KR102041384B1 - Colored curable resin composition - Google Patents

Abstract

[식에서, L은 2가의 탄화수소기 등, ＡＡ는 방향족기 등, X는 산소 원자, 유황 원자 등, R¹ 내지 R⁴는 각각 독립적으로 수소 원자, 1가의 탄화수소기 등, R⁵ 내지 R⁹는 각각 독립적으로 수소 원자, 할로겐 원자, 1가의 탄화수소기 등을 나타냄] A colorant comprising a compound having a coumarin skeleton, such as the compound represented by formula (1), formula (1 '), formula (2), formula (3), formula (4) or formula (5), and CI pigment yellow 129 , Colored curable resin composition comprising a resin, a polymerizable compound and a polymerization initiator.

[Wherein, L is a divalent hydrocarbon group, AA is an aromatic group, X is an oxygen atom, a sulfur atom or the like, and R ¹ to R ⁴ are each independently a hydrogen atom or a monovalent hydrocarbon group, and R ⁵ to R ⁹ are Each independently represent a hydrogen atom, a halogen atom, a monovalent hydrocarbon group, etc.]

Description

Colored curable resin composition {COLORED CURABLE RESIN COMPOSITION}

The present invention relates to a colored curable resin composition.

Colored curable resin composition is used, for example in order to manufacture color filters, such as a liquid crystal display device. As such a colored curable resin composition, the colored curable resin composition containing a zinc halide phthalocyanine pigment and a yellow azo dye as a coloring agent is known (JP2010-168531-A).

As said colored curable resin composition known conventionally, the brightness of the color filter obtained from the said colored curable resin composition was not necessarily fully satisfying.

The present invention provides the following [1] to [２９].

[1] Compound having a coumarin skeleton and C.I. Colored curable resin composition containing the pigment | dye containing pigment yellow 129, resin, a polymeric compound, and a polymerization initiator.

[2] The colored curable resin composition according to [1], wherein the colorant further contains a pigment.

[3] The colored curable resin composition according to [2], 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.

[4] The colored curable resin composition according to [2] or [3], wherein the pigment is at least one member selected from the group consisting of a chlorinated copper phthalocyanine pigment, a brominated copper phthalocyanine pigment and a zinc bromide phthalocyanine pigment.

[5] The colored curable resin composition according to any one of [2] to [4], wherein the pigment is a green pigment.

[6] 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 [2]-[5] which is 1 or more types chosen from the group which consists of pigment green 58.

[7] The pigment is C.I. The colored curable resin composition in any one of [2]-[6] which is Pigment Green 7.

[Iii] The colored curable resin composition according to any one of [1] to [7], wherein the compound having a coumarin skeleton is a compound represented by Formula (1).

Compound represented by the following formula (1):

[Formula (1),

L represents a divalent hydrocarbon group having 1 to 20 carbon atoms. The methylene group constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁰ )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the divalent hydrocarbon group is a cyano group, a nitro group, or a carbon group. It may be substituted by the baroyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, chlorine atom, bromine atom, imidazol-1-yl group or amino group.

X represents an oxygen atom, a sulfur atom or -N (R ¹⁰ )-.

AA represents a C6-C20 aromatic group. The hydrogen atom contained in the aromatic group may be a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, hydroxy group, imidazol-1-yl group, amino group or monovalent monovalent having 1 to 20 carbon atoms. The hydrocarbon group may be substituted. The methylene group, oxygen atom, sulfur atom, -N (R ¹⁰ )-, sulfonyl group or carbonyl group constituting the monovalent hydrocarbon group may be substituted, and the hydrogen atom contained in the monovalent hydrocarbon group is a halogen atom, cyano group, The nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, hydroxy group, imidazol-1-yl group or amino group may be substituted.

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 combine to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom. The methylene group which comprises the said monovalent hydrocarbon group may be substituted by the oxygen atom, the sulfur atom, -N (R <^10> )-, sulfonyl group, or carbonyl group, and the hydrogen atom contained in the said monovalent hydrocarbon group is a halogen atom, a cyano group, and a nitro. The group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, hydroxy group, imidazol-1-yl group or amino group may be substituted.

R ⁵ to R ⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxyl group, a hydroxyl group, an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Or R ⁵ and R ⁶ combine to form a ring with adjacent carbon atoms, or R ⁷ and R ⁸ combine to form a ring with adjacent carbon atoms. The methylene group which comprises the said monovalent hydrocarbon group may be substituted by the oxygen atom, the sulfur atom, -N (R <^10> )-, sulfonyl group, or carbonyl group, and the hydrogen atom contained in the said monovalent hydrocarbon group is a halogen atom, a cyano group, and a nitro. The group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, hydroxy group, imidazol-1-yl group or amino group may be substituted.

R ¹⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ¹⁰ are present, they are the same as or different from each other]

[Iii] The colored curable resin composition according to any one of [1] to [7], wherein the compound having a coumarin skeleton is a compound represented by Formula (1 ').

Compound represented by the following formula (1 '):

[In formula (1 '), R <^1> -R <^9> , X and L have the same meaning as the above, respectively.]

[10] The colored curable resin composition according to [i] or [i], wherein X is an oxygen atom or a sulfur atom.

[11] The colored curable resin composition according to any one of [i] to [10], wherein X is an oxygen atom.

[12] The colored curable resin composition according to any one of [i] to [11], wherein L is a methylene group or a sulfonyl group which may have a substituent.

[13] The colored curable resin composition according to any one of [i] to [12], wherein L is a dimethylmethylene group or a sulfonyl group.

[14] The colored curable resin composition according to any one of [i] to [13], wherein all of R ⁵ to R ⁹ are hydrogen atoms.

[15] The colored curable resin composition according to any one of [1] to [7], wherein the compound having a coumarin skeleton is a compound represented by Formula (2).

Compound represented by the following formula (2):

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

R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹¹ and R ¹³ combine to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom; Or R ¹² and R ¹⁴ combine to form a ring with carbon atoms and adjacent nitrogen atoms on adjacent benzene rings. The methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁵ )-, 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 ¹⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^{15 's} are present, they are the same as or different from each other.

M represents a hydrogen atom or an alkali metal atom]

[16] The colored curable resin composition according to any one of [1] to [7], wherein the compound having a coumarin skeleton is a compound represented by Formula (3).

Compound represented by the following formula (3):

[Equation (3),

L 'represents a C1-C20 bivalent hydrocarbon group. The methylene group constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ²⁵ )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the divalent 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. However, at least one of the hydrogen atoms contained in the divalent hydrocarbon group is substituted with a fluorine atom.

X 'represents a Group 16 atom, -N (R ²⁵ )-or -C (R ²⁵ ) (R ²⁶ )-in the periodic table.

R ¹⁶ to R ²⁴ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M ', -CO ₂ M', a hydroxyl group, an amino group or C1-C1 20 monovalent hydrocarbon groups, R ¹⁶ and R ¹⁸ combine to form a ring with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring, or R ¹⁷ and R ¹⁹ combine to form an adjacent benzene ring Together with the carbon atoms and the adjacent nitrogen atoms form a ring. The methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ²⁷ )-, 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 ²⁵ and R ²⁶ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ²⁷ )-, 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 ²⁷ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^{27 's} are present, they are the same as or different from each other.

M 'represents a hydrogen atom or an alkali metal atom]

[17] The colored curable resin composition according to [16], wherein X 'is an oxygen atom, a sulfur atom, -N (R ²⁵ )-, or -C (R ²⁵ ) (R ²⁶ )-.

[16] The colored curable resin composition according to [16] or [17], wherein X 'is an oxygen atom, a sulfur atom, or -N (R ²⁵ )-.

[16] The colored curable resin composition according to any one of [16] to [16], wherein X 'is an oxygen atom or a sulfur atom.

[20] The colored curable resin composition according to any one of [16] to [16], wherein X 'is an oxygen atom.

[21] The colored curable resin composition according to any one of [16] to [20], wherein L 'is a bis (trifluoromethyl) methylene group.

[22] The colored curable resin composition according to any one of [16] to [21], wherein all of R ¹⁸ to R ²⁴ are hydrogen atoms.

[23] The colored curable resin composition according to any one of [1] to [7], wherein the compound having a coumarin skeleton is a compound represented by Formula (4) or Formula (5).

Compound represented by the following formula (4):

Compound represented by the following formula (5):

[Formula (4) and Formula (5),

X '' represents a Group 16 atom, -N (R ³⁴ )-or -C (R ³⁴ ) (R ³⁵ )-in the periodic table.

R ²⁸ to R ⁴¹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M '', -CO ₂ M '', a hydroxyl group, an amino group, or a carbon number 1 to 20 monovalent hydrocarbon groups, R ²⁸ and R ³⁰ combine to form a ring with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom, or R ²⁹ and R ³¹ combine to form an adjacent carbon A ring containing atoms and adjacent nitrogen atoms and carbon atoms is formed. The methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ⁴² )-, 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 '', hydroxy group, imidazol-1-yl group or amino group may be substituted. Provided that at least one of R ³⁶ to R ⁴¹ is -SO ₃ M ''.

R ⁴² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^{42 's} are present, they are the same as or different from each other.

M '' represents a hydrogen atom or an alkali metal atom]

[24] The colored curable resin composition according to [24], wherein X '' is an oxygen atom, a sulfur atom, -N (R ³⁴ )-, or -C (R ³⁴ ) (R ³⁵ )-.

[25] The colored curable resin composition according to [24] or [24], wherein X '' is an oxygen atom.

[26] The colored curable resin composition according to any one of [23] to [25], wherein R ⁴⁰ is -SO ₃ M ''.

[27] The colored curability according to any one of [1] to [26], wherein the content of the compound represented by any one of Formulas (1) to (5) is 1% by mass to 65% by mass with respect to the total amount of the dye and the pigment. Resin composition.

[2X] The color filter formed using the colored curable resin composition in any one of [1]-[27].

[2 ′] A liquid crystal display device comprising the color filter described in [2 ′].

According to this invention, it is possible to provide the colored curable resin composition which can manufacture a high brightness color filter.

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

Colorants (A) are compounds having a coumarin skeleton and C.I. Pigment yellow 129.

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

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

A coloring agent (A) is a compound represented by Formula (1), Formula (1 '), Formula (2), Formula (3), Formula (4), or Formula (5) (Hereinafter, "Compound (1)", "Compound" Compound having a coumarin skeleton such as (1 ')' ', "Compound (2)", "Compound (3)", "Compound (4)" or "Compound (5)", and CI It is preferable that Pigment Yellow 129 is included and pigment (P) is further included.

Compound (1) is represented by Formula (1), and its tautomers and salts thereof are also included.

Compound (1 ') is represented by Formula (1'), and its tautomers and salts thereof are also included.

Sulfo group refers to a group represented by -SO ₃ M '''.

The carboxy group refers to the group represented by -CO ₂ M '''.

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.

As the group represented by L, for example, the groups represented by formulas (L1) to (L2９), and the hydrogen atoms contained in these groups are cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxy group, And groups substituted with a hydroxy group, a chlorine atom, a bromine atom, an imidazol-1-yl group or an amino group. In formulas (L1) to (L2９), ● represents a coupling arm.

It is preferable that L is a methylene group or sulfonyl group which may have a substituent. As such preferable L, the group represented by Formula (L1) and Formula (L3)-Formula (L14), respectively is mentioned specifically ,. Among these, groups represented by formulas (L1) and (L3) to (L14) are preferable, and are represented by formulas (L1), (L3), (L10), (L13), and (L14). Groups are more preferable, and the group represented by Formula (L1), Formula (L3), Formula (L13), and Formula (L14) is even more preferable. If L is such a group, it is easy to obtain a raw material.

X represents an oxygen atom, a sulfur atom or -N (R ¹⁰ )-, and an oxygen atom and a sulfur atom are preferable. Among these, an oxygen atom is more preferable. If X is an oxygen atom, the brightness of the green color filter tends to be increased.

As an aromatic group having 6 to 20 carbon atoms represented by AA, for example, groups represented by formulas (A1) to (A12), and hydrogen atoms contained in such groups are halogen atoms, cyano groups, nitro groups, carbamoyl groups, and sulfones. A group substituted with a pamoyl group, a sulfo group, a carboxy group, a hydroxyl group, an imidazol-1-yl group, an amino group, or a C1-C20 monovalent hydrocarbon group is mentioned. The methylene group constituting the monovalent hydrocarbon group may be substituted with a hydrogen atom, a sulfur atom, -N (R ¹⁰ )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the monovalent hydrocarbon group is a halogen atom, cyano group, nitro The group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, hydroxy group, imidazol-1-yl group or amino group may be substituted. Among these, the group represented by formula (A12) is preferable. If AA is a group represented by the formula (A12), the thermal decomposition temperature tends to be further increased. In addition, the sublimation tends to be low.

