KR20130105458A - Colored curable resin composition - Google Patents

Abstract

PURPOSE: A colored curable resin composition is provided to have small defect generation when a colored composition layer is manufactured by coating the composition on a substrate and drying the coating layer in a vacuum. CONSTITUTION: A colored curable resin composition includes a colorant, a resin, a polymerizable compound, a polymerization initiator, and a solvent. The resin composition includes a compound represented by chemical formula 1 and a pigment. The solvent includes a diacetone alcohol, and the content of the diacetone alcohol is 0.5-50 wt%.

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

This invention relates to a colored curable resin composition, a coloring pattern, and a color filter, More specifically, the colored curable resin composition suitable for formation of the colored image which comprises the color filter used for a liquid crystal display element or a solid-state image sensor, this coloring It relates to a coloring pattern and a color filter using the curable resin composition.

The colored curable resin composition is used in the production of color filters used in display devices such as liquid crystal display panels, electroluminescence panels, and plasma display panels. As such a colored curable resin composition, the colored curable resin composition containing ethyl lactate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate as a solvent is known (JP2010-211198-A).

In the said colored curable resin composition conventionally known, after apply | coating this colored curable resin composition to a board | substrate, when drying under reduced pressure and producing a colored composition layer, the solvent contained in a colored curable resin composition rubs and becomes a crater shape. A defect may occur.

The present invention includes the following inventions.

[1] A colored curable resin composition containing a coloring agent, a resin, a polymerizable compound, a polymerization initiator, and a solvent,

The colorant comprises a compound represented by the formula (1) and a pigment,

The solvent contains diacetone alcohol,

Colored curable resin composition whose content rate of diacetone alcohol is 0.5 mass% or more and 50 mass% or less with respect to the total amount of a solvent.

In Formula (1), R <^1> and R <^2> respectively independently represents the phenyl group which may have a substituent.

R <^3> and R <^4> respectively independently represents a C1-C10 monovalent saturated hydrocarbon group, The hydrogen atom contained in this saturated hydrocarbon group may be substituted by the C6-C10 aromatic hydrocarbon group or the halogen atom, and this aromatic hydrocarbon group The hydrogen atom contained may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ -contained in the saturated hydrocarbon group is substituted with -O-, -CO- or -NR ^11- . You may be.

R ¹ and R ³ may form a ring containing a nitrogen atom together with the nitrogen atom, and R ² and R ⁴ may form a ring containing a nitrogen atom together with the nitrogen atom.

R ⁵ is _{-OH, -SO 3 H, -SO 3} - of _{^{Z +, -CO 2 R 8,}} -SO 3 R 8 or _{^{-SO 2 NR 9 R 10 - Z}} +, -CO 2 H, -CO 2 Indicates.

R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents the integer of 0-4. When m is two or more, some R <^5> may mutually be same or different.

R <^8> represents a C1-C20 monovalent saturated hydrocarbon group, and the hydrogen atom contained in this saturated hydrocarbon group may be substituted by the halogen atom.

Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .

R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered nitrogen-containing heterocycle together with a nitrogen atom; .

Each R ¹¹ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.]

[2] The solvent further comprises at least one member selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, cyclohexanone and ethyl 3-ethoxypropionate [1] The colored curable resin composition of Claim.

[3] A color filter formed by the colored curable resin composition according to [1] or [2].

[4] A display device comprising the color filter according to [3].

According to the colored curable resin composition of this invention, even if it apply | coats to a board | substrate and produces a coloring composition layer by drying under reduced pressure, there is little generation of a crater-shaped defect.

The colored curable resin composition of this invention contains a coloring agent (A), alkali-soluble resin (B), a polymeric compound (C), a polymerization initiator (D), and a solvent (E).

A coloring agent (A) contains the compound represented by General formula (1) (henceforth a "compound (1)"), and a pigment (A2).

It is preferable that the colored curable resin composition of this invention contains a leveling agent (F) further.

The colored curable resin composition of the present invention may contain a polymerization initiator (D1).

In this specification, the compound illustrated as each component can be used individually or in combination of multiple types unless there is particular rejection.

<Coloring agent (A)>

The compound (1) is represented by the above formula (1).

As a C1-C20 monovalent saturated hydrocarbon group in R <^8> , R <^9> , R <^10> and R <^11> , for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group C1-C20 linear alkyl groups, such as a decyl group, a dodecyl group, a hexadecyl group, and an icosyl group; Branched alkyl groups having 3 to 20 carbon atoms such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; C3-C20 alicyclic saturated hydrocarbon groups, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group, are mentioned.

Examples of -OR ⁸ include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy and icosyloxy.

Examples of -CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, an isosyloxycarbonyl group, and the like.

Examples of -SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group and an icosylsulfanyl group.

Examples of -SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an icosylsulfonyl group.

Examples of -SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

-SO ₂ NR ⁹ R ^10, for example a sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, (1, 1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N-methylpyrrolyl group, N- (2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, an N-cyclopentylsulfamoyl group, an N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) An N-1-substituted sulfamoyl group such as a sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group and N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-diethylamino groups such as N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N-2-substituted sulfamoyl group, and the like.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered nitrogen-containing heterocycle together with a nitrogen atom. As this heterocycle, the following are mentioned, for example.

As a C1-C10 monovalent saturated hydrocarbon group in R <^3> and R <^4> , a C1-C10 thing is mentioned among what was mentioned as a saturated hydrocarbon group of R <^8> .

A phenyl group, a naphthyl group, etc. are mentioned as a C6-C10 aromatic hydrocarbon group. Among the groups in which the hydrogen atom contained in these C6-C10 aromatic hydrocarbon groups may be substituted, a C1-C3 alkyl group includes methyl group, ethyl group, n-propyl group and isopropyl group, and alkoxy having 1 to 3 carbon atoms. Examples of the group include methoxy group, ethoxy group, n-propoxy group and isopropoxy group.

Examples of the saturated hydrocarbon group substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms include benzyl group, phenylethyl group, phenylpropyl group, phenylbutyl group, toluylmethyl group, toluylethyl group, toluylpropyl group, toluylbutyl group and methoxyphenyl A methyl group, a methoxyphenyl ethyl group, a methoxyphenyl propyl group, a methoxyphenyl butyl group, etc. are mentioned.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.

