JP7093263B2 - Isoindoline compounds - Google Patents

Description

The present invention relates to isoindoline compounds.

The color curable resin composition is used for manufacturing a color filter used in a display device such as a liquid crystal display device, an electroluminescence display device and a plasma display. Such a color-curable resin composition contains a colorant in order to obtain a desired color tone or the like, and the colorant is a compound represented by the following formula (i) or formula (ii). Is known (Patent Document 1).

Japanese Unexamined Patent Publication No. 2017-137490

An object of the present invention is to provide a compound capable of forming a color filter having excellent heat resistance and light resistance.

［式（１）中、
Ｒ¹は、置換基を有していてもよい炭素数１～４０の炭化水素基、置換基を有していてもよい複素環基、又は水素原子を表し、該炭化水素基に含まれる－ＣＨ₂－及び該複素環基が環を構成しない－ＣＨ₂－を含むときの該－ＣＨ₂－は、－Ｏ－、－ＣＯ－、－Ｓ（Ｏ）₂－、又は－ＮＲ²⁰－に置き換わっていてもよい。
Ｒ²～Ｒ⁷は、互いに独立に、置換基を有していてもよい炭素数１～４０の炭化水素基、置換基を有していてもよい複素環基、水素原子、ハロゲン原子、シアノ基、ニトロ基、－ＣＯ₂Ｍ又は－Ｓ（Ｏ）₂ＯＭを表し、該炭化水素基に含まれる－ＣＨ₂－及び該複素環基が環を構成しない－ＣＨ₂－を含むときの該－ＣＨ₂－は、－Ｏ－、－ＣＯ－、－Ｓ（Ｏ）₂－、又は－ＮＲ²⁰－に置き換わっていてもよい。
Ｒ²とＲ³、Ｒ³とＲ⁴及びＲ⁴とＲ⁵は、各々が結合する炭素原子と一緒になって置換基を有していてもよい環を形成してもよく、該環が環を構成しない－ＣＨ₂－を含むときの該－ＣＨ₂－は、－Ｏ－、－ＣＯ－、－Ｓ（Ｏ）₂－、又は－ＮＲ²⁰－に置き換わっていてもよい。
Ｍは、水素原子又はアルカリ金属原子を表す。
Ｒ²⁰は、水素原子、置換基を有していてもよい炭素数１～４０の炭化水素基、又は置換基を有していてもよい複素環基を表す。
Ｒ²⁰及びＭが複数存在する場合、それらは同一であってもよく、異なっていてもよい。
Ｒ⁸及びＲ⁹は、互いに独立に、置換基を有していてもよいナフチル基を表す。Ｒ⁸及びＲ⁹のいずれかのナフチル基は、少なくとも１つの－ＣＯ₂Ｍを有する。
波線は、Ｅ体、Ｚ体又はそれらの混合物が含まれることを表す。］
[２] Ｒ¹が水素原子であり、Ｒ⁶及びＲ⁷が、互いに独立に、シアノ基又はニトロ基である[１]に記載の化合物。
[３] Ｒ⁶とＲ⁷とが同じ基であり、Ｒ⁸とＲ⁹とが同じ基である[１]又は[２]に記載の化合物。
[４] [１]～[３]のいずれかに記載の化合物を含む着色剤と樹脂とを含む着色組成物。
[５] 溶剤をさらに含む、[４]に記載の着色組成物。
[６] [５]に記載の着色組成物と、重合性化合物と、重合開始剤とを含む着色硬化性樹脂組成物。
[７] [６]に記載の着色硬化性樹脂組成物から形成されたカラーフィルタ。
[８] [７]に記載のカラーフィルタを含む表示装置。 The gist of the present invention is as follows.
[1] A compound represented by the formula (1).

