WO2020031799A1 - Coloring composition - Google Patents

Abstract

The present invention provides a coloring composition able to form a color filter having excellent lightfastness. The present invention relates to a coloring composition containing a compound represented by formula (I) and a compound represented by formula (II). [In formula (I) and formula (II), A¹ and A² each independently denote an optionally substituted heterocyclic group. D¹ and D² each independently denote an optionally substituted aromatic hydrocarbon group, with each of said aromatic hydrocarbon groups having at least one -CO₂M group. R^a1 and R^d1 each independently denote an optionally substituted hydrocarbon group having 1-40 carbon atoms, an optionally substituted heterocyclic group or a hydrogen atom, with -CH₂- groups contained in said hydrocarbon groups and -CH₂- groups that do not constitute the ring of said heterocyclic groups able to be substituted with -O-, -CO-, -S(O)₂- or -NR²⁰-. R^a2 to R^a7 and R^d2 to R^d7 each independently denote an optionally substituted hydrocarbon group having 1-40 carbon atoms, an optionally substituted heterocyclic group, a hydrogen atom, a halogen atom, a cyano group, a nitro group, -CO₂M or -S(O)₂OM, with -CH₂- groups contained in said hydrocarbon groups and -CH₂- groups that do not constitute the ring of said heterocyclic groups able to be substituted with -O-, -CO-, -S(O)₂- or -NR²⁰-. Carbon atoms in 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 bond to each other to form an optionally substituted ring, with -CH₂- groups that do not constitute said ring able to be substituted with -O-, -CO-, -S(O)₂- or -NR²⁰-. M denotes a hydrogen atom or an alkali metal atom. R²⁰ denotes a hydrogen atom, an optionally substituted hydrocarbon group having 1-40 carbon atoms or an optionally substituted heterocyclic group. In cases where a plurality of R²⁰ and M are present, these may be the same as, or different from, each other. A wavy line indicates that an E-isomer, a Z-isomer or a mixture thereof is contained.]

Description

Coloring composition

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

The colored curable resin composition is used for producing a color filter used for a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display. Such a colored curable resin composition contains a colorant in order to obtain a desired color tone and the like, and as the colorant, for example, an isoindoline compound is known (Patent Document 1).

JP 2017-137490 A

と す る An object of the present invention is to provide a coloring composition capable of forming a color filter having excellent light resistance.

The gist of the present invention is as follows.
[1] A colored composition containing a compound represented by the formula (I) and a compound represented by the formula (II).

[In the formulas (I) and (II),
A ¹ and A ² independently represent a heterocyclic group which may have a substituent.
D ¹ and D ² independently represent an optionally substituted aromatic hydrocarbon group, and the aromatic hydrocarbon group has at least one —CO ₂ M.
R ^a1 and R ^d1 each independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom; the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring - is, -O - -CH ₂ contained in the hydrocarbon group, - CO -, - S ( O) 2 - Or —NR ²⁰ —.
R ^a2 to R ^a7 and R ^d2 to R ^d7 each independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, atom, a halogen atom, a cyano group, a nitro group, -CO ₂ M or _{-S (O) 2 OM, -CH} 2 contained in the hydrocarbon group - -CH ₂ where and heterocyclic groups do not constitute a ring - it is, -O - - the -CH ₂ when containing, - CO -, - S ( O) 2 -, or -NR ²⁰ - may be replaced with.
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 are substituted together with the carbon atom to which each is attached. May form a ring which may have a group. When the ring contains -CH ₂ -which does not form a ring, -CH ₂ -is -O-, -CO-, -S (O ) ₂ -, or -NR ²⁰ - it may be replaced with.
M represents a hydrogen atom or an alkali metal atom.
R ²⁰ represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
When a plurality of R ²⁰ and M are present, they may be the same or different.
A wavy line indicates that an E-form, a Z-form or a mixture thereof is included. ]
[2] The colored composition according to [1], wherein A ¹ and A ² are independently a condensed heterocyclic group which may have a substituent.
[3] The colored composition according to [1] or [2], wherein R ^a1 and R ^d1 are a hydrogen atom, and R ^a6 to R ^a7 and R ^d6 to R ^d7 are a cyano group or a nitro group.
[4] The colored composition according to any one of [1] to [3], wherein A ¹ and A ² are the same, and R ^a6 and R ^a7 are the same group.
[5] The colored 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 colored composition according to any one of [1] to [5], wherein the mass ratio of the compound represented by the formula (I) to the compound represented by the formula (II) is 1 to 1000.
[7] The colored composition according to any one of [1] to [6], further comprising a resin (B).
[8] A colored curable resin composition comprising the colored composition according to any one of [1] to [7], a polymerizable compound (C), a polymerization initiator (D), and a solvent (E). .
[9] A color filter formed from the colored curable resin composition according to [8].
[10] A display device including the color filter according to [9].

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

<Coloring composition>
The coloring composition according to the present invention comprises a compound represented by the formula (I) (hereinafter also referred to as compound (I)) and a compound represented by the formula (II) (hereinafter also referred to as compound (II)). Including. The compound (I) and the compound (II) can be used as a coloring agent (A). The coloring composition according to the present invention may contain one or more of the compounds (I) and (II), respectively.
Further, the coloring composition according to the present invention preferably further contains a resin (hereinafter, also referred to as resin (B)).
The colored curable resin composition according to the present invention includes a colored composition of the present invention, a polymerizable compound (hereinafter, also referred to as a polymerizable compound (C)), and a polymerization initiator (hereinafter, also referred to as a polymerization initiator (D)). And a solvent (hereinafter, also referred to as a solvent (E)).
The colored curable resin composition according to the present invention may further contain a polymerization initiation aid (hereinafter, also referred to as a polymerization initiation aid (D1)).
The colored curable resin composition according to the present invention may further contain a leveling agent (hereinafter, also referred to as a leveling agent (F)) and an antioxidant.
In the present specification, compounds exemplified as each component can be used alone or in combination of two or more, unless otherwise specified.

<Colorant (A)>
The coloring agent (A) includes the compound (I) and the compound (II). The compounds (I) and (II) include tautomers and salts thereof.

[In the formulas (I) and (II),
A ¹ and A ² independently represent a heterocyclic group which may have a substituent.
D ¹ and D ² independently represent an optionally substituted aromatic hydrocarbon group, and the aromatic hydrocarbon group has at least one —CO ₂ M.
R ^a1 and R ^d1 each independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom; the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring - is, -O - -CH ₂ contained in the hydrocarbon group, - CO -, - S ( O) 2 - Or —NR ²⁰ —. However, -CO ₂ H and -S (O) ₂ OH do not form when -CH ₂ -is replaced.
R ^a2 to R ^a7 and R ^d2 to R ^d7 each independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, atom, a halogen atom, a cyano group, a nitro group, -CO ₂ M or _{-S (O) 2 OM, -CH} 2 contained in the hydrocarbon group - -CH ₂ where and heterocyclic groups do not constitute a ring - it is, -O - - the -CH ₂ when containing, - CO -, - S ( O) 2 -, or -NR ²⁰ - may be replaced with. However, -CO ₂ H and -S (O) ₂ OH do not form when -CH ₂ -is replaced.
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 are substituted together with the carbon atom to which each is attached. May form a ring which may have a group. When the ring contains -CH ₂ -which does not form a ring, -CH ₂ -is -O-, -CO-, -S (O ) ₂ -, or -NR ²⁰ - it may be replaced with. However, -CO ₂ H and -S (O) ₂ OH do not form when -CH ₂ -is replaced.
M represents a hydrogen atom or an alkali metal atom.
R ²⁰ represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
When a plurality of R ²⁰ and M are present, they may be the same or different.
A wavy line indicates that an E-form, a Z-form or a mixture thereof is included. ]

The hydrocarbon group having 1 to 40 carbon atoms represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ represents an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group is May be saturated or unsaturated, and may be linear or cyclic (alicyclic).

Examples of the saturated or unsaturated chain hydrocarbon group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group. Octyl group, nonyl group, decyl group, undecyl group, dodecyl group, heptadecyl group, octadecyl group, and straight chain alkyl group such as icosyl group; isopropyl group, (2-methyl) propyl group, isobutyl group, sec-butyl Group, tert-butyl group, (2-ethyl) butyl group, isopentyl group, neopentyl group, tert-pentyl group, (1-methyl) pentyl group, (2-methyl) pentyl group, (1-ethyl) pentyl group, Branched chains such as (3-ethyl) pentyl, isohexyl, (5-methyl) hexyl, (2-ethyl) hexyl, and (3-ethyl) heptyl Alkyl group, etc .; vinyl group, 1-propenyl group, 2-propenyl group (allyl group), isopropenyl group, (1-methyl) ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, Alkenyl groups such as (1- (2-propenyl)) ethenyl group, (1,2-dimethyl) propenyl group and 2-pentenyl group; and the like.

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

As the saturated or unsaturated alicyclic hydrocarbon group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ , a cyclopropyl group, a 1-methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group , Cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethyl Cyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl , 2,2-dimethylcyclohexyl group, 3,3-dimethyl Clohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group Cycloalkyl groups such as 4-pentylcyclohexyl group, 4-octylcyclohexyl group and 4-cyclohexylcyclohexyl group; cycloalkyl groups such as cyclohexenyl group (eg, cyclohex-2-ene and cyclohex-3-ene), cycloheptenyl group and cyclooctenyl group Alkenyl group; polycyclic alicyclic hydrocarbon group such as norbornane group, adamantyl group and bicyclo [2.2.2] octane;

The alicyclic hydrocarbon group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ preferably has 3 to 30, more preferably 3 to 20, and further preferably 4 carbon atoms. -20, even more preferably 4-15, even more preferably 5-15, and particularly preferably 5-10.