[In formula (A1)-(A12), R <^1> -R <^9> and X are the same as the above, and (*) shows a coupling arm.]

Examples of the halogen atom in R ¹ to R ⁹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁹ include methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, butyl group and iso Butyl group, 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 Aliphatic hydrocarbon groups such as heptyl group, (3-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 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 group which combined these is mentioned.

The hydrogen atom contained in the monovalent hydrocarbon group, the group in which the methylene group constituting such monovalent hydrocarbon group is substituted with an oxygen atom, a sulfur atom, -N (R ¹⁰ )-, a sulfonyl group or a carbonyl group, or a halogen atom, a cyano group, a nitro group, or a carbon group Examples of the group substituted with a barmoyl group, sulfamoyl group, sulfo group, carboxyl group, hydroxy group or amino group include, for example.

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

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-hexylsulfamoyl 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, perfluorode Real group, perfluoro dodecyl group, perfluoro jade To an aliphatic hydrocarbon having a fluorine atom such as a group 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 Bis (trifluoromethyl) phenylmethyl groups, such as a chloromethyl) phenylmethyl group, a 3, 4-bis (trifluoromethyl) phenylmethyl group, and a 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 them, an ethyl group, a butyl group, a hexyl group, a (2-ethyl) hexyl group and an octyl group are preferable, and among these, an ethyl group, a butyl group, a hexyl group and a (2-ethyl) hexyl group are more preferable, and (2-ethyl) Hexyl groups are even more preferred. If R ¹ is such a group, the solubility in a solvent is excellent.

As R <^{2>, a} C1-C10 aliphatic hydrocarbon group is preferable. Among them, an ethyl group, a butyl group, a hexyl group, a (2-ethyl) hexyl group and an octyl group are more preferable, and among these, an ethyl group, a butyl group, a hexyl group and a (2-ethyl) hexyl group are even more preferable, and a hexyl group and ( 2-ethyl) hexyl group is particularly preferred. If R <^2> is such a group, it will be excellent in solubility to a solvent.

It is preferable that all of R <^3> -R <^9> are hydrogen atoms.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹⁰ include methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, butyl group, isobutyl group, sec-butyl, tert-butyl, (2-ethyl) butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, 3-pentyl, neopentyl, tert-pent Methyl 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 Aliphatic hydrocarbon groups such as (3-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 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 group which combined these is mentioned.

In compound (1),

Is set to 'FF',

When "(k)" is represented and F is represented by FF- ', the group represented by Formula (F1)-Formula (F20) is mentioned as FF, respectively. In the formula, ● represents a coupling arm.

Examples of X include groups represented by formulas (X1) to (X10), respectively.

Compound (1) is illustrated in Tables 1 to 5 as a combination of the above F and X. In Tables 1 to 5, FFT and Q are each describe the numbers of the formulas of the groups illustrated above.

Then, in compound (1 ')

When "HH" is represented and the compound (1 ') is represented by FH-HF-F, examples of FF include groups represented by the formulas (F1) to (F20), respectively. For example, group represented by Formula (H1)-a formula (H3) is mentioned, respectively. In the formula, ● represents a coupling arm.

Compound (1 ') is shown to Tables 6-22 as a combination of said FH and HH. In Tables 6 to 22, FFT and HH each describe the numbers of the formulas of the groups exemplified above.

From the viewpoint of raw material availability, the compounds shown in Tables 23 to 27 are preferable, and the compounds shown in Tables 28 to 29 are more preferable as the compound (1) and the compound (1 ').

Compound (2) is represented by Formula (2), and its tautomers and salts thereof are also included.

In formula (2), a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned as a halogen atom in R <^11> -R <^14> .

Equation (2), R ¹¹ to Examples of C 1 -C 20 monovalent hydrocarbon group of 1 according to R ^14, for example, methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl, 2-propenyl Phenyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 1,3-butadienyl group, pentyl group, isopentyl group, (2-ethyl) butyl group, 3-pen Methyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, (3-ethyl) pentyl, hexyl, isohexyl, 5-methylhexyl, Aliphatic hydrocarbon groups such as 2-ethyl) hexyl, heptyl, (3-ethyl) heptyl, octyl, nonyl, decyl, undecyl, dodecyl and octadecyl;

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 group which combined these is mentioned.

The hydrogen atom contained in the monovalent hydrocarbon group, the group in which the methylene group constituting such a monovalent hydrocarbon group is substituted with an oxygen atom, a sulfur atom, -N (R ¹⁵ )-, a sulfonyl group or a carbonyl group, or a halogen atom, a cyano group, a nitro group, or a carbon group Examples of the group substituted with a barmoyl group, 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 Bis (trifluoromethyl) phenylmethyl groups, such as a chloromethyl) phenylmethyl group, a 3, 4-bis (trifluoromethyl) phenylmethyl group, and a 3, 5-bis (trifluoromethyl) phenylmethyl group, etc. are mentioned.

As R <^11> and R <^{12>, 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 <^{11>, a} C1-C10 aliphatic hydrocarbon group is preferable. Among them, an ethyl group, a butyl group, a hexyl group, a (2-ethyl) hexyl group and an octyl group are more preferable, an ethyl group, a butyl group, a hexyl group, and a (2-ethyl) hexyl group are even more preferable, and a (2-ethyl) hex Real groups are particularly preferred. If R ¹¹ is such a group, the compound of the present invention is excellent in solubility in a solvent.

As R <^{12>, a} C1-C10 aliphatic hydrocarbon group is preferable. Among them, 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 even more preferable, hexyl group and (2- Ethyl) hexyl group is particularly preferred. If R ¹² is such a group, the compound of the present invention is excellent in solubility in a solvent.

It is preferable that R <^13> and R <^14> are hydrogen atoms from the point which manufacture is easy.

R ¹¹ and R ¹³ combine to form a ring with carbon atoms and adjacent nitrogen atoms on adjacent benzene rings, or R ¹² and R ¹⁴ combine with carbon atoms and adjacent nitrogen atoms on adjacent benzene rings When forming a ring,

* -R ¹¹ -R ^13- * and * -R ¹² -R ^14- * 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- * are preferable. Among these, * -CH ₂ -C (CH ₃ ) _2- * is preferable. * Represents an arm.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms for R ¹⁵ 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 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 group which combined these is mentioned.

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

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

As a compound (2), as a compound (2) from a viewpoint of easy synthesis | combination, a compound (2-1)-a compound (2-15)-a compound (2-4), and a compound (2-4)-a compound (2) -2) and compound (2-5 ')-a compound (2-6) are preferable, A compound (2-1)-a compound (2-4), a compound (2-15)-a compound (2-3), Compound (2-3 ') to compound (2-4), compound (2-4) and compound (2-4'), compound (2-5 ') to compound (2-7'), and compound (2-3 ') to Compound (2-6) is more preferable, Among these, compound (2-1)-compound (2-4), compound (2-15)-compound (2-20), compound (2-27)-compound ( 2-23), compound (2-3) to compound (2-3), compound (2-3) to compound (2-4), compound (2-4) to hydrogenation Water (2-4), compound (2-5) and compound (2-6), compound (2-7) to compound (2-7), compound (2-7) to compound (2-7), and Compound (2-13) to compound (2--6) are even more preferable.

Compound (3) is represented by Formula (3), and its tautomers and salts thereof are also included.

In formula (3), X 'is a group 16 atom, -N (R ²⁵⁾ in the periodic table - or ^{-C (R 25) (R 26} ) - represents a. Examples of Group 16 atoms in the periodic table include oxygen atoms, sulfur atoms, selenium atoms, and tellurium atoms. From the viewpoint of optical properties and ease of manufacture, X 'is preferably an oxygen atom, a sulfur atom, -N (R ²⁵ )-or -C (R ²⁵ ) (R ²⁶ )-, and an oxygen atom, sulfur atom or -N (R ²⁵ )-is more preferable, an oxygen atom or a sulfur atom is even more preferable, and an oxygen atom is particularly preferable. When X 'is an oxygen atom, when the colored curable resin composition of this invention is made into the green color filter, its brightness tends to become more high.

In formula (3), as a halogen atom in R <^16> -R <^24> , a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.

In formula (3), R ¹⁶ to Examples 1 to 20 carbon atoms of the monovalent hydrocarbon group in R ^24, 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- dimethyl cyclohexyl group, 2,4, 6-trimethyl cyclohexyl group, 2, 2, 6, 6- tetramethyl cyclohexyl group, 3, 3, 5, 5- tetramethyl cyclohexyl 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;

Etc. can be mentioned.

The methylene group constituting such a monovalent hydrocarbon group is substituted with an oxygen atom, a sulfur atom, -N (R ²⁷ )-, 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 hydroxyl 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-hexylsulfamoyl 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, perfluoro (isopropyl) group, perfluoro (isopropenyl) group, perfluoro (1-propenyl) group, perfluoro ( 2-propenyl) group, perfluorobutyl group, perfluoro (isobutyl) group, perfluoro (sec-butyl) group, perfluoro (tert-butyl) group, perfluoro (2-butenyl ), 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, Perfluoro (isohexyl) group, perfluoro (5-methylhexyl) group, perfluoro ((2-ethyl) hexyl) group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group , Perfluorodecyl group, perfluorodecyl group, perfluorododecyl group, perflu Octadecyl aliphatic hydrocarbon group containing 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 containing 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 containing fluorine atoms 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 Alkoxy group containing fluorine atoms, 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 Bis (trifluoromethyl) phenylmethyl groups, such as a chloromethyl) phenylmethyl group, a 3, 4-bis (trifluoromethyl) phenylmethyl group, and a 3, 5-bis (trifluoromethyl) phenylmethyl group, etc. are mentioned.

As R <^16> and R <^17> , a C1-C20 aliphatic hydrocarbon group, a C3-C20 alicyclic hydrocarbon group, and a C6-C20 aromatic hydrocarbon group are preferable, A C1-C10 aliphatic hydrocarbon group is more preferable, C1-C20 Even more preferred are the aliphatic hydrocarbon groups of 5 to 5, and particularly preferred are aliphatic hydrocarbon groups of 2 to 4 carbon atoms.

Specific examples of the aliphatic hydrocarbon group for R ¹⁶ and R ¹⁷ include ethyl group, butyl group, hexyl group, (2-ethyl) hexyl group and octyl group, and ethyl group, butyl group, hexyl group and (2-ethyl) hex. Real groups are preferred, and ethyl and butyl groups are more preferred. If R <^16> and R <^17> is such a group, a raw material will be easy to obtain.

It is preferable that R <^18> , R <^19> , R <^22> , R <^23> and R <^24> are hydrogen atoms from the point which manufacture is easy.

R ¹⁶ and R ¹⁸ combine to form a ring with carbon atoms and adjacent nitrogen atoms on adjacent benzene rings, or R ¹⁷ and R ¹⁹ combine with carbon atoms and adjacent nitrogen atoms on adjacent benzene rings When forming a ring, * -R ¹⁶ -R ^18- * and * -R ¹⁷ -R ^19- * 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- * or * -CH ₂ -C (CH ₃ ) ₂ -* Is preferred, and among these, * -CH ₂ -C (CH ₃ ) _2- * is preferred. * Represents an arm.

Since R ²⁰ is easy to manufacture, a hydrogen atom, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group and an acyloxy group are preferable.

As R ^{21, a} hydrogen atom, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkoxycarbonyl group, an acyloxy group or a cyano group is preferable.

As R <^25> and R <^{26>, an} aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group is preferable.

The hydrogen atom contained in the aliphatic hydrocarbon group in R ²⁵ and R ²⁶ may be substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

The hydrogen atom contained in the alicyclic hydrocarbon group in R <^25> and R <^26> may be substituted by the aliphatic hydrocarbon group, alicyclic hydrocarbon group, or aromatic hydrocarbon group.

The hydrogen atom contained in the aromatic hydrocarbon group in R ²⁵ and R ²⁶ may be substituted with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

As an alkali metal atom in M ', a lithium atom, a potassium atom, and a sodium atom are mentioned. Preferably it is a potassium atom or a sodium atom, More preferably, it is a sodium atom.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms for R ²⁷ include methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 2-propenyl group, butyl group, isobutyl group, sec-butyl, tert-butyl, (2-ethyl) butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, 3-pentyl, neopentyl, tert-pent Methyl 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 Aliphatic hydrocarbon groups such as (3-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- dimethyl cyclohexyl group, 2,4, 6-trimethyl cyclohexyl group, 2, 2, 6, 6- tetramethyl cyclohexyl group, 3, 3, 5, 5- tetramethyl cyclohexyl 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 group which combined these is mentioned.

