CN112533999A

CN112533999A - Coloring composition

Info

Publication number: CN112533999A
Application number: CN201980051973.9A
Authority: CN
Inventors: 真锅仁美; 滨木裕史; 栂井学
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2018-08-08
Filing date: 2019-07-31
Publication date: 2021-03-19
Anticipated expiration: 2039-07-31
Also published as: TW202012393A; JP2020026521A; KR20210042849A; CN112533999B; JP7333221B2; WO2020031799A1; TWI804665B

Abstract

The invention provides a coloring composition capable of forming a color filter with excellent light resistance. The present invention provides a coloring composition comprising a compound represented by formula (I) and a compound represented by formula (II). [ formula (I) and formula (II) wherein A¹And A²Independent earth surfaceA heterocyclic group which may have a substituent is shown. D¹And D²Independently of one another, an optionally substituted aromatic hydrocarbon radical having at least 1-CO₂M。R^a1And R^d1Independently represent a C1-40 hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom, and-CH contained in the hydrocarbon group₂And the heterocyclic group contains-CH which does not form a ring₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰－。R^a2～R^a7And R^d2～R^d7Independently represent a C1-40 hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitro group or a-CO₂M or-S (O)₂OM-CH contained in the hydrocarbon group₂And the heterocyclic group contains-CH which does not form a ring₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰－。R^a2And R^a3、R^a3And R^a4、R^a4And R^a5、R^d2And R^d3、R^d3And R^d4And R^d4And R^d5May form a ring which may have a substituent containing-CH which does not constitute a ring, together with the carbon atom to which each is bonded₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰-. M represents a hydrogen atom or an alkali metal atom. R²⁰Represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent. In the presence of a plurality of R²⁰And M, they may be the same or different. The wavy line means a line containing E-mer, Z-mer or a mixture thereof.]

Description

Coloring composition

Technical Field

The present invention relates to a coloring composition comprising an isoindoline compound.

Background

The colored curable resin composition is used for producing color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays. Such a colored curable resin composition contains a colorant for obtaining a desired color tone or the like, and an isoindoline compound is known as a colorant (patent document 1).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2017-137490

Disclosure of Invention

The invention provides a coloring composition capable of forming a color filter with excellent light resistance.

The gist of the present invention is as follows.

[1] A coloring composition comprising a compound represented by formula (I) and a compound represented by formula (II).

[ formula (I) and formula (II),

A¹and A²Independently of each other, represents a heterocyclic group which may have a substituent.

D¹And D²Independently of one another, an optionally substituted aromatic hydrocarbon radical having at least 1-CO₂M。

R^a1And R^d1Independently represent a C1-40 hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom, and-CH contained in the hydrocarbon group₂And the heterocyclic group contains-CH which does not form a ring₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰-。

R^a2～R^a7And R^d2～R^d7Independently of each other, may have a substituentA hydrocarbon group having 1 to 40 carbon atoms, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitro group or a-CO₂M or-S (O)₂OM-CH contained in the hydrocarbon group₂And the heterocyclic group contains-CH which does not form a ring₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰-。

R^a2And R^a3、R^a3And R^a4、R^a4And R^a5、R^d2And R^d3、R^d3And R^d4And R^d4And R^d5May form a ring which may have a substituent containing-CH which does not constitute a ring, together with the carbon atom to which each is bonded₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰-。

M represents a hydrogen atom or an alkali metal atom.

R²⁰Represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

In the presence of a plurality of R²⁰And M, they may be the same or different.

The wavy line represents a line containing E-body, Z-body or a mixture thereof ]

[2]According to [1]The coloring composition, wherein A¹And A²Independently of each other, a condensed heterocyclic group which may have a substituent.

[3]According to [1]Or [ 2]]The coloring composition, wherein R^a1And R^d1Is a hydrogen atom, R^a6～R^a7And R^d6～R^d7Is cyano or nitro.

[4]According to [1]～[3]The coloring composition as described in any one of, wherein A¹And A²Same as R^a6And R^a7Are the same group.

[5]According to [1]～[4]The coloring composition according to any one of the above, wherein D¹And D²Same as R^d6And R^d7Are the same group.

[6] The coloring composition according to any one of [1] to [5], wherein the mass ratio of the compound represented by the formula (I) to the compound represented by the formula (II) is 1 to 1000.

[7] The coloring composition according to any one of [1] to [6], further comprising a resin (B).

[8] A colored curable resin composition comprising the colored composition according to any one of [1] to [7], a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

[9] A color filter comprising the colored curable resin composition according to [8 ].

[10] A display device comprising the color filter of [9 ].

According to the coloring composition of the invention, a color filter with excellent light resistance can be formed.

Detailed Description

< coloring composition >

The coloring composition of the present invention contains a compound represented by formula (I) (hereinafter, also referred to as compound (I)) and a compound represented by formula (II) (hereinafter, also referred to as compound (II)). The compound (I) and the compound (II) can be used as the colorant (A). The coloring composition of the present invention may contain 1 or 2 or more of the above-mentioned compound (I) and the above-mentioned compound (II), respectively.

The coloring composition of the present invention preferably further contains a resin (hereinafter, also referred to as resin (B)).

The colored curable resin composition of the present invention comprises the colored composition of the present invention, a polymerizable compound (hereinafter, also referred to as polymerizable compound (C)), a polymerization initiator (hereinafter, also referred to as polymerization initiator (D)), and a solvent (hereinafter, also referred to as solvent (E)).

The colored curable resin composition of the present invention may further contain a polymerization initiation aid (hereinafter, also referred to as a polymerization initiation aid (D1)).

The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, also referred to as leveling agent (F)) and an antioxidant.

In the present specification, the compounds exemplified as the respective components may be used alone or in combination of a plurality of them unless otherwise specified.

< colorant (A) >

The colorant (A) comprises a compound (I) and a compound (II). The above-mentioned compound (I) and the above-mentioned compound (II) also include tautomers thereof and salts thereof.

[ formula (I) and formula (II),

R^a1And R^d1Independently represent a C1-40 hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom, and-CH contained in the hydrocarbon group₂And the heterocyclic group contains-CH which does not form a ring₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰-. However, by substitution of-CH₂-to form-CO₂H and-S (O)₂OH。

R^a2～R^a7And R^d2～R^d7Independently represent a C1-40 hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitro group or a-CO₂M or-S (O)₂OM-CH contained in the hydrocarbon group₂And the heterocyclic group contains-CH which does not form a ring₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰-. However, not only by substitution of-CH₂-to form-CO₂H and-S (O)₂OH。

R^a2And R^a3、R^a3And R^a4、R^a4And R^a5、R^d2And R^d3、R^d3And R^d4And R^d4And R^d5May form a ring which may have a substituent containing-CH which does not constitute a ring, together with the carbon atom to which each is bonded₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰-. However, by substitution of-CH₂-to form-CO₂H and-S (O)₂OH。

M represents a hydrogen atom or an alkali metal atom.

R^a1～R^a7、R^d1～R^d7And R²⁰The hydrocarbon group having 1 to 40 carbon atoms represents an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated, or may be chain or cyclic (alicyclic).

As R^a1～R^a7、R^d1～R^d7And R²⁰Examples of the saturated or unsaturated chain hydrocarbon group include straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, heptadecyl, octadecyl, and eicosyl; branched alkyl groups such as isopropyl, (2-methyl) propyl, isobutyl, sec-butyl, tert-butyl, (2-ethyl) butyl, isopentyl, neopentyl, tert-pentyl, (1-methyl) pentyl, (2-methyl) pentyl, (1-ethyl) pentyl, (3-ethyl) pentyl, isohexyl, (5-methyl) hexyl, (2-ethyl) hexyl and (3-ethyl) heptyl; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, (1-methyl) vinyl, 2-butenyl, 3-butenyl, 1, 3-butadienyl, (1- (2-propenyl)) vinyl, (1, 2-dimethyl) propenyl, and 2-pentenyl.

R^a1～R^a7、R^d1～R^d7And R²⁰The saturated or unsaturated chain hydrocarbon group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, still more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, yet still more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

As R^a1～R^a7、R^d1～R^d7And R²⁰Examples of the saturated or unsaturated alicyclic hydrocarbon group include cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1, 2-dimethylcyclohexyl, 1, 3-dimethylcyclohexyl, 1, 4-dimethylcyclohexyl, 2, 3-dimethylcyclohexyl, 2, 4-dimethylcyclohexyl, 2, 5-dimethylcyclohexyl, 2, 6-dimethylcyclohexyl, 3, 4-dimethylcyclohexyl, 3, 5-dimethylcyclohexyl, 2-dimethylcyclohexyl, 3-dimethylcyclohexyl, 4-dimethylcyclohexyl, cyclooctyl, 2, 4, 6-trimethylcyclohexyl, and, Cycloalkyl groups such as 2, 2, 6, 6-tetramethylcyclohexyl, 3, 5, 5-tetramethylcyclohexyl, 4-pentylcyclohexyl, 4-octylcyclohexyl and 4-cyclohexylcyclohexyl; cycloalkenyl groups such as cyclohexenyl (e.g., cyclohex-2-ene, cyclohex-3-ene), cycloheptene, cyclooctene, and the like; norbornyl, adamantyl, bicyclo [2.2.2]Polycyclic alicyclic hydrocarbon groups such as octane.

R^a1～R^a7、R^d1～R^d7And R²⁰The alicyclic hydrocarbon group has preferably 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, still more preferably 4 to 20 carbon atoms, yet more preferably 4 to 15 carbon atoms, yet more preferably 5 to 15 carbon atoms, and particularly preferably 5 to 10 carbon atoms.

R^a1～R^a7、R^d1～R^d7And R²⁰The saturated or unsaturated hydrocarbon group may be a group obtained by combining the above-mentioned chain hydrocarbon group and alicyclic hydrocarbon group, and examples thereof include an alkyl group having 1 or more alicyclic hydrocarbon groups bonded thereto, such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group. The carbon number is preferably 4 to 30, more preferably 4 to E20, and more preferably 4 to 15.

As R^a1～R^a7、R^d1～R^d7And R²⁰The aromatic hydrocarbon group represented herein represents a group having a direct bonding site on the aromatic hydrocarbon ring, and examples thereof include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2, 3-dimethylphenyl group, a 2, 4-dimethylphenyl group, a 2, 5-dimethylphenyl group, a 2, 6-dimethylphenyl group, a 3, 4-dimethylphenyl group, a 3, 5-dimethylphenyl group, an o-isopropylphenyl group, a m-isopropylphenyl group, a p-isopropylphenyl group, an o-tert-butylphenyl group, a m-tert-butylphenyl group, a p-tert-butylphenyl group, a mesityl group, a 2, 6-bis (2-propyl) phenyl group, a 2, 4, 6-trimethylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 5, 6, 7, 8-tetrahydro-1-naphthyl group, a 5, 6, 7, 8, Fluorenyl, phenanthryl, and anthracyl, and the like. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 15.

R^a1～R^a7、R^d1～R^d7And R²⁰The aromatic hydrocarbon group represented may be a group obtained by combining at least one of the above-mentioned chain hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon group with the above-mentioned aromatic hydrocarbon group, and may include an aralkyl group such as a benzyl group, 2-methylbenzyl group, 3-methylbenzyl group, 4-methylbenzyl group, 3, 4-methylbenzyl group, phenylethyl group, phenylpropyl group and 1-methyl-1-phenylethyl group; an arylalkenyl group such as a phenylvinyl (phenylvinyl); arylalkynyl groups such as phenylethynyl; a phenyl group in which 1 or more phenyl groups such as a biphenyl group and a terphenyl group are bonded; the number of carbon atoms of the cyclohexylmethylphenyl group, benzylphenyl group, and (dimethyl (phenyl) methyl) phenyl group is preferably 7 to 30, more preferably 7 to 20, and still more preferably 7 to 15.