[In equation (1),
R ¹ represents 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, and is contained in the hydrocarbon group. When CH _2- and the heterocyclic group contain -CH _2- , which does not form a ring, the -CH _2- becomes -O-, -CO-, -S (O) _2- , or -NR ^20- . It may be replaced.
R ² to R ⁷ are independent of each other, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, and a cyano. The group represents a group, a nitro group, -CO ₂ M or -S (O) ₂ OM, and when it contains -CH _2- contained in the hydrocarbon group and -CH _2- in which the heterocyclic group does not form a ring. -CH _2- may be replaced with -O-, -CO-, -S (O) _2- , or -NR ^20- .
R ² and R ³ , R ³ and R ⁴ and R ⁴ and R ⁵ may each form a ring that may have a substituent together with the carbon atom to which the ring is bonded. The —CH ₂ − when it contains —CH ₂ − that does not form a ring may be replaced with —O—, —CO—, —S (O) ₂ −, or −NR ²⁰ −.
M represents a hydrogen atom or an alkali metal atom.
R ²⁰ represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
When there are a plurality of R ²⁰ and M, they may be the same or different.
R ⁸ and R ⁹ represent naphthyl groups which may have substituents independently of each other. The naphthyl group of any of R ⁸ and R ⁹ has at least one -CO ₂ M.
Wavy lines indicate that E-forms, Z-forms or mixtures thereof are included. ]
[2] The compound according to [1], wherein R ¹ is a hydrogen atom and R ⁶ and R ⁷ are independent of each other as a cyano group or a nitro group.
[3] The compound according to [1] or [2], wherein R ⁶ and R ⁷ are the same group, and R ⁸ and R ⁹ are the same group.
[4] A coloring composition containing a colorant containing the compound according to any one of [1] to [3] and a resin.
[5] The coloring composition according to [4], further comprising a solvent.
[6] A coloring curable resin composition containing the coloring composition according to [5], a polymerizable compound, and a polymerization initiator.
[7] A color filter formed from the colored curable resin composition according to [6].
[8] A display device including the color filter according to [7].

According to the present invention, it is possible to provide a compound capable of forming a color filter having excellent light resistance and heat resistance.

The compound according to the present invention is a compound represented by the formula (1) (hereinafter, also referred to as compound (1)). Hereinafter, the present invention will be described in detail using the formula (1), and the compound (1) also includes tautomers of the compound (1) and salts thereof.
Compound (1) can be used as a colorant.
The coloring composition of the present invention contains a coloring agent and a resin (hereinafter, also referred to as resin (B)), and the coloring agent contains the compound (1).
The coloring composition of the present invention may contain one kind or two or more kinds of compounds (1).
The coloring composition of the present invention may contain a solvent (hereinafter, also referred to as a solvent (E)) in addition to the compound (1) and the resin (B).
The colored curable resin composition of the present invention is also referred to as 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) are included.
The colored curable resin composition of the present invention may contain a polymerization initiation aid (hereinafter, also referred to as a polymerization initiation aid (D1)).
The colored curable resin composition of the present invention may further contain a leveling agent (hereinafter, also referred to as a leveling agent (F)) and an antioxidant.

<Compound (1)>
The compound (1) is a compound represented by the formula (1).