Examples of the group represented by L 'include a group represented by formulas (L'1) to (L'30), and a methylene group contained in these groups, for example, an oxygen atom, a sulfur atom, -N (R ²⁵ )-, The hydrogen atom substituted or contained in the sulfonyl group or the carbonyl group or a group thereof is a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, -SO ₃ M ', -CO ₂ M', hydroxy group or amino group. Substituted group is mentioned. In formulas (L'1) to (L'30),? Represents a coupling arm.

L 'is preferably a group represented by formulas (L'1) to (L'20), or (L'20') to (L'30). Among these, it is further more preferable that it is the trifluoromethyl methylene group which may have a substituent. As such preferable L ', the group represented by Formula (L'1)-a formula (L'17) is mentioned specifically, respectively. Formulas (L'1) to (L'10) are preferable, and formula (L'1) is more preferable. When L 'contains a fluorine atom, there exists a tendency for a foreign material to become difficult to precipitate in colored curable resin composition.

As compound (3), the compound shown in Tables 30-125, respectively, and these salts are mentioned, for example. In each table, among the numbers described in the R ¹⁶ to R ²⁶ columns, "cH '" represents a cyclohexyl group, "H'V" represents an n-hexyl group, "' H '" represents p-methylphenyl group, 2EHV "represents a 2-ethylhexyl group," 2NPｈ "represents a 2-naphthyl group," ｔＢｕ "represents a tert-butyl group," iFP "represents an isopropyl group, and" ｂｉＰｈ "represents a 4-phenylphenyl group. "FF1" represents a 4-trifluoromethylphenyl group, "FF2" represents a bis (trifluoromethyl) phenylmethyl group, "FF3" represents a perfluorocyclopentyl group, and "FF4" represents a perfluoro Represents a (3,5-dimethylcyclohexyl) group, "F5" represents a perfluoro (4-methylcyclohexyl) group, "FF6" represents a perfluorocyclohexyl group, and "F7" is purple. Represents an fluoroethyl group, "FF" represents a (perfluoroethyl) methoxy group, "FF" represents a perfluoro (isopropoxy) group, and "FF10" represents a 2,2,2-trifluoroethoxy. "FF11" represents a perfluoromethoxy group. In addition, the number of L 'column corresponds to the group represented by said formula (L'1)-a formula (L'30), respectively.

In Tables 30-43, the compound (3-1)-the compound (3-30) shown by a formula (3aO) are mentioned.

In Tables 44-57, the compound (3-30)-the compound (3-662) represented by a formula (3a-S) are mentioned.

In Table 58-71, the compound (3-663)-the compound (3-903) represented by a formula (3a-N) are mentioned.

In Table 72-Table 85, the compound (3-40) shown by the formula (3a-C)-the compound (3-20) are mentioned.

In Tables 86-87, the compound (3-1225)-the compound (3-1247) represented by a formula (3III-O) are mentioned.

In Tables 88-89, the compound (3-12 ') and the compound (3-12') shown by a formula (3'-S) are mentioned.

In Table 90-91, the compound (3-12'1)-the compound (3'1333) represented by Formula (3'-N) are mentioned.

In Table 92-Table 93, the compound (3-1343)-the compound (3-176) represented by Formula (3V-C) are mentioned.

In Table 94-95, the compound (3-17.3)-the compound (3-1141) represented by a formula (3c-O) are mentioned.

In Table 96-97, the compound (3-1420)-the compound (3-1462) represented by a formula (3c-S) are mentioned.

In Table 98-99, the compound (3-164)-the compound (3-150) represented by a formula (3c-N) are mentioned.

In Tables 100-101, the compound (3-15)-the compound (3-15) which are represented by a formula (3c-C) are mentioned.

In Table 102-105, the compound (3-155.5)-the compound (3-6,152) represented by a formula (3a-O) are mentioned.

In Table 106, the compound (3-165) to the compound (3-165) represented by the formula (3ｂ-O) are listed.

In Table 107, the compounds (3-66.5) to the compound (3-6,60) represented by the formula (3c-O) are listed.

In Table 108-111, the compound (3-661)-the compound (3-6,64) represented by a formula (3a-S) are mentioned.

In Table 112, the compound (3-769)-the compound (3-769) represented by Formula (3'-6) are mentioned.

In Table 113, the compound (3-769)-the compound (3-773) represented by a formula (3c-S) are mentioned.

In Tables 114-117, the compound (3-773)-the compound (3-1777) shown by Formula (3A-N) are mentioned.

In Table 118, the compound (3-1'7'7)-the compound (3'19'0) represented by a formula (3'-N) are mentioned.

In Table 119, the compound (3-1 19)-the compound (3-1 14) shown by a formula (3c-N) are mentioned.

In Table 120-123, the compound (3-15)-the compound (3-1) shown by Formula (3a-C) are mentioned.

In Table 124, the compound (3-1 ')-the compound (3-1'2) represented by a formula (3'-C) are mentioned.

In Table 125, the compound (3-1, 3)-compound (3-1, 6) represented by a formula (3c-C) are mentioned.

From the viewpoint of raw material availability, Compound (3-1), Compound (3-444), Compound (3-7), Compound (3-1300), Compound (3-173), Compound (3-261), Compound ( 3-25k), compound (3-30), compound (3-34.5), compound (3-383), compound (3-431), compound (3-447), compound (3-517), compound (3 -650, compound (3-663), compound (3-664), compound (3-686), compound (3-773), compound (3-775), compound (3-7), compound (3-3) VII6), compound (3-90), compound (3--447), compound (3-90), compound (3-1033), compound (3-1076), compound (3-1111), compound (3-1166) ), Compound (3-1220), compound (3-122.4), compound (3-1222), compound (31333), compound (3-17.3), compound (3-1204), compound (3-1462) , Unity The (3-1506), a compound (3-1549) and the compound (3-1592) are preferred. Among these, compound (3-1), compound (3-444), compound (3-7), compound (3-1300), compound (3-173), compound (3-261), compound (3-225) ), Compound (3-20), compound (3-1573), compound (3-1554) and compound (3-1552) are more preferable, and compound (3-1), compound (3-444), compound ( 3-25k), compound (3-20), compound (3-1573), compound (3-1554) and compound (3-1552) are even more preferable.

Compound (4) or compound (5) is represented by Formula (4) or Formula (5), and its tautomers and salts thereof are also included.

In formulas (4) and (5), X '' represents a group 16 atom, -N (R ³⁴ )-or -C (R ³⁴ ) (R ³⁵ )-in the periodic table. Examples of Group 16 atoms in the periodic table include oxygen atoms, sulfur atoms, selenium atoms, and tellurium atoms. From the viewpoint of optical properties and ease of manufacture, X '' is preferably an oxygen atom, a sulfur atom, -N (R ³⁴ )-or -C (R ³⁴ ) (R ³⁵ )-, and more preferably an oxygen atom. .

In formulas (4) and (5), examples of the halogen atom in R ²⁸ to R ⁴¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In formula (4) and formula (5), as a C1-C20 monovalent hydrocarbon group in R <^28> -R <^32> , for example

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-butenyl group, 1,3 Butadienyl, pentyl, isopentyl, 3-pentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, hexyl, isohexyl, Aliphatic hydrocarbon groups of up to 20 carbon atoms such as 5-methylhexyl group, (2-ethyl) hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, and octadecyl group;

Alicyclic hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexenyl group and cycloheptyl 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;

Can be mentioned.

The methylene group constituting such a monovalent hydrocarbon group is substituted with an oxygen atom, a sulfur atom, -N (R ⁴² )-, 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, sulfo group, carboxyl group, hydroxy group, imidazol-1-yl group or amino group include, for example.

Alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, phenoxy and benzyloxy;

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-hexylsulfamoyl 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;

And groups in which these are combined.

As R ²⁸ and R ^{29, an} aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group is preferable.

The hydrogen atom contained in the aliphatic hydrocarbon group in R <^28> and R <^29> may be substituted by the alicyclic hydrocarbon group or the aromatic hydrocarbon group.

R ²⁸ and a hydrogen atom contained in the alicyclic hydrocarbon groups R ²⁹ is optionally substituted aliphatic hydrocarbon group, alicyclic hydrocarbon group or an aromatic hydrocarbon.

R ²⁸ and a hydrogen atom contained groups aromatic hydrocarbon in R ²⁹ is optionally substituted aliphatic hydrocarbon group, alicyclic hydrocarbon group or an aromatic hydrocarbon.

Since R ³² is easy to manufacture, a hydrogen atom, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group or an acyloxy group is preferable.

As R ^33, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, etc. Aliphatic hydrocarbon groups having 1 to 6 carbon atoms; Ether groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, phenoxy and benzyloxy; Ester groups such as methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group and benzoyloxy group; Or cyano group is preferable.

As R ³⁴ to R ^{35, an} aliphatic hydrocarbon group, an alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group in combination thereof is preferable.

Any one of R ³⁶ to R ⁴¹ is —SO ₃ M ''. M '' represents an alkali metal atom, preferably a sodium atom or a potassium atom.

As compound (4), the compound shown in Table 126-Table 145, and its salt are mentioned, for example. In each table, "cHV" represents a cyclohexyl group, "VTH" is a p-methylphenyl group, "2EHV" represents a 2-ethylhexyl group, "2NPｈ" represents a 2-naphthyl group, and "ｔＢｕ" Represents a tert-butyl group, and "iPCr" represents an isopropyl group.

In Table 126-128, the compound (4-1)-the compound (4-7) which are represented by Formula (4a-0) are mentioned.

In Table 129-131, the compound (4-7) and the compound (4-40) represented by a formula (4a-S) are mentioned.

In Tables 132-134, the compound (4-14) and the compound (4-20) shown by a formula (4a-N) are mentioned.

In Table 135-137, the compound (4-211)-the compound (4-20) shown by Formula (4a-C) are mentioned.

In Table 138, the compound (4-2'11)-the compound (4-3 ') represented by a formula (4Pa-O) are mentioned.

In Table 139, the compound (4-3 ') shown by the formula (4'-S)-the compound (4-3'63) are mentioned.

In Table 140, the compound (4-337)-the compound (4-364) represented by a formula (4iv-N) are mentioned.

In Table 141, the compound (4-355) to the compound (4-3-2) represented by the formula (4-C) are given.

In Table 142, the compound (4-3９3) to the compound (4-420) represented by the formula (4c-O) are listed.

In Table 143, the compound (4-421) to the compound (4-4 Pa) represented by a formula (4c-S) are mentioned.

In Table 144, the compound (4-49.4)-the compound (4-476) represented by a formula (4c-N) are mentioned.

In Table 145, the compound (4-473)-the compound (4-554) represented by a formula (4c-C) are mentioned.

As compound (5), the compound shown in Table 146-Table 165, and its salt are mentioned, for example. In each table, "cHV" represents a cyclohexyl group, "VTH" is a p-methylphenyl group, "2EHV" represents a 2-ethylhexyl group, "2NPｈ" represents a 2-naphthyl group, and "ｔＢｕ" Represents a tert-butyl group, and "iPCr" represents an isopropyl group.

In Tables 146-148, the compound (5-1)-compound (5-70) shown by a formula (5a-O) are mentioned.

In Tables 149-151, the compound (5-70) and the compound (5-140) represented by a formula (5-AA) are mentioned.

In Tables 152 to 154, Compounds (5-14) to Compounds (5-20) represented by the formula (5A-N) are given.

In Tables 155-157, the compound (5-21) to the compound (5-22) shown by Formula (5-AA) are mentioned.

In Table 158, the compound (5-2'11)-the compound (5-300 ') represented by a formula (5XIO) are mentioned.

In Table 159, the compound (5-300 ')-the compound (5-36) represented by a formula (5-IX) are mentioned.

In Table 160, the compound (5-33)-the compound (5-3664) represented by a formula (5-V-N) are mentioned.

In Table 161, the compound (5-36) to the compound (5-33-2) represented by formula (5-V-C) are mentioned.

In Table 162, the compound (5-3９3) to the compound (5-420) represented by the formula (5c-O) are listed.

In Table 163, the compound (5-421)-the compound (5-44,000) represented by formula (5c-S) are mentioned.

In Table 164, the compound (5-4４) and the compound (5-476) represented by the formula (5c-N) are listed.

In Table 165, the compound (5-475) -compound (5-54) represented by a formula (5c-C) is mentioned.

