JP6844190B2 - Coloring compositions and color filters for color filters - Google Patents

Description

The present invention relates to a coloring composition for a color filter used for forming a filter segment constituting a color filter used in a color liquid crystal display device and a solid-state image sensor, and a color filter obtained by using the coloring composition for a color filter. ..

Generally, a coloring composition in which a colorant containing a pigment is dispersed in a dispersant, a resin, a monomer, an organic solvent, or the like is used for forming a filter segment of a color filter, but in order to obtain a uniform coating film. Is required to have low viscosity and high fluidity. Therefore, many proposals have been made for stabilizing the pigment dispersion in the coloring composition, and Patent Documents 1 to 4 have excellent dispersibility and storage stability by using a polyester dispersant having a specific structure. Coloring compositions for color filters that achieve high contrast ratio and heat resistance are disclosed. However, in recent years, the demand for high definition (high resolution) has been increasing more and more, and the above-mentioned coloring composition has not been able to meet these demands.
Further, Patent Documents 5 to 6 disclose a coloring composition having excellent heat resistance by using a polymer dispersant having a structural unit derived from a monomer forming a specific ring structure. However, since the structure of the dispersant is not controlled, the obtained colored composition cannot achieve sufficient dispersibility (viscosity stability, etc.) especially in a field where high dispersibility is required.
That is, the conventional coloring composition could not satisfy all of the dispersant, storage stability, contrast ratio, heat resistance, and high definition (high resolution).

International Publication No. 2008/007776 Japanese Unexamined Patent Publication No. 2008-298967 JP-A-2009-155406 Japanese Unexamined Patent Publication No. 2010-223988 JP-A-2010-168539 Japanese Unexamined Patent Publication No. 2011-45862

An object of the present invention is to provide a coloring composition for a color filter and a color filter which are excellent not only in dispersibility, storage stability and heat resistance but also in high definition (high resolution).

That is, the present invention is a coloring composition for a color filter containing a colorant, a dispersant (X), a binder resin and an organic solvent, and the dispersant (X) is the following (S1) or (S2). ) Containing a coloring composition for a color filter.
(S1) A resin which is a reaction product of a hydroxyl group of a polymer (A) having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride, and is a polymer having the hydroxyl group. (S1) has a structural unit derived from the monomer (c1) represented by the following general formula (1).
(S2) In the presence of a reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride, it is represented by the following general formula (1). A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer containing the monomer (c1) to be prepared.

General formula (1):

(In the general formula (1), R represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.)

The present invention further relates to the above-mentioned coloring composition for a color filter, which contains at least one selected from a photopolymerizable monomer and a photopolymerization initiator.

Furthermore, the present invention relates to a color filter including a filter segment formed from the coloring composition for a color filter.

The coloring composition for a color filter of the present invention can provide a coloring composition for a color filter that suppresses pigment aggregation, has excellent stability of the dispersion, and is also excellent in heat resistance and resolution.

<Coloring composition for color filters>
The coloring composition for a color filter of the present invention is a coloring composition for a color filter containing a colorant, a dispersant (X), a binder resin and an organic solvent, and the dispersant (X) is described below ( The most characteristic feature is that the coloring composition for a color filter is characterized by containing the resin of S1) or (S2).
(S1) A resin which is a reaction product of a hydroxyl group of a polymer (A) having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride, and is a polymer having the hydroxyl group. (S1) has a structural unit derived from the monomer (c1) represented by the following general formula (1).
(S2) In the presence of a reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride, it is represented by the following general formula (1). A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer containing the monomer (c1) to be prepared.

General formula (1):

(In the general formula (1), R represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.)

In the dispersant (X) of the present invention, a polycarboxylic acid moiety derived from a tricarboxylic acid anhydride and / or a tetracarboxylic dianhydride acts as a pigment adsorbing group. Further, the polymer chain derived from the polymer obtained by polymerizing the ethylenically unsaturated monomer acts as a pigment carrier-affinitive group, thereby suppressing the aggregation of the pigment and excellent in the stability of the dispersion, and further, the general formula (1). By having a structural unit derived from the monomer (c1) represented by), it is possible to exhibit excellent suitability for heat resistance and high definition (high resolution).

<Dispersant (X)>
The resins (S1) and (S2) contained in the dispersant (X) of the present invention are mainly subjected to two reactions, a polymerization reaction of an ethylenically unsaturated double bond and an esterification reaction of a hydroxyl group and an acid anhydride group. Since it has a complicated structure to be obtained and it is impossible or almost unrealistic to express it by a general formula (structure), it is described by a manufacturing method. Further, the pigment carrier in the present application represents a binder resin and / or a photopolymerizable monomer obtained by removing the pigment component and the dispersant from the solid content.

As described above, the dispersant (X) is characterized by containing the following resin (S1) or (S2).
(S1) A resin which is a reaction product of a hydroxyl group of a polymer (A) having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride, and is a polymer having the hydroxyl group. (S1) has a structural unit derived from the monomer (c1) represented by the following general formula (1).
(S2) In the presence of a reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride, it is represented by the following general formula (1). A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer containing the monomer (c1) to be prepared.

[Resin (S1)]
The resin (S1) can be produced by a known method such as WO2008 / 007776, Japanese Patent Application Laid-Open No. 2008-029901 and the like. The polymer (A) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal, for example, a monomer represented by the general formula (1) in the presence of the compound (B) having a hydroxyl group (1). It can be obtained as a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing c1). As the compound (B) having a hydroxyl group, as described later, a compound having a hydroxyl group and a thiol group in the molecule is preferable. Since the number of terminal hydroxyl groups is preferably plural, the compound (b1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

That is, a more preferable example, a polymer having two hydroxyl groups at one end contains a monomer (c1) in the presence of a compound (b1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (a1) obtained by polymerizing the ethylenically unsaturated monomer (C) contained therein. The hydroxyl group of the polymer (A) having a hydroxyl group reacts with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form an ester bond, while the anhydrous ring is opened and the carboxylic acid. Produces.

[Resin (S2)]
The resin (S2) can be produced by a known method such as JP-A-2010-185934. For example, the hydroxyl group of the compound (B) having a hydroxyl group, a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride can be produced. It is obtained by polymerizing an ethylenically unsaturated monomer (C) containing a monomer (c1) represented by the general formula (1) in the presence of a reaction product with an acid anhydride group of a substance. .. Above all, in the presence of a reaction product of the hydroxyl group of compound (b1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. It is preferably a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing the monomer (c1).

In (S1) and (S2), the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (C1) containing the acidic group-containing ethylenically unsaturated monomer (c1) is introduced first or later. Is the difference. The molecular weight etc. may differ slightly depending on various conditions, but if the reaction conditions are the same as the raw material, the same thing can be theoretically made.

[Synthesis of resins (S1) and (S2)]
(Production of Polymer (A) Having Hydroxyl Group)
As described above, the polymer (A) having a hydroxyl group in the resin (S1) contains an ethylenically unsaturated monomer (C) containing a monomer (c1) in the presence of the compound (B) having a hydroxyl group. It can be obtained as a polymerized polymer.