R^a1～R^a7、R^d1～R^d7And R²⁰The hydrocarbyl group represented may have a substituent having a valence of 1 or a substituent having a valence of 2.

As the substituent having a valence of 1, there may be mentioned

-CO₂M；

-S(O)₂OM；

Alkylsulfanyl groups having 1 to 10 carbon atoms such as methylsulfanyl, ethylsulfanyl, propylsulfanyl and butylsulfanyl;

halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom;

a nitro group;

a cyano group;

a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, in which all hydrogen atoms are substituted with fluorine atoms, such as a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, perfluorocyclohexyl group, perfluorophenyl group, etc.;

*-CO-SH；

*-CO-S-CH₃、*-CO-S-CH₂CH₃、*-CO-S-CH₂-CH₂-CH₃、*-CO-S-CH₂-CH₂-CH₂-CH₃a carbonyl group bonded to a sulfur atom bonded to an alkyl group having 1 to 10 carbon atoms;

*-CO-S-C₆H₅a carbonyl group bonded to a sulfur atom bonded to an aryl group having 6 to 20 carbon atoms;

*-OP(O)(OR³⁰)₂；

*-Si(R³⁰)(R³¹)(R³²) And the like. In the above, denotes a bonding site.

In the above formula, M represents the same meaning as above, R³⁰、R³¹And R³²Independently represent a C1-35 hydrocarbon group which may have a substituent or a heterocyclic group which may have a substituent, the-CH contained in the hydrocarbon group₂And the heterocyclic group contains-CH which does not form a ring₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰-. However, by substitution of-CH₂-to form-CO₂H and-S (O)₂OH。R²⁰The same meanings as described above are indicated. R³⁰、R³¹And R³²Specific examples and preferred ranges of (1) are not exclusive of those having 36 or more carbon atoms, andR^a1the same is true.

Examples of the substituent having a valence of 2 include thiocarbonyl, imino substituted with an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), imino substituted with an aryl group having 6 to 20 carbon atoms, and the like. As the alkyl-substituted imino group, CH may be mentioned₃-N＝、CH₃-CH₂-N＝、CH₃-(CH₂)₂-N＝、CH₃-(CH₂)₃-N ═ and the like. As the aryl-substituted imino group, there may be mentioned C₆H₅-N ═ and the like.

As R^a1～R^a7、R^d1～R^d7And R²⁰The substituents of the hydrocarbon group represented by (a) and (b) are, independently of each other, preferably a halogen atom; a nitro group; a cyano group; all hydrogen atoms are substituted by C1-20 alkyl of fluorine atoms; thiocarbonyl, and the like. In addition, R^a1～R^a7、R^d1～R^d7And R²⁰The substituent of the hydrocarbon group represented by (a) is more preferably a fluorine atom, a chlorine atom, a bromine atom; a nitro group; a cyano group; all hydrogen atoms are substituted by C1-10 alkyl of fluorine atoms; thiocarbonyl, etc., more preferably a fluorine atom; a hydrocarbon group having 1 to 5 carbon atoms wherein all hydrogen atoms are substituted with fluorine atoms.

The compounds (I) and (II) may have a general formula represented by R^a1～R^a7、R^d1～R^d7-CH contained in the hydrocarbon group represented by₂-substitution by-O-, -CO-, -S (O)₂-or-NR²⁰A group formed (hereinafter, sometimes referred to as "group (Z1)"). However, by substitution of-CH₂-to form-CO₂H and-S (O)₂OH。

As the group (Z1), there may be mentioned

An oxy group (alkoxy group and aryloxy group) to which a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms is bonded, such as a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, (2-ethyl) hexyloxy group, (2-trifluoromethyl) hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, phenoxy group, m-tolyloxy group, and 3, 4-xylyloxy group;

an ethylene oxide group;

a formyl group;

alkanoyl groups having 2 to 22 carbon atoms, preferably 2 to 12 carbon atoms, such as acetyl, propionyl, butyryl, tert-butyryl, pentanoyl, hexanoyl, (2-ethyl) hexanoyl, heptanoyl, octanoyl, nonanoyl and benzoyl;

an oxycarbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms is bonded, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, a (2-ethyl) hexyloxycarbonyl group, a heptyloxycarbonyl group, an octyloxycarbonyl group, a nonyloxycarbonyl group, a phenoxycarbonyl group, or an o-tolyloxycarbonyl group;

an amino group;

n-methylamino, N-dimethylamino, N-ethylamino, N-diethylamino, N-propylamino, N-dipropylamino, N-isopropylamino, N-diisopropylamino, N-butylamino, N-dibutylamino, N-isobutylamino, N-diisobutylamino, N-sec-butylamino, N-di-sec-butylamino, N-tert-butylamino, N-di-tert-butylamino, N-pentylamino, N-dipentylamino, N- (1-ethylpropyl) amino, N-di (1-ethylpropyl) amino, N-hexylamino, N-dihexylamino, N- (2-ethyl) hexylamino, N-diethylamino, N-propylamino, N-dipropylamino, N-isopropylamino, N-di-sec-butylamino, N-, Amino groups having a hydrocarbon group of 1 to 2 carbon atoms, preferably 1 to 20 carbon atoms, such as an N, N-di (2-ethyl) hexylamino group, an N-heptylamino group, an N, N-diheptylamino group, an N-octylamino group, an N, N-dioctylamino group, an N-nonylamino group, an N, N-dinonylamino group, an N-phenylamino group, an N, N-diphenylamino group, an N, N-ethylmethylamino group, an N, N-propylmethylamino group, an N, N-isopropylmethylamino group, an N, N-butylmethylamino group, an N, N-tert-butylmethylamino group, and an N, N-phenylmethylamino group;

a sulfamoyl group;

n-methylsulfamoyl, N-dimethylsulfamoyl, N-ethylsulfamoyl, N-diethylsulfamoyl, N-propylsulfamoyl, N-dipropylsulfamoyl, N-isopropylsulfamoyl, N-diisopropylsulfamoyl, N-butylsulfamoyl, N-dibutylsulfamoyl, N-isobutylsulfamoyl, N-diisobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-di-tert-butylsulfamoyl, N-pentylsulfamoyl, N-dipentylsulfamoyl, N- (1-ethylpropyl) sulfamoyl, N-di (1-ethylpropyl) sulfamoyl, N-diethylsulfamoyl, N-di (1-ethylpropyl) sulfamoyl, N-diethylsulfamoyl, N-butylsulfamoyl, N-di, N-hexylsulfamoyl, N-dihexylsulfamoyl, N- (2-ethyl) hexylsulfamoyl, N-di (2-ethyl) hexylsulfamoyl, N-heptylsulfamoyl, N-diheptylsulfamoyl, N-octylsulfamoyl, N-dioctylsulfamoyl, N-octylmethylsulfamoyl, N-nonylsulfamoyl, N-dinonylsulfamoyl, N-phenylsulfamoyl, N-diphenylsulfamoyl, N-ethylmethylsulfamoyl, N-propylmethylsulfamoyl, N-isopropylmethylsulfamoyl, N-butylmethylsulfamoyl, N-tert-butylmethylsulfamoyl and N, sulfamoyl groups having 1 or 2 hydrocarbon groups of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as N-phenylmethylsulfamoyl groups;

n-formylamino;

n-alkanoylamino group having 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms, such as N-acetylamino group, N-propionylamino group, N-butyrylamino group, N-2, 2-dimethylpropionylamino group, N-valerylamino group, N-hexanoylamino group, N- (2-ethyl) hexanoylamino group, N-heptanoylamino group, N-octanoylamino group, N-nonanoylamino group, N-decanoylamino group, N-undecanoylamino group, N-dodecanoylamino group, N-heneicosanoylamino group, or N-benzoylamino group;

a hydroxyl group;

alkanoyloxy groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as formyloxy, acetyloxy, propionyloxy, butyryloxy, 2-dimethylpropionyloxy, valeryloxy, hexanoyloxy, (2-ethyl) hexanoyloxy, heptanoyloxy, octanoyloxy, nonanoyloxy and benzoyloxy;

a C1-20, preferably C1-10 hydrocarbyl-substituted sulfonyl group such as a methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, (2-ethyl) hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, phenylsulfonyl group, or p-tolylsulfonyl group;

a carbamoyl group;

n-methylcarbamoyl, N-dimethylcarbamoyl, N-ethylcarbamoyl, N-diethylcarbamoyl, N-propylcarbamoyl, N-dipropylcarbamoyl, N-isopropylcarbamoyl, N-diisopropylcarbamoyl, N-butylcarbamoyl, N-dibutylcarbamoyl, N-isobutylcarbamoyl, N-diisobutylcarbamoyl, N-sec-butylcarbamoyl, N-di-sec-butylcarbamoyl, N-tert-butylcarbamoyl, N-di-tert-butylcarbamoyl, N-pentylcarbamoyl, N-dipentylcarbamoyl, N- (1-ethylpropyl) carbamoyl, N-ethylcarbamoyl, N-diethylcarbamoyl, N-isopropylcarbamoyl, N-diisopropylcarbamoyl, N-isopropylcarbamoyl, N, N, N-di (1-ethylpropyl) carbamoyl, N-hexylcarbamoyl, N-dihexylcarbamoyl, N- (2-ethyl) hexylcarbamoyl, N-di (2-ethyl) hexylcarbamoyl, N-heptylcarbamoyl, N-diheptylcarbamoyl, N-octylcarbamoyl, N-dioctylcarbamoyl, N-nonylcarbamoyl, N-dinonylcarbamoyl, N-phenylcarbamoyl, N-diphenylcarbamoyl, N-ethylmethylcarbamoyl, N-propylmethylcarbamoyl, N-isopropylmethylcarbamoyl, N-butylmethylcarbamoyl, N-ethylmethylcarbamoyl, N-ethylhexylcarbamoyl, N-diheptylcarbamoyl, N-octylcarbamoyl, N-dioctylcarbamoyl, N-nonylcarbamoyl, N-dino, Carbamoyl groups having 1 or 2 hydrocarbon groups of 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as N, N-t-butylmethylcarbamoyl group and N, N-phenylmethylcarbamoyl group;

*-COCOR²⁰；

*-OCON(R²⁰)₂；

*-N(R²⁰)COOR²⁰and the like. In the above, denotes a bonding site.

In the above formula, R²⁰They may be the same or different and have the same meaning as described above.

R^a1～R^a7、R^d1～R^d7、R²⁰、A¹And A²The heterocyclic group represented may be monocyclic or polycyclic. Examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom and the like.

R^a1～R^a7、R^d1～R^d7、R²⁰、A¹And A²The heterocyclic group represented by (A) preferably has 2 to 30 carbon atoms, more preferably 3 to 22 carbon atoms, still more preferably 3 to 20 carbon atoms, yet more preferably 3 to 18 carbon atoms, yet more preferably 3 to 15 carbon atoms, and particularly preferably 3 to 14 carbon atoms.

Examples of the heterocyclic group containing only a nitrogen atom as a hetero atom include monocyclic saturated heterocyclic groups such as aziridine, azetidine, pyrrolidine, piperidine, and piperazine; 5-membered ring unsaturated heterocyclic groups such as pyrrole, 2, 5-dimethylpyrrole and other pyrroles, 2-methylpyrazole, 3-methylpyrazole and other pyrazoles, imidazole, 1, 2, 3-triazole, 1, 2, 4-triazole and the like; a 6-membered ring-series unsaturated heterocyclic group such as a pyrimidine such as pyridine, pyridazine, pyrimidine and 6-methylpyrimidine, pyrazine, 1, 2, 4-triazine and 1, 3, 5-triazine; a fused bicyclic heterocyclic group such as quinoxaline (e.g., indazole, indoline, isoindoline, indole, indolizine, benzimidazole, quinoline, isoquinoline, 5, 6, 7, 8-tetrahydro (3-methyl) quinoxaline or 3-methylquinoxaline, quinazoline, cinnoline, phthalazine, naphthyridine, purine, pteridine, benzopyrazole or phenylpiperidine; fused tricyclic heterocyclic groups such as carbazole, acridine, and phenazine; heterocyclic groups represented by the following formulae, and the like. In the following formulae, a represents a bonding site.

