TWI621667B - Colored curable resin composition - Google Patents

Abstract

The colored curable resin composition of the present invention includes a compound represented by formula (1), a resin, a polymerizable compound, and a polymerization initiator. [In formula (1), Q ¹ and Q ² each independently represent a hydrogen atom or -CO ₂ M, and any one of Q ¹ and Q ² represents -CO ₂ M. R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ^{3 are} bonded to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom, or R ² and R ^{4 are} bonded to form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom, or R ¹ and R ^{2 are} bonded to form a ring with an adjacent nitrogen atom. R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ⁵ exist, these are the same or different from each other. M represents a hydrogen atom or an alkali metal atom. ]

Description

Colored curable resin composition

The present invention relates to a coloring curable resin composition.

Dyes are used, for example, to perform color display using reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, inkjet, and the like. As the dye, a coumarin compound such as coumarin 6 (a compound represented by the following formula) is known (Example 8 of JP2006-154740-A).

In the step of making a color filter from a coloring curable resin composition containing the above-mentioned coumarin compound, there is a problem in that the colorant is sublimated.

The present invention includes the following inventions.

[1] A colored curable resin composition comprising a compound represented by formula (1), a resin, a polymerizable compound, and a polymerization initiator, and formula (1)

[In formula (1), Q ¹ and Q ² each independently represent a hydrogen atom or -CO ₂ M, and any one of Q ¹ and Q ² represents -CO ₂ M; R ¹ to R ⁴ each independently represent hydrogen An atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ^{3 are} bonded to form a ring with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring, and R ² and R ^{4 are} bonded to an adjacent one The carbon atom on the benzene ring and the adjacent nitrogen atom form a ring together, or R ¹ and R ^{2 are} bonded to form a ring with the adjacent nitrogen atom; the methylene group constituting the monovalent hydrocarbon group may pass through an oxygen atom, a sulfur atom, -N (R ⁵ )-, sulfofluorenyl or carbonyl, the hydrogen atom contained in the monovalent hydrocarbon group may be substituted by halogen atom, cyano, nitro, carbamoyl, sulfamoyl, -SO ₃ M, -CO ₂ M, hydroxyl or amine group substitution; R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; when there are a plurality of R ⁵ , these are the same or different from each other; M represents a hydrogen atom or a base Metal atom].

[2] The colored curable resin composition according to [1], wherein R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ^{3 are} bonded to be adjacent to each other. The carbon atom on the benzene ring and the adjacent nitrogen atom form a ring together, or R ² and R ^{4 are} bonded to form a ring with the carbon atom on the adjacent benzene ring and the adjacent nitrogen atom.

[3] The colored hardening resin composition according to [1] or [2], wherein R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ^{3 are} bonded The carbon atom on the adjacent benzene ring and the adjacent nitrogen atom form a ring together, and R ² and R ^{4 are} bonded to form a ring with the carbon atom on the adjacent benzene ring and the adjacent nitrogen atom.

[4] The coloring curable resin composition according to any one of [1] to [3], further comprising a pigment material.

[5] The colored curable resin composition according to [4], wherein the pigment is at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment.

[6] The colored hardening resin composition according to [4] or [5], wherein the pigment is selected from the group consisting of a copper chloride phthalocyanine pigment, a copper bromide phthalocyanine pigment, and a zinc bromide phthalocyanine pigment. At least one.

[7] The colored curable resin composition according to any one of [4] to [6], wherein the pigment is a green pigment.

[8] The colored hardening resin composition according to any one of [4] to [7], wherein the pigment is at least one selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58 .

[9] The colored curable resin composition according to [8], wherein the pigment is C.I. Pigment Green 7.

[10] A color filter formed using the coloring curable resin composition according to any one of [1] to [9].

[11] A liquid crystal display device including the color filter as in [10].

According to the present invention, it is possible to provide a coloring curable resin composition capable of suppressing sublimation of a colorant to form a color filter.

The colored curable resin composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

The colorant (A) contains a compound represented by the formula (1).

The colored curable resin composition of the present invention preferably further contains at least one selected from the group consisting of a solvent (E) and a leveling agent (F).

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

In this specification, unless otherwise specified, the compounds exemplified as each component may be used alone or in combination of plural kinds.

<Colorant (A)>

The colorant (A) preferably contains a compound represented by formula (1) (hereinafter sometimes referred to as "compound (1)"), and further contains a pigment (P).

The compound (1) also includes a tautomer or a salt thereof.

In the formula (1), examples of the halogen atom in R ¹ to R ⁴ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ in formula (1) include methyl, ethyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, butyl, isobutyl, second butyl, third butyl, (2-ethyl) butyl, 2-butenyl, 1,3-butadienyl, pentyl, iso Pentyl, 3-pentyl, neopentyl, third pentyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, (3-ethyl) pentyl, hexyl, isohexyl , 5-methylhexyl, (2-ethyl) hexyl, heptyl, (3-ethyl) heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl And other aliphatic hydrocarbon groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4 -Dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2 -Dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4,4-di Cycloaliphatic hydrocarbon groups such as cyclohexyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl; benzene Methyl, o-tolyl, m-tolyl, p-tolyl, xylyl, 2,4,6-trimethylphenyl, o-cumyl, m-cumyl, p-cumyl, benzyl, benzene Aromatic hydrocarbon groups such as ethyl, biphenyl, 1-naphthyl, and 2-naphthyl; and groups formed from a combination of these.

