusable level due to coating unevenness due to foreign matter)

(Storage stability test method)
After the produced colored compositions (DB-1 to 51) are stored in a thermostatic chamber at 40 ° C. for 7 days, the foreign matter test is performed by the same method as the coating foreign matter test method already described. X is a difficult level to use.
◎◎: Less than 3 (very good)
A: 3 or more and less than 5 (good)
○: 5 or more and less than 20 (a level that causes no problem in use)
Δ: 20 or more and less than 100 (a level at which there is a large number of foreign matters but no problem in use)
×: 100 or more (unusable level due to coating unevenness due to foreign matter)

The colored composition (DB-1 to 32) containing a salt-forming compound (A-1 to 32) using a resin having a sulfate is generally excellent in heat resistance, coating property and storage stability, and foreign matter of the coating film. As a result, almost no occurrence occurred. In particular, the heat resistance of the one having the sulfate group of the present application was much better than that of the sulfo group. In particular, in a colored composition (DB-33 to 44) containing a salt-forming compound salted with a resin having a sulfate group using Dye 1, (DB-33 to 44) is further improved in heat resistance. It was. It is considered that this is derived from the skeleton of dye 1.
In addition, as the sulfuric acid monomer capable of interacting with the dye, Eleminol RS-3000, Aqualon KH-05 and Aqualon KH-10 are used, and a resin (A-33 to 30% or more) containing these sulfuric acid monomers in all the monomers. A colored composition (DB-33 to DB-36, DB40-43) using a salt-forming compound with A-36, A-40 to A-43) is used as a salt-forming compound with a resin composed of another sulfuric acid monomer. Compared with this, the heat resistance was further improved.
Among them, a salt-forming compound (DB-32) obtained by reacting a cationic dye and a resin containing a sulfate to remove a solvent is composed of a colored composition obtained with the same dye and resin (DB-13). In comparison, the generation of foreign matter and storage stability were inferior. It is probably derived from a salt consisting of a counter-ion of dye and resin, which are by-products.
In addition, the colored compositions (DB-13, 14) comprising the salt-forming compounds (A-13, 14) obtained by changing the salt-forming method are all excellent in heat resistance, coating property, and storage stability, As a result, almost no foreign matter was generated on the coating film.
On the other hand, the colored composition (DB-48) containing a salt-forming compound (A-48) with a low-molecular-weight compound having a carboxyl group (stearic acid) is more heat resistant than a salt-forming compound with a sulfate-containing resin. The coating property, coating property, storage stability, and coating film foreign matter were also poor. Further, the coloring composition (DB-45 to 47) containing a salt-forming compound (A-45 to 47) of 2-methylpropanesulfonic acid or a phosphonooxy group-containing resin and a cationic dye has a heat resistance of sulfate. It was shown to be inferior to a salt-forming compound using a resin having Furthermore, the coloring composition (DB-50) containing the mixture (A-50) of the binder resin solution 2 and the cationic dye generally has poor heat resistance, coating property, and storage stability when heated for a long time. When a coating film was prepared with the coloring composition stored over time, a large amount of foreign matter was precipitated. In addition, in the coloring composition (DB-51) using the mixture (A-51) in which the dye 1 is used as the dye skeleton and the binder resin solution 2 is salted, heat resistance, foreign matter, coating property, and storage stability are generally obtained. It was shown that gender is lacking.

[Example 45]
(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 46-58, 60-62, 64-67, 69-70, 72-76, 78-86, 88-94, Comparative Examples 8-10]
(Resist material (R-2 to 14, 16 to 18, 20 to 23, 25 to 26, 28 to 32, 34 to 42, 44 to 53))
Hereafter, except having changed the coloring composition (DB-1) into the coloring composition shown in Table 4, it carried out similarly to Example 45, and alkali-developable resist material (R-2-14, 16-18, 20-23). 25-26, 28-32, 34-42, 44-53).

[Example 59]
(Resist material (R-15))
An alkali developing resist material (R-15) was prepared in the same manner as the resist material (R-14) except that the binder resin solution 1 was replaced with a 20% PGMAC solution of “EHPE3150” manufactured by Daicel Chemical Industries, Ltd. .

[Example 63]
(Resist material (R-19))
An alkali developing resist material (R-19) was prepared in the same manner as the resist material (R-18) except that the binder resin solution 1 was replaced with a 20% PGMAC solution of “EHPE3150” manufactured by Daicel Chemical Industries, Ltd. .

[Example 68]
(Resist material (R-24))
An alkali developing resist material (R-24) was prepared in the same manner as the resist material (R-23) except that the binder resin solution 1 was replaced with a 20% PGMAC solution of “EHPE3150” manufactured by Daicel Chemical Industries, Ltd. .

[Example 71]
(Resist material (R-27))
An alkali developing resist material (R-27) was prepared in the same manner as the resist material (R-26) except that the binder resin solution 1 was replaced with a 20% PGMAC solution of “EHPE3150” manufactured by Daicel Chemical Industries, Ltd. .

[Example 77]
(Resist material (R-33))
An alkali developing resist material (R-33) was produced in the same manner as the resist material (R-32) except that the binder resin solution 1 was replaced with a 20% PGMAC solution of “EHPE3150” manufactured by Daicel Chemical Industries, Ltd. .

[Example 87]
(Resist material (R-43))
An alkali-developable resist material (R-43) was prepared in the same manner as the resist material (R-42) 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 53), 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. Table 4 shows the test results.

(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. X is a difficult level to use.
ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
◎◎◎: ΔEab * is less than 1.0 ◎◎: ΔEab * is 1.0 or more and less than 1.5 ◎: ΔEab * is 1.5 or more and less than 3.0 ○: ΔEab * is 3.0 or more, Less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: 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. X is a difficult level to use.
Film uniformity = t1 / t2 × 100 (%)
◎: 99.0% or more and less than 100.5% ◎: 98.5% or more and less than 99.0%, or 100.5% or more and less than 101.5% ○: 97.5% or more and less than 98.5% Or 101.5% or more and less than 102.5% Δ: 95.0% or more and less than 97.5%, or 102.5% or more and less than 105.0% ×: 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 a super high pressure mercury lamp through a photomask having a stripe-shaped opening, and the unexposed area was washed away with 5% aqueous sodium carbonate solution, and then at 230 ° C. for 20 minutes. 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.
◎◎: Less than 3 (very good)
A: 3 or more and less than 5 (good)
○: 5 or more and less than 20 (a level that causes no problem in use)
Δ: 20 or more and less than 100 (a level at which there is a large number of foreign matters but no problem in use)
×: 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. X is a difficult level to use.
◎◎: Less than 3 (very good)
A: 3 or more and less than 5 (good)
○: 5 or more and less than 20 (a level that causes no problem in use)
Δ: 20 or more and less than 100 (a level at which there is a large number of foreign matters but no problem in use)
×: 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 dry film thickness was 1.8 μm, and exposed at an exposure amount of 50 mJ / cm ² , then 23 ° C. The resist-coated substrate was obtained by spray development with an aqueous 0.2 wt% sodium carbonate solution for 30 seconds and baking at 230 ° C. in an oven. After removing 0.05 g of the resist coating film from the obtained coated substrate, it was immersed in 1.5 g of liquid crystal (MLC-2041 manufactured by Merck & Co., Inc.), aged in a 120 ° C. oven for 60 minutes, and at 4000 rpm. After centrifugation for 15 minutes, a supernatant liquid was collected to prepare a resist extraction liquid crystal sample liquid.
On the other hand, two glass substrates having an ITO transparent electrode with an effective electrode size of 10 mm × 10 mm are placed facing each other so that the ITO transparent electrode surfaces face each other, and a small cell is produced using a sealing agent so that the cell gap is 9 μm. did. A resist-extracted liquid crystal sample solution is injected into the small cell between the cell gaps, a voltage of 5 V is applied at 60 ° C. for 60 μsec, and the cell voltage [V ₁ ] after 16.67 msec has elapsed after the voltage release, Measured with Toyo Technica VHR-1S. The measurement was repeated 5 times, and the measured cell voltages were averaged. And using the obtained cell voltage, voltage retention (%) was calculated | required from the following formula, and the following reference | standard evaluated. X is a difficult level to use.
Voltage holding ratio (%) = ([V ₁ ] / 5) × 1 0 0
◎: 97% or more ◎: 95% or more and less than 97% ○: 90% or more and less than 95% △: 85% or more and less than 90% ×: less than 85%