［式（１）中、
Ｒ¹は、置換基を有していてもよい炭素数１～４０の炭化水素基、置換基を有していてもよい複素環基、又は水素原子を表し、該炭化水素基に含まれる－ＣＨ₂－及び該複素環基が環を構成しない－ＣＨ₂－を含むときの該－ＣＨ₂－は、－Ｏ－、－ＣＯ－、－Ｓ（Ｏ）₂－、又は－ＮＲ²⁰－に置き換わっていてもよい。ただし、－ＣＨ₂－が置き換わることで－ＣＯ₂Ｈ及び－Ｓ（Ｏ）₂ＯＨを形成することはない。
Ｒ²～Ｒ⁷は、互いに独立に、置換基を有していてもよい炭素数１～４０の炭化水素基、置換基を有していてもよい複素環基、水素原子、ハロゲン原子、シアノ基、ニトロ基、－ＣＯ₂Ｍ又は－Ｓ（Ｏ）₂ＯＭを表し、該炭化水素基に含まれる－ＣＨ₂－及び該複素環基が環を構成しない－ＣＨ₂－を含むときの該－ＣＨ₂－は、－Ｏ－、－ＣＯ－、－Ｓ（Ｏ）₂－、又は－ＮＲ²⁰－に置き換わっていてもよい。ただし、－ＣＨ₂－が置き換わることで－ＣＯ₂Ｈ及び－Ｓ（Ｏ）₂ＯＨを形成することはない。
Ｒ²とＲ³、Ｒ³とＲ⁴及びＲ⁴とＲ⁵は、各々が結合する炭素原子と一緒になって置換基を有していてもよい環を形成してもよく、該環が環を構成しない－ＣＨ₂－を含むときの該－ＣＨ₂－は、－Ｏ－、－ＣＯ－、－Ｓ（Ｏ）₂－、又は－ＮＲ²⁰－に置き換わっていてもよい。ただし、－ＣＨ₂－が置き換わることで－ＣＯ₂Ｈ及び－Ｓ（Ｏ）₂ＯＨを形成することはない。
Ｍは、水素原子又はアルカリ金属原子を表す。
Ｒ²⁰は、水素原子、置換基を有していてもよい炭素数１～４０の炭化水素基、又は置換基を有していてもよい複素環基を表す。
化合物（１）にＲ²⁰及びＭが複数存在する場合、それらは同一であってもよく、異なっていてもよい。
Ｒ⁸及びＲ⁹は、互いに独立に、置換基を有していてもよいナフチル基を表す。Ｒ⁸及びＲ⁹のいずれかのナフチル基は、少なくとも１つの－ＣＯ₂Ｍを有する。
波線は、Ｅ体、Ｚ体又はそれらの混合物が含まれることを表す。］

[In equation (1),
R ¹ represents 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, and is contained in the hydrocarbon group. When CH _2- and the heterocyclic group contain -CH _2- , which does not form a ring, the -CH _2- becomes -O-, -CO-, -S (O) _2- , or -NR ^20- . It may be replaced. However, the replacement of -CH _2- does not form -CO ₂ H and -S (O) ₂ OH.
R ² to R ⁷ are independent of each other, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, a heterocyclic group which may have a substituent, a hydrogen atom, a halogen atom, and a cyano. The group represents a group, a nitro group, -CO ₂ M or -S (O) ₂ OM, and when it contains -CH _2- contained in the hydrocarbon group and -CH _2- in which the heterocyclic group does not form a ring. -CH _2- may be replaced with -O-, -CO-, -S (O) _2- , or -NR ^20- . However, the replacement of -CH _2- does not form -CO ₂ H and -S (O) ₂ OH.
R ² and R ³ , R ³ and R ⁴ and R ⁴ and R ⁵ may each form a ring that may have a substituent together with the carbon atom to which the ring is bonded. The —CH ₂ − when it contains —CH ₂ − that does not form a ring may be replaced with —O—, —CO—, —S (O) ₂ −, or −NR ²⁰ −. However, the replacement of -CH _2- does not form -CO ₂ H and -S (O) ₂ OH.
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 in compound (1), they may be the same or different.
R ⁸ and R ⁹ represent naphthyl groups which may have substituents independently of each other. The naphthyl group of any of R ⁸ and R ⁹ has at least one -CO ₂ M.
Wavy lines indicate that E-forms, Z-forms or mixtures thereof are included. ]

The hydrocarbon groups having 1 to 40 carbon atoms represented by R ¹ to R ⁷ and R ²⁰ represent an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group is saturated or unsaturated. It may be chain-shaped or cyclic (aliphatic type).

