KR102044417B1 - Colored curable resin composition - Google Patents

Abstract

Colored curable resin composition containing the compound represented by Formula (1), resin, a polymeric compound, and a polymerization initiator. In the formula (1), Q ¹ and Q ² each independently represent a hydrogen atom or -CO ₂ M, or just either one of Q ¹ and Q ² represents a -CO ₂ M. R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ³ combine to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom; , R ² and R ⁴ combine to form a ring together with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring, or R ¹ and R ² combine to form a ring together with an adjacent nitrogen atom. R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^{5 's} are present, they are the same as or different from each other. M represents a hydrogen atom or an alkali metal atom]

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

Dye is used for color display using reflected light or transmitted light in the field of a fiber material, a liquid crystal display device, an inkjet, etc., for example. As such dyes, coumarin compounds such as coumarin 6 (compound represented by the following formula) are known (Example 8 of JP2006-154740-A).

It was a problem that a coloring agent sublimed in the process of producing a color filter from the colored curable resin composition containing the said coumarin compound.

The present invention includes the following inventions.

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

Formula (1)

In the formula (1), Q ¹ and Q ² are or represent a hydrogen atom or -CO ₂ M, each independently, any one of Q ¹ and Q ² represents a -CO ₂ M.

R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ³ combine to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom; , R ² and R ⁴ combine to form a ring together with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring, or R ¹ and R ² combine to form a ring together with an adjacent nitrogen atom. The methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a -N (R ⁵ )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the monovalent hydrocarbon group is a halogen atom, cyano group or nitro. The group, carbamoyl group, sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group or an amino group may be substituted.

R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^{5 's} are present, they are the same as or different from each other.

M represents a hydrogen atom or an alkali metal atom]

[2] 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 ring together with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring; The colored curable resin composition according to [1], wherein R ² and R ⁴ are bonded to each other to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom.

[3] 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 ring together with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring; The colored curable resin composition according to [1] or [2], wherein R ² and R ⁴ are bonded to each other to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom.

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

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

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

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

[Iii] The pigment is C.I. Pigment Green 7, C.I. Pigment Green 36 and C.I. The colored curable resin composition in any one of [4]-[7] which is 1 or more types chosen from the group which consists of pigment green 58.

[Iii] The pigment is C.I. Colored curable resin composition as described in [VII] which is Pigment Green 7.

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

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

According to this invention, sublimation of a coloring agent can be suppressed and it becomes possible to provide the colored curable resin composition which provides a color filter.

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

A coloring agent (A) contains the compound represented by Formula (1).

It is preferable that the colored curable resin composition of this invention further contains 1 or more types chosen from the group which consists of a solvent (E) and a surface leveling agent [F].

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

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

<Coloring agent (A)>

It is preferable that a coloring agent (A) contains the compound represented by Formula (1) (henceforth "a compound (1)"), and also contains a pigment (P) further.

Compound (1) also includes tautomers thereof and salts thereof.

In formula (1), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom in R <^1> -R <^4> .

Formula (1) as in, R ¹ to R ⁴ having 1 to 20 carbon atoms of the monovalent hydrocarbon group in, e.g.

Methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, (2-ethyl) butyl group, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, 3-pentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl , (3-ethyl) pentyl group, hexyl group, isohexyl group, 5-methylhexyl group, (2-ethyl) hexyl group, heptyl group, (3-ethyl) heptyl group, octyl group, nonyl group, decyl group, Aliphatic hydrocarbon groups such as undecyl group, dodecyl group, and octadecyl group;

Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclo Hexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2, 5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohex Real group, 4,4-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group, etc. Alicyclic hydrocarbon group;

Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, benzyl group, phenethyl group, biphenyl group, 1- Aromatic hydrocarbon groups such as naphthyl group and 2-naphthyl group;

And groups in which these are combined.

The methylene group constituting such a monovalent hydrocarbon group is substituted with an oxygen atom, a sulfur atom, -N (R ⁵ )-, a sulfonyl group or a carbonyl group, or the hydrogen atom contained in a monovalent hydrocarbon group is a halogen atom, cyano group, nitro group, carbamo Examples of the group substituted with a diary, sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxy group or an amino group include, for example.

Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy and (2-ethyl) hexyloxy;

Aryloxy groups such as phenoxy group;

Aralkyloxy groups such as benzyloxy group;

Alkoxycarbonyl groups such as methoxycarbonyl group, ethoxycarbonyl group and propoxycarbonyl group;

Acyloxy groups, such as an acetoxy group and a benzoyloxy group;

N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-isopropylcarbamoyl group, N-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec-butylcarb Barmoyl group, N-tert-butylcarbamoyl group, N-pentylcarbamoyl group, N- (1-ethylpropyl) carbamoyl group, N- (1,1-dimethylpropyl) carbamoyl group, N- (1, 2-dimethylpropyl) carbamoyl group, N- (2,2-dimethylpropyl) carbamoyl group, N- (1-methylbutyl) carbamoyl group, N- (2-methylbutyl) carbamoyl group, N- ( 3-methylbutyl) carbamoyl group, N-cyclopentylcarbamoyl group, N-hexylcarbamoyl group, N- (1,3-dimethylbutyl) carbamoyl group, N- (3,3-dimethylbutyl) carbamo Diary, N-heptylcarbamoyl group, N- (1-methylhexyl) carbamoyl group, N- (1,4-dimethylpentyl) carbamoyl group, N-octylcarbamoyl group, N- (2-ethylhexyl) Carbamoyl group, N- (1,5-dimethyl) hexylcarbamoyl group, N- (1,1,2,2-tetramethylbutyl) carbamoyl group, etc. N-1-substituted carbamoyl group;

N, N-dimethylcarbamoyl group, N, N-ethylmethylcarbamoyl group, N, N-diethylcarbamoyl group, N, N-propylmethylcarbamoyl group, N, N-isopropylmethylcarbamoyl group, N, N-tert-butylmethylcarbamoyl group, N, N-butylethylcarbamoyl group, N, N-bis (1-methylpropyl) carbamoyl group, N, N-heptylmethylcarbamoyl group, N, N N, N-2 substituted carbamoyl groups, such as -bis (2-ethylhexyl) carbamoyl group;

N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulf Pamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1, 2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- ( 3-methylbutyl) sulfamoyl group, N-cyclopentylsulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamo Diary, N-heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) N-1 substituted sulfamoyl groups, such as a sulfamoyl group, N- (1,5-dimethyl) hexyl sulfamoyl group, and N- (1,1,2,2- tetramethylbutyl) sulfamoyl group;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, N, N N, N-2 substituted sulfamoyl groups, such as -bis (2-ethylhexyl) sulfamoyl group;

N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, N-tert-butylamino group, N-pentylamino group , N- (1-ethylpropyl) amino group, N- (1,1-dimethylpropyl) amino group, N- (1,2-dimethylpropyl) amino group, N- (2,2-dimethylpropyl) amino group, N- ( 1-methylbutyl) amino group, N- (2-methylbutyl) amino group, N- (3-methylbutyl) amino group, N-cyclopentylamino group, N-hexylamino group, N- (1,3-dimethylbutyl) amino group, N- (3,3-dimethylbutyl) amino group, N-heptylamino group, N- (1-methylhexyl) amino group, N- (1,4-dimethylpentyl) amino group, N-octylamino group, N- (2-ethyl N-alkylamino groups such as hexyl) amino group, N- (1,5-dimethyl) hexylamino group and N- (1,1,2,2-tetramethylbutyl) amino group;

N, N-dimethylamino group, N, N-ethylmethylamino group, N, N-diethylamino group, N, N-propylmethylamino group, N, N-isopropylmethylamino group, N, N-tert-butylmethylamino group, N, N-dialkylamino groups such as N, N-butylethylamino group, N, N-bis (1-methylpropyl) amino group, N, N-heptylmethylamino group and N, N-bis (2-ethylhexyl) amino group ;

N-methylaminomethyl group, N-ethylaminomethyl group, N-propylaminomethyl group, N-isopropylaminomethyl group, N-butylaminomethyl group, N-isobutylaminomethyl group, N-sec-butylaminomethyl group, N-tert- Butylaminomethyl group, N-pentylaminomethyl group, N- (1-ethylpropyl) aminomethyl group, N- (1,1-dimethylpropyl) aminomethyl group, N- (1,2-dimethylpropyl) aminomethyl group, N- ( 2,2-dimethylpropyl) aminomethyl group, N- (1-methylbutyl) aminomethyl group, N- (2-methylbutyl) aminomethyl group, N- (3-methylbutyl) aminomethyl group, N-cyclopentylaminomethyl group, N-hexylaminomethyl group, N- (1,3-dimethylbutyl) aminomethyl group, N- (3,3-dimethylbutyl) aminomethyl group, N-heptylaminomethyl group, N- (1-methylhexyl) aminomethyl group, N -(1,4-dimethylpentyl) aminomethyl group, N-octylaminomethyl group, N- (2-ethylhexyl) aminomethyl group, N- (1,5-dimethyl) hexylaminomethyl group, N- (1,1,2 , 2-tetramethylbutyl) aminomethyl group N- alkyl-amino group;

N, N-dimethylaminomethyl group, N, N-ethylmethylaminomethyl group, N, N-diethylaminomethyl group, N, N-propylmethylaminomethyl group, N, N-isopropylmethylaminomethyl group, N, N-tert -Butylmethylaminomethyl group, N, N-butylethylaminomethyl group, N, N-bis (1-methylpropyl) aminomethyl group, N, N-heptylmethylaminomethyl group, N, N-bis (2-ethylhexyl) amino N, N-dialkylaminomethyl groups, such as a methyl group;

Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoroisopropenyl group, perfluoro (1-propenyl) group, perfluoro (2-propenyl) Group, perfluorobutyl group, perfluoroisobutyl group, perfluoro (sec-butyl) group, perfluoro (tert-butyl) group, perfluoro (2-butenyl) group, perfluoro ( 1,3-butadienyl) group, perfluoropentyl group, perfluoro (isopentyl) group, perfluoro (3-pentyl) group, perfluoro neopentyl group, perfluoro (tert-pentyl) group , Perfluoro (1-methylpentyl) group, perfluoro (2-methylpentyl) group, perfluoro (2-pentenyl) group, perfluorohexyl group, perfluoroisohexyl group, perfluoro (5-methylhexyl) group, perfluoro (2-ethylhexyl) group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, perfluorodecyl group, purple Luorododecyl, Perfluoroocta An aliphatic hydrocarbon group having a fluorine atom such as a group;

Perfluorocyclopropyl group, perfluorocyclobutyl group, perfluorocyclopentyl group, perfluorocyclohexyl group, perfluorocyclohexenyl group, perfluorocycloheptyl group, perfluoro (1-methyl Cyclohexyl) groups, perfluoro (2-methylcyclohexyl) groups, perfluoro (3-methylcyclohexyl) groups, perfluoro (4-methylcyclohexyl) groups, perfluoro (1,2-dimethyl Cyclohexyl) group, perfluoro (1,3-dimethylcyclohexyl) group, perfluoro (1,4-dimethylcyclohexyl) group, perfluoro (2,3-dimethylcyclohexyl) group, perfluoro (2,4-dimethylcyclohexyl) group, perfluoro (2,5-dimethylcyclohexyl) group, perfluoro (2,6-dimethylcyclohexyl) group, perfluoro (3,4-dimethylcyclohexyl) ), Perfluoro (3,5-dimethylcyclohexyl) group, perfluoro (2,2-dimethylcyclohexyl) group, perfluoro (3,3-dimethylcyclohex) Group), perfluoro (4,4-dimethylcyclohexyl) group, perfluoro (2,4,6-trimethylcyclohexyl) group, perfluoro (2,2,6,6-tetramethylcyclohexyl Alicyclic hydrocarbon group having a fluorine atom such as a) group and a perfluoro (3,3,5,5-tetramethylcyclohexyl) group;

Perfluorophenyl group, perfluoro (o-tolyl) group, perfluoro (m-tolyl) group, perfluoro (p-tolyl) group, perfluoroxylyl group, perfluoromethyl group, perfluoro (o-cumenyl) group, perfluoro (m-cumenyl) group, perfluoro (p-cumenyl) group, perfluorobenzyl group, perfluorophenethyl group, perfluorobiphenyl group, perfluoro (1-naphthyl) group, perfluoro (2-naphthyl) group, 1-trifluoromethylphenyl group, 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group Aromatic hydrocarbon groups having a fluorine atom such as;

Perfluoromethoxy group, perfluoroethoxy group, perfluoropropoxy group, perfluoro (isopropoxy) group, perfluorobutoxy group, perfluoro (isobutoxy) group, perfluoro (sec -Butoxy) group, perfluoro (tert-butoxy) group, perfluoropentyloxy group, perfluorophenoxy group, perfluorobenzyloxy group, 2,2,2-trifluoroethoxy group, (Perfluoroethyl) methoxy group, (perfluoropropyl) methoxy group, (perfluoro (isopropyl)) methoxy group, (perfluoro (isopropenyl)) methoxy group, (perfluoro (1- Propenyl)) methoxy group, (perfluoro (2-propenyl)) methoxy group, (perfluorobutyl) methoxy group, (perfluoro (isobutyl)) methoxy group, (perfluoro (sec-butyl) )) Methoxy group, (perfluoro (tert-butyl)) methoxy group, (perfluoro (2-butenyl)) methoxy group, (perfluoro (1,3-butadienyl)) methoxy group, ( Perfluoropentyl) methoxy group, (perfluoro (isopentyl) ) Methoxy group, (perfluoro (3-pentyl)) methoxy group, (perfluoro (neopentyl)) methoxy group, (perfluoro (tert-pentyl)) methoxy group, (perfluoro (1-methyl) Pentyl)) methoxy group, (perfluoro (2-methylpentyl)) methoxy group, (perfluoro (2-pentenyl)) methoxy group, (perfluorohexyl) methoxy group, (perfluoro (isohexyl) )) Methoxy group, (perfluoro (5-methylhexyl)) methoxy group, (perfluoro ((2-ethyl) hexyl)) methoxy group, (perfluoroheptyl) methoxy group, (perfluorooctyl) Methoxy group, (perfluorononyl) methoxy group, (perfluorodecyl) methoxy group, (perfluorodecyl) methoxy group, (perfluorododecyl) methoxy group, (perfluorooctadecyl) methoxy group Substituted oxy group which has a fluorine atom, such as these;

2,3-bis (trifluoromethyl) phenylmethyl group, 2,4-bis (trifluoromethyl) phenylmethyl group, 2,5-bis (trifluoromethyl) phenylmethyl group, 2,6-bis (trifluoro Rhomethyl) phenylmethyl group, 3, 4-bis (trifluoromethyl) phenylmethyl group, 3, 5-bis (trifluoromethyl) phenylmethyl group, etc. are mentioned.

As R <^1> and R <^{2>, an} aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group is preferable. 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, alicyclic hydrocarbon group or aromatic hydrocarbon group. The hydrogen atom contained in the said aromatic hydrocarbon group may be substituted by the aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group.

As R <^{1>, a} C1-C10 aliphatic hydrocarbon group is preferable. Among these, ethyl group, butyl group, hexyl group, (2-ethyl) hexyl group and octyl group are more preferable, ethyl group, butyl group, hexyl group and (2-ethyl) hexyl group are still more preferable, and (2-ethyl) hex Real groups are particularly preferred. R ¹ is such a group The compound of the present invention is excellent in solubility in a solvent.

As R <^{2>, a} C1-C10 aliphatic hydrocarbon group is preferable. Among these, ethyl group, butyl group, hexyl group, (2-ethyl) hexyl group and octyl group are more preferable, ethyl group, butyl group, hexyl group and (2-ethyl) hexyl group are still more preferable, hexyl group and (2- Ethyl) hexyl group is particularly preferred. R ² is such a group The compound of the present invention is excellent in solubility in a solvent.

It is preferable that R <^3> and R <^4> are hydrogen atoms from the point which manufacture is easy.

When R ¹ and R ³ combine to form a ring with carbon atoms on adjacent benzene rings and adjacent nitrogen atoms, and also R ² and R ⁴ combine to form carbon atoms on adjacent benzene rings and adjacent nitrogen atoms When forming a ring together with * -R ¹ -R ^3- * and * -R ² -R ^4- * are * -CH ₂ -CH _2- *, * -CF ₂ -CF _2- *, *- CH ₂ -C (CH ₂ ) _5- * or * -CH ₂ -C (CH ₃ ) _2- * and the like, and * -CH ₂ -CH _2- * and * -CH ₂ -C (CH _3). ) _2- * is preferable, and * -CH ₂ -C (CH ₃ ) _2- * is more preferable. * Represents a combined arm.

When R ¹ and R ² combine to form a ring together with an adjacent nitrogen atom, as * -R ¹ -R ^2- *, *-(CH ₂ ) _2- *, *-(CH ₂ ) _3- *, *-(CH ₂ ) _4- *, *-(CH ₂ ) _5- *, *-(CH ₂ ) _6- *, *-(CH ₂ ) _7- *, *-(CF ₂ ) _2- *, *-(CF ₂ ) _3- *, *-(CF ₂ ) _4- *, *-(CF ₂ ) _5- *, *-(CF ₂ ) _6- *, *-(CF ₂ ) _7- * *-(CH ₂ ) _4- *, *-(CH ₂ ) _5- *, *-(CH ₂ ) _6- *, *-(CF ₂ ) _4- *, *-(CF ₂ ) _5- * and *-(CF ₂ ) _6- * are preferred, among which *-(CH ₂ ) _4- *, *-(CH ₂ ) _5- * and *-(CH ₂ ) _6- * With preference, *-(CH ₂ ) _4- * and *-(CH ₂ ) _5- * are particularly preferred. * Represents an arm.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms for R ⁵ include methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, butyl group, isobutyl group and sec-butyl Group, tert-butyl group, (2-ethyl) butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, 3-pentyl group, neopentyl group, tert-pentyl group, 1 -Methylpentyl group, 2-methylpentyl group, 2-pentenyl group, (3-ethyl) pentyl group, hexyl group, isohexyl group, 5-methylhexyl group, (2-ethyl) hexyl group, heptyl group, (3 Aliphatic hydrocarbon groups such as -ethyl) heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group and octadecyl group;

Cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclo Hexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2, 5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohex Real group, 4,4-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group, etc. Alicyclic hydrocarbon group;

Phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, mesityl group, o-cumenyl, m-cumenyl, p-cumenyl, benzyl group, phenethyl group, biphenyl group, 1- Aromatic hydrocarbon groups such as naphthyl group and 2-naphthyl group;

And groups in which these are combined.

M represents a hydrogen atom or an alkali metal atom, Preferably it is a hydrogen atom, a sodium atom, or a potassium atom, More preferably, it is a hydrogen atom.

Examples of the compound (1) Q ¹ is -CO ₂ M, for example, there may be mentioned the respective compounds and salts thereof shown by the formula (1-1) to (1-44).

Examples of the compound (1), Q ² is -CO ₂ M, for example, there may be mentioned the respective compounds and salts thereof shown by the formula (1-45) to (1-88).

From the viewpoint of easy synthesis, as the compound (1), the compound (1-1) to the compound (1-1), the compound (1-15) to the compound (1-42), and the compound (1-4) to the compound (1) -5-2) and compound (1-5 ')-compound (1-6) are preferable, Among these, compound (1-1)-compound (1-4), compound (1-15)-compound (1-323) ), Compound (1-3 ') to compound (1-4'2), compound (1-4') and compound (1-4 '), compound (1-5') to compound (1-7 '), and compound (1'-3') ) To Compound (1-6) are more preferred, and among these, Compound (1-1) to Compound (1-4), Compound (1-15) to Compound (1-20) and Compound (1-277) to Compound (1-2), compound (1-3) to compound (1-3), compound (1-3) to compound (1-442), compound (1 45) to compound (1-4 '), compound (1-5') to compound (1-6), compound (1-7 ') to compound (1-7'), compound (1-7'7) to compound (1'76 ') ), And compounds (1-1-4) to (1-1-6) are even more preferable.