Examples of the heterocyclic group containing only an oxygen atom as a hetero atom include oxetane, tetrahydrofuran, tetrahydropyran, and 1, 3-bis

Alkane, 1, 4-di

Monocyclic saturated heterocyclic groups such as alkane and 1-cyclopentyldioxolane; 1, 4-dioxaspiro [4.5 ]]Decane, 1, 4-dioxaspiro [4.5 ]]A bicyclic saturated heterocyclic group such as nonane; lactone-based heterocyclic groups such as α -caprolactone, β -propiolactone, γ -butyrolactone and δ -valerolactone; 5-membered unsaturated heterocyclic groups such as furan, 2, 3-dimethylfuran, 2, 5-dimethylhydrofuran and the like; 6-membered ring unsaturated heterocyclic groups such as 3, 4-dihydro-2H-pyran and 3, 6-dihydro-2H-pyran; benzopyran and benzodiazepine such as benzofuran, isobenzofuran, and 4-methylbenzopyran

Fused bicyclic heterocyclic groups such as oxazole, chroman and isochroman; and fused tricyclic heterocyclic groups such as xanthene and dibenzofuran.

Examples of the heterocyclic group containing only a sulfur atom as a hetero atom include a 5-membered saturated heterocyclic group such as dithiane; 6-membered saturated heterocyclic groups such as thiane, 1, 3-dithiane, and 2-methyl-1, 3-dithiane; thiophenes such as thiophene, 3-methylthiophene, 2-carboxythiophene, thiophene 1-oxide and thiophene 1, 1-dioxide, and 5-membered ring-based unsaturated heterocyclic groups such as 4H-thiopyran; fused bicyclic heterocyclic groups such as benzothiophene, benzothiophene oxide, benzothiophene tetrahydropyran, and benzothiophene dioxide; fused tricyclic heterocyclic groups such as thianthrene and dibenzothiophene.

Examples of the heterocyclic group containing a nitrogen atom and an oxygen atom as hetero atoms include monocyclic saturated heterocyclic groups such as morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, and 2-methyl-2-piperidone;

azole, 4-methyl

Azoles and the like

Oxazole, iso

Azole, 2-methyliso

Azole, 3-methyliso

Azole or the like

Oxazole, 1, 2, 4-

Monocyclic unsaturated heterocyclic group such as oxadiazole; benzo (b) is

Azole, benzisoh

Azole, benzo

Fused bicyclic heterocyclic groups such as oxazines; phen

Fused tricyclic heterocyclic groups such as oxazines, and the like.

Examples of the heterocyclic group containing a nitrogen atom and a sulfur atom as hetero atoms include monocyclic heterocyclic groups such as thiazoles, e.g., thiazole such as 3-methylthiazole and 2, 4-dimethylthiazole, and isothiazoles; fused bicyclic heterocyclic groups such as benzothiazole, benzisothiazole, and benzothiadiazole; fused tricyclic heterocyclic groups such as phenothiazine.

Examples of the heterocyclic group containing a nitrogen atom as a heteroatom include a heterocyclic group containing only a nitrogen atom as a heteroatom, a heterocyclic group containing a nitrogen atom and an oxygen atom as heteroatoms, and a heterocyclic group containing a nitrogen atom and a sulfur atom as heteroatoms.

R^a1～R^a7、R^d1～R^d7And R²⁰The heterocyclic group represented may be a combination of the above-mentioned heterocyclic group and a hydrocarbon group, and examples thereof include a tetrahydrofurylmethyl group, a methyltetrahydrofuranyl group and the like.

The bonding position of the heterocyclic group is a portion from which any hydrogen atom contained in each ring is detached.

R^a1～R^a7、R^d1～R^d7、R²⁰、A¹And A²The heterocyclic group represented may have a substituent. The substituent includes R^a1～R^a7、R^d1～R^d7And R²⁰The substituent which the hydrocarbon group may have is the same as the substituent having a valence of 1 described in the substituent. When the heterocyclic group contains a nitrogen atom as an element, the above-mentioned hydrocarbon group may be bonded to the nitrogen atom as a substituent.

The substituent which the above-mentioned hydrocarbon group or heterocyclic group may have may be 1 or 2 or more, and 2 or more substituents may be the same or different independently of each other.

R^a1～R^a7、R^d1～R^d7And R²⁰The heterocyclic group represented contains-CH not constituting a ring₂When is, -CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰-substitution. However, by not substituting-CH₂-to form-CO₂H and-S (O)₂OH。-CH₂Substitution by-O-isochronal, R^a1～R^a7、R^d1～R^d7The heterocyclic group represented may have the above-mentioned group (Z1).

R^a2And R^a3、R^a3And R^a4、R^a4And R^a5、R^d2And R^d3、R^d3And R^d4Or R^d4And R^d5When a ring is formed by bonding, the ring may be a hydrocarbon ring or a heterocyclic ring. Examples of the hydrocarbon ring include an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring.

Examples of the aliphatic hydrocarbon ring include a cycloalkene ring such as a cyclohexene ring, cycloheptene ring, and cyclooctene ring; norbornene, bicyclo [2.2.2] octene, and the like. The aliphatic hydrocarbon ring has, for example, 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 4 to 20 carbon atoms, still more preferably 4 to 15 carbon atoms, yet more preferably 5 to 15 carbon atoms, and particularly preferably 5 to 10 carbon atoms.

Examples of the aromatic hydrocarbon ring include benzene, naphthalene, 1, 2, 3, 4-tetrahydronaphthalene, fluorene, phenanthrene, and anthracene. The number of carbon atoms of the aromatic hydrocarbon ring is, for example, 6 to 30, preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.

In addition, R^a2And R^a3、R^a3And R^a4、R^a4And R^a5、R^d2And R^d3、R^d3And R^d4Or R^d4And R^d5When bonded to form a heterocyclic ring, the heterocyclic ring may form a group with R^a1～R^a7、R^d1～R^d7、R²⁰、A¹And A²The heterocyclic group shown above is a ring similar to the heterocyclic ring in the above-mentioned heterocyclic group.

R^a2And R^a3、R^a3And R^a4、R^a4And R^a5、R^d2And R^d3、R^d3And R^d4Or R^d4And R^d5When bonded to form a heterocyclic ring, the heterocyclic ring is bonded to R^a2～R^a5、R^d2～R^d5The bonded benzene rings together form a 2-or more-ring structure. Examples of the 2-or more-ring structure include a heterocyclic ring having a structure represented by the following formula. The benzene ring in the following formula corresponds to the benzene ring in the isoindoline structure possessed by compound (I) or compound (II).

R^a2And R^a3、R^a3And R^a4、R^a4And R^a5、R^d2And R^d3、R^d3And R^d4Or R^d4And R^d5When a ring is bonded to form a ring, the ring may have a substituent. The substituent includes R^a1～R^a7、R^d1～R^d7And R²⁰To representThe substituent (c) of (a) is the same as the 1-valent substituent described above.

The ring may have 1 or 2 or more substituents, and 2 or more substituents may be the same or different independently from each other.

R^a2And R^a3、R^a3And R^a4、R^a4And R^a5、R^d2And R^d3、R^d3And R^d4Or R^d4And R^d5The ring formed by bonding may have the above-mentioned group (Z1).

As R^a2～R^a7And R^d2～R^d7The halogen atom represented by (a) includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom, a chlorine atom and a bromine atom, and more preferably a fluorine atom and a chlorine atom.

M represents a hydrogen atom or an alkali metal atom such as a lithium atom, a sodium atom, a potassium atom or the like, preferably a hydrogen atom, a sodium atom, a potassium atom, more preferably a hydrogen atom.

The presence of a plurality of R in Compound (I) or Compound (II)²⁰And M, they may be the same or different.

D¹And D²The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include^a1～R^a7、R^d1～R^d7And R²⁰The aromatic hydrocarbon group represented by the above-mentioned groups are preferably phenyl or naphthyl.

D¹And D²The aromatic hydrocarbon group represented has at least 1-CO₂M。D¹And D²having-CO-of an aromatic hydrocarbon group₂M is preferably 1 to 3, more preferably 1 to 2, and further preferably 1.

D¹And D²The aromatic hydrocarbon group represented has 1-CO₂When M is, the-CO₂The bonding position of M is not particularly limited, and for example, when the aromatic hydrocarbon group is naphthyl, it may be bonded to D¹And D²The same six-membered ring side as the bonding site of (A) has a structure of the following formula (D-a)The structure of the following formula (D-b) may be different on the six-membered ring side. In the following formulae, a represents a bonding site.

D¹And D²The aromatic hydrocarbon group represented may have other than the above-mentioned-CO₂Substituents other than M are exemplified by R^a1～R^a7、R^d1～R^d7And R²⁰wherein-CO is removed from a 1-valent substituent described as a substituent which may be contained in the hydrocarbon group₂The group of M. -CO of the aromatic hydrocarbon group₂The number of substituents other than M is preferably 0 to 6, more preferably 0 to 3, and further preferably 0.

D¹And D²The aromatic hydrocarbon group represented by (A) has at least 2-CO groups₂When the substituents other than M are used, they may be the same or different independently of each other.

Note that D¹And D²having-CO-of an aromatic hydrocarbon group₂Substituents other than M and-CO₂The number of M represents the number of the aromatic hydrocarbon groups relative to 1.

As the compound (I), R is preferred^a1～R^a7、A¹～A²And M is a compound as follows.

As R^a1Preferably a hydrogen atom.

As R^a2～R^a5Independently of one another, are preferably selected from hydrogen atoms; a saturated chain hydrocarbon group having 1 to 10 carbon atoms (preferably an alkyl group which may have a substituent) which may have a substituent, such as a butyl group or a trifluoromethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or a butoxy group; an alkanoyl group having 2 to 6 carbon atoms such as an acetyl group; an aryloxy group having 6 to 10 carbon atoms which may have a substituent (preferably a phenoxy group which may have a substituent), such as a 3, 4-xylyloxy group, an α, α, α -trifluoromethylcarbonyloxy group, etc.; halogen atoms such as fluorine atom and chlorine atom; a nitro group; a cyano group; an amino group; a hydroxyl group; a formyl group; a sulfamoyl group; a carboxyl group; in sulfo group or the likeMore preferably selected from hydrogen atoms; 1 kind of halogen atom such as fluorine atom, chlorine atom, etc., more preferably selected from hydrogen atom; 1 kind of chlorine atom.

R^a2And R^a3、R^a3And R^a4Or R^a4And R^a5When bonded and form a ring together with the carbon atoms to which each is bonded, an aromatic hydrocarbon ring having 6 to 10 carbon atoms such as benzene is preferable, and naphthalene is more preferable together with a benzene ring in the isoindoline structure.

R^a2～R^a5Preferably, no ring is formed.

As R^a6And R^a7Preferably 1 kind selected from the group consisting of a hydrogen atom, a cyano group and a nitro group, more preferably 1 kind selected from the group consisting of a cyano group and a nitro group, and still more preferably a cyano group. At this time, R^a6And R^a7Preferably the same groups.

