TW201343801A - Colored curable resin composition - Google Patents

Abstract

A colored curable resin composition comprising a compound of the formula (1), a resin, a polymerizable compound and a polymerization initiator; wherein Q1 and Q2 each independently represent a hydrogen atom or -CO2M with the proviso that either of Q1 and Q2 represents -CO2M, R1 to R4 each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms or R1 and R3 bond to form a ring together with carbon atoms on the adjoining benzene ring and with an adjoining nitrogen atom or R2 and R4 bond to form a ring together with carbon atoms on the adjoining benzene ring and with an adjoining nitrogen atom, the methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N(R5)-, a sulfonyl group or a carbonyl group, the hydrogen atom contained in the monovalent hydrocarbon group may be substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a sulfamoyl group, SO3M, -CO2M, a hydroxy group or an amino group, R5 represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and where a plurality of R5 present, they are mutually the same or different, and M represents a hydrogen atom or an alkali metal atom.

Description

Colored curable resin composition

The present invention relates to a color hardening resin composition.

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

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

The invention includes the following invention.

[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 the formula (1), Q ¹ and Q ² each independently represent a hydrogen atom or -CO ₂ M, and any of Q ¹ and Q ² represents -CO ₂ M; and 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 bonded to form a ring together with a carbon atom on the adjacent benzene ring and an adjacent nitrogen atom, and R ² and R ^{4 are} bonded to each other. 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 together with the adjacent nitrogen atom; the methylene group constituting the monovalent hydrocarbon group may be through an oxygen atom or a sulfur atom. -N(R ⁵ )-, a sulfonyl group or a carbonyl group, the hydrogen atom contained in the monovalent hydrocarbon group may be through a halogen atom, a cyano group, a nitro group, an aminomethyl group, an amine sulfonyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group or an amine group; R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; when a plurality of R ⁵ are present, 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 each other and adjacent thereto. 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 together with a carbon atom on the adjacent benzene ring and an adjacent nitrogen atom.

[3] The colored curable 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 a bond of R ¹ and R ³ And a carbon atom on the adjacent benzene ring and the adjacent nitrogen atom form a ring, and R ² and R ^{4 are} bonded to form a ring together with the carbon atom on the adjacent benzene ring and the adjacent nitrogen atom.

[4] The colored curable resin composition according to any one of [1] to [3], which further comprises 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 curable resin composition according to [4] or [5] wherein the pigment is selected from the group consisting of copper chloride phthalocyanine pigment, copper bromide phthalocyanine pigment, and 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 curable 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] A colored curable resin composition according to [8], wherein the pigment is C.I. Pigment Green 7.

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

[11] A liquid crystal display device comprising the color filter of [10].

According to the present invention, it is possible to provide a color-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 the 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 the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds unless otherwise specified.

<Colorant (A)>

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

The compound (1) also contains a tautomer thereof 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.

In the formula (1), examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁴ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, and a 1-propenyl group. 2-propenyl, butyl, isobutyl, t-butyl, tert-butyl, (2-ethyl)butyl, 2-butenyl, 1,3-butadienyl, pentyl, iso Pentyl, 3-pentyl, neopentyl, third amyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, (3-ethyl)pentyl, hexyl, isohexyl , 5-methylhexyl, (2-ethyl)hexyl, heptyl, (3-ethyl)heptyl, octyl, decyl, decyl, undecyl, dodecyl, octadecyl An aliphatic hydrocarbon group; 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 An alicyclic hydrocarbon group such as cyclohexyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl; benzene Base, o-tolyl, m-tolyl, p-tolyl, xylyl, 2,4,6-trimethylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-cumyl, benzyl, benzene An aromatic hydrocarbon group such as an ethyl group, a biphenyl group, a 1-naphthyl group or a 2-naphthyl group; and a group formed by the combination of the above.