The saturated or unsaturated hydrocarbon group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ is a group obtained by combining the above-mentioned chain hydrocarbon group and alicyclic hydrocarbon group. For example, one or more alicyclic carbons such as cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, etc. Examples include an alkyl group to which a hydrogen group is bonded. The carbon number is preferably from 4 to 30, more preferably from 4 to 20, and even more preferably from 4 to 15.

The aromatic hydrocarbon group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ represents a group having a direct bond on the aromatic hydrocarbon ring, and includes a phenyl group, an o-tolyl group, -Tolyl group, p-tolyl group, 2,3-dimethylphenyl group, 2,4-dimethylphenyl group, 2,5-dimethylphenyl group, 2,6-dimethylphenyl group, 3,4-dimethylphenyl group, 3 , 5-dimethylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, mesityl Group, 2,6-bis (2-propyl) phenyl group, 2,4,6-trimethylphenyl group, 1-naphthyl group, 2-naphthyl group, 5,6,7,8-tetrahydro-1 Naphthyl, 5,6,7,8-tetrahydro-2-naphthyl group, a fluorenyl group, and phenanthryl group and an anthryl group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15.

The aromatic hydrocarbon group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ is at least one of the above-mentioned chain hydrocarbon group, alicyclic hydrocarbon group, and aromatic hydrocarbon group. One of the groups may be a group obtained by combining one of the above-mentioned aromatic hydrocarbon groups, such as a benzyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a 4-methylbenzyl group, or a 3,4-methylbenzyl group. Aralkyl groups such as phenylethyl group, phenylpropyl group, 1-methyl-1-phenylethyl group; arylalkenyl groups such as phenylethenyl group (phenylvinyl group); arylalkynyl groups such as phenylethynyl group; biphenylyl group Phenyl group to which one or more phenyl groups such as terphenylyl group are bonded; cyclohexylmethylphenyl group, benzylphenyl group, (dimethyl (phenyl) methyl Phenyl group; and the like, and the number of carbon atoms is preferably 7-30, more preferably 7-20, more preferably from 7 to 15.

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

As the monovalent substituent,
—CO ₂ M;
—S (O) ₂ OM;
An alkylsulfanyl group having 1 to 10 carbon atoms such as a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group and a butylsulfanyl group;
Halogen atoms such as fluorine, chlorine, bromine and iodine;
Nitro group;
A cyano group;
Trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, perfluorodecyl, perfluorocyclohexyl, perfluoro A hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, in which all hydrogen atoms such as a phenyl group are substituted by fluorine atoms;
* -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- A carbonyl group bonded to a sulfur atom bonded to an alkyl group such as CH ₃ (the alkyl group has 1 to 10 carbon atoms);
* -CO-S-C ₆ aryl group H _5, etc. (the number of carbon atoms of the aryl group of 6 to 20) carbonyl bound to sulfur atom bonded with groups;
* -OP (O) (OR ³⁰ ) ₂ ;
* -Si (R ³⁰ ) (R ³¹ ) (R ³² ); In the above, * represents a bond.

In the above formula, M represents the same meaning as described above, and R ³⁰ , R ³¹ , and R ³² each independently represent a hydrocarbon group having 1 to 35 carbon atoms which may have a substituent, represents a heterocyclic group which may have a group, -CH ₂ - contained in the hydrocarbon group the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring, —O—, —CO—, —S (O) ₂ —, or —NR ²⁰ — may be substituted. However, -CO ₂ H and -S (O) ₂ OH do not form when -CH ₂ -is replaced. R ²⁰ has the same meaning as described above. Specific examples and preferred ranges of R ³⁰ , R ³¹ , and R ³² are the same as those of R ^a1 except that the examples having 36 or more carbon atoms are not included.

Examples of the divalent substituent include a thiocarbonyl group, an imino group, an imino group substituted with an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), and an imino group substituted with an aryl group having 6 to 20 carbon atoms. And the like. Examples of the imino group substituted with an alkyl group include CH ₃ —N ＝, CH ₃ —CH ₂ —N ＝, CH ₃ — (CH ₂ ) ₂ —N =, and CH ₃ — (CH ₂ ) ₃ —N =. No. Examples of the imino group substituted with an aryl group include C ₆ H ₅ —N ＝.

The substituents of the hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7, and R ²⁰ are, independently of each other, a halogen atom; a nitro group; a cyano group; A hydrocarbon group having 1 to 20 carbon atoms; a thiocarbonyl group; The substituent of the hydrocarbon group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ is a fluorine atom, a chlorine atom, a bromine atom; a nitro group; a cyano group; And more preferably a hydrocarbon group having 1 to 10 carbon atoms; a thiocarbonyl group; etc., more preferably a fluorine atom; a hydrocarbon group having 1 to 5 carbon atoms in which all of the hydrogen atoms have been replaced by fluorine atoms. preferable.

Compounds (I) and (II) are characterized in that —CH ₂ — contained in the hydrocarbon groups represented by R ^a1 to R ^a7 and R ^d1 to R ^d7 is —O—, —CO—, —S (O) ₂ -, or -NR ²⁰ - group formed by replacing the (hereinafter sometimes referred to as "group (Z1)") may have. However, -CO ₂ H and -S (O) ₂ OH do not form when -CH ₂ -is replaced.

As the group (Z1),
Methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, (2-ethyl) hexyloxy, (2 (Trifluoromethyl) hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, phenyloxy group, m-tolyloxy group, 3,4-xylyloxy group, etc., having 1 to 20 carbon atoms, more preferably 1 to 10 hydrocarbon-bonded oxy groups (alkoxy groups and aryloxy groups);
An oxiranyl group;
Formyl group;
An acetyl group, a propanoyl group, a butanoyl group, a tert-butanoyl group, a pentanoyl group, a hexanoyl group, a (2-ethyl) hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a benzoyl group, etc., having 2 to 22 carbon atoms, preferably An alkanoyl group having 2 to 12 carbon atoms;
Methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, (2-ethyl) hexyloxycarbonyl group, heptyloxycarbonyl group and octyloxycarbonyl An oxycarbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a group, a nonyloxycarbonyl group, a phenyloxycarbonyl group, an o-tolyloxycarbonyl group is bonded;
An amino group;
N-methylamino group, N, N-dimethylamino group, N-ethylamino group, N, N-diethylamino group, N-propylamino group, N, N-dipropylamino group, N-isopropylamino group, N-diisopropylamino group, N-butylamino group, N, N-dibutylamino group, N-isobutylamino group, N, N-diisobutylamino group, N-sec-butylamino group, N, N-disec-butyl Amino group, N-tert-butylamino group, N, N-ditert-butylamino group, N-pentylamino group, N, N-dipentylamino group, N- (1-ethylpropyl) amino group, N, N -Di (1-ethylpropyl) amino group, N-hexylamino group, N, N-dihexylamino group, N- (2-ethyl) hexylamino group, N, N-di (2-ethyl) Xylamino group, N-heptylamino group, N, N-diheptylamino group, N-octylamino group, N, N-dioctylamino group, N-nonylamino group, N, N-dinonylamino group, N-phenylamino group, N, N-diphenylamino group, N, N-ethylmethylamino group, N, N-propylmethylamino group, N, N-isopropylmethylamino group, N, N-butylmethylamino group, N, N-tert- One or two amino groups having a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a butylmethylamino group and an N, N-phenylmethylamino group;
A sulfamoyl group;
N-methylsulfamoyl group, N, N-dimethylsulfamoyl group, N-ethylsulfamoyl group, N, N-diethylsulfamoyl group, N-propylsulfamoyl group, N, N-dipropyls Rufamoyl group, N-isopropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N-butylsulfamoyl group, N, N-dibutylsulfamoyl group, N-isobutylsulfamoyl group, N, N-diisobutylsulfamoyl group, N-sec-butylsulfamoyl group, N, N-disec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N, N-ditert-butylsulfur Famoyl group, N-pentylsulfamoyl group, N, N-dipentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, , N-di (1-ethylpropyl) sulfamoyl group, N-hexylsulfamoyl group, N, N-dihexylsulfamoyl group, N- (2-ethyl) hexylsulfamoyl group, N, N-di ( 2-ethyl) hexylsulfamoyl group, N-heptylsulfamoyl group, N, N-diheptylsulfamoyl group, N-octylsulfamoyl group, N, N-dioctylsulfamoyl group, N, N -Octylmethylsulfamoyl group, N-nonylsulfamoyl group, N, N-dinonylsulfamoyl group, N-phenylsulfamoyl group, N, N-diphenylsulfamoyl group, N, N-ethylmethyl Sulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-butylmethylsulfamoyl , N, N-tert-butylmethylsulfamoyl group and N, N-phenylmethylsulfamoyl group and one or two hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. A sulfamoyl group;
An N-formylamino group;
N-acetylamino group, N-propanoylamino group, N-butanoylamino group, N-2,2-dimethylpropanoylamino group, N-pentanoylamino group, N-hexanoylamino group, N- (2 -Ethyl) hexanoylamino group, N-heptanoylamino group, N-octanoylamino group, N-nonanoylamino group, N-decanoylamino group, N-undecanoylamino group, N-dodecanoylamino group , An N-alkanoylamino group having 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms, such as N-henicosanoylamino group, N-benzoylamino group;
A hydroxy group;
Formyloxy, acetoxy, propanoyloxy, butanoyloxy, 2,2-dimethylpropanoyloxy, pentanoyloxy, hexanoyloxy, (2-ethyl) hexanoyloxy, heptanoyloxy An alkanoyloxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a group, an octanoyloxy group, a nonanoyloxy group and a benzoyloxy group;
Methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, (2-ethyl) hexylsulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, phenyl A sulfonyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, such as a sulfonyl group and a p-tolylsulfonyl group;
A carbamoyl group;
N-methylcarbamoyl group, N, N-dimethylcarbamoyl group, N-ethylcarbamoyl group, N, N-diethylcarbamoyl group, N-propylcarbamoyl group, N, N-dipropylcarbamoyl group, N-isopropylcarbamoyl group, N , N-diisopropylcarbamoyl group, N-butylcarbamoyl group, N, N-dibutylcarbamoyl group, N-isobutylcarbamoyl group, N, N-diisobutylcarbamoyl group, N-sec-butylcarbamoyl group, N, N-disec- Butylcarbamoyl group, N-tert-butylcarbamoyl group, N, N-ditert-butylcarbamoyl group, N-pentylcarbamoyl group, N, N-dipentylcarbamoyl group, N- (1-ethylpropyl) carbamoyl group, N, N-di (1-ethylpropyl) carba Yl, N-hexylcarbamoyl, N, N-dihexylcarbamoyl, N- (2-ethyl) hexylcarbamoyl, N, N-di (2-ethyl) hexylcarbamoyl, N-heptylcarbamoyl, N-diheptylcarbamoyl, N-octylcarbamoyl, N, N-dioctylcarbamoyl, N-nonylcarbamoyl, N, N-dinonylcarbamoyl, N-phenylcarbamoyl, N, N-diphenylcarbamoyl, N, N-ethylmethylcarbamoyl, N, N-propylmethylcarbamoyl, N, N-isopropylmethylcarbamoyl, N, N-butylmethylcarbamoyl, N, N-tert-butylmethylcarbamoyl and N, N One or two carbon atoms, such as a phenylmethylcarbamoyl group To 20, a carbamoyl group preferably having a hydrocarbon group having 1 to 10 carbon atoms;
* -COCOR ²⁰ ;
* -OCON (R ²⁰ ) ₂ ;
* -N (R ²⁰ ) COOR ²⁰ ; In the above, * represents a bond.
In the above formula, R ²⁰ may be the same or different, and has the same meaning as described above.