As A¹And A²The condensed heterocyclic group which may have a substituent such as a condensed bicyclic heterocyclic group which may have a substituent, a condensed tricyclic heterocyclic group which may have a substituent or the like is preferable, the condensed heterocyclic group which may have a substituent is more preferable, the condensed bicyclic heterocyclic group which may have a nitrogen atom as a hetero atom (the condensed heterocyclic group may have a substituent is further preferable, the condensed bicyclic heterocyclic group which may have a substituent is further preferable, and the quinolyl group which may have a substituent, the indolyl group which may have a substituent or the benzothiazolyl group which may have a substituent is further preferable. In addition, A¹And A²Preferably, no substituent is present. A. the¹And A²Preferably the same. A. the¹And A²In the case of a condensed heterocyclic group comprising a heterocyclic ring and a hydrocarbon ring such as an aromatic hydrocarbon, a structure having a bonding site on the side of the heterocyclic ring is preferable (for example, A)¹And A²In the case of a quinolyl group, the structure is represented by the following formula).

When M is present in the compound (I), M is preferably a hydrogen atom.

As specific compounds (I)For example, a compound represented by the formula (Ia) wherein R is^a1、R^a6～R^a7、A¹～A²And B¹B²The combinations of (A) to (B) are compounds (I-1) to (I-966) each having a substituent shown in any one of tables 1 to 11.

The compound (I) is preferably a compound (I-1) to a compound (I-460),

more preferably from compound (I-1) to compound (I-46),

further preferred are compound (I-1), compound (I-2), compound (I-3), compound (I-25), compound (I-28), compound (I-30), compound (I-34), compound (I-36), compound (I-38), compound (I-45) and compound (I-46).

In the table, H represents a hydrogen atom, and CN represents a cyano group.

A¹～A²Represents a heterocyclic group represented by the formulae (AA1) to (AA 46).

B¹B²Represents any partial structure represented by formula (BB1) to formula (BB 21).

In the formulae (AAl) to (AA46) and (BB1) to (BB21), and B¹B²Each represents a bonding site.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

[ Table 5]

[ Table 6]

[ Table 7]

[ Table 8]

[ Table 9]

[ Table 10]

[ Table 11]

	A¹，A²	R^a1	R^a6，R^a7	B¹B²
					(I-921)	AA1	H	CN	BB21
(I-922)	AA2	H	CN	BB21
					(I-923)	AA3	H	CN	BB21
(I-924)	AA4	H	CN	BB21
					(I-925)	AA5	H	CN	BB21
(I-926)	AA6	H	CN	BB21
					(I-927)	AA7	H	CN	BB21
(I-928)	AA8	H	CN	BB21
					(I-929)	AA9	H	CN	BB21
(I-930)	AA10	H	CN	BB21
					(I-931)	AA11	H	CN	BB21
(I-932)	AA12	H	CN	BB21
					(I-933)	AA13	H	CN	BB21
(I-934)	AA14	H	CN	BB21
					(I-935)	AA15	H	CN	BB21
(I-936)	AA16	H	CN	BB21
					(I-937)	AA17	H	CN	BB21
(I-938)	AA18	H	CN	BB21
					(I-939)	AA19	H	CN	BB21
(I-940)	AA20	H	CN	BB21
					(I-941)	AA21	H	CN	BB21
(I-942)	AA22	H	CN	BB21
					(I-943)	AA23	H	CN	BB21
(I-944)	AA24	H	CN	BB21
					(I-945)	AA25	H	CN	BB21
(I-946)	AA26	H	CN	BB21
					(I-947)	AA27	H	CN	BB21
(I-948)	AA28	H	CN	BB21
					(I-949)	AA29	H	CN	BB21
(I-950)	AA30	H	CN	BB21
					(I-951)	AA31	H	CN	BB21
(I-952)	AA32	H	CN	BB21
					(I-953)	AA33	H	CN	BB21
(I-954)	AA34	H	CN	BB21
					(I-955)	AA35	H	CN	BB21
(I-956)	AA36	H	CN	BB21
					(I-957)	AA37	H	CN	BB21
(I-958)	AA38	H	CN	BB21
					(I-959)	AA39	H	CN	BB21
(I-960)	AA40	H	CN	BB21
					(I-961)	AA41	H	CN	BB21
(I-962)	AA42	H	CN	BB21
					(I-963)	AA43	H	CN	BB21
(I-964)	AA44	H	CN	BB21
					(I-965)	AA45	H	CN	BB21
(I-966)	AA46	H	CN	BB21

As the compound (II), R is preferred^d1～R^d7、D¹～D²And M is a compound as follows.

As R^d1Preferably a hydrogen atom.

As R^d2～R^d5Independently of one another, are preferably selected from hydrogen atoms; a saturated chain hydrocarbon group having 1 to 10 carbon atoms (preferably an alkyl group which may have a substituent) which may have a substituent, such as a butyl group or a trifluoromethyl group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group or a butoxy group; carbon atom of acetyl group or the likeA number of alkanoyl groups of 2 to 6; an aryloxy group having 6 to 10 carbon atoms which may have a substituent (preferably a phenoxy group which may have a substituent), such as a 3, 4-xylyloxy group, an α, α, α -trifluoromethylcarbonyloxy group, etc.; halogen atoms such as fluorine atom and chlorine atom; a nitro group; a cyano group; an amino group; a hydroxyl group; a formyl group; a sulfamoyl group; a carboxyl group; 1 kind of sulfo group, etc., more preferably selected from hydrogen atom; 1 kind of halogen atom such as fluorine atom, chlorine atom, etc., more preferably selected from hydrogen atom; 1 kind of chlorine atom.

R^d2And R^d3、R^d3And R^d4Or R^d4And R^d5When bonded and form a ring together with the carbon atoms to which each is bonded, an aromatic hydrocarbon ring having 6 to 10 carbon atoms such as benzene is preferable, and naphthalene is more preferable together with a benzene ring in the isoindoline structure.

R^d2～R^d5Preferably, no ring is formed.

As R^d6And R^d7Preferably 1 kind selected from the group consisting of a hydrogen atom, a cyano group and a nitro group, more preferably 1 kind selected from the group consisting of a cyano group and a nitro group, and still more preferably a cyano group. At this time, R^d6And R^d7Preferably the same groups.

D¹And D²Preferably having at least 1-CO₂M and may have a-CO₂The C6-12 aromatic hydrocarbon group of the substituent other than M is more preferably a group having 1-CO₂M and may have-CO₂Phenyl having a substituent other than M or having-CO₂Naphthyl for substituents other than M. In addition, D¹And D²Preferably do not have-CO₂A substituent other than M. D¹And D²Preferably the same.

When M is present in the compound (II), M is preferably a hydrogen atom.

Specific examples of the compound (II) include, for example, R in the compound represented by the formula (IIa)^d1、R^d6～R^d7、D¹～D²And B¹B²The combinations of (1) to (II-147) each having a substituent in any one of tables 12 to 14.

The compound (II) is preferably a compound (II-1) to a compound (II-70),

more preferably compounds (II-1) to (II-35),

further preferred are compounds (II-1) to (II-14).

In the table, H represents a hydrogen atom, and CN represents a cyano group.

D¹～D²Represents an aromatic hydrocarbon group represented by the formulae (DD1) to (DD 7).

B¹B²Represents any partial structure of the formulae (BB1) to (BB 21).

In formulae (DD1) to (DD7), a represents a bonding site.

[ Table 12]

[ Table 13]

[ Table 14]

	D¹，D²	R^d1	R^d6，R^d7	B¹B²
					(II-141)	DD1	H	CN	BB21
(II-142)	DD2	H	CN	BB21
					(II-143)	DD3	H	CN	BB21
(II-144)	DD4	H	CN	BB21
					(II-145)	DD5	H	CN	BB21
(II-146)	DD6	H	CN	BB21
					(II-147)	DD7	H	CN	BB21

The following describes the production methods of compound (I) and compound (II). In the following, in the compound (I) or the compound (II), R is^a1Or R^d1A compound which is a hydrogen atom is described as "Compound (1-H)", and in Compound (I) or Compound (II), R is^a1Or R^d1Compounds other than hydrogen atoms are described as "Compound (1-R)".

The compound (1-H) can be produced by reacting a compound represented by the formula (pt1) (hereinafter, may be referred to as a phthalonitrile compound) with a compound represented by the formula (pt2) (hereinafter, may be referred to as an alkoxide compound), and then further reacting the compound represented by the formula (pt3) (hereinafter, may be referred to as a compound (pt3)) with a compound represented by the formula (pt4) (hereinafter, may be referred to as a compound (pt4)) in the presence of an acid.

The compound (1-H) can be produced by reacting a compound represented by the formula (pt5) (hereinafter, may be referred to as a1, 3-diiminoisoindoline compound) with the compound (pt3) and the compound (pt 4).

The compound (1-R) can be produced by reacting the compound (1-H) with a compound represented by the formula (pt6) (hereinafter, may be referred to as a compound (pt 6)).

[ formulae (pt1) to (pt6), formulae (1-H) and formulae (1-R),

R¹～R⁷in the compound (I), each represents the same as R^a1～R^a7The same meaning as that of R in the compound (II)^d1～R^d7The same meaning is used.

R⁸～R⁹In the compound (I), each represents the same as A¹And A²The same meaning as that of D in the compound (II)¹And D²The same meaning is used.

R³¹Represents an alkyl group having 1 to 20 carbon atoms.

M¹Represents an alkali metal atom.

LG represents a halogen atom, a methanesulfonyloxy group, a toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group ]

As R³¹Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl and the like, and preferred examples thereof include alkyl groups having 1 to 6 carbon atoms.

As M¹Examples of the alkali metal atom include a lithium atom, a sodium atom and a potassium atom.

The amount of the alkoxide compound represented by the formula (pt2) used is usually 0.1 to 10 moles, preferably 0.2 to 5 moles, more preferably 0.3 to 3 moles, and still more preferably 0.4 to 2 moles, based on 1 mole of the phthalonitrile compound.

The total amount of the compound (pt3) and the compound (pt4) used is usually 2 to 20 moles, preferably 2 to 10 moles, more preferably 2 to 6 moles, and still more preferably 2 to 4 moles, based on 1 mole of the phthalonitrile compound. The compound (pt3) and the compound (pt4) may be the same.

Examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, fluorosulfonic acid, and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid, and p-toluenesulfonic acid; carboxylic acids such as acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and carboxylic acids, more preferably acetic acid.

The amount of the acid used is usually 1 to 20 mol, preferably 1 to 10 mol, more preferably 1 to 8 mol, and still more preferably 1 to 6 mol, based on 1 mol of the phthalonitrile compound.

The reaction of the phthalonitrile compound, the alkoxide compound, the compound (pt3) and the compound (pt4) is usually carried out in the presence of a solvent for reaction.

As the solvent for the reaction, water may be mentioned; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, and 1-octanol; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as dichloromethane and chloroform; amide solvents such as N, N-dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide, preferably include water, nitrile solvents, alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents and sulfoxide solvents, more preferably include water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, ethyl acetate, toluene, dichloromethane, chloroform, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidinone and dimethyl sulfoxide, and further preferably include water, acetonitrile, methanol, ethanol, 2-propanol, 1-pentanol, 1-octanol, 1-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidinone and dimethyl sulfoxide, 1-butanol, 1-pentanol, 1-octanol, acetone, dichloromethane, chloroform, N-dimethylformamide, N-dimethylacetamide, 1, 3-dimethyl-2-imidazolidinone, and 1, 3-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidinone, N-methylpyrrolidone, and dimethyl sulfoxide, and further more preferably water, acetonitrile, methanol, ethanol, 2-propanol, N-methylpyrrolidone, and dimethyl sulfoxide can be cited.

The amount of the solvent for reaction is usually 1 to 1000 parts by mass based on 1 part by mass of the phthalonitrile compound.

The reaction temperature of the phthalonitrile compound, alkoxide compound, compound (pt3) and compound (pt4) is usually 0 to 200 ℃, preferably 0 to 100 ℃, and more preferably 0 to 50 ℃. The reaction time is usually 0.5 to 300 hours.