From the viewpoint of raw material availability, compound (4) is represented by compounds (4-1) to (4-4), compound (4-7) to compound (4-1 '), and compounds (4-14.1) to compound (4-4). 18 '), compound (4-211) to compound (4-2'), compound (4-281) to compound (4-287), compound (4-3 ') to compound (4-315), compound (4-337) ) To compound (4-343), compound (4-365) to compound (4-371), compound (4-393) to compound (4-393), compound (4-421) to compound (4-427) , Compounds (4-4) to (4-4) and Compounds (4-47) to (4-483) are preferred, and among these, compounds (4-1) to (4-4) and compounds (4-281) to the compound (4-287), and compounds (4-393) to the compound (4-393k) are more preferable, Among the compounds (4-5), the compound (4-12), Compound (4-285) and the compound (4-397) are more preferred.

From the viewpoint of raw material availability, compound (5) is compound (5-1) to compound (5-4 '), compound (5-7'1) to compound (5-1'1) and compound (5-141) to compound (5-5). 18 '), compound (5-211) to compound (5-2'), compound (5-281) to compound (5-278), compound (5-3 ') to compound (5-315), compound (5-337) ) To compound (5-343), compound (5-365) to compound (5-373), compound (5-393) to compound (5-39), compound (5-421) to compound (5-427) , Compound (5-44) to Compound (5-45.5), and Compound (5-477) to Compound (5-483) are preferred, and among these, Compound (5-1) to Compound (5-14.4) and compound (5-281) to compound (5-287), and compounds (5-393) to compound (5-399) are more preferable, Among the compounds (5-5), the compound (5-12), Compound (5-285) and the compound (5-397) are more preferred.

As a manufacturing method of the compound (1) of this invention, the method according to the method of Dyes and Pigments (2008), 77, 556-558. Is mentioned, for example. 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. 0 degreeC-200 degreeC is preferable, and 100 degreeC-150 degreeC of reaction temperature is more preferable. The reaction time is preferably 1 hour to 24 hours, more preferably 8 hours to 18 hours, even 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 formulas (X1) and (X2), R ¹ to R ⁵ , R ⁷ to R ⁹ , AA, X, and L each represent the same meaning as described above.]

In the preparation of compound (1), the amount of the compound represented by formula (X1) is preferably 1 mol to 10 mol, and more preferably 1 mol to 2 mol, with respect to 1 mol of the compound represented by formula (X2). And even more preferably 1 mole.

In the preparation of compound (1), the amount of ethyl cyanoacetate used is preferably 1 mole to 10 moles, more preferably 1 mole to 2 moles, and even more based on 1 mole of the compound represented by formula (X2). Preferably it is 1 mol.

In the preparation of compound (1), the amount of benzoic acid used is usually 0.3 mol to 3 mol, preferably 0.3 to 0.6 mol, more preferably 0.3 to 0.4 with respect to 1 mol of the compound represented by formula (X2). It's a mole.

In addition, compound (1 ') in compound (1) can be manufactured by cyclizing-reacting the compound represented by Formula (X1), the compound represented by Formula (X3), and ethyl cyanoacetate in presence of benzoic acid and a solvent. 0 degreeC-200 degreeC is preferable, and 100 degreeC-150 degreeC of reaction temperature is more preferable. The reaction time is preferably 1 hour to 24 hours, more preferably 8 hours to 18 hours, even 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 (13), R <^7> -R <^9> , X and L have the same meaning as the above.

In preparation of compound (1 '), the usage-amount of the compound represented by Formula (X1) is 2 mol or more and 20 mol or less with respect to 1 mol of compounds represented by Formula (X3), Preferably it is 2-4 mol. And still more preferably 2 mole.

In the preparation of compound (1 '), the amount of ethyl cyanoacetate used is usually 2 mol to 20 mol, preferably 2 to 4 mol, and even more preferably based on 1 mol of the compound represented by the formula (13). Is 2 moles.

In the preparation of compound (1 '), the amount of benzoic acid used is usually 0.6 mol to 6 mol, preferably 0.6 to 1.2 mol, and more preferably 0.6 to 1 mol relative to 1 mol of the compound represented by formula (XIII). 0.7 moles.

The method for obtaining the compound (1) or the compound (1 ') of the present invention which is the target compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, a column chromatography method, a method of appropriately adjusting the temperature of the reaction mixture to precipitate crystals and filtering the crystals, or dissolving the reaction mixture in compound (1) or compound (1 '). It is preferable to precipitate a crystal | crystallization by the method of adding to the solvent which is not used, 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 or a mixture thereof It is preferable to wash with a solvent such as and then to dry. Furthermore, if necessary, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, chloroform or their You may further refine | purify by well-known methods, such as the method of melt | dissolving in a solvent, such as a mixed liquid, washing with aqueous sodium hydroxide solution, and drying, and column chromatography or recrystallization.

Compound (2) can be manufactured according to the method described, for example in Dyes and Pigments (2008), 77, 556-558. Specifically, compound (2) can be manufactured by cyclizing-reacting the compound represented by Formula (VII'1), the compound represented by Formula (VII'2), and ethyl cyanoacetate in presence of benzoic acid and a solvent. 0 degreeC-200 degreeC is preferable, and 100 degreeC-150 degreeC of reaction temperature is more preferable. 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 (X'1) and (X'2), R <^11> -R <^14> , Q <^1> and Q <^2> represent the same meaning as the above respectively.]

In the preparation of compound (2), the amount of the compound represented by formula (VII'1) is preferably 1 mol to 10 mol, more preferably 1 to 1 mol of compound represented by formula (VII'2). Moles to 4 moles, even more preferably 1 to 3 moles, even more preferably 1 mole.

In the preparation of compound (2), the amount of ethyl cyanoacetate used is preferably 1 mol to 10 mol, more preferably 1 mol to 4 mol, with respect to 1 mol of the compound represented by the formula (VII'2). Still more preferably 1 mol to 3 mol, even more preferably 1 mol.

In the preparation of compound (2), 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, relative to 1 mol of the compound represented by formula (VII'2). Preferably 0.3 to 1.2 mol, even more preferably 0.3 to 0.4 mol.

The method of obtaining the compound (2) 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 the crystals by column chromatography, to adjust the temperature of the reaction mixture appropriately, or to add the reaction mixture to a solvent in which compound (2) is not dissolved to obtain the crystals by filtration. Do. 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.

Compound (3) can be manufactured by the method shown below, for example. First, the compound represented by Formula (VII''1) and diethyl malonate are made to react, and the compound represented by Formula (VII "2) is obtained. Subsequently, the compound represented by Formula (VII''2), phosphoric chloride, and N, N-dimethylformamide are reacted to obtain a compound represented by Formula (VII''3). Finally, compound (3) is obtained by making the compound represented by Formula (VIII ") and the compound represented by Formula (VIII" 4) react. What is marketed may respectively be used for the compound represented by Formula (VIII "1), and the compound represented by Formula (VIII" 4) may be manufactured and used by arbitrary well-known methods.

Equation (pp''1), formula (pp''2), in equation (pp''3) and formula (pp''4), R ¹⁶ to R ^24, X 'and L' are the same and the respective Indicates meaning]

In the preparation of the compound represented by formula (VII''2), the amount of diethyl malonate used is preferably 1 mol or more and 10 mol or less, more preferably 1 mol of the compound represented by formula (VII''1). Preferably 1 to 3 moles.

It is preferable to carry out manufacture of the compound represented by Formula (VII''2) in presence of organic bases, such as amines, such as a triethylamine, a tributylamine, a pyrrolidine, a piperidine, a pyrazine, or a pyridine, It is more preferable to carry out in the presence of piperidine. Moreover, it is preferable to carry out in presence of a solvent, As such a solvent, C1-C10 alcohol, tetrahydrofuran, acetone, methyl isobutyl ketone, acetic acid, glacial acetic acid, ethyl acetate, acetonitrile, water, hexane, toluene, Chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone are preferable, and among these, ethanol is more preferable. The reaction temperature is preferably -5 ° C to 140 ° C, and even more preferably 10 ° C to 100 ° C.

In the preparation of the compound represented by the formula (VII''3), the amount of phosphoric chloride used is preferably 1 mol or more and 10 mol or less, more preferably to 1 mol of the compound represented by the formula (VII''2). Is 1 to 5 moles.

In the preparation of the compound represented by formula (VII '' 3), the amount of N, N-dimethylformamide used is preferably 1 mol or more and 10 mol or less with respect to 1 mol of the compound represented by formula (VII''2). More preferably 1 to 5 moles.

It is preferable to perform manufacture of the compound represented by Formula (VIII "3) in presence of a solvent, As such a solvent, C1-C10 alcohol, tetrahydrofuran, acetone, methyl isobutyl ketone, acetic acid, glacial acetic acid, acetic acid Ethyl, acetonitrile, water, hexane, toluene, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone are preferred, and N, N-dimethylformamide is more preferred. desirable. The reaction temperature is preferably -5 ° C to 100 ° C, and more preferably -5 ° C to 60 ° C.

In the preparation of compound (3), the amount of the compound represented by formula (VII''3) is preferably 2 mol or more and 20 mol or less, more preferably to 1 mol of the compound represented by formula (VII''4). Preferably 2 to 3 moles.

The preparation of compound (3) is preferably carried out in the presence of an organic base such as sodium acetate, potassium acetate or lithium acetate, more preferably in the presence of sodium acetate. Moreover, it is preferable to carry out in presence of a solvent, As such a solvent, C1-C10 alcohol, tetrahydrofuran, acetone, methyl isobutyl ketone, acetic acid, glacial acetic acid, ethyl acetate, acetonitrile, water, hexane, toluene, It is preferable to use chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone, among which glacial acetic acid is more preferable. The reaction temperature is preferably 0 ° C to 140 ° C, and even more preferably 70 ° C to 110 ° C.

The method of obtaining the compound (3) which is a target compound from a reaction mixture is not specifically limited, Various well-known methods can be employ | adopted. For example, the column chromatography method or the method of obtaining water by adding water to a reaction mixture and depositing a crystal | crystallization and filtering the said crystal | crystallization is mentioned. 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, dichloromethane, You may wash | clean with solvent, such as chloroform, tetrachloromethane, or these liquid mixture, and you may dry. Furthermore, if necessary, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, dichloromethane, chloroform It may be dissolved in a solvent such as tetrachloromethane or a mixture thereof, washed with an aqueous sodium hydroxide solution and then dried, or further purified by a known method such as column chromatography or recrystallization.

As a manufacturing method of the compound (3) of this invention, for example,Dys and Pigments 2008,77, 556. can also be produced according to the method described. Specifically, the compound represented by the formula (VII''1), the compound represented by the formula (VII''4) and ethyl cyanoacetate can be produced by cyclization reaction in the presence of benzoic acid and a solvent. 0 degreeC-200 degreeC is preferable, and 100 degreeC-150 degreeC of reaction temperature is more preferable. The reaction time is preferably 1 hour to 24 hours, more preferably 8 hours to 18 hours, and even 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 the preparation of compound (3), the amount of the compound represented by formula (VII''1) is usually 2 mol or more and 20 mol or less with respect to 1 mol of the compound represented by formula (VII''4), preferably Is 2 to 4 moles, and preferably 2 moles among them.

In the preparation of compound (3), the amount of ethyl cyanoacetate used is usually 2 mol to 20 mol, preferably 2 to 4 mol, with respect to 1 mol of the compound represented by the formula (VII''4), Among these, Preferably it is 2 mol.

In the preparation of compound (3), the amount of benzoic acid used is usually from 0.6 mol to 6 mol, preferably from 0.6 to 1.2 mol, among these, with respect to 1 mol of the compound represented by formula (VII''4). Preferably 0.6 to 0.7 mol.

The method for obtaining the compound (3) of the present invention which is the target compound from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, the crystals are precipitated by column chromatography, a method of appropriately adjusting the temperature of the reaction mixture to precipitate crystals and filtering the crystals, or by adding the reaction mixture to a solvent in which compound (3) is not dissolved. It is preferable that the crystals are obtained by filtration. 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 or a mixture thereof It is preferable to wash with a solvent such as and then to dry. Furthermore, if necessary, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, chloroform or their You may further refine | purify by well-known methods, such as the method of melt | dissolving in a solvent, such as a mixed liquid, washing with aqueous sodium hydroxide solution, and drying, and column chromatography or recrystallization.

As a manufacturing method of compound (4) or compound (5) of this invention, the method of manufacturing according to the method of Dyes and Pigments (2008), 77, 556-558. Is mentioned, for example.