The heterocyclic group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 , R ²⁰ , A ¹ and A ² may be monocyclic or polycyclic. Examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom.

The heterocyclic group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 , R ²⁰ , A ¹ and A ² preferably has 2 to 30 carbon atoms, more preferably 3 to 22 carbon atoms. It is preferably 3 to 20, still more preferably 3 to 18, still more preferably 3 to 15, and particularly preferably 3 to 14.

Examples of the heterocyclic group containing only a nitrogen atom as a hetero atom include monocyclic saturated heterocyclic groups such as aziridine, azetidine, pyrrolidine, piperidine, and piperazine; pyrrole, pyrrole such as 2,5-dimethylpyrrole, 2-methylpyrazole, 5-membered unsaturated heterocyclic groups such as pyrazole such as 3-methylpyrazole, imidazole, 1,2,3-triazole and 1,2,4-triazole; pyrimidines such as pyridine, pyridazine, pyrimidine and 6-methylpyrimidine , Pyrazine, 1,2,4-triazine, 1,3,5-triazine and other 6-membered unsaturated heterocyclic groups; indazole, indoline, isoindoline, indole, indolizine, benzimidazole, quinoline, isoquinoline, 5 , 6,7,8-Tetrahydro (3-methyl) quinoxaline, 3-methyl Condensed bicyclic heterocyclic groups such as quinoxaline such as noxaline, quinazoline, cinnoline, phthalazine, naphthyridine, purine, pteridine, benzopyrazole and benzopiperidine; condensed tricyclic heterocyclic groups such as carbazole, acridine and phenazine; And the like heterocyclic groups represented. In the following formula, * represents a bond.

Examples of the heterocyclic group containing only an oxygen atom as a hetero atom include monocyclic saturated heterocyclic groups such as oxirane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, and 1-cyclopentyldioxolane; Bicyclic saturated heterocyclic groups such as 1,4-dioxaspiro [4.5] decane and 1,4-dioxaspiro [4.5] nonane; α-acetolactone, β-propiolactone, γ-butyrolactone, δ-valero A lactone heterocyclic group such as lactone; a 5-membered unsaturated heterocyclic group such as furan such as furan, 2,3-dimethylfuran and 2,5-dimethylhydrofuran; 3,4-dihydro-2H-pyran; 6-membered unsaturated heterocyclic group such as 3,6-dihydro-2H-pyran; benzene such as benzofuran, isobenzofuran and 4-methylbenzopyran Pyran, benzodioxole, chroman, fused bicyclic heterocyclic groups such as isochroman, xanthene, fused tricyclic heterocyclic groups such as dibenzofuran; and the like.

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

Examples of the heterocyclic group containing a nitrogen atom and an oxygen atom as a hetero atom include monocyclic saturated heterocyclic groups such as morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone and 2-methyl-2-piperidone. An oxazole such as oxazole and 4-methyloxazole, an isoxazole, an isoxazole such as 2-methylisoxazole and 3-methylisoxazole, and a monocyclic unsaturated heterocyclic group such as 1,2,4-oxadiazole; Condensed bicyclic heterocyclic groups such as benzoxazole, benzoisoxazole, and benzoxazine; condensed tricyclic heterocyclic groups such as phenoxazine; and the like.

Examples of the heterocyclic group containing a nitrogen atom and a sulfur atom as a hetero atom include monocyclic heterocyclic groups such as thiazole such as thiazole, 3-methylthiazole and 2,4-dimethylthiazole, and isothiazole; benzothiazole and benzoisobenzene. Condensed bicyclic heterocyclic groups such as thiazole and benzothiadiazole; condensed tricyclic heterocyclic groups such as phenothiazine;

As the heterocyclic group containing a nitrogen atom as a hetero atom, a heterocyclic group containing only a nitrogen atom as a hetero atom, a heterocyclic group containing a nitrogen atom and an oxygen atom as a hetero atom, and containing a nitrogen atom and a sulfur atom as a hetero atom And heterocyclic groups.

The heterocyclic group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ may be a group obtained by combining the above-mentioned heterocyclic group and a hydrocarbon group, for example, tetrahydrofurylmethyl Group, methyltetrahydrofuryl group and the like.

The bond position of the above-mentioned heterocyclic group is a portion from which an arbitrary hydrogen atom contained in each ring is eliminated.

The heterocyclic group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 , R ²⁰ , A ¹ and A ² may have a substituent. Examples of the substituent include the same as the monovalent substituent described as the substituent which the hydrocarbon group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ may have. . When the heterocyclic group contains a nitrogen atom as a constituent element, the above-mentioned hydrocarbon group may be bonded to the nitrogen atom as a substituent.

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

When the heterocyclic group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ contains —CH ₂ — which does not form a ring, the —CH ₂ — is represented by —O—, —CO—, —S (O) ₂ — or —NR ²⁰ — may be substituted. However, -CO ₂ H and -S (O) ₂ OH do not form when -CH ₂ -is replaced. When —CH ₂ — is replaced by —O— or the like, the heterocyclic group represented by R ^a1 to R ^a7 or R ^d1 to R ^d7 may have the above 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 combine to form a ring, the ring is , A hydrocarbon ring or a heterocyclic ring. Examples of the hydrocarbon ring include an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring.

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

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

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 combine to form a heterocyclic ring, 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 combine to form a heterocyclic ring, The ring forms two or more ring structures together with the benzene ring to which R ^a2 to R ^a5 and R ^d2 to R ^d5 are bonded. Examples of the two or more ring structures include a heterocyclic ring having a structure represented by the following formula. The benzene ring in the following formula corresponds to the benzene ring in the isoindoline structure of the compound (I) or the 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 combine to form a ring, the ring is , May have a substituent. Examples of the substituent include the same as the monovalent substituent described as the substituent which the hydrocarbon group represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ may have. .

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

The ring formed by the combination of 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 is formed by the above group (Z1 ) May be included.

Examples of the halogen atom represented by R ^a2 to R ^a7 and R ^d2 to R ^d7 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and are preferably a fluorine atom, a chlorine atom, and a bromine atom. Preferably, they are a fluorine atom and a chlorine atom.

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

When a plurality of R ²⁰ and M are present in compound (I) or compound (II), they may be the same or different.

The aromatic hydrocarbon group represented by D ¹ and D ² is preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms. Examples of the aromatic hydrocarbon group include the same groups as those exemplified for the aromatic hydrocarbon groups represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ²⁰ , and preferably a phenyl group or a naphthyl group It is.

The aromatic hydrocarbon group represented by D ¹ and D ² has at least one —CO ₂ M. The aromatic hydrocarbon group represented by D ¹ and D ² has preferably 1 to 3 —CO ₂ M, more preferably 1 to 2 and more preferably 1 More preferred.
When the aromatic hydrocarbon groups represented by D ¹ and D ² has one -CO ₂ M, the bonding position of the -CO ₂ M is not particularly limited, for example, an aromatic hydrocarbon group is naphthyl group In some cases, the structure of the following formula (Da) on the same six-membered ring side as the bond of D ¹ and D ² may be used, or the structure of the following formula (Db) on the different six-membered ring side may be used. There may be. In the following formula, * represents a bond.

The aromatic hydrocarbon group represented by D ¹ and D ² may have a substituent other than —CO ₂ M, and is represented by R ^a1 to R ^a7 , R ^d1 to R ^d7 and R ^20. Examples of the substituent which the hydrocarbon group may have include those obtained by removing -CO ₂ M from the monovalent substituent described above. The number of substituents other than -CO ₂ M in the aromatic hydrocarbon group is preferably from 0 to 6, more preferably from 0 to 3, and even 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, they may be, independently of each other, identical or different. Good.
Note D ¹ and the number of substituents and -CO ₂ M other than -CO ₂ M having aromatic hydrocarbon groups represented by D ² represents the number per aromatic hydrocarbon group.