The reaction of the 1, 3-diiminoisoindoline compound, the compound (pt3) and the compound (pt4) is usually carried out in the presence of a solvent for the reaction. As the solvent for the reaction, water may be mentioned; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, and 1-octanol; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as dichloromethane and chloroform; amide solvents such as N, N-dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide, preferably nitrile solvents, alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents and sulfoxide solvents, more preferably acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, ethyl acetate, toluene, dichloromethane, chloroform, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, 1, 3-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidinone and dimethyl sulfoxide, and further preferably acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, dichloromethane, chloroform, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and 1, 3-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidinone, and dimethyl sulfoxide, and further more preferably, N-dimethylformamide, N-dimethylacetamide, 1-butanol, N-methylpyrrolidone, 3-dimethyl-2-imidazolidinone, and 1, 3-dimethyl-3, 4, 5, 6-tetrahydro-2 (1H) -pyrimidinone, and dimethyl sulfoxide can be cited.

The amount of the solvent for reaction is usually 1 to 1000 parts by mass based on 1 part by mass of the 1, 3-diiminoisoindoline compound.

The reaction temperature of the 1, 3-diiminoisoindoline compound, the compound (pt3) and the compound (pt4) is usually 0 to 200 ℃, preferably 0 to 100 ℃, and more preferably 0 to 80 ℃. The reaction time is usually 0.5 to 300 hours.

The amount of the compound (pt6) used is usually 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 3 moles, and still more preferably 1 to 2 moles, based on 1 mole of the compound (1-H).

In addition, when the compound (pt6) is reacted, a base is preferably coexistent. Examples of the base include organic bases such as triethylamine, 4- (N, N-dimethylamino) pyridine, and piperidine, metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide, and potassium tert-butoxide, and organic metal compounds such as butyllithium, tert-butyllithium, and phenyllithium; inorganic bases such as lithium hydroxide, sodium hydroxide and potassium hydroxide.

The amount of the base to be used is usually 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 3 moles, and still more preferably 1 to 2 moles, based on 1 mole of the compound (1-H).

In addition, the reaction of the compound (pt6) is usually carried out in the presence of a solvent for reaction. The solvent for the reaction can be selected from the same ranges as described above.

The amount of the solvent for reaction is usually 1 to 1000 parts by mass per 1 part by mass of the compound (1-R) in the compound (I) or the compound (II). The reaction temperature of the compound (pt6) is usually-90 to 200 ℃, preferably-80 to 100 ℃, and more preferably 0 to 50 ℃. The reaction time is usually 0.5 to 300 hours.

The method for removing compound (I) or compound (II) from the reaction mixture is not particularly limited, and it can be removed by various known methods. For example, after the reaction is completed, the reaction mixture may be filtered to remove the compound (I) or the compound (II). After filtration, the obtained residue may be washed with a washing solvent. Further, after filtration, column chromatography, drying under reduced pressure, recrystallization, sublimation purification, or the like may be performed.

The cleaning solvent may be selected from the above-mentioned reaction solvents and acids such as acetic acid.

The mass ratio of the compound (I) to the compound (II) (compound (I)/compound (II)) is preferably 1 to 1000, more preferably 2 to 100, and still more preferably 5 to 20. From the viewpoint of dispersion stability, the upper limit of the mass ratio is preferably 1000 or less. In particular, when compound (I) is used in an equal amount or in an excess amount relative to compound (II), compound (II) can improve the dispersibility of compound (I).

The content ratio of the compound (I) and the compound (II) in the colorant (a) is preferably 10% by mass or more, more preferably 50% by mass or more, further preferably 80% by mass or more, further preferably 90% by mass or more, preferably 100% by mass or less, and may be 95% by mass or less.

In the coloring composition of the present invention, the compound (I) and the compound (II) are preferably dispersed in the solvent (E).

When the compound (I) and the compound (II) are dispersed in the solvent (E) to prepare a coloring composition, the dispersion stability in preparing the coloring composition can be further improved by previously containing the resin (B).

The content of the resin (B) in the coloring composition is, for example, 1 to 500 parts by mass, preferably 5 to 200 parts by mass, and more preferably 10 to 100 parts by mass, based on 100 parts by mass of the total of the compound (I) and the compound (II).

The compound (I) and the compound (II) may be subjected to, if necessary, rosin treatment, surface treatment using a derivative or the like into which an acidic group or a basic group is introduced, grafting treatment of the surfaces of the compound (I) and the compound (II) with a polymer compound or the like, micronization treatment with a sulfuric acid micronization method or the like, washing treatment with an organic solvent, water or the like for removing impurities, removal treatment with an ion exchange method or the like for removing ionic impurities, or the like. The particle diameters of the compound (I) and the compound (II) are preferably substantially uniform. The compound (I) and the compound (II) can be dispersed in the coloring composition uniformly by dispersing the compound (I) and the compound (II) with a dispersant.

The dispersant may be any of cationic, anionic, nonionic and amphoteric surfactants. Specifically, there may be mentioned polyester, polyamine, acrylic and other surfactants. These dispersants may be used alone or in combination of two or more. Examples of the dispersant include KP (manufactured by shin-Etsu chemical industry Co., Ltd.), Flowsen (manufactured by Kyoeisha chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by ZENECA Co., Ltd.), EFKA (registered trademark) (manufactured by BASF Co., Ltd.), Ajiser (registered trademark) (manufactured by Ajizhi Kogyo Technique Co., Ltd.), Disperbyk (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), BYK (registered trademark) (manufactured by BYK-Chemie Co., Ltd.), and the like.

When the dispersant is used, the amount of the dispersant (solid content) to be used is preferably 400 parts by mass or less, more preferably 200 parts by mass or less, further preferably 5 to 200 parts by mass, and further more preferably 5 to 150 parts by mass, based on 100 parts by mass of the total of the compound (I) and the compound (II). If the amount of the dispersant used is within the above range, there is a tendency that a more uniform dispersed state of the coloring composition can be obtained.

The total content of the compound (I) and the compound (II) in the coloring composition is usually 0.1 to 60% by mass, preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on the total amount of the coloring composition.

The total content of the compound (I) and the compound (II) in the coloring composition is usually 1 to 90% by mass, preferably 1 to 80% by mass, more preferably 2 to 75% by mass, and still more preferably 5 to 75% by mass, based on the total amount of the solid content.

The coloring composition of the present invention may contain, as the colorant (a), a colorant other than the compound (I) and the compound (II) (hereinafter, may be referred to as a colorant (a 1)). In the present specification, the compound (I), the compound (II), and the colorant (a1) are sometimes collectively referred to as "colorant (a)". The colorant (a1) may contain 1 or 2 or more colorants.

The colorant (a1) may be a dye or a pigment. Examples of The dye include known dyes described in The color index (published by The Society of Dyers and Colourists) and notes on dyeing (available from color dyeing Co., Ltd.). Further, depending on the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, and squaric acid may be mentioned

Dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes and the like. Among these, organic solvent-soluble dyes are preferable. These dyes may be used in combination of 2 or more.

Specifically, the following dyes are given by the color index (c.i.) number. C.i. acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

c.i. solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

c.i. direct yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

c.i. disperse yellow 51, 54, 76;

c.i. reactive yellow 2, 76, 116;

c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

c.i. solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

c.i. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

c.i. reactive orange 16;

c.i. acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 57, 66, 73, 76, 80, 88, 91, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 382, 383, 394, 401, 412, 417, 418, 422, 349, 426;

c.i. solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247;

c.i. direct red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;

c.i. mordant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;

c.i. acid violet 34;

c.i. disperse violet 26, 27;

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

c.i. solvent blue 14, 18, 35, 36, 45, 58, 59: 1. 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

c.i. acid blue 25, 27, 40, 45, 78, 80, 112;

c.i. direct blue 40;

c.i. disperse blue 1, 14, 56, 60;

c.i. solvent green 1, 3, 5, 28, 29, 32, 33;

c.i. acid green 3, 5, 9, 25, 27, 28, 41;

c.i. alkaline green 1;

c.i. vat green 1, etc.

As The pigment, known pigments can be used, and for example, pigments classified as pigments in The color index (published by The Society of Dyers and Colourists) can be cited. These may be used alone, or 2 or more of them may be used in combination.

Specifically, there may be mentioned yellow pigments such as 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, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

red pigments such as 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, 266, 268, 269, 273 and the like;

c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60, etc. blue pigments;

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

c.i. pigment green 7, 36, 58, 59 and the like.

When the coloring composition of the present invention contains the colorant (a1) and the solvent (E), a liquid containing the colorant (a1) containing the colorant (a1) and the solvent (E) may be prepared in advance, and then the liquid containing the colorant (a1) may be used to prepare the coloring composition. When the colorant (a1) is insoluble in the solvent (E), a liquid containing the colorant (a1) can be prepared by dispersing and mixing the colorant (a1) in the solvent (E). The liquid containing the colorant (a1) may contain a part or all of the solvent (E) contained in the coloring composition.

In order to prepare the above liquid containing the colorant (a1), when a dispersant is used, the amount of the dispersant (solid content) used is preferably 400 parts by mass or less, more preferably 200 parts by mass or less, further preferably 5 parts by mass to 200 parts by mass, and further more preferably 5 parts by mass to 150 parts by mass, relative to 100 parts by mass of the colorant (a 1). If the amount of the dispersant used is within the above range, a more uniformly dispersed liquid containing the colorant (a1) tends to be obtained.

The content of the colorant (A1) in the liquid containing the colorant (A1) is usually 0.1 to 60% by mass, preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on the total amount of the liquid containing the colorant (A1).

The content of the colorant (a1) in the liquid containing the colorant (a1) is usually 1 to 90% by mass, preferably 1 to 80% by mass, more preferably 2 to 75% by mass, and still more preferably 5 to 75% by mass, based on the total amount of the solid content.

When the liquid containing the colorant (a1) containing the colorant (a1) and the solvent (E) is prepared in advance and then the liquid containing the colorant (a1) is used to prepare the coloring composition of the present invention, the liquid containing the colorant (a1) may contain in advance a part or all, preferably a part, of the resin (B) contained in the coloring composition. By containing the resin (B) in advance, the dispersion stability of the liquid containing the colorant (a1) can be further improved.

The content of the resin (B) in the liquid containing the colorant (a1) is, for example, 1 to 500 parts by mass, preferably 5 to 200 parts by mass, and more preferably 10 to 100 parts by mass, based on 100 parts by mass of the colorant (a 1).

In the coloring composition, the content of the colorant (a) in the total of the compound (I), the compound (II) and the colorant (a1) is usually 1 to 90% by mass, preferably 1 to 80% by mass, more preferably 2 to 75% by mass, and still more preferably 5 to 75% by mass, based on the total amount of solid components.

When the colorant (a1) is contained, the content of the colorant (a1) is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, further preferably 1 part by mass or more, preferably 10000 parts by mass or less, and more preferably 5000 parts by mass or less, based on 100 parts by mass of the total of the compound (I) and the compound (II).

< resin (B) >

The resin (B) is preferably an alkali-soluble resin, and is preferably a polymer having a structural unit derived from at least 1 monomer (hereinafter, sometimes referred to as "monomer (a)") selected from an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride.

The resin (B) is preferably a copolymer having a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (B)") and other structural units.

Examples of the other structural units include structural units derived from a monomer copolymerizable with the monomer (a) (however, different from the monomer (a) and the monomer (b): hereinafter, sometimes referred to as "monomer (c)"), structural units having an ethylenically unsaturated bond, and the like.

Examples of the monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

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

carboxyl group-containing bicyclic unsaturated compounds such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxymethylbicyclo [2.2.1] hept-2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;

carboxylic acid anhydrides such as anhydrides of the above unsaturated dicarboxylic acids except fumaric acid and mesaconic acid;

unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [2- (meth) acryloyloxyethyl ] ester;

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

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

The monomer (b) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least 1 selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. The monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Examples of the monomer (b) include a monomer having an oxirane group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 2)"), a monomer having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b 3)"), and the like.