Saturated or unsaturated chain hydrocarbon groups represented by R ¹ to R ⁷ and R ²⁰ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group and nonyl group. , Decyl group, undecyl group, dodecyl group, heptadecyl group, octadecyl group, linear 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, (3-ethyl) pentyl Branched chain alkyl groups such as groups, isohexyl groups, (5-methyl) hexyl groups, (2-ethyl) hexyl groups, and (3-ethyl) heptyl groups; vinyl groups, 1-propenyl groups, 2-propenyl groups, etc. Group (allyl group), isopropenyl group, (1-methyl) ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1- (2-propenyl)) ethenyl group, (1, 2-dimethyl) alkenyl groups such as propenyl group and 2-pentenyl group; and the like.

The saturated or unsaturated chain hydrocarbon group represented by R ¹ to R ⁷ and R ²⁰ has preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and further preferably 1 to 15 carbon atoms. Yes, more preferably 1 to 10, even more preferably 1 to 8, and particularly preferably 1 to 5.

Saturated or unsaturated alicyclic hydrocarbon groups represented by R ¹ to R ⁷ and R ²⁰ include cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1 -Methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 1,4-dimethylcyclohexyl group, 2,3 -Dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethyl Cyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3 Cycloalkyl groups such as 5,5-tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group, 4-cyclohexylcyclohexyl group; cyclohexenyl group (eg, cyclohex-2-ene, cyclohexa-3-ene), Cycloalkenyl groups such as cycloheptenyl group and cyclooctenyl group; polycyclic alicyclic hydrocarbon group such as norbornan group, adamantyl group and bicyclo [2.2.2] octane; can be mentioned.

The alicyclic hydrocarbon group represented by R ¹ to R ⁷ and R ²⁰ has preferably 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, still more preferably 4 to 20 carbon atoms, and further preferably 4 to 20 carbon atoms. It is more preferably 4 to 15, even more preferably 5 to 15, and particularly preferably 5 to 10.

The saturated or unsaturated hydrocarbon group represented by R ¹ to R ⁷ and R ²⁰ may be a group in which the above-mentioned chain hydrocarbon group and alicyclic hydrocarbon group are combined, and may be, for example, cyclo. Alkyl to which one or more alicyclic hydrocarbon groups such as propylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, cyclohexylethyl group are bonded. Group is mentioned. The carbon number is preferably 4 to 30, more preferably 4 to 20, and even more preferably 4 to 15.

The aromatic hydrocarbon group represented by R ¹ to R ⁷ and R ²⁰ represents a group having a direct bond to the aromatic hydrocarbon ring, and represents a phenyl group, an o-tolyl group, an m-tolyl group, p-. Trill 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, 1-naphthyl group, 2-naphthyl group, 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro-2-naphthyl group, fluorenyl Examples include a group, a phenyl group, an anthryl group and the like. 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 ¹ to R ⁷ and R ²⁰ includes at least one of the above-mentioned chain hydrocarbon group, alicyclic hydrogen group, and aromatic hydrocarbon group as described above. It may be a group combined with the above-mentioned aromatic hydrocarbon group, and may be a benzyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a 4-methylbenzyl group, a 3,4-methylbenzyl group, a phenylethyl group, Aralkyl groups such as phenylpropyl group and 1-methyl-1-phenylethyl group; arylalkenyl groups such as phenylethenyl group (phenylvinyl group); arylalkynyl groups such as phenylethynyl group; biphenylyl group, terphenylyl group and the like 1 Examples thereof include a phenyl group to which one or more phenyl groups are bonded; a cyclohexylmethylphenyl group, a benzylphenyl group, a (dimethyl (phenyl) methyl) phenyl group; and the like, and the number of carbon atoms thereof is preferably 7 to 30, more preferably. Is 7 to 20, more preferably 7 to 15.