(Compound having a hydroxyl group (B))
The compound (B) having a hydroxyl group in the present invention preferably contains a compound having a hydroxyl group and a thiol group in the molecule, and the compound having a hydroxyl group and a thiol group in the molecule has a hydroxyl group and a thiol group. , Not limited. Such compounds include, for example, compounds having two hydroxyl groups and one thiol group in the molecule described later, as well as compounds having one thiol group.
A compound having one hydroxyl group and one thiol group in the molecule such as mercaptoethanol;
Compounds having one hydroxyl group and two thiol groups in the molecule, such as 1,2-dimercapto-3-propanol and 1,3-dimercapto-2-propanol;
Compounds having one hydroxyl group and three or more thiol groups in the molecule such as pentaerythritol tris (3-mercaptoacetylate) and dipentaerythritol pentakis (3-mercaptopropionate);
A compound having two hydroxyl groups and two thiol groups in the molecule, such as 1,2-dimercapto-1,2-ethanediol;
A compound having three or more hydroxyl groups and two thiol groups in the molecule, such as dimercaptodipentaerythritol;
A compound having two or more hydroxyl groups and three or more thiol groups in a molecule such as trimercaptodipentaerythritol;
Compounds having three or more hydroxyl groups and one thiol group in the molecule, such as 1-mercapto-1,2,2'-ethanetriol; and the like. Of these, the compound (b1) having two hydroxyl groups and one thiol group in the molecule is preferable.

(Compound (b1) having two hydroxyl groups and one thiol group in the molecule)
Examples of the compound having two hydroxyl groups and one thiol group in the molecule used in the present invention include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto-. 1,2-Propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propane Examples thereof include diol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like. Of these, 3-mercapto-1,2-propanediol is preferable.

The compound (B) having a hydroxyl group may contain a compound other than the compound having a hydroxyl group and a thiol group in the molecule. For example, polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, or hexanetriol;
Polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol;
Modified polyether polyols obtained by ring-opening polymerization of the above polyhydric alcohols with a (cyclic) ether bond-containing compound such as ethylene oxide, propylene oxide, or allyl glycidyl ether;
Polyester polyols obtained by copolymerizing one or more of the above polyhydric alcohols with polyvalent carboxylic acids, wherein the polyvalent carboxylic acids are succinic acid, adipic acid, or 2,5,7-naphthalene. Polyesters such as tricarboxylic acids;
Lactone-based polyester polyols obtained by polycondensation reaction between one or more of the above polyhydric alcohols and lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone;
Lactone-modified polyester polyols obtained by polycondensation reaction of the above polyhydric alcohols, polyvalent carboxylic acids, and various lactones;
Polyester with various epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monovalent and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids. Epoxy-modified polyester polyols obtained by using one or more kinds in combination during the synthesis of polyols;
Examples thereof include polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound or hydroxyl group-containing silicon resin. ..

The compound having a hydroxyl group and a thiol group is preferably bulk polymerization or solution polymerization using 1 to 10% by weight based on the total monomer weight of the ethylenically unsaturated monomer (C) described later. , More preferably 2-9% by weight, still more preferably 3-8% by weight. Within the above range, a good balance can be maintained as an affinity site for the pigment carrier and the solvent, and both dispersibility and suppression of pigment aggregation can be achieved at the same time.

(Ethylene unsaturated monomer (C))
The ethylenically unsaturated monomer (C) of the present invention contains a monomer (c1) represented by the following general formula (1).

(Polymer represented by the general formula (1) (c1))
General formula (1):

(In the general formula (1), R represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.)

For example, the monomer (c1) represented by the general formula (1) and another copolymerizable ethylenically unsaturated monomer (c2) are contained in the molecule with two hydroxyl groups and one thiol group. When copolymerizing in the presence of the compound (b1) having the above to obtain a polymer (a1) having two hydroxyl groups at one end, the monomer (c1) represented by the general formula (1) is obtained at the same time as the polymerization. The cyclization reaction of the above proceeds to form a tetrahydrofuran ring structure. It is considered that the formation of the tetrahydrofuran ring structure in the resin suppresses the movement of molecules, so that the resin becomes rigid and the heat resistance and fineness (resolution) are improved.

The monomer (c1) represented by the general formula (1) is preferably 0.5% by weight to 100% by weight, more preferably 2% by weight, based on the weight of the totally ethylenically unsaturated monomer (C). % To 50% by weight, more preferably 5 to 50% by weight. With 20% by weight or more, heat resistance and resolution are significantly improved.

Examples of the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent in R of the general formula (1) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and t-. Linear or branched alkyl groups such as butyl, t-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl , Alicyclic groups such as adamantyl, 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy such as 1-methoxyethyl and 1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl; etc. Can be mentioned. Among these, hydrocarbon groups such as methyl, ethyl, cyclohexyl, and benzyl, which are difficult to be desorbed by acid or heat, are particularly preferable in terms of heat resistance.

Specific examples of the monomer (c1) represented by the general formula (1) include α-allyloxymethylacrylate, α-allyloxymethylacrylate methyl, α-allyloxymethylacrylate ethyl, and α. -N-propyl allyloxymethylacrylate, i-propyl α-allyloxymethylacrylate, n-butyl α-allyloxymethylacrylate, s-butyl α-allyloxymethylacrylate, α-allyloxymethylacrylate t-butyl, α-allyloxymethylacrylate n-amyl, α-allyloxymethylacrylate s-amyl, α-allyloxymethylacrylate t-amyl, α-allyloxymethylacrylate neopentyl, α-allyloxy N-hexyl methylacrylate, s-hexyl α-allyloxymethylacrylate, n-heptyl α-allyloxymethylacrylate, n-octyl α-allyloxymethylacrylate, s-octyl α-allyloxymethylacrylate , Α-allyloxymethylacrylate t-octyl, α-allyloxymethylacrylate 2-ethylhexyl, α-allyloxymethylacrylate capril, α-allyloxymethylacrylate nonyl, α-allyloxymethylacrylate decyl, Undecyl α-allyloxymethylacrylate, lauryl α-allyloxymethylacrylate, tridecyl α-allyloxymethylacrylate, myristyl α-allyloxymethylacrylate, pentadecyl α-allyloxymethylacrylate, α-allyloxymethyl Cetyl acrylate, heptadecyl α-allyloxymethylacrylate, stearyl α-allyloxymethylacrylate, nonadecil α-allyloxymethylacrylate, eikosyl α-allyloxymethylacrylate, ceryl α-allyloxymethylacrylate, α -A chain saturated hydrocarbon group-containing α- (allyloxymethyl) acrylate such as melicyl acrylate.
Α- (allyloxymethyl) acrylate containing hydroxy-substituted chain saturated hydrocarbon groups such as hydroxyethyl α-allyloxymethylacrylate, hydroxypropyl α-allyloxymethylacrylate, and hydroxybutyl α-allyloxymethylacrylate;
Fluoroethyl α-allyloxymethylacrylate, difluoroethyl α-allyloxymethylacrylate, chloroethyl α-allyloxymethylacrylate, dichloroethyl α-allyloxymethylacrylate, bromoethyl α-allyloxymethylacrylate, α- Α- (allyloxymethyl) acrylate containing a halogen-substituted chain saturated hydrocarbon group such as dibromoethyl allyloxymethyl acrylate;
Cyclopentyl α-allyloxymethylacrylate, cyclopentylmethyl α-allyloxymethylacrylate, cyclohexyl α-allyloxymethylacrylate, cyclohexylmethylα-allyloxymethylacrylate, 4-methylcyclohexylα-allyloxymethylacrylate, 4-t-Butylcyclohexyl α-allyloxymethylacrylate, tricyclodecanyl α-allyloxymethylacrylate, isobornyl α-allyloxymethylacrylate, adamantyl α-allyloxymethylacrylate, α-allyloxymethylacrylic acid Α- (allyloxymethyl) acrylate containing alicyclic hydrocarbon groups such as dicyclopentanyl acid and dicyclopentenyl α-allyloxymethyl acrylate;
phenyl α-allyloxymethylacrylate, methylphenyl α-allyloxymethylacrylate, dimethylphenyl α-allyloxymethylacrylate, trimethylphenyl α-allyloxymethylacrylate, 4-t-allyloxymethylacrylate Butylphenyl, benzyl α-allyloxymethylacrylate, diphenylmethyl α-allyloxymethylacrylate, diphenylethyl α-allyloxymethylacrylate, triphenylmethylα-allyloxymethylacrylate, α-allyloxymethylacrylate Α- (allyloxymethyl) acrylate containing aromatic hydrocarbon groups such as naphthyl and anthranyl α-allyloxymethylacrylate;
methoxyethyl α-allyloxymethylacrylate, methoxyethoxyethyl α-allyloxymethylacrylate, methoxyethoxyethoxyethyl α-allyloxymethylacrylate, 3-methoxybutyl α-allyloxymethylacrylate, α-allyloxymethyl Chain ether group-based saturated hydrocarbon group-containing α- such as ethoxyethyl acrylate, ethoxyethoxyethyl α-allyloxymethyl acrylate, phenoxyethyl α-allyloxymethyl acrylate, phenoxyethoxyethyl α-allyloxymethyl acrylate, etc. (Allyloxymethyl) acrylate;
Cyclopentoxyethyl α-allyloxymethylacrylate, cyclohexyloxylethyl α-allyloxymethylacrylate, cyclopentoxyethoxyethyl α-allyloxymethylacrylate, cyclohexyloxyethoxyethyl α-allyloxymethylacrylate, α- Α- (allyloxymethyl) acrylate having both an alicyclic hydrocarbon group such as dicyclopentenyloxyethyl allyloxymethylacrylate and a chain ether group;
Α- (allyloxymethyl) acrylate having both aromatic hydrocarbon groups such as α-allyloxymethylacrylate phenoxyethyl and α-allyloxymethylacrylate phenoxyethoxyethyl and a chain ether group;
Glycidyl α-allyloxymethylacrylate, β-methylglycidyl α-allyloxymethylacrylate, β-ethylglycidyl α-allyloxymethylacrylate, 3,4-epoxycyclohexylmethyl α-allyloxymethylacrylate, α- 2-oxetanmethyl allyloxymethyl acrylate, 3-methyl-3-oxetanmethyl α-allyloxymethyl acrylate, 3-ethyl-3-oxetanmethyl α-allyloxymethyl acrylate, tetrahydrofla of α-allyloxymethyl acrylate Cyclic ether-based saturated hydrocarbons such as Nyl, tetrahydrofurfuryl α-allyloxymethylacrylate, tetrahydropyranyl α-allyloxymethylacrylate, dioxazolanyl α-allyloxymethylacrylate, and dioxanyl α-allyloxymethylacrylate. Group-containing α- (allyloxymethyl) acrylate; and the like.
These monomers (c1) represented by the general formula (1) can be used alone or in admixture of two or more at any ratio as required.