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

The monomer (b1-1) is preferably a monomer having a glycidyl group and an ethylenically unsaturated bond. Specific examples of the monomer (b1-1) include glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, α -methylvinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2, 3, 4-tris (glycidoxymethyl) styrene, 2, 3, 5-tris (glycidoxymethyl) styrene, 2, 3, 6-tris (glycidoxymethyl) styrene, 3, 4, 5-tris (glycidoxymethyl) styrene, 2, 4, 6-tris (glycidoxymethyl) styrene and the like.

Examples of the monomer (b1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000 (manufactured by Daicel Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) A400 (manufactured by Daicel Co., Ltd.), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer (registered trademark) M100 (manufactured by Daicel Co., Ltd.)), the compound represented by the formula (BI), and the compound represented by the formula (BII).

[ formula (BI) and formula (BII) wherein R^aAnd R^bIndependently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X^aAnd X^bIndependently of one another, represents a single bond, -R^c-、*-R^c-O-、*-R^c-S-or R^c-NH-。

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

Indicates a bonding site with O ]

Examples of the compound represented by formula (BI) include compounds represented by any one of formulae (BI-1) to (BI-15). Among them, preferred are compounds represented by formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) and formulae (BI-11) to (BI-15), and more preferred are compounds represented by formula (BI-1), formula (BI-7), formula (BI-9) and formula (BI-15).

Examples of the compound represented by formula (BII) include compounds represented by any one of formulae (BII-1) to (BII-15), among which compounds represented by formulae (BII-1), (BII-3), formula (BII-5), formula (BII-7), formula (BII-9), and formulae (BII-11) to (BII-15) are preferable, and compounds represented by formulae (BII-1), formula (BII-7), formula (BII-9), and formula (BII-15) are more preferable.

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination. When they are used in combination, the content ratio of the compound represented by the formula (BI) to the compound represented by the formula (BII) is preferably 5: 95 to 95: 5, more preferably 10: 90 to 90: 10, and further preferably 20: 80 to 80: 20 on a molar basis.

Examples of the monomer (c) include 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, and tricyclo [5.2.1.0 ] meth) acrylate^2，6]Decan-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2，6]Decan-9-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2，6]Decen-8-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2，6](meth) acrylates such as decen-9-yl ester, dicyclopentyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

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

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [2.2.1] hept-2-ene, 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, bicyclic unsaturated compounds such as 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

vinyl group-containing aromatic compounds such as styrene, α -methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-containing amides such as (meth) acrylic acid amide; esters such as vinyl acetate; dienes such as 1, 3-butadiene, isoprene and 2, 3-dimethyl-1, 3-butadiene.

Among these, styrene, vinyltoluene and tricyclo [5.2.1.0 ] are preferable from the viewpoint of copolymerization reactivity and heat resistance^2，6]Decan-8-yl (meth) acrylates, tricyclo [5.2.1.0^2，6]Decan-9-yl (meth) acrylates, tricyclo [5.2.1.0^2，6]Decen-8-yl (meth) acrylate, tricyclo [5.2.1.0^2，6]Decen-9-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1]Hept-2-ene, benzyl (meth) acrylate, and the like.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group. The resin having such a structural unit can be obtained by adding a monomer having a group reactive with the groups of the monomer (a) and the monomer (b) and an ethylenically unsaturated bond to a polymer having a structural unit derived from the monomer (a) and the monomer (b).

Examples of such a structural unit include a structural unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit, a structural unit obtained by adding 2-hydroxyethyl (meth) acrylate to a maleic anhydride unit, and a structural unit obtained by adding (meth) acrylic acid to a glycidyl (meth) acrylate unit. When these structural units have a hydroxyl group, a structural unit obtained by further adding a carboxylic anhydride may be mentioned as a structural unit having an ethylenically unsaturated bond.

The polymer having a structural unit derived from the monomer (a) can be produced, for example, by polymerizing a monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator and the solvent are not particularly limited, and polymerization initiators and solvents generally used in this field can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and organic peroxides (e.g., benzoyl peroxide), and examples of the solvent include a solvent (E) described later, as long as the monomers are dissolved therein.

The polymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a solid (powder) taken out by a method such as reprecipitation.

If necessary, a reaction catalyst of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (for example, tris (dimethylaminomethyl) phenol) or the like, a polymerization inhibitor (for example, hydroquinone or the like) or the like may be used.

Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3, 4, 5, 6-tetrahydrophthalic anhydride, 1, 2, 3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.

Specific examples of the resin (B) include a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, and a 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2，6]Decyl ester/(meth) acrylic acid copolymer, and glycidyl (meth) acrylateGlyceride/(methyl) benzyl acrylate/(methyl) acrylic acid copolymer, glycidyl (methyl) acrylate/styrene/(methyl) acrylic acid copolymer, 3, 4-epoxy tricyclic [5.2.1.0 ] of (methyl) acrylic acid^2，6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] of (meth) acrylic acid^2，6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2，6]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] of (meth) acrylic acid^2，6]Decyl ester/(meth) acrylic acid 2-ethylhexyl ester copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] meth (acrylic acid)^2，6]Decyl ester/(meth) acrylic acid tricyclo [5.2.1.0^2，6]Decenyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer, benzyl (meth) acrylate/(meth) acrylic acid copolymer, styrene/(meth) acrylic acid copolymer, and resins described in each of Japanese patent application laid-open Nos. 9-106071, 2004-29518 and 2004-361455.

Among these, the resin (B) is preferably a copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (B).

The resin (B) may be used in combination of 2 or more, and in this case, the resin (B) preferably contains at least one member selected from the group consisting of 3, 4-epoxytricyclo [5.2.1.0 ] s of (meth) acrylic acid^2，6]Decyl ester/(meth) acrylic acid copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] meth (acrylic acid)^2，6]Decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide/(meth) acrylic acid 2-hydroxyethyl ester copolymer, 3, 4-epoxytricyclo [5.2.1.0 ] meth (acrylic acid)^2，6]Decyl ester/(meth) acrylic acid/vinyltoluene copolymer, 3, 4-epoxy tricyclo [5.2.1.0 ] of (meth) acrylic acid^2，6]1 or more of decyl ester/(meth) acrylic acid 2-ethylhexyl ester copolymer.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. The dispersity [ weight average molecular weight (Mw)/number average molecular weight (Mn) ] of the resin (B) is preferably 1.1 to 6, more preferably 1.2 to 4.

The acid value (solid content equivalent value) of the resin (B) is preferably 10 to 300mg-KOH/g, more preferably 20 to 250mg-KOH/g, still more preferably 20 to 200mg-KOH/g, still more preferably 20 to 170mg-KOH/g, still more preferably 30 to 170mg-KOH/g, still more preferably 50 to 150mg-KOH/g, particularly preferably 60 to 140mg-KOH/g, and most preferably 60 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

The content of the resin (B) in the coloring composition is, for example, 1 to 1200 parts by mass, preferably 30 to 1000 parts by mass, and more preferably 50 to 800 parts by mass, based on 100 parts by mass of the total of the compound (I) and the compound (II).

In addition, the content of the resin (B) in the coloring composition is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 7 to 99% by mass, further preferably 13 to 99% by mass, and particularly preferably 17 to 95% by mass, based on the total amount of solid components.

In the present specification, the "total amount of solid components" refers to the total amount of components obtained by removing the solvent (E) from the colored composition or colored curable resin composition of the present invention. The total amount of the solid components and the contents of the respective components relative to the total amount of the solid components can be measured by a known analytical method such as liquid chromatography or gas chromatography.

< polymerizable Compound (C) >

The polymerizable compound (C) is a compound polymerizable by an active radical and/or an acid generated by the polymerization initiator (D), and is, for example, a compound having a polymerizable ethylenically unsaturated bond, and is preferably a (meth) acrylate compound.

Examples of the polymerizable compound having 1 ethylenically unsaturated bond include nonylphenylcarbinol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the above-mentioned monomer (a), monomer (b) and monomer (c).

Examples of the polymerizable compound having 2 ethylenically unsaturated bonds include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol a, and 3-methylpentanediol di (meth) acrylate.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, 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, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate Esters and the like, and dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferably used.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 to 2900, more preferably 250 to 1500.

The content of the polymerizable compound (C) in the colored curable resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, further preferably 7 to 65% by mass, further preferably 13 to 60% by mass, and particularly preferably 17 to 55% by mass, based on the total amount of solid components.

< polymerization initiator (D) >

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

Examples of the polymerization initiator (D) include an O-acyloxime compound, an alkylphenone compound, a bisimidazole compound, a triazine compound, and an acylphosphine oxide compound.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-one-2-iminoimine Amines, 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-dioxopentylmethyloxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine -6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine and the like. Further, as the O-acyloxime compound, commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF Co., Ltd.), N-1919 (manufactured by ADEKA Co., Ltd.) and the like can be used. Among them, as the O-acyloxime compound, at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, and the like, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzyl dimethyl ketal, and the like. As the alkylphenone compound, commercially available products such as Irgacure 369, 907 and 379 (as described above, manufactured by BASF corporation) can be used.

Examples of the biimidazole compound include 2, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole, 2, 2 ' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole (see, for example, japanese patent application laid-open No. 6-75372, japanese patent application laid-open No. 6-75373, etc.), 2, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (alkoxyphenyl) biimidazole, 2, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (dialkoxyphenyl) biimidazole, 2, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, see Japanese Kokoku publication No. 48-38403 and Japanese Kokai publication No. 62-174204) and biimidazole compounds in which the phenyl group at the 4, 4 ', 5, 5' -position is substituted with an alkoxycarbonyl group (see, for example, Japanese Kokoku publication No. 7-10913).

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

Examples of the acylphosphine oxide compound include 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide and the like.

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 3 ', 4, 4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone and 2, 4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl phenylglyoxylate, titanocene compounds, and the like.

These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a bisimidazole compound, and more preferably a polymerization initiator containing an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.001 to 40% by mass, and more preferably 0.01 to 30% by mass, based on the total amount of solid components in the colored curable resin composition.

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, and more preferably 1 to 35 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).

< polymerization initiation aid (D1) >

The polymerization initiation aid (D1) is a compound or sensitizer for promoting the polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N-dimethyl-p-toluidine, 4 '-bis (dimethylamino) benzophenone (commonly known as michelson), 4' -bis (diethylamino) benzophenone, and 4, 4 '-bis (ethylmethylamino) benzophenone, and preferred examples thereof include 4, 4' -bis (diethylamino) benzophenone. As the amine compound, a commercially available compound such as EAB-F (manufactured by UK chemical Co., Ltd.) can be used.

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

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone and 1-chloro-4-propoxythioxanthone.

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthyloxyacetic acid.

When the polymerization initiator aid (D1) is used, the content thereof is preferably 0.001 to 30% by mass, more preferably 0.01 to 20% by mass, based on the total amount of solid components in the colored curable resin composition.

When the polymerization initiator aid (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).

< solvent (E) >

Examples of the solvent (E) include an ester solvent (a solvent containing-COO-and not containing-O-in the molecule), an ether solvent (a solvent containing-O-and not containing-COO-in the molecule), an ether ester solvent (a solvent containing-COO-and not containing-COO-in the molecule), a ketone solvent (a solvent containing-CO-and not containing-COO-in the molecule), an alcohol solvent (a solvent containing OH and not containing-O-, -CO-, and-COO-, an aromatic hydrocarbon solvent, an amide solvent, and dimethyl sulfoxide.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 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-dibutylene glycol

Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

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

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

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

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

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

These solvents may be used in combination of 2 or more.