As a manufacturing method of compound (4), a cyclization reaction is carried out specifically, the compound represented by Formula (VII '' '1), the compound represented by Formula (VII' '' 2), and ethyl cyanoacetate in presence of benzoic acid and a solvent. The manufacturing method is mentioned. 0 degreeC-200 degreeC is preferable, and 100 degreeC-150 degreeC of reaction temperature is more preferable. 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.

Equation (pp '''1) and the equation (pp' in '' 2), R ²⁸ to R ^32, R ³⁶ to R ⁴¹ and X '' represents the same meanings, respectively;

In the preparation of compound (4), the amount of the compound represented by the formula (VII '' '1) is preferably 1 mol to 10 mol, more preferably 1 mole to 1 mol of the compound represented by the formula (VII' '' 2). It is preferably 1 to 4 mol, even more preferably 1 to 3 mol, even more preferably 1 mol.

In the preparation of compound (4), the amount of ethyl cyanoacetate used is preferably 1 mol to 10 mol, more preferably 1 mol to 4 mol, based on 1 mol of the compound represented by the formula (VII ′ '' 2). Moles, even more preferably 1 to 3 moles, even more preferably 1 mole.

In the preparation of compound (4), the amount of benzoic acid used is preferably 0.1 mol to 3 mol, more preferably 0.3 mol to 3 mol, with respect to 1 mol of the compound represented by the formula (VII ′ '' 2), Even more preferably 0.3 to 1.2 moles, even more preferably 0.3 to 0.4 moles.

As a manufacturing method of the compound (5) of this invention, the compound specifically represented by Formula (VII '' '1), the compound represented by Formula (VII' '' 3), and ethyl cyanoacetate are carried out in the presence of benzoic acid and a solvent, The method of manufacturing by cyclization reaction is mentioned. 0 degreeC-200 degreeC is preferable, and 100 degreeC-150 degreeC of reaction temperature is more preferable. 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 (VII '''3), R <^36> -R <^41> and X "respectively represent the same meaning as the above.)

In the preparation of compound (5), the amount of the compound represented by the formula (VII '' '1) is preferably 1 mol to 10 mol, more preferably 1 mol of the compound represented by the formula (VII' '' 3). It is preferably 1 to 4 mol, even more preferably 1 to 3 mol, even more preferably 1 mol.

In the preparation of compound (5), the amount of ethyl cyanoacetate used is preferably 1 mol to 10 mol, more preferably 1 mol to 4 mol, based on 1 mol of the compound represented by the formula (VII '' '3). Moles, even more preferably 1 to 3 moles, even more preferably 1 mole.

In the preparation of compound (5), the amount of benzoic acid used is preferably 0.1 mol to 3 mol, more preferably 0.3 mol to 3 mol, with respect to 1 mol of the compound represented by the formula (VII ′ '' 3), Even more preferably 0.3 mol to 1.2 mol, even more preferably 0.3 to 0.4 mol.

The method for obtaining the compound (4) or the compound (5) of the present invention which is the target compound from the reaction mixture is not particularly limited, and various known methods can be adopted. For example, by column chromatography, a method of appropriately adjusting the temperature of the reaction mixture to precipitate crystals and filtering the crystals, or adding the reaction mixture to a solvent in which compound (4) or compound (5) is not dissolved. It is preferable to precipitate a crystal | crystallization by the method of making it, and to obtain the said crystal 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 or a mixture thereof It is preferable to wash with a solvent such as and then to dry. Furthermore, if necessary, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, ethyl acetate, hexane, toluene, chloroform or their You may further refine | purify by well-known methods, such as the method of melt | dissolving in a solvent, such as a mixed liquid, washing with aqueous sodium hydroxide solution, and drying, and column chromatography or recrystallization.

The compound having a coumarin skeleton contains a compound having a coumarin skeleton such as compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5) as an active ingredient. The compound which has a coumarin skeleton may consist only of compound (1), compound (1 '), compound (2), compound (3), compound (4), or compound (5), and may include the dye mentioned later. The compound having a coumarin skeleton is preferably a compound having a coumarin skeleton such as compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5). It is contained in the ratio of%.

In this invention, the compound which has a coumarin skeleton is useful as dye contained in the colored curable resin composition used for color filters of display apparatuses, such as a liquid crystal display device.

The coloring agent (A) is a compound (1), in addition to a compound having a coumarin skeleton such as compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5). Dye and / or pigment different from the compound which has coumarin skeleton, such as a compound (1 '), a compound (2), a compound (3), a compound (4), or a compound (5), may be included.

As dyes other than compounds having a coumarin skeleton such as Compound (1), Compound (1 '), Compound (2), Compound (3), Compound (4) or Compound (5), the Color Index [The Dyes classified as Solvent, Acid, Basic, Reactive, Direct, Disperse or Bat in the Society of Dyers and Colourists. Can be mentioned. More specifically, dyes having the following color index (C.I.) numbers may be mentioned, but are not limited thereto.

C.I. Solvent yellow 25, 79, 81, 82, 83, 89;

C.I. Acid yellow 7, 23, 25, 42, 65, 76;

C.I. Reactive yellow 2, 76, 116;

C.I. Direct yellow 4, 28, 44, 86, 132;

C.I. Dispulse yellow 54, 76;

C.I. Solvent orange 41, 54, 56, 99;

C.I. Acid orange 56, 74, 95, 108, 149, 162;

C.I. Reactive orange 16;

C.I. Direct orange 26;

C.I. Solvent red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218;

C.I. Acid red 73, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Acid violet 102;

C.I. Solvent green 1, 5;

C.I. Acid green 3, 5, 9, 25, 28;

C.I. Basic Green 1;

C.I. Bat Green 1 etc.

A coloring agent (A) contains the compound which has coumarin skeleton, such as a compound (1), a compound (1 '), a compound (2), a compound (3), a compound (4), or a compound (5), and further a pigment (P) It is preferable to include).

The pigment (P) which may be contained in the coloring agent (A) is not particularly limited, and known pigments can be used. For example, pigments classified as pigments in the color index (The Society of Dyers and Colourists) can be used. Can be mentioned.

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, 194, and 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, 19, 23, 29, 32, 36 and 38;

C.I. Green pigments such as pigment green 7, 36 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 selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments, still more preferably chlorinated copper phthalocyanine pigments, brominated copper phthalocyanine pigments and brominated At least one selected from the group consisting of zinc phthalocyanine pigments, even more preferably CI Pigment green 7, 36, and 58 or more selected from the group consisting of. The said pigment is used suitably as a green pigment, and by including the said pigment, optimization of a transmission spectrum is easy and the light resistance and chemical-resistance of a color filter become favorable.

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. In order to do this, a washing treatment with an organic solvent, water, or the like, a removal treatment by an ion exchange method of ionic impurities, 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 company), 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.

Compound (A) is a compound (1), in addition to the compound which has coumarin skeleton, such as a compound (1), a compound (1 '), a compound (2), a compound (3), a compound (4), or a compound (5), When it contains dye and / or pigment different from compound which has coumarin skeleton, such as compound (1 '), compound (2), compound (3), compound (4), or compound (5), compound (1), The content of the compound having a coumarin skeleton such as compound (1 '), compound (2), compound (3), compound (4) or compound (5) is preferably 1% by mass based on the total amount of the colorant (A). 100 mass% or less, More preferably, they are 1 mass% or more and 65 mass% or less, More preferably, they are 2 mass% or more and 60 mass% or less.

Compounds having coumarin skeletons such as compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5) and C.I. The content of Pigment Yellow 129 is preferably 1% by mass or more and 100% by mass or less, more preferably 1% by mass or more and 65% by mass or less, and even more preferably 2% by mass with respect to the total amount of the coloring agent (A). It is more than 60 mass%.

When it contains a pigment (P), its content rate is 1 mass% or more and 99 mass% or less with respect to the total amount of a coloring agent (A), More preferably, it is 35 mass% or more and 99 mass% or less, More preferably Preferably it is 40 mass% or more and 98 mass% or less.

The content rate of the coloring agent (A) is preferably 1% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 70% by mass or less, even more preferably 5% by mass or more and 60% by mass to the total amount of solids. It is% or less, More preferably, it is 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 acrylic acids containing a hydroxyl group and a carboxyl group in the same molecule such as α- (hydroxymethyl) acrylic acid.

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

(iii) represents, for example, an ethylenically unsaturated bond with a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) Eggplant refers to a polymerizable compound. (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 The compound represented by a rate, a compound represented by Formula (I), and a 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.

As R ^<a> and R <^b> , a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and 2-hydroxyethyl group are mentioned preferably, A hydrogen atom and a methyl group are preferable.

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 include a single bond, a methylene group, an ethylene group, * -CH ₂ -O- and * -CH ₂ CH ₂ -O-, and a single bond, * -CH ₂ CH ₂ -O- desirable. * Represents a binding 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-1 11) to Formula (I-15) ) Is preferable, and the compound represented by Formula (I-1), Formula (I-7), Formula (I-1) 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-X), or formulas (II-1 11) to formula (II-15) ) Is preferable, and the compound represented by formula (II-1), formula (II-7), formula (II-X), 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 based on molar basis, Preferably it is 5: 95-95: 5, More preferably, it is 10: 90-90: 10. And even more preferably 20:80 to 80:20.

As (b2), the monomer which has an oxetanyl group and a (meth) acryloyloxy group is preferable. As (b2), 3-methyl-3-methacryloyloxymethyl oxetane, 3-methyl-3- acryloyloxymethyl 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 (v3), the monomer which has a tetrahydrofuryl group and a (meth) acryloyloxy group is 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, Preference is given to N-cyclohexylmaleimide, N-benzylmaleimide and bicyclo [2.2.1] hepto-2-ene.

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 favorable. Since the reactivity of a cyclic ether is high and it is hard to remain unreacted (iv), (v1) is preferable and (v1-1) is more preferable as (v) used for resin [4].

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 compounding method, reaction temperature, and time, can be suitably adjusted in consideration of the amount of heat generated by a manufacturing facility, 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 (i), as (i) used for resin [K5], (K1) is preferable and (K1-1) is 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 (VIII) 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 [K2] is still more preferable from the viewpoint of the 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, Even more 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 to 170 mg-KOH / g, preferably 30 to 170 mg-KOH / g, more preferably 40 to 170 mg-KOH / g, even more preferably 50 to 170 mg-KOH / g, even more preferably 50 to 150 mg-KOH / g, particularly preferably 60 to 150 mg-KOH / g, particularly preferably 60 to 135 mg-KOH / g, most preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be obtained by, for example, titration using an aqueous potassium hydroxide solution.

The content of the resin is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, even more preferably 13 to 60% by mass, even more preferably based on the total amount of solids. 17 to 55 mass%. When content of resin exists in the said range, formation of a coloring pattern 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 150 or more and 1,500 or less, still more preferably 150 or more and 800 or less, even more preferably 190 or more and 700 or less.

The content of the polymerizable compound (C) is usually 5 to 65% by mass, preferably 7 to 65% by mass, more preferably 10 to 60% by mass, even more preferably 13 to 30% by mass based on the total amount of solids. 60 mass%, even more preferably 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 O-acyl oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, acylphosphine oxide 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, eg, JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis (2-chlorophenyl ) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4' , 5,5'-tetra (trialkoxyphenyl) biimidazole (see, eg, JPS48-38403-B, JPS62-174204-A, etc.), phenyl group at 4,4 ', 5,5'-position And imidazole compounds substituted with carboalkoxy groups (see, for example, 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 it is 1-30 mass parts, More preferably, it is 1-20 mass parts.

<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 Preference is given to ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide and N-methylpyrrolidone, 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-ethoxypropionic acid More preferred are ethyl and N-methylpyrrolidone.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, still more preferably 75 to 90% by mass relative to the total amount of the colored curable resin composition. 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%, More preferably, it is 10-25 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)>

The surface smoothing agent (F) may be contained in the colored curable resin composition of this invention. 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, toray silicon DC3PA, toray silicon SH7PA, toray silicon DC11PA, toray silicon SH21PA, toray silicon SH28PA, toray silicon SH29PA, toray silicon SH30PA, toray silicon SH8400 [brand name: Toray Dow Corning Co., Ltd.], KP321, KP322 , KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452 and TSF4460 [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 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, further preferably 0.005, based on the total amount of the colored curable resin composition. It is 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.

Compounds having coumarin skeletons such as compound (1), compound (1 '), compound (2), compound (3), compound (4) or compound (5) may be dissolved in some or all of the solvent (E) in advance. It is preferable 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 or use, 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 to be.