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

Specifically, compound (1) can be manufactured by cyclizing-reacting the compound represented by Formula (X1), the compound represented by Formula (X2), and ethyl cyanoacetate in presence of benzoic acid and a solvent. The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 100 ° C to 150 ° C. The reaction time is preferably 1 hour to 24 hours, more preferably 8 hours to 16 hours. As said solvent, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, N-methylpyrrolidone, etc. are mentioned, 1-pentanol is preferable.

[In formula (X1) and formula (X2), R <^1> -R <^4> , Q <^1> and Q <^2> represent the same meaning as the above, respectively.]

In the preparation of compound (1), the amount of the compound represented by formula (X1) is preferably 1 mol to 10 mol, more preferably 1 mol to 4 mol, with respect to 1 mol of the compound represented by formula (X2). Still more preferably 1 mol to 3 mol, even more preferably 1 mol.

In the preparation of compound (1), the amount of ethyl cyanoacetate used is preferably 1 mole to 10 moles, more preferably 1 mole to 4 moles, and still more preferably 1 mole of compound represented by formula (X2). Preferably 1 to 3 mol, even more preferably 1 mol.

In the preparation of compound (1), the amount of benzoic acid used is preferably 0.1 mol to 3 mol, more preferably 0.3 mol to 3 mol, and even more preferably 0.3 to 1 mol of the compound represented by formula (XII). Moles to 1.2 moles, even more preferably 0.3 moles to 0.4 moles.

The method of obtaining the compound (1) which is a target compound from a reaction mixture is not specifically limited, Various well-known methods can be employ | adopted. For example, it is preferable to precipitate a crystal | crystallization by the method of adjusting the temperature of a reaction mixture suitably, or to add the reaction mixture to the solvent in which compound (1) does not melt | dissolve, and to obtain the said crystal | crystallization by filtering. The crystals obtained by filtration are water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, N, N It is preferable to wash or recrystallize with a solvent such as -dimethylformamide, N-methylpyrrolidone, chloroform or a mixture thereof, and then dry. Moreover, you may refine | purify further by well-known methods, such as column chromatography or recrystallization as needed.

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

As the pigment, for example, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139 Yellow pigments such as, 147, 148, 150, 153, 154, 166, 173, 180, 194, 214;

C.I. Pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like orange pigments;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, etc. ;

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

C.I. Violet pigments such as pigment violet 1, 14, 19, 23, 29, 32, 33, 36, 37, 38;

C.I. Green pigments such as pigment green 7, 10, 15, 25, 36, 47 and 58;

C.I. Brown pigments such as Pigment Brown 23 and 25;

C.I. Black pigments, such as pigment black 1 and 7, etc. are mentioned.

Pigment (P) is preferably a phthalocyanine pigment, more preferably at least one member selected from the group consisting of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment, still more preferably C.I. Pigment green 7, 36, and 58 or more selected from the group consisting of. Such a pigment is suitably used as a green pigment, and by including the above pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

Pigments may be rosin-treated, surface-treated using a pigment derivative having an acidic or basic group introduced therein, graft treatment on the surface of the pigment with a high molecular compound, atomization by sulfuric acid atomization, or the like, or removing impurities. To this end, washing with an organic solvent, water, or the like, removal with ionic impurities by ion exchange, or the like may be performed. It is preferable that the particle diameter of a pigment is respectively uniform.

A pigment can be made into the pigment dispersion liquid of the form disperse | distributed uniformly in the pigment dispersant solution by containing and disperse | distributing a pigment dispersant. The pigments may be individually subjected to dispersion treatment, or a plurality of species may be mixed and dispersed.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used alone or in combination of two or more thereof. As a pigment dispersant, brand names KP [made by Shin-Etsu Chemical Co., Ltd.], Floren [made by Kyoeisha Chemical Co., Ltd.], Solsperth [made by Geneca Co., Ltd.], EFKA (made by CIBA Corporation), Ajisper [Ajinomoto Fine Co., Ltd.] Techno Co., Ltd.], Disperbyk (made by BIC Chem), etc. are mentioned.

When using a pigment dispersant, its usage-amount is preferably 100 mass parts or less with respect to 100 mass parts of pigments, More preferably, they are 5 mass parts or more and 50 mass parts or less. When the usage-amount of a pigment dispersant exists in said range, there exists a tendency for the pigment dispersion liquid of a more uniform dispersion state to be obtained.

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 even more preferably 1% by mass with respect to the total amount of the coloring agent (A). It is 65 mass% or more, More preferably, it is 2 mass% or more and 60 mass% or less.

When it contains a pigment (P), its content rate is 10 mass% or more and 99.99 mass% or less with respect to the total amount of a coloring agent (A), More preferably, it is 20 mass% or more and 99.9 mass% or less, More preferably Preferably it is 35 mass% or more and 99 mass% or less, More preferably, they are 40 mass% or more and 98 mass% or less.

The content rate of a coloring agent (A) is 1 mass% or more and 99 mass% or less with respect to the total amount of solid content normally, Preferably they are 2 mass% or more and 90 mass% or less, More preferably, they are 3 mass% or more and 80 mass%. Or less, still more preferably 5 mass% or more and 70 mass% or less, even more preferably 5 mass% or more and 60 mass% or less, and particularly preferably 5 mass% or more and 50 mass% or less. If the content rate of a coloring agent (A) exists in the said range, desired spectroscopy and color density can be obtained.

In this specification, "total amount of solid content" means the total amount of the component remove | excluding the solvent (E) from the colored curable resin composition of this invention. The total amount of solids and the content of each component thereof can be measured by known analytical means, such as liquid chromatography or gas chromatography, for example.

<Resin>

Although resin (B) is not specifically limited, It is preferable that it is alkali-soluble resin, The addition polymer which has a structural unit derived from 1 or more types chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride is more preferable. As such resin, the following resin [K1]-[K6] etc. are mentioned.

Resin [1] At least one selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter referred to as "a"), a cyclic ether structure having 2 to 4 carbon atoms and ethylenically unsaturated Copolymers of monomers having a bond (hereinafter referred to as "(iii)");

The resin (a) and (b) and the air of the monomer (c) copolymerizable with (a), but different from (a) and (v) (hereinafter referred to as "(c)"). coalescence;

Copolymers of the resins (a) and (c);

Resin [4] Resin which (v) was made to react with the copolymer of (a) and (c);

Resin [A5] (a) was made to react the copolymer of (b) and (c);

Resin [6] Resin which (a) was made to react with the copolymer of (b) and (c), and the carboxylic anhydride was made to react.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinyl benzoic acid;

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

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2-ene, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene , 5-carboxy-5-methylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-carboxy-6-methylbicyclo Bicyclo unsaturated compounds containing a carboxyl group such as [2.2.1] hepto-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hepto-2-ene;

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

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

and unsaturated acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid.

Among them, acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity or the solubility of the obtained resin in an aqueous alkali solution.

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

Moreover, in this specification, "(meth) acrylic acid" represents 1 or more types chosen from the group which consists of acrylic acid and methacrylic acid. Notation, such as "(meth) acryloyl" and "(meth) acrylate", has the same meaning.

As (iii), for example, a monomer (X1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter referred to as "(X1)") and a monomer (X2) having an oxetanyl group and an ethylenically unsaturated bond [hereinafter, "(B2)", the monomer (3) (henceforth "(3)") etc. which have a tetrahydrofuryl group and ethylenically unsaturated bond are mentioned.

As (b1), for example, a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (X1-1) (hereinafter referred to as "(X1-1)"), and an alicyclic unsaturated hydrocarbon is epoxy. Monomer (X12) (hereinafter, referred to as "(X1-2)") having a structured structure is mentioned.

As (191-1) glycidyl (meth) acrylate, (beta) -methylglycidyl (meth) acrylate, (beta) -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, and o-vinyl benzylglycol Cylyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α- Methyl-p-vinylbenzylglycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl ) Styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5-tris (glycidyloxymethyl) styrene, 2 , 3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (glycidyloxymethyl) styrene, and the like. have.

Examples of (B1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl (meth) acrylate, and 3,4-epoxycyclohexylmethyl (meth) acrylic Rate [eg, cyclomer M100; Daicel Corporation], the compound represented by Formula (I), the compound represented by Formula (II), etc. are mentioned.

[In formula (I) and formula (II), R ^<a> and R <^b> represent a hydrogen atom or a C1-C4 alkyl group, and the hydrogen atom contained in the said alkyl group may be substituted by the hydroxy group.

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

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

* Represents the arm with O]

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

As an alkyl group in which a hydrogen atom was substituted by hydroxy, it is a hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy The -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4-hydroxybutyl group, etc. are mentioned.

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

Examples of the alkanediyl group are methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group, butane-1,4-diyl group, pentane-1,5-diyl group, hexane-1, 6-diyl group etc. are mentioned.

X ^a and X ^{b are} preferably a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and more preferably a single bond and * -CH ₂ CH ₂ -O- (* represents a bonding arm with O).

As a compound represented by Formula (I), the compound etc. which are represented by either of Formula (I-1)-Formula (I-15) are mentioned. Among these, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-V), or formulas (I- 11) to formula (I-15) ) Is preferable, and the compound represented by formula (I-1), formula (I-7), formula (I-X) or formula (I-15) is more preferable.

Examples of the compound represented by formula (II) include compounds represented by any one of formulas (II-1) to (II-15). Among these, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-V) or formulas (II-1 11) to formula (II-15) ) Is preferable, and the compound represented by formula (II-1), formula (II-7), formula (II-1) or formula (II-15) is more preferable.