The hydrocarbon group represented by R ¹ to R ⁷ 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 atom, chlorine atom, bromine atom and iodine atom;
Nitro group;
Cyano group;
Trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, perfluorocyclohexyl group, 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 with a fluorine atom;
* -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);
* _-Carbonyl group bonded to a sulfur atom bonded to an aryl group such as CO-SC 6H ₅ (the aryl group has 6 to 20 carbon atoms);
* -OP (O) (OR ³⁰ ) ₂ ;
* -Si (R ³⁰ ) (R ³¹ ) (R ³² ); etc. (* represents a bond).
In the above formula, R ³⁰ , R ³¹ , and R ³² are independent of each other and may have a hydrocarbon group having 1 to 35 carbon atoms, or a heterocycle which may have a substituent. Representing a group, -CH _2- contained in the hydrocarbon group and -CH _2- when the heterocyclic group does not form a ring-CH _2- represents -O-, -CO-, -S. (O) It may be replaced with _2- or -NR ^20- . However, the replacement of -CH _2- does not form -CO ₂ H and -S (O) ₂ OH. 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 R ¹ except that they do not include examples of having 36 or more carbon atoms.

The divalent substituent includes 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. The group etc. can be mentioned. Examples of the imino group substituted with the alkyl group include CH ₃ -N =, CH ₃ -CH ₂ -N =, CH _3- (CH ₂ ) ₂ -N =, CH _3- (CH ₂ ) ₃ -N = and the like. Can be mentioned. Examples of the imino group substituted with the aryl group include C ₆ H ₅ -N = and the like.

The substituents of the hydrocarbon groups represented by R ¹ to R ⁷ and R ²⁰ are independent of each other.
Halogen atoms; nitro groups; cyano groups; hydrocarbon groups having 1 to 20 carbon atoms in which all hydrogen atoms are replaced with fluorine atoms; thiocarbonyl groups; etc. are preferable.
A fluorine atom, a chlorine atom, a bromine atom; a nitro group; a cyano group; a hydrocarbon group having 1 to 10 carbon atoms in which all hydrogen atoms are substituted with a fluorine atom; a thiocarbonyl group; etc. are more preferable.
Fluorine atoms; hydrocarbon groups having 1 to 5 carbon atoms in which all hydrogen atoms are replaced with fluorine atoms; and the like are more preferable.

In compound (1), -CH ₂ -contained in the hydrocarbon groups represented by R ¹ to R ⁷ is replaced with -O-, -CO-, -S (O) _2- , or -NR ^20- . It may have a group formed by (hereinafter, may be referred to as "group (Z1)"). However, the replacement of -CH _2- does not form -CO ₂ H and -S (O) ₂ OH.