As the compound (I), those in which R ^a1 to R ^a7 , A ¹ to A ² and M are as follows are preferable.
R ^a1 is preferably a hydrogen atom.
R ^a2 to R ^a5 each independently represent 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 substituted An alkyl group which may have a group); an alkoxy group having 1 to 10 carbon atoms such as methoxy group and butoxy; an alkanoyl group having 2 to 6 carbon atoms such as acetyl group; 3,4-xylyloxy group, α, α An aryloxy group having 6 to 10 carbon atoms which may have a substituent (such as a phenyloxy group which may have a substituent), such as an α, trifluorotoluyloxy group; a fluorine atom, chlorine A halogen atom such as an atom; a nitro group; a cyano group; an amino group; a hydroxy group; a formyl group; a sulfamoyl group; a carboxy group; a sulfo group; It is more preferably one kind selected from halogen atoms such as an elementary atom and a chlorine atom, and even more preferably one kind selected from a hydrogen atom and a chlorine atom.
When 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, an aromatic compound having 6 to 10 carbon atoms such as benzene. It is preferably an aromatic hydrocarbon ring, and more preferably a naphthalene together with a benzene ring in the isoindoline structure.
It is preferable that R ^a2 to R ^a5 do not form a ring.
R ^a6 and R ^a7 are preferably one kind selected from the group consisting of a hydrogen atom, a cyano group, and a nitro group, and more preferably one kind selected from the group consisting of a cyano group and a nitro group. It is more preferably a cyano group. In this case, R ^a6 and R ^a7 are preferably the same group.
A ¹ and A ² each have a substituent such as a condensed bicyclic heterocyclic group which may have a substituent or a condensed tricyclic heterocyclic group which may have a substituent. And a fused heterocyclic group containing a nitrogen atom as a hetero atom (the fused heterocyclic group may have a substituent) is more preferred, and a fused heterocyclic group containing a nitrogen atom as a hetero atom. A bicyclic heterocyclic group (the condensed bicyclic heterocyclic group may have a substituent) is more preferable, and a quinoline group optionally having a substituent, A good indole group or a benzothiazole group which may have a substituent is more preferable. A ¹ and A ² preferably do not have a substituent. A ¹ and A ² are preferably the same. When A ¹ and A ² are a condensed heterocyclic group comprising a heterocyclic ring and a hydrocarbon ring such as an aromatic hydrocarbon, a structure in which a bond is on the heterocyclic side (for example, A ¹ and A ² are quinoline groups In some cases, a structure represented by the following formula) is preferable.

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

Specific examples of the compound (I) include, for example, in the compound represented by the formula (Ia), combinations of R ^a1 , R ^a6 to R ^a7 , A ¹ to A ² and B ¹ B ² are shown in Tables 1 to 11. Compounds (I-1) to (I-966) each having a substituent represented by any of the above.
Compound (I) is preferably compounds (I-1) to (I-460),
More preferred are compounds (I-1) to (I-46),
More 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) and compound (I-46).

In the table, H represents a hydrogen atom, and CN represents a cyano group.
A ¹ and A ^{2 each} represent a heterocyclic group represented by Formulas (AA1) to (AA46).
B ¹ B ² represents any of the partial structures represented by the formulas (BB1) to (BB21).
In formulas (AA1) to (AA46) and (BB1) to (BB21), * and B ¹ B ² each represent a bond.

As the compound (II), those in which R ^d1 to R ^d7 , D ¹ to D ² and M are as follows are preferable.
R ^d1 is preferably a hydrogen atom.
R ^d2 to R ^d5 each independently represent a hydrogen atom; a saturated chain hydrocarbon group having 1 to 10 carbon atoms which may have a substituent such as a butyl group and a trifluoromethyl group (preferably, An alkyl group which may have a group); an alkoxy group having 1 to 10 carbon atoms such as methoxy group and butoxy; an alkanoyl group having 2 to 6 carbon atoms such as acetyl group; 3,4-xylyloxy group, α, α An aryloxy group having 6 to 10 carbon atoms which may have a substituent (such as a phenyloxy group which may have a substituent), such as an α, trifluorotoluyloxy group; a fluorine atom, chlorine A halogen atom such as an atom; a nitro group; a cyano group; an amino group; a hydroxyl group; a formyl group; a sulfamoyl group; a carboxy group; It is more preferably one kind selected from halogen atoms such as an elementary atom and a chlorine atom, and even more preferably one kind selected from a hydrogen atom and a chlorine atom.
When R ^d2 and R ^d3 , R ^d3 and R ^d4, or R ^d4 and R ^d5 combine to form a ring together with the carbon atoms to which they are attached, an aromatic group having 6 to 10 carbon atoms such as benzene It is preferably a hydrocarbon ring, and more preferably, forms a naphthalene together with a benzene ring in the isoindoline structure.
It is preferable that R ^d2 to R ^d5 do not form a ring.
R ^d6 and R ^d7 are preferably one kind selected from the group consisting of a hydrogen atom, a cyano group, and a nitro group, and more preferably one kind selected from the group consisting of a cyano group and a nitro group. It is more preferably a cyano group. In this case, R ^d6 and R ^d7 are preferably the same group.
D ¹ and D ² are each an aromatic hydrocarbon group having 6 to 12 carbon atoms which has at least one —CO ₂ M and may have a substituent other than —CO ₂ M. preferably, a one -CO ₂ M, and, in -CO ₂ M other which may have a substituent phenyl group or -CO ₂ M other which may have a substituent naphthyl group More preferably, there is. Further, it is desirable that D ¹ and D ² have no substituent other than —CO ₂ M. Preferably, D ¹ and D ² are the same.
When M is present 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), combinations of R ^d1 , R ^d6 to R ^d7 , D ¹ to D ² and B ¹ B ² are shown in Tables 12 to 14. Compounds (II-1) to (II-147) having a substituent represented by any of the above.
Compound (II) is preferably compounds (II-1) to (II-70),
More preferred are compounds (II-1) to (II-35),
More preferred are compounds (II-1) to (II-14).

In the table, H represents a hydrogen atom, and CN represents a cyano group.
D ¹ and D ² represent aromatic hydrocarbon groups represented by the formulas (DD1) to (DD7).
B ¹ B ² represents any of the partial structures represented by the formulas (BB1) to (BB21).
In formulas (DD1) to (DD7), * represents a bond.

Hereinafter, the method for producing the compound (I) and the compound (II) will be described. Hereinafter, in the compound (I) or the compound (II), a compound in which R ^a1 or R ^d1 is a hydrogen atom is referred to as “compound (1-H)”, and in the compound (I) or the compound (II), A compound in which R ^a1 or R ^d1 is other than a hydrogen atom is referred to as “compound (1-R)”.

The compound (1-H) includes a compound represented by the formula (pt1) (hereinafter, sometimes referred to as a phthalonitrile compound) and a compound represented by the formula (pt2) (hereinafter, sometimes referred to as an alkoxide compound). After the reaction, a compound represented by the formula (pt3) (hereinafter sometimes referred to as compound (pt3)) and a compound represented by the formula (pt4) (hereinafter sometimes referred to as compound (pt4)) are obtained. It can be produced by further reacting in the presence of an acid.
The compound (1-H) is obtained by reacting a compound represented by the formula (pt5) (hereinafter, sometimes referred to as a 1,3-diiminoisoindoline compound) with a compound (pt3) and a compound (pt4). Can be manufactured.
The compound (1-R) can be produced by reacting the compound (1-H) with a compound represented by the formula (pt6) (hereinafter sometimes referred to as compound (pt6)).

[In the formulas (pt1) to (pt6), the formulas (1-H) and (1-R),
R ¹ to R ⁷ have the same meanings as R ^a1 to R ^a7 in the case of compound (I), and have the same meanings as R ^d1 to R ^d7 in the case of compound (II).
R ⁸ to R ⁹ have the same meanings as A ¹ and A ² in the case of compound (I), and have the same meanings as D ¹ and D ² in the case of compound (II).
R ³¹ represents an alkyl group having 1 to 20 carbon atoms.
M ¹ represents an alkali metal atom.
LG represents a halogen atom, a methanesulfonyloxy group, a toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group. ]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ³¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group and a tert-butyl group. Is an alkyl group having 1 to 6 carbon atoms.
Examples of the alkali metal atom represented by M ¹ include a lithium atom, a sodium atom, and a potassium atom.

The amount of the alkoxide compound represented by the formula (pt2) to be used is generally 0.1 to 10 mol, preferably 0.2 to 5 mol, more preferably 0 to 1 mol, per 1 mol of the phthalonitrile compound. 0.3 to 3 mol, more preferably 0.4 to 2 mol.

The total amount of the compound (pt3) and the compound (pt4) used is usually 2 to 20 mol, preferably 2 to 10 mol, more preferably 2 to 6 mol, per 1 mol of the phthalonitrile compound. And more preferably 2 to 4 mol. The compound (pt3) and the compound (pt4) may be the same.

Examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, fluorosulfonic acid and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid; Examples include carboxylic acids such as acetic acid, citric acid, formic acid, gluconic acid, lactic acid, oxalic acid and tartaric acid, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and Carboxylic acids are mentioned, and acetic acid is more preferable.
The amount of the acid to be used is generally 1 to 20 mol, preferably 1 to 10 mol, more preferably 1 to 8 mol, and still more preferably 1 to 6 mol, per 1 mol of the phthalonitrile compound. is there.

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

Examples of the reaction solvent include water; a nitrile solvent such as acetonitrile; an alcohol solvent such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and 1-octanol; an ether solvent such as tetrahydrofuran; and a ketone solvent 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; N, N-dimethylformamide and N-methylpyrrolidone; Amide solvents; sulfoxide solvents such as dimethyl sulfoxide; and the like. Preferred are water, nitrile solvents, alcohol solvents, ether solvents, ketone solvents, ester solvents, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, amide solvents and sulfoxide solvents. But , 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-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone and dimethylsulfoxide And more preferably water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N, N-dimethylformamide, N-dimethylacetamide, 3- Methyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone N-methylpyrrolidone and dimethyl sulfoxide, more preferably water, acetonitrile, methanol , Ethanol, 2-propanol, N-methylpyrrolidone and dimethylsulfoxide.

使用 The amount of the reaction solvent used is usually 1 to 1000 parts by mass with respect to 1 part by mass of the phthalonitrile compound.

The reaction temperature of the phthalonitrile compound, the alkoxide compound, the compound (pt3) and the compound (pt4) is usually 0 to 200 ° C, preferably 0 to 100 ° C, more preferably 0 to 50 ° C. The reaction time is generally 0.5 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. Examples of the reaction solvent include water; a nitrile solvent such as acetonitrile; an alcohol solvent such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and 1-octanol; an ether solvent such as tetrahydrofuran; and a ketone solvent 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; N, N-dimethylformamide and N-methylpyrrolidone; An amide solvent; a sulfoxide solvent such as dimethyl sulfoxide; and preferably a nitrile solvent, an alcohol solvent, an ether solvent, a ketone solvent, an ester solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an amide solvent and a sulfoxide solvent. Are you 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. Preferably, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl Pyrrolidone, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone and dimethylsulfoxide, even more preferably N, N -Dimethylformamide, N, N-dimethylacetamide, 1-butanol, N-methylpyrrolidone, 3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -Pyrimidinone and dimethylsulfoxide.

使用 The amount of the reaction solvent is usually 1 to 1000 parts by mass with respect to 1 part by mass of the 1,3-diiminoisoindoline compound.

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

The amount of compound (pt6) to be used is generally 1 to 10 mol, preferably 1 to 5 mol, more preferably 1 to 3 mol, and still more preferably 1 mol of compound (1-H). Is 1 to 2 mol.

When the compound (pt6) is reacted, it is preferable that a base coexists. Examples of the base include organic bases such as triethylamine, 4- (N, N-dimethylamino) pyridine, pyridine and piperidine; metal alkoxides such as sodium methoxide, sodium ethoxide, sodium tert-butoxide and potassium tert-butoxide; And organic metal compounds such as tert-butyllithium and phenyllithium; and inorganic bases such as lithium hydroxide, sodium hydroxide and potassium hydroxide.

The amount of the base to be used is generally 1 to 10 mol, preferably 1 to 5 mol, more preferably 1 to 3 mol, and still more preferably 1 to 2 mol, per 1 mol of compound (1-H). Is a mole.

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

使用 The amount of the reaction solvent to be used is generally 1 to 1,000 parts by mass relative to 1 part by mass of compound (1-R) in compound (I) or compound (II). The reaction temperature of the compound (pt6) is usually -90 to 200 ° C, preferably -80 to 100 ° C, more preferably 0 to 50 ° C. The reaction time is generally 0.5 to 300 hours.

方法 The method of extracting compound (I) or compound (II) from the reaction mixture is not particularly limited, and can be extracted by various known methods. For example, after completion of the reaction, compound (I) or compound (II) can be taken out by filtering the reaction mixture. After filtration, the obtained residue may be washed with a washing solvent. After filtration, column chromatography, drying under reduced pressure, recrystallization or sublimation purification may be performed.

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

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

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

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

When the coloring composition is prepared by dispersing the compound (I) and the compound (II) in the solvent (E), by adding the resin (B), the dispersion stability of the coloring composition can be improved. Can be further improved.
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 with respect to 100 parts by mass of the total of the compound (I) and the compound (II). And more preferably 10 to 100 parts by mass.

The compound (I) and the compound (II) may be, if necessary, treated with a rosin, a surface treatment using a derivative into which an acidic group or a basic group is introduced, a compound (I) and a compound (II) with a polymer compound or the like. ) Even if a surface is subjected to a grafting treatment, an atomization treatment by a sulfuric acid atomization method or the like, a washing treatment with an organic solvent or water for removing impurities, or a removal treatment of an ionic impurity by an ion exchange method or the like. Good. It is preferable that the particle diameters of the compound (I) and the compound (II) are substantially uniform. The compound (I) and the compound (II) can be made to be in a state where the compound (I) and the compound (II) are uniformly dispersed in the coloring composition by performing a dispersion treatment by adding a dispersant. .

Examples of the dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples include polyester-based, polyamine-based, and acrylic-based surfactants. These dispersants may be used alone or in combination of two or more. As dispersants, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Corporation), EFKA (registered trademark) (Manufactured by BASF Corp.), Ajispar (registered trademark) (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie), BYK (registered trademark) (manufactured by Big Chemie), etc. No.

When a dispersant is used, the amount of the dispersant (solid content) to be used is preferably 400 parts by mass or less, more preferably 200 parts by mass, based on 100 parts by mass of compound (I) and compound (II) in total. Or less, more preferably 5 to 200 parts by mass, and still more preferably 5 to 150 parts by mass. When the amount of the dispersant used is in the above range, the coloring composition in a more uniform dispersed state tends to be obtained.

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

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

The coloring composition according to the present invention may contain a coloring agent other than the compound (I) and the compound (II) (hereinafter, may be referred to as a coloring agent (A1)) as the coloring agent (A). . In this specification, the compound (I), the compound (II) and the colorant (A1) may be collectively referred to as “colorant (A)”. The colorant (A1) may contain one or more colorants.

The colorant (A1) may be a dye or a pigment. Examples of the dye include known dyes described in Color Index (published by The Society of Dyers and Colorists) and Dyeing Note (Shishome Co., Ltd.). According to the chemical structure, azo dye, anthraquinone dye, triphenylmethane dye, xanthene dye, cyanine dye, naphthoquinone dye, quinone imine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline Dyes, nitro dyes and phthalocyanine dyes. Of these, organic solvent-soluble dyes are preferred. These dyes may be used in combination of two or more kinds.

Specific examples include dyes having the following color index (CI) numbers. C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;
C. I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C. I. Disperse Yellow 51, 54, 76;
C. I. Reactive yellow 2, 76, 116;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;
C. I. Solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99;
C. I. Direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Reactive orange 16;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 57, 66, 73, 76, 80, 88, 91, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 394, 401, 412, 417, 418, 422, 426;
C. I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C. I. Modant red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 29, 30, 32, 33, 36, 37, 38, 39 , 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Acid violet 34;
C. I. Disperse Violet 26, 27;
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112;
C. I. Direct blue 40;
C. I. Disperse Blue 1, 14, 56, 60;
C. I. Solvent Green 1, 3, 5, 28, 29, 32, 33;
C. I. Acid green 3, 5, 9, 25, 27, 28, 41;
C. I. Basic Green 1;
C. I. Bat Green 1 etc.

As the pigment, known pigments can be used, and examples thereof include pigments classified into pigments by a color index (published by The Society of Dyers and Colorists). These may be used alone or in combination of two or more.

Specifically, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, Yellow pigments such as 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, Red pigments such as 269, 273;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60;
C. I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. And green pigments such as CI Pigment Green 7, 36, 58 and 59.

When the coloring composition of the present invention contains the coloring agent (A1) and the solvent (E), a coloring agent (A1) -containing liquid containing the coloring agent (A1) and the solvent (E) is prepared in advance, and then the coloring is performed. The coloring composition may be prepared using the liquid containing the agent (A1). When the colorant (A1) does not dissolve in the solvent (E), the colorant (A1) -containing liquid can be prepared by dispersing the colorant (A1) in the solvent (E) and mixing. The coloring agent (A1) -containing liquid may contain a part or all of the solvent (E) contained in the coloring composition.

When a dispersant is used to prepare the colorant (A1) -containing liquid, the amount of the dispersant (solid content) is preferably 400 parts by mass or less based on 100 parts by mass of the colorant (A1). Yes, more preferably 200 parts by mass or less, still more preferably 5 parts by mass or more and 200 parts by mass or less, still more preferably 5 parts by mass or more and 150 parts by mass or less. When the amount of the dispersant used is within the above range, a more uniform dispersion of the colorant (A1) -containing liquid tends to be obtained.

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

In the coloring agent (A1) -containing liquid, the content of the coloring agent (A1) is usually from 1% by mass to 90% by mass, and preferably from 1% by mass to 80% by mass, based on the total amount of solids. Yes, more preferably 2% by mass to 75% by mass, still more preferably 5% by mass to 75% by mass.

After preparing a colorant (A1) -containing liquid containing the colorant (A1) and the solvent (E) in advance, when preparing the coloring composition of the present invention using the colorant (A1) -containing liquid, The agent (A1) -containing liquid may contain a part or all, preferably a part, of the resin (B) contained in the coloring composition in advance. By including the resin (B) in advance, the dispersion stability of the liquid containing the colorant (A1) can be further improved.
The content of the resin (B) in the colorant (A1) -containing liquid is, for example, 1 to 500 parts by mass, and preferably 5 to 200 parts by mass, based on 100 parts by mass of the colorant (A1). More preferably, it is 10 to 100 parts by mass.

In the coloring composition, the content of the coloring agent (A) obtained by combining the compound (I), the compound (II) and the coloring agent (A1) is usually 1% by mass or more and 90% by mass or less based on the total amount of solids. , Preferably from 1% by mass to 80% by mass, more preferably from 2% by mass to 75% by mass, and still more preferably from 5% by mass to 75% by mass.

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

<Resin (B)>
The resin (B) is preferably an alkali-soluble resin, and is at least one monomer selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as “monomer (a)”). It is preferably a polymer having a structural unit derived from
The resin (B) is a structural unit derived from a monomer having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as “monomer (b)”), and other components. It is preferred that the copolymer has a structural unit of
Other structural units include a monomer copolymerizable with the monomer (a) (however, the monomer (a) and the monomer (b) are different. Hereinafter, the “monomer (c)”) In some cases), a structural unit having an ethylenically unsaturated bond, and the like.

Examples of the monomer (a) include acrylic acid, methacrylic acid, crotonic acid and unsaturated monocarboxylic acids such as o-, m-, 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, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, Bicyclo unsaturated compounds containing a carboxy group such as 5-carboxymethylbicyclo [2.2.1] hept-2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;
Carboxylic anhydrides such as anhydrides of the above-mentioned unsaturated dicarboxylic acids except fumaric acid and mesaconic acid;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of di- or higher-valent polycarboxylic acids such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate Kind;
Examples include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

The monomer (b) is a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. The monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.
Examples of the monomer (b) include a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter, may be referred to as “monomer (b1)”), an oxetanyl group and an ethylenically unsaturated bond. (Hereinafter sometimes referred to as “monomer (b2)”) and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “monomer (b3)”) ) And the like.

As the monomer (b1), for example, a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “monomer (b1-1)” And a monomer having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “monomer (b1-2)”).

As the monomer (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferable. Specific examples of the monomer (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, vinylbenzyl glycidyl ether, α- Methylvinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxy) Methyl) 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 (glycidyloxy) styrene, and the like.

Examples of the monomer (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (Meth) acrylate (for example, Cyclomer (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, cyclomer (registered trademark) M100; manufactured by Daicel Corporation) , A compound represented by the formula (BI) and a compound represented by the formula (BII).

[In the formulas (BI) and (BII), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is a hydroxy group May be substituted.
X ^a and X ^b are each independently a single ^{bond, * - R c -, *} - R c -O -, * - represents the R ^c -S- or * -R ^c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

化合物 Examples of the compound represented by the formula (BI) include compounds represented by any of the formulas (BI-1) to (BI-15). Among them, Formula (BI-1), Formula (BI-3), Formula (BI-5), Formula (BI-7), Formula (BI-9), and Formulas (BI-11) to (BI-15) The compounds represented by the formulas (BI-1), (BI-7), (BI-9) and (BI-15) are more preferred.

Examples of the compound represented by the formula (BII) include compounds represented by any one of the formulas (BII-1) to (BII-15). Among them, the compounds represented by the formulas (BII-1) and (BII-1) are preferable. And compounds represented by formulas (BII-3), (BII-5), (BII-7), (BII-9) and (BII-11) to (BII-15). Preferred are the compounds represented by formula (BII-1), formula (BII-7), formula (BII-9) and formula (BII-15).

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used alone or in combination with the compound represented by the formula (BI) and the compound represented by the formula (BII) May be. When these are used in combination, 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 10:95 to 95: 5. The ratio is 90 to 90:10, and more preferably 20:80 to 80:20.

Examples of the monomer (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (Meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) 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 ] decene-8-yl (meth) acrylate, tricyclo [ 5.2.1.0 ^{2, 6]} decene-9-yl (meth) acrylate, dicyclopentanyl oxyethylates (Meth) acrylates such as (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate ) Acrylate esters;
Hydroxy group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (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 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene A bicyclo unsaturated compound;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3 Dicarbonyl imide derivatives such as maleimide propionate and N- (9-acridinyl) maleimide;
Vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; (meth) acrylamide And vinyl group-containing amides; esters such as vinyl acetate; diene such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;
Among them, styrene, vinyltoluene, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, tricyclo [5.2.1] from the viewpoint of copolymerization reactivity and heat resistance. 0.0 ^2,6 ] decane-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] Decene-9-yl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and benzyl (meth) acrylate are preferred.

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 is obtained by adding a polymer having a structural unit derived from the monomer (a) or the monomer (b) to a group having the monomer (a) or the monomer (b). It can be obtained by adding a monomer having a group capable of reacting with a monomer and an ethylenically unsaturated bond.
Examples of such a structural unit include a structural unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit, a structural unit obtained by adding 2-hydroxyethyl (meth) acrylate to a maleic anhydride unit, and glycidyl (meth) ) Structural units in which (meth) acrylic acid is added to acrylate units. When these structural units have a hydroxy group, structural units to which a carboxylic anhydride is further added are also exemplified as structural units having an ethylenically unsaturated bond.

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

The obtained polymer may be used as it is after the reaction, may be used as a concentrated or diluted solution, or may be obtained as a solid (powder) by a method such as reprecipitation. May be used.
If necessary, a reaction catalyst (for example, tris (dimethylaminomethyl) phenol or the like) between a carboxylic acid or a carboxylic anhydride and a cyclic ether, a polymerization inhibitor (for example, hydroquinone, or the like) may be used.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] Decyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth)
Acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^{2 , 6]} decyl (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth ) Acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / - ethylhexyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / tricyclo [5.2.1.0 ^{2, 6]} decenyl ( (Meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer, benzyl (meth) acrylate / (Meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, resins described in JP-A-9-106071, JP-A-2004-29518 and JP-A-2004-361455 Is mentioned.
Among them, as the resin (B), a copolymer containing a structural unit derived from the monomer (a) and a structural unit derived from the monomer (b) is preferable.
The resin (B) may be a combination of two or more kinds. In this case, the resin (B) is at least 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (Meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (Meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyltoluene copolymer, 3,4-epoxy It is preferable to contain one or more selected from tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and still more preferably from 5,000 to 30,000. 000. The degree of dispersion [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

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

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, based on 100 parts by mass of the total of the compound (I) and the compound (II). And more preferably 50 to 800 parts by mass.
Further, the content of the resin (B) in the coloring composition is preferably 3% by mass or more, more preferably 5% by mass or more, and still more preferably 7 to 99% by mass, based on the total amount of the solid components. It is even more preferably from 13 to 99% by mass, particularly preferably from 17 to 95% by mass.
In the present specification, the “total amount of solid content” refers to the total amount of components obtained by removing the solvent (E) from the coloring composition or the coloring curable resin composition of the present invention. The total amount of the solid content and the content of each component with respect to the solid content can be measured by a 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 an active radical and / or an acid generated from the polymerization initiator (D), and is, for example, a compound having a polymerizable ethylenically unsaturated bond, and is preferably It is a (meth) acrylate compound.

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

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. As such a polymerizable compound, for example, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol Hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate And preferably dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

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

The content of the polymerizable compound (C) is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably the total amount of solids in the colored curable resin composition. The content is 5% by mass or more, even more preferably 7 to 65% by mass, still more preferably 13 to 60% by mass, and particularly preferably 17 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 an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include an O-acyl oxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, and an acylphosphine oxide compound.

Examples of the O-acyl oxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl)- 3-cyclopentylpropan-1-one-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropan-1-one-2-imine, N-acetoxy-1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1- Mine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3- Yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. As the O-acyl oxime compound, commercially available products such as Irgacure OXE01 and OXE02 (both manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyl oxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- At least one selected from the group consisting of 1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferable, and N-benzoyl Oxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferred.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1- On and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy-2-methyl-1-phenyl Propan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- Oligomers of (4-isopropenylphenyl) propan-1-one, α, α-diethoxyacetophenone, benzyldimethyl ketone Tar and the like. As the alkylphenone compound, a commercially available product such as Irgacure 369, 907, 379 (all manufactured by BASF Corporation) may be used.

Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole and 2,2′-bis (2,3-dichlorophenyl) -4 , 4 ', 5,5'-Tetraphenylbiimidazole (for example, refer to JP-A-6-75372 and JP-A-6-75373), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2 ' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (for example, JP-B-48-38403, JP-A-62-17420) And a biimidazole compound in which the phenyl group at the 4,4 ', 5,5'-position is substituted with a carboalkoxy group (see, for example, JP-A-7-10913). .

Triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl)- 1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis ( Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) etheni ] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

(2) Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, and 4-benzoyl- Benzophenone compounds such as 4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone; Quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds and the like.
These are preferably used in combination with a polymerization initiation assistant (D1) (especially amines) described below.

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

The content of the polymerization initiator (D) is preferably 0.001 to 40% by mass, more preferably 0.01 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 from 0.1 to 40 parts by mass, more preferably from 1 to 35 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). Parts by weight.

<Polymerization initiation aid (D1)>
The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound (C) whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (D1) is included, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 4,4'-bis ( Ethylmethylamino) benzophenone and the like, and preferably 4,4′-bis (diethylamino) benzophenone. A commercially available product such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may be used as the amine compound.

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

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

As the carboxylic acid compound, phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When these polymerization initiation aids (D1) are used, their content is preferably 0.001 to 30% by mass, more preferably 0.01 to 30% by mass, based on the total amount of solids in the colored curable resin composition. -20% by mass.
When these polymerization initiation aids (D1) are used, the content thereof is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). , More preferably 1 to 20 parts by mass.

<Solvent (E)>
The solvent (E) includes, for example, an ester solvent (a solvent containing -COO- in the molecule and containing no -O-), an ether solvent (a solvent containing -O- in the molecule and containing no -COO-), Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule, not containing -COO-), alcohol solvent (containing OH in the molecule) , -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents and dimethyl sulfoxide.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol monoethyl ether. Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, die Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, include phenetol and methyl anisole and the like.

Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, and 3-ethoxy. Ethyl propionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, Ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl acetate Le 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 and dipropylene glycol methyl ether acetate and the like.

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 And the like.

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

ベ ン ゼ ン 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 and N-methylpyrrolidone.

溶 剤 Two or more of these solvents may be used in combination.

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

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

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Dow Corning Toray), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan GK).

と し て Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in a molecule. Specifically, Florado (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554 R30, RS-718-K (manufactured by DIC Corporation), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals, Inc.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

シ リ コ ー ン Examples of the silicone-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

When the leveling agent (F) is contained, its content is usually 0.0005% by mass or more and 1% by mass or less, preferably 0.001% by mass or more and 0% by mass or less, based on the total amount of the colored curable resin composition. 0.5% by mass, more preferably 0.001% by mass to 0.2% by mass, still more preferably 0.002% by mass to 0.1% by mass, and still more preferably 0.005% by mass. It is not less than 0.1% by mass and not more than 0.1% by mass. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Antioxidant>
From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use an antioxidant alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.