Examples of the saturated hydrocarbon group substituted with a halogen atom include a fluoromethyl group, difluoromethyl group, trifluoromethyl group, perfluoroethyl group, chlorobutyl group and the like.

As R <^3> and R <^4>, an unsubstituted C1-C10 monovalent saturated hydrocarbon group is preferable, A C1-C4 monovalent saturated hydrocarbon group is more preferable, A C1-C3 monovalent saturated hydrocarbon group is more preferable.

Examples of the alkyl group having 1 to 6 carbon atoms in R ⁶ and R ⁷ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group , Isopentyl group, neopentyl group and the like.

Examples of the aralkyl group having 7 to 10 carbon atoms for R ¹¹ include a benzyl group, a phenylethyl group and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .

As said ⁺ N (R <^11> ) ₄ , it is preferable that at least two of four R <^11> is a C5-C20 monovalent saturated hydrocarbon group. Moreover, 20-80 are preferable and, as for the total carbon number of four R <^11> , 20-60 are more preferable.

The phenyl group which represents R <^1> and R <^2> may have a substituent. These substituents include halogen atoms, -R ⁸ , -OH, -OR ⁸ , -SO ₃ H, -SO ₃ ^- Z ⁺ , -CO ₂ H, -CO ₂ R ⁸ , -SR ⁸ , -SO ₂ R ⁸ , -SO ₃ R ⁸ and -SO ₂ NR ⁹ R ¹⁰ . Among these substituents, -R ⁸ is preferable and a C 1-10 monovalent saturated hydrocarbon group is more preferable. In this case, -SO ₃ ^- Z ⁺ is preferably -SO ₃ ^{- +} N (R ¹¹ ) ₄ .

Examples of the phenyl group having a substituent include toluyl group, dimethylphenyl group, ethylphenyl group, propylphenyl group, isopropylphenyl group, methylsulfanylphenyl group, methylsulfonylphenyl group and the like. Especially, the phenyl group which has a substituent in ortho position with respect to the bond number with nitrogen is preferable.

R ¹ and R ² are each independently a phenyl group having a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms, more preferably a toluyl group or a dimethylphenyl group, more preferably an o-toluyl group or a 2,6-dimethylphenyl group More preferred.

R ¹ and R ³ may form a ring containing a nitrogen atom together with the nitrogen atom, and R ² and R ⁴ may form a ring containing a nitrogen atom together with the nitrogen atom. As a ring containing this nitrogen atom, the following are mentioned, for example.

R ⁵ -SO ₃ H, -SO ₃ Examples ^- the Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ are preferred.

As R ⁶ and R ⁷ , a hydrogen atom, a methyl group and an ethyl group are preferable, and a hydrogen atom is more preferable.

The integer of 0-2 is preferable, and, as for m, it is more preferable that it is 1 or 2.

As compound (1), the compound represented by general formula (2) is preferable.

In Formula (2), R <^21> , R <^22> , R <^23> and R <^24> represent a C1-C4 alkyl group each independently.

p and q respectively independently represent the integer of 0-5. When p is 2 or more, the plurality of R ²³ may be the same as or different from each other. When q is 2 or more, the plurality of R ²⁴ may be the same as or different from each other.]

Examples of the alkyl group having 1 to 4 carbon atoms for R ²¹ , R ²² , R ²³ and R ²⁴ include methyl group, ethyl group, propyl group, butyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. Can be mentioned.

It is preferable that R <^21> and R <^22> are a C1-C3 monovalent saturated hydrocarbon group each independently. R ²³ and R ²⁴ are preferably methyl.

The integer of 0-2 is preferable, and, as for p and q, it is more preferable that it is 1 or 2.

As compound (1), the compound represented by general formula (3) is preferable.

In General formula (3), R <^31> and R <^32> respectively independently represents a C1-C4 alkyl group.

R ³³ , R ³⁴ , R ³⁵ and R ³⁶ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.]

The above-mentioned thing is mentioned as a C1-C4 alkyl group which shows R <^31> -R <^36> .

It is preferable that R <^31> and R <^32> is a C1-C3 monovalent saturated hydrocarbon group each independently. It is preferable that R ³³ to R ³⁶ each independently represent a hydrogen atom or a methyl group.

Examples of the compound (1) include compounds represented by any one of formulas (1-1) to (1-15). Especially, the compound represented by general formula (1-1), general formula (1-2), or general formula (1-5)-general formula (1-12) is preferable at the point which is excellent in solubility with respect to an organic solvent.

As a method for producing compound (1), a compound represented by the formula (1a), a compound represented by the formula (1b) and a compound represented by the formula (1c) are reacted in the presence of an organic solvent or in the absence of a solvent. Can be mentioned. In terms of yield, it is preferable to react with a solvent. 30 degreeC-180 degreeC is preferable, and, as for reaction temperature, 80 degreeC-130 degreeC is more preferable. 1 hour-12 hours are preferable, and, as for reaction time, 3 hours-8 hours are more preferable.

[In formula (1b) and general formula (1c), R <^1> -R <^4> shows the same meaning as the above respectively.]

As said organic solvent, Hydrocarbon solvent, such as toluene and xylene; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; Alcohol solvents such as methanol, ethanol and butanol; Nitrohydrocarbon solvents such as nitrobenzene; Ketone solvents such as methyl isobutyl ketone; Amide solvents such as 1-methyl-2-pyrrolidone; And the like.

The amount of the compound represented by the formula (1b) and the compound represented by the formula (1c) is preferably 1 mol or more and 8 mol or less, more preferably 1 mol, with respect to 1 mol of the compound represented by the formula (1a). It is more than 5 mol. The reaction may be carried out step by step, or may be reacted simultaneously.

It is preferable that the compound represented by General formula (1b) and the compound represented by General formula (1c) have the same structure from the point which manufacture of compound (1) is easy.

The method of obtaining the compound (1) which is a target compound from a reaction mixture is not specifically limited, Various well-known methods can be employ | adopted. For example, the reaction mixture may be mixed with an acid (eg acetic acid, etc.) and the precipitated crystals may be filtered off. It is preferable that the said acid prepares the aqueous solution of an acid previously, and then adds a reaction mixture to the said aqueous solution. The temperature at the time of adding a reaction mixture becomes like this. Preferably it is 10 degreeC or more and 50 degrees C or less. Moreover, after that, it is preferable to stir at this temperature for about 0.5 to 2 hours. The crystals taken by filtration are preferably washed with water or the like and subsequently dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization as needed.