The methylene group constituting the monovalent hydrocarbon group is substituted with an oxygen atom, a sulfur atom, -N (R ⁵ )-, a sulfonyl group or a carbonyl group, or a hydrogen atom contained in the monovalent hydrocarbon group is substituted with a halogen atom, a cyano group, or a nitrate A group substituted with a carbamoyl group, amidinomethyl group, sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group, or an amine group. Examples include methoxy, ethoxy, propoxy, and isopropyl. Alkoxy groups such as oxy, butoxy, isobutoxy, second butoxy, third butoxy, pentyloxy, (2-ethyl) hexyloxy; aryloxy such as phenoxy; Aryloxy groups such as benzyloxy; alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, and propoxycarbonyl; fluorenyl groups such as ethoxyl and benzyloxy; N-methylamine methyl Fluorenyl, N-ethylaminoformamyl, N-propylaminoformamyl, N-isopropylamineformamyl, N-butylamineformamyl, N-isobutylamineformamyl, N-second butylaminoformamyl, N-third butylaminoformamyl, N-pentylaminoformamyl, N- (1-ethylpropyl) aminoformamyl, N- (1 , 1-dimethylpropyl) carbamoyl, N- (1,2-dimethylpropyl) carbamoyl, N- (2,2-dimethylpropyl) carbamoyl, N- (1-methylbutyl) amine Fluorenyl, N- (2-methylbutyl) aminomethane, N- (3-methylbutyl) aminomethane, N-cyclopentylaminomethane, N-hexylaminemethane , N- (1,3-dimethylbutyl) aminomethyl, N- (3,3-dimethylbutyl) aminomethyl, N-heptylaminomethyl, N- (1 -Methylhexyl) carbamyl, N- (1,4-dimethylpentyl) carbamyl, N-octylaminocarbamyl, N- (2-ethylhexyl) carbamyl N-1 substituted carbamoyl groups, such as N- (1,5-dimethyl) hexylaminocarbamyl, N- (1,1,2,2-tetramethylbutyl) aminoformamyl; N , N-dimethylaminoformamyl, N, N-ethylmethylaminoformamyl, N, N-diethylaminoformamyl, N, N-propylmethylaminoformamyl, N , N-Isopropylmethylamine formamyl, N, N-Third-butylmethylamine formamyl, N, N-butylethylamine formamyl, N, N-bis (1-methylpropane N) N-2 substituted carbamoyl groups such as carbamoyl, N, N-heptylmethylcarbamoyl, N, N-bis (2-ethylhexyl) carbamoyl; N- Methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-isopropylaminesulfonyl, N-butylaminesulfonyl, N-isobutylamine Sulfonyl, N-second butylamine, sulfonyl, N-third butylamine Fluorenyl, N-pentylaminosulfonyl, N- (1-ethylpropyl) sulfanilino, N- (1,1-dimethylpropyl) sulfanilino, N- (1, 2-dimethylpropyl) sulfamomidino, N- (2,2-dimethylpropyl) sulfamomidino, N- (1-methylbutyl) sulfamomidino, N- (2 -Methylbutyl) sulfamomidino, N- (3-methylbutyl) sulfamomidino, N-cyclopentylaminesulfonamidino, N-hexylaminesulfamonium, N- (1,3 -Dimethylbutyl) sulfamoyl, N- (3,3-dimethylbutyl) sulfamoyl, N-heptylaminesulfamoyl, N- (1-methylhexyl) sulfamoyl Fluorenyl, N- (1,4-dimethylpentyl) aminosulfonyl, N-octylaminesulfonyl, N- (2-ethylhexyl) aminesulfonyl, N- (1,5 -Dimethyl) hexylaminesulfonyl, N- (1,1,2,2-tetramethylbutyl) aminesulfonyl and other N-1 substituted aminesulfonyl; N, N-dimethylamine Sulfonyl, N, N-ethylmethylaminesulfonyl, N, N-diethylaminesulfonyl, N, N-propylmethylaminesulfonyl, N, N-isopropylmethyl N-aminosulfonyl, N, N-tert-butylmethylaminesulfonyl, N, N-butylethylaminesulfonyl, N, N-bis (1-methylpropyl) aminesulfonyl, N, N-Heptylmethylaminesulfonyl, N, N-bis (2-ethylhexyl) aminesulfonyl and other N, N-2 substituted amines Fluorenyl; N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamino, N-isobutylamino, N- Dibutylamino, N-thirdbutylamino, N-pentylamino, N- (1-ethylpropyl) amino, N- (1,1-dimethylpropyl) amino , N- (1,2-dimethylpropyl) amino, N- (2,2-dimethylpropyl) amino, N- (1-methylbutyl) amino, N- (2 -Methylbutyl) amino, N- (3-methylbutyl) amino, N-cyclopentylamino, N-hexylamino, N- (1,3-dimethylbutyl) amine Base, N- (3,3-dimethylbutyl) amino, N-heptylamino, N- (1-methylhexyl) amino, N- (1,4-dimethylpentyl) Amine, N-octylamino, N- (2-ethylhexyl) amino, N- (1,5-dimethyl) hexylamino, N- (1,1,2,2-tetramethyl) N-alkylamino groups such as butyl) amino groups; N, N-dimethylamino groups, N, N-ethylmethylamino groups, N, N-diethylamino groups, N, N-propyl Methylmethylamino, N, N-isopropylmethylamino, N, N-third butylmethylamino, N, N-butylethylamino, N, N-bis (1-methyl (Propyl) amino, N, N-heptylmethylamino, N, N-bis (2-ethylhexyl) amino, and other N, N-dialkylamino groups; N-methylaminomethyl , N-ethylaminomethyl, N-propylaminomethyl, N-isopropylaminomethyl, N-butylaminomethyl, N-isobutylaminomethyl, N- Second butylaminomethyl, N-third butylaminomethyl, N-pentylaminomethyl, N- (1-ethylpropyl) aminomethyl, N- (1,1 -Dimethylpropyl) aminomethyl, N- (1,2-dimethylpropyl) aminomethyl, N- (2,2-dimethylpropyl) aminomethyl, N- (1-methylbutyl) aminomethyl, N- (2-methylbutyl) aminomethyl, N- (3-methylbutyl) aminomethyl, N-cyclopentylamino Methyl, N-hexylaminomethyl, N- (1,3-dimethylbutyl) aminomethyl, N- (3,3-dimethylbutyl) aminomethyl, N-heptyl Aminoaminomethyl, N- (1-methylhexyl) aminomethyl, N- (1,4-dimethylpentyl) aminomethyl, N-octylaminomethyl, N- ( 2-ethylhexyl) aminomethyl, N- (1,5-dimethyl) hexylaminomethyl, N- (1,1,2,2-tetramethylbutyl) aminomethyl, etc. N-alkylaminomethyl; N, N-dimethylaminomethyl, N, N-ethylmethylaminomethyl, N, N-diethylaminomethyl, N, N- Propylmethylaminomethyl, N, N-isopropylmethylaminomethyl, N, N-third butyl Aminoaminomethyl, N, N-butylethylaminomethyl, N, N-bis (1-methylpropyl) aminomethyl, N, N-heptylmethylaminomethyl, N, N-bis (2-ethylhexyl) aminomethyl and other N, N-dialkylaminomethyl; trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, Perfluoroisopropenyl, perfluoro (1-propenyl), perfluoro (2-propenyl), perfluorobutyl, perfluoroisobutyl, perfluoro (second butyl), perfluoro (third butyl) Group), perfluoro (2-butenyl), perfluoro (1,3-butadienyl), perfluoropentyl, perfluoro (isopentyl), perfluoro (3-pentyl), perfluoro Neopentyl, perfluoro (third pentyl), perfluoro (1-methylpentyl), perfluoro (2-methylpentyl), perfluoro (2-pentenyl), perfluorohexyl, perfluoro Fluoroisohexyl, perfluoro (5-methylhexyl), perfluoro (2-ethylhexyl), perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, perfluoroundecyl , Perfluorododecyl, perfluorooctadecyl and other aliphatic hydrocarbon groups having a fluorine atom; perfluorocyclopropyl, perfluorocyclobutyl, perfluorocyclopentyl, perfluorocyclohexyl, perfluorocyclohexyl Alkenyl, perfluorocycloheptyl, perfluoro (1-methylcyclohexyl), perfluoro (2- Cyclohexyl), perfluoro (3-methylcyclohexyl), perfluoro (4-methylcyclohexyl), perfluoro (1,2-dimethylcyclohexyl), perfluoro (1,3-dimethyl Cyclohexyl), perfluoro (1,4-dimethylcyclohexyl), perfluoro (2,3-dimethylcyclohexyl), perfluoro (2,4-dimethylcyclohexyl), perfluoro ( 2,5-dimethylcyclohexyl), perfluoro (2,6-dimethylcyclohexyl), perfluoro (3,4-dimethylcyclohexyl), perfluoro (3,5-dimethylcyclo Hexyl), perfluoro (2,2-dimethylcyclohexyl), perfluoro (3,3-dimethylcyclohexyl), perfluoro (4,4-dimethylcyclohexyl), perfluoro (2, 4,6-trimethylcyclohexyl), perfluoro (2,2,6,6-tetramethylcyclohexyl), perfluoro (3,3,5,5-tetramethylcyclohexyl), etc. have fluorine atoms Alicyclic hydrocarbon groups; perfluorophenyl, perfluoro (o-tolyl), perfluoro (m-tolyl), perfluoro (p-tolyl), perfluoroxylyl, perfluoro2,4,6-tri Tolyl, perfluoro (o-cumyl), perfluoro (m-cumyl), perfluoro (p-cumyl), perfluorobenzyl, perfluorophenethyl, perfluorobiphenyl, Perfluoro (1-naphthyl), perfluoro (2-naphthyl), 1-trifluoromethylphenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethyl Phenylbenzene Aromatic hydrocarbon groups having a fluorine atom, such as perfluoromethoxy; perfluoromethoxy, perfluoroethoxy, perfluoropropoxy, perfluoro (isopropoxy), perfluorobutoxy, perfluoro (isobutoxy ), Perfluoro (second butoxy), perfluoro (third butoxy), perfluoropentoxy, perfluorophenoxy, perfluorobenzyloxy, 2,2,2-trifluoroethoxy (Perfluoroethyl) methoxy, (perfluoropropyl) methoxy, (perfluoro (isopropyl)) methoxy, (perfluoro (isopropenyl)) methoxy, (all Fluoro (1-propenyl)) methoxy, (perfluoro (2-propenyl)) methoxy, (perfluorobutyl) methoxy, (perfluoro (isobutyl)) methoxy, ( Perfluoro (second butyl)) methoxy, (perfluoro (third butyl)) methoxy, (perfluoro (2-butenyl)) methoxy, (perfluoro (1,3- Butadienyl)) methoxy, (perfluoropentyl) methoxy, (perfluoro (isopentyl)) methoxy, (perfluoro (3-pentyl)) methoxy, (perfluoro (Neopentyl)) methoxy, (perfluoro (third pentyl)) methoxy, (perfluoro (1-methylpentyl)) methoxy, (perfluoro (2-methylpentyl) )) Methoxy, (perfluoro (2-pentenyl)) methoxy, (perfluorohexyl) methoxy, (perfluoro (isohexyl)) methoxy, (perfluoro (5-methyl )) Methoxy, (perfluoro ((2-ethyl) hexyl)) methoxy, (perfluoroheptyl) methoxy, (perfluorooctyl) methoxy, (perfluorononyl) Methoxy, (perfluorodecyl) methoxy, (perfluoroundecyl) methoxy, (perfluorododecyl) methoxy, (perfluorooctadecyl) methoxy, etc. Substituted oxygen with a fluorine atom; 2,3-bis (trifluoromethyl) phenylmethyl, 2,4-bis (trifluoromethyl) phenylmethyl, 2,5-bis (trifluoromethyl) ) Phenylmethyl, 2,6-bis (trifluoromethyl) phenylmethyl, 3,4-bis (trifluoromethyl) phenylmethyl, 3,5-bis (trifluoromethyl) benzene Methyl and so on.

R ¹ and R ^{2 are} preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group. The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

R ^{1 is} preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Among these, ethyl, butyl, hexyl, (2-ethyl) hexyl, and octyl are more preferred, and ethyl, butyl, hexyl, and (2-ethyl) hexyl are more preferred, and (2- (Ethyl) hexyl. The compound of the present invention in which R ^{1 is} such a group has excellent solubility in a solvent.

R ^{2 is} preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Among these, ethyl, butyl, hexyl, (2-ethyl) hexyl, and octyl are more preferred, and ethyl, butyl, hexyl, and (2-ethyl) hexyl are more preferred, and hexyl and ( 2-ethyl) hexyl. The compound of the present invention in which R ^{2 is} such a group has excellent solubility in a solvent.

In terms of ease of production, R ³ and R ^{4 are} preferably hydrogen atoms.

When R ¹ and R ^{3 are} bonded to form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom, and / or R ² and R ^{4 are} bonded to a carbon atom on an adjacent benzene ring and When adjacent nitrogen atoms form a ring together, examples of * -R ¹ -R ^3- * and * -R ² -R ^4- * include: * -CH ₂ -CH _2- *, * -CF _2- CF _2- *, * -CH ₂ -C (CH ₂ ) _5- * or * -CH ₂ -C (CH ₃ ) _2- *, etc., preferably * -CH ₂ -CH _2- * and * -CH ₂ -C (CH ₃ ) _2- *, more preferably * -CH ₂ -C (CH ₃ ) _2- *. * Indicates a bond key.