Examples of the phenolic antioxidant include Irganox 1010 (Irganox # 1010: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation) Irganox 1076 (Irganox # 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corporation), Irganox 1330 (Irganox # 1330: 3, 3 ', 3') ', 5,5', 5 ''-hexa-tert-butyl-a, a ', a' '-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Corporation; Irganox 3114: 1,3,5-Tris (3 5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by BASF), Irganox 3790 (Irganox @ 3790) : 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H)- Irionox 1035 (Irganox # 1035: thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF Corporation), Irganox 1135 (Irganox @ 1135: benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C Side chain alkyl ester, manufactured by BASF Corporation, Irganox 1520L (Irganox # 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF Corporation), Irganox 3125 (Irganox # 3125, BASF) Irganox 565 (Irganox @ 565: 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ′, 5′-di-tert-butylanilino) -1,3,5-triazine; BASF Corporation), ADK STAB AO-80 (ADK STAB 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, ( ADEKA Corporation), Sumilizer BHT (Sumilizer @ BHT, Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer @ GA-80, Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer @ GS, Sumitomo Chemical Co., Ltd.) ), Cyanox 1790 (Cyanox # 1790, manufactured by Cytec Corporation) and vitamin E (manufactured by Eisai Co., Ltd.).

Examples of the phosphorus-based antioxidant include Irgafos 168 (Irgafos # 168: Tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF) and Irgafos 12 (Irgafos # 12: Tris [2- [[2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, BASF Corporation; Irgafos 38 (Irgafos # 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Corporation), ADK STAB 329K (manufactured by ADEKA Corporation), ADK STAB PEP-36 (made by ADEKA Corporation), ADK STAB PEP-8 (made by ADEKA Corporation), San stab @ P-EPQ (Clariant), Weston 618 (Weston 618, GE), Weston 619G (Weston 619G, GE), Ultranox 626 (Ultranox 626, GE), and Sumilizer GP (Sumilizer GP: 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1.3.2] di Oxaphosphepin) (manufactured by Sumitomo Chemical Co., Ltd.).

Examples of the sulfur-based antioxidant include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl and distearyl, and β-alkylmercaptopropion of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane. Acid ester compounds and the like.

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

<Method for producing colored curable resin composition>
The colored curable resin composition includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E), and a polymerization initiation aid used as needed. It can be prepared by mixing the agent (D1), the leveling agent (F), the antioxidant and other components.

<Color filter>
A colored pattern can be formed from the colored curable resin composition of the present invention. Examples of a method for forming a colored pattern include a photolithographic method, an inkjet method, a printing method, and the like. Among them, the photolithographic method is preferred. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, exposed to light through a photomask, and developed. In the photolithographic method, a colored coating film which is a cured product of the colored composition layer can be formed by not using a photomask at the time of exposure and / or not developing. The colored pattern or the colored coating film thus formed is the color filter of the present invention.

The thickness of the color filter to be produced is not particularly limited, and can be appropriately adjusted depending on the purpose and application. For example, the thickness is 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably. Is 0.5 to 6 μm.

Examples of the substrate include quartz glass, borosilicate glass, alumina silicate glass, a glass plate such as soda lime glass having a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, and the like. Formed with a thin film of aluminum, silver, silver / copper / palladium alloy, or the like. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

The formation of each color pixel by the photolithographic method can be performed by a known or commonly used device or condition. For example, it can be manufactured as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent and dried to obtain a smooth colored composition layer.
Examples of the coating method include a spin coating method, a slit coating method and a slit and spin coating method.

(4) The temperature for heating and drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, and more preferably from 30 seconds to 30 minutes.

(4) When drying under reduced pressure, it is preferable to perform drying under a pressure of 50 to 150 Pa and a temperature range of 20 to 25 ° C.

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

Next, the coloring composition layer is exposed through a photomask for forming a desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.

光源 As a light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light of less than 350 nm is cut using a filter that cuts this wavelength range, and light of about 436 nm, 408 nm, and 365 nm is selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, mercury lamps, light emitting diodes, metal halide lamps, halogen lamps and the like can be mentioned.

Use of an exposure device such as a mask aligner and a stepper can uniformly irradiate a parallel light beam on the entire exposed surface or perform accurate alignment between the photomask and the substrate on which the coloring composition layer is formed. Is preferred.

着色 A colored pattern is formed on the substrate by bringing the colored composition layer after exposure into contact with a developing solution and developing. By the development, the unexposed portions of the colored composition layer are dissolved in the developer and removed.

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

The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be inclined at an arbitrary angle during development.
The substrate after development is preferably washed with water.

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

着色 According to the coloring 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, electronic paper, and the like) and a solid-state imaging device, and is particularly useful as a color filter used in a liquid crystal display device.

Hereinafter, the present invention will be described more specifically with reference to Examples. However, the present invention is not limited to the following Examples, and may be appropriately modified within a range that can conform to the purpose of the preceding and the following. It is, of course, possible to implement them, and all of them are included in the technical scope of the present invention. In the following, “parts” means “parts by mass” and “%” means “% by mass” unless otherwise specified.

In the following, the structure of the compound was confirmed by mass spectrometry (LC; model 1200 manufactured by Agilent, MASS; model LC / MSD6130 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, Ltd.) and 300 parts of 1-butanol were mixed. To the resulting mixture, 24 parts of β-oxo-2-quinolinepropanenitrile (synthesized according to the method described in WO2011 / 089132) was added, and the mixture was stirred at 45 ° C. under a reduced pressure of 10 kPa for 10 hours. The obtained mixture was filtered, 100 parts of acetic acid was added to the residue, and the mixture was stirred at 80 ° C for 2 hours. The obtained mixture was filtered, 300 parts of water was added to 9.8 parts of the residue, and the mixture was stirred at 80 ° C for 2 hours. The obtained mixture was filtered, and the residue after filtration was washed with 300 parts of methanol to obtain 9.5 parts of a residue. 15 parts of N, N-dimethylformamide was added to 9.5 parts of the residue after washing, followed by stirring at 80 ° C. for 2 hours. Cooled to 0 ° C. and stirred for 2 hours. The obtained mixture was filtered and washed with 60 parts of methanol, and the obtained residue was dried under reduced pressure at 60 ° C. to obtain 16 parts of a compound represented by the formula (I-1). (Yield 79%). A wavy line indicates that an E-form, a Z-form, or a mixture thereof is included (the same applies to synthesis examples below).

<Identification of Compound I-1>
(Mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 504
Exact Mass: 503

Synthesis Example 2
In the same manner as in Synthesis Example 1, except that 24 parts of β-oxo-2-quinolinepropanenitrile in Synthesis Example 1 was replaced with 23 parts of β-oxo-1H-indole-3-propanenitrile (manufactured by Aldrich). Synthesis was performed. 14 parts of the compound represented by the formula (I-2) were obtained (yield: 69%).

<Identification of Compound I-2>
(Mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 480
Exact Mass: 479

Synthesis Example 3
Synthesis Example 1 was the same as Synthesis Example 1 except that 24 parts of β-oxo-2-quinolinepropanenitrile in Synthesis Example 1 was changed to 25 parts of β-oxo-2-benzothiazolepropanenitrile (synthesized according to the method described in WO2011 / 016528). Synthesis was performed in a similar manner. 8.8 parts of a compound represented by the formula (I-3) was obtained (yield: 41%).

<Identification of compound I-3>
(Mass spectrometry) Ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 516
Exact Mass: 515

Synthesis Example 4
Same as Synthesis Example 1 except that 24 parts of β-oxo-2-quinolinepropanenitrile in Synthesis Example 1 was replaced with 23 parts of 4- (2-cyanoacetyl) benzoic acid (synthesized according to the method described in US Pat. No. 2,680,731). The synthesis was performed by the method. 16 parts of the compound represented by the formula (II-1) were obtained (yield: 77%).

<Identification of compound II-1>
(Mass Spectrometry) ionization mode ^{= ESI -: m / z =} [M-H] - 488
Exact Mass: 489

Synthesis Example 5
6.0 parts of dimethyl 2,6-naphthalenedicarboxylate (manufactured by Tokyo Chemical Industry Co., Ltd.) was suspended in 47 parts of acenitrile (manufactured by Wako Pure Chemical Industries, Ltd.). While maintaining the temperature of the obtained mixture at 60 ° C., 3.5 parts of tert-butoxy sodium (manufactured by Kanto Chemical Co., Ltd.) was added over 1 minute, and the mixture was stirred for 90 minutes. While keeping the temperature at 5 ° C or lower, 2.2 parts of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Ltd.) and 45 parts of water were added dropwise over 30 minutes, the temperature was raised to 25 ° C, and the mixture was stirred at 25 ° C for 1 hour. The resulting mixture was filtered, and the residue after filtration was washed with 30 parts of water and 10 parts of methanol. The obtained residue was dried under reduced pressure at 60 ° C to give 6- (2-cyanoacetyl) -2-. 3.7 parts of methyl naphthalenecarboxylate were obtained (60% yield).
3.7 parts of methyl 6- (2-cyanoacetyl) -2-naphthalenecarboxylate were suspended in 15 parts of water. While maintaining the temperature of the obtained mixture at 80 ° C., 0.88 parts of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 25 minutes. While keeping the temperature at 5 ° C or lower, 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 resulting mixture was filtered, and the residue after filtration was washed with 30 parts of water and 10 parts of methanol. The obtained residue was dried under reduced pressure at 60 ° C to give 6- (2-cyanoacetyl) -2-. 2.6 parts of naphthalenecarboxylic acid were obtained (75% yield).
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 acid was added to the obtained mixture, and the mixture was stirred at 45 ° C. for 10 hours. The obtained mixture was filtered, 100 parts of acetic acid was added to the residue, and the mixture was stirred at 80 ° C for 2 hours. The obtained mixture was filtered, 300 parts of water was added to 9.8 parts of the residue, and the mixture was stirred at 80 ° C for 2 hours. The obtained mixture was filtered, and the residue after filtration was washed with 300 parts of methanol to obtain a residue. After washing, 15 parts of N, N-dimethylformamide was added to the residue, and the mixture was stirred at 80 ° C. for 2 hours. Cooled to 0 ° C. and stirred for 2 hours. The obtained mixture was filtered and washed with 60 parts of methanol, and the obtained residue was dried under reduced pressure at 60 ° C. to obtain 18 parts of a compound represented by the formula (II-2). (Yield 76%).

<Identification of compound II-2>
(Mass Spectrometry) ionization mode ^{= ESI -: m / z =} [M-H] - 588
Exact Mass: 589

Synthesis Example 6
Same as Synthesis Example 1 except that 24 parts of β-oxo-2-quinolinepropanenitrile in Synthesis Example 1 was replaced with 24 parts of β-oxo-2-thiazolepropanenitrile (synthesized according to the method described in WO2011 / 016528). The synthesis was carried out by the following method. 14.4 parts of a compound represented by the formula (I-14) was obtained (yield: 73%).

Synthesis Example 7
Same as Synthesis Example 1 except that 24 parts of β-oxo-2-quinolinepropanenitrile in Synthesis Example 1 was changed to 24 parts of β-oxo-2-pyrazinepropanenitrile (synthesized according to the method described in WO2011 / 016528). The synthesis was carried out by the following method. 12 parts of a compound represented by the formula (I-19) was obtained (yield: 65%).

Resin synthesis example 1
An appropriate amount of nitrogen was flown into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere of nitrogen, and 280 parts of propylene glycol monomethyl ether acetate was added. Subsequently, 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} ] Mixture of decane-9-yl acrylate (content ratio is 1: 1 in molar ratio)
A mixed solution of 289 parts and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution in which 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) was dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at 80 ° C. for 4 hours, then cooled to room temperature, and a copolymer (resin B1) solution having a solid content of 35.1% and a viscosity of 125 mPa · s measured by a B-type viscometer (23 ° C.) I got 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 polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: tetrahydrofuran Flow rate: 1.0 mL / min Solid concentration of analytical sample: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Standard material for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight in terms of polystyrene obtained above was defined as the degree of dispersion.

Example 1
(1) Preparation of Colored Composition and Colored Curable Resin Composition The following components were mixed, and the compound (I-1) and the compound (II-1) were dispersed using a bead mill to obtain a colored composition 1. . In the following components, BYK-LPN6919 (manufactured by BYK Japan KK) was used as a dispersant, and propylene glycol monomethyl ether acetate was used as a solvent (E).
Colorant (A): Compound (I-1) 45 parts Compound (II-1) 5 parts Dispersant 58 parts Resin (B): Resin B1 solution 93 parts Solvent (E): 800 parts

After the colored composition 1 was allowed to stand at 23 ° C. for 14 hours, the following components were mixed to obtain a colored curable resin composition 1. In the following components, dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) was used as the polymerizable compound (C), and N-benzoyloxy-1- () was used as the polymerization initiator (D). 4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF), propylene glycol monomethyl ether acetate as a solvent (E), and polyether as a leveling agent A modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was used.
Coloring composition 1: 400 parts Resin (B): Resin B1 solution 45 parts Polymerizable compound (C): 25 parts Polymerization initiator (D): 15 parts Solvent (E): 86 parts Leveling agent: 0.12 parts

(2) Preparation of Colored Coating Film A colored curable resin composition was applied on a 5 cm square glass substrate (Eagle XG; manufactured by Corning) by spin coating so that the film thickness after post-baking was 2 μm. Thereafter, prebaking was performed at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the colored composition layer formed on the substrate was exposed to light using an exposure machine (TME-150RSK; manufactured by Topcon Corporation) at an exposure amount of 80 mJ / cm ² (based on 365 nm) in an air atmosphere. Irradiated. After the 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 The absorption of the obtained colored coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The obtained colored coating film was further heated at 230 ° C. for 120 minutes in an oven under an air atmosphere, and the absorption was measured with a colorimeter. The absorbance retention was determined from the change in absorbance at the maximum absorption wavelength of the colored coating film before and after the test.

(4) Light fastness test An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya; cuts light of 380 nm or less) was placed on the obtained colored coating film, and a light fastness tester (SUNEST CPS +: Toyo) After irradiating with a xenon lamp for 48 hours using a Seiki Co., Ltd.), the absorption was measured with a colorimeter. The absorbance retention was determined from the change in absorbance at the maximum absorption wavelength of the colored coating film before and after the test.

Examples 2 to 8 and Comparative Examples 1 to 4
Example 2 was the same as Example 1 except that 45 parts of compound (I-2) was used instead of 45 parts of compound (I-1) as the colorant (A).
In Example 3, 45 parts of the compound (I-3) and 5 parts of the compound (II) were used in place of 45 parts of the compound (I-1) and 5 parts of the compound (II-1) as the colorant (A). Same as Example 1 except that -2) was used.
In Examples 4 to 6, 45 parts of the compound (II-1) was used in Example 4 instead of 5 parts of the compound (II-1) as the coloring agent (A), and 0.5 part of the compound (II) was used in Example 5. Compound (II-1) was prepared in the same manner as in Example 1 except that 0.1 part of compound (II-1) was used in Example 6.
In Examples 7 and 8, 45 parts of the compound (I-14) was used in Example 7 instead of 45 parts of the compound (I-1) as the colorant (A), and 45 parts of the compound (I) was used in Example 8. Example 19 was the same as Example 1 except that I-19) was used.
In Comparative Examples 1 to 4, 50 parts of the compound (I-1) was used in Comparative Example 1 instead of 45 parts of the compound (I-1) and 5 parts of the compound (II-1) as the colorant (A). Comparative Example 2 was carried out except that 50 parts of the compound (I-2) was used, Comparative Example 3 used 50 parts of the compound (I-3), and Comparative Example 4 used 50 parts of the compound (II-1). Same as Example 1.
Table 15 shows the results of Examples 2 to 8 and Comparative Examples 1 to 4.

The stability of the dispersions (that is, the coloring compositions) prepared in Examples and Comparative Examples was evaluated according to the following criteria. 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 does not substantially change, and the production of a colored coating film and the heat resistance and light resistance tests can be carried out without any problem.
B: After standing at 23 ° C. for 14 hours, the viscosity increases, but the preparation of a colored coating film and the heat resistance and light resistance tests can be carried out without any problem.
C: After standing at 23 ° C. for 14 hours, it hardens and a colored coating film cannot be produced.

In Comparative Examples 1 to 3, it was found that when the resulting dispersion was allowed to stand at 23 ° C. for 14 hours, it hardened and the stability of the dispersion was low.

示 す As shown in Table 15, it can be seen that the color composition according to the present invention can form a color filter having excellent light fastness. Further, the coloring composition according to the present invention has good heat resistance. Furthermore, it turns out that the coloring composition concerning this invention is also excellent in the stability of a dispersion liquid.

Claims (10)

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

   

   [In the formulas (I) and (II),
   A ¹ and A ² independently represent a heterocyclic group which may have a substituent.
   D ¹ and D ² independently represent an optionally substituted aromatic hydrocarbon group, and the aromatic hydrocarbon group has at least one —CO ₂ M.
   R ^a1 and R ^d1 each independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, or a hydrogen atom; the -CH ₂ when including - - and heterocyclic group is -CH ₂ does not constitute a ring - is, -O - -CH ₂ contained in the hydrocarbon group, - CO -, - S ( O) 2 - Or —NR ²⁰ —.
   R ^a2 to R ^a7 and R ^d2 to R ^d7 each independently represent a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, atom, a halogen atom, a cyano group, a nitro group, -CO ₂ M or _{-S (O) 2 OM, -CH} 2 contained in the hydrocarbon group - -CH ₂ where and heterocyclic groups do not constitute a ring - it is, -O - - the -CH ₂ when containing, - CO -, - S ( O) 2 -, or -NR ²⁰ - may be replaced with.
   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 are substituted together with the carbon atom to which each is attached. May form a ring which may have a group. When the ring contains -CH ₂ -which does not form a ring, -CH ₂ -is -O-, -CO-, -S (O ) ₂ -, or -NR ²⁰ - it may be replaced with.
   M represents a hydrogen atom or an alkali metal atom.
   R ²⁰ represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
   When a plurality of R ²⁰ and M are present, they may be the same or different.
   A wavy line indicates that an E-form, a Z-form or a mixture thereof is included. ]
2. The colored composition according to claim 1, wherein A ¹ and A ² are each independently a condensed heterocyclic group which may have a substituent.
3. 3. The colored composition according to claim 1, wherein R ^a1 and R ^d1 are a hydrogen atom, and R ^a6 to R ^a7 and R ^d6 to R ^d7 are a cyano group or a nitro group.
4. ^4. The coloring composition according to claim ^1, wherein A ¹ and A ² are the same, and R ^a6 and R ^a7 are the same group.
5. ^5. The coloring composition according to claim ^1, wherein D ¹ and D ² are the same, and R ^d6 and R ^d7 are the same group.
6. (6) The colored composition according to any one of (1) to (5), wherein the mass ratio of the compound represented by the formula (I) to the compound represented by the formula (II) is 1 to 1,000.
7. 着色 The colored composition according to any one of claims 1 to 6, further comprising a resin (B).
8. (8) A colored curable resin composition comprising the colored composition according to any one of (1) to (7), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).
9. A color filter formed from the colored curable resin composition according to claim 8.
10. A display device including the color filter according to claim 9.