Among these, α- (allyloxymethyl) acrylate containing a chain saturated hydrocarbon group is preferable, and α-allyloxymethylacrylic acid and methyl α-allyloxymethylacrylate are preferable.

(Other monomers (c2))
Examples of the ethylenically unsaturated monomer (c2) include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, and isobutyl (meth) acrylate. , Tashalibutyl (meth) acrylate, isoamyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) ) Linear or branched alkyl (meth) acrylates such as acrylates, lauryl (meth) acrylates, tridecyl (meth) acrylates, isomyristyl (meth) acrylates, stearyl (meth) acrylates, or isostearyl (meth) acrylates;
Cyclohexyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) ) Cyclic alkyl (meth) acrylates such as acrylate or isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meta) Acryloxy-modified polydimethylsiloxane (silicone macromer);
(Meta) acrylates having a heterocycle 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, nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meta) acrylates having an aromatic ring of
(Meta) Acrylate, Acrylic Acid Dimer, 2- (Meta) Acryloyloxyethyl Phthrate, 2- (Meta) Acryloyloxypropyl Phthrate, 2- (Meta) Acryloyloxyethyl Hexahydrophthalate, 2- (Meta) (Meta) 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;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
N-substituted (meth) acrylamide such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloyl morpholine. ) Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate or N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meta) acrylonitrile;
Methoxyethyl (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, methoxypolytetramethylene glycol (meth) acrylate, methoxypolyethylene glycol polypropylene glycol (meth) acrylate, ethyl vinyl ether, n-propyl vinyl ether , An ethylenically unsaturated monomer having an ether group, such as vinyl ethers such as isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; or a mixture thereof.

At the time of polymerization, 0.001 to 5 parts by weight of the polymerization initiator can be optionally used with respect to 100 parts by weight of the ethylenically unsaturated monomer (C). As the polymerization initiator, an azo compound and an organic peroxide can be used. Examples of azo compounds include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'-azobis (cyclohexane1-carbonitrile), and 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), 2,2'-azobis [2- (2-imidazolin-2-yl)) Propane] and the like. Examples of organic peroxides are benzoyl peroxide, t-butylperbenzoate, cumenehydroperoxide, diisopropylperoxydicarbonate, di-n-propylperoxydicarbonate, di (2-ethoxyethyl) peroxy. Examples thereof include dicarbonate, t-butylperoxyneodecanoate, t-butylperoxyvivarate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more.

In the case of solution polymerization, as the polymerization solvent, 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 mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like are used, but are not particularly limited thereto. Two or more kinds of these polymerization solvents may be mixed and used. After the reaction is completed, the solvent used in the polymerization reaction can be removed by an operation such as distillation, or can be used as it is as a solvent in the next step, or can be used as a part of a product.

The reaction temperature is preferably 40 to 150 ° C, more preferably 50 to 110 ° C. Further, the polymerization reaction in the resin (S2) is the same as described above.

The weight average molecular weight of the polymer (A) is preferably 1,000 to 15,000, more preferably 2,000 to 13,000, and even more preferably 3,000 to 12,000. This site serves as an affinity site for the pigment carrier and the solvent. The molecular weight of the polymer (A) can be easily adjusted to the above range, and the polymer (A) in the above range has a good affinity for the solvent.

(Reaction of polymer (A) having an acid group with an acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic dianhydride (polyester synthesis))
(Tricarboxylic acid anhydride)
Examples of the tricarboxylic acid anhydride include an aliphatic tricarboxylic acid anhydride and an aromatic tricarboxylic acid anhydride. Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, and cis-propen-1,2,3-tricarboxylic acid-. Examples thereof include 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride and the like. Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride], etc.) and naphthalene tricarboxylic acid. Acid anhydrides (1,2,4-naphthalentricarboxylic acid anhydrides, 1,4,5-naphthalenetricarboxylic acid anhydrides, 2,3,6-naphthalentricarboxylic acid anhydrides, 1,2,8-naphthalentricarboxylic acid anhydrides , 3,4,4'-benzophenone tricarboxylic acid anhydride, 3,4,4'-biphenyl ether tricarboxylic acid anhydride, 3,4,4'-biphenyl tricarboxylic acid anhydride, 2,3,2' Examples thereof include −biphenyltricarboxylic acid anhydride, 3,4,4′-biphenylmethanetricarboxylic acid anhydride, 3,4,4′-biphenylsulfonetricarboxylic acid anhydride and the like.
In the present invention, it is preferable to use an aromatic tricarboxylic acid anhydride from the viewpoint of adsorptivity to pigments.

(Tetracarboxylic dianhydride)
Examples of the tetracarboxylic dianhydride used in the present invention include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 1,3-. Didimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3 , 5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3 An aliphatic tetracarboxylic acid such as −cyclohexene-1,2-dicarboxylic dianhydride or bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride Dianide or
Pyromellitic dianhydride, ethylene glycol dianhydride trimellitic acid ester, propylene glycol dianhydride trimellitic acid ester, butylene glycol dianhydride trimellitic acid ester, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride , 3,3', 4,4'-biphenylsulfonetetracarboxylic hydride, 1,4,5,8-naphthalenetetracarboxylic hydride, 2,3,6,7-naphthalenetetracarboxylic hydride Anhydride, 3,3', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3', 4,4 '-Tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furtetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4 , 4'-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4' -Perfluoroisopropyridendiphthalic hydride, 3,3', 4,4'-biphenyltetracarboxylic hydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenyl) Phthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4, 4'-Diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride , 3,4-Dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic hydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1 -Aromatic tetracarboxylic dianhydrides such as naphthalene succinic hydride can be mentioned.
In the present invention, it is preferable to use aromatic tetracarboxylic dianhydride from the viewpoint of adsorptivity to pigments.