When R ¹ and R ^{2 are} bonded to form a ring with an adjacent nitrogen atom, examples of * -R ¹ -R ^2- * include: *-(CH ₂ ) _2- *, *-(CH ₂ ) _3- *, *-(CH ₂ ) _4- *, *-(CH ₂ ) _5- *, *-(CH ₂ ) _6- *, *-(CH ₂ ) _7- *, *-(CF ₂ ) _2- *, *-(CF ₂ ) _3- *, *-(CF ₂ ) _4- *, *-(CF ₂ ) _5- *, *-(CF ₂ ) _6- *, *-(CF ₂ ) _7- *, etc., preferably *-(CH ₂ ) _4- *, *-(CH ₂ ) _5- *, *-(CH ₂ ) _6- *, *-(CF ₂ ) _4- *, * -(CF ₂ ) _5- * and *-(CF ₂ ) _6- , more preferably *-(CH ₂ ) _4- *, *-(CH ₂ ) _5- * and *-(CH ₂ ) _6- *, Particularly preferably *-(CH ₂ ) _4- * and *-(CH ₂ ) _5- *. * Indicates a bond key.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ⁵ include methyl, ethyl, propyl, isopropyl, isopropenyl, 1-propenyl, 2-propenyl, butyl, and isobutyl Base, second butyl, third butyl, (2-ethyl) butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, 3-pentyl, neopentyl Base, tertiary pentyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, (3-ethyl) pentyl, hexyl, isohexyl, 5-methylhexyl, (2- (Ethyl) hexyl, heptyl, (3-ethyl) heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl and other aliphatic hydrocarbon groups; cyclopropyl, cyclo Butyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2 -Dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5 -Dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3 -Dimethylcyclohexyl, 4,4-dimethylcyclohexyl, 2,4,6- Alicyclic hydrocarbon groups such as trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl; phenyl, o-tolyl, m-tolyl, P-tolyl, xylyl, 2,4,6-trimethylphenyl, o-cumyl, m-cumyl, p-cumyl, benzyl, phenethyl, biphenyl, 1-naphthalene Aromatic hydrocarbon groups such as methyl, 2-naphthyl, and the like; and groups formed from a combination of these.

M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom, a sodium atom, or a potassium atom, and more preferably a hydrogen atom.

Examples of the compound (1) in which Q ¹ is -CO ₂ M include compounds represented by the formulae (1-1) to (1-44), and salts thereof.

Examples of the compound (1) in which Q ² is -CO ₂ M include compounds represented by the formulae (1-45) to (1-88), and salts thereof.

From the viewpoint of ease of synthesis, the compound (1) is preferably a compound (1-1) to a compound (1-8), a compound (1-15) to a compound (1-42), and a compound (1). -45) ~ compound (1-52) and compound (1-59) ~ compound (1-86), more preferably compound (1-1) ~ compound (1-4), compound (1-15) ~ Compound (1-32), compound (1-39) to compound (1-42), compound (1-45) to compound (1-48), compound (1-59) to compound (1-76), and compound (1-83) to compound (1-86), among which compound (1-1) to compound (1- 4), compound (1-15) to compound (1-20), compound (1-27) to compound (1-28), compound (1-31) to compound (1-32), compound (1-39 ) ~ Compound (1-42), Compound (1-45) ~ Compound (1-48), Compound (1-59) ~ Compound (1-64), Compound (1-71) ~ Compound (1-72) Compound (1-75) to compound (1-76) and compound (1-83) to compound (1-86).

The compound (1) can be produced, for example, according to the method described in Dyes and Pigments (2008), 77, 556-558.

Specifically, the compound (1) can be produced by subjecting a compound represented by the formula (q1), a compound represented by the formula (q2), and ethyl cyanoacetate to a cyclization reaction in the presence of benzoic acid and a solvent. The reaction temperature is preferably 0 ° C to 200 ° C, and more preferably 100 ° C to 150 ° C. The reaction time is preferably 1 hour to 24 hours, and more preferably 8 hours to 16 hours. As said solvent, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, N-methylpyrrolidone, etc. are preferable, and 1-pentanol is preferable.

[In formulae (q1) and (q2), R ¹ to R ⁴ , Q ¹ and Q ² each have the same meaning as described above. ]

In the production of the compound (1), the amount of the compound represented by the formula (q1) is 1 mole, preferably 1 mole to 10 moles, and more preferably 1 mole relative to the compound represented by the formula (q2). Ears to 4 moles, more preferably 1 mole to 3 moles, even more preferably 1 mole.

In the production of compound (1), the amount of ethyl cyanoacetate used is 1 mole, preferably 1 mole to 10 moles, and more preferably 1 mole to 4 relative to the compound represented by formula (q2). The mole is more preferably 1 to 3 moles, and even more preferably 1 mole.

In the production of compound (1), the amount of benzoic acid used is 1 mole, preferably 0.1 mole to 3 moles, more preferably 0.3 mole to 3 moles, relative to the compound represented by formula (q2). It is more preferably 0.3 to 1.2 moles, and still more preferably 0.3 to 0.4 moles.

The method for obtaining the compound (1) as a target compound from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, it is preferable to precipitate the crystals by a method of appropriately adjusting the temperature of the reaction mixture or a method of adding the reaction mixture to a solvent that does not dissolve the compound (1), and the crystals are collected by filtration. The filtered crystals are preferably water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, Toluene, N, N-dimethylformamidine, N-methylpyrrolidone, chloroform, or a mixture of these solvents are used for washing or recrystallization, and then drying. If necessary, further purification can be performed by a known method such as column chromatography or recrystallization.

The pigment (P) is not particularly limited, and known pigments can be used, and examples thereof include those classified as pigments by the Color Index (published by The Society of Dyers and Colourists). pigment.

Examples of the pigment include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 194, 214 and other yellow pigments; CI pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; CI Pigment Violet 1, 14, 19, 23 , 29, 32, 33, 36, 37, 38 and other purple pigments; C.I. Pigment Green 7, 10, 15, 25, 36, 47, 58 and other green pigments; C.I. Pigment Brown 23 and 25 and other brown pigments; C.I. Pigment Black 1, 7 and other black pigments.

The pigment (P) is preferably a phthalocyanine pigment, more preferably at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment, and further preferably selected from CI Pigment Green 7, 36, and 58 At least one of the groups formed. These pigments can be preferably used for green pigments. By containing the pigments described above, it is easy to optimize the transmission spectrum, so that the light resistance and chemical resistance of the color filter become good.

If necessary, the pigment may be subjected to rosin treatment, surface treatment using pigment derivatives introduced with an acidic group or a basic group, grafting treatment of the pigment surface with a polymer compound, etc., and micronization by a sulfuric acid micronization method, etc. Treatment, or cleaning treatment using organic solvents or water to remove impurities, removal treatment using ionic exchange methods, etc. for ionic impurities. The particle diameters of the pigments are preferably each uniform.

The pigment is subjected to a dispersion treatment by containing a pigment dispersant, and can be made into a pigment dispersion liquid in a state where the pigment is uniformly dispersed in the pigment dispersant solution. The pigment may be separately dispersed, or a plurality of pigments may be mixed and dispersed.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more. Examples of pigment dispersants include KP (made by Shin-Etsu Chemical Industry Co., Ltd.), Flowlen (made by Kyoeisha Chemical Co., Ltd.), Solsperse (made by Zeneca Co., Ltd.), EFKA (made by CIBA), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie), and the like.

When a pigment dispersant is used, its use amount is preferably 100 parts by mass or less with respect to 100 parts by mass of the pigment, and more preferably 5 parts by mass or more and 50 parts by mass or less. If the amount of the pigment dispersant is within the above range, it is possible to obtain a pigment component with a more uniform dispersion state. The tendency to spit.

The content rate of the compound (1) with respect to the total amount of the colorant (A) is preferably 0.01 mass% or more and 90 mass% or less, more preferably 0.1 mass% or more and 80 mass% or less, and further preferably 1 mass % To 65% by mass, and more preferably 2% to 60% by mass.

When the pigment (P) is contained, its content rate is preferably 10% by mass or more and 99.99% by mass or less, more preferably 20% by mass or more and 99.9% by mass or less with respect to the total amount of the colorant (A). It is more preferably 35 mass% or more and 99 mass% or less, and still more preferably 40 mass% or more and 98 mass% or less.

The content of the colorant (A) is usually 1% by mass or more and 99% by mass or less, preferably 2% by mass or more and 90% by mass or less, more preferably 3% by mass or more with respect to the total amount of the solid components. 80 mass% or less, more preferably 5 mass% or more and 70 mass% or less, still more preferably 5 mass% or more and 60 mass% or less, even more preferably 5 mass% or more and 50 mass% or less. When the content of the colorant (A) is within the above range, a desired spectroscopic or color density can be obtained.

As used herein, the "total amount of solid components" refers to the total amount of components after the solvent (E) is removed from the colored curable resin composition of the present invention. The total amount of the solid component and the content of each component with respect to the solid component can be measured by a known analysis method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and more preferably an addition polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. Examples of such resins include the following resins [K1] to [K6].