The methylene group constituting the monovalent hydrocarbon group is substituted with an oxygen atom, a sulfur atom, a -N(R ⁵ )-, a sulfonyl group or a carbonyl group, or a hydrogen atom contained in the monovalent hydrocarbon group is passed through a halogen atom, a cyano group or a nitrate atom. A group obtained by substituting a group of an aminomethyl group, an amine sulfonyl group, a -SO ₃ M, a -CO ₂ M, a hydroxyl group or an amine group, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropyl group. An alkoxy group such as an oxy group, a butoxy group, an isobutoxy group, a second butoxy group, a third butoxy group, a pentyloxy group or a (2-ethyl)hexyloxy group; an aryloxy group such as a phenoxy group; An aralkoxy group such as a benzyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group or a propoxycarbonyl group; a decyloxy group such as an ethoxycarbonyl group or a benzhydryloxy group; and an N-methylamine group; Indenyl, N-ethylamine, mercapto, N-propylamine, mercapto, N-isopropylamine, N-butylamine, N-isobutylamine, N-isobutylamine N-tert-butylamine-methyl sulfhydryl, N-t-butylamine, decyl, N-pentylamine, fluorenyl, N-(1-ethylpropyl)amine, fluorenyl, N-(1 ,1-dimethylpropyl)aminecarboxymethyl, N-(1,2-dimethylpropyl)aminecarbamyl, N-(2,2-dimethylpropyl)aminecarbamyl, N-(1-methylbutyl)amine Indenyl, N-(2-methylbutyl)amine, mercapto, N-(3-methylbutyl)amine, mercapto, N-cyclopentylamine, mercapto, N-hexylamine, mercapto , N-(1,3-dimethylbutyl)amine, mercapto, N-(3,3-dimethylbutyl)amine, mercapto, N-heptylamine, mercapto, N-(1 -Methylhexyl)amine,carboxylidene, N-(1,4-dimethylpentyl)amine,carboxylidene, N-octylamine,carboxylidene, N-(2-ethylhexyl)amine,carbenyl N-substituted amine mercapto group such as N-(1,5-dimethyl)hexylamine-methyl indenyl or N-(1,1,2,2-tetramethylbutyl)amine indenyl; N , N-dimethylaminecarbamyl, N,N-ethylmethylamine, mercapto, N,N-diethylamine, N,N-propylmethylamine, mercapto, N , N-isopropylmethylamine-methyl sulfhydryl, N,N-tert-butylmethylamine, fluorenyl, N,N-butylethylamine, fluorenyl, N,N-bis(1-methylpropane N,N-2 substituted amine carbenyl group such as N-N-h-heptylmethylamine methyl sulfonyl group, N,N-bis(2-ethylhexyl)aminomethane group; N- Methylamine sulfonyl, N-ethylamine sulfonyl, N-propylamine sulfonyl, N-isopropylamine sulfonyl, N-butylamine sulfonyl, N-isobutylamine Sulfonyl, N-second butylamine sulfonyl, N-tert-butylamine Sulfhydryl, N-pentylamine sulfonyl, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonyl, N-(1, 2-dimethylpropyl)aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)aminesulfonyl, N-(2 -Methylbutyl)aminesulfonyl, N-(3-methylbutyl)aminesulfonyl, N-cyclopentylaminesulfonyl, N-hexylaminesulfonyl, N-(1,3 - dimethylbutyl)amine sulfonyl, N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1-methylhexyl)amine sulfonate Sulfhydryl, N-(1,4-dimethylpentyl)amine sulfonyl, N-octylamine sulfonyl, N-(2-ethylhexyl)amine sulfonyl, N-(1,5 N-substituted sulfonyl group such as N-dimethyl)hexylamine sulfonyl, N-(1,1,2,2-tetramethylbutyl)amine sulfonyl; N,N-dimethylamine Sulfonyl, N,N-ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N-propylmethylamine sulfonyl, N,N-isopropyl Amidoxime, N,N-t-butylmethylaminesulfonyl, N,N-butylethylaminesulfonyl, N,N-bis(1-methylpropyl)aminesulfonyl, N,N-heptylmethylamine sulfonyl, N,N-bis(2-ethylhexyl)amine sulfonyl and other N,N-2 substituted amines Sulfhydryl; N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamino, N-isobutylamino, N- Dibutylamino, N-tert-butylamino, 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 , N-(3,3-dimethylbutyl)amino, N-heptylamino, N-(1-methylhexyl)amino, N-(1,4-dimethylpentyl) Amino, N-octylamino, N-(2-ethylhexyl)amino, N-(1,5-dimethyl)hexylamino, N-(1,1,2,2-tetramethyl N-alkylamino group such as butyl)amino group; N,N-dimethylamino group, N,N-ethylmethylamino group, N,N-diethylamino group, N,N-propyl Methylamino, N,N-isopropylmethylamino, N,N-tert-butylmethylamino, N,N-butylethylamino, N,N-bis(1-methyl N,N-dialkylamino group such as propyl)amino, N,N-heptylmethylamino, N,N-bis(2-ethylhexyl)amine; N-methylamino , N-ethylaminomethyl, N-propylaminomethyl, N-isopropylaminomethyl, N-butylaminomethyl, N-isobutylaminomethyl, N- Second butylaminomethyl, N-tert-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-g Aminomethyl, 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-t-butyl Aminomethyl, N,N-butylethylaminomethyl, N,N-bis(1-methylpropyl)aminomethyl, N,N-heptylmethylaminomethyl, N,N-dialkylaminomethyl such as N,N-bis(2-ethylhexyl)aminomethyl; trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, Perfluoroisopropenyl, perfluoro(1-propenyl), perfluoro(2-propenyl), perfluorobutyl, perfluoroisobutyl, perfluoro(second butyl), perfluoro(third butyl) Base), perfluoro(2-butenyl), perfluoro(1,3-butadienyl), perfluoropentyl, perfluoro(isopentyl), perfluoro(3-pentyl), perfluoro Neopentyl, perfluoro(third amyl), perfluoro(1-methylpentyl), perfluoro(2-methylpentyl), perfluoro(2-pentenyl), perfluorohexyl, all Fluoroisohexyl, perfluoro(5-methylhexyl), perfluoro(2-ethylhexyl), perfluoroheptyl, perfluorooctyl, perfluorodecyl, perfluorodecyl, perfluoroundecyl An aliphatic hydrocarbon group having a fluorine atom such as perfluorododecyl group or perfluorooctadecyl group; perfluorocyclopropyl group, perfluorocyclobutyl group, perfluorocyclopentyl group, perfluorocyclohexyl group, perfluorocyclohexane 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. having a fluorine atom An alicyclic hydrocarbon group; perfluorophenyl, perfluoro(o-tolyl), perfluoro(m-tolyl), perfluoro(p-tolyl), perfluoromethylphenyl, perfluoro 2,4,6-three Tolyl, perfluoro(o-isopropylphenyl), perfluoro(p-isopropylphenyl), perfluoro(p-isopropylphenyl), perfluorobenzyl, perfluorophenethyl, perfluorobiphenyl, Perfluoro(1-naphthyl), perfluoro(2-naphthyl), 1-trifluoromethylphenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethyl Base benzene An aromatic hydrocarbon group having a fluorine atom; a perfluoromethoxy group, a perfluoroethoxy group, a perfluoropropoxy group, a perfluoro(isopropoxy group), a perfluorobutoxy group, a perfluoro(isobutoxy group) ), perfluoro(second butoxy), perfluoro(tert-butoxy), perfluoropentyloxy, 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(t-butyl))methoxy, (perfluoro(2-butenyl))methoxy, (perfluoro(1,3-) Butadienyl)) methoxy, (perfluoropentyl)methoxy, (perfluoro(isopentyl))methoxy, (perfluoro(3-pentyl))methoxy, (perfluoro) (neopentyl)) methoxy, (perfluoro(tripentyl))methoxy, (perfluoro(1-methylpentyl))methoxy, (perfluoro(2-methylpentyl) )) methoxy, (perfluoro(2-pentenyl))methoxy, (perfluorohexyl)methoxy, (perfluoro(isohexyl))methoxy, (perfluoro (5-methyl) Base)) methoxy, (perfluoro((2-ethyl)hexyl))methoxy), (perfluoroheptyl)methoxy, (perfluorooctyl)methoxy, (perfluorodecyl) Methoxy, (perfluorodecyl)methoxy, (perfluoroundecyl)methoxy, (perfluorododecyl)methoxy, (perfluorooctadecyl)methoxy, etc. a substituted oxy group having 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 group and the like.

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. More preferably, it is ethyl, butyl, hexyl, (2-ethyl)hexyl and octyl, and further preferably ethyl, butyl, hexyl and (2-ethyl)hexyl, and more preferably (2- Ethyl) hexyl. The compound of the present invention in which R ^{1 is} such a group is excellent in solubility in a solvent.

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

R ³ and R ^{4 are} preferably a hydrogen atom in terms of ease of production.

a case where R ¹ and R ^{3 are} bonded to form a ring together with a carbon atom on the adjacent benzene ring and an adjacent nitrogen atom, and/or R ² and R ^{4 are} bonded to a carbon atom on the adjacent benzene ring and When the adjacent nitrogen atoms form a ring together, as *-R ¹ -R ³ -* and *-R ² -R ⁴ -*, *-CH ₂ -CH ₂ -*, *-CF ₂ - may be mentioned. 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 the key combination.

When R ¹ and R ^{2 are} bonded to form a ring together with an adjacent nitrogen atom, as *-R ¹ -R ² -*, *-(CH ₂ ) ₂ -*, *-(CH ₂ may be mentioned) 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 - *, especially preferably *-(CH ₂ ) ₄ -* and *-(CH ₂ ) ₅ -*. * indicates the key combination.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ⁵ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, a butyl group, and an isobutyl group. Base, second butyl, tert-butyl, (2-ethyl)butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, 3-pentyl, neopentyl Base, third amyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, (3-ethyl)pentyl, hexyl, isohexyl, 5-methylhexyl, (2- An aliphatic hydrocarbon group such as ethyl)hexyl, heptyl, (3-ethyl)heptyl, octyl, nonyl, decyl, undecyl, dodecyl or octadecyl; 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- An alicyclic hydrocarbon group 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-isopropylphenyl, m-isopropylphenyl, p-cumylphenyl, benzyl, phenethyl, biphenyl, 1-naphthalene An aromatic hydrocarbon group such as a group or a 2-naphthyl group; and a group formed by a combination of the above.