The tricarboxylic acid anhydride and tetracarboxylic dianhydride in the resins (S1) and (S2) are preferably tetracarboxylic dianhydride and more preferably aromatic tetracarboxylic dianhydride from the viewpoint of adsorptivity to pigments. .. Among them, pyromellitic acid dianhydride is preferable. Aromatic carboxylic acids have higher pigment adsorbing ability than aliphatic carboxylic acids. The tricarboxylic acid anhydride and tetracarboxylic dianhydride used in the present invention are not limited to the compounds exemplified above, and may have any structure as long as they have two carboxylic acid anhydride groups. These may be used alone or in combination.

(Reaction solvent)
The polyester synthesis can be produced using only the raw materials mentioned above, but it is preferable to use a solvent in order to avoid problems such as high viscosity and non-uniform reaction. The solvent used is not particularly limited, and known solvents can be used. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile and the like can be mentioned. After the reaction is completed, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a solvent in the next step, or can be used as a part of a product.

(Reaction catalyst)
As the catalyst used for polyester synthesis, a known catalyst can be used. The catalyst is preferably a tertiary amine compound, for example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1, Examples thereof include 5-diazabicyclo- [4.3.0] -5-nonen.

(Reaction temperature)
The reaction temperature of polyester synthesis is 50 ° C. to 180 ° C., preferably 80 ° C. to 140 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the carboxyl group and the hydroxyl group undergo an esterification reaction, which may reduce the acid value or cause gelation. Ideally, the reaction should be stopped until the absorption of the acid anhydride is eliminated by infrared absorption, but when the acid value of the polyester is in the range of 5 to 200, or the hydroxyl value is 20 to 200. The reaction may be stopped when it enters the range.

(Molecular weight)
The weight average molecular weights of the resins (S1) and (S2) are preferably 2,000 to 35,000, more preferably 4,000 to 30,000, and even more preferably 6,000 to 20,000. If the weight average molecular weight is less than 2000, the stability of the pigment composition may decrease, and if it exceeds 35,000, the interaction between the resins becomes strong, and thickening of the coloring composition for a color filter may occur. is there.

(Acid value)
The acid values of the resins (S1) and (S2) are preferably 5 to 200. It is more preferably 10 to 150, and even more preferably 20 to 100. If the acid value is less than 5, the pigment adsorption ability may decrease and a problem may occur in the pigment dispersibility, and if it exceeds 200, the interaction between the resins may become strong and the viscosity of the pigment dispersion composition may increase.

The reaction between the hydroxyl group of the compound (B) having a hydroxyl group in the resin (S2) and the acid anhydride group of the tricarboxylic acid anhydride and / or the tetracarboxylic dianhydride is the same as described above.

The content of the dispersant (X) in the coloring composition for a color filter is preferably 0.01 to 100% by weight, more preferably 0.01 to 60% by weight, still more preferably 5 based on the weight of the pigment. ~ 40% by weight. If the content of the dispersant (X) is less than 0.01% by weight, the dispersion effect becomes insufficient, and if it exceeds 100% by weight, the dispersibility may also deteriorate.

<Colorant>
The colorant that can be used in the coloring composition of the present invention can be arbitrarily selected from various conventionally known pigments and dyes. Hereinafter, typical pigments and dyes that can be used in the present invention are listed.

The red pigments that can be used in the present invention include, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 221 224, 226, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, Examples thereof include, but are not limited to, 284, 285, 286, 287, or the diketopyrrolopyrrole pigments described in JP-A-2011-523433. Further, red dyes such as xanthene-based, azo-based, disazo-based, and anthraquinone-based dyes can also be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene-based acid dyes such as Acid Red 52, 87, 92, 289, and 338.

The orange pigments that can be used in the present invention include, for example, C.I. I. Pigment Orange 38, 43, 71, 73 and the like, but are not particularly limited thereto.

Yellow dyes include azo dyes, azo metal complex salt dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, and quinoline dyes. , Naftquinone dyes, oxazine dyes and the like.

Therefore, specific examples of the yellow dye include C.I. I. Acid Yellow 2,3,4,5,6,7,8,9,9: 1,10,11,11: 1,12,13,14,15,16,17,17: 1,18,20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191 and 192, 199 and the like can be mentioned.

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

In addition, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19,
21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, 105, 106 and the like can be mentioned.

In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13
, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64 , 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131 , 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186. , 187, 188, 190, 191 and 192, 194, 195 and the like.

In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 , 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 , 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

As the yellow pigment, an organic or inorganic pigment can be used alone or in combination of two or more, and a pigment having high color development and high heat resistance, particularly a pigment having high heat resistance decomposition property is preferable, and usually Organic pigments are used. As the organic pigment, a commercially available pigment can be used, and a natural pigment or an inorganic pigment can be used in combination depending on the desired hue of the filter segment.

Specific examples of the yellow organic pigment that can be used in the coloring composition are shown below. Examples of the yellow pigment include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 1
5, 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, Use yellow pigments such as 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214. Can be done. In particular, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, C.I. I. Pigment Yellow 138, 139, 150 and 185 are preferred.
These yellow pigments can be used alone or in admixture of two or more, depending on the desired color characteristics.

The green pigments that can be used in the present invention include, for example, C.I. I. Pigment Green 7, 10, 36, 37, 58, 62, 63 and the like, but are not particularly limited thereto.

The blue pigments that can be used in the present invention include, for example, C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP-A-2004-333817, Examples thereof include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but the present invention is not particularly limited thereto.

The content of the colorant preferable in all the non-volatile components of the coloring composition according to the present invention is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of sufficient color reproducibility and stability. Most preferably, it is 20 to 80% by weight.

<Dye derivative>
The coloring composition of the present invention can arbitrarily select and contain various conventionally known dye derivatives. Examples of the dye derivative include compounds in which an organic pigment, anthraquinone, acrydone or triazine is introduced with a basic substituent, an acidic substituent, or a phthalimide methyl group which may have a substituent. No. 63-305173, No. 57-15620, No. 59-40172, No. 63-17102, No. 5-9469, No. 2001-335717, No. 2003-2003. 128669, 2003-167112, 2004-091497, 2004-307854, 2007-156395, 2008-094873, 2008-094986. Those described in Japanese Patent Application Laid-Open No. 2008-905007, Japanese Patent Application Laid-Open No. 2008-195916, Japanese Patent Application Laid-Open No. 4585781, and the like can be used.

The following is an example of a dye derivative having a basic group of the present invention, but the present invention is not limited thereto.

Compound 1:

Compound 2:

Compound 3:

Compound 4:

Compound 5:

(Pigment miniaturization)
When the colorant used in the coloring composition of the present invention is a pigment, it can be made finer by salt milling or the like. The average primary particle size determined by the TEM (transmission electron microscope) of the pigment is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse it in an organic solvent, and if it is larger than 90 nm, a sufficient contrast ratio cannot be obtained. For this reason, the more preferable average primary particle size is in the range of 10 to 70 nm.