Resin [K1] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)"), and a cyclic ether having 2 to 4 carbon atoms A copolymer of a monomer (b) (hereinafter sometimes referred to as "(b)") having a structure and an ethylenically unsaturated bond; Resin [K2] (a), (b), and monomer (c) copolymerizable with (a) (wherein (a) and (b) are different) (hereinafter sometimes referred to as "(c)") Copolymers of resins; copolymers of resins [K3] (a) and (c); resins [K4] resins made by reacting (b) with copolymers of (a) and (c); resins [K5] make ( a) Resin formed by reacting with copolymers of (b) and (c); Resin [K6] is a resin formed by reacting (a) with copolymers of (b) and (c) and then reacting with carboxylic anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, butenoic acid, o-, m-, and p-vinylbenzoic acid; maleic acid and fumaric acid , Citraconic acid, mesaconic acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, Unsaturated dicarboxylic acids such as 3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid; methyl-5-decane Ene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methyl Dicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo [2.2.1] hept-2 -Ene, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene, and other bicyclic unsaturated compounds containing carboxyl groups; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl Phthalic anhydride, 4-vinyl phthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Unsaturated dicarboxylic anhydrides such as tetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride; succinic acid mono [2- (meth) acrylic acid ethoxyethyl Unsaturated mono [(meth) acrylic alkoxyalkyl] esters of polyvalent carboxylic acids, such as poly] carboxylic acid esters, mono [2- (meth) acryloxyethyl] phthalates, and the like ; For example, α- (hydroxymethyl) acrylic unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule. Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable in terms of the copolymerization reactivity or the solubility of the obtained resin in an alkaline aqueous solution.

(b) a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond Polymerizable compound. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acrylic fluorenyloxy group is preferred.

In addition, in this specification, "(meth) acrylic acid" means at least 1 sort (s) chosen from the group which consists of acrylic acid and methacrylic acid. The terms "(meth) acrylfluorenyl" and "(meth) acrylate" also have the same meaning.

Examples of (b) include a monomer (b1) having an epoxyethyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), an oxetanyl group and an ethylenic unsaturated group. A monomer (b2) (hereinafter sometimes referred to as "(b2)"), a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), and the like.

Examples of (b1) include a monomer (b1-1) (hereinafter referred to as "(b1-1)") having an epoxidized structure of a linear or branched aliphatic unsaturated hydrocarbon. A monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter sometimes referred to as "(b1-2)").

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, and glycidyl vinyl ether. , O-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinyl Benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) benzene Ethylene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) benzene Ethylene, 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxy) (Methyl) benzene Ethylene, 2,4,6-tris (glycidyloxymethyl) styrene, etc.

Examples of (b1-2) include vinyl cyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexyl methyl (meth) acrylate, ( 3,4-epoxycyclohexyl methyl methacrylate (for example, Cyclomer M100; manufactured by Daicel Co., Ltd.), a compound represented by formula (I), a compound represented by formula (II), and the like.

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

X ^a and X ^b represents 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.

* Indicates bonding with O. ]

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

Examples of the hydroxy-substituted alkyl group include hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, and 1-hydroxyl. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

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, and more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group include methylene, ethylene, propane-1,2-diyl, propane-1,3-diyl, butane-1,4-diyl, and pentane-1,5. -Diyl, hexane-1,6-diyl and the like.

As X ^a and X ^b , a single bond, methylene, ethylidene, * -CH ₂ -O- and * -CH ₂ CH ₂ -O- are preferred, and a single bond and *-are more preferred. CH ₂ CH ₂ -O- (* indicates a bond with O).

Examples of the compound represented by the formula (I) include compounds represented by any one of the formulae (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9), or formula (I-11) to formula (I) are preferred. The compound represented by -15) is more preferably a compound represented by formula (I-1), formula (I-7), formula (I-9) or formula (I-15).

Examples of the compound represented by the formula (II) include compounds represented by any one of the formulae (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9), or formula (II-11) to formula (II) are preferred. The compound represented by -15) is more preferably a compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15).

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone, or the compound represented by the formula (I) and the compound represented by the formula (II) may be used in combination. When these are used in combination, the content ratio of the compound represented by the formula (I) and the compound represented by the formula (II) is preferably 5:95 to 95: 5, more preferably 10:90 on a Moore basis. ~ 90: 10, more preferably 20: 80 ~ 80: 20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, 3- Ethyl-3-methacryloxymethyloxetane, 3-ethyl-3-propenemethyloxetane, 3-methyl-3-methacryloxy Ethylethyloxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methacryloxyethyloxetane, 3 -Ethyl-3-propenyloxyethyloxetane and the like.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth) acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Viscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and tetrahydrofurfuryl methacrylate. Wait.

As (b), (b1) is preferable in terms of further improving the reliability such as heat resistance and chemical resistance of the obtained color filter. Furthermore, (b1-2) is more preferable at the point which is excellent in the storage stability of a coloring curable resin composition.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and Tributyl, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, (meth) acrylic ring Amyl ester, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2.6 ] decane-8-ester (in the technical field As a common name, it is called "dicyclopentyl (meth) acrylate". It is also sometimes called "tricyclodecyl (meth) acrylate", and tricyclo (meth) acrylate [5.2.1.0 ^2.6 ] Decene-8-ester (in this technical field, as a common name, "dicyclopentenyl (meth) acrylate"), dicyclopentyloxyethyl (meth) acrylate, (methyl Acrylic iso Ester, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (meth) acrylic acid (Meth) acrylates such as benzyl esters; (meth) acrylates containing hydroxyl groups such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; maleic acid di Dicarboxylic acid diesters such as ethyl acetate, diethyl fumarate, diethyl iconate; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2 -Ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene , 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1 ] Hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6 -Bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxy Bicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene Ene, 5-hydroxymethyl-5- Dicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl bicyclo [2.2.1] hept-2-ene Ene, 5-phenoxycarbonyl bicyclo [2.2.1] hept-2-ene, 5,6-bis (third butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (Cyclohexyloxycarbonyl) Bicyclic unsaturated compounds such as bicyclo [2.2.1] hept-2-ene; N-phenylcis-butenedifluorene imine, N-cyclohexylcisbutenedifluorene, N -Benzyl cis-butene diimide, N- succinimide imide 3-cis-butene diimide benzoate, N-butanimide-imino-4- cis butadiene Iminobutyrate, N-butanebiimino-6-cisbutenediamidohexanoate, N-butadiamidoimino-3-cisbutanediiminopropionate, N- (9-acridyl) cis-butene difluorenimide and other dicarbonylfluorenimine derivatives; styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyl Toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene Ene, 2,3-dimethyl-1,3-butadiene and the like.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth) acrylate, and tricyclic (meth) acrylate [5.2.1.0 ^2.6 ] decane are preferred. Alk-8-ester, N-phenylcis-butenedifluoreneimine, N-cyclohexylcisbutenedifluoreneimine, N-benzylcisbutenedifluoreneimine, bicyclo [2.2.1] heptane- 2-ene and so on.

In the resin [K1], the ratio of the structural unit derived from each is preferably the structural unit derived from (a) among all the structural units constituting the resin [K1]: 2 to 60 mol% derived from (b ) Structural unit: 40 ~ 98 mol%, more preferably the structural unit derived from (a): 10 ~ 50 mol% structural unit derived from (b): 50 ~ 90 mol%.

When the ratio of the structural unit of the resin [K1] is within the above range, there are storage stability of the colored curable resin composition, developability when a colored pattern is formed, and obtained color The filter tends to have excellent solvent resistance.

The resin [K1] can be referred to, for example, the method described in the document "Experimental Method of Polymer Synthesis" (by Otsu Takayuki, Issuer: Chemical Dojin Co., Ltd., 1st Edition, 1st Brush, March 1, 1972) and It is manufactured by citing documents described in this document.

Specifically, the following methods can be cited: adding a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like to a reaction vessel, for example, forming a deoxidizing environment by replacing oxygen with nitrogen, and heating while stirring And insulation. The polymerization initiator, solvent, and the like used herein are not particularly limited, and ordinary users in the field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or organic compounds. The solvent (such as benzamyl peroxide) may be any solvent as long as it dissolves each monomer. Examples of the solvent include solvents listed below as the solvent (E) of the coloring curable resin composition of the present invention. Wait.

In addition, the obtained copolymer may be used directly after the reaction, or may be a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation. Especially during the polymerization, by using the solvent contained in the colored curable resin composition of the present invention as a solvent, the solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention, so that it can be simplified. The manufacturing process of the coloring curable resin composition of this invention.

In the resin [K2], the ratio of the structural unit derived from each is preferably the structural unit derived from (a) among all the structural units constituting the resin [K2]: 2 to 45 mol% derived from (b ) Structural unit: 2 ~ 95 mole% from (c) structural unit: 1 ~ 65 mole%, more preferably from (a) structural unit: 5 ~ 40 mole% from (b) Structural unit: 5 ~ 80 mole% Structural unit derived from (c): 5 ~ 60 mole%.

When the ratio of the structural unit of the resin [K2] is within the above range, there are storage stability of the colored curable resin composition, developability when a colored pattern is formed, and solvent resistance and heat resistance of the obtained color filter It tends to have excellent properties and mechanical strength.

The resin [K2] can be produced in the same manner as the method described as the method for producing the resin [K1], for example.

In the resin [K3], the ratio of the structural unit derived from each is preferably the structural unit derived from (a) among all the structural units constituting the resin [K3]: 2 to 60 mol% derived from (c ) Structural unit: 40 ~ 98 mol%, more preferably the structural unit derived from (a): 10 ~ 50 mol% structural unit derived from (c): 50 ~ 90 mol%.

The resin [K3] can be produced in the same manner as the method described as the method for producing the resin [K1], for example.

The resin [K4] can be obtained by copolymerizing (a) and (c), and adding a cyclic ether having 2 to 4 carbon atoms in (b) to a carboxylic acid and / or carboxylic acid anhydride in (a). While manufacturing.

First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of the resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as those listed in the resin [K3].

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

Following the manufacture of the copolymer of (a) and (c), the environment in the flask is replaced by nitrogen with air, and the reaction catalyst of (b), carboxylic acid or carboxylic anhydride and cyclic ether (such as tris (dimethyl) Aminomethyl) phenol, etc.) and polymerization inhibitors (such as hydroquinone, etc.) are added to the flask, and reacted at, for example, 60 to 130 ° C for 1 to 10 hours, thereby producing a resin [K4].