As a group (Z1),
Methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, (2-ethyl) hexyloxy group, (2) -Trifluoromethyl) hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, phenyloxy group, m-tolyloxy group, 3,4-xysilyloxy group and the like have 1 to 20 carbon atoms, more preferably carbon atoms. 1-10 oxy groups to which a hydrocarbon group is bonded (alkoxy group and aryloxy group);
Oxylanyl group;
Holmil group;
The acetyl group, propanoyl group, butanoyl group, tert-butanoyl group, pentanoyl group, hexanoyl group, (2-ethyl) hexanoyl group, heptanoyle group, octanoyl group, nonanoyl group, benzoyl group and the like have 2 to 22 carbon atoms, preferably 2 to 22 carbon atoms. 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 group 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, and an o-tolyloxycarbonyl group is bonded;
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, 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) hexylamino 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-butylmethylamino An amino group having one or two carbon atoms 1 to 20, preferably 1 to 10 carbon atoms, such as a group and an N, N-phenylmethylamino group;
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-butylsul Famoyl group, N-pentylsulfamoyl group, N, N-dipentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N, N-di (1-ethylpropyl) sulfamoyl group, N-hexyl Sulfamoyl group, N, N-dihexyl sulfamoyl group, N- (2-ethyl) hexyl sulfamoyl group, N, N-di (2-ethyl) hexyl sulfamoyl group, N-heptyl sulfamoyl Group, N, N-diheptyl sulfamoyl group, N-octyl sulfamoyl group, N, N-dioctyl sulfamoyl group, N, N-octylmethyl sulfamoyl group, N-nonyl sulfamoyl group, N, N-dinonyl sulfamoyl group, N-phenyl sulfamoyl group, N, N-diphenyl sulfamoyl group, N, N-ethylmethyl sulfamoyl group, N, N-propylmethyl sulfamoyl group, One of N, N-isopropylmethylsulfamoyl group, N, N-butylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-phenylmethylsulfamoyl group, etc. A sulfamoyl group having two hydrocarbon groups having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms;
N-formylamino group;
N-acetylamino group, N-propanolamino group, N-butanoylamino group, N-2,2-dimethylpropanolamino 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 , N-Henicosanoylamino group, N-benzoylamino group and the like, N-alkanoylamino group having 1 to 22 carbon atoms, preferably 1 to 12 carbon atoms;
Hydroxy group;
Formyloxy group, acetoxy group, propanoyloxy group, butanoyloxy group, 2,2-dimethylpropanoyloxy group, pentanoyloxy group, hexanoyloxy group, (2-ethyl) hexanoyloxy group, heptanoyleoxy 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 group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, pentylsulfonyl group, hexylsulfonyl group, (2-ethyl) hexylsulfonyl group, heptylsulfonyl group, octylsulfonyl group, nonylsulfonyl group, decylsulfonyl group, 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;
Carbamic 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) carbamoyl group, N-hexylcarbamoyl group, N, N-dihexylcarbamoyl group, N- (2-ethyl) hexylcarbamoyl group, N, N-di (2-ethyl) hexylcarbamoyl group , N-Heptylcarbamoyl group, N, N-diheptylcarbamoyl group, N-octylcarbamoyl group, N, N-dioctylcarbamoyl group, N-nonylcarbamoyl group, N, N-dinonylcarbamoyl group, N-phenylcarbamoyl group. , N, N-diphenylcarbamoyl group, N, N-ethylmethylcarbamoyl group, N, N-propylmethylcarbamoyl group, N, N-isopropylmethylcarbamoyl group, N, N-butylmethylcarbamoyl group, N, N-tert -Carbamoyl group having one or two carbon atoms 1 to 20, preferably 1 to 10 carbon atoms, such as a butylmethylcarbamoyl group and an N, N-phenylmethylcarbamoyl group;
* -COCOR ²⁰ ;
* -OCON (R ²⁰ ) ₂ ;
* -N (R ²⁰ ) COOR ²⁰ ; etc. (* 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 ¹ to R ⁷ and R ²⁰ may be monocyclic or polycyclic. Examples of the hetero atom contained in the heterocycle include a nitrogen atom, an oxygen atom, a sulfur atom and the like.

The number of carbon atoms of the heterocyclic group represented by R ¹ to R ⁷ and R ²⁰ is preferably 2 to 30, more preferably 3 to 22, still more preferably 3 to 20, and even more preferably. It is 3 to 18, even 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; pyrol, pyrol such as 2,5-dimethylpyrazole, 2-methylpyrazole, and the like. Pyrazole such as 3-methylpyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole and other 5-membered cyclic unsaturated heterocyclic groups; pyrimidine such as pyridine, pyridazine, pyrimidine, 6-methylpyrimidine and the like. , Pyrazole, 1,2,4-triazine, 1,3,5-triazine and other 6-membered ring-based unsaturated heterocyclic groups; indazole, indolin, isoindolin, indol, indolidine, benzoimidazole, quinoline, isoquinoline, 5 , 6,7,8-Tetrahydro (3-methyl) quinoxalin, quinoxalin such as 3-methylquinoxalin, quinazoline, cinnoline, phthalazine, naphthylidine, purine, pteridine, benzopyrazole, benzopiperidin and the like; