TWI804665B - Colored composition, colored curable resin composition, color filter, and display device - Google Patents

Abstract

The present invention provides a colored composition capable of forming a color filter having excellent light resistance. A coloring composition comprising: a compound represented by formula (I) and a compound represented by formula (II).

[In formula (I) and formula (II), A ¹ and A ² independently represent a heterocyclic group that may have a substituent; D ¹ and D ² independently represent an aromatic hydrocarbon group that may have a substituent, and the aromatic The hydrocarbon group has at least one -CO ₂ M; R ^a1 and R ^d1 independently represent a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and the hydrocarbon group contained When -CH ₂ - and the heterocyclic group contains -CH ₂ - that does not constitute a ring, the -CH ₂ - may be substituted with -O-, -CO-, -S(O) ₂ -, or -NR ^20- ; R ^a2 to R ^a7 and R ^d2 to R ^d7 independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitrate -CO ₂ M or -S(O) ₂ OM, the -CH ₂ - contained in the hydrocarbon group and the -CH ₂ - when the heterocyclic group contains -CH ₂ - which does not constitute a ring can be substituted is -O-, -CO-, -S(O) ₂ -, or -NR ²⁰ -; R ^a2 and R ^a3 , R ^a3 and R a4 , R ^a4 and R ^a5 , ^{R d2 and} R ^d3 , R ^d3 and R ^d4 , and R ^d4 and R ^d5 may form a ring which may have a substituent together with the carbon atoms to which they are bonded, and when the ring contains -CH ₂ - which does not constitute a ring, the -CH ₂ - may be substituted with -O-, -CO-, -S(O) ₂ -, or -NR ²⁰ -; M represents a hydrogen atom or an alkali metal atom; R ²⁰ represents a hydrogen atom, a hydrocarbon group with 1 to 40 carbons that may have substituents, Or a heterocyclic group that may have a substituent; in the case of multiple R ²⁰ and M, these may be the same or different; the wavy line indicates the inclusion of E body, Z body or a mixture of these]

Description

Coloring composition, coloring curable resin composition, color filter Light sheet and display device

The present invention relates to a coloring composition containing isoindoline compound.

The colored curable resin composition is used in the production of 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 in order to obtain a desired color tone and the like. As a colorant, for example, an isoindoline compound is known (Patent Document 1).

[Prior art literature]

[Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2017-137490

An object of the present invention is to provide a colored composition capable of forming a color filter excellent in 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),

[In formula (I) and formula (II), A ¹ and A ² independently represent a heterocyclic group that may have a substituent; D ¹ and D ² independently represent an aromatic hydrocarbon group that may have a substituent, and the aromatic The hydrocarbon group has at least one -CO ₂ M; R ^a1 and R ^d1 independently represent a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and the hydrocarbon group contained When -CH ₂ - and the heterocyclic group contains -CH ₂ - that does not constitute a ring, the -CH ₂ - may be substituted with -O-, -CO-, -S(O) ₂ -, or -NR ^20- ; R ^a2 ~ R ^a7 and R ^d2 ~ R ^d7 independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitrate -CO ₂ M or -S(O) ₂ OM, the -CH ₂ - contained in the hydrocarbon group and the -CH ₂ - when the heterocyclic group contains -CH ₂ - which does not constitute a ring can be substituted is -O-, -CO-, -S(O) ₂ -, or -NR ²⁰ -; R ^a2 and R ^a3 , R ^a3 and R a4 , R ^a4 and R ^a5 , ^{R d2 and} R ^d3 , R ^d3 and R ^d4 , and R ^d4 and R ^d5 may form a ring which may have a substituent together with the carbon atoms to which they are bonded, and when the ring contains -CH ₂ - which does not constitute a ring, the -CH ₂ - may be substituted with -O-, -CO-, -S(O) ₂ -, or -NR ²⁰ -; M represents a hydrogen atom or an alkali metal atom; R ²⁰ represents a hydrogen atom, a hydrocarbon group with 1 to 40 carbons that may have substituents, Or a heterocyclic group that may have a substituent; in the case of multiple R ²⁰ and M, these may be the same or different; the wavy line indicates the inclusion of E body, Z body or a mixture of these].

[2] The coloring composition as described in [1], wherein A ¹ and A ² are independently condensed heterocyclic groups which may have substituents.

[3] The coloring composition as described in [1] or [2], wherein R ^a1 and R ^d1 are hydrogen atoms, and R ^a6 to R ^a7 and R ^d6 to R ^d7 are cyano or nitro groups.

[4] The coloring composition according to any one of [1] to [3], wherein ^A1 and ^A2 are the same, and R ^a6 and R ^a7 are the same group.

[5] The coloring composition according to any one of [1] to [4], wherein D ¹ and D ² are the same, and R ^d6 and R ^d7 are the same group.

[6] The coloring composition according to any one of [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 [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 Solvent (E).

[9] A color filter formed of the colored curable resin composition as described in [8].

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

According to the colored composition of the present invention, a color filter excellent in light resistance can be formed.

<Coloring composition>

The coloring composition of the present invention includes 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 a colorant (A). The coloring composition of the present invention may contain one kind or two or more kinds of the compound (I) and the compound (II), respectively.

Moreover, it is preferable that the coloring composition of this invention further contains resin (it describes also as resin (B) hereafter).

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

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

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

In this specification, unless otherwise specified, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>

The coloring agent (A) contains compound (I) and compound (II). The compound (I) and the compound (II) also include their tautomers or their salts.

[In formula (I) and formula (II), A ¹ and A ² independently represent a heterocyclic group that may have a substituent; D ¹ and D ² independently represent an aromatic hydrocarbon group that may have a substituent, and the aromatic The hydrocarbon group has at least one -CO ₂ M; R ^a1 and R ^d1 independently represent a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and the hydrocarbon group contained When -CH ₂ - and the heterocyclic group contains -CH ₂ - that does not constitute a ring, the -CH ₂ - may be substituted with -O-, -CO-, -S(O) ₂ -, or -NR ²⁰ -; wherein -CO ₂ H and -S(O) ₂ OH are not formed by substituting -CH ₂ -; R ^a2 ~ R ^a7 and R ^d2 ~ R ^d7 independently represent carbons that may have substituents A hydrocarbon group with a number of 1 to 40, a heterocyclic group that may have a substituent, a hydrogen atom, a halogen atom, a cyano group, a nitro group, -CO ₂ M or -S(O) ₂ OM, the -CH ₂ contained in the hydrocarbon group - and the heterocyclic group contains -CH ₂ - which does not constitute a ring, the -CH ₂ - may be substituted with -O-, -CO-, -S(O) ₂ -, or -NR ²⁰ -; wherein , did not form -CO ₂ H and -S(O) ₂ OH by substituting -CH ₂ -; R ^a2 and R ^a3 , R ^a3 and R a4 , R ^a4 and R ^a5 , ^{R d2 and} R ^d3 , R ^d3 and R ^d4 , and R ^d4 and R ^d5 may form a ring which may have a substituent together with the carbon atoms to which they are bonded. When the ring contains -CH ₂ - which does not constitute a ring, the -CH ₂ - may be Substituted by -O-, -CO-, -S(O) ₂ -, or -NR ²⁰ -; wherein -CO ₂ H and -S(O) ₂ OH are not formed by substituting -CH ₂ -; M represents a hydrogen atom or an alkali metal atom; ^R20 represents a hydrogen atom, a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, or a heterocyclic group that may have a substituent; when there are multiple ^R20 and M, These may be the same or different; the wavy line indicates the inclusion of E body, Z body or a mixture of these]

R ^a1 ~R ^a7 , R ^d1 ~R ^d7 and R ²⁰ represent aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon groups can be saturated or unsaturated, and can be chain or cyclic (alicyclic).

The saturated or unsaturated chain hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl Straight-chain alkyl groups such as base, nonyl, decyl, undecyl, dodecyl, heptadecyl, octadecyl and eicosyl; isopropyl, (2-methyl)propyl, isobutyl Base, second butyl, third butyl, (2-ethyl) butyl, isopentyl, neopentyl, third pentyl, (1-methyl) pentyl, (2-methyl) pentyl Base, (1-ethyl)pentyl, (3-ethyl)pentyl, isohexyl, (5-methyl)hexyl, (2-ethyl)hexyl, and (3-ethyl)heptyl and other branches Chain alkyl, etc.; vinyl, 1-propenyl, 2-propenyl (allyl), isopropenyl, (1-methyl) vinyl, 2-butenyl, 3-butenyl, 1 , 3-butadienyl, (1-(2-propenyl))ethenyl, (1,2-dimethyl)propenyl and alkenyl such as 2-pentenyl, etc.

The carbon number of the saturated or unsaturated chain hydrocarbon group represented by R ^a1 ~R ^a7 , R ^d1 ~R ^d7 and R ²⁰ is preferably 1~30, more preferably 1~20, more preferably 1~15, and more preferably 1-10 is preferable, 1-8 is more preferable, and 1-5 is particularly preferable.

The saturated or unsaturated alicyclic hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ include cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, Cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-di Methylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-di Methylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4,4-di Methylcyclohexyl, cyclooctyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl, 4 -cycloalkyl such as pentylcyclohexyl, 4-octylcyclohexyl, 4-cyclohexylcyclohexyl; cyclohexenyl (such as cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, Cycloalkenyl groups such as cyclooctenyl; polycyclic alicyclic hydrocarbon groups such as norbornyl, adamantyl, and bicyclo[2.2.2]octane, etc.

The carbon number of the alicyclic hydrocarbon group represented by R ^a1 ~R ^a7 , R ^d1 ~R ^d7 and R ²⁰ is preferably 3~30, more preferably 3~20, more preferably 4~20, even more preferably 4 ~15, preferably 5~15, and especially 5~10.

The saturated or unsaturated hydrocarbon groups represented by R ^a1 ~ R ^a7 , R ^d1 ~ R ^d7 and R ²⁰ may be a group formed by combining the listed chain hydrocarbon groups and alicyclic hydrocarbon groups, for example: cyclopropyl Methyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, etc. are bonded with more than one alicyclic Alkyl of hydrocarbyl. The carbon number is preferably 4-30, more preferably 4-20, and still more preferably 4-15.

As the aromatic hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ , the group having a bond directly on the aromatic hydrocarbon ring includes: phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl phenyl, 3,5-dimethylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, o-tert-butylphenyl, m-tert-butyl Phenyl, p-tert-butylphenyl, mesityl, 2,6-bis(2-propyl)phenyl, 2,4,6-trimethylphenyl, 1-naphthyl, 2- Naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, 5,6,7,8-tetrahydro-2-naphthyl, fluorenyl, phenanthrenyl and anthracenyl, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably from 6 to 30, more preferably from 6 to 20, and still more preferably from 6 to 15.

The aromatic hydrocarbon group represented by R ^a1 ~ R ^a7 , R ^d1 ~ R ^d7 and R ²⁰ may be a combination of at least one of the listed chain hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group with the above listed aromatic hydrocarbon group. Groups composed of hydrocarbon groups, such as: benzyl, 2-methylbenzyl, 3-methylbenzyl, 4-methylbenzyl, 3,4-methylbenzyl, phenylethyl, benzene Aralkyl groups such as propyl, 1-methyl-1-phenylethyl; Aralkyl groups such as phenyl ethyl (phenyl vinyl) and other aryl alkenyl groups; Aryl groups such as phenyl ethynyl phenyl alkynyl; biphenyl, terphenyl and other phenyl groups bonded to more than one phenyl group; cyclohexylmethylphenyl, benzylphenyl, (dimethyl(phenyl)methyl)phenyl etc., the carbon number is preferably 7-30, more preferably 7-20, and still more preferably 7-15.

The hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ may have a monovalent substituent or a divalent substituent.

Examples of the monovalent substituent include: -CO ₂ M; -S(O) ₂ OM; alkylthio groups having 1 to 10 carbon atoms such as methylthio, ethylthio, propylthio, and butylthio; fluorine Atom, chlorine atom, bromine atom and iodine atom and other halogen atoms; nitro group; cyano group; trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl , perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, perfluorocyclohexyl, perfluorophenyl and other hydrogen atoms are replaced by fluorine atoms with carbon number 1~20 , preferably a hydrocarbon group with 1 to 10 carbons; *-CO-SH; *-CO-S-CH ₃ , *-CO-S-CH ₂ CH ₃ , *-CO-S-CH ₂ -CH ₂ - CH ₃ , *-CO-S-CH ₂ -CH ₂ -CH ₂ -CH ₃ etc. and a carbonyl group bonded to a sulfur atom bonded to an alkyl group (the carbon number of the alkyl group is 1 to 10); *-CO -SC ₆ H ₅ etc. and a carbonyl group bonded to a sulfur atom bonded to an aryl group (the carbon number of the aryl group is 6~20); *-OP(O)(OR ³⁰ ) ₂ ; *-Si(R ³⁰ )(R ³¹ )(R ³² ) and the like. In the above, * represents a bond.

In the formula, M represents the same meaning as described above, and R ³⁰ , R ³¹ and R ³² independently represent a hydrocarbon group with 1 to 35 carbon atoms that may have a substituent, or a heterocyclic group that may have a substituent, and the -CH ₂ - contained in the hydrocarbon group and -CH ₂ - when the heterocyclic group contains -CH ₂ - that does not constitute a ring may be substituted with -O-, -CO-, -S(O) ₂ - , or -NR ²⁰ -. Wherein, -CO ₂ H and -S(O) ₂ OH are not formed by substituting -CH ₂ -. R ²⁰ represents the same meaning as described above. Specific examples and preferred ranges of R ³⁰ , R ³¹ , and R ³² are the same as R ^a1 except that examples with carbon numbers of 36 or more are not included.

Examples of the divalent substituent include: thiocarbonyl, imino, imino substituted with an alkyl group having 1 to 20 carbons (preferably 1 to 10 carbons), and an imino group substituted with an alkyl group having 6 to 20 carbons. Aryl imino groups, etc. Examples of imino groups substituted with alkyl groups include CH ₃ -N=, CH ₃ -CH ₂ -N=, CH ₃ -(CH ₂ ) ₂ -N=, CH ₃ -(CH ₂ ) ₃ -N= wait. Examples of the imino group substituted with an aryl group include C ₆ H ₅ -N= and the like.

As the substituents of the hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ , preferably independently of each other: a halogen atom; a nitro group; a cyano group; all hydrogen atoms are substituted with fluorine atoms A hydrocarbon group with a carbon number of 1 to 20; a thiocarbonyl group, etc. In addition, the substituents of the hydrocarbon groups represented by R ^a1 ~ R ^a7 , R ^d1 ~ R ^d7 and R ²⁰ are more preferably: fluorine atom, chlorine atom, bromine atom; nitro group; cyano group; all hydrogen atoms are substituted with fluorine A hydrocarbon group with 1 to 10 carbon atoms; a thiocarbonyl group, etc., more preferably a fluorine atom; a hydrocarbon group with 1 to 5 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms, etc.

Compound (I) and compound (II) may have -CH ₂ - contained in the hydrocarbon group represented by R ^a1 ~ R ^a7 , R ^d1 ~ R ^d7 is replaced by -O-, -CO-, -S( A group formed by O) ₂ -, or -NR ²⁰ - (hereinafter, sometimes referred to as "group (Z1)"). Wherein, -CO ₂ H and -S(O) ₂ OH are not formed by substituting -CH ₂ -.

Examples of the group (Z1) include: methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, second butoxy, third butoxy, pentyl Oxygen, hexyloxy, (2-ethyl)hexyloxy, (2-trifluoromethyl)hexyloxy, heptyloxy, octyloxy, nonyloxy, phenyloxy, meta Oxygen groups such as tolyloxy and 3,4-xylyloxy are bonded to a hydrocarbon group with a carbon number of 1 to 20, more preferably a carbon number of 1 to 10 (alkoxy and aryloxy); Oxycyclopropyl; Formyl; Acetyl, Propionyl, Butyl, Tertiary Butyl, Pentyl, Hexyl, (2-Ethyl)hexyl, Heptyl, Octyl, Nonyl Alkanoyl groups with 2 to 22 carbon atoms, preferably 2 to 12 carbon atoms, such as radicals and benzoyl groups; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl , the third butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, (2-ethyl) hexyloxycarbonyl, heptyloxycarbonyl and octyloxycarbonyl, nonyloxycarbonyl, phenyl Oxycarbonyl, o-tolyloxycarbonyl and other oxycarbonyl groups bonded with a carbon number of 1 to 20, preferably a carbon number of 1 to 10; amine group; N-methylamino group, N,N-di Methylamino, N-ethylamino, N,N-diethylamino, N-propylamino, N,N-dipropylamino, N-isopropylamino, N,N -Diisopropylamino, N-butylamino, N,N-dibutylamino, N-isobutylamino, N,N-diisobutylamino, N-second butyl Amine, N,N-di-2-butylamino, N-tert-butylamino, N,N-di-tert-butylamino, N-pentylamino, N,N-dipentyl Amino, N-(1-ethylpropyl)amino, N,N-di(1-ethylpropyl)amino, N-hexylamino, N,N-dihexylamino, N-( 2-Ethyl)hexylamino, N,N-di(2-ethyl)hexylamino, N-heptylamino, N,N-diheptylamino, N-octylamino, N, N-dioctylamino, N-nonylamino, N,N-dinonylamino, N-phenylamino, N,N-diphenylamino, N,N-ethylmethyl Amino group, N,N-propylmethylamino group, N,N-isopropylmethylamino group, N,N-butylmethylamino group, N,N-tert-butylmethylamino group and N,N- Amino groups having one or two hydrocarbon groups with 1 to 20 carbons, preferably 1 to 10 carbons, such as phenylmethylamino; sulfamoyl; N-methylsulfamoyl, N,N- Dimethylsulfamoyl, N-ethylsulfamoyl, N,N-diethylsulfamoyl, N-propylsulfamoyl, N,N-dipropylsulfamoyl, N-isopropylsulfamoyl, N,N-diisopropylsulfamoyl, N-butylsulfamoyl, N,N-dibutylsulfamoyl, N-isobutylamine Sulfonyl, N, N-diisobutyl sulfamoyl, N-second butyl sulfamoyl, N, N-di-second butyl sulfamoyl, N-tert-butyl sulfamoyl Acyl, N,N-di-tert-butylsulfamoyl, N-pentylsulfamoyl, N,N-dipentylsulfamoyl, N-(1-ethylpropyl)sulfamoyl Acyl, N,N-bis(1-ethylpropyl)sulfamoyl, N-hexylsulfamoyl, N,N-dihexylsulfamoyl, N-(2-ethyl)hexylamine Sulfonyl, N,N-di(2-ethyl)hexylsulfamoyl, N-heptylsulfamoyl, N,N-diheptylsulfamoyl, N-octylsulfamoyl , N,N-dioctylsulfamoyl, N,N-octylmethylsulfamoyl, N-nonylsulfamoyl, N,N-dinonylsulfamoyl, N-benzene Aminosulfamoyl, N,N-diphenylsulfamoyl, N,N-ethylmethylsulfamoyl, N,N-propylmethylsulfamoyl, N,N-isopropyl One or two Carbon number 1-20, preferably sulfamoyl group of hydrocarbon group with carbon number 1-10; N-formyl amine group; N-acetyl amine group, N-propionyl amine group, N-butyryl amine group Base, N-2,2-Dimethylpropionylamino, N-pentylamino, N-hexylamino, N-(2-ethyl)hexylamino, N-heptyl N-octylamine, N-octylamine, N-nonylamine, N-decylamine, N-undecylamine, N-dodecylamine, N-twenty-one N-alkanylamino groups with 1 to 22 carbon atoms, preferably N-alkanylamino groups with 1 to 12 carbon atoms, such as acylamino groups and N-benzoylamino groups; hydroxyl groups; formyloxy groups, acetyloxy groups, Propyloxy, Butyloxy, 2,2-Dimethylpropionyloxy, Pentyloxy, Hexyloxy, (2-Ethyl)hexyloxy, Heptyloxy Oxygen, octyloxy, nonyloxy and benzoyloxy, such as alkyloxy with 1 to 20 carbons, preferably alkyloxy with 1 to 10 carbons; methylsulfonyl, ethylsulfonyl Acyl, Propylsulfonyl, Butylsulfonyl, Pentylsulfonyl, Hexylsulfonyl, (2-Ethyl)hexylsulfonyl, Heptylsulfonyl, Octylsulfonyl, Nonyl Sulfonyl, decylsulfonyl, phenylsulfonyl, and p-tolylsulfonyl, etc., substituted with a carbon number of 1 to 20, preferably a carbon number of 1 to 10 hydrocarbon groups; carbamoyl N-methylaminoformyl, N,N-dimethylaminoformyl, N-ethylaminoformyl, N,N-diethylaminoformyl, N-propylaminoformyl Acyl, N,N-dipropylaminoformyl, N-isopropylaminoformyl, N,N-diisopropylaminoformyl, N-butylaminoformyl, N,N -Dibutylaminoformyl, N-isobutylaminoformyl, N,N-diisobutylaminoformyl, N-second butylaminoformyl, N,N-disecond Butylaminoformyl, N-tert-butylaminoformyl, N,N-di-tert-butylaminoformyl, N-pentylaminoformyl, N,N-dipentylaminoformyl Acyl, N-(1-ethylpropyl)aminoformyl, N,N-bis(1-ethylpropyl)aminoformyl, N-hexylaminoformyl, N,N-dihexyl Aminoformyl, N-(2-ethyl)hexylaminoformyl, N,N-di(2-ethyl)hexylaminoformyl, N-heptylaminoformyl, N,N-di Heptylaminoformyl, N-octylaminoformyl, N,N-dioctylaminoformyl, N-nonylaminoformyl, N,N-dinonylaminoformyl, N -Phenylaminoformyl, N,N-Diphenylaminoformyl, N,N-Ethylmethylaminoformyl, N,N-Propylmethylaminoformyl, N,N- Isopropylmethylaminoformyl, N,N-butylmethylaminoformyl, N,N-tert-butylmethylaminoformyl and N,N-phenylmethylaminoformyl have one or Two carbamate groups with 1-20 carbons, preferably hydrocarbon groups with 1-10 carbons; *-COCOR ²⁰ ; *-OCON(R ²⁰ ) ₂ ; *-N(R ²⁰ )COOR ²⁰ etc. In the above, * represents a bond.

In the formula, R ²⁰ may be the same or different, and represents the same meaning as described above.

The heterocyclic groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 , R ²⁰ , A ¹ and A ² may be monocyclic or polycyclic. As a hetero atom, a nitrogen atom, an oxygen atom, a sulfur atom, etc. are mentioned.

The carbon number of the heterocyclic group represented by R ^a1 ~R ^a7 , R ^d1 ~R ^d7 , R ²⁰ , A ¹ and A ² is preferably 2~30, more preferably 3~22, still more preferably 3~20, Still more preferably, it is 3-18, still more preferably, it is 3-15, and it is especially preferable that it is 3-14.

As a heterocyclic group containing only a nitrogen atom as a heteroatom, there may be mentioned monocyclic saturated heterocyclic groups such as aziridine, azetidine, pyrrolidine, piperidine, and piperazine; pyrrole, 2,5- 5-membered ring system unsaturated Heterocyclic group; pyridine, pyridazine, pyrimidine, pyrimidine such as 6-methylpyrimidine, pyrazine, 1,2,4-triazine, 1,3,5-triazine and other 6-membered unsaturated heterocyclic group; Indazole, indoline, isoindoline, indole, indoxazine, benzimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro(3-methyl)quinoxaline, 3-Methylquinoxaline and other quinoxalines, quinazoline, cinnoline, phthalazine, naphthyridine, purine, pteridine, benzopyrazole, benzopiperidine and other condensed bicyclic heterocyclic groups; carbazole , acridine, phenazine and other condensed tricyclic heterocyclic groups; heterocyclic groups represented by the following formulas, etc. In the following formulae, * represents a bonding bond.

[Chem 3]

Examples of the heterocyclic group containing only an oxygen atom as a heteroatom include: oxirane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, Monocyclic saturated heterocyclic groups such as 1-cyclopentyldioxolane; 1,4-dioxaspiro[4.5]decane, 1,4-dioxaspiro[4.5]nonane, etc. Bicyclic saturated heterocyclic group; α-acetone, β-propiolactone, γ-butyrolactone, δ-valerolactone and other lactone heterocyclic groups; furan, 2,3-dimethylfuran, 2,5-Dimethylhydrofuran and other furan and other 5-membered unsaturated heterocyclic rings; 3,4-dihydro-2H-pyran, 3,6-dihydro-2H-pyran and other 6-membered ring systems Unsaturated heterocyclic group; benzofuran, isobenzofuran, 4-methylbenzopyran and other benzopyrans, benzodioxole, chromane, isochromatic Condensed bicyclic heterocyclic groups such as alkanes; condensed tricyclic heterocyclic groups such as xanthene and dibenzofuran, etc.

Examples of the heterocyclic group containing only a sulfur atom as a heteroatom include: 5-membered saturated heterocyclic groups such as dithiolane; thiane, 1,3-dithiane, 2-methyl-1, 3-dithiane and other 6-membered ring saturated heterocyclic groups; thiophene, 3-methylthiophene, 2-carboxythiophene, thiophene-1-oxide, thiophene-1,1-dioxide and other thiophenes, 4H-sulfur 5-membered ring system unsaturated heterocyclic groups such as pyran; condensed bicyclic heterocyclic groups such as benzothiophene, benzothiophene oxide, benzotetrahydrothiopyran, and benzothiophene dioxide; thianthracene , dibenzothiophene and other condensed tricyclic heterocyclic groups, etc.

As a heterocyclic group containing a nitrogen atom and an oxygen atom as a heteroatom, it can be listed For example: morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, 2-methyl-2-piperidone and other monocyclic saturated heterocyclic groups; oxazole, Oxazoles such as 4-methyloxazole, isoxazole, 2-methylisoxazole, 3-methylisoxazole and other isoxazoles, 1,2,4-oxadiazole and other monocyclic unsaturated hetero Cyclic groups; condensed bicyclic heterocyclic groups such as benzoxazole, benzisoxazole, and benzoxazine; condensed tricyclic heterocyclic groups such as phenoxazine, etc.

Examples of the heterocyclic group containing a nitrogen atom and a sulfur atom as a heteroatom include monocyclic heterocyclic groups such as thiazoles such as thiazole, 3-methylthiazole, and 2,4-dimethylthiazole, and isothiazole; Condensed bicyclic heterocyclic groups such as thiazole, benzisothiazole, and benzothiadiazole; condensed tricyclic heterocyclic groups such as phenthiazine, etc.

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 a heteroatom, and a heterocyclic group containing a nitrogen atom and a sulfur atom as a heteroatom. Atom heterocyclyl.

The heterocyclic group represented by R ^a1 ~ R ^a7 , R ^d1 ~ R ^d7 and R ²⁰ can be a group formed by combining the listed heterocyclic group and hydrocarbon group, for example, tetrahydrofuranylmethyl, methyltetrahydrofuranyl wait.

In addition, the bonding site of the heterocyclic group is a part from which any hydrogen atom contained in each ring is removed.

The heterocyclic groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 , R ²⁰ , A ¹ and A ² may have substituents. Examples of such substituents include the same monovalent substituents described as substituents that the hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 , and R ²⁰ may have. In addition, when the heterocyclic group contains a nitrogen atom as its constituent element, the hydrocarbon group listed above may be bonded to the nitrogen atom as a substituent.

The hydrocarbon group or heterocyclic group may have one or two or more substituents, and the two or more substituents may be the same or different independently of each other.

When the heterocyclic ring represented by R ^a1 ~ R ^a7 , R ^d1 ~ R ^d7 and R ²⁰ contains -CH ₂ - which does not constitute a ring, the -CH ₂ - can be passed through -O-, -CO-, -S( O) ₂ -or -NR ²⁰ -substituted. Wherein, -CO ₂ H and -S(O) ₂ OH are not formed by substituting -CH ₂ -. When -CH ₂ - is substituted with -O-, etc., the heterocyclic groups represented by R ^a1 to R ^a7 and R ^d1 to R ^d7 may have the group (Z1).

When R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^d2 and R ^d3 , R ^d3 and R ^d4 , or R ^d4 and R ^d5 are bonded to form a ring, the ring may be A hydrocarbon ring may also be a heterocycle. As a hydrocarbon ring, an aliphatic hydrocarbon ring, an aromatic hydrocarbon ring, etc. are mentioned.

Examples of the aliphatic hydrocarbon ring include cycloolefin rings such as cyclohexene rings, cycloheptene rings, and cyclooctene rings; norbornene, bicyclo[2.2.2]octene, and the like. The carbon number of the aliphatic hydrocarbon ring is, for example, 3-30, preferably 3-20, more preferably 4-20, still more preferably 4-15, still more preferably 5-15, particularly preferably 5-10.

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

In addition, when R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^d2 and R ^d3 , R ^d3 and R ^d4 , or R ^d4 and R ^d5 are bonded to form a heterocycle, the The heterocyclic ring may form the same ring as the heterocyclic ring in the heterocyclic group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 , R ²⁰ , A ¹ and A ² .

When R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^d2 and R ^d3 , R ^d3 and R ^d4 , or R ^d4 and R ^d5 are bonded to form a heterocycle, the heterocycle Together with the benzene rings to which R ^a2 to R ^a5 and R ^d2 to R ^d5 are bonded, a ring structure of more than two rings is formed. Examples of the ring structure having two or more rings include heterocyclic rings having a structure of the following formula. The benzene ring in the following formula corresponds to the benzene ring in the isoindoline structure of compound (I) or compound (II).

When R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^d2 and R ^d3 , R ^d3 and R ^d4 , or R ^d4 and R ^d5 are bonded to form a ring, the ring may have Substituents. Examples of such substituents include the same monovalent substituents described as substituents that the hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 , and R ²⁰ may have.

The ring may have one or two or more substituents, and the two or more substituents may be the same or different independently of each other.

The ring formed by bonding R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^d2 and R ^d3 , R ^d3 and R ^d4 , or R ^d4 and R ^d5 may have the group (Z1) .

Examples of the halogen atom represented by R ^a2 to R ^a7 and R ^d2 to R ^d7 include: fluorine atom, chlorine atom, bromine atom and iodine atom, preferably fluorine atom, chlorine atom, bromine atom, more preferably fluorine atom , Chlorine atom.

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

When multiple R ²⁰ and M exist in compound (I) or compound (II), these may be the same or different.

The aromatic hydrocarbon groups represented by ^D1 and ^D2 are preferably aromatic hydrocarbon groups having 6 to 12 carbon atoms. As the aromatic hydrocarbon group, the same ones as those exemplified in the aromatic hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ can be exemplified, and phenyl or naphthyl is preferable.

The aromatic hydrocarbon groups represented by D ¹ and D ² have at least one —CO ₂ M. The aromatic hydrocarbon groups represented by D ¹ and D ² have -CO ₂ M, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1.

When the aromatic hydrocarbon groups represented by ^D1 and ^D2 have one -CO ₂ M, the bonding position of the -CO ₂ M is not particularly limited. For example, when the aromatic hydrocarbon group is naphthyl, it can be It is a structure of the following formula (Da) in which the bonding bonds of ^D1 and ^D2 are on the same side of the six-membered ring, or it may be the structure of the following formula in which the bonding bonds of D1 and D2 are on the side of the six-membered ring different from those of ^D1 and ^D2 (Db) structure. In the following formulae, * represents a bonding bond.

The aromatic hydrocarbon groups represented by D ¹ and D ² may have substituents other than the above-mentioned -CO ₂ M, and examples thereof include substituents that the hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 , and R ²⁰ may have. The monovalent substituent described as the group is obtained by removing -CO ₂ M. The number of substituents other than -CO ₂ M that the aromatic hydrocarbon group has is preferably 0-6, more preferably 0-3, and still more preferably 0.

When the aromatic hydrocarbon groups represented by D ¹ and D ² have two or more substituents other than —CO ₂ M, these may be the same or different independently of each other.

In addition, the number of substituents other than _-CO2M and _-CO2M which the aromatic hydrocarbon group represented by ^D1 and ^D2 has represents the number for each aromatic hydrocarbon group.

As compound (I), R ^a1 to R ^a7 , A ¹ to A ² and M are preferably as described below.

R ^a1 is preferably a hydrogen atom.

R ^a2 to R ^a5 are independently preferably selected from a hydrogen atom; a butyl group, a trifluoromethyl group, and a saturated chain hydrocarbon group having 1 to 10 carbon atoms that may have a substituent (preferably a substituent Alkyl); methoxy, butoxy and other alkoxy groups with 1 to 10 carbons; acetyl and other alkyl groups with 2 to 6 carbons; 3,4-xylyloxy, α, α, Aryloxy groups with 6 to 10 carbon atoms that may have substituents such as α-trifluorotoluyloxy (preferably phenyloxy groups that may have substituents); halogen atoms such as fluorine atoms and chlorine atoms; A nitro group; a cyano group; an amino group; a hydroxyl group; a formyl group; a sulfamoyl group; a carboxyl group; One of them; more preferably selected from hydrogen atoms; one of chlorine atoms.

In the case where R ^a2 and R ^a3 , R ^a3 and R ^a4 , or R ^a4 and R ^a5 are bonded to form a ring together with the carbon atoms to which they are bonded, it is preferably an aromatic hydrocarbon with 6 to 10 carbon atoms such as benzene ring, more preferably naphthalene together with the benzene ring in the isoindoline structure.

R ^a2 to R ^a5 preferably do not form a ring.

R ^a6 and R ^a7 are preferably one selected from the group consisting of a hydrogen atom, a cyano group, and a nitro group, more preferably one selected from the group consisting of a cyano group and a nitro group, More preferably, it is a cyano group. In this case, R ^a6 and R ^a7 are preferably the same group.

A ¹ and A ² are preferably a condensed bicyclic heterocyclic group which may have a substituent, a condensed tricyclic heterocyclic group which may have a substituent, or a condensed heterocyclic group which may have a substituent, and more preferably include A condensed heterocyclic group having a nitrogen atom as a heteroatom (the condensed heterocyclic group may have a substituent), further preferably a condensed bicyclic heterocyclic group containing a nitrogen atom as a heteroatom (the condensed bicyclic heterocyclic group may have substituent), and more preferably quinolinyl which may have a substituent, indolyl which may have a substituent, or benzothiazolyl which may have a substituent. In addition, ^A1 and ^A2 preferably do not have a substituent. ^A1 and ^A2 are preferably the same. When ^A1 and ^A2 are condensed heterocyclic groups formed by heterocyclic rings and hydrocarbon rings such as aromatic hydrocarbons, it is preferable to have a structure in which the bond is located on the side of the heterocyclic ring (for example, ^A1 and ^A2 are quinoline In the case of a group, it is a structure represented by the following formula).

In the case where M exists in compound (I), M is preferably a hydrogen atom.

As a specific example of the compound (I), for example, in the compound represented by the formula (Ia), the combination of R ^a1 , R ^a6 to R ^a7 , A ¹ to A ² and B ¹ B ² has Table 1 to Table 1. Compound (I-1) to compound (I-966) having the substituent shown in any one of 11.

As compound (I), preferably compound (I-1) ~ compound (I-460), more preferably compound (I-1) ~ compound (I-46), and further preferably 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), compound (I-46).

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

A ¹ to A ² represent heterocyclic groups represented by formula (AA1) to formula (AA46).

B ¹ B ² represents any partial structure represented by formula (BB1) to formula (BB21).

In addition, in the formula (AA1) to the formula (AA46) and the formula (BB1) to the formula (BB21), * and B ¹ B ² respectively mean a bond.

[chemical 9]

As the compound (II), it is preferable that R ^d1 to R ^d7 , D ¹ to D ² and M are as described below.

R ^d1 is preferably a hydrogen atom.

^Rd2 to ^Rd5 are independently preferably selected from a hydrogen atom; a saturated chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent such as a butyl group or a trifluoromethyl group (preferably a substituent Alkyl); methoxy, butoxy and other alkoxy groups with 1 to 10 carbons; acetyl and other alkyl groups with 2 to 6 carbons; 3,4-xylyloxy, α, α, Aryloxy groups with 6 to 10 carbon atoms that may have substituents such as α-trifluorotoluyloxy (preferably phenyloxy groups that may have substituents); halogen atoms such as fluorine atoms and chlorine atoms; A nitro group; a cyano group; an amino group; a hydroxyl group; a formyl group; a sulfamoyl group; a carboxyl group; One of them; more preferably selected from hydrogen atoms; one of chlorine atoms.

When ^Rd2 and ^Rd3 , ^Rd3 and ^Rd4 , or ^Rd4 and ^Rd5 are bonded to form a ring together with the carbon atoms to which they are bonded, it is preferably an aromatic hydrocarbon with 6 to 10 carbon atoms such as benzene ring, more preferably naphthalene together with the benzene ring in the isoindoline structure.

R ^d2 to R ^d5 preferably do not form a ring.

^Rd6 and ^Rd7 are preferably one selected from the group consisting of a hydrogen atom, a cyano group, and a nitro group, more preferably one selected from the group consisting of a cyano group and a nitro group, More preferably, it is a cyano group. In this case, R ^d6 and R ^d7 are preferably the same group.

D ¹ and D ² are preferably aromatic hydrocarbon groups with 6 to 12 carbons having at least one -CO ₂ M and may have substituents other than -CO ₂ M, more preferably having one -CO ₂ M and may have A phenyl group having a substituent other than -CO ₂ M or a naphthyl group which may have a substituent other than -CO ₂ M. In addition, D ¹ and D ² preferably do not have a substituent other than -CO ₂ M. D ¹ and D ² are preferably the same.

In the case where M exists in compound (II), M is preferably a hydrogen atom.

As a specific example of the compound (II), for example, in the compound represented by the formula (IIa), the combinations of R ^d1 , R ^d6 to R ^d7 , D ¹ to D ² and B ¹ B ² have Table 12 to Table 12. Compound (II-1) to compound (II-147) having the substituent shown in any one of 14.

As compound (II), preferably compound (II-1) ~ compound (II-70), more preferably compound (II-1) ~ compound (II-35), and further preferably compound (II-1) ~ Compound (II-14).

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

D ¹ to D ² represent aromatic hydrocarbon groups represented by formula (DD1) to formula (DD7).

B ¹ B ² represents any partial structure represented by the formula (BB1) to formula (BB21).

In addition, in formula (DD1) to formula (DD7), * means a bond.

[Table 12]

[Table 13]

Hereinafter, the production methods of compound (I) and compound (II) will be described. Furthermore, in the following, a compound in which R ^a1 or R ^d1 is a hydrogen atom in compound (I) or compound (II) is described as "compound (1-H)", and R in compound (I) or compound (II) is The compound in which ^a1 or ^Rd1 is other than a hydrogen atom is described as "compound (1-R)".

The compound (1-H) can be produced by combining a compound represented by formula (pt1) (hereinafter, sometimes referred to as a phthalonitrile compound) and a compound represented by formula (pt2) (hereinafter , there is a case called an alkoxide compound) after the reaction, the compound represented by formula (pt3) (hereinafter, there is a case called compound (pt3)) and the compound represented by formula (pt4) (hereinafter, there is called In the case of the compound (pt4)), it reacts further in the presence of an acid.

In addition, the compound (1-H) can be produced by making a compound represented by the formula (pt5) (hereinafter referred to as a 1,3-diiminoisoindoline compound) and a compound (pt3) reacts with compound (pt4).

In addition, the compound (1-R) can be produced by making the compound (1-H) and a compound represented by the formula (pt6) (hereinafter, the existence is referred to as compound (pt6) case) response.

[In formula (pt1) ~ formula (pt6), formula (1-H) and formula (1-R), in compound (I), R ¹ ~ R ⁷ respectively represent the same meaning as R ^a1 ~ R ^a7 , In compound (II), R ¹ ~ R ⁷ respectively represent the same meaning as R ^d1 ~ R ^d7 ; in compound (I), R ⁸ ~ R ⁹ respectively represent the same meaning as A ¹ and A ² , in compound In (II), R ⁸ ~ R ⁹ respectively represent the same meaning as D ¹ and D ² ; R ³¹ represents an alkyl group with 1 to 20 carbons; M ¹ represents a basic metal atom; LG represents a halogen atom, methanesulfonyl oxy, tosyloxy or trifluoromethanesulfonyloxy]

As the alkyl group with 1 to 20 carbons represented by ^R , methyl, ethyl, propyl, isopropyl, butyl, isobutyl, second butyl and tertiary butyl etc. can be enumerated, preferably It is an alkyl group having 1 to 6 carbon atoms.

Examples of the alkali metal atom represented by ^M1 include a lithium atom, a sodium atom, and a potassium atom.

With respect to 1 mole of the phthalonitrile compound, the usage amount of the alkoxide compound represented by the formula (pt2) is usually 0.1 mole to 10 mole, preferably 0.2 mole to 5 mole, more preferably 0.3 mol to 3 mol, more preferably 0.4 mol to 2 mol.

The total amount of the compound (pt3) and the compound (pt4) used is usually 2 mol to 20 mol, preferably 2 mol to 10 mol, more preferably 2 mol to 6 mol, and more preferably 2 mol to 4 mol. In addition, compound (pt3) and 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; acetic acid, lemon Carboxylic acids such as 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 Preferably, acetic acid is mentioned.

Relative to 1 mole of the phthalonitrile compound, the amount of acid used is usually 1 mole to 20 moles, preferably 1 mole to 10 moles, more preferably 1 mole to 8 moles, and even more preferably It is 1 mole to 6 mole.

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 the reaction.

Examples of the reaction solvent include: water; nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, and 1-octanol; ethers such as tetrahydrofuran Solvents; 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 methylene chloride and chloroform; Amide solvents such as methacrylamide and N-methylpyrrolidone; ethylene oxide solvents such as dimethyl sulfide, preferably water, nitrile solvents, alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic solvents, etc. A group of hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents, and ethylene oxide solvents, more preferably water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran , acetone, ethyl acetate, toluene, methylene chloride, chloroform, N,N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl Base-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone and dimethylsulfoxide, more preferably water, acetonitrile, Methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N,N-dimethylformamide, N-dimethylethyl Amide, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone, N-methylpyrrolidine Ketones and dimethyloxide, more preferably water, acetonitrile, methanol, ethanol, 2-propanol, N-methylpyrrolidone and dimethyloxide.

The usage-amount of the solvent for reaction is 1 mass part - 1000 mass parts normally with respect to 1 mass part of phthalonitrile compounds.

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

The reaction of the 1,3-diiminoisoindoline compound, compound (pt3) and compound (pt4) is usually carried out in the presence of a reaction solvent. As a solvent for the reaction, Examples include: water; 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; ethyl acetate Ester solvents; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride and chloroform; amides such as N,N-dimethylformamide and N-methylpyrrolidone Amine solvents; ethylene oxide solvents such as dimethyl sulfide, preferably nitrile solvents, alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents, and ethylene oxide solvents, More preferably, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, ethyl acetate, toluene, methylene chloride, chloroform, N, N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl- 3,4,5,6-tetrahydro-2(1H)-pyrimidinone and dimethylsulfoxide, more preferably acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol , 1-octanol, acetone, methylene chloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, 1,3-di Methyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone and dimethylsulfoxide, and more preferably N, N-dimethylformamide, N,N-dimethylacetamide, 1-butanol, N-methylpyrrolidone, 3-dimethyl-2-imidazolidinone and 1,3-bis Methyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone and dimethylsulfoxide.

The usage-amount of the solvent for reaction is 1 mass part - 1000 mass parts normally with respect to 1 mass part of 1, 3- diiminoisoindoline compounds.

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

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

In addition, when compound (pt6) is reacted, it is preferable to coexist with a base. Examples of the base include organic bases such as triethylamine, 4-(N,N-dimethylamino)pyridine, pyridine, and piperidine, sodium methoxide, sodium ethoxide, sodium tertiary butoxide, third Metal alkoxides such as potassium butoxide, organometallic compounds such as butyllithium, tertiary butyllithium, and phenyllithium; inorganic bases such as lithium hydroxide, sodium hydroxide, and potassium hydroxide.

Relative to 1 mole of compound (1-H), the amount of base used is usually 1 mole to 10 moles, preferably 1 mole to 5 moles, more preferably 1 mole to 3 moles, and even more preferably It is 1 mole to 2 mole.

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

The usage-amount of the solvent for reaction is 1 mass part - 1,000 mass parts normally with respect to 1 mass part of compound (I-R) in compound (I) or compound (II). The reaction temperature of compound (pt6) is usually -90°C~200°C, preferably -80°C~100°C, more preferably 0°C~50°C. The reaction time is usually 0.5 hours to 300 hours.

The method for taking out compound (I) or compound (II) from the reaction mixture is not particularly limited, and it can be taken out by various known methods. For example, compound (I) or compound (II) can be taken out by filtering the reaction mixture after completion of the reaction. Moreover, you may wash|clean the obtained residue with the solvent for washing|cleaning after filtration. In addition, after filtration, column chromatography, drying under reduced pressure, recrystallization or sublimation can also be carried out. System etc.

The solvent for washing can be selected from the solvent for the above-mentioned reaction, or an acid such as acetic acid.

The mass ratio of compound (I) to compound (II) (compound (I)/compound (II)) is preferably 1-1000, more preferably 2-100, and still more preferably 5-20. In addition, from the viewpoint of dispersion stability, the upper limit of the mass ratio is preferably 1,000 or less. In particular, when compound (I) is used in the same amount or in excess relative to compound (II), compound (II) can improve the dispersibility of compound (I).

The content of compound (I) and compound (II) in the colorant (A) is preferably at least 10% by mass, more preferably at least 50% by mass, still more preferably at least 80% by mass, still more preferably at least 90% by mass Above, and preferably 100% by mass or less, may be 95% by mass or less.

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

When preparing a colored composition by dispersing compound (I) and compound (II) in a solvent (E), the dispersion stability of the colored composition can be further improved by including the resin (B) in advance.

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, more preferably Preferably, it is 10 to 100 parts by mass.

Compound (I) and compound (II) may also be subjected to rosin treatment, surface treatment using a derivative having an acidic group or a basic group introduced therein, or the use of a polymer Grafting treatment of compound (I) and compound (II) surface, micronization treatment by sulfuric acid micronization method, etc., washing treatment with organic solvent or water for removal of impurities, removal of ionic impurities Removal treatment by an ion exchange method or the like. The particle diameters of compound (I) and compound (II) are preferably substantially uniform. Compound (I) and compound (II) can be brought into a state where compound (I) and compound (II) are uniformly dispersed in the coloring composition by containing a dispersant and performing a dispersion treatment.

Surfactant etc. are mentioned as a dispersing agent, Any of cationic, anionic, nonionic, and amphoteric surfactants may be sufficient. Specifically, surfactants, such as polyester type, polyamine type, and acrylic type, etc. are mentioned. These dispersants can be used alone or in combination of two or more. As a dispersant, when expressed by a trade name, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Kyoeisha Chemical Co., Ltd.), Registered trademark) (manufactured by Zeneca), EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (Ajinomoto Fine-Techno (stock) manufacturing), Disperbyk (registered trademark) (BYK-chemie (BYK-chemie) (stock) manufacturing), BYK (registered trademark) (BYK-chemie (BYK-chemie) ) (stock) manufacturing), etc.

When using a dispersant, the amount of the dispersant (solid content) used is preferably 400 parts by mass or less, more preferably 200 parts by mass or less, based on 100 parts by mass of the total of compound (I) and compound (II), More preferably, it is 5 mass parts or more and 200 mass parts or less, Still more preferably, it is 5 mass parts or more and 150 mass parts or less. If the usage amount of the dispersant is in the above range, there is a possibility that a more uniform dispersed state can be obtained. The tendency of the colored composition of the state.

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

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

The coloring composition of the present invention may contain a coloring agent other than the compound (I) and the compound (II) (hereinafter, sometimes referred to as a coloring agent (A1)) as the coloring agent (A). Moreover, in this specification, compound (I), compound (II), and coloring agent (A1) may be collectively called "coloring agent (A)." The coloring agent (A1) may contain one kind or two or more kinds of coloring agents.

The colorant (A1) may be a dye or a pigment. Examples of dyes include known dyes described in Color Index (published by The Society of Dyers and Colourists) and dyeing notes (Shikisensha Co., Ltd.). In addition, depending on the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, and azomethine dyes are listed. , squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes and phthalocyanine dyes, etc. Among these, organic solvent-soluble dyes are preferable. These dyes may be used in combination of two or more.

Concretely, dyes of the following dye index (C.I.) numbers are exemplified. 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 (Solvent Yellow) 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; C.I. Direct Yellow (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 (Disperse Yellow) 51, 54, 76; C.I. Active Yellow (Reactive Yellow) 2, 76, 116; C.I. Acid Orange (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 (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, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426; C.I. Solvent Red (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 (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 (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 (Acid Violet) 34; C.I. Disperse Violet (Disperse Violet) )26, 27; C.I. Solvent Violet (Solvent Violet) 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue (Solvent Blue) 14, 18, 35, 36, 45, 58, 59, 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 (Solvent Green) 1, 3, 5, 28, 29, 32, 33; C.I. Acid Green (Acid Green) 3, 5, 9, 25, 27, 28, 41; C.I. Basic Green (Basic Green) 1; C.I. Restored green (Vat Green) 1 and so on.

As the pigment, known pigments can be used, and examples thereof include pigments classified as pigments in the Dye Index (published by The Society of Dyers and Colourists). These may be used alone or in combination of two or more.

Specifically, C.I. Pigment Yellow (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 and other yellow pigments; C.I. Pigment Orange (Pigment Orange) 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; C.I. Pigment Red (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 other red pigments; C.I. Pigment Blue (Pigment Blue) 15, 15:3, 15:4, 15:6, 60 and other blue pigments; C.I. Pigment Violet (Pigment Violet) 1, 19, 23, 29, 32, 36, 38 and other purple pigments; C.I. Pigment Green (Pigment Violet) 7, 36, 58, 59 and other green pigments.

When the coloring composition of the present invention contains the coloring agent (A1) and the solvent (E), it is possible to prepare a coloring agent (A1) containing liquid containing the coloring agent (A1) and the solvent (E) in advance, and then use the coloring agent (A1) A coloring composition is prepared by containing a liquid. When the coloring agent (A1) is not dissolved in the solvent (E), the liquid containing the coloring agent (A1) can be prepared by dispersing and mixing the coloring agent (A1) in the solvent (E). The colorant (A1)-containing liquid may contain a part or all of the solvent (E) contained in the coloring composition.

In order to prepare the liquid containing the coloring agent (A1), when a dispersing agent is used, the amount of the dispersing agent (solid content) used is preferably 400 parts by mass or less, more preferably 100 parts by mass of the coloring agent (A1). Preferably it is 200 mass parts or less, More preferably, it is 5 mass parts or more and 200 mass parts or less, More preferably, it is 5 mass parts or more and 150 mass parts or less. When the usage-amount of this dispersant exists in the said range, there exists a tendency for the coloring agent (A1) containing liquid of a more uniform dispersion state to be obtained.

In the total amount of the coloring agent (A1) containing liquid, the coloring agent (A1) contains The content rate of the coloring agent (A1) in a liquid is 0.1 mass %-60 mass % normally, Preferably it is 0.5 mass %-50 mass %, More preferably, it is 1 mass %-40 mass %.

In the coloring agent (A1)-containing liquid, the content of the coloring agent (A1) is usually 1% by mass to 90% by mass, preferably 1% by mass to 80% by mass, based on the total amount of solid content, More preferably, it is 2 mass % or more and 75 mass % or less, More preferably, it is 5 mass % or more and 75 mass % or less.

In the case of preparing the coloring composition of the present invention using the colorant (A1)-containing liquid containing the colorant (A1) and the solvent (E) after previously preparing the colorant (A1)-containing liquid, the colorant (A1) The containing liquid may previously contain part or all of the resin (B) contained in the coloring composition, preferably a part. By containing the resin (B) in advance, the dispersion stability of the colorant (A1)-containing liquid can be further improved.

The content of the resin (B) in the colorant (A1)-containing liquid is, for example, 1 to 500 parts by mass, preferably 5 to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass.

In the coloring composition, the content of the coloring agent (A) in which the compound (I), the compound (II) and the coloring agent (A1) are combined is usually 1% by mass or more and 90% by mass relative to the total amount of solid content. % or less, preferably more than 1 mass % and less than 80 mass %, more preferably more than 2 mass % and less than 75 mass %, still more preferably more than 5 mass % and less than 75 mass %.

When the coloring agent (A1) is included, the content of the coloring agent (A1) is preferably at least 0.1 parts by mass, more preferably at least 0.5 parts by mass, based on 100 parts by mass of the total of compound (I) and compound (II). , and more preferably 1 mass part or more, and Preferably it is 10000 mass parts or less, More preferably, it is 5000 mass parts or less.

<Resin (B)>

The resin (B) is preferably an alkali-soluble resin, and preferably has at least one monomer (hereinafter referred to as "monomer ( a) A polymer of structural units in the case of ").

The resin (B) preferably has 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 copolymers of other structural units.

As other structural units, there can be mentioned monomers derived from monomers (a) copolymerizable with monomers (however, different from monomers (a) and monomers (b). Hereinafter, there are "monomers ( c) "in the case of"), a structural unit having an ethylenically unsaturated bond, etc.

Examples of the monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; 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 and other unsaturated dicarboxylic acids; 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 and other carboxyl-containing bicyclic unsaturated compounds; Carboxylic acid anhydrides such as anhydrides of unsaturated dicarboxylic acids other than fumaric acid and mesaconic acid; succinic acid mono[2-(meth)acryloxyethyl] ester and phthalic acid mono[ Unsaturated mono[(meth)acryloxyalkyl]esters of polybasic carboxylic acids with more than two valences such as 2-(meth)acryloxyethyl]ester; α-(hydroxymethyl) Acrylate-like unsaturated acrylic esters containing hydroxyl and carboxyl groups in the same molecule.

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

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

Examples of the monomer (b) include: a monomer having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "monomer (b1)"), a monomer having an oxetane group, A monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "monomer (b2)") and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "monomer (b2)") (b3)", etc.

Examples of the monomer (b1) include: a monomer having a structure in which a straight-chain or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as "monomer (b1-1)") case) and those with alicyclic unsaturated hydrocarbon epoxidized structure Monomer (hereinafter sometimes referred to as "monosome (b1-2)").

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, and β-ethylglycidyl (meth)acrylate. , glycidyl vinyl ether, vinylbenzyl glycidyl ether, α-methylvinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis (glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3, 4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl) Styrene, 3,4,5-tris(glycidyloxymethyl)styrene and 2,4,6-tris(glycidyloxymethyl)styrene, etc.

Examples of the monomer (b1-2) include: vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel (Stock)), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Cyclomer (registered trademark) A400; Daicel (Daicel) manufactured), 3,4-epoxycyclohexylmethyl (meth)acrylate (for example, Shakema (Cyclomer) (registered trademark) M100; manufactured by Daicel (Daicel) (stock)), represented by formula (BI) Compounds, compounds represented by formula (BII), and the like.

[chemical 13]

[In formula (BI) and formula (BII), R ^a and R ^b independently represent a hydrogen atom or an alkyl group with 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group can be substituted by a hydroxyl group; X ^a and X ^b independently represent a single bond, *-R ^c -, *-R ^c -O-, *-R ^c -S- or *-R ^c -NH-; R ^c represents an alkane with 1 to 6 carbons Dibase; * indicates a bond with O]

As a compound represented by formula (BI), the compound etc. which are represented by any one of formula (BI-1) - a formula (BI-15) are mentioned. Among them, preferably formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) and formula (BI-11) ~ formula (BI The compound represented by -15) is more preferably a compound represented by formula (BI-1), formula (BI-7), formula (BI-9) and formula (BI-15).

[chemical 14]

As the compound represented by formula (BII), a compound represented by any one of formula (BII-1) to formula (BII-15) can be mentioned, among which, formula (BII-1), formula Compounds represented by (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) and formula (BII-11) ~ formula (BII-15), more preferably Compounds represented by formula (BII-1), formula (BII-7), formula (BII-9) and formula (BII-15).

[chemical 15]

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

Examples of the monomer (c) include: methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second-butyl (meth)acrylate, (meth)acrylate ) tert-butyl acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth) Cyclopentyl acrylate, Tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, Tricyclo[5.2.1.0 ^2,6 ]decane-9-yl (meth)acrylate , Tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate, Tricyclo[5.2.1.0 ^2,6 ]decen-9-yl (meth)acrylate, (methyl ) dicyclopentyloxyethyl acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, (meth) (meth)acrylates such as phenyl acrylate, naphthyl (meth)acrylate and benzyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate, etc. Hydroxyl-containing (meth)acrylates; 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-hydroxymethyl Bicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2- ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2 .1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept- 2-ene, 5,6-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, 5-tert-butoxycarbonylbicyclo[2.2.1] Hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(th Bicyclic unsaturated compounds such as tributoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-benzene N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimide N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-succinimidyl-3-maleimide Propionate and N-(9-acridyl)maleimide and other dicarbonyl imide derivatives; styrene, α-methylstyrene, vinyltoluene and p-methoxystyrene containing ethylene Aromatic compounds containing vinyl groups; (meth)acrylonitrile and other vinyl-containing nitriles; vinyl chloride and vinylidene chloride and other halogenated hydrocarbons; (meth)acrylamide and other vinyl-containing amides; vinyl acetate and other esters ; 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene and other dienes.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate, ( Tricyclo[5.2.1.0 ^2,6 ]decen-9-yl meth)acrylate, Tricyclo[5.2.1.0 ^2,6 ]decen-8-yl (meth)acrylate, (meth)acrylic acid Tricyclo[5.2.1.0 ^2,6 ]decen-9-yl ester, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[ 2.2.1] Hept-2-ene and benzyl (meth)acrylate, etc.

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 combined with the monomer (a) or the monomer (b) by adding a polymer having a structural unit derived from the monomer (a) or the monomer (b). ) is obtained as a monomer of a group reacted with an ethylenically unsaturated bond.

Examples of such structural units include those obtained by adding glycidyl (meth)acrylate to (meth)acrylic acid units, and those obtained by adding 2-hydroxyethyl (meth)acrylate to maleic anhydride units. The structural unit and p-(meth)glycidyl acrylate A structural unit obtained by adding (meth)acrylic acid to a unit, etc. Moreover, when these structural units have a hydroxyl group, the structural unit which further added carboxylic anhydride can also be mentioned as a structural unit which has an ethylenically unsaturated bond.

A polymer having a structural unit derived from a monomer (a) can be produced, for example, by polymerizing a monomer constituting a structural unit of a polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, solvent, and the like are not particularly limited, and those commonly used in the field can be used. For example, examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) or organic peroxides. The oxide (benzoyl peroxide, etc.) may be a solvent as long as it dissolves each monomer, and examples thereof include solvent (E) described later.

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

Reaction catalysts (for example, tris(dimethylaminomethyl)phenol, etc.) and polymerization inhibitors (for example, hydroquinone, etc.) of carboxylic acids or carboxylic acid anhydrides and cyclic ethers can also be used as needed.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer, 3,4-epoxycyclohexyl (meth)acrylate 5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate Ester/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleic acid Imine copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide/(meth)acrylic acid 2-Hydroxyethyl ester copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/vinyl toluene copolymer, (meth)acrylic acid 3 , 4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/2-ethylhexyl (meth)acrylate copolymer, 3,4-epoxytricyclo(meth)acrylate Cyclo[5.2.1.0 ^2,6 ]decyl ester/tricyclo[5.2.1.0 ^2,6 ]decenyl (meth)acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3 -Methyl-3-(meth)acryloxymethyloxetane/(meth)acrylic acid/styrene copolymer, benzyl (meth)acrylate/(meth)acrylic acid copolymer, Styrene/(meth)acrylic acid copolymers, resins described in JP-A-9-106071, JP-A-2004-29518, and JP-A-2004-361455, etc.

Among them, 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).

Resin (B) may also combine two or more types. In this case, resin (B) preferably contains at least 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate (Meth)acrylic acid copolymer, (meth)acrylic acid 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl ester/(meth)acrylic acid/N-cyclohexylmaleimide/(meth)acrylic acid base) 2-hydroxyethyl acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate/(meth)acrylic acid/vinyl toluene copolymer, (meth) ) One or more kinds of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/2-ethylhexyl (meth)acrylate copolymer.

The polystyrene conversion weight average molecular weight (Mw) of resin (B) becomes like this. Preferably it is 3,000-100,000, More preferably, it is 5,000-50,000, More preferably, it is 5,000-30,000. The dispersion degree [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1-6, more preferably 1.2-4.

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

In the coloring composition, the content of the resin (B) is, for example, 1 to 1200 parts by mass, preferably 30 to 1000 parts by mass, more preferably Preferably, it is 50 to 800 parts by mass.

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

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

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound that can be polymerized by active radicals and/or acids generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenically unsaturated bond, etc., preferably (meth)acrylate compounds.

Examples of polymerizable compounds having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylate. , 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., and the monomer (a), monomer (b) and monomer (c).

As a polymerizable compound having two ethylenically unsaturated bonds, for example, 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di( Meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloxyethyl)ether of bisphenol A, 3-methylpentanediol di(meth)acrylate, etc.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylate. Dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate ester, tris(2-(meth)acryloxyethyl)isocyanurate, glycol modified pentaerythritol tetra(meth)acrylate, glycol modified dipentaerythritol Tetrol 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 As for lactone-modified dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate are preferable.

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

In the colored curable resin composition, the content of the polymerizable compound (C) is preferably at least 1% by mass, more preferably at least 3% by mass, further preferably at least 5% by mass, and further preferably at least 5% by mass based on the total amount of solid content. More preferably, it is 7% by mass to 65% by mass, still more preferably, it is 13% by mass to 60% by mass, and most preferably, it is 17% by mass to 55% by mass.

<Polymerization initiator (D)>

The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids, etc. by the action of light or heat to initiate polymerization, and known polymerization initiators can be used.

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

Examples of O-acyl oxime compounds include N-benzoyloxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzoyl Oxy-1-(4-phenylthiophenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclo Pentylpropane-1-one-2-imine, N-acetyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N- Acetyloxy-1-(4-phenylthiophenyl)-3-cyclohexylpropan-1-one -2-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine , N-acetyloxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxolylmethyloxy) Benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetyloxy-1-[9-ethyl-6-(2-methylbenzoyl) -9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine and N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl Base)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine, etc. In addition, as the O-acyl oxime compound, Irgacure OXE01, OXE02 (above, manufactured by BASF Co., Ltd.) and N-1919 (manufactured by ADEKA Co., Ltd.) can also be used. and other commercial products. Among them, as the O-acyl oxime compound, it is preferably selected from N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzene Formyloxy-1-(4-phenylthiophenyl)octan-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)- At least one of the group consisting of 3-cyclopentylpropane-1-one-2-imine, more preferably N-benzoyloxy-1-(4-phenylthiophenyl)octane -1-keto-2-imine.

As the phenyl alkyl ketone compound, 2-methyl-2-morpholinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4 -morpholinophenyl)-2-benzylbutan-1-one and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-( 4-morpholinyl)phenyl]butane-1-one, 2-hydroxyl-2-methyl-1-phenylpropan-1-one, 2-hydroxyl-2-methyl-1-[4-( 2-Hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propan-1-one oligomers, α,α-diethoxyacetophenone, benzyl dimethyl ketal, etc. As the phenyl alkyl ketone compound, Irgacure 369, 907, 379 (above, manufactured by BASF Co., Ltd.) can also be used. Made) and other commercially available products.

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 (for example, refer to Japanese Patent Laid-Open No. 6-75372, Japanese Patent Laid-Open No. 6-75373, etc.), 2,2 '-Bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4' ,5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl) ) biimidazole (for example, referring to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62-174204, etc.) and 4,4 ', 5,5'-position phenyl is composed of alkoxycarbonyl (carboalkoxy ) substituted biimidazole compounds (for example, refer to Japanese Patent Application Laid-Open No. 7-10913, etc.) and the like.

Examples of triazine compounds include: 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl) base)-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)ethylene Base]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1 ,3,5-triazine and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. .

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

Furthermore, examples of the polymerization initiator (D) include: benzoin, benzoin Benzoin compounds such as methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl O-benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl -4'-Methyldiphenylsulfide, 3,3',4,4'-tetrakis(tert-butylcarbonylperoxy)benzophenone and 2,4,6-trimethylbenzophenone Benzophenone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone and camphorquinone and other quinone compounds; 10-butyl-2-chloroacridone, benzoyl, methyl phenylglyoxylate and titanocene compounds, etc.

These are preferably used in combination with a polymerization initiation aid (D1) (especially amines) described later.

The polymerization initiator (D) preferably contains at least one compound selected from the group consisting of phenalkyl ketone compounds, triazine compounds, acyl phosphine oxide compounds, O-acyl oxime compounds, and biimidazole compounds. The polymerization initiator is more preferably a polymerization initiator containing an O-acyl oxime compound.

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

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, 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 Auxiliary (D1)>

The polymerization initiation aid (D1) is a compound or a sensitizer for accelerating the polymerization of the polymerizable compound (C) whose polymerization is started by a polymerization initiator. In the case of containing the polymerization initiation aid (D1), it is usually used in combination with the polymerization initiator (D). do 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, and 4-dimethylamine Isoamyl benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4' -Bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone and 4,4'-bis(ethyl (methylamino)benzophenone and the like, preferably 4,4'-bis(diethylamino)benzophenone. In addition, commercial items such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used as the amine compound.

Examples of alkoxyanthracene compounds 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, etc.

Examples of thioxanthone compounds include: 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothiaxanthone Anthrone and 1-chloro-4-propoxythioxanthone, etc.

Examples of the carboxylic acid compound include: phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and Naphthyloxyacetic acid, etc.

In the case of using these polymerization initiation aids (D1), the content rate is at The total amount of solids in the colored curable resin composition is preferably from 0.001% by mass to 30% by mass, more preferably from 0.01% by mass to 20% by mass.

When using these polymerization initiation aids (D1), the content thereof is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C), and more preferably Preferably, it is 1 mass part - 20 mass parts.

<Solvent (E)>

Examples of the solvent (E) include: ester solvents (solvents containing -COO- and not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether esters Solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (solvents containing OH and not containing -O in the molecule -, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfide, etc.

Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, and isoamyl acetate. , Butyl propionate, Isopropyl butyrate, Ethyl butyrate, Butyl butyrate, Methyl pyruvate, Ethyl pyruvate, Propyl pyruvate, Methyl acetylacetate, Ethyl acetylacetate, Cyclo Hexanol acetate and γ-butyrolactone, etc.

Examples of ether solvents 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, Ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, Tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol di Diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole, etc.

Examples of ether ester solvents include: methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionate Ethyl ester, Propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, Ethyl 2-ethoxypropionate, Methyl 2-methoxy-2-methylpropionate, 2- Ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Diethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Ester and Dipropylene Glycol Methyl Ether Acetate etc.

Examples of ketone solvents include: 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2- Pentanone, cyclopentanone, cyclohexanone and isophorone, etc.

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,N-dimethylacetamide, N-methylpyrrolidone, and the like.

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

The content of the solvent (E) is preferably 40% by mass to 99% by mass, more preferably 50% by mass to 95% by mass, further preferably 65% by mass to 95% by mass, and further preferably More preferably, it is 70% by mass to 90% by mass.

<Leveling agent (F)>

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

As a silicone type surfactant, the surfactant etc. which have a siloxane bond in a molecule|numerator are mentioned. Specifically, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone 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 Co., Ltd.); Mention Performance Materials Japan) Co., Ltd.) etc.

As said fluorine-type surfactant, the thing which has a fluorocarbon chain in a molecule|numerator, etc. are mentioned. Specifically, examples include: Fluorad (registered trademark) FC430, Fluorad (Fluorad) FC431 (manufactured by Sumitomo 3M Co., Ltd.); Megafac (registered trademark) F142D, Megafac )F171, Megafae F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac R30, Megafac RS-718 -K (manufactured by DIC); Eftop (registered trademark) EF301, Eftop EF303, Eftop EF351, Eftop EF352 ( Manufactured by Mitsubishi Materials Corporation); Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (Asahi Glass Co., Ltd. Manufactured) and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.), etc.

Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule, and the like. Specifically, examples include: Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477 and Megafac F443 (DIC ) (stock) manufacturing), etc.

When the leveling agent (F) is contained, its content is usually not less than 0.0005% by mass and not more than 1% by mass, preferably not less than 0.001% by mass and not more than 0.5% by mass, based on the total amount of the colored curable resin composition , more preferably from 0.001% by mass to 0.2% by mass, still more preferably from 0.002% by mass to 0.1% by mass, still more preferably from 0.005% by mass to 0.1% by mass. When content of a leveling agent (F) exists in the said range, the flatness of a color filter can be made favorable.

<Antioxidant>

From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to Chemical agents are used alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an antioxidant commonly used industrially, and phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, 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], BASF (BASF) Co., Ltd.), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, BASF (BASF) (Shares) Manufacturing), Irganox 1330 (Irganox 1330: 3,3',3",5,5',5"-hexa-tertiary butyl-a,a',a"-(Mesitylene -2,4,6-triyl)tri-p-cresol, BASF (BASF) (stock) manufacture), Irganox 3114 (Irganox 3114: 1,3,5-tri(3,5-di-di- Tributyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd., Egalex 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)-Triketone, manufactured by BASF (Stock)), Irganox 1035 (Irganox 1035: thiobisethylenebis[3-(3,5-di-tertiary Butyl-4-hydroxyphenyl)propionate], BASF (BASF) Co., Ltd.), Irganox 1135 (Irganox 1135: phenylpropionic acid, 3,5-bis(1,1-dimethyl Ethyl)-4-hydroxyl, C7-C9 side chain alkyl ester, BASF (BASF) (stock) manufacturing), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o Cresol, BASF (BASF) Co., Ltd.), Irganox 3125 (Irganox 3125, BASF (BASF) Co., Ltd. base)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, BASF (BASF) Co., Ltd.), Eddie Costa 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, Sumitomo Chemical Co., Ltd. Manufactured), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Shanox 1790 (Cyanox 1790, Cytec Co., Ltd.), vitamin E (Eisai Co., Ltd.), etc.

Examples of the phosphorus-based antioxidant include: Igrafos 168 (Igrafos 168: tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF Co., Ltd.), Igrafos 12 (Igrafos 12: Tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-6 -yl]oxy]ethyl]amine, manufactured by BASF (BASF), Igrafos 38 (Igrafos 38: bis(2,4-bis(1,1-dimethylethyl) phosphite -6-Methylphenyl) ethyl ester, BASF (BASF) (stock) manufacture), Adekastab (Adekastab) 329K (Adeka (ADEKA) (stock) manufacture), Adekastab ( Adekastab) PEP-36 (manufactured by ADEKA), Adekastab PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, GE company) 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]dioxaphosphaheptin) (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, etc.

<other ingredients>

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

<Manufacturing method of colored curable resin composition>

The colored curable resin composition can be prepared, for example, by mixing a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and optionally a polymerization initiator. Additive (D1), leveling agent (F), antioxidant and other ingredients are mixed and prepared.

<Color filter>

A colored pattern can be formed from the colored curable resin composition of the present invention. As a method of forming a colored pattern, a photolithography method, an inkjet method, a printing method, etc. are mentioned. Among them, photolithography is preferred. Photolithography is a method of applying the colored curable resin composition on a substrate, drying it to form a colored composition layer, and exposing and developing the colored composition layer through a photomask. In the photolithography method, by not using a photomask and/or not performing development at the time of exposure, it is possible to form a colored coating film that is a cured product of the above-mentioned colored composition layer. The colored pattern or colored coating film formed in this way is the color filter of this invention.

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

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or polycarbonate, polymethyl methacrylate, poly Resin boards such as ethylene terephthalate, silicon, aluminum, silver, silver/ketone/palladium alloy thin films, etc. are formed on the substrate. Other color filter layers, resin layers, transistors, circuits, etc. can also be formed on these substrates.

The formation of pixels of each color by photolithography can be performed by known or commonly used devices or conditions. For example, it can be produced as follows.

First, a colored curable resin composition is applied on a substrate, and then heat-dried (pre-baked) and/or reduced-pressure dried to remove volatile components such as solvents and dry to obtain a smooth colored composition layer .

As a coating method, a spin coating method, a slit coating method, a slit and spin coating method, etc. are mentioned.

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

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

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

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on this photomask is not specifically limited, The pattern according to the intended use can be used.

As a light source used for exposure, the light source which generate|occur|produces the light of the wavelength of 250nm-450nm is preferable. For example, it is also possible to use a filter that cuts off the wavelength region for light less than 350nm, or for light near 436nm, 408nm, and 365nm, use a bandpass filter that extracts these wavelength regions to selectively Take it out. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

In order to uniformly irradiate the entire exposure surface with parallel light rays, or to perform accurate alignment between the mask and the substrate on which the colored composition layer is formed, it is preferable to use a mask aligner (Mask Aligner) and a stepper ( Stepper) and other exposure devices.

A colored pattern is formed on the substrate by making the exposed colored composition layer contact with a developer and developing it. By developing, the unexposed part of the colored composition layer is dissolved in a developing solution and removed.

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

The developing method may be any one of a liquid covering method, a dipping method, a spraying method, and the like. Furthermore, the substrate can also be inclined at an arbitrary angle during image development.

The developed substrate is preferably washed with water.

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

According to the colored composition of the present invention, a color filter having particularly excellent light resistance can be produced. 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, an electronic paper, etc.) and a solid-state imaging element, wherein, as a color filter used in a liquid crystal display device Light sheet but useful.

[Example]

Hereinafter, examples are given to illustrate the present invention more specifically, but the present invention is not limited to the following examples at all, and of course can be implemented by appropriately adding changes within the scope of the gist described and described below. included in the technical scope of the present invention. In addition, hereinafter, unless otherwise specified, "part" means "mass part", and "%" means "mass %".

Hereinafter, the structures of the compounds were confirmed by mass spectrometry (LC; 1200 type manufactured by Agilent, MASS; LC/MSD6130 type manufactured 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. 24 parts of (beta)-oxo-2-quinoline propionitrile (synthesized according to the method described in WO2011/089132) was added to the obtained mixture, and it stirred at 45 degreeC and 10 kPa of reduced pressure for 10 hours. The resulting mixture was filtered, and the residue was added Add 100 parts of acetic acid, and stir at 80° C. for 2 hours. The obtained mixture was filtered, 300 parts of water were added to 9.8 parts of residues, and it stirred at 80 degreeC for 2 hours. The obtained mixture was filtered, and the filtered residue was washed with 300 parts of methanol to obtain 9.5 parts of residues. 15 parts of N,N- dimethylformamides were added to 9.5 parts of residues after washing|cleaning, and it stirred at 80 degreeC for 2 hours. Cool to 0°C and stir for 2 hours. The obtained mixture was filtered, and after washing with 60 parts of methanol, the obtained residue was dried under reduced pressure at 60° C. to obtain 16 parts of compounds comprising compounds represented by formula (I-1) (yield 79%). The wavy line indicates that the E-body, the Z-body, or a mixture thereof are included (in the synthesis examples, the same applies hereinafter).

<Identification of Compound I-1>

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

Exact Mass: 503

Synthesis example 2

24 parts of β-oxo-2-quinolinepropionitrile in Synthesis Example 1 were made into 23 parts of β-oxo-1H-indole-3-propionitrile (manufactured by Aldrich Co., Ltd.), except Other than that, it synthesize|combined by the method similar to the synthesis example 1. Obtain 14 parts represented by formula (I-2) Compound (69% yield).

<Identification of compound I-2>

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

Exact Mass: 479

Synthesis example 3

24 parts of β-oxo-2-quinolinepropionitrile in Synthesis Example 1 were used as 25 parts of β-oxo-2-benzothiazolepropionitrile (synthesized according to the method described in WO2011/016528), and in addition , was synthesized by the same method as Synthesis Example 1. 8.8 parts of the compound represented by formula (I-3) were obtained (yield 41%).

<Identification of Compound I-3>

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

Exact Mass: 515

Synthesis Example 4

24 parts of β-oxo-2-quinoline propionitrile in Synthesis Example 1 were made into 23 parts of 4-(2-cyanoacetyl)benzoic acid (synthesized according to the method described in US2680731), in addition, Synthesis was performed by the same method as in Synthesis Example 1. 16 parts of the compound represented by formula (II-1) were obtained (yield 77%).

<Identification of Compound II-1>

(mass analysis) ionization mode = ESI ^- : m/z = [MH] ^- 488

Exact Mass: 489

Synthesis Example 5

6.0 parts of dimethyl 2,6-naphthalene dicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in 47 parts of acetonitrile (manufactured by Wako Pure Chemical Industries, Ltd.). While maintaining the temperature of the obtained mixture at 60° C., 3.5 parts of sodium tert-butoxide (manufactured by Kanto Chemical Co., Ltd.) was added over 1 minute, and stirred for 90 minutes. While keeping the temperature below 5°C, 2.2 parts of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) and water were added dropwise over 30 minutes. 45 parts, heated up to 25°C, and stirred at 25°C for 1 hour. The obtained mixture was filtered, and the filtered residue was washed with 30 parts of water and 10 parts of methanol, and then dried under reduced pressure at 60° C. to obtain 6-(2-cyanoacetyl 3.7 parts of methyl)-2-naphthalenecarboxylate (yield 60%).

3.7 parts of methyl 6-(2-cyanoacetyl)-2-naphthalenecarboxylate were suspended in 15 parts of water. While keeping the temperature of the obtained mixture at 80° C., 0.88 parts of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, followed by stirring for 25 minutes. While keeping the temperature below 5°C, 2.8 parts of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) was added dropwise over 30 minutes, the temperature was raised to 25°C, and the mixture was stirred at 25°C for 1 hour. The obtained mixture was filtered, and the filtered residue was washed with 30 parts of water and 10 parts of methanol, and then dried under reduced pressure at 60° C. to obtain 6-(2-cyanoacetyl 2.6 parts of -2-naphthalenecarboxylic 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. 30 parts of 6-(2-cyanoacetyl)-2-naphthalenecarboxylic acids were added to the obtained mixture, and it stirred at 45 degreeC for 10 hours. The obtained mixture was filtered, 100 parts of acetic acid was added to the residue, and it stirred at 80 degreeC for 2 hours. The obtained mixture was filtered, 300 parts of water were added to 9.8 parts of residues, and it stirred at 80 degreeC for 2 hours. The obtained mixture was filtered, and the filtered residue was washed with 300 parts of methanol to obtain a residue. 15 parts of N,N-dimethylformamide were added to the residue after washing|cleaning, and it stirred at 80 degreeC for 2 hours. Cool to 0°C and stir for 2 hours. The obtained mixture was filtered, and after washing with 60 parts of methanol, the obtained residue was dried under reduced pressure at 60° C. to obtain 18 parts of Compound of the compound represented by formula (II-2) (yield 76%).

<Identification of Compound II-2>

(mass analysis) ionization mode = ESI ^- : m/z = [MH] ^- 588

Exact Mass: 589

Synthesis Example 6

24 parts of β-oxo-2-quinoline propionitrile in Synthesis Example 1 were made into 24 parts of β-oxo-2-thiazole propionitrile (synthesized according to the method described in WO2011/016528), in addition, using Synthesis was carried out in the same manner as in Synthesis Example 1. 14.4 parts of the compound represented by the formula (I-14) were obtained (yield 73%).

Synthesis Example 7

24 parts of β-oxo-2-quinolinepropionitrile in Synthesis Example 1 were used as 24 parts of β-oxo-2-pyrazinepropionitrile (synthesized according to the method described in WO2011/016528), in addition, Synthesis was performed by the same method as in Synthesis Example 1. 12 parts of the compound represented by the formula (I-19) were obtained (yield 65%).

Resin Synthesis Example 1

An appropriate amount of nitrogen gas was circulated in a flask including a reflux cooler, a dropping funnel, and a stirrer to replace it with a nitrogen atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was put in, and heated to 80° C. while stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^{2 , 6} ] A mixture of decane-9-yl esters (containing a molar ratio of 1:1) 289 parts, 125 parts of propylene glycol monomethyl ether acetate mixed solution. On the other hand, a solution obtained 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 the dropwise addition, it was kept at 80° C. for 4 hours, and then cooled to room temperature to obtain a solid content of 35.1% and a viscosity of 125 mPa measured with a B-type viscometer (23° C.). s copolymer (resin B1) solution. The weight average molecular weight Mw of the produced copolymer was 9.2×10 ³ , the degree of dispersion was 2.08, and the acid value in terms of solid content was 77 mg-KOH/g. Resin B1 has the following structural units.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the polystyrene conversion of resin was performed by gel permeation chromatography (Gel Permeation Chromatography, GPC) under the following conditions.

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

Column: TSK-GELG2000HXL

Column temperature: 40°C

Solvent: THF

Flow rate: 1.0mL/min

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

Injection volume: 50μL

Detector: RI

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

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

Example 1

(1) Preparation of Colored Composition and Colored Curable Resin Composition

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

The coloring composition 1 was left to stand at 23° C. for 14 hours, and then the following components were mixed to obtain a coloring curable resin composition 1 . Among the following components, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) was used for the polymerizable compound (C), and polymerization initiator (D) was used N-benzoyloxy-1-(4-phenylthiophenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; BASF (BASF) (stock) manufacturing), solvent (E) is to use propylene glycol monomethyl ether acetate, leveling agent is to use polyether modified silicone oil (Toray Silicone (Toray Silicone) SH8400; Toray Dow Corning (Toray Dow Corning) ( shares) manufacturing).

(2) Preparation of colored coating film

On a 5 cm square glass substrate (eagle XG; manufactured by Corning Corporation), the colored curable resin composition was coated by spin coating so that the film thickness after baking was 2 μm, and then the curable resin composition was applied at 100 Pre-baking at ℃ for 3 minutes to form a colored composition layer. After standing to cool, the coloring composition layer formed on the substrate was subjected to an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) at an exposure dose of 80mJ/cm ² (based on 365nm) in an atmospheric environment. light exposure. After light irradiation, post-baking was performed in an oven at 230° C. for 30 minutes to obtain a colored coating film.

(3) Heat resistance test

Absorption of the obtained colored coating film was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation). The obtained colored coating film was further heated at 230° C. for 120 minutes in an oven under an air environment, and then the absorption was measured with a colorimeter. The absorbance retention rate was calculated from the change in absorbance at the maximum absorption wavelength of the colored coating film before and after the test.

(4) Light fastness test

Arrange ultraviolet cut filter (colored optical glass) on the obtained colored coating film Glass (COLORED OPTICAL GLASS) L38; manufactured by Hoya Co., Ltd.; cut off light below 380 nm), was irradiated with xenon light for 48 hours by a light resistance tester (SUNTEST CPS+: manufactured by Toyo Seiki Co., Ltd.), and then used Absorption is measured by a colorimeter. The absorbance retention rate was calculated from the change in absorbance at the maximum absorption wavelength of the colored coating film before and after the test.

Embodiment 2 ~ embodiment 8 and comparative example 1 ~ comparative example 4

About Example 2, it carried out similarly to Example 1 except having used 45 parts of compounds (I-2) instead of 45 parts of compounds (I-1) as a coloring agent (A).

Regarding Example 3, as the coloring agent (A), 45 parts of compound (I-3) and 5 parts of compound (II) were used instead of 45 parts of compound (I-1) and 5 parts of compound (II-1). -2), except for this, it carried out similarly to Example 1.

Regarding Examples 4 to 6, as the coloring agent (A), instead of 5 parts of compound (II-1), 45 parts of compound (II-1) were used in Example 4, and 0.5 parts were used in Example 5. 1 part of compound (II-1) and 0.1 part of compound (II-1) were used in Example 6, and it carried out similarly to Example 1.

Regarding Example 7 and Example 8, as the colorant (A), instead of 45 parts of compound (I-1), 45 parts of compound (I-14) were used in Example 7, and 45 parts were used in Example 8. Parts of compound (I-19), except that it was carried out in the same manner as in Example 1.

Regarding Comparative Examples 1 to 4, as the colorant (A), instead of 45 parts of Compound (I-1) and 5 parts of Compound (II-1), 50 parts of Compound (I-1) were used in Comparative Example 1. 1), use 50 parts of compound (I-2) in comparative example 2, in comparison In Example 3, it carried out similarly to Example 1 except having used 50 parts of compound (I-3) and comparative example 4 using 50 parts of compound (II-1).

Table 15 shows the results of Example 2 to Example 8 and Comparative Example 1 to Comparative Example 4.

In addition, the stability of the dispersion liquid (namely, the coloring composition) prepared in the Example and the comparative example was evaluated by the following reference|standard. A means that the stability of the dispersion is high, and C means that the stability of the dispersion is low.

A: Even after standing at 23°C for 14 hours, the viscosity hardly changed, and the production of the colored coating film and the heat resistance and light resistance tests could be carried out without any problems.

B: After standing still at 23 degreeC for 14 hours, the viscosity increased, but the preparation of the colored coating film, heat resistance, and light resistance test were implemented without a problem.

C: After standing still at 23 degreeC for 14 hours, it solidified and the colored coating film could not be produced.

It was found that in Comparative Examples 1 to 3, when the resulting dispersion liquid was left to stand at 23° C. for 14 hours, it solidified, and the stability of the dispersion liquid was low.

As shown in the above-mentioned Table 15, it was found that according to the coloring composition of the present invention, a color filter excellent in light resistance can be formed. In addition, the heat resistance of the colored composition of the present invention is also good. Furthermore, it turned out that the stability of the dispersion liquid of the coloring composition of this invention is also excellent.

Claims (9)

A coloring composition, comprising: a compound represented by formula (I); and a compound represented by formula (II):

[In formula (I) and formula (II), A ¹ and A ² independently represent a condensed heterocyclic group that may have a substituent; D ¹ and D ² independently represent an aromatic hydrocarbon group that may have a substituent, so The aromatic hydrocarbon group has at least one -CO ₂ M; R ^a1 and R ^d1 independently represent a hydrocarbon group with a carbon number of 1 to 40 that may have a substituent, a heterocyclic group that may have a substituent, or a hydrogen atom, and the hydrocarbon group -CH ₂ - contained in and the -CH ₂ - when the heterocyclic group contains -CH ₂ - that does not constitute a ring may be substituted with -O-, -CO-, -S(O) ₂ -, or -NR ²⁰ -; R ^a2 to R ^a7 and R ^d2 to R ^d7 independently represent a hydrocarbon group with 1 to 40 carbon atoms that may have a substituent, a heterocyclic group that may have a substituent, a hydrogen atom, or a halogen atom , cyano, nitro, -CO ₂ M or -S(O) ₂ OM, when the -CH ₂ - contained in the hydrocarbon group and the -CH ₂ - that does not constitute a ring are contained in the heterocyclic group, all The -CH ₂ - can be substituted with -O-, -CO-, -S(O) ₂ -, or -NR ²⁰ -; R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R When ^d2 and R ^d3 , R ^d3 and R ^d4 , and R ^d4 and R ^d5 may form a ring which may have a substituent together with the carbon atoms to which they are bonded, and the ring contains -CH ₂ - which does not constitute a ring. The -CH ₂ - can be substituted with -O-, -CO-, -S(O) ₂ -, or -NR ²⁰ -; M represents a hydrogen atom or an alkali metal atom; R ²⁰ represents a hydrogen atom and can be substituted A hydrocarbon group with 1 to 40 carbon atoms, or a heterocyclic group that may have a substituent; in the case of multiple R ²⁰ and M, these may be the same or different; the wavy line indicates that E body and Z body are included or a mixture of these]. The coloring composition as described in item 1 of the scope of the patent application, wherein R ^a1 and R ^d1 are hydrogen atoms, and R ^a6 ~ R ^a7 and R ^d6 ~ R ^d7 are cyano or nitro groups. The coloring composition as described in item 1 or item 2 of the patent application, wherein ^A1 and ^A2 are the same, and R ^a6 and R ^a7 are the same group. The coloring composition as described in item 1 or item 2 of the patent application, wherein D ¹ and D ² are the same, and R ^d6 and R ^d7 are the same group. The coloring composition as described in item 1 or item 2 of the patent application, wherein the mass ratio of the compound represented by the formula (I) to the compound represented by the formula (II) is 1-1000. The coloring composition as described in claim 1 or claim 2, further comprising a resin (B). A colored curable resin composition, comprising: the colored composition described in any one of items 1 to 6 in the scope of the patent application; a polymerizable compound (C); a polymerization initiator (D); and a solvent ( E). A color filter formed of the colored curable resin composition described in claim 7 of the patent application. A display device comprising the color filter described in item 8 of the patent application.