The content of the solvent (E) is preferably 40 to 99% by mass, more preferably 50 to 95% by mass, even more preferably 65 to 95% by mass, and even more preferably 70 to 90% by mass, based on the total amount of the coloring composition.

< leveling agent (F) >

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

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by shin-Etsu chemical industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Moviive Performance Properties Japan contract Co., Ltd.), and the like can be cited.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, examples thereof include Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718-K (manufactured by DIC Co., Ltd.), Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 (manufactured by Mitsubishi Material electronics Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Nitron Co., Ltd.) and E5844 (manufactured by King Fine chemical research Co., Ltd.).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Co., Ltd.) may be mentioned.

When the leveling agent (F) is contained, the content thereof is usually 0.0005 to 1% by mass, preferably 0.001 to 0.5% by mass, more preferably 0.001 to 0.2% by mass, still more preferably 0.002 to 0.1% by mass, and still more preferably 0.005 to 0.1% by mass, based on the total amount of the colored curable resin composition. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

< antioxidant >

From the viewpoint of improving the heat resistance and light resistance of the colorant, 2 or more antioxidants are preferably used alone or in combination. The antioxidant is not particularly limited as long as it is an industrially commonly used antioxidant, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.

Examples of the phenolic antioxidant include Irganox 1010(Irganox 1010: pentaerythritol tetrakis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF corporation), Irganox 1076(Irganox 1076: octadecyl-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF corporation), Irganox 1330(Irganox 1330: 3, 3 ', 5, 5 ' -hexa-tert-butyl-a, a ' - (mesitylene-2, 4, 6-triyl) tri-p-cresol, manufactured by BASF corporation), Irganox 3114(Irganox 3114: 1, 3, 5-tris (3, 5-di-tert-butyl-4-hydroxybenzyl) -1, 3, 5-triazine-2, 4, 6(1H, 3H, 5H) -trione, manufactured by BASF (ltd.), Irganox 3790(Irganox 3790: 1, 3, 5-tris ((4-tert-butyl-3-hydroxy-2, 6-xylyl) methyl) -1, 3, 5-triazine-2, 4, 6(1H, 3H, 5H) -trione, manufactured by BASF (ltd.), Irganox 1035(Irganox 1035: thiodiethylene bis [3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], manufactured by BASF corporation), Irganox 1135(Irganox 1135: phenylpropionic acid 3, 5-bis (1, 1-dimethylethyl) -4-hydroxy C7-C9 side chain alkyl ester manufactured by BASF corporation), Irganox 1520L (Irganox 1520L: 4, 6-bis (octylthiomethyl) -o-cresol, manufactured by BASF (ltd.), Irganox 3125(Irganox 3125, manufactured by BASF (ltd.), Irganox 565(Irganox 565: 2, 4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5' -di-tert-butylanilino) -1, 3, 5-triazine manufactured by BASF (ltd)), Adekastab AO-80(Adekastab AO-80: 3, 9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1, 1-dimethylethyl) -2, 4, 8, 10-tetraoxaspiro (5, 5) undecane, (manufactured by ADEKA), Sumilizer BHT (Sumilizer BHT, manufactured by Sumilizer chemical Co., Ltd.), Sumilizer GA-80(Sumilizer GA-80, manufactured by Sumilizer chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, manufactured by Sumilizer chemical Co., Ltd.), Cyanox 1790(Cyanox 1790, (manufactured by Cytec) and vitamin E (manufactured by Eisai Co., Ltd.), etc.

Examples of the phosphorus-based antioxidant include Irgafos 168(Irgafos 168: tris (2, 4-di-tert-butylphenyl) phosphite, manufactured by BASF corporation), Irgafos 12(Irgafos 12: tris [2- [ [2, 4, 8, 10-tetra-tert-butylbenzo [ d, f ] s][1，3，2]Dioxaphosphin-6-yl]Oxy radical]Ethyl radical]Amine, manufactured by BASF corporation), Irgafos 38(Irgafos 38: bis (2, 4-bis (1, 1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF corporation, Adekastab 329K (manufactured by ADEKA corporation), Adekastab PEP-36 (manufactured by ADEKA corporation), Adekastab PEP-8 (manufactured by ADEKA corporation), Sandstab P-EPQ (manufactured by Clariant corporation), Weston 618(Weston 618, manufactured by GE corporation), Weston 619G (Weston 619G, manufactured by GE corporation), Ultranox 626(Ultranox 626, manufactured by GE corporation) and Sumilizer GP (Sumilizer GP: 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy]-2, 4, 8, 10-tetra-tert-butyldibenzo [ d, f ]][1.3.2]II

Phosphaheptine) (manufactured by Sumitomo chemical Co., Ltd.)) And the like.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate and distearyl thiodipropionate, and β -alkylmercaptopropionate compounds of polyhydric alcohols such as tetrakis [ methylene (3-dodecylthio) propionate ] methane.

< other ingredients >

The colored curable resin composition of the present invention may contain additives known in the art, such as a filler, another polymer compound, an adhesion promoter, a light stabilizer, and a chain transfer agent, as required.

< method for producing colored curable resin composition >

The colored curable resin composition can be prepared, for example, by mixing the colorant (a), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the solvent (E), and, if necessary, the polymerization initiation aid (D1), the leveling agent (F), the antioxidant, and other components.

< color Filter >

A colored pattern can be formed from the colored curable resin composition of the present invention. Examples of a method for forming a colored pattern include a photolithography method, an ink jet method, a printing method, and the like. Among them, photolithography is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film as a cured product of the colored composition layer can be formed without using a photomask and/or without developing at the time of exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.

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

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, a substrate of silicon, a substrate having a thin film of aluminum, silver/copper/palladium alloy, or the like formed on the substrate, or the like can be used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The formation of each color pixel by photolithography can be performed under known or conventional apparatus and conditions. For example, it can be produced as follows.

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

Examples of the coating method include spin coating, slit and spin coating.

The temperature for heating and drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.

When the drying is carried out under reduced pressure, the drying is preferably carried out under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃.

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

Next, the colored composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the intended use may be used.

The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light of less than 350nm may be cut off by a filter that cuts off the wavelength region, or light of around 436nm, 408nm, or 365nm may be selectively extracted by a band-pass filter that extracts these wavelength regions. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like can be given.

In order to uniformly irradiate the entire exposure surface with parallel light beams or to precisely align the photomask with the substrate on which the colored composition layer is formed, it is preferable to use an exposure device such as a mask aligner or a stepper.

The exposed colored composition layer is brought into contact with a developer to develop the colored composition layer, thereby forming a colored pattern on the substrate. The unexposed portion of the colored composition layer is dissolved in a developer and removed by development.

As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these basic compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant.

The developing method may be any of a paddle (paddle) method, a dipping method, a spraying method, and the like. The substrate may be further inclined at an arbitrary angle during development.

The developed substrate is preferably washed with water.

The obtained colored pattern is preferably subjected to post-baking. The post-baking temperature is preferably 150-250 ℃, and more preferably 160-235 ℃. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

According to the coloring composition of the invention, a color filter with particularly excellent light resistance can be manufactured. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) and a solid-state imaging element, and is particularly useful as a color filter used in a liquid crystal display device.

Examples

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples at all, and can be carried out by appropriately changing the examples within the scope that can be adapted to the gist described above and below, and these examples are included in the technical scope of the present invention. In the following description, "part" means "part by mass" and "%" means "% by mass" unless otherwise specified.

Hereinafter, the structure of the compound was confirmed by MASS analysis (LC; model 1200 by Agilent, MASS; model LC/MSD6130 by Agilent).

Synthesis example 1

6.0 parts of 1, 3-diiminoisoindoline (manufactured by Tokyo chemical industry Co., Ltd.), 5.0 parts of acetic acid (manufactured by Wako pure chemical industries Co., Ltd.) and 300 parts of 1-butanol were mixed. To the resulting mixture, 24 parts of β -oxo-2-quinolinepropanitrile (synthesized according to the method described in WO 2011/089132) was added, and the mixture was stirred at 45 ℃ under reduced pressure of 10kPa for 10 hours. The resulting mixture was filtered, and 100 parts of acetic acid was added to the residue, followed by stirring at 80 ℃ for 2 hours. The resulting mixture was filtered, and 300 parts of water was added to 9.8 parts of the residue, followed by stirring at 80 ℃ for 2 hours. The resulting mixture was filtered, and the filtered residue was washed with 300 parts of methanol to obtain 9.5 parts of a residue. To 9.5 parts of the washed residue, 15 parts of N, N-dimethylformamide was added, and the mixture was stirred at 80 ℃ for 2 hours. Cooled to 0 ℃ and stirred for 2 hours. The resulting mixture was filtered, washed with 60 parts of methanol, and the resulting residue was dried under reduced pressure at 60 ℃ to obtain 16 parts of a compound represented by formula (I-1) (yield 79%). The wavy line indicates the inclusion of E-mer, Z-mer or a mixture thereof (in the synthesis example, the same applies hereinafter).

< identification of Compound I-1 >

(Mass analysis) ionization mode (ESI)⁺：m/z＝[M+H]⁺504

Exact Mass (Exact Mass): 503

Synthesis example 2

Synthesis was carried out in the same manner as in Synthesis example 1 except that 24 parts of β -oxo-2-quinolinecarbonitrile in Synthesis example 1 was changed to 23 parts of β -oxo-1H-indole-3-propionitrile (manufactured by Aldrich Co.). 14 parts of the compound represented by the formula (I-2) was obtained (yield 69%).

< identification of Compound I-2 >

(Mass analysis) ionization mode (ESI)⁺：m/z＝[M+H]⁺480

Accurate quality: 479

Synthesis example 3

The synthesis was carried out in the same manner as in synthesis example 1, except that 24 parts of β -oxo-2-quinolinepropanitrile in synthesis example 1 was changed to 25 parts of β -oxo-2-benzothiazolpropionitrile (synthesized according to the method described in WO 2011/016528). 8.8 parts of the compound represented by the formula (I-3) was obtained (yield: 41%).

< identification of Compound I-3 >

(Mass analysis) ionization mode (ESI)⁺：m/z＝[M+H]⁺516

Accurate quality: 515

Synthesis example 4

The synthesis was carried out in the same manner as in synthesis example 1, except that 24 parts of β -oxo-2-quinolinepropanitrile in synthesis example 1 was changed to 23 parts of 4- (2-cyanoacetyl) benzoic acid (synthesized according to the method described in US 2680731). 16 parts of the compound represented by the formula (II-1) was obtained (yield 77%).

< identification of Compound II-1 >

(Mass analysis) ionization mode (ESI)^-：m/z＝[M-H]^-488

Accurate quality: 489

Synthesis example 5

6.0 parts of dimethyl 2, 6-naphthalenedicarboxylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.) was suspended in 47 parts of acetonitrile (manufactured by Wako pure chemical industries, Ltd.). While the temperature of the resulting mixture was maintained at 60 ℃, 3.5 parts of sodium tert-butoxide (manufactured by Kanto chemical Co., Ltd.) was added over 1 minute, and the mixture was stirred for 90 minutes. While keeping the temperature at 5 ℃ or lower, 2.2 parts of concentrated sulfuric acid (manufactured by Kanto chemical Co., Ltd.) and 45 parts of water were added dropwise over 30 minutes, and the mixture was heated to 25 ℃ and stirred at 25 ℃ for 1 hour. The resulting mixture was filtered, and the filtered residue was washed with 30 parts of water and 10 parts of methanol, and the resulting residue was dried at 60 ℃ under reduced pressure to obtain 3.7 parts of methyl 6- (2-cyanoacetyl) -2-naphthoate (yield 60%).