Salt milling is a machine in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is heated by a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

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

The water-soluble organic solvent has a function of wetting 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 used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

When the pigment is subjected to salt milling treatment, a resin may be added if necessary. The type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, 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 used in the coloring composition of the present invention is for dispersing, dyeing, or permeating a coloring agent, and examples thereof include thermoplastic resins. When used in the form of an alkali-developable colored resist material, it is preferable to use an alkali-soluble vinyl-based resin copolymerized with an acidic group-containing ethylenically unsaturated monomer. Further, in order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain as an alkali-developable colored resist material, the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film. By doing so, the colorant is fixed, the heat resistance is improved, and fading (deterioration of spectral characteristics) due to the heat of the colorant can be suppressed. It also has the effect of suppressing aggregation and precipitation of colorant components in the developing process.

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.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 7,000 to 80,000 in order to preferably disperse the colorant. The number average molecular weight (Mn) is preferably in the range of 2,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

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

Since the binder resin has good film forming properties and various resistances, it is preferable to use the binder resin in an amount of 20 parts by weight or more based on 100 parts by weight of the total weight of the colorant, and the colorant concentration is high and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 1000 parts by weight or less.

Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, and polyvinyl acetate. , Polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resin and the like. .. Above all, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include a resin having an acidic group such as a carboxyl group and a sulfone group.
Specifically, the alkali-soluble resin includes an acrylic resin having an acidic group, an α-olefin / (maleic anhydride) maleic anhydride copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples thereof include isobutylene / (anhydrous) maleic anhydride copolymer. Among them, an acrylic resin having an acidic group and at least one resin selected from 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.

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include a resin in which an unsaturated ethylenically double bond is introduced by the methods (i) and (ii) shown below.

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

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

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

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and these may be used alone or in combination of two or more. It doesn't matter. If necessary, such as by increasing the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride may be used to obtain the remaining anhydride. The group can also be hydrolyzed. Further, when etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenically double bond is used as the polybasic acid anhydride, the unsaturated ethylenically double bond can be further increased.

As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers. There is a method of introducing an unsaturated ethylenic double bond and a carboxyl group by addition-reacting an unsaturated ethylenic monomer having an epoxy group to a part of the carboxyl group.

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

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

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, but the present invention is limited thereto. However, two or more types can be used together.

(Thermosetting compound)
In the present invention, a thermosetting compound may be further contained in combination with a thermoplastic resin which is a binder resin. Thermosetting compounds include, for example, 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, but are not limited to, urea compounds and / or resins, phenolic compounds and / or resins.

<Organic solvent>
In the coloring composition of the present invention, the coloring agent is sufficiently dispersed and permeated into the coloring agent carrier, and applied onto a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm to form a coloring film. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of the solubility of each component of the coloring composition and the safety in addition to the good coatability of the coloring composition.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl-. 1,3-Propanediol, 3,5,5-trimethyl-2-cyclohexene-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, N, N-dimethyl Acetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-diethylbenzene, 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 monotersial 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 mono Methyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene Glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , Propylene acetate, dibasic acid ester and the like. These solvents can be used alone or in admixture of two or more in any ratio as required.

Among them, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl are good because of the good dispersibility and permeability of the colorant and the applicability of the coloring composition. It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

Further, 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 coloring composition can be adjusted to an appropriate viscosity and a colored film having a desired uniform film thickness can be formed. Is preferable.

<Photopolymerizable monomer>
The photopolymerizable monomer that may be added to the coloring composition of the present invention includes a monomer or an oligomer that is cured by ultraviolet rays, heat, or the like to produce a transparent resin. 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 ( Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Pentaerythritol Tri (Meta) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, 1,6-Hexanediol Diglycidyl Ether Di (Meta) Acrylate, Bisphenol A Diglycidyl Etherdi (Meta) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, methylolated melamine (Meta) acrylic acid ester, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate and methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol tri Examples thereof include, but are not limited to, vinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile. These photopolymerizable compounds may be used alone or in admixture of two or more at any ratio as required.

The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight based on the total weight of the colorant (100 parts by weight), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Photopolymerization initiator>
To the coloring composition of the present invention, a photopolymerization initiator is added to cure the composition by ultraviolet irradiation and to form a filter segment by a photolithography method, and a solvent-developed or alkali-developed photosensitive coloring composition is added. 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-. Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetphenone compounds such as − [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one; benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4' -Methyldiphenyl sulfide, or benzophenone compounds such as 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4 Thioxanthone compounds such as −diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2-( p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6- Bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s- Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4- Triazine compounds such as trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyl) Oxime)], or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6) -Trimethylbenzoyl) phenylphosphine oxide, or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrene quinone, camphorquinone, ethylanthraquinone; borate compounds; A carbazole-based compound; an imidazole-based compound; or a titanosen-based compound or the like is used. These photopolymerization initiators can be used alone or in admixture of two or more at any ratio as required.

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

<Sensitizer>
Further, the coloring composition of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinone derivatives. , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives and other polymethine dyes, acrydin derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indolin derivatives, Azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalyloporphyrazine derivative , Naphthalocyanine derivative, Subphthalocyanine derivative, Pyrylium derivative, Thiopyrylium derivative, Tetraphyllin derivative, Anurene derivative, Spiropyran derivative, Spiroxazine derivative, Thiospiropirane derivative, Metal allene complex, Organic ruthenium complex, or Michler ketone derivative, Biimidazole derivative, α -Acyloxyester, acylphosphine oxide, methylphenylglycolate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3', or Examples thereof include 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-diethylaminobenzophenone. These sensitizers can be used alone or in admixture of two or more at any ratio as required.

More specifically, Ogawara Nobu et al., "Dye Handbook" (1986, Kodansha), Ogawara Nobu et al., "Functional Dye Chemistry" (1981, CMC), Ikemori Chuzaburo et al., And " Examples thereof include, but are not limited to, the sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet to the near infrared region can also be contained.

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

<Multifunctional thiol>
The coloring composition of the present invention can contain a polyfunctional thiol that acts as a chain transfer agent. The polyfunctional thiol may be a compound having two or more thiol groups, for example, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene. Glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropanthithioglycolate, trimethylolpropanetristhiopropionate, trimethylolpropanthris (3-mercaptobutyrate), pentaerythritol tetraxthioglycolate, Pentaerythritol tetraxthiopropionate, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-) Dibutylamino) -4,6-dimercapto-s-triazine and the like can be mentioned. These polyfunctional thiols can be used alone or in admixture of two or more at any ratio as required.

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 of the total solid content of the coloring composition for a color filter (100% by weight). .. 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 may be too high and the resolution may be lowered.

<Antioxidant>
The coloring composition of the present invention can contain an antioxidant. The antioxidant increases the transmittance of the coating film in order to prevent the photopolymerization initiator and the thermosetting compound contained in the coloring composition from being oxidized and yellowed by the thermal process at the time of thermosetting or ITO annealing. be able to. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

The "antioxidant" in the present invention may be a compound having an ultraviolet absorbing function, a radical catching function, or a peroxide decomposition function. Specifically, the antioxidant is a hindered phenolic or hindered amine compound. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, sulcylic acid ester-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used. Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, the ones preferable are hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Agents can be mentioned. Further, more preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant. These antioxidants can be used alone or in admixture of two or more at any ratio as required.

The content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the coloring composition for a color filter because the brightness and sensitivity are good.

<Amine compounds>
Further, the coloring composition of the present invention may contain an amine compound having a function of reducing dissolved oxygen. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, and 2-dimethylaminobenzoate. Examples thereof include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

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

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water, and when added to a coloring composition, the same. It is useful to have a feature of low surface tension lowering ability and good wettability to the glass plate despite low surface tension lowering ability, and the amount of addition does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

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 polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane 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 to these.

Anionic, cationic, nonionic, or amphoteric surfactants can be added as an adjunct to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants to be added as an auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalin sulfonate, and alkyldiphenyl ether disulfonic acid. Sodium, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include ester.

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like; alkyl betaines such as alkyldimethylaminoacetic acid betaine, amphoteric surfactants such as alkylimidazoline, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Further, the coloring composition of the present invention may contain a curing agent, a curing accelerator, or the like, if necessary, in order to assist the curing of the thermosetting resin. Phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective as the curing agent, but the curing agent is not particularly limited to these, and is a thermosetting resin. Any curing agent may be used as long as it can react with. Further, among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine-based curing agent are preferably mentioned. 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 amidin compounds and salts thereof (eg, eg). Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Ethyl-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6, etc.) -Methacryloxyethyl-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.) and the like can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

<Other additive ingredients>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity over time. Further, an adhesion improver such as a silane coupling agent can be contained in order to improve the adhesion with the transparent substrate. Examples of the storage stabilizer include quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphorous acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine and the like. Examples thereof include organic phosphine and phosphite. 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 improvers include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and 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-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-amino Examples thereof include aminosilanes such as propyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and silane coupling agents such as 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, based on 100 parts by weight of the colorant in the coloring composition.

<Manufacturing method of coloring composition>
The coloring composition of the present invention comprises a colorant in a colorant carrier such as a binder resin and / or a solvent, preferably with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, and the like. It can be produced by finely dispersing it using various dispersion means such as a vertical sand mill, an annual bead mill, or an attritor (colorant dispersion). At this time, two or more kinds of colorants and the like may be dispersed in the colorant carrier at the same time, or those dispersed separately in the colorant carrier may be mixed. If the colorant such as a dye is highly soluble, specifically, if it is highly soluble in the solvent used, dissolved by stirring, and no foreign matter is confirmed, it is manufactured by finely dispersing as described above. No need.

When used as a photosensitive coloring composition (resist material) for a color filter, it can be prepared as a solvent-developing type or alkali-developing type coloring composition. The solvent-developed or alkaline-developed coloring composition includes the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and if necessary, a solvent, other pigment dispersants, and additives. Etc. can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

<Dispersion aid>
When the colorant is dispersed in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a great effect of preventing the reaggregation of the colorant after dispersion, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has high lightness and viscosity stability. Become good. The dye derivative is as described above.

<Resin type dispersant>
The resin-type dispersant has a colorant-affinitive portion having a property of adsorbing to the additive colorant and a portion compatible with the colorant carrier, and is adsorbed on the additive colorant and dispersed on the colorant carrier. It works to stabilize. Specifically, as the resin type dispersant, 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, and modified products of these, amides and salts thereof formed by the reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group. Oil-based dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, water-soluble such as polyvinylpyrrolidone. Resins, water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide-added compounds, phosphoric acid ester-based, etc. are used, and these can be used alone or in admixture of two or more. It is not necessarily limited to these.

A polymer dispersant having a basic functional group is preferable because the viscosity of the dispersion becomes low and a high contrast is exhibited with a small amount of the dispersant added, and it is preferable for a nitrogen atom-containing graft copolymer or a side chain. Nitrogen atom-containing acrylic block copolymers and urethane polymer dispersants having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocycle and the like are preferable. The resin type dispersant is preferably used in an amount of about 5 to 200% by weight, more preferably about 10 to 100% by weight, based on the total amount of the colorant.

Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167 manufactured by Big Chemie Japan. 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 or Anti -Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, manufactured by Japan Lubrizol. 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. , BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310. 4,320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Examples thereof include Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by the same company.

<Surfactant>
Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkylnaphthalin sulfonate, sodium alkyldiphenyl ether disulfonate. , Monoethanolamine lauryl sulfate, Triethanolamine lauryl sulfate, Ammonium lauryl sulfate, Monoethanolamine stearate, Monoethanolamine styrene-acrylic acid copolymer, Anionic surfactants such as polyoxyethylene alkyl ether phosphate; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate; alkyl Chaotic surfactants such as quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline, which may be used alone or in combination of two or more. They can be mixed and used, but are not necessarily limited to these.

When a surfactant is added, it is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, based on 100 parts by weight of the colorant. If the blending amount of the surfactant is less than 0.1 parts by weight, it is difficult to obtain the effect of addition, and if the content is more than 55 parts by weight, the dispersion may be affected by the excess dispersant. ..

<Removal of coarse particles>
The colored composition of the present invention comprises 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 of 5 μm or more, preferably coarse particles of 0.5 μm or more, by means such as centrifugation, filtration by a sintering filter or a membrane filter. It is preferable to remove the mixed dust. As described above, it is preferable that the coloring composition does not substantially contain particles having a size of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention comprises a filter segment or a black matrix formed from the coloring composition of the present invention on a transparent substrate, and a general color filter has at least one red filter segment and at least one. It comprises a green filter segment and at least one blue filter segment, or at least one magenta color filter segment, at least one cyan color filter segment, and at least one yellow color filter segment.

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

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

Each color filter segment and black matrix are formed by the photolithography method by the following method. That is, the dry film thickness of the photosensitive coloring composition prepared as a solvent-developed or alkali-developed colored resist material is reduced to 0 by a coating method such as spray coating, spin coating, slit coating, or roll coating on a transparent substrate. Apply to a thickness of 2 to 10 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film.

After that, the filter segment and the black matrix can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove the uncured portion and form a desired pattern. Further, in order to promote the polymerization of the filter segment and the black matrix formed by the development, heating can be applied if necessary. According to the photolithography method, a filter segment and a black matrix with higher accuracy than the printing method can be formed.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Further, an antifoaming agent or a surfactant can be added to the developing solution. As the development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid filling) development method and the like can be applied.

In order to increase the UV exposure sensitivity, the photosensitive coloring composition is applied and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition by oxygen. It is also possible to perform ultraviolet exposure after forming the above.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. The "parts" and "%" mean "parts by mass" and "% by mass". PGMAc represents propylene glycol monomethyl ether acetate.

<Manufacturing of finely divided pigments>
(Manufacturing of refined pigment (G-1))
120 parts of halogenated copper phthalocyanine green pigment PG36 (“Lionol Green 6YK” manufactured by Toyo Color Co., Ltd.), 1500 parts of crushed salt, and 250 parts of diethylene glycol are charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. Kneaded for 15 hours. This mixture is put into 5000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It was dried to obtain 117 parts of a finely divided pigment (G-1).

(Manufacturing of refined pigment (Y-1))
100 parts of quinophthalone yellow pigment PY138 (BASF's "Pariotol Yellow K0961HD"), 3 parts of dye derivative (compound 1 mentioned above), 800 parts of crushed salt, and 180 parts of diethylene glycol are made of stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). ), And kneaded at 70 ° C. for 4 hours. This mixture is put into 3000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 98 parts of a finely divided pigment (Y-1).

(Manufacturing of refined pigment (Y-2))
500 parts of the metal complex yellow pigment PY150 (“E4GN” manufactured by LANXESS), 2500 parts of sodium chloride, and 250 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 100 ° C. for 6 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 98 parts of a finely divided pigment (Y-2).

(Manufacturing of refined pigment (R-1))
Diketopyrrolopyrrole red pigment PR254 (BASF's "Irgafore Red B-CF") 100 parts, dye derivative (compound 2 mentioned above) 10 parts, crushed salt 1000 parts, diethylene glycol 120 parts 1 gallon made of stainless steel It was charged in a kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 8 hours. This mixture is put into 2000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It was dried to obtain 100 parts of a finely divided pigment (R-1).

(Manufacturing of refined pigment (R-2))
100 parts of anthraquinone red pigment PR177 (BASF's "Chromophthalred A2B"), 5 parts of dye derivative (compound 3 mentioned above), 800 parts of crushed salt, and 180 parts of diethylene glycol are made of stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). ), And kneaded at 70 ° C. for 5 hours. This mixture is put into 4000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. It was dried to obtain 100 parts of a finely divided pigment (R-2).

(Manufacturing of refined pigment (B-1))
Copper phthalocyanine blue pigment PB15: 6 ("Rionol Blue ES" manufactured by Toyo Color Co., Ltd.) 100 parts, dye derivative (compound 4 mentioned above) 5 parts, crushed salt 1000 parts, and diethylene glycol 100 parts made of stainless steel 1 gallon kneader It was charged in (manufactured by Inoue Seisakusho) and kneaded at 50 ° C. for 12 hours. This mixture is poured into 3000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 98 parts of a finely divided pigment (B-1).

(Manufacturing of refined pigment (V-1))
300 parts of the dioxazine-based purple pigment PV23 (“Rionogen Violet RL” manufactured by Toyo Color Co., Ltd.) was put into 3000 parts of 96% sulfuric acid, stirred for 1 hour, and then poured into water at 5 ° C. After stirring for 1 hour, the mixture was filtered, washed with warm water until the washing liquid became neutral, and dried at 70 ° C. 120 parts of the obtained acid paced pigment, 5 parts of the dye derivative (compound 5 described above), 1500 parts of crushed salt, and 100 parts of diethylene glycol were charged in a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and 20 at 70 ° C. Time kneaded. This mixture is put into 5000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. for 24 hours. The mixture was dried to obtain 115 parts of a finely divided pigment (V-1).

<Manufacturing of binder resin solution>
370 parts of propylene glycol monomethyl ether acetate (PGMAc) is placed in a reaction vessel, heated to 80 ° C. while injecting nitrogen gas into the vessel, and a mixture of the following monomer and thermal polymerization initiator is added dropwise at the same temperature over 1 hour. The polymerization reaction was carried out.
Methacrylic acid: 13.0 parts 2-Hydroxyethyl methacrylate: 14.0 parts Glycerol monomethacrylate: 25.0 parts Benzyl methacrylate: 25.0 parts Butyl methacrylate: 23.0 parts 2,2'-azobisisobutyronitrile : 4.0 copies

After completion of the dropping, the reaction was further carried out at 80 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of propylene glycol monomethyl ether acetate (PGMAc) was added, and further 1 at 80 ° C. The reaction for a time was continued to obtain a copolymer solution. After cooling to room temperature, about 2 g of the alkali-soluble resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, so that the non-volatile content is 20% by weight in the previously synthesized alkali-soluble resin solution. Propylene glycol monomethyl ether acetate (PGMAc) was added. The obtained non-photosensitive transparent resin had a weight average molecular weight of 32000 and an acid value of 78.

<Manufacturing of dispersant (X1)>
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.0 parts of 3-mercapto-1,2-propanediol and pyromellitic acid dianhydride (manufactured by Daicel Chemical Industry Co., Ltd.) were added at 9.7. 31.7 parts of PGMAc were charged and replaced with nitrogen gas. 0.2 part of 1,8-diazabicyclo- [5.4.0] -7-undecene was added as a catalyst, and the mixture was reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. Next, 50.0 parts of methyl methacrylate and 50.0 parts of methyl α-allyloxymethylacrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., a solution prepared by dissolving 0.1 part of 2,2'-azobisisobutyronitrile in 45.4 parts of propylene glycol monomethyl ether acetate was added, and the reaction was carried out for 10 hours. It was confirmed by solid content measurement that 95% had reacted. After completion of the reaction, propylene glycol monomethyl ether acetate was added so as to have a non-volatile content of 60% by weight, and a solution of a polyester dispersant (X1) having an acid value of 43 mgKOH / g and a weight average molecular weight of 9500 was obtained.

(Manufacturing of dispersant (X2))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 40.0 parts of methyl methacrylate, 50.0 parts of methyl α-allyloxymethyl acrylate, and 10.0 parts of t-butyl methacrylate are charged, and nitrogen gas is charged. Replaced with. The inside of the reaction vessel was heated to 80 ° C., and 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2'-azobisisobutyronitrile were added to propylene glycol monomethyl ether acetate 45. The dissolved solution was added to 4 parts and reacted for 10 hours. It was confirmed by solid content measurement that 95% had reacted. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic acid dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 31.7 parts of PGMAc, and 1,8-diazabicyclo- [5.4.0] -7-undecene 0.2 as a catalyst. Parts were added and reacted at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. After completion of the reaction, propylene glycol monomethyl ether acetate was added so as to have a non-volatile content of 60% by weight, and a solution of a polyester dispersant (X2) having an acid value of 43 mgKOH / g and a weight average molecular weight of 9500 was obtained.

(Manufacturing of dispersants (X3 to X8))
Synthesis was carried out in the same manner as the dispersant (X2) except that the raw materials and the amount charged shown in Table 1 were used to obtain propylene glycol monomethyl ether acetate solutions of the dispersants (X3) to (X8).

(Manufacturing of dispersant (X9))
50.0 parts of benzyl methacrylate and 50.0 parts of n-butyl methacrylate were charged in a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, and replaced with nitrogen gas. The inside of the reaction vessel is heated to 80 ° C., and 6 parts of 3-mercapto-1,2-propanediol and 0.1 part of 2,2'-azobisisobutyronitrile are added to 45.4 parts of propylene glycol monomethyl ether acetate. The solution dissolved in was added and reacted for 10 hours. It was confirmed by solid content measurement that 95% had reacted. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic acid dianhydride, 31.7 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. Then, the reaction was carried out at 120 ° C. for 7 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. After completion of the reaction, propylene glycol monomethyl ether acetate was added so as to have a non-volatile content of 60% by weight, and a solution of a dispersant (X9) having an acid value of 43 mgKOH / g and a weight average molecular weight of 9500 was obtained.

(Manufacturing of dispersant (X10))
Synthesis was carried out in the same manner as the dispersant (X9) except that the raw materials and the amount charged shown in Table 1 were used to obtain a propylene glycol monomethyl ether acetate solution of the dispersant (X10).

The abbreviations in Table 1 are shown below.
MMA: Methyl methacrylate, EA: Ethyl acrylate, MAA: Methacrylic acid, n-BMA: n-butyl acrylate, BzMA: Benzyl methacrylate, t-BMA: t-butyl acrylate, thioglycerol: 3-mercapto-1,2- Propanediol ・ AIBN: 2,2'-azobisisobutyronitrile ・ PGMAc: propylene glycol monomethyl ether acetate ・ PMA: pyromellitic acid dianhydride ・ TMA: trimellitic acid anhydride ・ DBU: 1,8-diazabicyclo- [5.4.0] -7-Undecene M-402; Aronix M-402: Dipenter Erythritol Pentaacrylate / Dipenta Erythritol Hexaacrylate (manufactured by Toa Synthetic Chemical Co., Ltd.)
-Irgacure 907: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by BASF)
-EAB-F: 4,4'-bis (diethylamino) benzophenone (manufactured by Hodogaya Chemical Co., Ltd.)

<Adjustment of photosensitive coloring composition>
[Example 1]
(Adjustment of photosensitive coloring composition (C1))
The mixture having the following composition is uniformly stirred and mixed, dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 2 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. , A green pigment dispersion (D1) was prepared.

Fine pigment (G-1) 8.0 parts Fine pigment (Y-1) 6.0 parts Polyester dispersant (X1) solution 6.0 parts Binder resin solution 16.0 parts PGMAc 64.0 parts

Then, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive coloring composition (C1) for a green color filter.

Green pigment dispersion (D1) 54.0 parts Binder resin solution 6.0 parts Photopolymerizable monomer (M-402) 2.0 parts Photopolymerization initiator (Irgacure 907) 1.8 parts Sensitizer ( EAB-F) 0.2 parts PGMAc 37.0 parts

[Examples 2 to 8 and Comparative Examples 1 to 2]
(Adjustment of photosensitive coloring composition (C2 to C10))
A green pigment dispersion (D2 to 10) was prepared by changing the polyester dispersant solution to the dispersant shown in Table 2, and a photosensitive coloring composition for a green color filter was prepared in the same manner as in Example 1 except that it was used. (C2-10) was obtained.

[Example 9]
(Adjustment of photosensitive coloring composition (C11))
The mixture having the following composition is uniformly stirred and mixed, dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 2 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. , A red pigment dispersion (D11) was prepared.

Fine pigment (R-1) 5.0 parts Fine pigment (R-2) 4.0 parts Fine pigment (Y-2) 2.0 parts Polyester dispersant (X2) 5.0 parts Binder resin solution 28 .0 copies PGMAc 55.0 copies

Then, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive coloring composition for a red color filter.

Red pigment dispersion (D11) 44.0 parts Binder resin solution 13.0 parts Photopolymerizable monomer (M402) 2.0 parts Photopolymerization initiator (Irgacure 907) 1.8 parts Sensitizer (EAB- F) 0.2 parts PGMAc 40.0 parts

[Examples 10 to 12, Comparative Example 3]
(Adjustment of photosensitive coloring compositions (C12 to C15))
The polyester dispersant solution was changed to the dispersant shown in Table 2 and blended, and a photosensitive coloring composition for a red color filter was obtained in the same manner as in Example 9 except for the above. A red pigment dispersion (D12 to 15) was prepared by changing the polyester dispersant solution to the dispersant shown in Table 2, and a photosensitive coloring composition for a red color filter was prepared in the same manner as in Example 9 except that it was used. (C12 to 15) were obtained.

[Example 13]
(Adjustment of photosensitive coloring composition (C16))
The mixture having the following composition is uniformly stirred and mixed, dispersed with an Eiger mill (“Mini model M-250 MKII” manufactured by Eiger Japan) for 2 hours using zirconia beads having a diameter of 1 mm, and then filtered through a 5 μm filter. , A blue pigment dispersion (D16) was prepared.

Fine pigment (B-1) 13.0 parts Fine pigment (V-1) 1.0 part Polyester dispersant (X2) solution 6.0 parts Binder resin solution 16.0 parts PGMAc 64.0 parts

Then, the mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a photosensitive coloring composition for a blue color filter.

Blue pigment dispersion (D16) 32.0 parts Binder resin solution 13.0 parts Photopolymerizable monomer (M402) 5.0 parts Photopolymerization initiator (Irgacure 907) 1.8 parts Sensitizer (EAB- F) 0.2 copies PGMAc 49.0 copies

[Examples 14 to 16, Comparative Example 4]
(Adjustment of photosensitive coloring compositions (C17 to C20))
A blue pigment dispersion (D17 to 20) was prepared by changing the polyester dispersant solution to the dispersant shown in Table 2, and a photosensitive coloring composition for a red color filter was prepared in the same manner as in Example 9 except that it was used. (C17-20) were obtained.

<Evaluation of photosensitive coloring composition>
(Contrast ratio)
The obtained coloring composition for a color filter is applied onto a glass substrate having a thickness of 100 mm × 100 mm and 0.7 mm at a rotation speed of 500 rpm, 1000 rpm, and 1500 rpm using a spin coater, and three kinds of coatings having different film thicknesses are applied. Obtained a substrate. The colored composition-coated substrate for a color filter was dried at 70 ° C. for 20 minutes, exposed to ultraviolet rays at an integrated light intensity of 150 mJ using an ultra-high pressure mercury lamp, heated at 230 ° C. for 1 hour, allowed to cool, and then the contrast ratio was measured. .. Then, the chromaticity (Y, x, y) of the coating film at the C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). From the contrast ratio and chromaticity measurement results of the three sets, y = 0.14 for the blue coating film, y = 0.60 for the green coating film, and x = for the red coating film on the color filter coating substrate. The contrast ratio at 0.64 was determined by using an approximation method.

(Viscosity stability)
The viscosity stability of the obtained coloring composition for a color filter was evaluated by the following method. Using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.), the initial viscosity of the day after the coloring composition for the color filter was prepared and the viscosity with time accelerated at 40 ° C. for 1 week were measured. The measurement was performed at 25 ° C. under the condition of a rotation speed of 50 rpm. From the values of the initial viscosity and the viscosity with time, the rate of change in viscosity with time was calculated by the following formula, and the viscosity stability was evaluated in three stages.

[Ratio of change in viscosity over time] = | ([Initial viscosity]-[Viscosity over time]) / [Initial viscosity] | × 100
○: Change rate less than 5% △: Change rate 5% or more and less than 10% ×: Change rate 10% or more

(Evaluation of heat resistance (weight loss) of coating film)
The obtained coloring composition for a color filter was applied to glass, the solvent was removed, and then the weight loss (%) before and after heating at 200 ° C. for 1 hour was calculated and evaluated according to the description standard.
◯: Weight loss is within 5% ×: Weight loss is greater than 5%

(Resolution evaluation)
The obtained photosensitive coloring composition was applied onto a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm, and then heated in a clean oven at 70 ° C. for 20 minutes to remove the solvent, and a coating film having a thickness of about 2 μm was removed. Got Then, after cooling this substrate to room temperature, ultraviolet rays were exposed through a photomask having a stripe pattern having a width of 100 μm (pitch 200 μm) and a width of 25 μm (pitch 50 μm) using an ultra-high pressure mercury lamp. Then, this substrate was spray-developed with an aqueous sodium carbonate solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 ° C. for 330 minutes. The spray development was carried out for the coating film with each photosensitive coloring composition in the shortest time during which a pattern could be formed without any development residue, and this was set as the appropriate development time. The alkaline developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant ("Perex NBL" manufactured by Kao Corporation), and 90% by weight of water. The one consisting of was used. The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

The pattern of the filter segment formed by the above method at the 25 μm photomask portion was observed and evaluated using an optical microscope. The evaluation ranks are as follows. Poor resolution means that adjacent stripe patterns are connected or chipped. The resolution evaluation was determined according to the following criteria.
◎: Good resolution and linearity ○: Slightly inferior in terms of linearity but good resolution ×: Partially poor resolution

The above results are shown in Table 3.

As shown in Table 3, the color filter of the present invention using the dispersants X1 to 8 containing the resin (S1) or (S2) having a structural unit derived from the monomer (c1) represented by the general formula (1). Compared with those using the dispersants X9 to 10, the coloring composition for use was excellent in heat resistance and resolution while maintaining a high contrast ratio.

Claims (3)

A coloring composition for a color filter containing a colorant, a dispersant (X), a binder resin and an organic solvent, wherein the dispersant (X) contains the resin of the following (S1) or (S2). A coloring composition for a color filter.
(S1) A resin that is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride, and is the polymer having the hydroxyl group. (A) is an ethylenically unsaturated monocell containing a monomer (c1) represented by the following general formula (1) in the presence of a compound (b1) having two hydroxyl groups and one thiol group in the molecule. A resin which is a polymer having two hydroxyl groups at one end having a polymer (a-1) obtained by polymerizing a polymer (C).
(S2) Presence of a reaction product of the hydroxyl group of compound (b1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride. Below, a resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing a monomer (c1) represented by the following general formula (1).
General formula (1):


(In the general formula (1), R represents a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.) The coloring composition for a color filter according to claim 1, further comprising at least one selected from a photopolymerizable monomer and a photopolymerization initiator. A color filter comprising a filter segment formed from the coloring composition for a color filter according to claim 1 or 2.