The compound represented by Formula (I) and the compound represented by Formula (II) may be used independently, respectively, and may use the compound represented by Formula (I) and the compound represented by Formula (II) together. When using these together, the content rate of the compound represented by Formula (I) and the compound represented by Formula (II) is preferably from 5:95 to 95: 5, more preferably from 10:90 to 90:10 on a molar basis. And even more preferably 20:80 to 80:20.

As (b2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is more preferable. As (b2), 3-methyl-3-methacryloyloxy methyl oxetane, 3-methyl-3- acryloyloxy methyl oxetane, 3-ethyl-3-methacryloyloxy methyl oxetane, 3- Ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacrylo Iloxy ethyl oxetane, 3-ethyl-3- acryloyloxy ethyl oxetane, etc. are mentioned.

As (b3), the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is more preferable. Specific examples of (iii) include tetrahydrofurfuryl acrylate (for example, biscot V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(b) It is preferable that it is (b1) from the point which can further improve reliability, such as heat resistance and chemical-resistance of the color filter obtained. Furthermore, (b 1-2) is more preferable at the point which is excellent in the storage stability of colored curable resin composition.

As (c), for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- butyl (meth) acrylate, 2 Ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2 -Methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate (in the art, it is commonly known as "dicyclopentanyl (meth) acrylate" Also referred to as "tricyclodecyl (meth) acrylate", tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate (in the art, the common name is "dicyclopentenyl ( Methacrylate)), dicycle Lofentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, aryl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, (Meth) acrylic acid esters such as naphthyl (meth) acrylate and benzyl (meth) acrylate;

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

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

Bicyclo [2.2.1] hepto-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxybi Cyclo [2.2.1] hepto-2-ene, 5-hydroxymethylbicyclo [2.2.1] hepto-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hepto-2 -Ene, 5-methoxybicyclo [2.2.1] hepto-2-ene, 5-ethoxybicyclo [2.2.1] hepto-2-ene, 5,6-dihydroxybicyclo [2.2.1 ] Hepto-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hepto-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2.1] Hepto-2-ene, 5,6-dimethoxybicyclo [2.2.1] hepto-2-ene, 5,6-diethoxybicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5 -Methylbicyclo [2.2.1] hepto-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hepto-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2. 1] hepto-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5- Cyclohexyloxycarbonylbicyclo [2.2.1] hepto-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl Bicyclo unsaturated compounds, such as) bicyclo [2.2.1] hepto-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexyl maleimide, N-benzyl maleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl- Dicarbonylimide derivatives such as 6-maleimide caproate, N-succinimidyl-3-maleimide propionate and N- (9-acridinyl) maleimide;

Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, acetic acid Vinyl, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among them, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hepto-2-ene and the like are preferred.

In resin [K1], the ratio of the structural unit derived from each is in all the structural units which comprise resin [K1],

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

structural units derived from (iii); 40 to 98 mol%

Is preferably,

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

structural units derived from (iii); 50 to 90 mol%

More preferably.

When the ratio of the structural unit of resin [X1] exists in the said range, there exists a tendency for the storage stability of colored curable resin composition, the developability at the time of forming a coloring pattern, and the solvent resistance of the color filter obtained to be excellent.

Resin [1] is, for example, the method described in the document "Experimental method of polymer synthesis" [Okasu Takayuki, published by Chemical Co., Ltd., First Edition, First Edition, issued March 1, 1972] and the documents described above. It may be prepared with reference to the cited literature.

Specifically, the method of heating and keeping warm while putting predetermined amount of (a) and (iv), a polymerization initiator, a solvent, etc. in a reaction container, and replacing oxygen with nitrogen, for example, stirring in a deoxidation atmosphere is mentioned. have. Moreover, the polymerization initiator, solvent, etc. which are used here are not specifically limited, What is normally used in the said field | area can be used. For example, as a polymerization initiator, an azo compound [2,2'- azobisisobutyronitrile, 2,2'- azobis (2, 4- dimethylvaleronitrile), etc.], an organic peroxide (benzoyl peroxide etc.) Examples of the solvent may be those obtained by dissolving respective monomers, and examples of the solvent (E) described below as the solvent (E) of the colored curable resin composition of the present invention may be mentioned.

Moreover, the obtained copolymer may use the solution after reaction as it is, may use the concentrated or diluted solution, and may use what extracted as solid (powder) by methods, such as reprecipitation. In particular, since the solution after reaction can be used for preparation of the colored curable resin composition of this invention as it is by using the solvent contained in the colored curable resin composition of this invention as a solvent at the time of this superposition | polymerization, of the colored curable resin composition of this invention The manufacturing process can be simplified.

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

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

structural units derived from (iii); 2 to 95 mol%

structural unit derived from (c); 1 to 65 mol%

Is preferably,

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

structural units derived from (iii); 5 to 80 mol%

structural unit derived from (c); 5 to 60 mol%

More preferably.

When the ratio of the structural unit of resin is in the said range, the storage stability of a colored curable resin composition, developability at the time of forming a colored pattern, and the solvent resistance, heat resistance, and mechanical strength of the color filter obtained tend to become excellent. There is this.

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

In resin [K3], the ratio of the structural unit derived from each is in the all the structural units which comprise resin [K3],

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

structural unit derived from (c); 40 to 98 mol%

Is preferably,

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

structural unit derived from (c); 50 to 90 mol%

More preferably.

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

Resin [4] can be manufactured by obtaining the copolymer of (a) and (c), and adding the C2-C4 cyclic ether which (b) has to the carboxylic acid and / or carboxylic anhydride which (a) has Can be.

First, the copolymer of (a) and (c) is manufactured similarly to the method described as a manufacturing method of resin [K1]. In this case, it is preferable that the ratio of the structural unit derived from each is the same ratio as what was heard with resin [K3].

Next, the C2-C4 cyclic ether which (b) has is made to react with a part of carboxylic acid and / or carboxylic anhydride derived from (a) in the said copolymer.

Subsequent to the production of the copolymers of (a) and (c), the atmosphere in the flask was replaced with nitrogen from air, and (i) a reaction catalyst of carboxylic acid or carboxylic anhydride with a cyclic ether [for example, Tris (dimethylaminomethyl) phenol and the like] and a polymerization inhibitor (for example, hydroquinone and the like) and the like are placed in a flask and reacted at 60 to 130 ° C. for 1 to 10 hours to produce a resin [4]. Can be.

The use amount of (iii) is preferably 5 to 80 moles, more preferably 10 to 75 moles, relative to 100 moles of (a). By setting it as this range, there exists a tendency for the balance of the storage stability of colored curable resin composition, the developability at the time of forming a pattern, and the solvent resistance, heat resistance, mechanical strength, and the sensitivity of the pattern obtained to become more favorable. Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (iv), as (v) used for resin [4], (b1) is preferable and (b1-1) is still more preferable.

As for the usage-amount of the said reaction catalyst, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (iii) and (c). As for the usage-amount of the said polymerization inhibitor, 0.001-5 mass parts is preferable with respect to 100 mass parts of total amounts of (a), (iv) and (c).

Reaction conditions, such as a mixing | blending method, reaction temperature, and time, can be suitably adjusted in consideration of a heat generation amount by a manufacturing facility, superposition | polymerization, etc. In addition, the mixing method and the reaction temperature can be appropriately adjusted in consideration of the amount of heat generated by the production equipment, polymerization, and the like in the same manner as the polymerization conditions.

Resin [K5] is carried out similarly to the manufacturing method of resin [K1] mentioned above as a 1st step, and obtains the copolymer of (i) and (c). In the same manner as described above, the obtained copolymer may be used as it is, the concentrated or diluted solution may be used, or the extracted copolymer may be used as a solid (powder) by a method such as reprecipitation.

The ratio of the structural unit derived from (iii) and (c) is respectively with respect to the total number of moles of all the structural units which comprise the said copolymer.

structural units derived from (iii); 5 to 95 mol%

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

Is preferably,

structural units derived from (iii); 10 to 90 mol%

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

More preferably.

Furthermore, the carboxylic acid or carboxylic anhydride which (a) has reacts with the cyclic ether derived from (i) which the copolymer of (i) and (c) has on the same conditions as the manufacturing method of resin [4]. By doing so, resin [K5] can be obtained.

As for the usage-amount of (a) made to react with said copolymer, 5-80 mol is preferable with respect to 100 mol of (iv). Since the reactivity of a cyclic ether is high and it is hard to remain unreacted, (b) is preferable as (b) used for resin [k5], and (b1-1) is still more preferable.

Resin [6] is resin which made carboxylic anhydride further react with resin [5]. A carboxylic anhydride is made to react with the hydroxyl group which arises by reaction of a cyclic ether and carboxylic acid or carboxylic anhydride.

As the carboxylic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetra Hydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hepto-2-ene anhydride, and the like. As for the usage-amount of carboxylic anhydride, 0.5-1 mol is preferable with respect to 1 mol of use of (a).

Specific examples of the resin include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxycyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth Resins such as) acrylic acid copolymer; Glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxy cicyclo [5.2 .1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl (meth) acrylate / (meth) acrylic acid / Resins such as vinyltoluene copolymer and 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; Resins such as benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [3] ]; Glycidyl (meth) to a resin in which glycidyl (meth) acrylate is added to a benzyl (meth) acrylate / (meth) acrylic acid copolymer, and tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer Resin, such as resin which added the acrylate and resin which added glycidyl (meth) acrylate to the tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer; Of resin which made (meth) acrylic acid react with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, and tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resins such as resins in which (meth) acrylic acid is reacted with a copolymer; Resins, such as resin which made tetrahydrophthalic anhydride react with resin which (meth) acrylic acid reacted with the copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, etc. are mentioned. .

Resin (B) is preferably 1 type selected from the group which consists of resin [K1], resin [K2], and resin [K3], More preferably, it is selected from the group which consists of resin [K2] and resin [K3]. It is one kind. If it is such resin, colored curable resin composition is excellent in developability. Resin [B2] is still more preferable from a viewpoint of adhesiveness of a coloring pattern and a board | substrate.