In the resist materials (R-1 to R-50) of Examples 45 to 94, the coating film foreign matter was in a range that can be used as a color filter, and the voltage holding ratio was also satisfactory. Moreover, the resist material (R-15, R-19, R-24, R-27, R-33, and R-43) using an epoxy resin was more excellent from the viewpoint of heat resistance. The resist materials (R-15, R-19, R-24, R-27, R-33, and R-43) are salt-forming compounds (A-15, A-19, A-24, A-27). , A-33, and A-43) were most excellent in heat resistance due to thermal crosslinking between the OH group contained in the resin portion salted with the epoxy resin and the epoxy resin.
Also, various resist materials (R-1 to 6, 13, 14, and) made of a colored composition using a salt-forming compound obtained by salting various dyes with a resin (resin 2) containing the same sulfate. , R-39), the resist material using dye 1 (R-39) has heat resistance, coating properties, coating foreign matter, storage stability, and voltage holding ratio as compared with the case where other dyes are used. It was the best result from the point of view.
Furthermore, the resist materials (R-38 to R-50) of Examples 82 to 94 made of a colored composition (DB-33 to DB-44) made of a salt-forming compound using Dye 1 are generally heat resistant, It was shown that foreign matter, coating property, storage stability and voltage holding ratio are high.
On the other hand, the resist material (R-53) of Comparative Example 10 was generally poor in heat resistance, and did not reach a grade usable as a color filter.
In addition, a resist material (R-37) using a mixture obtained by reacting a resin containing a cationic dye and a sulfate is used as a resist material (R-13) using a salt-forming product made of the same resin and dye. In comparison, the heat resistance and the 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 the salt-forming compound formed by salting a cationic dye and a sulfate-containing resin is washed with water to remove the counterproduct-derived salt as a by-product.
The resists (R-1 to R-50) used in the examples were found to have relatively good heat resistance even after heat treatment. In addition, there was almost no decrease in transmittance in the transmission spectrum of these resists. Than these. The resists (R-1 to R-50) used in the examples can form a coating film with high brightness. However, since the resists (R-51 to 53) used in the comparative examples have poor heat resistance, the transmittance in the transmission spectrum of these resists decreased. Therefore, the brightness was inferior compared to the resists (R-1 to R-50) used in the examples.

  In addition, thereby, the coloring composition containing a salt-forming compound using a resin having a sulfate group is excellent in heat resistance, coating property, and storage stability, and can provide an excellent color filter having no coating film foreign matter. Is clear.

Claims (8)

A color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant contains an ethylenically unsaturated monomer (a-1) represented by the following general formula (1) A color composition for a color filter, comprising a salt-forming compound obtained by reacting a resin obtained by radical polymerization of a polymerizable unsaturated monomer (a) with a cationic dye.
General formula (1)

[In General Formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a single bond or a divalent linking group, A represents the general formula (2), and Y ⁺ represents an inorganic or organic cation. ]
General formula (2)

[In General Formula (2), R ⁴ represents an alkylene group which may have a substituent, and n is an integer of 1 to 20. ] In General Formula (1), the divalent linking group of R ² is —CH ₂ —O—CH ₂ CH (R ³ ) O—, and R ³ represents a monovalent alkyl group having 1 to 30 carbon atoms. The color filter coloring composition according to claim 1, wherein   The colored composition for a color filter according to claim 1 or 2, wherein the cationic dye is a triarylmethane-based basic dye. The coloring composition for a color filter according to claim 3, wherein the triarylmethane-based basic dye is represented by the general formula (3).
General formula (3)

[In General Formula (3), R1A to R1F each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group. R1G and R1H each independently represent a hydrogen atom, a methyl group, or an ethyl group. ]   A resin in which the salt-forming compound is obtained by radical polymerization of an ethylenically unsaturated monomer (a) containing the ethylenically unsaturated monomer (a-1) represented by the general formula (1) in an aqueous solution; A compound obtained by mixing a cationic dye and removing a salt composed of a counter cation of the resin containing the structural unit represented by the general formula (1) and a counter anion of the cationic dye. Item 5. A colored composition for a color filter according to any one of Items 1 to 4.   The coloring composition for a color filter according to any one of claims 1 to 5, wherein the colorant further contains a pigment.   Furthermore, the coloring composition for color filters in any one of Claims 1-6 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter formed from the coloring composition for a color filter according to claim 1.