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 around 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.

The coloring patterning coating film 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. 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 the obtained colored patterned coating film. 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 this invention, it becomes possible to provide the colored curable resin composition which can manufacture especially a high brightness color filter. The color filter can be suitably used for a display device (for example, a liquid crystal display device, an organic EL device, an electronic paper, etc.), and a solid-state imaging device.

Example

The present invention will be described more specifically with reference to the following examples. "%" And "part" are mass% and a mass part in an example unless there is particular notice.

In the following synthesis examples, the structure of the compound is NMR [JMM-ECA-500; Japan Electronics Co., Ltd.] or mass spectrometry (LC; Agilent 1200, MASS; Agilent LC / MSDD6130).

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

Bis (3-amino-4-hydroxyphenyl) sulfone (manufactured by Tokyo Kasei Co., Ltd.) 10.6 parts, 4- (diethylamino) salicylic [manufactured by Tokyo Kasei Industry Co., Ltd.] 14.6 parts, Benzoic acid [Tokyo] 3.17 parts of Kasei Kogyo Co., Ltd., 183 parts of 1-pentanol [made by Tokyo Kasei Co., Ltd.] and 8.61 part of ethyl cyanoacetate (made by Tokyo Kasei Co., Ltd.), and stirred at 120 degreeC for 3 hours. It was. 14.6 parts of 4- (diethylamino) salicylic [Tokyo Kasei Co., Ltd.], 3.17 parts of benzoic acid [Tokyo Kasei Co., Ltd.] and ethyl cyanoacetate (Tokyo Kasei Co., Ltd.) to this reaction solution 8.61 parts were added and stirred at 120 ° C for 12 hours. After cooling the said reaction liquid to room temperature, the precipitated crystal | crystallization was obtained as a residue of suction filtration. 236 parts of acetonitrile and 234 parts of isopropyl alcohol were added to this residue, and after stirring, an insoluble matter was obtained as a residue of suction filtration. 236 parts of acetonitrile and 234 parts of isopropyl alcohol were added to this residue, and after stirring, an insoluble matter was obtained as a residue of suction filtration. To this residue was added 2220 parts of chloroform, stirred and filtered. 530 parts of 5% aqueous sodium hydroxide solution was added to the filtrate, followed by stirring, and the chloroform solution layer was extracted. 610 parts of 18% sodium chloride aqueous solution was added to this chloroform solution, it stirred, and the chloroform solution layer was extracted. 10 parts of magnesium sulfate was added to this chloroform solution, the mixture was stirred, and then filtered. The filtrate was removed by evaporation of the solvent with a rotary evaporator, and then dried under reduced pressure at 60 ° C to obtain 19.5 parts of the compound represented by the formula (1-14 Pa). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (I-14)

Synthesis Example 2

Bis (3-amino-4-hydroxyphenyl) dimethylmethane [manufactured by Changzhou Sunlight Pharmaceutical Co., Ltd.] 10.1 parts, 4- (diethylamino) salicylic aldehyde [Tokyo Kasei Co., Ltd. Note] 15.2 parts, benzoic acid [Tokyo Kasei Co., Ltd.] 3.26 parts, 1-pentanol [Tokyo Kasei Co., Ltd.] 191 parts and ethyl cyanoacetate [Tokyo Kasei Co., Ltd.] 8.89 The parts were mixed and stirred at 120 ° C. for 3 hours. 8.39 parts of 4- (diethylamino) salicylic [Tokyo Kasei Co., Ltd.], 1.80 parts of benzoic acid [Tokyo Kasei Co., Ltd.], 1-pentanol [Tokyo Kasei Co., Ltd.] 8.40 parts and 4.91 parts of ethyl cyanoacetate (made by Tokyo Kasei Co., Ltd.) were added, and it stirred at 120 degreeC for 12 hours. After the reaction solution was cooled to room temperature, precipitated crystals were obtained as a residue of suction filtration. 332 parts of acetonitrile were added to this residue, and after stirring, an insoluble matter was obtained as a residue of suction filtration. 315 parts of acetonitrile were added to this residue, and after stirring, an insoluble matter was obtained as a residue of suction filtration. This residue was dried under reduced pressure at 60 ° C. to obtain 23.6 parts of the compound represented by the formula (1-16). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (16-6)>

Synthesis Example 3

o -amino- p -benzylphenol [Journal of the American Chemical Society (1935), 57, 1697-8. Reference] 10.3 parts, 4- (diethylamino) salicylic aldehyde [Tokyo Kasei Co., Ltd.] 10.0 parts, benzoic acid [Tokyo Kasei Co., Ltd.] 2.16 parts, 1-pentanol [Tokyo Kasei Co., Ltd. ) 125 parts and 5.85 parts of ethyl cyanoacetate (made by Tokyo Kasei Co., Ltd.) were mixed, and it stirred at 120 degreeC for 3 hours. 10.0 parts of 4- (diethylamino) salicylic [Tokyo Kasei Co., Ltd.], 2.16 parts of benzoic acid (Tokyo Kasei Co., Ltd. product), 1-pentanol [Tokyo Kasei Co., Ltd. product] ] 12.5 parts and 5.85 parts of ethyl cyanoacetate (made by Tokyo Kasei Co., Ltd.) were mixed, 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 (1-1).

Synthesis Example 4

o -amino- p -phenylsulfonylphenol (see Japanese Patent Application Laid-Open No. 49-126979) 12.9 parts, 4- (diethylamino) salicylic [manufactured by Tokyo Kasei Co., Ltd.] 10.0 parts, benzoic acid [Tokyo Kasei Industry Co., Ltd. 2.16 parts, 125 parts of 1-pentanol (made by Tokyo Kasei Co., Ltd.) and 5.85 parts of ethyl cyano acetate (made by Tokyo Kasei Co., Ltd.) were mixed, and it stirred at 120 degreeC for 3 hours. 10.0 parts of 4- (diethylamino) salicylic [Tokyo Kasei Co., Ltd.], 2.16 parts of benzoic acid (Tokyo Kasei Co., Ltd. product), 1-pentanol [Tokyo Kasei Co., Ltd. product] ] 12.5 parts and 5.85 parts of ethyl cyanoacetate (made by Tokyo Kasei Co., Ltd.) were mixed, 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 a compound represented by the formula (1-6).

Synthesis Example 5

9,9-bis (3-amino-4-hydroxyphenyl) fluorene [made by Tokyo Kasei Co., Ltd.] 9.84 parts, 4- (diethylamino) salicylic aldehyde [made by Tokyo Kasei Co., Ltd.] 10.0 2.16 parts of benzoic acid [Tokyo Kasei Co., Ltd.] 2.16 parts, 1-pentanol [Tokyo Kasei Co., Ltd.] 125 parts and ethyl cyanoacetate [Tokyo Kasei Co., Ltd.] 5.86 parts are mixed, 120 Stirred for 3 hours at ℃. 10.0 parts of 4- (diethylamino) salicylic [Tokyo Kasei Co., Ltd.], 2.16 parts of benzoic acid [Tokyo Kasei Co., Ltd.], 1-pentanol [Tokyo Kasei Co., Ltd.] to this reaction solution First] 12.5 parts and 5.86 parts of ethyl cyanoacetate (manufactured by Tokyo Kasei Co., Ltd.) were mixed and stirred at 120 ° C 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 a compound represented by the formula (1-23).

Synthesis Example 6

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 reaction solution to room temperature, precipitated crystals were obtained as a residue of suction filtration. 140 parts of tetrahydrofuran was added to the residue, and the mixture was stirred at 70 ° C for 1 hour to obtain an insoluble matter as a residue of suction filtration. 120 parts of tetrahydrofuran was added to the residue, and the mixture was stirred at 70 ° C for 1 hour, and an insoluble matter was obtained as a residue of suction filtration. 340 parts of N, N-dimethylformamide was added to this residue, heated to 90 ° C to dissolve, and left to stand 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 (2-1) were obtained. ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (2-1)>

Synthesis Example 7 Synthesis of Compound [Hereinafter, Compound (3-1)] Represented by Formula (3-1)

<Synthesis of 7-diethylaminocoumarin>

1.93 g (10 mmol) of 4-diethylaminosalicylaldehyde represented by the formula (VII''1-1), 3.20 g (20 mmol) of diethyl malonic acid represented by the formula (VII''5-1), 1 mL of piperidine was dissolved in 50 mL of absolute ethanol. Subsequently, the reaction was performed while stirring under reflux for 6 hours. After the reaction was completed, ethanol was removed by evaporation under reduced pressure, 10 mL of concentrated hydrochloric acid and 10 mL of glacial acetic acid were added to the reaction mixture, and the mixture was stirred for further 6 hours. After cooling the reaction mixture to room temperature, it was further cooled in 200 mL of ice water, and then the pH of the reaction mixture was adjusted to about 5 by dropping 30 mass% aqueous sodium hydroxide solution into the reaction mixture. After the reaction mixture was stirred for 30 minutes, the resulting precipitate was filtered, washed with water and dried. The precipitate obtained in this way was recrystallized with toluene, and 7-diethylamino coumarin represented by a formula (VII "2-1) was obtained. The yield was 1.74 g (8.0 mmol) and the yield was 80%.

<Identification of Compound Represented by Formula (XIII '2-1)>

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 218.1

                          Exact Mass: 217.1

<Synthesis of 7-diethylaminocoumarin-3-aldehyde>

2 mL of dehydrated dimethylformamide was slowly added dropwise to a reaction vessel containing 2 mL of phosphoryl chloride under 0 ° C and a nitrogen atmosphere, and then heated to room temperature and stirred for 30 minutes. Subsequently, 1.50 g (6.91 mmol) of 7-diethylaminocoumarin represented by the formula (VII''2-1-1) was dissolved in 10 mL of dehydrated dimethylformamide, placed in a reaction vessel, and stirred at 50 ° C for 12 hours. The reaction mixture was placed in 200 mL of ice water and 20 mass% aqueous sodium hydroxide solution was added. The resulting precipitate was filtered off, washed with water and dried. The precipitate thus obtained was recrystallized from ethanol to obtain 7-diethylaminocoumarin-3-aldehyde represented by the formula (VII '' 3-1). The yield was 1.20 g (4.89 mmol) and the yield was 70%.

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

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 246.1

                          Exact Mass: 245.1

<Synthesis of Compound (3-1)>

7-diethylaminocoumarin-3-aldehyde 2.0 g (8.15 mmol) represented by the formula (VII '' 3-1), and 2,2-bis (3-amino-) represented by formula (VII '' 4-1) 1.49 g (4.08 mmol) of 4-hydroxyphenyl) hexafluoropropane and 12.6 g (163 mmol) of sodium acetate were dissolved in 40 mL of glacial acetic acid and stirred at 90 ° C for 10 hours. The reaction mixture was then placed in 200 mL of water. The resulting precipitate was filtered, dissolved in dichloromethane, put into a separatory funnel with water and washed. The dichloromethane layer recovered from the separating funnel was dried over sodium sulfate, and then purified by silica gel column chromatography to obtain compound (3-1). The yield was 1.67 g (2.04 mmol) and the yield was 50%.

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

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 817.3

                          Exact Mass: 816.2

Synthesis Example 8

1-amino-2-naphthol-4-sulfonic acid [Tokyo Kasei Co., Ltd.] 14.9 parts, 4- (diethylamino) salicylic aldehyde [Tokyo Kasei Industry Co., Ltd.] 12.0 parts, benzoic acid [Tokyo Kasei Industry] Co., Ltd. 2.61 parts, 151 parts of 1-pentanol (made by Tokyo Kasei Co., Ltd.), and 7.12 parts of ethyl cyano acetate (made by Tokyo Kasei Co., Ltd.) were mixed, and it stirred at 120 degreeC for 12 hours. After the reaction solution was cooled to room temperature, precipitated crystals were obtained as a residue of suction filtration. To this residue was added 320 parts of acetonitrile and after stirring, an insoluble was obtained as a residue of suction filtration. 236 parts of acetonitrile were added to this residue, and after stirring, an insoluble matter was obtained as a residue of suction filtration. This residue was dried under reduced pressure at 60 degreeC, and 25.7 parts of compounds represented by Formula (4-5) were obtained. ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (4-5)>

Synthesis Example 9

1-amino-2-naphthol-4-sulfonic acid [Tokyo Kasei Co., Ltd.] 14.9 parts, 4- (dibutylamino) salicylic aldehyde [Tokyo Kasei Industry Co., Ltd.] 15.5 parts, Benzoic acid [Tokyo Kasei Industry] Co., Ltd. 2.59 parts, 150 parts of 1-pentanol (made by Tokyo Kasei Co., Ltd.) and 7.02 parts of ethyl cyano acetate (made by Tokyo Kasei Co., Ltd.) were mixed, 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 (4-12).