The weight average molecular weight of polystyrene conversion of resin (K) is normally 3,000-100,000, Preferably it is 5,000-50,000, More preferably, it is 5,000-35,000, More preferably, it is 5,000-30,000, Especially preferably, 6,000 To 30,000. When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is also high, and the solubility in the developer of the unexposed part is good, so that the resolution of the colored pattern tends to be improved.

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

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

The content of the resin is preferably 7% by mass to 65% by mass, more preferably 10% by mass to 60% by mass, even more preferably 13% by mass to 60% by mass relative to the total amount of solids. And particularly preferably 17% by mass to 55% by mass. When content of resin exists in the said range, coloring pattern formation is easy and there exists a tendency for the resolution and residual film rate of a coloring pattern to improve.

<Polymeric Compound (C)>

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

As a polymeric compound which has one ethylenically unsaturated bond, nonylphenyl carbitol acrylate, 2-hydroxy-3- phenoxy propyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl, for example Acrylate, N-vinylpyrrolidone, etc., and (a), (iv), and (c) mentioned above are mentioned.

As a polymeric compound which has two ethylenically unsaturated bonds, for example, 1, 6- hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene Glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

Among these, it is preferable that a polymeric compound (C) is a polymeric compound which has three or more ethylenically unsaturated bonds. As such a polymeric compound, a trimethylol propane tri (meth) acrylate, a pentaerythritol tri (meth) acrylate, a pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, for example , Dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (Meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol Modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate Y, a caprolactone modified pentaerythritol tetra (meth) acrylate, a caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Among these, 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.

It is preferable that content of a polymeric compound (C) is 1-70 mass% with respect to the total amount of solid content, Among these, it is preferable that it is 2-65 mass%, Among these, it is preferable that it is 5-65 mass%, It is 7- 65 mass% is preferable, Among these, More preferably, it is 10-60 mass%, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%.

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

When content of a polymeric compound (C) exists in the said range, it exists in the tendency for the residual film ratio at the time of coloring pattern formation, and the chemical-resistance of a color filter to improve.

<Polymerization Initiator (D)>

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

Examples of the polymerization initiator (D) include alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds, biimidazole compounds and the like.

The O-acyl oxime compound is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a coupling arm.

As said O-acyl oxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl, for example) ) Octan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3 , 3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl] -3-cyclopentylpropane-1-one-2-imine, and the like. You may use commercially available products, such as monocure OXE01, OXE02 (above, BASF Corporation), and N-1919 (ADEKA Corporation). Among these, the O-acyl oxime compound is N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane At least one selected from the group consisting of -1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferred, And N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

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

As a compound which has a partial structure represented by a formula (d2), for example, 2-methyl- 2-morpholino- 1- (4-methylsulfanylphenyl) propane- 1-one, 2-dimethylamino-1- ( 4-morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane -1-one etc. are mentioned. You may use commercial items, such as Ilgacure 369, 907, 379 (above, BASF Corporation make).

As a compound which has a partial structure represented by a formula (d3), for example, 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2 Oligomers of -hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, (alpha), (alpha)-diethoxy acetophenone, benzyl dimethyl ketal, etc. are mentioned.

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

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

[In formula (d5), R <^51> -R <^56> represents the C6-C10 aryl group which may have a substituent.]

As a C6-C10 aryl group, a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, etc. are mentioned, for example, Preferably it is a phenyl group.

As a substituent, a halogen atom, a C1-C4 alkoxy group, etc. are mentioned, for example. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, butoxy group etc. are mentioned, for example, Preferably it is a methoxy group.

As a biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl biimidazole, 2,2'-bis (2,3-dichloro, for example). Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis (2-chloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), phenyl group at 4,4', 5,5'-position And imidazole compounds substituted with a carboalkoxy group (for example, see JPH07-10913-A). Among these, compounds represented by the following formula and mixtures thereof are preferable.

As said triazine compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

2,4,6-trimethylbenzoyl diphenylphosphine oxide etc. are mentioned as said acylphosphine oxide compound.

Furthermore, as a polymerization initiator (D), Benzoin compounds, such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; Benzophenone, methyl o-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, Benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphor quinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compound and the like. It is preferable to use these in combination with the polymerization initiator adjuvant (D1) [especially amines] mentioned later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one member selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyl oxime compounds and biimidazole compounds, more preferably. Preferably it is a polymerization initiator containing an O-acyl oxime compound.

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

<Polymerization start preparation (D1)>

The polymerization initiator (D1) is a compound or sensitizer used to promote the polymerization of the polymerizable compound in which polymerization is initiated by the polymerization initiator. When it contains a polymerization initiator (D1), it is normally used in combination with a polymerization initiator (D).

Examples of the polymerization initiator (D1) include an amine compound, an alkoxy anthracene compound, a thioxanthone compound, a carboxylic acid compound, and the like.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoic acid, 4-dimethylaminobenzoic acid ethyl, 4-dimethylaminobenzoic acid isoamyl, 2-dimethylaminoethyl benzoic acid and 4-dimethylaminobenzoic acid 2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone [commonly known as Michler's ketone], 4,4'-bis (diethylamino) benzophenone, 4,4 '-Bis (ethylmethylamino) benzophenone and the like can be cited. Among these, 4,4'-bis (diethylamino) benzophenone is preferable. You may use commercial items, such as EAB-F (made by Hodogaya Chemical Co., Ltd.).

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

As said thioxanthone compound, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy city Oxanthone etc. are mentioned.

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

When using such a polymerization initiator (D1), its content becomes like this. Preferably it is 0.1-30 mass parts with respect to 100 mass parts of total amounts of resin (K) and a polymeric compound (C), More preferably, it is 1-20. It is a mass part. When the amount of the polymerization initiator (D1) is within this range, the coloring pattern can be formed with higher sensitivity, and the productivity of the color filter tends to improve.

<Solvent (E)>

Although solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (solvent containing -COO- in a molecule and not containing -O-), an ether solvent (solvent containing -O- in a molecule and not containing -COO-), ether ester Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and no -COO-), alcoholic solvents (containing OH in the molecule,- Solvents not containing O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

As the ester solvent, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyric acid Butyl, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetic acid, ethyl acetoacetic acid, cyclohexanol acetate, gamma -butyrolactone, and the like.

As the ether solvent, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene 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-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methylethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phentol, methyl anisole, etc. Can be mentioned.

As an ether ester solvent, methyl methoxy acetate, ethyl methoxy acetate, methoxy acetate butyl, ethoxy acetate methyl, ethoxy acetate ethyl, 3-methoxy propionate methyl, 3-methoxy propionate ethyl, 3-ethoxy propionate methyl, Ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionic acid, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-methoxy-2-methyl Methyl propionate, 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol mono There may be mentioned ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.

As the ketone solvent, 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentane Warm, cyclohexanone, isophorone and the like.

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

Benzene, toluene, xylene, mesitylene etc. are mentioned as an aromatic hydrocarbon solvent.

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

These solvents may be used independently or may use 2 or more types together.

Among these, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, 3-ethoxy propionate ethyl, 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-dimethylformamide, N-methylpyrrolidone and the like are preferred. , 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, 3-ethoxy Ethyl propionate, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are more preferable.

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

<Surface Leveler (F)>

Examples of the surface leveling agent (F) include silicone-based surfactants, fluorine-based surfactants, and silicone-based surfactants having fluorine atoms. These may have a polymeric group in a side chain.

As silicone type surfactant, surfactant etc. which have a siloxane bond in a molecule | numerator are mentioned. Specifically, Torre silicon DC3PA, toray silicon SH7PA, toray silicon DC11PA, toray silicon SH21PA, toray silicon SH28PA, toray silicon SH29PA, toray silicon SH30PA, toray silicon SH8400 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 [Momental Performance Materials Japan] Joint venture company] etc. are mentioned.

As said fluorine-type surfactant, surfactant etc. which have a fluoro carbon chain in a molecule | numerator are mentioned. Specifically, Floroid (registered trademark) FC430, Floride FC431 (manufactured by Sumitomo 3M Co., Ltd.), Mega Pack (registered trademark) F142D, Mega Pack F171, Mega Pack F172, Mega Pack F173, Mega Pack F177, Mega Pack F183, Megapack F554, Megapack R30, Megapack RS-718-K [manufactured by DIC Corporation], FTOP® EF301, Ftop EF303, Ftop EF351, Ftop EF352 [Mitsubishi Material Electronic Chemicals Saffron (registered trademark) S381, Saffron S382, Saffron SC101, Saffron SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.). have.

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

The content of the surface leveling agent (F) is preferably 0.0005% by mass or more and 0.6% by mass or less, more preferably 0.001% by mass or more and 0.5% by mass or less, even more preferably 0.001 with respect to the total amount of the colored curable resin composition. It is mass% or more and 0.2 mass% or less, More preferably, they are 0.002 mass% or more and 0.1 mass% or less, Especially preferably, they are 0.005 mass% or more and 0.07 mass% or less. If the content of the surface leveling agent (F) is within the above range, the flatness of the color filter may be good.

<Other Ingredients>

The colored curable resin composition of this invention may contain additives known in the art, such as a filler, another high molecular compound, an adhesion promoter, antioxidant, an optical stabilizer, a chain transfer agent, as needed.

<The manufacturing method of colored curable resin composition>

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

The pigment in the case of containing a pigment (P) is previously mixed with a part or all of the solvent (E), and it disperse | distributes using a beads mill etc. until the average particle diameter of a pigment becomes about 0.2 micrometer or less. It is preferable. Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin as needed. The target colored curable resin composition can be prepared by mixing in the pigment dispersion liquid obtained in this way and making the remaining component into a predetermined density | concentration.

It is preferable to dissolve compound (1) in one part or all part of solvent (E) in advance, and to prepare a solution. It is preferable to filter the said solution with the filter of about 0.01-1 micrometer of pore diameters.

It is preferable to filter the colored curable resin composition after mixing with the filter of about 0.01-10 micrometers of pore diameters.

<Method of manufacturing color filter>

As a method of manufacturing a coloring pattern from the colored curable resin composition of this invention, the photolithographic method, the inkjet method, the printing method, etc. are mentioned. Among these, the photolithographic method is preferable. The photolithographic method is a method of apply | coating the said colored curable resin composition to a board | substrate, drying to form a coloring composition layer, exposing the said coloring composition layer by photomask insertion, and developing. In the photolithographic method, the colored coating film which is the hardened | cured material of the said coloring composition layer can be formed by not using a photomask and / or developing at the time of exposure. The coloring pattern and coloring coating film formed in this way are the color filter of this invention.

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

Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass coated with silica on the surface, resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and aluminum on the substrate. And silver, and the thing which formed the silver / copper / palladium alloy thin film etc. can be used. Another color filter layer, a resin layer, a transistor, a circuit, etc. may be formed on such a board | substrate.

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

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

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

30-120 degreeC is preferable and, as for the temperature in the case of heat-drying, 50-110 degreeC is more preferable. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes.

When drying under reduced pressure, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.

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

Next, the coloring composition layer is exposed by sandwiching a photomask in order to form a desired coloring pattern. Although the pattern on the said photomask is not specifically limited, The pattern according to the intended use can be used.

As a light source used for exposure, the light source which produces the light of the wavelength of 250-450 nm is preferable. For example, light below 350 nm can be cut using a filter that cuts this wavelength range, or a band pass filter can be used that extracts light around 436 nm, near 408 nm and 365 nm. May be selectively extracted. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp etc. are mentioned.

An exposure apparatus such as a mask aligner and a stepper is used to irradiate the parallel light beam uniformly on the entire exposure surface or to perform a precise position combination between the photomask and the substrate on which the colored composition layer is formed. It is desirable to.

A colored pattern is formed on a board | substrate by developing the coloring composition layer after exposure contacting with a developing solution. By development, the unexposed part of a coloring composition layer melt | dissolves in a developing solution and is removed. As a developing solution, aqueous solution of alkaline compounds, such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate, tetramethylammonium hydroxide, is preferable, for example. The concentration in the aqueous solution of such an alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass, even more preferably 0.03 to 5% by mass. Furthermore, the developing solution may contain surfactant.

The developing method may be any of a paddle method, a dipping method and a spray method. Further, the substrate may be tilted at any angle during development.

It is preferable to wash with water after image development.

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

According to the colored curable resin composition of this invention, sublimation of a coloring agent is suppressed and especially a high-brightness color filter can be manufactured. The said color filter is useful as a color filter used for a display apparatus (for example, a liquid crystal display device, an organic electroluminescent apparatus, an electronic paper, etc.) and a solid-state image sensor.

Example

The present invention will be described more specifically with reference to the following examples.

In an Example and a comparative example,% and part which show content-usage-amount are a mass reference | standard unless there is particular notice.

In the following examples, the structure of the compound is NMR [JMM-ECA-500; Japan Electronics Co., Ltd.] or mass spectrometry (LC; Agilent 1200, MASS; Agilent LC / MSD 6130).

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

Equipment: HLC-8120GPC [manufactured by Tosso Corporation]

Column: TSK-GELG2000HXL

Column temperature: 40 ℃

Solvent: THF

Flow rate: 1.0 mL / min

Test liquid solid concentration: 0.001 to 0.01 mass%

Injection volume: 50 μL

Detector: RI

Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500

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

Synthesis Example 1

4-amino-3-hydroxybenzoic acid [Tokyo Kasei Co., Ltd.] 10.0 parts, 4- (diethylamino) salicylic aldehyde [Tokyo Kasei Industry Co., Ltd.] 12.8 parts, benzoic acid [Tokyo Kasei Co., Ltd. 2.73 parts, 157 parts of 1-pentanol (made by Tokyo Kasei Co., Ltd.), and 7.43 parts of ethyl cyano acetate (made by Tokyo Kasei Co., Ltd.) were mixed, and it stirred at 120 degreeC for 3 hours. 7.46 parts of cyanoacetic acid ethyl (Tokyo Kasei Co., Ltd. product), 2.79 parts of benzoic acid (Tokyo Kasei Industry Co., Ltd. product), 49.8 parts of 1-pentanol (Tokyo Kasei Industry Co., Ltd. product), and 4- (diethyl 12.7 parts of amino) salicylic aldehyde (manufactured by Tokyo Kasei Co., Ltd.) was added, and stirred at 120 ° C. for 14 hours. 3.76 parts of cyanoacetate ethyl [made by Tokyo Kasei Co., Ltd.], 1.41 parts of benzoic acid [made by Tokyo Kasei Co., Ltd.], 52.5 parts by 1-pentanol [made by Tokyo Kasei Co., Ltd.] and 4- (diethyl 6.35 parts of amino) salicylic aldehyde (manufactured by Tokyo Kasei Co., Ltd.) was added and stirred at 120 ° C for 8 hours. After cooling the said reaction liquid to room temperature, the precipitated crystal | crystallization was obtained as a residue of suction filtration. 140 parts of tetrahydrofuran was added to this residue, and after stirring at 70 ° C for 1 hour, an insoluble matter was obtained as a residue of suction filtration. 120 parts of tetrahydrofuran was added to this residue, and after stirring at 70 degreeC for 1 hour, an insoluble matter was obtained as a residue of suction filtration. 340 parts of N, N-dimethylformamide was added to the residue, heated to 90 ° C. to dissolve, and left at 0 ° C. to 5 ° C. The precipitated crystals were obtained as a residue of suction filtration. This residue was dried under reduced pressure at 60 degreeC, and 5.69 parts of compounds represented by Formula (1-1) were obtained. ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (1-1)>

Synthesis Example 2

24.8 parts of 4- (dibutylamino) salicylic [manufactured by Tokyo Kasei Co., Ltd.], 15.3 parts of 4-amino-3-hydroxy benzoic acid [Tokyo Kasei Co., Ltd.], benzoic acid [Tokyo Kasei Co., Ltd. ) 4.20 parts, 242 parts of 1-pentanol (made by Tokyo Kasei Co., Ltd.), and 11.3 parts of ethyl cyano acetate (made by Tokyo Kasei Co., Ltd.) were mixed, and it stirred at 120 degreeC for 5 hours. Ethyl cyanoacetate (manufactured by Tokyo Kasei Co., Ltd.) 4.61 parts, benzoic acid [Tokyo Kasei Industry Co., Ltd.] 1.70 parts, 4- (dibutylamino) salicylic aldehyde [Tokyo Kasei Industry Co., Ltd.] 10.1 parts And 10.0 parts of 1-pentanol (manufactured by Tokyo Kasei Co., Ltd.) were added and stirred at 120 ° C for 3 hours. Ethyl cyanoacetate [Tokyo Kasei Co., Ltd.] 4.60 parts, Benzoic acid [Tokyo Kasei Industry Co., Ltd.] 1.70 parts, 4- (dibutylamino) salicylic aldehyde [Tokyo Kasei Industry Co., Ltd.] 10.2 parts And 10.0 parts of 1-pentanol (manufactured by Tokyo Kasei Co., Ltd.) were added and stirred at 120 ° C for 3 hours. 4.61 parts of ethyl cyanoacetate (manufactured by Tokyo Kasei Co., Ltd.), 1.71 parts of benzoic acid (manufactured by Tokyo Kasei Co., Ltd.) and 10.3 parts of 4- (dibutylamino) salicylic [manufactured by Tokyo Kasei Co., Ltd.] It added and stirred at 120 degreeC for 18 hours. The reaction solution was cooled to room temperature and then added to 1900 parts of hexane and stirred. The precipitated crystals were obtained as a residue of suction filtration. To this residue was added 328 parts of tetrahydrofuran and recrystallized at 60 ° C. The precipitated crystals were obtained as a residue of suction filtration. 160 parts of tetrahydrofuran was added to this residue and stirred to obtain an insoluble matter as a residue of suction filtration. This residue was dried under reduced pressure at 60 degreeC, and 18.9 parts of compounds represented by Formula (1-3) were obtained. ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (1-3)>

Synthesis Example 3

4-amino-3-hydroxybenzoic acid [manufactured by Tokyo Kasei Co., Ltd.] 4.32 parts, 4- (bis (2-ethylhexyl) amino) salicylicaldehyde [synthesized according to the method described in Table 2007-508275] 10.2 1,18 parts of 1-pentanol (made by Tokyo Kasei Co., Ltd.) and 3.19 parts of ethyl cyanoacetate (made by Tokyo Kasei Co., Ltd.), 120 parts Stirred for 3 hours at ℃. To this reaction solution, 15.3 parts of 4- (bis (2-ethylhexyl) amino) salicylicaldehyde (synthesized according to the method described in JP 2007-508275), benzoic acid (manufactured by Tokyo Kasei Co., Ltd.), 1.80 parts, 1- 10.0 parts of pentanol (made by Tokyo Kasei Co., Ltd.) and 4.80 parts of ethyl cyano acetate (made by Tokyo Kasei Co., Ltd.) were added, and it stirred at 120 degreeC for 12 hours. After cooling the said reaction liquid to room temperature, the solvent was evaporated and removed by the rotary evaporator and the residue was obtained. This residue was purified by column chromatography to obtain 6.32 parts of the compound represented by Formula (1-15).

<Identification of 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 (made by Tokyo Kasei Co., Ltd.) and 101 parts of n-hexylamine (made by Tokyo Kasei Co., Ltd.) were mixed, and it stirred for 20 hours, removing the water produced | generated at 150-155 degreeC. After cooling, the reaction mixture was dissolved in 433 parts of toluene, and the toluene solution was washed three times with 1000 parts of water. 50 parts of anhydrous magnesium sulfate was added to this toluene solution, it stirred, and it filtered. The solvent of the filtrate was evaporated and removed to obtain a crude product. This crude product was dissolved in 234 parts of toluene, stirred at 0 ° C. or lower, and the crystals were collected by filtration. This crystallized product was dried under reduced pressure at 50 degreeC, and 95.7 parts of compounds which are represented by a formula (pt1) were obtained.