The amount of (b) used is preferably 5 to 80 mols, and more preferably 10 to 75 mols relative to (a) 100 mols. By setting it as this range, the storage stability of the colored curable resin composition is stable The balance of the properties, the developability during pattern formation, and the solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern tend to be good. Since the cyclic ether has high reactivity and unreacted (b) does not easily remain, the (b) used in the resin [K4] is preferably (b1), and more preferably (b1-1).

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

The reaction conditions such as the addition method, reaction temperature, and time can be appropriately adjusted in consideration of the amount of heat generated by the manufacturing equipment or polymerization. In addition, the addition method and reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the manufacturing equipment or polymerization, as with the polymerization conditions.

As for the resin [K5], as the first stage, the copolymers of (b) and (c) were obtained in the same manner as the method for producing the above-mentioned resin [K1]. In the same manner as above, the obtained copolymer may be used directly after the reaction, or may be a concentrated or diluted solution, or may be taken out as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) is preferably relative to the total number of moles of all the structural units constituting the above copolymer, which are the structural units derived from (b): 5 ~ 95 mole% Structural unit derived from (c): 5 ~ 95 mole%, more preferably structural unit derived from (b): 10 ~ 90 mole% structural unit derived from (c): 10 ~ 90 mole%.

Furthermore, under the same conditions as in the method for producing the resin [K4], the carboxylic acid or carboxylic anhydride possessed by (a) and the cyclic ether derived from (b) possessed by the copolymer of (b) and (c) were reacted. In this way, a resin [K5] can be obtained.

The amount of (a) used in the reaction with the copolymer is preferably 5 to 80 moles relative to (b) 100 moles. Since the cyclic ether has high reactivity and unreacted (b) is difficult to remain, (b) used as the resin [K5] is preferably (b1), and more preferably (b1-1).

The resin [K6] is a resin obtained by further reacting a carboxylic anhydride with a resin [K5]. The carboxylic acid anhydride is reacted with a hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetraphthalic anhydride Hydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2- Ene anhydride, etc. The amount of carboxylic acid anhydride used is 1 mole, preferably 0.5 to 1 mole, relative to the amount of (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic copolymer, and 3,4-epoxy tricyclic (meth) acrylate. [5.2.1.0 ^2.6 ] resins such as decyl ester / (meth) acrylic copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, (meth) ) Glycidyl acrylate / styrene / (meth) acrylic copolymer, 3,4-epoxy tricyclic (meth) acrylate [5.2.1.0 ^2.6 ] decyl ester / (meth) acrylic acid / N-cyclohexylcis Butene difluorene imine copolymer, 3,4-epoxy tricyclic (meth) acrylic acid [5.2.1.0 ^2.6 ] decyl / (meth) acrylic acid / vinyl toluene copolymer, 3-methyl-3- Resins such as (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymers [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymers, styrene / (Meth) acrylic copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic copolymer and other resins [K3]; add glycidyl (meth) acrylate Resin made from benzyl (meth) acrylate / (meth) acrylic copolymer, Glycidyl acrylate is added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, and glycidyl (meth) acrylate is added to (meth) Tricyclodecyl acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer resin [K4]; (meth) acrylic acid and tricyclodecyl (meth) acrylate / (formaldehyde) A resin obtained by reacting a copolymer of glycidyl acrylate and a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin and other resins [K5]; a resin obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and further reacting with tetrahydrophthalic anhydride The obtained resin [K6] and the like.

The resin (B) is preferably selected from the group consisting of the resin [K1], the resin [K2], and the resin [K3], and more preferably selected from the group consisting of the resin [K2] and the resin [K3] One kind. With these resins, the developability of the colored curable resin composition is excellent. From the viewpoint of adhesion between the colored pattern and the substrate, the resin [K2] is more preferable.

The polystyrene equivalent weight average molecular weight of the resin (B) is usually 3,000 to 100,000, preferably 5,000 to 50,000, more preferably 5,000 to 35,000, still more preferably 5,000 to 30,000, and even more preferably 6,000 to 30,000. When the molecular weight is within the above range, there is a tendency that the hardness of the coating film is increased, the residual film ratio is also high, the solubility of the unexposed portion to the developing solution is good, and the resolution of the colored pattern is improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value of the resin (B) is usually 20mg-KOH / g ~ 170mg-KOH / g, preferably 30mg-KOH / g ~ 170mg-KOH / g, more preferably 40mg-KOH / g ~ 170mg-KOH / g , And more preferably 50 mg-KOH / g to 170 mg-KOH / g. Among them, 50 mg-KOH / g to 150 mg-KOH / g is preferred, 60 mg-KOH / g to 150 mg-KOH / g is more preferred, and 60 mg-KOH / g to 135 mg-KOH / g is more preferred, and particularly preferred It is 70mg-KOH / g ~ 135mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and it can be obtained by, for example, titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 mass% to 65 mass%, more preferably 10 mass% to 60 mass%, and further preferably 13 mass% to 60 mass%, particularly preferably It is preferably 17% by mass to 55% by mass. When the content of the resin (B) is within the above range, a colored pattern tends to be easily formed, and the resolution and residual film rate of the colored pattern tend to increase.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by living radicals and / or acids generated from the polymerization initiator (D), and examples thereof include polymerizable compounds having an ethylenically unsaturated bond. The compound or the like is preferably a (meth) acrylate compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexylcarbitol acrylic acid. Esters, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the like; and (a), (a), and (c) above.

Examples of the polymerizable compound having two ethylenically unsaturated bonds include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, and neopentyl glycol di ( (Meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, and dipentaerythritol penta (meth) acrylic acid. Ester, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nine (meth) acrylate Ester, tris (2- (meth) acryloxyethyl) isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylic acid Ester, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa ( (Meth) acrylates and the like.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferred.

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 1 to 70% by mass, and more preferably 2 to 65% by mass, more preferably 5 to 65% by mass, and more preferably 7 to the total amount of solid components. ~ 65 mass%, more preferably 10 to 60 mass%, more preferably 13 to 60 mass%, and still more preferably 17 to 55 mass%.

The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20 on a mass basis, and more preferably 35: 65 ~ 80: 20.

When the content of the polymerizable compound (C) is within the above range, the residual film rate at the time of forming a colored 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 that can start polymerization by generating active radicals, acids, and the like by the action of light or heat, and a known polymerization initiator can be used.

Examples of the polymerization initiator (D) include benzoyl ketone compounds, Compounds, fluorenyl phosphine oxide compounds, O-fluorenyl oxime compounds, biimidazole compounds, and the like.

The O-fluorenyl oxime compound is a compound having a partial structure represented by formula (d1). In the following, * indicates a bond key.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-benzidine Oxy-1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) -3- Cyclopentylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl ] Ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-di Alkylcyclopentylmethoxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-ethoxyl-1- [9-ethyl-6- (2 -Methylbenzyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzyloxy-1- [9-ethyl-6- ( 2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (the above are manufactured by BASF), and N-1919 (made by ADEKA) can also be used. Among these, the O-fluorenyl oxime compound is preferably selected from the group consisting of N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine, and N-benzidine Oxy-1- (4-phenylthiophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylthiophenyl) -3- At least one of the group consisting of cyclopentylpropane-1-one-2-imine, more preferably N-benzyloxy-1- (4-phenylthiophenyl) octane-1 -Keto-2-imine.

The benzoalkyl ketone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In 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- Phenyl-1- (4-methylthiophenyl) propane-1-one, 2-dimethylamino-1- (4- Phenylphenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4- Phenyl) phenyl] butane-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above manufactured by BASF) can also be used.

Examples of the compound having a partial structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-hydroxy-2-methyl-1- [4 -(2-hydroxyethoxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1 -Oligomers of ketones, α, α-diethoxyacetophenone, benzophenone dimethyl ketal and the like.

In terms of sensitivity, as the benzoalkyl ketone compound, it is preferable to have a formula (d2) A compound of partial structure indicated.

The biimidazole compound is, for example, a compound represented by formula (d5).

[In the formula (d5), R ⁵¹ to R ⁵⁶ represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolylmethyl, xylyl, ethylphenyl, and naphthyl, and phenyl is preferred.

Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A chlorine atom is preferred. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferred.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (for example, refer to JPH06-75372-A, JPH06-75373-A, etc.) Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (alkoxyphenyl) ) Biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chloro (Phenyl) -4,4 ', 5,5'-tetrakis (trialkoxyphenyl) biimidazole (for example, see JPS48-38403-B, JPS62-174204-A, etc.) An imidazole compound in which the phenyl group at the -position is substituted with a carboalkoxy group (for example, refer to JPH07-10913-A). Among them, a compound represented by the following formula and a mixture thereof are preferred.

As above three Examples of the compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-sunfloweryl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylidenediphenylphosphine oxide and the like.

Further, 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 and methyl benzophenethylbenzoate , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetrakis (third butylperoxycarbonyl) di Benzophenone compounds such as benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone and other quinone compounds; 10-butyl-2 -Chloroacridone, benzodiazone, methyl phenylglyoxylate, titanocene compound and the like. These are preferably used in combination with the following polymerization initiation aid (D1) (especially amines).

The polymerization initiator (D) preferably contains a compound selected from the group consisting of The polymerization initiator of at least one of the group consisting of a compound, a fluorenylphosphine oxide compound, an O-fluorenyl oxime compound, and a biimidazole compound, more preferably a polymerization initiator containing an O-fluorenyl oxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, and more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is 1 to 30 parts by mass.

<Polymerization starter (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer for promoting the polymerization of a polymerizable compound that is polymerized by a polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, and 9-oxosulfur. Compounds and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4, 4'-bis (dimethylamino) benzophenone (commonly known as Michelin), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis (ethyl Methylamino) benzophenone and the like, among them, 4,4′-bis (diethylamino) benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the above 9-oxysulfur Compounds, including: 2-isopropyl-9-oxysulfur 4-isopropyl-9-oxysulfur , 2,4-diethyl-9-oxysulfur , 2,4-dichloro-9-oxysulfur , 1-chloro-4-propoxy-9-oxysulfur Wait.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioethyl Acid, dichlorophenylthioglycolic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid, naphthyloxyacetic acid, and the like.

When using these polymerization initiation aids (D1), the content is 100 parts by mass with respect to the total amount of the resin (B) and the polymerizable compound (C), preferably 0.1 to 30 parts by mass, and more preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, there is a tendency that a colored pattern can be formed with high sensitivity, and the productivity of a color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and solvents commonly used in this field can be used. Examples include: ester solvents (solvents containing -COO- without -O- in the molecule), ether solvents (solvents containing -O- without -COO- in the molecule), ether ester solvents (in the molecule Solvents containing -COO- and -O-), ketone solvents (solvents containing -CO- without -COO- in the molecule), alcohol solvents (containing OH without -O-, -CO in the molecule) -And -COO- solvents), aromatic hydrocarbon solvents, amidine solvents, dimethyl sulfene, and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetate, ethyl acetate, cyclamate Hexanol acetate, γ-butyrolactone and the like.

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether, methyl Anisole and so on.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate , Ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol Monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.

Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, and 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone, isophorone and so on.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

Examples of the amidine solvents include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

These solvents may be used alone or in combination of two or more.

Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, and diethylene glycol are preferred. Monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-di Methylformamide, N-methylpyrrolidone and the like, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethyl Methylformamide, N-methylpyrrolidone and the like.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 92% by mass based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, and more preferably 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating tends to be good, and the color density is not insufficient when the color filter is formed, so that the display characteristics become good.

<Leveling agent (F)>

Examples of the leveling agent (F) include a polysiloxane-based surfactant, a fluorine-based surfactant, and a polysiloxane-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the polysiloxane-based surfactant include a surfactant having a silicon-oxygen bond in the molecule. Specific examples include: Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: Dow Corning Toray Co., Ltd.) , KP321, KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 Momentive Performance Materials Japan).

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples include: Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Precision Chemical Research Institute Co., Ltd.).

Examples of the polysiloxane-based surfactant having a fluorine atom include a surfactant having a silicon-oxygen bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Corporation).

The content of the leveling agent (F) is preferably 0.0005 mass% or more and 0.6 mass% or less, more preferably 0.001 mass% or more and 0.5 mass% or less, and more preferably 0.001% with respect to the total amount of the coloring curable resin composition. Mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, even more preferably 0.005 mass% or more and 0.07 mass% or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be made good.

<Other ingredients>

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

<Manufacturing method of colored curable resin composition>

The coloring curable resin composition of the present invention can be prepared by, for example, coloring agent (A), resin (B), polymerizable compound (C), polymerization initiator (D), and solvent (E) as needed, A leveling agent (F), a polymerization initiation aid (D1), and other components are prepared by mixing.

In the case where the pigment (P) is contained, the pigment is preferably partially or fully mixed with the solvent (E) in advance, and dispersed using a ball mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less. In this case, a part or all of the pigment dispersant and the resin (B) may be blended if necessary. Residual components are mixed in the pigment dispersion liquid obtained in this way so as to have a specific concentration, whereby the intended colored curable resin composition can be prepared.

The compound (1) is preferably prepared by dissolving a part or all of the solvent (E) in advance to prepare a solution. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.

It is preferable to filter the colored hardening resin composition after mixing with a filter having a pore size of about 0.01 to 10 μm.

<Manufacturing method of color filter>

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithography method, an inkjet method, and a printing method. Among them, photolithography is preferred. The photolithography method is a method in which the colored curable resin composition is coated on a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film, which is a hardened product of the coloring composition layer described above, can be formed without using a mask and / or developing during exposure. The colored pattern or colored coating film thus formed is the color filter of the present invention.

The film thickness of the produced color filter is not particularly limited, and can be appropriately adjusted according to the purpose or application, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, and soda-lime glass coated with silicon dioxide can be used. Polycarbonate, polymethyl methacrylate, and polyterephthalic acid can be used. Resin plates, such as ethylene glycol, and silicon, are formed on the substrate with aluminum, silver, silver / copper / palladium alloy films, or the like. Another color filter layer, resin layer, transistor, circuit, etc. can also be formed on these substrates.

The formation of the pixels of each color by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows.

First, a colored curable resin composition is coated on a substrate, and volatile components such as solvents are removed by drying under heat (pre-baking) and / or reduced pressure to dry, thereby obtaining a smooth colored composition layer.

Examples of the coating method include a spin coating method, a slit coating method, a slit and Spin coating method and the like.

In the case of heating and drying, the temperature is preferably 30 to 120 ° C, and more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably carried out under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.

The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Then, the coloring composition layer is exposed through a mask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used.

As a light source for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferred. For example, light below 350 nm can be cut off with a filter that cuts off that wavelength region, or light near 436 nm, 408 nm, and 365 nm can be cut by a band-pass filter that takes out those wavelength regions. Selectively remove. Specific examples include a mercury lamp, a light-emitting diode, a metal halide lamp, and a halogen lamp.

In order to uniformly radiate parallel light to the entire exposure surface, or to align the mask with the correct position of the substrate on which the coloring composition layer is formed, it is preferable to use a mask aligner and stepping method. Exposure equipment such as an exposure machine (stepper).

A coloring pattern is formed on a substrate by developing the coloring composition layer after exposure with a developing solution. The unexposed portion of the coloring composition layer can be dissolved in a developing solution and removed by development. The developing solution is preferably an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, tetramethylammonium hydroxide, and the like. The concentration of the basic compound in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, and even more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain a surfactant.

The developing method may be any one of a puddle method, a dipping method, a spray method, and the like. Furthermore, the substrate can be tilted to an arbitrary angle during development. degree.

After development, washing with water is preferred.

Furthermore, it is preferable to post-bake the obtained colored pattern. The post-baking temperature is preferably 150 to 250 ° C, and more preferably 160 to 235 ° C. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

According to the colored curable resin composition of the present invention, it is possible to produce a color filter with a sublimation of a colorant and a particularly high brightness. This color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL (Electroluminescence) device, an electronic paper, etc.) and a solid-state imaging element.

Examples

Next, the present invention will be further specifically described with examples and the like.

In the examples and comparative examples, the percentages and parts indicating the content or the amount used are the basis of quality unless otherwise specified.

In the following examples, the structure of the compound is analyzed by NMR (Nuclear Magnetic Resource, nuclear magnetic resonance) (JMM-ECA-500; manufactured by Japan Electronics Co., Ltd.) or mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; Agilent Manufactured LC / MSD6130).

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC (Gel Permeation Chromatography, gel permeation chromatography) method under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

Column: TSK-GEL G2000HXL

Column temperature: 40 ℃

Solvent: THF (tetrahydrofuran)

Flow rate: 1.0mL / min

Concentration of solid content of test liquid: 0.001 ~ 0.01% by mass

Injection volume: 50 μL

Detector: RI (Refractive Index, refractive index)

Calibration reference materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

The ratio of the weight-average molecular weight and the number-average molecular weight (Mw / Mn) in terms of polystyrene obtained in the above was defined as the molecular weight distribution.

Synthesis Example 1

10.0 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 12.8 parts of 4- (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and benzoic acid (Tokyo 2.73 parts of Chemical Industry Co., Ltd., 157 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 7.43 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. 3 hours. Added 7.46 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.79 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 49.8 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4- 12.7 parts of (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 14 hours. Add 3.76 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.41 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 52.5 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4- (Diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) 6.35 parts, and stirred at 120 ° C for 8 hours. After the reaction solution was cooled to room temperature, the residue was filtered by suction to obtain precipitated crystals. To this residue was added 140 parts of tetrahydrofuran, and the mixture was stirred at 70 ° C. for 1 hour, and then the residue was filtered by suction to obtain an insoluble matter. 120 parts of tetrahydrofuran was added to the residue, and the mixture was stirred at 70 ° C. for 1 hour, and then the residue was filtered by suction to obtain an insoluble matter. To this residue was added 340 parts of N, N-dimethylformamide, and the mixture was heated to 90 ° C to dissolve it, and then allowed to stand at 0 ° C to 5 ° C. Precipitated crystals were obtained by suction filtration of the residue. This residue was dried under reduced pressure at 60 ° C to obtain 5.69 parts of a compound represented by formula (1-1). The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (1-1)>

¹ H-NMR (500MHz, DMSO-d6): 1.14 (6H, t), 3.47 (4H, q), 6.57 (1H, d), 6.78 (1H, dd), 7.68 (1H, d), 7.79 (1H , d), 7.96 (1H, dd), 8.15 (1H, d), 8.80 (1H, s), 13.11 (1H, s).

Synthesis Example 2

24.8 parts of 4- (dibutylamino) salixaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.3 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and benzoic acid (Tokyo 4.20 parts of Chemical Industry Co., Ltd., 242 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 11.3 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. 5 hours. Added 4.61 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.70 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4- (dibutylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) (Manufactured) 10.1 parts and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 3 hours. Added 4.60 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.70 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4- (dibutylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) (Manufactured) 10.2 parts and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 3 hours. Added 4.61 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.71 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4- (dibutylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) (Manufactured) 10.3 parts, and stirred at 120 ° C for 18 hours. The reaction solution was cooled to room temperature, and then added to 1900 parts of hexane and stirred. Precipitated crystals were obtained by suction filtration of the residue. 328 parts of tetrahydrofuran was added to the residue, and recrystallization was performed at 60 ° C. Precipitated crystals were obtained by suction filtration of the residue. To this residue, 160 parts of tetrahydrofuran was added and stirred, and the residue was filtered by suction to obtain an insoluble matter. This residue was dried under reduced pressure at 60 ° C to obtain 18.9 parts of a compound represented by formula (1-3). The structure was confirmed by ¹ H-NMR.

<Identification of compound represented by formula (1-3)>

¹ H-NMR (500MHz, DMSO-d6): 0.92 (6H, t), 1.34 (4H, qt), 1.54 (4H, tt), 3.41 (4H, t), 6.56 (1H, d), 6.78 (1H , dd), 7.69 (1H, d), 7.80 (1H, d), 7.98 (1H, dd), 8.17 (1H, d), 8.82 (1H, s), 13.11 (1H, s).

Synthesis Example 3

4.32 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4- (bis (2-ethylhexyl) amino) salicaldehyde (according to Japanese Patent Publication No. 2007-508275) 10.2 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.18 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) (Production) 3.19 parts were mixed and stirred at 120 ° C for 3 hours. To this reaction solution was added 4- (bis (2-ethylhexyl) amino) salixaldehyde (depending on day (Synthesized by the method described in this patent special table 2007-508275) 15.3 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.80 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.0 parts and cyanoacetic acid 4.80 parts of ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 12 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off by a rotary evaporator to obtain a residue. This residue was purified by column chromatography to obtain 6.32 parts of a compound represented by formula (1-15).

<Identification of compound represented by formula (1-15)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 547.3

Exact Mass: 546.3

Synthesis Example 4

275 parts of resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 101 parts of n-hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the generated water was removed at 150 to 155 ° C and stirred for 20 hours. . After allowing to cool, the reaction mixture was dissolved in 433 parts of toluene, and the toluene solution was washed three times with 1,000 parts of water. To this toluene solution, 50 parts of anhydrous magnesium sulfate was added and stirred, and then filtered. The solvent of the filtrate was distilled off to obtain a crude product. This crude product was dissolved in 234 parts of toluene, and stirred at 0 ° C or lower, and the crystallized product was collected by filtration. This crystallized product was dried under reduced pressure at 50 ° C to obtain 95.7 parts of a compound represented by formula (pt1).

<Identification of compound represented by formula (pt1)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 194.2

Exact molecular weight: 193.2

95.3 parts of the compound represented by formula (pt1) and 48.0 parts of water were mixed and stirred at 80 ° C. Next, 107 parts of 1-bromo-2-ethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and after stirring at 80 ° C for 3 hours, 22.4 parts of a 48% sodium hydroxide aqueous solution was added. The mixture was stirred at 110 ° C for 18 hours. After allowing to cool, the pH of the reaction mixture was adjusted to 5 using a 10% sodium hydroxide aqueous solution, 130 parts of toluene was added and stirred, and the toluene layer was extracted. The toluene extract was washed twice with 500 parts of water, 25.0 parts of anhydrous magnesium sulfate was added, stirred, and filtered. The solvent of the filtrate was distilled off to obtain 154 parts of a residue containing a compound represented by the formula (pt2) as a main component.

<Identification of compound represented by formula (pt2)>

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 306.3

Exact molecular weight: 305.3

154 parts of the residue containing the obtained compound represented by the formula (pt2) as a main component It was mixed with 597 parts of N, N-dimethylformamidine and stirred at -6 ° C to 3 ° C. While maintaining the liquid temperature at -6 ° C to 3 ° C, 258 parts of phosphatidyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto. After the mixture was stirred at room temperature for 1 hour, it was stirred at 60 ° C for 4 hours. After allowing to cool, the reaction mixture was added to 1500 parts of ice, and neutralized with a 48% sodium hydroxide aqueous solution. 867 parts of toluene was added thereto, and the toluene layer was extracted. This toluene extract was washed twice with 1,200 parts of a 15% sodium chloride aqueous solution. After adding 60.0 parts of anhydrous magnesium sulfate to this toluene extract, the mixture was stirred, and then filtered. The solvent of the filtrate was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 94.4 parts of a compound represented by formula (pt3).

<Identification of compound represented by formula (pt3)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 334.3

Exact molecular weight: 333.3

6.89 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.0 parts of a compound represented by formula (pt3), 1.87 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1- 110 parts of amyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.09 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C for 3 hours. In this reaction solution, 22.5 parts of a compound represented by formula (pt3), 2.85 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and cyanoacetic acid were mixed. 7.66 parts of ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 12 hours. Cool the reaction solution to After room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 8.86 parts of a compound represented by formula (1-17).

<Identification of compound represented by formula (1-17)>

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 519.3

Exact molecular weight: 518.3

Synthesis Example 5

64.5 parts of 2-ethylhexylamine was added to 138 parts of resorcinol, and the mixture was stirred for 18 hours while removing the generated water at 150 ° C to 155 ° C. After allowing to cool, 250 parts of toluene was added to the reaction mixture, and the reaction mixture was washed three times with 500 parts of water. 20.0 parts of anhydrous magnesium sulfate was added to this toluene solution, and after stirring, it filtered. The solvent of the filtrate was distilled off to obtain 113 parts of a residue containing a compound represented by the formula (pt4) as a main component.

<Identification of compound represented by formula (pt4)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 222.2

Exact molecular weight: 221.2

23.0 parts of water was added to 58.5 parts of the residue containing the compound represented by formula (pt4) as a main component, and the liquid temperature was 60 ° C. while stirring. Add at this temperature Add 39.3 parts of diethyl sulfate and 10.6 parts of a 48% aqueous sodium hydroxide solution and stir for 9 hours. Then, it stirred at 60 degreeC for 5 hours. After allowing to cool, the reaction mixture was neutralized with a 10% sodium hydroxide aqueous solution, and 300 parts of toluene was added. This toluene solution was washed three times with 500 parts of water. 20.0 parts of anhydrous magnesium sulfate was added to this toluene solution, and after stirring, it filtered. The solvent of the filtrate was distilled off to obtain 67.5 parts of a residue containing a compound represented by the formula (pt5) as a main component.

<Identification of compound represented by formula (pt5)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 250.2

Exact molecular weight: 249.2

323 parts of N, N-dimethylformamide was added to 67.5 parts of the obtained residue containing the compound represented by formula (pt5) as a main component. While maintaining the temperature of the mixed solution at -6 ° C to 4 ° C, 105 parts of phosphorus oxychloride was added. After the temperature of the reaction solution was returned to room temperature and stirred for 1 hour, the temperature of the reaction solution was raised to 60 ° C and stirred for 3 hours. After allowing to cool, the reaction mixture was added to 1,500 parts of ice water, and a 48% sodium hydroxide aqueous solution was added while stirring to neutralize. 500 parts of toluene was added thereto, and the toluene layer was extracted. This toluene solution was washed with 1,000 parts of water. Then, this toluene solution was washed with 1500 parts of a saturated sodium chloride aqueous solution. 25.0 parts of anhydrous magnesium sulfate was added to this toluene solution, and after stirring, it filtered. The solvent of the filtrate was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 36.7 parts of a compound represented by formula (pt6).

<Identification of compound represented by formula (pt6)>

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 278.2

Exact molecular weight: 277.2

8.28 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.0 parts of the compound represented by formula (pt6), 2.25 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1- 130 parts of amyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 6.12 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C for 3 hours. In the reaction solution, 22.5 parts of a compound represented by formula (pt6), 3.40 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and cyanoacetic acid were mixed. 9.20 parts of ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 12 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 8.75 parts of a compound represented by formula (1-19).

<Identification of compound represented by formula (1-19)>

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 463.2

Exact molecular weight: 462.2

Synthesis Example 6

8.01 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2-hydroxy-4- (pyrrolidin-1-yl) benzaldehyde (according to Chem. Commun. 2011, 47, 2435) (Synthesis) 10.0 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.18 Parts, 127 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.91 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C for 3 hours. To this reaction solution were mixed 15.0 parts of 2-hydroxy-4- (pyrrolidin-1-yl) benzaldehyde (synthesized according to Chem. Commun. 2011, 47, 2435.), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.30 parts, 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.90 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C. for 12 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 6.50 parts of a compound represented by formula (1-39).

<Identification of compound represented by formula (1-39)>

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 377.1

Exact molecular weight: 376.1

Synthesis Example 7

9.21 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 8-hydroxy 13.1 parts of 8-Hydroxyjulolidine-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.51 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1-pentanol (Tokyo Chemical Industry Co., Ltd.) 145 parts of Co., Ltd.) and 6.80 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C for 3 hours. Added 10.2 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.80 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 8-hydroxyl 19.6 parts of pyridin-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C. for 12 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off by a rotary evaporator to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (1-5).

Synthesis Example 8

9.21 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 8-hydroxy-1,1,7,7-tetramethyl 16.4 parts of pyridin-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.51 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 145 parts of 1-pentanol (made by Tokyo Chemical Industry Co., Ltd.) 6.80 parts of ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C for 3 hours. Added 10.2 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.80 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 8-hydroxy-1,1,7,7-tetramethyl 24.7 parts of pyridin-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 12 hours. After the reaction solution was cooled to room temperature, the solvent was distilled off by a rotary evaporator to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (1-7).

Synthesis Example 9

Pass a proper amount of nitrogen into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to form a nitrogen atmosphere. Add 100 parts of propylene glycol monomethyl ether acetate, and heat to 85 ° C while stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decane-8-ester, and 3,4-acrylic acid were added dropwise to the flask using a dropping pump over about 5 hours. An epoxy tricyclo [5.2.1.0 ^2.6 ] decane-9-ester mixture (containing a molar ratio of 50:50) 171 parts was dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, 26 parts of the polymerization initiator 2,2'-azobis (2,4-dimethylvaleronitrile) was dissolved in propylene glycol monomethyl ether dropwise into the flask using another drop pump over about 5 hours. A solution of 120 parts of acetate. After the dropwise addition of the polymerization initiator was completed, it was kept at this temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B1) having a solid content of 43.5%. The weight average molecular weight of the obtained resin B1 was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid content was 53 mgKOH / g.

[Preparation of colored curable resin composition] Example 1

Colorant (A): 27 parts of CI Pigment Green 7 (pigment), 12 parts of acrylic pigment dispersant, resin (B): 9.5 parts of resin B1 (solid content conversion), and solvent (E): propylene glycol monomethyl 180 parts of ether acetate were mixed, and the pigment was sufficiently dispersed using a ball mill to obtain a pigment dispersion liquid; colorant (A): 3.0 parts of the compound represented by formula (1-15), resin (B): resin B1 (solid form 40 parts, polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts, polymerization initiator (D): N-benzyl Ethoxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation; O-fluorenyl oxime compound) 9.8 parts Solvent (E): 670 parts of propylene glycol monomethyl ether acetate, and Leveling agent (F): Polyether-modified polysiloxane (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.15 parts

These were mixed to obtain a colored curable resin composition.

Example 2

A colored curable resin composition was obtained in the same manner as in Example 1 except that C.I. Pigment Green 7 (pigment) of the colorant (A) was replaced with C.I. Pigment Green 36 (pigment).

Example 3

A colored curable resin composition was obtained in the same manner as in Example 1 except that C.I. Pigment Green 7 (pigment) of the colorant (A) was replaced with C.I. Pigment Green 58 (pigment).

[Measurement of film thickness]

As for the film thickness, the film thickness was measured using DEKTAK3 manufactured by Japan Vacuum Technology Co., Ltd.

[Preparation of resin composition (SJS) for sublimation test]

Resin: methacrylic acid / benzyl methacrylate (mol ratio: 30/70) copolymer (manufactured by Taoka Chemical Industry Co., Ltd., average molecular weight 10700, acid value 70mgKOH / g) 33.8% propylene glycol monomethyl ether acetic acid 40.2 parts of an ester solution, polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts, polymerization initiator: N-benzyloxy-1- (4 -Phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE01; manufactured by BASF Japan) 0.58 part, leveling agent: polyether modified polysiloxane (Toray Silicone SH8400 ; Manufactured by Dow Corning Toray Co., Ltd.) 0.01 parts, solvent: 46.6 parts of propylene glycol monomethyl ether, and solvent: 6.8 parts of propylene glycol monomethyl ether acetate

These were mixed to obtain a resin composition (SJS) for a sublimation test.

[Formation of Sublimation Test Resin Coating Film (SJSM)]

On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), the above-obtained sublimation test resin composition (SJS) was applied by a spin coating method, and the volatile components were volatilized at 100 ° C for 3 minutes. . After cooling, light exposure was performed using 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 atmospheric environment. It heated at 220 degreeC in the oven for 2 hours, and formed the resin coating film (SJSM) for sublimation test (film thickness 2.2 micrometers).

Example 4 [Preparation of coloring pattern and evaluation of sublimation property]

The colored hardening resin composition obtained in Example 1 was applied on a 2-inch square glass substrate (Eagle XG; manufactured by Corning) by a spin coating method, and then pre-baked at 100 ° C for 3 minutes. To form a coloring composition layer. After cooling, the substrate is formed of a colored composition layer and the spacer photomask made of quartz glass is set to 200 m, using an exposure machine (TME-150RSK; TOPCON Co., Ltd.), under the atmosphere at 80 mJ / cm ² of The exposure was performed (based on 365 nm). In addition, as the photomask, a 100 μm line and gap pattern was used. The coloring composition layer after exposure was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for 70 seconds for development, and then washed with water. The film thickness was measured. The results are shown in Table 1.

This colored coating film and the resin coating film (SJSM) for sublimation test obtained above were opposed to each other with a gap of 70 μm, and then baked at 220 ° C. for 40 minutes to obtain a colored pattern. The color difference (ΔEab *) of the resin coating film (SJSM) for sublimation test before and after heating was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). A color difference (ΔEab *) of 5.0 or more indicates that the colorant has sublimability. The results are shown in Table 1. In Table 1, in each of the examples, ○ indicates that the colorant does not have sublimability, and X indicates that the colorant has sublimability.

Example 5 to Example 6

A colored pattern was obtained in the same manner as in Example 4 except that the colored curable resin composition obtained in Example 1 was replaced with the colored curable resin composition obtained in Example QQ. In addition, sublimation evaluation was performed. The results are shown in Table 1. The above-mentioned embodiments QQQ respectively represent the embodiments QQQ shown in Table 1.

Comparative Example 1

Colorant (A): Coumarin 6 3.6 parts, Resin (B): Resin (B1) (solid content conversion) 180 parts, Solvent (E): Propylene glycol monomethyl ether acetate 230 parts, Solvent (E): 590 parts of N, N-dimethylformamide, and leveling agent (F): polyether-modified polysiloxane (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.063 parts

They were mixed to obtain a colored resin composition.

Comparative Example 2 [Sublimation evaluation]

On a 2-inch square glass substrate (Eagle XG; manufactured by Corning), the colored resin composition obtained in Comparative Example 1 was applied by a spin coating method, and then pre-baked at 100 ° C for 3 minutes, and A colored composition layer is formed. The film thickness was measured using DEKTAK3 manufactured by Japan Vacuum Technology Co., Ltd., and it was 1.9 μm. The colored coating film and the resin coating film for sublimation test (SJSM) obtained as described above were opposed to each other with a gap of 70 μm, and the baking was performed at 220 ° C. for 40 minutes. The color difference (ΔEab *) of the resin coating film (SJSM) for sublimation test before and after heating was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). As a result, the color difference (ΔEab *) was 5.0 or more. A color difference (ΔEab *) of 5.0 or more indicates that the colorant has sublimability.

From the above results, it was confirmed that the present invention can provide a coloring curable resin composition which forms a color filter without sublimation.

According to the present invention, it is possible to provide a coloring curable resin composition that forms a color filter without sublimation of the colorant, and the color filter can be preferably used for display devices such as a liquid crystal display device.

Claims (11)

A colored hardening resin composition comprising a compound represented by the formula (1), a resin, a polymerizable compound, and a polymerization initiator. The content of the compound represented by the formula (1) with respect to the total amount of the solid components is 0.0001% by mass to 89.1% by mass, the content of the polymerizable compound is 1 to 70% by mass based on the total amount of the solid components, and the content of the polymerization initiator is 100 parts by mass relative to the total amount of the resin and the polymerizable compound. 0.1 to 40 parts by mass, [In formula (1), Q ¹ and Q ² each independently represent a hydrogen atom or -CO ₂ M, wherein any one of Q ¹ and Q ² represents -CO ₂ M; R ¹ to R ⁴ each independently represent A hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ^{3 are} bonded to form a ring with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring, and R ² and R ^{4 are} bonded to be adjacent The carbon atom on the benzene ring and the adjacent nitrogen atom form a ring together, or R ¹ and R ^{2 are} bonded to form a ring with the adjacent nitrogen atom; the methylene group constituting the monovalent hydrocarbon group may pass an oxygen atom and a sulfur atom. , -N (R ⁵ )-, sulfofluorenyl or carbonyl, the hydrogen atom contained in the monovalent hydrocarbon group may be halogen atom, cyano, nitro, carbamoyl, sulfamoyl, -SO ₃ M , -CO ₂ M, hydroxyl or amine group substitution; R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; when there are a plurality of R ⁵ , these are the same or different from each other; M represents a hydrogen atom or Alkali metal atom]. The colored curable resin composition according to claim 1, wherein R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ^{3 are} bonded to an adjacent benzene ring The carbon atom and the adjacent nitrogen atom form a ring together, or R ² and R ^{4 are} bonded to form a ring with the carbon atom on the adjacent benzene ring and the adjacent nitrogen atom. The colored curable resin composition according to claim 1 or 2, wherein R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ^{3 are} bonded to an adjacent benzene The carbon atom on the ring and the adjacent nitrogen atom form a ring together, and R ² and R ^{4 are} bonded to form a ring with the carbon atom on the adjacent benzene ring and the adjacent nitrogen atom. The colored curable resin composition as claimed in claim 1 or 2, further comprising a pigment. The colored curable resin composition according to claim 4, wherein the pigment is at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment. The colored curable resin composition according to claim 5, wherein the pigment is at least one selected from the group consisting of a copper chloride phthalocyanine pigment, a copper bromide phthalocyanine pigment, and a zinc bromide phthalocyanine pigment. The coloring curable resin composition according to claim 4, wherein the pigment is a green pigment. The coloring curable resin composition according to claim 7, wherein the pigment is at least one selected from the group consisting of C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 58. The coloring curable resin composition according to claim 8, wherein the pigment is C.I. Pigment Green 7. A color filter formed by using the coloring curable resin composition according to any one of claims 1 to 9. A liquid crystal display device includes a color filter as claimed in claim 10.