Synthesis Example 10

14.9 parts of 1-amino-2-naphthol-4-sulfonic acid (manufactured by Tokyo Kasei Co., Ltd.), 13.5 parts by 8-hydroxyjulolidine-9-carboxyaldehyde (manufactured by Tokyo Kasei Co., Ltd.), 2.59 parts of benzoic acid (Tokyo Kasei Co., Ltd. make) 2.59 parts, 1-pentanol [Tokyo Kasei Co., Ltd. make] 150 parts, and cyano acetate ethyl [Tokyo Kasei Co., Ltd. make] 7.02 parts are mixed, and it is 120 degreeC. Stir 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 a compound represented by formula (4-2８5).

Synthesis Example 11

1-amino-2-naphthol-4-sulfonic acid (Tokyo Kasei Kogyo Co., Ltd. product) 14.9 parts, 8-hydroxy-1,1,7,7-tetramethyl zulolidine-9-carboxyaldehyde [Tokyo Kasei Co., Ltd. ] 17.0 parts, benzoic acid [Tokyo Kasei Co., Ltd.] 2.59 parts, 1-pentanol [Tokyo Kasei Co., Ltd.] 150 parts and cyano acetate ethyl [Tokyo Kasei Co., Ltd.] 7.02 parts were mixed and stirred at 120 ° C. 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 a compound represented by the formula (4-3９7).

Synthesis Example 12

An appropriate amount of nitrogen was flowed into a flask equipped with a reflux cooler, a dropping funnel, and a stirrer to obtain a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added thereto, and the mixture was heated to 85 ° C while stirring. 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, molecular weight distribution was 1.98, and the acid value of solid content conversion was 53 mgKOH / g.

Synthesis Example 13

333 g of propylene glycol monomethyl ether acetate was introduced into a 1000 ml flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and gas introduction tube. Thereafter, nitrogen gas was introduced into the flask using a gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas. Thereafter, the solution in the flask was heated to 100 ° C., and then dicyclopentanyl methacrylate [FA-513M; Hitachi Kasei Kogyo Co., Ltd.] 22.0 g (0.10 mol), benzyl methacrylate 70.5 g (0.40 mol), methacrylic acid 43.0 g (0.5 mol), azobisisobutyronitrile 3.6 g and propylene glycol monomethyl ether The mixture consisting of 164 g of acetate was added dropwise into the flask over 2 hours using a dropping funnel, and further stirring was continued at 100 ° C. for 5 hours after the completion of dropping.

After completion of the stirring, air was introduced into the flask using a gas introduction tube, and after the atmosphere in the flask became air, 35.5 g [0.25 mol of glycidyl methacrylate (mole fraction relative to methacrylic acid used in this reaction) 50 mol%)], 0.9 g of trisdimethylaminomethylphenol and 0.145 g of hydroquinone were charged into a flask, and the reaction was continued at 110 ° C for 6 hours to obtain a resin X2 solution having a solid content of 38.7% by mass. The weight average molecular weight of Resin # 2 was 9,800, and the acid value of solid content conversion was 82 mgKOH / g.

[Preparation of Colored Curable Resin Composition]

Example 1

Colorant (A): C.I. Pigment Green 7 (pigment) 48 copies,

22 parts of acrylic pigment dispersant,

Resin: 17 parts of Resin B1 (in terms of solid content), and

Solvent (E): 310 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 7.5 parts

6.0 parts of an acrylic pigment dispersant, and

Solvent (E): 44 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): 7.5 parts of compounds represented by Formula (1-14);

Resin (VIII): 10 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.4 parts;

Solvent (E): 13 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 490 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 2

Colorant (A): C.I. Pigment green 7 (pigment) 37 parts,

17 parts of an acrylic pigment dispersant,

Resin (13): 13 parts of Resin B1 (solid content conversion), and

Solvent (E): 240 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 13 copies,

10 parts of an acrylic pigment dispersant, and

Solvent (E): 77 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): 13 parts of compounds represented by Formula (16-6);

Resin (VIII): 14 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.4 parts;

Solvent (E): 18 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 510 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 3

Colorant (A): C.I. Pigment green 7 (pigment) 46 copies,

21 parts of an acrylic pigment dispersant,

Resin: 16 parts of Resin B1 (in terms of solid content), and

Solvent (E): 300 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 8.6 parts,

6.9 parts of an acrylic pigment dispersant, and

Solvent (E): 51 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): 8.6 parts of compounds represented by Formula (2-1);

Resin (VIII): 11 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.4 parts;

Solvent (E): 14 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 490 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 4

Colorant (A): C.I. Pigment green 7 (pigment) 40 copies,

18 parts acrylic pigment dispersant,

Resin: 14 parts of Resin B1 (in terms of solid content), and

Solvent (E): 260 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 12 copies,

9.2 parts of an acrylic pigment dispersant, and

Solvent (E): 68 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): 12 parts of compounds represented by Formula (3-1);

Resin (VIII): 13 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.4 parts;

Solvent (E): 17 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 500 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 5

Colorant (A): C.I. Pigment green 7 (pigment) 49 copies,

22 parts of acrylic pigment dispersant,

Resin (B): 17 parts of Resin B1 (in terms of solids), and

Solvent (E): 320 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 6.8 parts,

5.5 parts of an acrylic pigment dispersant, and

Solvent (E): 40 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): 6.8 parts of compound represented by formula (4-5);

Resin (VIII): 9.5 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 12 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 480 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 6

Colorant (A): C.I. Pigment green 36 (pigment) 58 parts,

26 parts of acrylic pigment dispersant,

Resin: 20 parts of Resin B1 (in terms of solid content), and

Solvent (E): 380 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 2.3 parts

1.8 parts of an acrylic pigment dispersant, and

Solvent (E): 13 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): 2.3 parts of compounds represented by Formula (1-14);

Resin (VIII): 6.1 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 7.9 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 450 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 7

Colorant (A): C.I. Pigment green 36 (pigment) 53 parts,

24 parts of acrylic pigment dispersant,

Resin (Ｂ): 19 parts of Resin B1 (in terms of solid content), and

Solvent (E): 350 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 4.8 parts,

3.8 parts of an acrylic pigment dispersant, and

Solvent (E): 28 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): 4.8 parts of compound represented by Formula (16-6);

Resin (VIII): 7.9 parts of Resin X1 (in terms of solid content);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 10 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 460 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 8

Colorant (A): C.I. Pigment green 36 (pigment) 58 parts,

26 parts of acrylic pigment dispersant,

Resin: 20 parts of Resin B1 (in terms of solid content), and

Solvent (E): 380 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 2.7 parts,

2.2 parts of an acrylic pigment dispersant, and

Solvent (E): 16 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): 2.7 parts of compound represented by formula (2-1);

Resin (VIII): 6.4 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 8.3 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 450 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 9

Colorant (A): C.I. Pigment green 36 (pigment) 55 parts,

25 parts of acrylic pigment dispersant,

Resin (Ｂ): 19 parts of Resin B1 (in terms of solid content), and

Solvent (E): 360 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 4.0 parts,

3.2 parts of an acrylic pigment dispersant, and

Solvent (E): 24 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): 4.0 parts of compounds represented by formula (3-1);

Resin (VIII): 7.4 parts of resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 10 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 460 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 10

Colorant (A): C.I. Pigment green 36 (pigment) 59 copies,

27 parts of an acrylic pigment dispersant,

Resin: 21 parts of Resin B1 (in terms of solid content), and

Solvent (E): 390 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 2.0 parts

1.6 parts of an acrylic pigment dispersant, and

Solvent (E): 12 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): 2.0 parts of compound represented by Formula (4-5);

Resin (VIII): 5.9 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 7.6 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 450 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 11

Colorant (A): C.I. 60 pieces of pigment green 58 (pigment),

27 parts of an acrylic pigment dispersant,

Resin: 21 parts of Resin B1 (in terms of solid content), and

Solvent (E): 390 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 1.4 parts

1.1 parts of an acrylic pigment dispersant, and

Solvent (E): Propylene glycol monomethyl ether acetate 8.1 parts

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

Colorant (A): 1.4 parts of compound represented by formula (1-14);

Resin (VIII): 5.4 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 26 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 7.0 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 440 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 12

Colorant (A): C.I. Pigment green 58 (pigment) 57 copies,

26 parts of acrylic pigment dispersant,

Resin: 20 parts of Resin B1 (in terms of solid content), and

Solvent (E): 370 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 2.9 parts

2.3 parts of an acrylic pigment dispersant, and

Solvent (E): 17 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): 2.9 parts of compound represented by formula (16-6);

Resin (VIII): 6.5 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 8.5 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 450 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 13

Colorant (A): C.I. 60 pieces of pigment green 58 (pigment),

27 parts of an acrylic pigment dispersant,

Resin: 21 parts of Resin B1 (in terms of solid content), and

Solvent (E): 390 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 1.6 parts

1.3 parts of an acrylic pigment dispersant, and

Solvent (E): Propylene glycol monomethyl ether acetate 9.6 parts

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

Coloring agent (A): 1.6 parts of compounds represented by Formula (2-1);

Resin (VIII): 5.6 parts of Resin X1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 7.3 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 440 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 14

Colorant (A): C.I. Pigment green 58 (pigment) 58

26 parts of acrylic pigment dispersant,

Resin: 20 parts of Resin B1 (in terms of solid content), and

Solvent (E): 380 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 2.4 parts

1.9 parts of an acrylic pigment dispersant, and

Solvent (E): 14 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): 2.4 parts of compounds represented by Formula (3-1);

Resin (VIII): 6.2 parts of Resin V1 (solid content conversion);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 27 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 8.0 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 450 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Example 15

Colorant (A): C.I. Pigment green 58 (pigment) 61 copies,

27 parts of an acrylic pigment dispersant,

Resin: 21 parts of Resin B1 (in terms of solid content), and

Solvent (E): 400 parts of propylene glycol monomethyl ether acetate

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

Colorant (A): C.I. Pigment Yellow 129 (pigment) 1.2 parts

0.96 parts of an acrylic pigment dispersant, and

Solvent (E): propylene glycol monomethyl ether acetate 7.0 parts

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

Coloring agent (A): 1.2 parts of compounds represented by Formula (4-5);

Resin (VIII): 5.3 parts of Resin X1 (in terms of solid content);

Polymerizable compound (C): dipentaerythritol hexaacrylate [KAYARAD® DPHA; Nihon Kayaku Co., Ltd.] 26 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine [Igurecure® OXE-01; Made by BASF Corporation; O-acyl oxime compound] 5.3 parts;

Solvent (E): 6.8 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 440 parts of N-methylpyrrolidone; And

Surface leveling agent (F): polyether modified silicone oil [Torre silicone SH8400; Torre Dow Corning Co., Ltd.] 0.50 part

Was mixed to obtain a colored curable resin composition.

Comparative Example 1

Colorant (A): C.I. Pigment green 58 (pigment) 66 parts,

30 parts of a pigment dispersant,

Resin (B): 23 parts of Resin B2 (in terms of solid content), and

Solvent (E): 429 parts of propylene glycol monomethyl ether acetate

Pigment dispersion liquid which was mixed and dispersed;

Coloring agent: 48 parts of the compound represented by formula (iii);

Resin (VIII): 32 parts of Resin X2 (solid content conversion);

Polymeric compound (C): 45 parts of dipentaerythritol hexaacrylate;

Polymerization initiator (D): 20 parts of Monocure® 369 (manufactured by BASF Corporation);

Polymerization initiator (D1): 7.0 parts of 4,4'-bis (diethylamino) benzophenone;

Surfactant: 0.91 parts of MegaPak® F475 (manufactured by DIC Corporation);

Solvent (E): 878 parts of propylene glycol monomethyl ether acetate; And

Solvent (E): 231 parts of propylene glycol monomethyl ether

Was mixed to obtain a colored curable resin composition.

[Production of colored pattern]

After apply | coating the said colored curable resin composition on the 2-inch square glass substrate (Eggle XG; Corning Corporation make) by the spin coat method, it prebaked at 100 degreeC for 3 minutes, and formed the coloring composition layer. After cooling, the space | interval of the board | substrate with which the coloring composition layer was formed, and the quartz glass photomask 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. After exposure, the coloring composition layer was immersed in an aqueous solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for 70 seconds, developed, washed with water, and then postbaked at 230 ° C for 20 minutes in an oven. ), A coloring pattern was obtained.

[Film thickness measurement]

About the obtained coloring pattern, film thickness measuring apparatus [DEKTAK3; The film thickness was measured using Japan Vacuum Technology Co., Ltd. product. The results are shown in Table 166.

[Color evaluation]

About the obtained coloring pattern, a colorimeter [OSP-SP-200; Spectrophotometry was measured using Olympus Co., Ltd., and the xy chromaticity coordinates (x, y) and tristimulus values [Y] in the XYZ colorimetric system of CIE were measured using the characteristic coefficient of the C light source. It was. The larger the value of Y, the higher the brightness. The results are shown in Table 166.

Example 16

Instead of the compound synthesize | combined by the synthesis example 1, except having used the compound synthesize | combined by the synthesis example 3, it carried out similarly to Example 1, and obtained the colored curable resin composition and the color filter.

Example 17

Instead of the compound synthesize | combined by the synthesis example 1, it carried out similarly to Example 1 except having used the compound synthesize | combined in the synthesis example 4, and obtained the colored curable resin composition and the color filter.

Example 18

Instead of the compound synthesize | combined by the synthesis example 1, except having used the compound synthesize | combined in the synthesis example 5, it carried out similarly to Example 1, and obtained the colored curable resin composition and the color filter.

Example 19

A colored curable resin composition and a color filter were obtained in the same manner as in Example 5 except that the compound synthesized in Synthesis Example 9 was used instead of the compound synthesized in Synthesis Example 8.

Example 20

Instead of the compound synthesize | combined by the synthesis example 8, it carried out similarly to Example 5 except having used the compound synthesize | combined in the synthesis example 10, and the colored curable resin composition and the color filter were obtained.

Example 21

A colored curable resin composition and a color filter were obtained in the same manner as in Example 5 except that the compound synthesized in Synthesis Example 11 was used instead of the compound synthesized in Synthesis Example 8.

Example 22

Instead of the compound synthesize | combined by the synthesis example 1, it carried out similarly to Example 6 except having used the compound synthesize | combined by the synthesis example 3, and obtained the colored curable resin composition and the color filter.

Example 23

Instead of the compound synthesize | combined by the synthesis example 1, except having used the compound synthesize | combined by the synthesis example 4, it carried out similarly to Example 6, and obtained the colored curable resin composition and the color filter.

Example 24

Instead of the compound synthesize | combined by the synthesis example 1, it carried out similarly to Example 6 except having used the compound synthesize | combined in the synthesis example 5, and the colored curable resin composition and the color filter were obtained.

Example 25

A colored curable resin composition and a color filter were obtained in the same manner as in Example 10 except that the compound synthesized in Synthesis Example 9 was used instead of the compound synthesized in Synthesis Example 8.

Example 26

Instead of the compound synthesize | combined by the synthesis example 8, it carried out similarly to Example 10 except having used the compound synthesize | combined in the synthesis example 10, and the colored curable resin composition and the color filter were obtained.

Example 27

Instead of the compound synthesize | combined by the synthesis example 8, it carried out similarly to Example 10 except having used the compound synthesize | combined in the synthesis example 11, and the colored curable resin composition and the color filter were obtained.

Example 28

Instead of the compound synthesize | combined by the synthesis example 1, it carried out similarly to Example 11 except having used the compound synthesize | combined by the synthesis example 3, and the colored curable resin composition and the color filter were obtained.

Example 29

A colored curable resin composition and a color filter were obtained in the same manner as in Example 11 except that the compound synthesized in Synthesis Example 4 was used instead of the compound synthesized in Synthesis Example 1.

Example 30

A colored curable resin composition and a color filter were obtained in the same manner as in Example 11 except that the compound synthesized in Synthesis Example 5 was used instead of the compound synthesized in Synthesis Example 1.

Example 31

A colored curable resin composition and a color filter were obtained in the same manner as in Example 15 except that the compound synthesized in Synthesis Example 9 was used instead of the compound synthesized in Synthesis Example 8.

Example 32

Instead of the compound synthesize | combined by the synthesis example 8, it carried out similarly to Example 15 except having used the compound synthesize | combined in the synthesis example 10, and the colored curable resin composition and the color filter were obtained.

Example 33

Instead of the compound synthesize | combined by the synthesis example 8, it carried out similarly to Example 15 except having used the compound synthesize | combined in the synthesis example 11, and the colored curable resin composition and the color filter were obtained.

ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the colored curable resin composition which can manufacture a high brightness color filter, The high brightness color filter manufactured from the said colored curable resin composition is a liquid crystal display device, an organic electroluminescent apparatus, an electronic paper, etc. It can be used suitably for a display device or a solid-state image sensor.

Claims (29)

A colorant comprising a compound having a coumarin skeleton and a CI pigment yellow 129, a resin, a polymerizable compound and a polymerization initiator,
The colored curable resin composition which is a compound represented by Formula (1), Formula (1 '), Formula (2), Formula (3), Formula (4), or Formula (5).
Compound represented by formula (1):

[Formula (1),
L represents a divalent hydrocarbon group having 1 to 20 carbon atoms. The methylene group constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁰ )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the divalent hydrocarbon group is a cyano group, a nitro group, or a carbon group. It may be substituted by the baroyl group, sulfamoyl group, sulfo group, carboxy group, hydroxy group, chlorine atom, bromine atom, imidazol-1-yl group or amino group.
X represents an oxygen atom, a sulfur atom or -N (R ¹⁰ )-.
AA represents a C6-C20 aromatic group. The hydrogen atom contained in the aromatic group may be a halogen atom, cyano group, nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, hydroxy group, imidazol-1-yl group, amino group or monovalent monovalent having 1 to 20 carbon atoms. The hydrocarbon group may be substituted. The methylene group which comprises the said monovalent hydrocarbon group may be substituted by the oxygen atom, the sulfur atom, -N (R <^10> )-, sulfonyl group, or carbonyl group, and the hydrogen atom contained in the said monovalent hydrocarbon group is a halogen atom, a cyano group, The nitro group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, hydroxy group, imidazol-1-yl group or amino group may be substituted.
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 combine to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom. The methylene group which comprises the said monovalent hydrocarbon group may be substituted by the oxygen atom, the sulfur atom, -N (R <^10> )-, sulfonyl group, or carbonyl group, and the hydrogen atom contained in the said monovalent hydrocarbon group is a halogen atom, a cyano group, and a nitro. The group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, hydroxy group, imidazol-1-yl group or amino group may be substituted.
R ⁵ to R ⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxyl group, a hydroxyl group, an amino group or a monovalent hydrocarbon group having 1 to 20 carbon atoms. Or R ⁵ and R ⁶ combine to form a ring with adjacent carbon atoms, or R ⁷ and R ⁸ combine to form a ring with adjacent carbon atoms. The methylene group which comprises the said monovalent hydrocarbon group may be substituted by the oxygen atom, the sulfur atom, -N (R <^10> )-, sulfonyl group, or carbonyl group, and the hydrogen atom contained in the said monovalent hydrocarbon group is a halogen atom, a cyano group, and a nitro. The group, carbamoyl group, sulfamoyl group, sulfo group, carboxyl group, hydroxy group, imidazol-1-yl group or amino group may be substituted.
R ¹⁰ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ¹⁰ are present, they are the same as or different from each other]
Compound represented by formula (1 '):

[In formula (1 '), R <^1> -R <^9> , X and L have the same meaning as the above, respectively.]
Compound represented by formula (2):

In the formula (2), Q ¹ and Q ² each independently represents a hydrogen atom or -CO ₂ M, Q ¹ and Q ² represents any one of the -CO ₂ M.
R ¹¹ to R ¹⁴ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, or R ¹¹ and R ¹³ combine to form a ring together with a carbon atom on an adjacent benzene ring and an adjacent nitrogen atom; Or R ¹² and R ¹⁴ combine to form a ring with carbon atoms and adjacent nitrogen atoms on adjacent benzene rings. The methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ¹⁵ )-, 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 ¹⁵ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^{15 's} are present, they are the same as or different from each other.
M represents a hydrogen atom or an alkali metal atom]
Compound represented by Formula (3):

[Equation (3),
L 'represents a C1-C20 bivalent hydrocarbon group. The methylene group constituting the divalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ²⁵ )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the divalent 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. However, at least one of the hydrogen atoms contained in the divalent hydrocarbon group is substituted with a fluorine atom.
X 'represents a Group 16 atom, -N (R ²⁵ )-or -C (R ²⁵ ) (R ²⁶ )-in the periodic table.
R ¹⁶ to R ²⁴ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M ', -CO ₂ M', a hydroxyl group, an amino group or C1-C1 20 monovalent hydrocarbon groups, R ¹⁶ and R ¹⁸ combine to form a ring with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring, or R ¹⁷ and R ¹⁹ combine to form an adjacent benzene ring Together with the carbon atoms and the adjacent nitrogen atoms form a ring. The methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ²⁷ )-, 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 ²⁵ and R ²⁶ each independently represent a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ²⁷ )-, 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 ²⁷ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^{27 's} are present, they are the same as or different from each other.
M 'represents a hydrogen atom or an alkali metal atom]
Compound represented by formula (4):

Compound represented by formula (5):

[Formula (4) and Formula (5),
X '' represents a Group 16 atom, -N (R ³⁴ )-or -C (R ³⁴ ) (R ³⁵ )-in the periodic table.
R ²⁸ to R ⁴¹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO ₃ M '', -CO ₂ M '', a hydroxyl group, an amino group, or a carbon number Or represents 1 to 20 monovalent hydrocarbon groups, or R ²⁸ and R ³⁰ combine to form a ring with a carbon atom and an adjacent nitrogen atom on an adjacent benzene ring, or R ²⁹ and R ³¹ combine to form an adjacent benzene Together with the carbon atoms on the ring and the adjacent nitrogen atoms, they form a ring. The methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, -N (R ⁴² )-, 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 '', hydroxy group, imidazol-1-yl group or amino group may be substituted. Provided that at least one of R ³⁶ to R ⁴¹ is -SO ₃ M ''.
R ⁴² represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms. When a plurality of R ^{42 '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,
Colored curable resin composition in which the said coloring agent contains a pigment further. The method of claim 2,
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 2,
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 2,
Colored curable resin composition whose said pigment is a green pigment. The method of claim 2,
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 2,
Colored curable resin composition whose said pigment is CI pigment green 7. The method according to any one of claims 1 to 7,
Colored curable resin composition whose said X is an oxygen atom or a sulfur atom. The method according to any one of claims 1 to 7,
Colored curable resin composition whose said X is an oxygen atom. The method according to any one of claims 1 to 7,
Colored curable resin composition whose said L is a methylene group or sulfonyl group which may have a substituent. The method according to any one of claims 1 to 7,
Colored curable resin composition whose said L is a dimethyl methylene group or a sulfonyl group. The method according to any one of claims 1 to 7,
Colored curable resin composition whose said R <^5> -R <^9> is all a hydrogen atom. The method according to any one of claims 1 to 7,
The colored curable resin composition wherein X 'is an oxygen atom, a sulfur atom, -N (R ²⁵ )-or -C (R ²⁵ ) (R ²⁶ )-. The method according to any one of claims 1 to 7,
Wherein X 'is an oxygen atom, a sulfur atom or -N (R ²⁵⁾ - the colored curable resin composition. The method according to any one of claims 1 to 7,
Colored curable resin composition whose said X 'is an oxygen atom or a sulfur atom. The method according to any one of claims 1 to 7,
Colored curable resin composition whose said X 'is an oxygen atom. The method according to any one of claims 1 to 7,
Colored curable resin composition whose said L 'is bis (trifluoromethyl) methylene group. The method according to any one of claims 1 to 7,
The colored curable resin composition wherein all of R ¹⁸ to R ²⁴ are hydrogen atoms. The method according to any one of claims 1 to 7,
The colored curable resin composition wherein X '' is an oxygen atom, a sulfur atom, -N (R ³⁴ )-or -C (R ³⁴ ) (R ³⁵ )-. The method according to any one of claims 1 to 7,
The colored curable resin composition wherein X '' is an oxygen atom. The method according to any one of claims 1 to 7,
The colored curable resin composition wherein R ⁴⁰ is -SO ₃ M ''. The method according to any one of claims 1 to 7,
Colored curable resin composition whose content of the compound represented by either of said Formula (1)-Formula (5) is 1 mass% or more and 65 mass% or less with respect to the total amount of dye and a pigment. The color filter formed using the colored curable resin composition of any one of Claims 1-7. A liquid crystal display device comprising the color filter of claim 23. delete delete delete delete delete