<Identification of Compound Represented by Formula (VT1)>

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

                          Exact Mass: 193.2

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

<Identification of Compound Represented by Formula (VT2)>

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

                          Exact Mass: 305.3

154 parts of residue which contains the compound represented by obtained formula (pt2) as a main component, and 597 parts of N, N- dimethylformamide were mixed, and it stirred at -6 degreeC-3 degreeC. To this, 258 parts of phosphoryl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added while maintaining the liquid temperature at -6 ° C to 3 ° C. The mixture was stirred at room temperature for 1 hour and then at 60 ° C for 4 hours. After cooling, the reaction mixture was added to 1500 parts of ice and neutralized with 48% aqueous sodium hydroxide solution. 867 parts of toluene was added here and the toluene layer was extracted. This toluene extract was washed twice with 1200 parts of 15% aqueous sodium chloride solution. 60.0 parts of anhydrous magnesium sulfate was added to this toluene extract, it stirred, and it filtered. The solvent in the filtrate was evaporated off to give a residue. This residue was purified by column chromatography to obtain 94.4 parts of the compound represented by formula (pt3).

<Identification of Compound Represented by Formula (VII3)>

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

                          Exact Mass: 333.3

6.89 parts of 4-amino-3-hydroxybenzoic acid manufactured by Tokyo Kasei Co., Ltd., 15.0 parts of a compound represented by the formula (VII-3), 1.87 parts of Benzoic acid [manufactured by Tokyo Kasei Co., Ltd.], 1-pentanol [Tokyo 110 parts of Kasei Kogyo Co., Ltd. and 5.09 parts of ethyl cyanoacetate (Tokyo Kasei Co., Ltd. product) were mixed, and it stirred at 120 degreeC for 3 hours. To this reaction solution, 22.5 parts of the compound represented by the formula (VII3), 2.85 parts of benzoic acid (manufactured by Tokyo Kasei Co., Ltd.), 10.0 parts of 1-pentanol (manufactured by Tokyo Kasei Co., Ltd.), and ethyl cyanoacetate [Tokyo Kasei] Industrial Co., Ltd.] 7.66 parts were mixed, and it stirred at 120 degreeC for 12 hours. After cooling the reaction solution to room temperature, the solvent was evaporated to remove the residue. This residue was purified by column chromatography to obtain 8.86 parts of the compound represented by formula (1-1).

<Identification of Compound Represented by Formula (1-173)>

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

Exact Mass: 518.3

Synthesis Example 5

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

<Identification of Compound Represented by Formula (VII4)>

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

Exact Mass: 221.2

23.0 parts of water were added to 58.5 parts of the residue which consists of the obtained compound represented by Formula (pt4) as a main component, and the liquid temperature was 60 degreeC, stirring. At this temperature, the mixture was stirred for 9 hours while adding 39.3 parts of diethyl sulfate and 10.6 parts of 48% aqueous sodium hydroxide solution. Thereafter, the mixture was stirred at 60 ° C for 5 hours. After cooling, the reaction mixture was neutralized with 10% aqueous sodium hydroxide solution and 300 parts of toluene was added. This toluene solution was washed three times with 500 parts of water. 20.0 parts of anhydrous magnesium sulfate was added to this toluene solution, it stirred, and it filtered. The solvent of the filtrate was evaporated and removed, and 67.5 parts of residue which contains the compound shown by a formula (pt5) as a main component was obtained.

<Identification of Compound Represented by Formula (VT5)>

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

                          Exact Mass: 249.2

323 parts of N, N-dimethylformamide was added to 67.5 parts of the residue which consists as a main component of the obtained compound represented by Formula (pt5). 105 parts of phosphorus oxychloride was added, maintaining the temperature of this mixed solution at -6 degreeC-4 degreeC. After returning the temperature of this reaction liquid to room temperature and stirring for 1 hour, the temperature of the reaction liquid was raised to 60 degreeC and stirred for 3 hours. After cooling, the reaction mixture was added to 1500 parts of ice water and neutralized by addition of an aqueous 48% sodium hydroxide solution while stirring. 500 parts of toluene was added here, and the toluene layer was extracted. This toluene solution was washed with 1000 parts of water. Subsequently, this toluene solution was washed with 1500 parts of saturated aqueous sodium chloride solution. 25.0 parts of anhydrous magnesium sulfate was added to this toluene solution, and it stirred, and was filtered. The solvent in the filtrate was evaporated off to give a residue. This residue was purified by column chromatography to obtain 36.7 parts of the compound represented by formula (pt6).

<Identification of Compound Represented by Formula (VII6)>

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

                          Exact Mass: 277.2

4-amino-3-hydroxybenzoic acid [manufactured by Tokyo Kasei Co., Ltd.] 8.28 parts, 15.0 parts of a compound represented by the formula (VII6), 2.25 parts of benzoic acid [manufactured by Tokyo Kasei Industry Co., Ltd.], 1-pentanol [Tokyo] 130 parts of Kasei Kogyo Co., Ltd. and 6.12 parts of ethyl cyanoacetate (Tokyo Kasei Co., Ltd. product) were mixed, and it stirred at 120 degreeC for 3 hours. To this reaction solution, 22.5 parts of the compound represented by the formula (VII), 3.40 parts of benzoic acid (manufactured by Tokyo Kasei Co., Ltd.), 10.0 parts of 1-pentanol (manufactured by Tokyo Kasei Co., Ltd.), and ethyl cyanoacetate [Tokyo Kasei] Industrial Co., Ltd.] 9.20 parts were mixed, and it stirred at 120 degreeC for 12 hours. After cooling the reaction solution to room temperature, the solvent was evaporated to remove the residue. This residue was purified by column chromatography to obtain 8.75 parts of the compound represented by formula (1-1).

<Identification of Compound Represented by Formula (1-1)

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

Exact Mass: 462.2

Synthesis Example 6

4-amino-3-hydroxybenzoic acid [manufactured by Tokyo Kasei Co., Ltd.] 8.01 parts, 2-hydroxy-4- (pyrrolidin-1-yl) benzaldehyde [ Chem . Commun . Synthesized according to 2011, 47 , 2435.] 10.0 parts, benzoic acid [Tokyo Kasei Co., Ltd.] 2.18 parts, 1-pentanol [Tokyo Kasei Co., Ltd.] 127 parts and ethyl cyanoacetate [Tokyo Kasei] Industrial Co., Ltd.] 5.91 parts were mixed, and it stirred at 120 degreeC for 3 hours. 2-hydroxy-4- (pyrrolidin-1-yl) benzaldehyde [ Chem . Commun . Synthesized according to 2011, 47 , 2435.] 15.0 parts, benzoic acid [manufactured by Tokyo Kasei Co., Ltd.] 3.30 parts, 1-pentanol [manufactured by Tokyo Kasei Co., Ltd.] 10.0 parts, and ethyl cyanoacetate [Tokyo Kasei] Ind. Co., Ltd.] 8.90 parts were mixed, and it stirred at 120 degreeC for 12 hours. After cooling the reaction solution to room temperature, the solvent was evaporated to remove the residue. This residue was purified by column chromatography to obtain 6.50 parts of the compound represented by the formula (13-3).

<Identification of Compound Represented by Formula (13-3)>

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

Exact Mass: 376.1

Synthesis Example 7

4-amino-3-hydroxybenzoic acid [manufactured by Tokyo Kasei Industry Co., Ltd.] 9.21 parts, 8-hydroxyjulolidine-9-carboxyaldehyde [manufactured by Tokyo Kasei Industry Co., Ltd.] 13.1 parts, Benzoic Acid [ Tokyo Kasei Industry Co., Ltd.] 2.51 parts, 1-pentanol [Tokyo Kasei Industry Co., Ltd.] 145 parts, and cyano acetate ethyl [Tokyo Kasei Co., Ltd.] 6.80 parts are mixed, and it is 3 hours at 120 degreeC. Stirred. Ethyl cyanoacetic acid [Tokyo Kasei Co., Ltd.] 10.2 parts, benzoic acid [Tokyo Kasei Industry Co., Ltd.] 3.80 parts, 8-hydroxy julolidine-9-carboxyaldehyde [Tokyo Kasei Co., Ltd. ) 19.6 parts and 10.0 parts of 1-pentanol (made by Tokyo Kasei Co., Ltd.) were added, and it stirred at 120 degreeC for 12 hours. After cooling the reaction solution to room temperature, the solvent was evaporated and removed by a rotary evaporator to obtain a residue. This residue was purified by column chromatography to obtain the compound represented by formula (1-5).

Synthesis Example 8

4-amino-3-hydroxybenzoic acid [manufactured by Tokyo Kasei Co., Ltd.] 9.21 parts, 8-hydroxy-1,1,7,7-tetramethyljulolidine-9-carboxyaldehyde [Tokyo Kasei Industrial Co., Ltd.] 16.4 parts, benzoic acid [Tokyo Kasei Co., Ltd.] 2.51 parts, 1-pentanol [Tokyo Kasei Co., Ltd.] 145 parts and ethyl cyanoacetate [Tokyo Kasei Co., Ltd.] 6.80 parts were mixed and stirred at 120 ° C. for 3 hours. 10.2 parts of ethyl cyanoacetate (manufactured by Tokyo Kasei Co., Ltd.), 3.80 parts of benzoic acid (manufactured by Tokyo Kasei Co., Ltd.), 8-hydroxy-1,1,7,7-tetramethyljulolidine (julolidine) 24.7 parts of -9-carboxyaldehyde (made by Tokyo Kasei Co., Ltd.) and 10.0 parts of 1-pentanol (made by Tokyo Kasei Co., Ltd.) were added, and it stirred at 120 degreeC for 12 hours. After cooling the reaction solution to room temperature, the solvent was evaporated and removed by a rotary evaporator to obtain a residue. This residue was purified by column chromatography to obtain the compound represented by formula (1-7).