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

The compound (1) wherein Q ¹ is -CO ₂ M, for example, a compound represented by the formula (1-1) to the formula (1-44) and a salt thereof.

Examples of the compound (1) wherein Q ² is -CO ₂ M include a compound represented by the formula (1-45) to the formula (1-88), and a salt thereof.

From the viewpoint of easiness of synthesis, as the compound (1), the compound (1-1) to the compound (1-8), the compound (1-15) to the compound (1-42), and the compound (1) are preferable. -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)~ compound (1-86), further preferably a compound (1-1) to a 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 a benzoic acid and a solvent. The reaction temperature is preferably from 0 ° C to 200 ° C, more preferably from 100 ° C to 150 ° C. The reaction time is preferably from 1 hour to 24 hours, more preferably from 8 hours to 16 hours. The solvent is preferably methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol or N-methylpyrrolidone, and preferably 1-pentanol.

In the 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 compound represented by the formula (q1) is used in an amount of 1 mol per mol of the compound represented by the formula (q2), preferably 1 mol to 10 mol, more preferably 1 mol. The ear is ~4 moles, and more preferably 1 mole to 3 moles, and even more preferably 1 mole.

In the production of the compound (1), the ethyl cyanoacetate is used in an amount of 1 mol per mol of the compound represented by the formula (q2), preferably 1 mol to 10 mol, more preferably 1 mol to 4 Mohr, and further preferably 1 mole to 3 moles, and more preferably 1 mole.

In the production of the compound (1), the amount of the benzoic acid used is preferably 0.1 mol to 3 mol, more preferably 0.3 mol to 3 mol, based on the compound 1 mol expressed by the formula (q2). Further preferably, it is from 0.3 mol to 1.2 mol, and more preferably from 0.3 to 0.4 mol.

The method of obtaining the compound (1) as the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferred to precipitate crystals by appropriately adjusting the temperature of the reaction mixture or by adding a reaction mixture to a solvent in which the compound (1) is not dissolved, and filtering the crystals. The crystals to be filtered are preferably water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, Washing or recrystallization is carried out in a solvent such as toluene, N,N-dimethylformamide, N-methylpyrrolidone, chloroform or a mixture thereof, followed by drying. Further, it may be further purified by a known method such as column chromatography or recrystallization, as needed.

The pigment (P) is not particularly limited, and a known pigment can be used, and for example, it can be classified into a pigment by a Colour Index (published by The Society of Dyers and Colourists). pigment.

As the pigment, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, Yellow pigments such as 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 194, 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, Orange pigments such as 55, 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, Red pigments such as 216, 224, 242, 254, 255, 264, 265; blue pigments such as CI Pigment Blue 15, 15:3, 15:4, 15:6, 60; CI Pigment Violet 1, 14, 19, 23 , 29, 32, 33, 36, 37, 38 and other purple pigments; C.I. Pigment green 7,7,15,25,36,47,58 and other green pigments; C.I. Pigment brown 23, 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 group consisting of. These pigments can be preferably used for a green coloring matter, and by containing the above-mentioned pigment, it is easy to optimize the transmission spectrum, and the light resistance and chemical resistance of the color filter are improved.

The pigment may be subjected to a rosin treatment, a surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, a graft treatment on the surface of the pigment by a polymer compound or the like, and a micronization by a sulfuric acid micronization method or the like. The treatment or the cleaning treatment using an organic solvent or water for removing impurities, the removal treatment of the ionic impurities by an ion exchange method, or the like. The particle size of the pigment is preferably uniform.

The pigment is dispersed by a pigment dispersant to form a pigment dispersion in a state in which it is uniformly dispersed in a pigment dispersant solution. The pigments may be separately subjected to dispersion treatment, or a plurality of types 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 singly or in combination of two or more. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoei Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), and Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

In the case of using a pigment dispersant, the amount thereof is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. If the amount of the pigment dispersant used is within the above range, it is possible to obtain a pigment having a more uniform dispersion state. The tendency of loose liquid.

The content of the compound (1) is preferably 0.01% by mass or more and 90% by mass or less, more preferably 0.1% by mass or more and 80% by mass or less, and further preferably 1% by mass based on the total amount of the coloring agent (A). % or more and 65% by mass or less, and more preferably 2% by mass or more and 60% by mass or less.

When the pigment (P) is contained, the content thereof 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 based on the total amount of the coloring agent (A). Further, it is preferably 35 mass% or more and 99 mass% or less, and more preferably 40 mass% or more and 98 mass% or less.

The content of the coloring agent (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, and more preferably 3% by mass or more based on the total amount of the solid content component. 80% by mass or less, more preferably 5% by mass or more and 70% by mass or less, further preferably 5% by mass or more and 60% by mass or less, and particularly preferably 5% by mass or more and 50% by mass or less. When the content of the colorant (A) is within the above range, a desired spectral or color density can be obtained.

In the present specification, the "total amount of the solid content component" means the total amount of the components after removing the solvent (E) from the colored curable resin composition of the present invention. The total amount of the solid content component and the content of each component relative to the component can be measured, for example, by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, and 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 unsaturated carboxylic acids and unsaturated carboxylic anhydrides. Examples of such a resin include the following resins [K1] to [K6].

The 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 cyclic ether having a carbon number of 2 to 4. a copolymer of a monomer (b) having a structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); Resin [K2] (a), (b), and monomer (c) copolymerizable with (a) (where (a) and (b) are different) (hereinafter sometimes referred to as "(c)") Copolymer; resin [K3] copolymer of (a) and (c); resin [K4] resin obtained by reacting (b) with the copolymer of (a) and (c); resin [K5] a) a resin obtained by reacting a copolymer of (b) and (c); a resin [K6] which is obtained by reacting a copolymer of (a) with (b) and (c) and further reacting with a carboxylic anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid; maleic acid and fumaric acid; , citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2, Unsaturated dicarboxylic acids such as 3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid; methyl-5-lower Alkene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-A Bicyclo[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 - alkene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene and other carboxyl-containing bicyclic unsaturated compounds; maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinyl Phthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyl Unsaturated dicarboxylic acid anhydride such as tetrahydrophthalic anhydride or 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono[2-(methyl)acryloxyloxy Unsaturated mono[(methyl)propenyloxyalkyl]ester of a divalent or higher polycarboxylic acid such as an ester or a mono[2-(methyl)propenyloxyethyl] phthalate For example, α-(hydroxymethyl)acrylic acid is an unsaturated acrylate having a hydroxyl group and a carboxyl group in the same molecule. Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable in terms of the aspect of the copolymerization reactivity or the solubility of the obtained resin in an aqueous alkaline solution.

(b) is a cyclic ether structure having a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. A polymeric compound. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

In the present specification, the term "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The notation of "(meth)acrylonitrile" and "(meth)acrylate" has the same meaning.

(b), for example, a monomer (b1) having an epoxy group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), having an oxetanyl group and an ethylenic unsaturated group The monomer (b2) of the bond (hereinafter sometimes referred to as "(b2)"), the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)")).

(b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)") A monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (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-divinyl Benzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl)benzene Ethylene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)benzene Ethylene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidyloxy) Methyl)benzene Ethylene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

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

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

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

Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. 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 or a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

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

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

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

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

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination with the compound represented by the formula (II). In the case where 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 from 5:95 to 95:5, more preferably 10:90 on a molar basis. ~90:10, and further 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-methylpropenyloxymethyloxetane, 3-methyl-3-propenyloxymethyloxetane, and 3- Ethyl-3-methylpropenyloxymethyloxetane, 3-ethyl-3-propenyloxymethyloxetane, 3-methyl-3-methylpropene oxime Ethyloxyoxetane, 3-methyl-3-propenyloxyethyloxetane, 3-ethyl-3-methylpropenyloxyethyloxetane, 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 Co., Ltd.), tetrahydrofurfuryl methacrylate. Wait.

(b) is preferably (b1) in terms of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, in terms of excellent storage stability of the colored curable resin composition, (b1-2) is more preferable.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid 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 conventional name, it is called "dicyclopentanyl (meth) acrylate." Also, it is sometimes called "tricyclodecyl (meth) acrylate"), tricyclo(meth) acrylate [5.2.1.0 ^2.6 Terpene-8-ester (in the technical field, as a conventional name, it is called "dicyclopentenyl (meth)acrylate)", dicyclopentyloxyethyl (meth)acrylate, (methyl) Acrylic Ester, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, (meth)acrylic acid (meth) acrylates such as benzyl ester; (hydroxy) (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; maleic acid a dicarboxylic acid diester such as ethyl ester, diethyl fumarate or diethyl itaconate; bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]heptane-2 - alkene, 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-di(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- Alkene, 5-hydroxymethyl-5- Bicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2- Alkene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-double a bicyclic unsaturated compound such as (cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N-cyclohexylmethyleneimine, N -benzyl succinimide, N-butyl succinimide-3-succinimide benzoate, N-butyl succinimide-4-sandene Iminobutyrate, N-butylenediamine-6-methyleneimide hexanoate, N-butylenediamine-3-oxenimide propionate, Dicarbonyl ruthenium derivatives such as N-(9-acridinyl) maleimide; 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 Alkene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, styrene, vinyl toluene, benzyl (meth)acrylate, and trimethyl (meth)acrylate [5.2.1.0 ^2.6 ]癸 are preferable in terms of copolymerization reactivity and heat resistance. Alkan-8-ester, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide, bicyclo [2.2.1] g- 2-ene and the like.

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

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

The resin [K1] can be referred to, for example, the method described in the "Experimental Method for Polymer Synthesis" (Otsuka Ryo, Distribution Co., Ltd., Chemical Co., Ltd., 1st Edition, 1st brush, issued on March 1, 1972). It is manufactured by reference to the documents described in the literature.

Specifically, a method in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are added to a reaction container, for example, a gas deoxidation atmosphere is formed by replacing oxygen with nitrogen, and heating is performed while stirring. And insulation. In addition, the polymerization initiator, the solvent, and the like used herein are not particularly limited, and a general user in the field can be used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic. The peroxide (such as benzoyl peroxide) may be used as a solvent, and the solvent (E) exemplified as the color-curable resin composition of the present invention is exemplified below. Wait.

Further, the obtained copolymer may be directly used as a solution after the reaction, or a solution which is concentrated or diluted, or may be taken out as a solid (powder) by a method such as reprecipitation. In particular, in 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 in the preparation of the color-curable resin composition of the present invention, so that the simplification can be simplified. A manufacturing step of the colored curable resin composition of the present invention.

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

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

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

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

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

The resin [K4] can be obtained by obtaining a copolymer of (a) and (c), and adding (b) a cyclic ether having a carbon number of 2 to 4 to (a) having a carboxylic acid and/or a carboxylic anhydride. And manufacturing.

First, a copolymer of (a) and (c) is produced in the same manner as the method described in the method for producing 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, (b) a cyclic ether having 2 to 4 carbon atoms is partially reacted with one of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer.

After the manufacture of the copolymer of (a) and (c), the environment inside the flask is replaced with nitrogen by nitrogen, and the reaction catalyst of (b), a carboxylic acid or a carboxylic anhydride with a cyclic ether (for example, tris(dimethyl) Addition of a polymerization inhibitor (for example, hydroquinone or the like) and a polymerization inhibitor (for example, hydroquinone) to the flask, for example, at 60 to 130 ° C for 1 to 10 hours, whereby a resin [K4] can be produced.

The amount of use of (b) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. By setting it as the range, the coloring curable resin composition is stable in storage. The balance between the developability at the time of pattern formation, the solvent resistance, the heat resistance, the mechanical strength, and the sensitivity of the obtained pattern tends to be good. Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily left, the (b) used as the resin [K4] is preferably (b1), more preferably (b1-1).

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

The reaction conditions such as the addition method, the reaction temperature, and the time can be appropriately adjusted in consideration of the heat generation amount due to the production equipment or the polymerization. Further, similarly to the polymerization conditions, the addition method or the reaction temperature can be appropriately adjusted in consideration of the heat generation amount due to the production equipment or the polymerization.

Regarding the resin [K5], as the first stage, the copolymers of (b) and (c) were obtained in the same manner as in the above-mentioned production method of the resin [K1]. Similarly to the above, the obtained copolymer may be used as it is, or may be used as a solid (powder) by a method such as reprecipitation.

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

Further, the carboxylic acid or carboxylic anhydride having (a) and the copolymer of (b) and (c) having a cyclic ether derived from (b) are reacted under the same conditions as in the production method of the resin [K4]. Thereby, the resin [K5] can be obtained.

The amount of (a) used in the reaction with the above copolymer is preferably from 5 to 80 moles per 100 moles of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is not easily left, the (b) used as the resin [K5] is preferably (b1), 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, and 3,4,5,6-tetra. Hydrogen phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]heptan-2- Alkenic anhydride and the like. The amount of the carboxylic anhydride used is 1 mole based on the amount used in (a), preferably 0.5 to 1 mole.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxy tricyclo(meth)acrylate. [5.2.1.0 ^2.6 ] Resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, (methyl) ) acrylate / styrene / (meth) acrylic acid copolymer, (meth) acrylate, 3,4-epoxy-tricyclo [5.2.1.0 ^2.6] decyl acrylate / (meth) acrylic acid / N- cyclohexyl cis Butenylenediamine copolymer, 3,4-epoxytricyclo(5.4-epoxy)[5.2.1.0 ^2.6 ]decyl/(meth)acrylic/vinyltoluene copolymer, 3-methyl-3-(meth)acrylate Resin such as (meth) propylene methoxymethyl oxetane / (meth) acrylate / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylate copolymer, styrene Resin such as /(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer [K3]; and glycidyl (meth)acrylate a resin made of a benzyl (meth) acrylate / (meth) acrylate copolymer, Addition of glycidyl acrylate to a resin of tricyclodecyl (meth) acrylate/styrene/(meth)acrylic acid copolymer, and addition of glycidyl (meth)acrylate to (methyl) Resin such as resin of tricyclodecyl acrylate/benzyl (meth) acrylate/(meth)acrylic acid copolymer [K4]; trimethyl decyl (meth) acrylate and (meth) acrylate a resin obtained by reacting a copolymer of glycidyl acrylate, a copolymer of (meth)acrylic acid and tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate a resin such as a resin [K5]; a resin obtained by reacting a copolymer of (meth)acrylic acid with tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate to further react with tetrahydrophthalic anhydride A resin such as a resin obtained [K6] or the like.

The resin (B) is preferably one selected from the group consisting of a resin [K1], a resin [K2], and a resin [K3], and more preferably selected from the group consisting of a resin [K2] and a resin [K3]. One of them. When it is such a resin, the coloring curable resin composition is excellent in developability. From the viewpoint of the adhesion between the colored pattern and the substrate, the resin [K2] is further 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, still more preferably 6,000 to 30,000. When the molecular weight is within the above range, the coating film has a high hardness and a high residual film ratio, and the solubility of the unexposed portion in the developer 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 from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B) is usually from 20 mg-KOH/g to 170 mg-KOH/g, preferably from 30 mg-KOH/g to 170 mg-KOH/g, more preferably from 40 mg-KOH/g to 170 mg-KOH/g. Further, it is preferably 50 mg-KOH/g to 170 mg-KOH/g. Among them, it is preferably 50 mg-KOH/g to 150 mg-KOH/g, more preferably 60 mg-KOH/g to 150 mg-KOH/g, further preferably 60 mg-KOH/g to 135 mg-KOH/g, particularly preferably It is 70 mg-KOH/g to 135 mg-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 can be obtained, for example, by titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably from 7% by mass to 65% by mass, more preferably from 10% by mass to 60% by mass, even more preferably from 13% by mass to 60% by mass, based on the total amount of the solid content component. Good is 17% by mass to 55% by mass. When the content of the resin (B) is within the above range, the coloring pattern is likely to be formed, and the resolution of the colored pattern and the residual film ratio tend to be improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which can be polymerized by an active radical and/or an acid generated from the polymerization initiator (D), and examples thereof include a polymerizable ethylenically unsaturated bond. A compound or the like is preferably a (meth) acrylate compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylic acid. Ester, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc.; 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( Methyl) acrylate, triethylene glycol di(meth) acrylate, bisphenol A bis(acryloxyethyl) ether, 3-methyl pentanediol 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 a polymerizable compound 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, pentaerythritol deca (meth) acrylate, pentaerythritol nin (meth) acrylate Ester, tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate Ester, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modified pentaerythritol tetra(meth) acrylate, caprolactone modified dipentaerythritol hexa Methyl) acrylate or the like.

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

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

The content of the polymerizable compound (C) is preferably from 1 to 70% by mass, more preferably from 2 to 65% by mass, more preferably from 5 to 65% by mass, more preferably 7%, based on the total amount of the solid content component. ~65 mass%, more preferably 10 to 60 mass%, more preferably 13 to 60 mass%, still more preferably 17 to 55 mass%.

Further, the content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is preferably 20:80 to 80:20, more preferably 35: by mass: 65~80:20.

When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of formation of the 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 which can initiate polymerization by the action of light or heat, and a known polymerization initiator can be used.

As the polymerization initiator (D), a phenylalkyl ketone compound, three a compound, a mercaptophosphine oxide compound, an O-mercaptopurine compound, a biimidazole compound, and the like.

The above O-indenyl ruthenium compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * indicates a keying key.

Examples of the above O-indenyl ruthenium compound include N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine and N-benzidine. Oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3- Cyclopentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzylidene)-9H-indazol-3-yl Ethyl-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di) Alkylcyclopentylmethoxy)benzhydryl}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-(2 -Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylideneoxy-1-[9-ethyl-6-( 2-Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (above, manufactured by BASF Corporation), and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used. Wherein, the O-indenyl hydrazine compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzidine Oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylthiophenyl)-3- At least one of the group consisting of cyclopentylpropan-1-one-2-imine, more preferably N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1 - keto-2-imine.

The phenylalkyl 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.

As a compound having a partial structure represented by the formula (d2), for example, 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Polinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (above, manufactured by BASF Corporation) can also be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4] -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 a ketone oligomer, α,α-diethoxyacetophenone, benzoin dimethyl ketal or the like.

In terms of sensitivity, as the phenylalkyl ketone compound, it is preferred to have the formula (d2) A compound representing a portion of the structure.

The biimidazole compound is, for example, a compound represented by the 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 a phenyl group, a tolylmethyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferred.

Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, 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.), 2,2'-bis(2-chlorobenzene) -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to JPS48-38403-B, JPS62-174204-A, etc.), 4,4'5,5' An imidazole compound in which a phenyl group at the position is substituted with a carboalkoxy group (for example, refer to JPH07-10913-A, etc.) and the like. Among them, preferred are compounds represented by the following formulas and mixtures thereof.

As the above three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-three Wait.

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

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 benzoyl benzoate; , 4-phenylbenzophenone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl) a benzophenone compound such as benzophenone or 2,4,6-trimethylbenzophenone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine or camphorquinone; 10-butyl-2 - chloroacridone, benzoin, methyl phenylglyoxylate, titanocene compound, and the like. These are preferably used in combination with the following polymerization starting assistants (D1), especially amines.

The polymerization initiator (D) preferably contains a compound selected from the group consisting of a phenylalkyl ketone compound, three A polymerization initiator which is at least one of a group consisting of a compound, a mercaptophosphine oxide compound, an O-mercaptophosphonium compound, and a biimidazole compound is more preferably a polymerization initiator containing an O-mercaptopurine 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, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total 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 polymerization of a polymerizable compound which starts polymerization by a polymerization initiator. In the case of containing the polymerization starting assistant (D1), it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiation assistant (D1) include an amine compound, an alkoxy fluorene compound, and 9-oxosulfuric acid. Compounds, carboxylic acid compounds, and the like.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethyl Isoamyl benzoate benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)benzophenone (commonly known as miconesone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethyl Methylamino)benzophenone or the like, of which 4,4'-bis(diethylamino)benzophenone is preferred. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The above alkoxy fluorene compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the above 9-oxygen sulfur Compounds can be exemplified by 2-isopropyl-9-oxosulfur 4-isopropyl-9-oxosulfur 2,4-diethyl-9-oxosulfur 2,4-dichloro-9-oxosulfur 1-chloro-4-propoxy-9-oxosulfur Wait.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenylthioacetic acid. Methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthio B Acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, and the like.

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

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent which is usually used in the field can be used. For example, an ester solvent (a solvent containing -COO- in the molecule and not containing -O-), an ether solvent (a solvent containing -O- in the molecule and not containing -COO-), and an ether ester solvent (in the molecule) a solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule and not containing -COO-), an alcohol solvent (containing OH in the molecule and not containing -O-, -CO - and -COO-solvent), aromatic hydrocarbon solvent, guanamine solvent, dimethyl hydrazine, 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, ring 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 two. 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-two 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 the like.

Examples of the ether ester solvent include methyl methoxyacetate and ethyl methoxyacetate. Butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate , 3-ethoxypropionate ethyl ester, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate , 2-ethoxypropionic acid ethyl ester, 2-methoxy-2-methylpropionic acid methyl ester, 2-ethoxy-2-methylpropionic acid ethyl ester, 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 the like.

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 guanamine solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

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

Among them, preferred are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol. 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, etc., 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 Mercaptoamine, 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 component of the colored curable resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of application is good, and the color density is not insufficient when the color filter is formed, so that the display characteristics are good.

<Leveling agent (F)>

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

Examples of the polyoxymethylene surfactant include a surfactant having a oxime bond in the molecule. Specifically, 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.) can be cited. , KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 (Mitto Advanced Materials Japan ( Momentive Performance Materials Japan) manufactured by a contract company).

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in the molecule. Specifically, 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 Co., Ltd.).

The polyfluorene-based surfactant having a fluorine atom may, for example, be a surfactant having a ruthenium bond or 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%, more preferably 0.001, based on the total amount of the coloring curable resin composition. The mass% or more is 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, and particularly preferably 0.005% by mass or more and 0.07% by mass or less. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

The colored curable resin composition of the present invention may contain additives such as a filler, other polymer compound, adhesion promoter, antioxidant, light stabilizer, chain transfer agent, etc., which are known in the art, as needed.

<Method for Producing Colored Curable Resin Composition>

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

The pigment containing the pigment (P) is preferably partially or completely mixed with one of the solvents (E), and is dispersed by a ball mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. At this time, part or all of the above pigment dispersant and resin (B) may be blended as needed. In the pigment dispersion liquid obtained in this manner, the remaining components are mixed so as to have a specific concentration, whereby the intended color-curable resin composition can be prepared.

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

Preferably, the mixed color-curable resin composition is filtered by a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

The method of producing a colored pattern by the colored curable resin composition of the present invention includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. The photolithography method is a method in which the colored curable resin composition is applied onto a substrate, dried, and a colored composition layer is formed, and the colored composition layer is exposed and developed through a photomask. In the photolithography method, a coloring coating film which is a cured product of the coloring composition layer can be formed without using a photomask and/or without developing. 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 depending on the purpose, use, and the like, 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, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, or soda-lime glass coated with cerium oxide, polycarbonate, polymethyl methacrylate or polyterephthalic acid can be used. A resin plate such as ethylene glycol or the like, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Another color filter layer, a resin layer, a transistor, a circuit, or the like may be formed on the substrates.

The formation of the pixels of the respective colors by the photolithography method can be carried out by known or customary devices or conditions. For example, it can be produced as follows.

First, the colored curable resin composition is applied onto a substrate, and the volatile components such as a solvent are removed by heat drying (prebaking) and/or drying under reduced pressure to be dried, thereby obtaining a smooth colored composition layer.

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

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

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

The film thickness of the colored composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.

The colored composition layer is then exposed through a reticle that forms a colored pattern of the target. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use can be used.

As the light source for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, a light of less than 350 nm may be cut off using a filter that cuts off the wavelength region, or light of a vicinity of 436 nm, around 408 nm, and around 365 nm may be used to take out a band-pass filter of the wavelength regions. Selectively removed. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

In order to uniformly illuminate the entire surface of the exposed surface, or to align the correct position of the reticle with the substrate on which the colored composition layer is formed, it is preferred to use a mask aligner and a step type. An exposure device such as a stepper.

The coloring pattern is formed on the substrate by developing the exposed coloring composition layer in contact with the developing solution. The unexposed portion of the colored composition layer can be removed by dissolving in the developing solution by development. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. 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, still more preferably 0.03 to 5% by mass. Further, the developer may also contain a surfactant.

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

After development, it is preferably washed with water.

Further, it is preferred to post-bake the obtained color pattern. The post-baking temperature is preferably from 150 to 250 ° C, more preferably from 160 to 235 ° C. The post-baking time is preferably from 1 to 120 minutes, more preferably from 10 to 60 minutes.

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

Example

Hereinafter, the present invention will be further specifically described by way of examples and the like.

In the examples and comparative examples, the % and the parts indicating the content or the amount used are based on mass unless otherwise specified.

In the following examples, the structure of the compound is NMR (Nuclear Magnetic Resource) (JMM-ECA-500; manufactured by JEOL Ltd.) or mass spectrometry (LC; Model 1200 manufactured by Agilent, MASS; Agilent Confirmed by the manufactured LC/MSD6130 type).

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene of the resin was carried out by GPC (Gel Permeation Chromatography) under the following conditions.

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

Column: TSK-GEL G2000HXL

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran, tetrahydrofuran)

Flow rate: 1.0mL/min

The concentration of the solid content of the test liquid: 0.001~0.01% by mass

Injection volume: 50μL

Detector: RI (Refractive Index, refractive index)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio (Mw/Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as a 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.), benzoic acid (Tokyo) Manufactured by Chemical Industry Co., Ltd., 2.73 parts, 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. 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. 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- 6.35 parts of (diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 8 hours. After the reaction solution was cooled to room temperature, the precipitated crystals were obtained by suction filtration. 140 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 under suction to obtain an insoluble material. 120 parts of tetrahydrofuran was added to the residue, and the mixture was stirred at 70 ° C for 1 hour, and then an insoluble matter was obtained by suction filtration. 340 parts of N,N-dimethylformamide was added to the residue, and the mixture was heated to 90 ° C to be dissolved, and then allowed to stand at 0 ° C to 5 ° C. The precipitated crystals were obtained by suction filtration. This residue was dried under reduced pressure at 60 ° C to obtain 5.69 parts of the compound represented by formula (1-1). The structure was confirmed by ¹ H-NMR.

<Identification of the 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) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 14.3 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), benzoic acid (Tokyo) Manufactured by Chemical Industry Co., Ltd., 4.20 parts, 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. 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.) 10.1 parts and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were produced, and stirred at 120 ° C for 3 hours. 4.60 parts of cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.70 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4-(dibutylamino) tartaraldehyde (Tokyo Chemical Industry Co., Ltd.) 10.2 parts and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were produced and stirred at 120 ° C for 3 hours. 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. After cooling the above reaction liquid to room temperature, it was added to 1900 parts of hexane and stirred. The precipitated crystals were obtained by suction filtration. 328 parts of tetrahydrofuran was added to the residue, and recrystallization was carried out at 60 °C. The precipitated crystals were obtained by suction filtration. To the residue, 160 parts of tetrahydrofuran was added and stirred, and the residue was filtered by suction to obtain an insoluble matter. The residue was dried under reduced pressure at 60 ° C to obtain 18.9 parts of the compound of formula (1-3). The structure was confirmed by ¹ H-NMR.

<Identification of the 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-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.32 parts, 4-(bis(2-ethylhexyl)amino) sulphonaldehyde (according to Japanese Patent Publication No. 2007-508275) In this way, 10.2 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.18 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 68.0 parts, and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) Manufactured 3.19 parts were mixed and stirred at 120 ° C for 3 hours. Add 4-(bis(2-ethylhexyl)amino) salicylaldehyde to the reaction solution (depending on the day) 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, synthesized by the method described in JP-A-2007-508275 4.80 parts of ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 12 hours. After cooling the above reaction liquid 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 the compound represented by formula (1-15).

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

(mass spectrometry) 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 resulting water was removed while stirring at 150 to 155 ° C 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 1000 parts of water. To the toluene solution, 50 parts of anhydrous magnesium sulfate was added and stirred, followed by filtration. The solvent of the filtrate was distilled off to obtain a crude product. This crude product was dissolved in 234 parts of toluene, stirred at 0 ° C or lower, and the crystallization product was collected by filtration. The crystallization product was dried under reduced pressure at 50 ° C to obtain 95.7 parts of the compound represented by formula (pt1).

<Identification of the compound represented by formula (pt1)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 194.2

Exact molecular weight: 193.2

95.3 parts of the compound represented by the formula (pt1) and 48.0 parts of water were mixed, and stirred at 80 °C. Then, 107 parts of 1-bromo-2-ethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at 80 ° C for 3 hours, and then 22.4 parts of a 48% aqueous sodium hydroxide 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% aqueous sodium hydroxide solution, and 130 parts of toluene was added thereto and stirred to extract a toluene layer. The toluene extract was washed twice with 500 parts of water, and 25.0 parts of anhydrous magnesium sulfate was added thereto, and the mixture was 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 the 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 obtained residue containing the compound represented by formula (pt2) as a main component The mixture was mixed with 597 parts of N,N-dimethylformamide and stirred at -6 ° C to 3 ° C. While maintaining the liquid temperature at -6 ° C to 3 ° C, 258 parts of phosphonium chloride (manufactured by Wako Pure Chemical Industries Co., Ltd.) were added thereto. The mixture was stirred at room temperature for 1 hour and then stirred at 60 ° C for 4 hours. After allowing to cool, the reaction mixture was added to 1500 parts of ice and neutralized using a 48% aqueous sodium hydroxide solution. To the mixture was added 867 parts of toluene, and the toluene layer was extracted. The toluene extract was washed twice with 1200 parts of a 15% aqueous sodium chloride solution. To the toluene extract, 60.0 parts of anhydrous magnesium sulfate was added and stirred, followed by filtration. 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 the compound represented by formula (pt3)>

(mass spectrometry) 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 the formula (pt3), and 1.87 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1- 110 parts of pentanol (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. 22.5 parts of the compound represented by the 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 in the reaction solution. 7.66 parts of ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 12 hours. Cooling the above 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 the compound represented by formula (1-17).

<Identification of the 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 resorcin, and the mixture was stirred for 18 hours while removing water formed at 150 to 155 °C. After allowing to cool, 250 parts of toluene was added to the reaction mixture, and the mixture was washed three times with 500 parts of water. To the toluene solution, 20.0 parts of anhydrous magnesium sulfate was added and stirred, followed by filtration. 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 the compound represented by formula (pt4)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 222.2

Exact molecular weight: 221.2

To 58.5 parts of the residue containing the compound represented by the formula (pt4) obtained as a main component, 23.0 parts of water was added, and the liquid temperature was adjusted to 60 ° C while stirring. Add at this temperature 39.3 parts of diethyl sulfate and 10.6 parts of 48% aqueous sodium hydroxide solution were stirred for 9 hours. Thereafter, the mixture was stirred at 60 ° C for 5 hours. After allowing to cool, the reaction mixture was neutralized with a 10% aqueous sodium hydroxide solution, and 300 parts of toluene was added. The toluene solution was washed 3 times with 500 parts of water. To the toluene solution, 20.0 parts of anhydrous magnesium sulfate was added and stirred, followed by filtration. 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 the compound represented by formula (pt5)>

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 250.2

Exact molecular weight: 249.2

To the 67.5 parts of the residue containing the compound represented by the formula (pt5) obtained as a main component, 323 parts of N,N-dimethylformamide was added. 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 mixture was returned to room temperature and stirred for 1 hour, the temperature of the reaction liquid 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 neutralized while adding a 48% aqueous sodium hydroxide solution while stirring. 500 parts of toluene was added thereto, and a toluene layer was extracted. The toluene solution was washed with 1000 parts of water. Then, the toluene solution was washed with 1500 parts of a saturated aqueous sodium chloride solution. To the toluene solution, 25.0 parts of anhydrous magnesium sulfate was added and stirred, followed by filtration. 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 the compound represented by formula (pt6)>

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

Exact molecular weight: 277.2

8.18 parts of 4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 15.0 parts of a compound represented by the formula (pt6), and 2.25 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1- 130 parts of pentanol (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 the compound represented by the formula (pt6), 3.00 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. Ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was 9.20 parts, and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid 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 the compound represented by formula (1-19).

<Identification of the 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.), 2-hydroxy-4-(pyrrolidin-1-yl)benzaldehyde (according to Chem. Commun. 2011, 47, 2435) And synthesized) 10.0 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.18 A portion, 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 the reaction solution, 2-hydroxy-4-(pyrrolidin-1-yl)benzaldehyde (synthesized according to Chem. Commun. 2011, 47, 2435.) was mixed with 15.0 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.). 3.00 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.) were stirred at 120 ° C for 12 hours. After cooling the above reaction liquid 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 the compound represented by formula (1-39).

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

(mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 377.1

Exact molecular weight: 376.1

Synthesis Example 7

4-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.21 parts, 8-hydroxyl 13.1 parts of 8-Hydroxyjulolidine-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.51 parts, 1-pentanol (Tokyo Chemical Industry Co., Ltd.) Manufactured by 145 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.80 parts were mixed, and stirred at 120 ° C for 3 hours. 10.2 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.80 parts, 8-hydroxyl group 19.6 parts of a pyridin-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 120 ° C for 12 hours. After cooling the above reaction liquid 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

2-amino-3-hydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 9.21 parts, 8-hydroxy-1,1,7,7-tetramethyl 15.4 parts of bromo-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 (manufactured by Tokyo Chemical Industry Co., Ltd.), and cyanide 6.00 parts of ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 120 ° C for 3 hours. 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 group were added. 24.7 parts of a pyridin-9-carboxaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 120 ° C for 12 hours. After cooling the above reaction liquid 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

An appropriate amount of nitrogen gas was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 85 ° C while stirring. Then, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2.6 ]decane-8-acrylate and 3,4-acrylic acid were added dropwise to the flask over a period of about 5 hours using a dropping pump. A mixture of epoxidized tricyclo[5.2.1.0 ^2.6 ]decane-9-ester (containing 50:50 by molar ratio) of 171 parts dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, another pump was added to the flask over a period of about 5 hours to dissolve the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) 26 parts in propylene glycol monomethyl ether. A solution of 120 parts of acetate. After completion of the dropwise addition of the polymerization initiator, 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 obtained resin B1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value of 53 mgKOH/g in terms of solid content.

[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): Resin B1 (in terms of solid content) 9.5 parts, and solvent (E): propylene glycol monomethyl 180 parts of ether acetate was mixed, and the pigment was sufficiently dispersed using a ball mill to obtain a pigment dispersion; the coloring agent (A): 3.0 parts of the compound represented by the formula (1-15), and the resin (B): resin B1 (solid type) 40 parts, polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 49 parts, polymerization initiator (D): N-benzoic acid醯oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-mercaptopurine compound) 9.8 parts Solvent (E): 670 parts of propylene glycol monomethyl ether acetate, and leveling agent (F): polyether modified polyoxyxide oil (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 by 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 by C.I. Pigment Green 58 (pigment).

[Measurement of film thickness]

Regarding the film thickness, the film thickness was measured using DEKTAK3 manufactured by Nippon Vacuum Technology Co., Ltd.

[Preparation of Sublimation Test Resin Composition (SJS)]

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

The resin composition for sublimation test (SJS) was obtained by mixing.

[Formation of resin coating film (SJSM) for sublimation test]

The resin composition for sublimation test (SJS) obtained above was applied by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) of 2 inches, 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. The film was heated at 220 ° C for 2 hours in an oven to form a resin coating film (SJSM) for sublimation test (film thickness: 2.2 μm).

Example 4 [Coloring pattern production and sublimation evaluation]

The colored hardening resin composition obtained in Example 1 was applied by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning Co., Ltd.) of 2 inches, and then prebaked at 100 ° C for 3 minutes. And forming a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was set to 200 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) was used at 80 mJ/cm ² in an atmosphere. The exposure amount (based on 365 nm) was exposed. Further, as the photomask, a pattern in which a line and a gap of 100 μm were formed was used. The exposed coloring composition layer was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for development for 70 seconds, and then washed with water. The film thickness was measured. The results are shown in Table 1.

The colored coating film and the above-mentioned sublimation test resin coating film (SJSM) were opposed to each other at a space of 70 μm, and 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). When the color difference (?Eab*) is 5.0 or more, it means that the coloring agent has sublimation property. The results are shown in Table 1. In Table 1, in each of the examples, ○ indicates that the colorant does not have sublimation property, and × indicates that the colorant has sublimation property.

Embodiment 5 to Embodiment 6

A coloring 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 QQQ. In addition, sublimation evaluation was performed. The results are shown in Table 1. The above embodiment QQQ represents the embodiment QQQ shown in Table 1, respectively.

Comparative example 1

Colorant (A): 3.6 parts of coumarin 6 , resin (B): resin (B1) (in terms of solid content), 180 parts, solvent (E): propylene glycol monomethyl ether acetate, 230 parts, Solvent (E): N,N-dimethylformamide 590 parts, and leveling agent (F): polyether modified polyoxyxide oil (Toray Silicone SH8400; manufactured by Dow Corning Toray Co., Ltd.) 0.063 parts

These were mixed to obtain a colored resin composition.

Comparative example 2 [sublimation evaluation]

The colored resin composition obtained in Comparative Example 1 was applied by a spin coating method on a glass substrate (Eagle XG; manufactured by Corning) of 2 inches, and then prebaked at 100 ° C for 3 minutes. A colored composition layer is formed. The film thickness was measured using DEKTAK3 manufactured by Nippon Vacuum Technology Co., Ltd., and found to be 1.9 μm. The colored coating film and the above-mentioned sublimation test resin coating film (SJSM) were placed in a state of being separated by a gap of 70 μm, and baked 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. When the color difference (?Eab*) is 5.0 or more, it means that the coloring agent has sublimation property.

From the above results, it was confirmed that according to the present invention, it is possible to provide a color-curable resin composition in which a coloring agent is not sublimated to form a color filter.

According to the present invention, it is possible to provide a color-curable resin composition in which a coloring agent is not sublimated to form a color filter, and the color filter can be preferably used for a display device such as a liquid crystal display device.

Claims (11)

A colored curable resin composition comprising a compound represented by the formula (1), a resin, a polymerizable compound, and a polymerization initiator; [In the formula (1), Q ¹ and Q ² each independently represent a hydrogen atom or -CO ₂ M, wherein any of Q ¹ and Q ² represents -CO ₂ M; and R ¹ to R ⁴ are independently represented a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ³ bonded to form a ring together with a carbon atom on the adjacent benzene ring and an adjacent nitrogen atom, and R ² and R ^{4 are} bonded to each other. 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 together with the adjacent nitrogen atom; the methylene group constituting the monovalent hydrocarbon group may pass through an oxygen atom or a sulfur atom. Substituting -N(R ⁵ )-, sulfonyl or carbonyl, the hydrogen atom contained in the monovalent hydrocarbon group may be through a halogen atom, a cyano group, a nitro group, an amine methyl group, an amine sulfonyl group, -SO ₃ M , -CO ₂ M, a hydroxyl group or an amine group; R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms; when a plurality of R ⁵ are present, the same or different from each other; M represents a hydrogen atom or Alkali metal atom]. The colored curable resin composition of 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 the 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 together with a carbon atom on the adjacent benzene ring and an 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 a benzene adjacent thereto. 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 together with a carbon atom on the adjacent benzene ring and an adjacent nitrogen atom. The colored curable resin composition according to any one of claims 1 to 3, which further comprises a pigment. The colored curable resin composition of 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 of claim 5, wherein the pigment is at least one selected from the group consisting of copper chloride phthalocyanine pigment, copper bromide phthalocyanine pigment, and zinc bromide phthalocyanine pigment. The colored curable resin composition according to any one of claims 4 to 6, wherein the pigment is a green pigment. The colored curable resin composition of 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 colored curable resin composition of claim 8, wherein the pigment is C.I. Pigment Green 7. A color filter formed by using the color hardening resin composition according to any one of claims 1 to 9. A liquid crystal display device comprising a color filter as claimed in claim 10.