Methyl 6- (2-cyanoacetyl) -2-naphthoate (3.7 parts) was suspended in water (15 parts). While the temperature of the resulting mixture was maintained at 80 ℃, 0.88 part of sodium hydroxide (manufactured by Wako pure chemical industries, Ltd.) was added thereto and stirred for 25 minutes. While keeping the temperature at 5 ℃ or lower, 2.8 parts of concentrated sulfuric acid (manufactured by Kanto chemical Co., Ltd.) was added dropwise over 30 minutes, and the mixture was heated to 25 ℃ and stirred at 25 ℃ for 1 hour. The resulting mixture was filtered, and the filtered residue was washed with 30 parts of water and 10 parts of methanol, and the resulting residue was dried at 60 ℃ under reduced pressure to obtain 2.6 parts of 6- (2-cyanoacetyl) -2-naphthoic acid (yield 75%).

6.0 parts of 1, 3-diiminoisoindoline (manufactured by Tokyo chemical industry Co., Ltd.) and 300 parts of N, N-dimethylformamide were mixed. To the resulting mixture was added 30 parts of 6- (2-cyanoacetyl) -2-naphthoic acid, and the mixture was stirred at 45 ℃ for 10 hours. The resulting mixture was filtered, and 100 parts of acetic acid was added to the residue, followed by stirring at 80 ℃ for 2 hours. The resulting mixture was filtered, and 300 parts of water was added to 9.8 parts of the residue, followed by stirring at 80 ℃ for 2 hours. The resulting mixture was filtered, and the filtered residue was washed with 300 parts of methanol to obtain a residue. To the washed residue, 15 parts of N, N-dimethylformamide was added, and the mixture was stirred at 80 ℃ for 2 hours. Cooled to 0 ℃ and stirred for 2 hours. The resulting mixture was filtered, washed with 60 parts of methanol, and the resulting residue was dried under reduced pressure at 60 ℃ to obtain 18 parts of a compound represented by formula (II-2) (yield 76%).

< identification of Compound II-2 >

(Mass analysis) ionization mode (ESI)^-：m/z＝[M-H]^-588

Accurate quality: 589

Synthesis example 6

The synthesis was carried out in the same manner as in synthesis example 1, except that 24 parts of β -oxo-2-quinolinepropanitrile in synthesis example 1 was changed to 24 parts of β -oxo-2-thiazolepropanitrile (synthesized according to the method described in WO 2011/016528). 14.4 parts of the compound represented by the formula (I-14) was obtained (yield 73%).

Synthesis example 7

Synthesis was performed in the same manner as in synthesis example 1, except that 24 parts of β -oxo-2-quinolinepropanitrile in synthesis example 1 was changed to 24 parts of β -oxo-2-pyrazinepropanitrile (synthesized according to the method described in WO 2011/016528). 12 parts of the compound represented by the formula (I-19) was obtained (yield 65%).

Resin Synthesis example 1

An appropriate amount of nitrogen was introduced into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and replaced with a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was placed therein and heated to 80 ℃ with stirring. Then, 38 parts of acrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] were added dropwise over 5 hours^2，6]Decane-8-yl acrylate and 3, 4-epoxytricyclo [5.2.1.0^2，6]A mixture of decane-9-yl acrylate (containing 1: 1 in terms of molar ratio) 289 parts, propylene glycol monomethyl ether acetate 125 parts. On the other hand, a solution prepared by dissolving 33 parts of 2, 2-azobis (2, 4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was held at 80 ℃ for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution containing 35.1% of a solid content and having a viscosity of 125 mPas as measured with a type B viscometer (23 ℃). The weight-average molecular weight Mw of the resulting copolymer was 9.2X 10³Dispersion degree 2.08, and acid value in terms of solid content 77mg-KOH/g. The resin B1 has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin in terms of polystyrene were measured by GPC under the following conditions.

The device comprises the following steps: HLC-8120GPC (manufactured by Tosoh corporation)

Column: TSK-GELG2000HXL

Column temperature: 40 deg.C

Solvent: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

Solid content concentration of the analysis sample: 0.001 to 0.01% by mass

Injection amount: 50 μ L

A detector: RI (Ri)

Calibration standard substance: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

The ratio (Mw/Mn) of the weight average molecular weight to the number average molecular weight in terms of polystyrene obtained above was defined as the degree of dispersion.

Example 1

(1) Coloring composition and preparation of coloring curable resin composition

The following components were mixed, and compound (I-1) and compound (II-1) were dispersed by a bead mill to obtain coloring composition 1. In the following components, BYK-LPN6919 (manufactured by BYK-Chemie. Japan) was used as a dispersant, and propylene glycol monomethyl ether acetate was used as a solvent (E).

The colored composition 1 was left to stand at 23 ℃ for 14 hours, and then the following components were mixed to obtain a colored curable resin composition 1. In the following components, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Chemicals, Inc.) was used as the polymerizable compound (C), N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF, Inc.) was used as the polymerization initiator (D), propylene glycol monomethyl ether acetate was used as the solvent (E), and polyether-modified Silicone oil (Toray Silicone SH 8400; manufactured by Toray Dow Corning, Inc.) was used as the leveling agent.

(2) Production of colored coating film

The colored curable resin composition was applied onto a 5cm square glass substrate (Eagle XG; manufactured by Corning) by spin coating so that the film thickness after post baking became 2 μm, and then pre-baked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the resultant was exposed to an exposure apparatus (TME-150 RSK; manufactured by Topcon, Ltd.) at 80mJ/cm in an atmospheric air atmosphere²The exposure amount (365nm basis) of (a) is used to irradiate the colored composition layer formed on the substrate with light. After irradiation with light, the film was baked in an oven at 230 ℃ for 30 minutes to obtain a colored coating film.

(3) Heat resistance test

The absorption of the obtained colored coating film was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). The obtained colored coating film was further heated in an oven at 230 ℃ for 120 minutes under an air atmosphere, and then the absorption was measured by a color measuring machine. The absorbance retention was determined from the absorbance change at the maximum absorption wavelength of the colored coating film before and after the test.

(4) Light resistance test

An ultraviolet cut filter (color OPTICAL GLASS L38; manufactured by HOYA, cut off light of 380nm or less) was placed on the obtained COLORED coating film, and xenon lamp light was irradiated for 48 hours with a lightfastness tester (SUNTEST CPS +; manufacturedby toyoyo seiki) and then the absorption was measured with a color measuring machine. The absorbance retention was determined from the absorbance change at the maximum absorption wavelength of the colored coating film before and after the test.

Examples 2 to 8 and comparative examples 1 to 4

Example 2 the procedure of example 1 was repeated, except that 45 parts of compound (I-2) was used in place of 45 parts of compound (I-1) as the colorant (A).

Example 3 the procedure of example 1 was repeated except that 45 parts of compound (I-3) and 5 parts of compound (II-2) were used instead of 45 parts of compound (I-1) and 5 parts of compound (II-1) as the colorant (A).

The procedure of examples 4 to 6 was carried out in the same manner as in example 1 except that 45 parts of compound (II-1) was used as the colorant (A) in example 4 in place of 5 parts of compound (II-1), 0.5 parts of compound (II-1) was used as the colorant (A) in example 5 in place of 5 parts of compound (II-1), and 0.1 parts of compound (II-1) was used as the colorant (A) in example 6 in place of 5 parts of compound (II-1).

The procedure of examples 7 and 8 was carried out in the same manner as in example 1 except that in example 7, 45 parts of compound (I-14) was used in place of 45 parts of compound (I-1) as colorant (A), and in example 8, 45 parts of compound (I-19) was used in place of 45 parts of compound (I-1) as colorant (A).

For comparative examples 1 to 4, 50 parts of compound (I-1) was used in place of 45 parts of compound (I-1) and 5 parts of compound (II-1) in comparative example 1 as colorant (A), in comparative example 2 wherein 50 parts of compound (I-2) was used in place of 45 parts of compound (I-1) and 5 parts of compound (II-1) as colorant (A), in comparative example 3 wherein 50 parts of compound (I-3) was used in place of 45 parts of compound (I-1) and 5 parts of compound (II-1) as colorant (A), the procedure of example 1 was repeated except that in comparative example 4, 50 parts of compound (II-1) was used instead of 45 parts of compound (I-1) and 5 parts of compound (II-1) as colorant (A).

The results of examples 2 to 8 and comparative examples 1 to 4 are shown in Table 15.

The stability of the dispersions (i.e., the coloring compositions) prepared in the examples and comparative examples was evaluated according to the following criteria. A means that the dispersion has high stability, and C means that the dispersion has low stability.

A: after leaving at 23 ℃ for 14 hours, the viscosity was almost unchanged, and the preparation of a colored coating film and the heat resistance and light resistance tests were carried out without any problem.

B: after leaving at 23 ℃ for 14 hours, the viscosity increased, but the preparation of a colored coating film and the heat resistance and light resistance tests were also carried out without any problem.

C: after left standing at 23 ℃ for 14 hours, the film became hard and a colored coating film could not be formed.

It is understood that in comparative examples 1 to 3, if the resulting dispersion is left standing at 23 ℃ for 14 hours, the dispersion becomes hard and the stability of the dispersion is low.

[ Table 15]

As shown in table 15, the color filter having excellent light resistance can be formed from the colored composition of the present invention. The coloring composition of the present invention also has good heat resistance. Further, it was found that the dispersion liquid of the coloring composition of the present invention is also excellent in stability.

Claims

1. A coloring composition comprising a compound represented by the formula (I) and a compound represented by the formula (II),

in the formula (I) and the formula (II),

A¹and A²Independently of each other, a heterocyclic group which may have a substituent,

D¹and D²Independently of one another, an optionally substituted aromatic hydrocarbon radical having at least 1-CO₂M，

R^a1And R^d1Independently represent a C1-40 hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom, and-CH contained in the hydrocarbon group₂And the heterocyclic group contains-CH which does not form a ring₂When is-CH₂Can be substituted as-O－、－CO－、－S(O)₂-or-NR²⁰－，

R^a2～R^a7And R^d2～R^d7Independently represent a C1-40 hydrocarbon group which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitro group or a-CO₂M or-S (O)₂OM-CH contained in the hydrocarbon group₂And the heterocyclic group contains-CH which does not form a ring₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰－，

R^a2And R^a3、R^a3And R^a4、R^a4And R^a5、R^d2And R^d3、R^d3And R^d4And R^d4And R^d5May form a ring which may have a substituent containing-CH which does not constitute a ring, together with the carbon atom to which each is bonded₂When is-CH₂May be substituted by-O-, -CO-, -S (O)₂-or-NR²⁰－，

M represents a hydrogen atom or an alkali metal atom,

R²⁰represents a hydrogen atom, an optionally substituted hydrocarbon group having 1 to 40 carbon atoms or an optionally substituted heterocyclic group,

in the presence of a plurality of R²⁰And M, which may be the same or different,

the wavy line means a line containing E-mer, Z-mer or a mixture thereof.

2. The coloring composition according to claim 1, wherein A is¹And A²Independently of each other, a condensed heterocyclic group which may have a substituent.

3. The coloring composition according to claim 1 or 2, wherein R^a1And R^d1Is a hydrogen atom, R^a6～R^a7And R^d6～R^d7Is cyano or nitro.

4. The coloring composition according to any one of claims 1 to 3, wherein A is¹And A²Same as R^a6And R^a7Are the same group.

5. The coloring composition according to any one of claims 1 to 4, wherein D is¹And D²Same as R^d6And R^d7Are the same group.

6. The coloring composition according to any one of claims 1 to 5, wherein the mass ratio of the compound represented by formula (I) to the compound represented by formula (II) is 1 to 1000.

7. The coloring composition according to any one of claims 1 to 6, further comprising a resin (B).

8. A colored curable resin composition comprising the colored composition according to any one of claims 1 to 7, a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

9. A color filter comprising the colored curable resin composition according to claim 8.

10. A display device comprising the color filter of claim 9.