Examples of the pigment (A2) include organic pigments and inorganic pigments, and compounds classified as pigments in the color index (Published by The Society of Dyers and Colourists).

Specifically as a pigment, C.I. Red pigments such as Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, ;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Green pigments, such as pigment green 7, 36, and 58, etc. are mentioned.

Among them, C.I. Pigment Red Violet 23, C.I. Pigment Blue 15: 3, 15: 6 are preferred, and C.I. Pigment Blue 15: 6 is more preferable.

The above-mentioned pigments may be optionally treated with rosin treatment, surface treatment using a pigment derivative or a pigment dispersant having an acidic group or a basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound or the like, or by atomization by sulfuric acid atomization. A washing treatment with an organic solvent, water or the like for removing impurities, or a removal treatment by an ion exchange method of ionic impurities, or the like may be performed. It is preferable that the pigment has a uniform particle size. By containing a pigment dispersant and performing a dispersion process, the pigment dispersion liquid of the state in which the pigment was disperse | distributed uniformly in the solution can be obtained.

Commercially available surfactants may be used as the pigment dispersant, for example, surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and the like. These can be mentioned, respectively, and can be used individually or in combination of 2 or more types. As said surfactant, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, polyethyleneimine KP [manufactured by Shin-Etsukagaku Kogyo Co., Ltd.], polyflow [manufactured by Kyoeisha Kagaku Co., Ltd.], F-Top [Mitsubishi Material Denshikasei Co., Ltd.], Mega Pack [DIC Co., Ltd.] Manufactured], Fluoride [manufactured by Sumitomo 3M Co., Ltd.], Asahi Gadard [manufactured by Asahi Glass Co., Ltd.], Supron [manufactured by AGC Seiko Chemical Co., Ltd.], Solsperth [manufactured by Geneka Co., Ltd.], EFKA (Made by CIBA Corporation), Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (manufactured by BICCHEM Corporation), and the like.

When using a pigment dispersant, the usage-amount is per mass part of pigment, Preferably it is 1 mass part or less, More preferably, it is 0.05 mass part or more and 0.5 mass part or less. When the usage-amount of a pigment dispersant exists in the said range, since the pigment dispersion liquid of a uniform dispersion state tends to be obtained, it is preferable.

0.1 mass% or more and 60 mass% or less are preferable with respect to the total amount of a coloring agent (A), and, as for content of a compound (1), 0.1 mass% or more and 30 mass% or less are more preferable.

40 mass% or more and 99.9 mass% or less are preferable with respect to the total amount of a coloring agent (A), and, as for content of a pigment (A2), 70 mass% or more and 99.9 mass% or less are more preferable.

The coloring agent (A) may contain the coloring agent different from compound (1) and pigment (A2) in the range which does not impair the color performance of the colored curable resin composition of this invention.

The content of the colorant (A) is preferably from 5 to 60% by mass, more preferably from 8 to 55% by mass, and still more preferably from 10 to 50% by mass, based on the total amount of solids. When content of a coloring agent (A) exists in the said range, since the color density at the time of setting it as a color filter can be sufficient, and a resin and a polymeric compound can be contained in a composition in a required amount, a pattern with sufficient mechanical strength can be formed. have. Here, the "total amount of solid content" in this specification means the quantity remove | excluding content of a solvent from the total amount of colored curable resin composition. The total amount of solids and the content of each component thereof can be measured by known analysis means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].

(A) (hereinafter sometimes referred to as "(a)") selected from the group consisting of a resin [K1] unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, a cyclic ether structure having a carbon number of 2 to 4 And a monomer (b) having an ethylenically unsaturated bond (hereinafter occasionally referred to as "(b)");

Monomer (c) copolymerizable with resin (K2) (a) and (b), and (a), but different from (a) and (b) [hereinafter may be referred to as "(c)" Copolymers with;

Copolymer of resin [K3] (a) and (c);

Resin [K4] Resin which (b) was made to react with the copolymer of (a) and (c);

Resin [K5] Resin which (a) was made to react with the copolymer of (b) and (c);

Resin [K6] Resin which (a) was made to react with the copolymer of (b) and (c), and the carboxylic acid anhydride was made to further react.

(a) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept- 5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept- [2.2.1] hept-2-ene, and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride Unsaturated dicarboxylic acid anhydrides such as dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

Unsaturated mono [(meth) acryloyloxyalkyl of a divalent or higher polyhydric carboxylic acid such as succinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] ] Esters;

and unsaturated acrylates containing a hydroxy group and a carboxyl group in the same molecule as?-(hydroxymethyl) acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable at the point of copolymerization reactivity, or the solubility with respect to the aqueous alkali solution of obtained resin.

(b) refers to a polymerizable compound having an ethylenically unsaturated bond with, for example, a cyclic ether structure having 2 to 4 carbon atoms (eg, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring). As for (b), the monomer which has a C2-C4 cyclic ether structure and a (meth) acryloyloxy group is preferable.

In addition, in this specification, "(meth) acrylic acid" represents at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. Quot ;, &quot; (meth) acryloyl &quot;, and &quot; (meth) acrylate &quot;

(b1) having an oxiranyl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter referred to as " (B2) "), a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond [hereinafter sometimes referred to as" (b3) "), and the like.

Examples of the monomer (b1) include a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized [hereinafter sometimes referred to as "(b1-1)"), an alicyclic unsaturated hydrocarbon And a monomer (b1-2) having an epoxidized structure (hereinafter occasionally referred to as "(b1-2)").

(meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl Vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? -Methyl-o-vinylbenzyl glycidyl ether,? Methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5- Styrenes such as 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, (Glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) .

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane [e.g., Celloxide 2000; Daicel Corporation], 3, 4- epoxycyclohexylmethyl (meth) acrylate [for example, cyclomer A400; Daicel Corporation], 3, 4- epoxycyclohexyl methyl (meth) acrylate [For example, cyclomer M100; Daicel Co., Ltd.], the compound represented by general formula (I), the compound represented by general formula (II), etc. are mentioned.

In the formulas (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.

X ^a and X ^b represent a single bond, -R ^c- , * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-.

R ^c represents an alkanediyl group having 1 to 6 carbon atoms.

* Represents the number of bonds with O.]

Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and tert-butyl group.

Examples of the alkyl group in which the hydrogen atom is substituted with hydroxy include a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy A hydroxy-1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of alkanediyl groups include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl and hexane-1 And a 6-diyl group.

X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and more preferably a single bond and * -CH. ₂ CH ₂ -O- (* indicates the number of bonds with O).

Examples of the compound represented by the formula (I) include compounds represented by the formulas (I-1) to (I-15). (I-1), (I-3), (I-5), (I-7) ). &Lt; / RTI &gt; More preferably, the compound represented by the formula (I-1), the compound represented by the formula (I-7), the compound represented by the formula (I-9) or the compound represented by the formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by the formula (II-1) to (II-15). (II-1), (II-3), (II-5), (II-7), ). &Lt; / RTI &gt; More preferably, the compound represented by the formula (II-1), the compound represented by the formula (II-7), the compound represented by the formula (II-9) or the compound represented by the formula (II-15)

The compound represented by general formula (I) and the compound represented by general formula (II) may be used independently, respectively and may use 2 or more types together. When using the compound represented by general formula (I) and the compound represented by general formula (II) together, these content ratios are [the compound represented by general formula (I): the compound represented by general formula (II)], on a molar basis, Preferably it is 5: 95-95: 5, More preferably, it is 20: 80-80: 20.

(b2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxy ethyl oxetane, 3-ethyl-3- acryloyloxy ethyl oxetane, etc. are mentioned.

As the monomer (b3), a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of the compound (b3) include tetrahydrofurfuryl acrylate [e.g., Viscot V # 150, manufactured by Osaka Yuki Kagaku Kogyo Co., Ltd.], tetrahydrofurfuryl methacrylate, and the like.

(b) is preferably (b1) in that reliability of the obtained color filter can be further improved, such as heat resistance and chemical resistance. Moreover, (b1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethyl Hexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methyl Cyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, it is commonly known as "dicyclopentanyl (meth) acrylate". , May be referred to as "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the art, the common name is "dicyclopentenyl (Meth) acrylate), dicyclopenta Oxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naph (Meth) acrylic acid esters such as methyl (meth) acrylate and benzyl (meth) acrylate;

Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis 2,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene and the like such as bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept- Cyclo-unsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

And examples thereof include styrene,? -Methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.

Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable in terms of copolymerization reactivity and heat resistance. Do.

In the resin [K1], the ratio of the structural units derived from each other is preferably such that, among the total structural units constituting the resin [K1]

structural unit derived from (a); 2 to 60 mol%

structural unit derived from (b); Is preferably 40 to 98 mol%

structural unit derived from (a); 10-50 mol%

structural unit derived from (b); It is more preferable that it is 50-90 mol%.

When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency that storage stability of the colored curable resin composition, developability in forming a colored pattern, and solvent resistance of the resulting color filter are excellent.

Resin [K1] can be synthesized by, for example, the method described in the "Experimental Method of Polymer Synthesis" (published by Ohtsu Takayuki, 1st Edition, First Edition, published by the Chemical Society of Japan, March 1, 1972) and the references cited in this document Can be produced by reference.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator and a solvent are placed in a reaction vessel and oxygen is replaced by, for example, nitrogen to form a deoxidized atmosphere, followed by heating and keeping the mixture under stirring . In addition, the polymerization initiator, solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), organic peroxides (such as benzoyl peroxide) And the solvent may be one which dissolves the respective monomers, and as the solvent (E) of the colored curable resin composition of the present invention, there may be mentioned a solvent to be described later.

In addition, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what was extracted as solid (powder) by methods, such as reprecipitation. Particularly, since the solution after the reaction can be directly used for preparing the colored curable resin composition of the present invention by using a solvent contained in the colored curable resin composition of the present invention as a solvent in the polymerization, the color curable resin composition of the present invention The manufacturing process can be simplified.

In resin [K2], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K2],

structural unit derived from (a); 2 to 45 mol%

structural unit derived from (b); 2 to 95 mol%

structural unit derived from (c); It is preferable that it is 1-65 mol%,

structural unit derived from (a); 5-40 mol%

structural unit derived from (b); 5 to 80 mol%

structural unit derived from (c); It is more preferable that it is 5-60 mol%.

When the ratio of the structural unit of the resin [K2] is within the above-mentioned range, the storage stability of the colored curable resin composition, developability in forming a colored pattern, and solvent resistance, heat resistance and mechanical strength of the obtained color filter tend to be excellent .

Resin [K2] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

In the resin [K3], the ratio of the respective structural units derived from the respective resins is, among the total structural units constituting the resin [K3]

structural unit derived from (a); 2 to 60 mol%

structural unit derived from (c); It is preferable that it is 40-98 mol%,

structural unit derived from (a); 10-50 mol%

structural unit derived from (c); And more preferably 50 to 90 mol%.

Resin [K3] can be manufactured similarly to the method described as a manufacturing method of resin [K1], for example.

Resin [K4] is obtained by obtaining the copolymer of (a) and (c), and adding the C2-C4 cyclic ether which (b) has to the carboxylic acid and / or carboxylic anhydride which (a) has can do.

First, the copolymer of (a) and (c) is manufactured similarly to the method described as a manufacturing method of resin [K1]. In this case, it is preferable that the proportion of the structural units derived from each of them is a ratio as exemplified in Resin [K3].

Next, a cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer.

(b) reacting a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (for example, a reaction product of tris (dimethylamino) Methyl] phenol) and a polymerization inhibitor (such as hydroquinone) are placed in a flask and reacted at 60 ° C to 130 ° C for 1 to 10 hours to prepare resin [K4].

(b) is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By setting it as this range, there exists a tendency for the balance of the storage stability of the colored curable resin composition, the developability at the time of forming a colored pattern, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the obtained colored pattern to become favorable. (B1) is more preferable and (b1-1) is more preferable for (b) used for the resin [K4] since the reactivity of the cyclic ether is high and unreacted (b)

The amount of the reaction catalyst to be used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b) and (c).

Reaction conditions, such as an injection | throwing-in method, reaction temperature, and time, can be adjusted suitably in consideration of heat generation amount by a manufacturing facility, superposition | polymerization, etc. In addition, as in the case of the polymerization conditions, the injection method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production facility or polymerization.

The resin [K5] is a first step, and a copolymer of (b) and (c) is obtained in the same manner as in the above-mentioned production method of the resin [K1]. Similarly to the above, the solution obtained after the reaction may be used as it is, or a solution obtained by concentrating or diluting it may be used, or a solid (powder) obtained by re-precipitation or the like may be used.

the proportion of the structural units derived from (b) and (c) is preferably such that the total number of moles of the total structural units constituting the copolymer is

structural unit derived from (b); 5 to 95 mol%

structural unit derived from (c); It is preferable that it is 5-95 mol%,

structural unit derived from (b); 10 to 90 mol%

structural unit derived from (c); It is more preferable that it is 10-90 mol%.

The carboxylic acid or carboxylic acid anhydride of (a) may be added to the cyclic ether derived from (b) in the copolymer of (b) and (c) under the same conditions as the method for producing the resin [K4] The resin [K5] can be obtained by reacting.

The amount of (a) to be reacted with the copolymer is preferably 5 to 80 moles per 100 moles of (b). (B1) is more preferable, and (b1-1) is more preferable for the resin (K5) because the reactivity of the cyclic ether is high and unreacted (b)

Resin [K6] is resin which made carboxylic anhydride further react with resin [K5].

The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3, 6-tetrahydrophthalic anhydride, dimethyl tetrahydrophthalic anhydride, 5, 6- dicarboxy bicyclo [2.2.1] hept-2-ene anhydride, etc. are mentioned. The amount of the carboxylic acid anhydride to be used is preferably 0.5 to 1 mole based on 1 mole of the amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / A resin [K1] such as an acrylic acid copolymer; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2 .1.0 ^2.6 ] Resin, such as decyl acrylate / (meth) acrylic acid / N-cyclohexyl maleimide copolymer, 3-methyl- 3- (meth) acryloyloxy methyl oxetane / (meth) acrylic acid / styrene copolymer [K2]; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer; Resin which glycidyl (meth) acrylate was added to the benzyl (meth) acrylate / (meth) acrylic acid copolymer, and glycidyl (meth) to the tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin [K4], such as resin which added acrylate, and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resin, tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate Resins [K5] such as resins in which (meth) acrylic acid is reacted with a copolymer; Resin [K6], such as resin which further made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, etc. are mentioned. .

Among them, resin [K1] and resin [K2] are preferable as resin (B).

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is in the above-described range, the residual film ratio is high, solubility in the developing solution of the unexposed portion is good, and there is a tendency to obtain a high resolution and high hardness coloring pattern.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of resin (B) becomes like this. Preferably it is 1.1-6, More preferably, it is 1.2-4.

The acid value of the resin (B) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total solid content. When content of resin (B) exists in the said range, a coloring pattern can be formed and there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

<Polymeric Compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D). Examples thereof include a compound having a polymerizable ethylenically unsaturated bond, and the like. It is a (meth) acrylic acid ester compound.

Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. As such a polymerizable compound, there may be mentioned, for example, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (Meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, tripentaerythritol hexa (meth) acrylate, (Meth) acryloyloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra , Propylene glycol-modified dipentaerythritol hexa (meth) acrylate , Caprolactone and the like can be modified pentaerythritol tetra (meth) acrylate, caprolactone-modified dipentaerythritol hexa (meth) acrylate.

Especially, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 to 1,500 or less.

The content of the polymerizable compound (C) is preferably from 7 to 65% by mass, more preferably from 13 to 60% by mass, and still more preferably from 17 to 55% by mass, based on the total amount of solids. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a color pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization Initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical or an acid by the action of light or heat and capable of initiating polymerization, and a known polymerization initiator can be used.

As a polymerization initiator (D), the polymerization initiator containing at least 1 sort (s) chosen from the group which consists of an alkylphenone compound, a triazine compound, an acyl phosphine oxide compound, an O-acyl oxime compound, and a biimidazole compound is preferable, and O The polymerization initiator containing an acyl oxime compound is more preferable.

The O-acyloxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond number.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- Ethyl-6- (2-methylbenzyl) -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- (3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethan- 1-imine, N- acetoxy- 1- [ Carbamoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan- 1-imine, N-benzoyloxy- 3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. You may use commercially available products, such as Irgacure OXE01, OXE02 (above BASF Corporation), and N-1919 (ADEKA Corporation). Among them, the O-acyl oxime compound is N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane At least one selected from the group consisting of -1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferred. If it is these O-acyl oxime compounds, there exists a tendency which can obtain a high brightness color filter.

The alkylphenone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). Of these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- (4-morpholinyl) phenyl] butane-1-one, 2- (dimethylamino) -1-one. You may use commercial items, such as Irgacure 369, 907, 379 (above, BASF Corporation make).

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy- -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan- ?,? - diethoxyacetophenone, and benzyl dimethyl ketal.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and the like. You may use a commercial item, such as Irgacure (trademark) 819 (made by BASF Corporation).

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see eg JP H06-75372-A, JP H06-75373-A, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2 , 2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, eg, JP S48-38403-B, JP S62-174204-A, etc.), the phenyl group at the 4,4 ', 5,5'-position carbo The imidazole compound substituted with the alkoxy group (for example, JP H07-10913-A etc.) etc. are mentioned.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone, and campquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds. These are preferably used in combination with a polymerization initiator (D1) (particularly amines) to be described later.

Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, di Onium salts such as phenyl iodonium hexafluoroantimonate, and nitrobenzyl tosylates and benzoin tosylates.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). When the content of the polymerization initiator (D) is within the above range, the productivity of the color filter is improved because the sensitivity is increased and the exposure time is shortened.

<Polymerization start preparation (D1)>

A polymerization start adjuvant (D1) is a compound or sensitizer used in order to accelerate superposition | polymerization of the polymeric compound in which superposition | polymerization was started with a polymerization initiator. When including a polymerization start adjuvant (D1), it is normally used in combination with a polymerization initiator (D).

An amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, etc. are mentioned as a polymerization start adjuvant (D1).

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, (Diethylamino) benzophenone, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'- 4'-bis (ethylmethylamino) benzophenone, and the like, among which 4,4'-bis (diethylamino) benzophenone is preferable. You may use a commercial item, such as EAB-F (made by Hodogaya Kagaku Kogyo Co., Ltd.).

Examples of the alkoxy anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10- Dibutoxy anthracene, 2-ethyl-9, 10- dibutoxy anthracene, etc. are mentioned.

As the thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichloro thioxanthone, 1-chloro-4-propoxy Citioxanthone etc. are mentioned.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, Chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxy acetic acid, naphthylthioacetic acid, N-naphthyl glycine, naphthoxy acetic acid, and the like.

When these polymerization initiator (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) Wealth. When the amount of the polymerization initiator (D1) is within this range, the coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

&Lt; Solvent (E) >

The solvent (E) contains diacetone alcohol (that is, 4-hydroxy-4-methylpentan-2-one), and the content rate of diacetone alcohol is 0.5 mass% or more and 50 mass% or less with respect to the total amount of a solvent, Preferably they are 1 mass% or more and 30 mass% or less.

The solvent to be combined with diacetone alcohol, Preferably, it is at least selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, cyclohexanone, and ethyl 3-ethoxypropionate. It is 1 type, More preferably, it is at least 1 sort (s) chosen from the group which consists of propylene glycol monomethyl ether acetate and ethyl lactate.

Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to colored curable resin composition, More preferably, it is 75-92 mass%. In other words, solid content of colored curable resin composition becomes like this. Preferably it is 5-30 mass%, More preferably, it is 8-25 mass%. When content of a solvent (E) exists in the said range, since flatness at the time of application | coating becomes favorable and color density does not run short when a color filter is formed, it is preferable because there exists a tendency for favorable display characteristics.

<Leveling agent (F)>

As a leveling agent (F), silicone type surfactant which has a silicone type surfactant, a fluorine type surfactant, and a fluorine atom is mentioned.

As said silicone type surfactant, surfactant etc. which have a siloxane bond are mentioned. Specifically, doray silicon DC3PA, doray silicon SH7PA, doray silicon DC11PA, doray silicon SH21PA, doray silicon SH28PA, doray silicon SH29PA, doray silicon SH30PA, polyether modified silicone oil SH8400 [brand name: doray silicon silicon; Toore Dow Corning Co., Ltd.], KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsukagaku Kogyo), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, TSF4460 And Momentive Performance Materials Japan Co., Ltd.

As said fluorine-type surfactant, surfactant etc. which have a fluorocarbon chain | strand are mentioned. Specifically, fluoride FC430, fluoride FC431 (manufactured by Sumitomo 3M Co., Ltd.), megapack (brand name) F142D, megapack F171, megapack F172, megapack F173, megapack F177, megapack F183, Mega pack R30, Mega pack F554 (manufactured by DIC Corporation), F top (brand name) EF301, F top EF303, F top EF351, F top EF352 (manufactured by Mitsubishi Material Denshi Kasei Co., Ltd.), suffron (brand name) ) S381, Supron S382, Supron SC101, Supron SC105 (manufactured by Asahi Glass Co., Ltd.), E5844 [manufactured by Daikin Fine Chemical Co., Ltd.], BM-1000, BM-1100 (all brand names: BM Chemie Corporation) etc. are mentioned.

As a silicone type surfactant which has the said fluorine atom, surfactant etc. which have a siloxane bond and a fluorocarbon chain | strand are mentioned. Specifically, Mega Pack (R) R08, Mega Pack BL20, Mega Pack F475, Mega Pack F477, Mega Pack F443 (manufactured by DIC Corporation), and the like.

Content of the leveling agent (F) becomes like this. Preferably it is 0.001 mass% or more and 0.2 mass% or less, More preferably, it is 0.002 mass% or more and 0.1 mass% or less, More preferably, it is 0.005 mass% or more and 0.05 mass% or less.

&Lt; Other components >

The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, and chain transfer agents, if necessary.

<The manufacturing method of colored curable resin composition>

The colored curable resin composition of this invention is a coloring agent (A), resin (B), a polymeric compound (C), a polymerization initiator (D), a solvent (E), and the leveling agent (F) used as needed, It can prepare by mixing a polymerization start adjuvant (D1) and other components.

It is preferable to mix a pigment (A2) with one part or all part of the solvent (E) previously, and to disperse | distribute using a bead mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. At this time, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components with the pigment dispersion liquid thus obtained so as to have a predetermined concentration.

The compound (1) may be previously dissolved in part or all of the solvent (E) to prepare a solution. The solution is preferably filtered through a filter having a pore diameter of about 0.01 to 1 mu m.

It is preferable to filter the colored curable resin composition after mixing with the filter of about 0.1-10 micrometers of pore diameters.

<Manufacturing Method of Color Filter>

As a method of manufacturing a coloring pattern with the colored curable resin composition of this invention, a photolithography method, an inkjet method, the printing method, etc. are mentioned. Especially, the photolithographic method is preferable. The photolithographic method is a method of applying the colored curable resin composition to a substrate, drying to form a colored composition layer, and exposing and developing the colored composition layer through a photomask. In the present invention, the colored pattern means a patterned colored coating film. In the photolithographic method, the colored coating film which is the hardened | cured material of the said coloring composition layer can be formed by not using a photomask and / or developing at the time of exposure. The coloring pattern and colored coating film formed in this way are the color filter of this invention.

The film thickness of the produced color filter is not specifically limited, It can adjust suitably according to the objective, a use, etc., for example, 0.1-30 micrometers, Preferably it is 0.1-20 micrometers, More preferably, it is 0.5-6 micrometers.

As a board | substrate, glass plates, such as quartz glass, borosilicate glass, alumina silicate glass, and soda-lime glass which silica-coated the surface, resin plates, such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and aluminum on the said board | substrate , Silver, and a silver / copper / palladium alloy thin film or the like are used. Separate color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

Formation of each color pixel by the photolithographic method can be performed by a well-known or usual apparatus and conditions. For example, it can produce as follows.

First, a coloring curable resin composition is apply | coated on a board | substrate, and volatile components, such as a solvent, are removed and dried by heat-drying (prebaking) and / or drying under reduced pressure, and a smooth composition layer is obtained.

As a coating method, a spin coat method, the slit coat method, the slit and spin coat method, etc. are mentioned.

30 degreeC-120 degreeC is preferable, and, as for the temperature at the time of heat-drying, 50 degreeC-110 degreeC is more preferable. Moreover, as heating time, it is preferable that it is for 10 second-60 minutes, and it is more preferable that it is for 30 seconds-30 minutes.

In the case of performing the reduced-pressure drying, it is preferable that the drying is carried out in a temperature range of 20 to 25 캜 under a pressure of 50 to 150 Pa. The colored curable resin composition of this invention exhibits the effect that generation | occurrence | production of a crater-shaped defect is few, even when drying under reduced pressure on such conditions.

The film thickness of a coloring composition layer is not specifically limited, What is necessary is just to select suitably according to the film thickness of the target color filter.

Next, a coloring composition layer is exposed through the photomask for forming a desired coloring pattern. The pattern on this photomask is not specifically limited, The pattern according to the intended use is used.

As a light source used for exposure, the light source which produces the light of 250-450 nm wavelength is preferable. For example, light of less than 350 nm may be cut using a filter that cuts the wavelength region, or light of around 436 nm, 408 nm, or 365 nm region may be selectively selected using a band pass filter that extracts these wavelength ranges. It may take out. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

It is preferable to use exposure apparatuses, such as a mask aligner and a stepper, since the parallel light beam can be irradiated uniformly to the whole exposure surface, or the exact alignment of a photomask and the board | substrate with a coloring composition layer can be performed.

A colored pattern is formed on a board | substrate by developing the coloring composition layer after exposure contacting with a developing solution. By development, the unexposed part of a coloring composition layer melt | dissolves in a developing solution and is removed.

As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example. The density | concentration in the aqueous solution of these alkaline compounds becomes like this. Preferably it is 0.01-10 mass%, More preferably, it is 0.03-5 mass%. In addition, the developing solution may contain surfactant.

The developing method may be any of a paddle method, a dipping method and a spray method. In addition, you may tilt the board | substrate at arbitrary angles at the time of image development.

It is preferable to wash with water after image development.

Moreover, it is preferable to post-bake to the obtained coloring pattern. 150 degreeC-250 degreeC is preferable, and, as for post-baking temperature, 160 degreeC-235 degreeC is more preferable. 1-120 minutes are preferable and, as for post-baking time, 10 to 60 minutes are more preferable.

According to the colored curable resin composition of this invention, the color filter with few defects can be produced especially. This color filter is useful as a color filter used for a display apparatus (for example, a liquid crystal display device, an organic electroluminescent apparatus, an electronic paper, etc.) and a solid-state image sensor.

Example

Hereinafter, the colored curable resin composition of this invention is demonstrated in detail by an Example.

In the examples, &quot;% &quot; and &quot; part &quot; are parts by mass and parts by mass unless otherwise specified.

Synthesis Example 1

20 parts of the compound represented by the formula (1x) and 200 parts of N-ethyl-o-toluidine (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed under light shielding conditions, and the resulting solution was stirred at 110 ° C for 6 hours. The obtained reaction solution was cooled to room temperature, then added to a mixed solution of 800 parts of water and 50 parts of 35% hydrochloric acid, and stirred at room temperature for 1 hour to precipitate crystals. The precipitated crystals were obtained as a residue of suction filtration and dried to obtain 24 parts of the compound represented by the formula (1-1). The yield was 80%.

Identification of the compound represented by general formula (1-1);

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 603.4

                        Exact Mass: 602.2

[Synthesis Example 2]

A compound represented by the formula (1-6) was obtained in the same manner as in Synthesis example 1 except that N-isopropyl-2,6-dimethylaniline was used instead of N-ethyl-o-toluidine.

Identification of Compounds Represented by Formula (1-6)

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 659.4

                        Exact Mass: 658.3

[Synthesis Example 3]

In a flask equipped with a cooling tube and a stirring device, a mixture of the compound represented by the formula (X0-1) and the compound represented by the formula (X0-2) (trade name Chugai Aminol Fast Pink R; manufactured by Jugaikasei Co., Ltd.) was 15 150 parts of chloroform and 8.9 parts of N, N-dimethylformamide were added thereto, and 10.9 parts of thionyl chloride was added dropwise while maintaining the temperature at 20 ° C. or lower while stirring. After completion of the dropwise addition, the temperature was raised to 50 占 폚, and the reaction was maintained at the same temperature for 5 hours and then cooled to 20 占 폚. The cooled reaction solution was added dropwise with a mixed solution of 12.5 parts of 2-ethylhexylamine and 22.1 parts of triethylamine while maintaining the temperature below 20 ° C with stirring. Thereafter, the mixture was reacted at the same temperature for 5 hours with stirring. Subsequently, the solvent was distilled off using a rotary evaporator, followed by addition of a small amount of methanol, followed by vigorous stirring. This mixture was added to a mixed solution of 375 parts of ion-exchanged water with stirring to precipitate crystals. The precipitated crystals were separated by filtration, washed well with ion-exchanged water, dried under reduced pressure at 60 ° C, and a xanthene dye X1 [a mixture of compounds represented by formulas (X-1-1) to (X-1-8)]. 11.3 parts were obtained.

[Synthesis Example 4]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was flowed at 0.02 L / min to a nitrogen atmosphere, and 220 parts of ethyl lactate was added and heated to 70 ° C while stirring. Subsequently, 84 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate [a mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) [ The content ratio (molar ratio) was dissolved in 330 parts of 50:50, 140 parts of ethyl lactate to prepare a solution, and the solution was added dropwise into a flask kept at 70 ° C. over 4 hours using a dropping funnel.

On the other hand, the solution which melt | dissolved 30 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 95 parts of ethyl lactates was dripped in the flask over 4 hours using the other dropping funnel. After completion of the dropwise addition of the polymerization initiator solution, the mixture was maintained at 70 ° C for 4 hours, and then cooled to room temperature to obtain a resin B1 solution having a solid content of 48%. Resin B1 had a weight average molecular weight of 8.0 × 10 ³ , a molecular weight distribution (Mw / Mn) of 2.5, and an acid value of solid content conversion of 104 mg-KOH / g. Resin B1 has a structural unit shown below.

The measurement of the weight average molecular weight (Mw) and number average molecular weight (Mn) of polystyrene conversion of resin obtained by the synthesis example was performed on condition of the following using GPC method.

Device; K2479 [manufactured by Shimadzu Seisakusho Corporation]

column; SHIMADZU Shim-pack GPC-80M

Column temperature; 40 ℃

menstruum; THF (tetrahydrofuran)

Flow rate; 1.0 ml / min

Detector; RI

Calibration standards; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio (Mw / Mn) of the weight average molecular weight and number average molecular weight of polystyrene conversion obtained above was made into molecular weight distribution.

Examples 1 to 6 and Comparative Example 1

[Preparation of Colored Curable Resin Composition]

Each component was mixed so that it might become the composition shown in Table 1, and the coloring curable resin composition was obtained.

In Table 1, "A2-1" mixed with the acrylic pigment dispersant and the propylene glycol monomethyl ether acetate of the quantity described in the "E-3 ²⁾ " column, and used previously, was used.

The "E-3 ¹⁾ " column shows the sum total of propylene glycol monomethyl ether acetate content.

In Table 1, each component shows the following. Resin (B) shows content (part) of a solution.

Colorant (A): 1-1: compound represented by general formula (1-1)

Colorant (A): 1-6: compound represented by general formula (1-6)

Colorant (A): X-1: Xanthene Dye X1

Colorant (A): A2-1: C.I. Pigment Blue 15: 6 (pigment)

Resin (B): Resin B1 Solution

Polymerizable compound (C): dipentaerythritol hexaacrylate [manufactured by Nihon Kayaku Co., Ltd .; KAYARAD (registered trademark) DPHA]

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Irgacure® OXE01; BASF Corporation]

Solvent (E): E-1: diacetone alcohol

Solvent (E): E-2: ethyl lactate

Solvent (E): E-3: Propylene glycol monomethyl ether acetate

Solvent (E): E-4: Propylene glycol monomethyl ether

Leveling agent (F): fluorine-based surfactant [Megapack® F554; DIC Corporation]

The content rate of each solvent contained in the prepared colored curable resin composition is as showing in Table 2 with respect to the total amount of the solvent contained.

<Production of colored pattern>

After apply | coating the colored curable resin composition on the square glass substrate (Eagle 2000; Corning Corporation make) with a side of 5 cm by the spin coat method, it prebaked at 100 degreeC for 3 minutes, and obtained the coloring composition layer. After cooling, the interval between the substrate on which the coloring composition layer was formed and the photomask made of quartz glass was set to 100 m, and an exposure machine [TME-150RSK; (Manufactured by Topcon Co., Ltd.) at an exposure amount of 150 mJ / cm 2 (based on 365 nm) in an air atmosphere. As the photomask, a 100 μm line and space pattern was formed. The colored composition layer after light irradiation was immersed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 24 ° C. for 60 seconds and washed with water, followed by post-baking at 230 ° C. for 30 minutes in an oven. A pattern was obtained.

[Film thickness measurement]

About the obtained coloring pattern, film thickness measuring apparatus [DEKTAK3; Nihon Shinkugi Jutsu Co., Ltd.] was used to measure the film thickness.

[Color evaluation]

The obtained coloring pattern was measured with a colorimeter (OSP-SP-200; (X, y) and a tristimulus value Y in an XYZ colorimetric system of CIE were measured using a characteristic function of a C light source. The larger the value of Y, the higher the brightness. The results are shown in Table 3.

[Defect assessment]

After apply | coating the colored curable resin composition by the spin coat method on the glass substrate (Eagle 2000; Corning Corporation make) which is one side of 2 inches so that the film thickness after drying may be 2.3 micrometers, a pressure reduction dryer [VCD Microtech Co., Ltd. product] ] Was dried under reduced pressure to 100 Pa of arrival pressure, and the coloring composition layer was obtained. Surface shape optical microscope [magnification 250 times; about the obtained coloring composition layer; The surface was observed using VF-7510; (Circle) and the case where 3 or more and 10 or less were cases where (circle) and the number of crater-shaped defects were three or less on the board | substrate were made into x. The results are shown in Table 2.

[Evaluation of foreign object]

The surface of the colored composition layer obtained in the same manner as the defect evaluation was subjected to a surface shape optical microscope [magnification of 250 times; VF-7510; manufactured by Keyence Co., Ltd.] was observed, and the case where foreign matter was confirmed was ○, and the case where it was not confirmed was ×. The results are shown in Table 2.

After apply | coating to the board | substrate the colored curable resin composition of this invention, even if it carries out reduced pressure drying and produces a colored composition layer, there is little generation of a crater-shaped defect.

Claims (4)

As colored curable resin composition containing a coloring agent, resin, a polymeric compound, a polymerization initiator, and a solvent,
The colorant comprises a compound represented by the formula (1) and a pigment,
The solvent contains diacetone alcohol,
Colored curable resin composition whose content rate of diacetone alcohol is 0.5 mass% or more and 50 mass% or less with respect to the total amount of a solvent.

In Formula (1), R <^1> and R <^2> respectively independently represents the phenyl group which may have a substituent.
R <^3> and R <^4> respectively independently represents a C1-C10 monovalent saturated hydrocarbon group, The hydrogen atom contained in this saturated hydrocarbon group may be substituted by the C6-C10 aromatic hydrocarbon group or the halogen atom, and this aromatic hydrocarbon group The hydrogen atom contained may be substituted with an alkyl group having 1 to 3 carbon atoms or an alkoxy group having 1 to 3 carbon atoms, and -CH ₂ -contained in the saturated hydrocarbon group is substituted with -O-, -CO- or -NR ^11- . You may be.
R ¹ and R ³ may form a ring containing a nitrogen atom together with the nitrogen atom, and R ² and R ⁴ may form a ring containing a nitrogen atom together with the nitrogen atom.
R ⁵ is _{-OH, -SO 3 H, -SO 3} - of _{^{Z +, -CO 2 R 8,}} -SO 3 R 8 or _{^{-SO 2 NR 9 R 10 - Z}} +, -CO 2 H, -CO 2 Indicates.
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents the integer of 0-4. When m is two or more, some R <^5> may mutually be same or different.
R <^8> represents a C1-C20 monovalent saturated hydrocarbon group, and the hydrogen atom contained in this saturated hydrocarbon group may be substituted by the halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ may be bonded to each other to form a 3 to 10 membered nitrogen-containing heterocycle together with a nitrogen atom; .
Each R ¹¹ independently represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.] The method of claim 1, wherein the solvent further comprises at least one member selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, cyclohexanone and ethyl 3-ethoxypropionate. Colored curable resin composition. The color filter formed with the colored curable resin composition of Claim 1 or 2. A display device comprising the color filter according to claim 3.