Synthesis Example 9

An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to obtain a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C while stirring. Subsequently, in the flask, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decane-9- A solution in which 171 parts of a mixture of monoacrylate (content: 50:50 in molar ratio) was dissolved in 40 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours using a dropping pump. In addition, the flask which melt | dissolved the solution which melt | dissolved 26 parts of polymerization initiators 2,2'- azobis (2, 4- dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetates, was used over the flask for about 5 hours using a separate dropping pump. It dripped in the inside. After completion of the dropping of the polymerization initiator, the mixture was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin # 1) having a solid content of 43.5%. The weight average molecular weight of obtained resin # 1 was 8000, the molecular weight distribution was 1.98, and the acid value of conversion of solid content was 53 mgKOH / g.

[Preparation of Colored Curable Resin Composition]

Example 1

Colorant (A): C.I. Pigment green 7 (pigment) 27 copies,

12 parts of acrylic pigment dispersant,

Resin (Ｂ): 9.5 parts of Resin B1 (in terms of solid content), and

Solvent (E): 180 parts of propylene glycol monomethyl ether acetate

A pigment dispersion obtained by mixing the mixture and sufficiently dispersing the pigment using a beads mill;

Coloring agent (A): 3.0 parts of compound represented by formula (1-15);

Resin (VIII): 40 parts of Resin V1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 49 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; 0-acyl oxime compound] 9.8 parts;

Solvent (E): 670 parts of propylene glycol monomethyl ether acetate; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.15 part

Was mixed to obtain a colored curable resin composition.

Example 2

A coloring curable resin composition was obtained like Example 1 except having replaced CI Pigment Green 7 (pigment) of a coloring agent (A) with CI Pigment Green 36 (pigment).

Example 3

C.I. of the colorant (A). Pigment Green 7 (pigment) to C.I. Except having changed into pigment green 58 (pigment), it carried out similarly to Example 1, and obtained colored curable resin composition.

[Film thickness measurement]

The film thickness is DEKTAK3; The film thickness was measured using the Japan Vacuum Technology Co., Ltd. product.

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

Resin: Methacrylic acid / benzyl methacrylate (molar ratio: 30/70) copolymer [manufactured by Taoka Chemical Co., Ltd., average molecular weight 10700, acid value 70 mgKOH / g] 33.8%

40.2 parts of a propylene glycol monomethyl ether acetate solution;

Polymerizable compound: dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 5.8 parts;

Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE01; BASF Japan company] 0.58 parts;

Surface leveling agent: polyether-modified silicone oil [Torre Silicone SH8400; Torre Dow Corning Co., Ltd.] 0.01 part

Solvent: 46.6 parts of propylene glycol monomethyl ether;

Solvent: propylene glycol monomethyl ether acetate 6.8 parts

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

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

The sublimation test resin composition (SJS) obtained above was apply | coated by the spin coat method on the 2-inch square glass substrate (Eagle XG; product made by Corning Corporation), and the volatile component was volatilized for 3 minutes at 100 degreeC. After cooling, the exposure machine [TME-150RSK; Topcon Co., Ltd.] was used to irradiate light at an exposure amount (365 nm standard) of 150 mJ / cm 2 under an air atmosphere. It heated at 220 degreeC in oven for 2 hours, and formed the resin coating film (SJSM) [film thickness of 2.2 micrometers] for a sublimation test.

Example 4

[Production and Sublimation Evaluation of Colored Pattern]

After apply | coating the colored curable resin composition obtained in Example 1 by the spin coat method on a 2-inch square glass substrate (Eagle XG; product made by Corning Corporation), it prebaked at 100 degreeC for 3 minutes, and forms a coloring composition layer. It was. After cooling, the space | interval of the board | substrate with which the coloring composition layer was formed, and the photomask made from quartz glass was set to 200 micrometers, and the exposure machine [TME-150RSK; Topcon Co., Ltd.] was used for exposure at an exposure dose (365 nm standard) of 80 mJ / cm 2 under an air atmosphere. Furthermore, as the photomask, one having a line and space pattern of 100 mu m was used. The coloring composition layer after exposure was immersed in 25 degreeC for 70 second in aqueous solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide, and it developed and wash | cleaned with water. The film thickness was measured. The results are shown in Table 1.

This coloring coating film and the resin coating film (SJSM) for sublimation test obtained above were made to oppose in the form with the space | interval of 70 micrometers, and a post-baking was performed at 220 degreeC for 40 minutes, and the coloring pattern was obtained. Color difference (ΔEab *) before and after heating of the resin coating film (SJSM) for the sublimation test was measured using a colorimeter (OSP-SP-200; manufactured by Olympus). When the color difference (ΔEab *) is 5.0 or more, it indicates that the colorant has sublimability. The results are shown in Table 1. In Table 1, in each Example, (circle) shows that a colorant does not have sublimation, and x shows that a colorant has sublimation.

Examples 5-6

A colored pattern was obtained in the same manner as in Example 4 except that the colored curable resin composition obtained in Example 1 was changed to the colored curable resin composition obtained in Example VII. Sublimation evaluation was also performed. The results are shown in Table 1. The said Example 9 shows Example 9 shown in Table 1, respectively.

Comparative Example 1

Colorant (A): coumarin 6 3.6 parts;

Resin: 180 parts of Resin (1) (solid content conversion);

Solvent (E): 230 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 590 parts of N, N-dimethylformamide; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd. 0.063 parts

It mixed and obtained the colored resin composition.

Comparative Example 2

After apply | coating the colored resin composition obtained by the comparative example 1 on the 2-inch square glass substrate (Eagle XG; Corning Corporation make) by the spin coat method, it prebaked at 100 degreeC for 3 minutes, and formed the coloring composition layer. . Membrane thickness DEKTAK3; It was 1.9 micrometers when the film thickness was measured using the Japan Vacuum Technology Co., Ltd. product. The colored coating film and the resin coating film (SJSM) for sublimation test obtained above were opposed to each other in a form having a space of 70 μm, and postbaking was performed at 220 ° C. for 40 minutes. Color difference (ΔEab *) before and after heating of the resin coating film (SJSM) for the sublimation test was measured using a colorimeter (OSP-SP-200; manufactured by Olympus). As a result, the color difference (ΔEab *) was 5.0 or more. When the color difference (ΔEab *) is 5.0 or more, it indicates that the colorant has sublimability.

According to this invention from the said result, it was confirmed that it becomes possible to provide the colored curable resin composition which provides a color filter, without a coloring agent subliming.

According to this invention, a coloring curable resin composition which provides a color filter can be provided without a coloring agent subliming, and the said color filter can be used suitably for display apparatuses, such as a liquid crystal display device.

Claims (23)

Colored curable resin composition containing the compound represented by Formula (1), resin, a polymeric compound, and a polymerization initiator.
Equation (1):

In the formula (1), Q ¹ and Q ² each independently represent a hydrogen atom or -CO ₂ M, or just either one of Q ¹ and Q ² represents a -CO ₂ M.
R ¹ to R ⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹ and R ³ combine to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom; , R ² and R ⁴ combine to form a ring together with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring, or R ¹ and R ² combine to form a ring together with an adjacent nitrogen atom. The methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a -N (R ⁵ )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the monovalent hydrocarbon group is a halogen atom, cyano group or nitro. The group, carbamoyl group, sulfamoyl group, -SO ₃ M, -CO ₂ M, a hydroxyl group or an amino group may be substituted.
R ⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^{5 's} are present, they are the same as or different from each other.
M represents a hydrogen atom or an alkali metal atom] The method of claim 1,
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 combine to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom Or R ² and R ⁴ are bonded to each other to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom. The method of claim 1,
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 combine to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom And R ² and R ⁴ are bonded to each other to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom. The method of claim 1,
Colored curable resin composition containing a pigment further. The method of claim 4, wherein
Colored curable resin composition whose said pigment is 1 or more types chosen from the group which consists of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment. The method of claim 5,
The coloring curable resin composition whose said pigment is 1 or more types chosen from the group which consists of a chlorinated copper phthalocyanine pigment, a brominated copper phthalocyanine pigment, and a zinc bromide phthalocyanine pigment. The method of claim 4, wherein
Colored curable resin composition whose said pigment is a green pigment. The method of claim 7, wherein
The colored curable resin composition whose said pigment is 1 or more types chosen from the group which consists of CI pigment green 7, CI pigment green 36, and CI pigment green 58. The method of claim 8,
Colored curable resin composition whose said pigment is CI pigment green 7. The method of claim 2,
Colored curable resin composition containing a pigment further. The method of claim 10,
Colored curable resin composition whose said pigment is 1 or more types chosen from the group which consists of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment. The method of claim 11,
The coloring curable resin composition whose said pigment is 1 or more types chosen from the group which consists of a chlorinated copper phthalocyanine pigment, a brominated copper phthalocyanine pigment, and a zinc bromide phthalocyanine pigment. The method of claim 10,
Colored curable resin composition whose said pigment is a green pigment. The method of claim 13,
The colored curable resin composition whose said pigment is 1 or more types chosen from the group which consists of CI pigment green 7, CI pigment green 36, and CI pigment green 58. The method of claim 14,
Colored curable resin composition whose said pigment is CI pigment green 7. The method of claim 3, wherein
Colored curable resin composition containing a pigment further. The method of claim 16,
Colored curable resin composition whose said pigment is 1 or more types chosen from the group which consists of a halogenated copper phthalocyanine pigment and a halogenated zinc phthalocyanine pigment. The method of claim 17,
The coloring curable resin composition whose said pigment is 1 or more types chosen from the group which consists of a chlorinated copper phthalocyanine pigment, a brominated copper phthalocyanine pigment, and a zinc bromide phthalocyanine pigment. The method of claim 16,
Colored curable resin composition whose said pigment is a green pigment. The method of claim 19,
The colored curable resin composition whose said pigment is 1 or more types chosen from the group which consists of CI pigment green 7, CI pigment green 36, and CI pigment green 58. The method of claim 20,
Colored curable resin composition whose said pigment is CI pigment green 7. The color filter formed using the colored curable resin composition of any one of Claims 1-21. A liquid crystal display device comprising the color filter of claim 22.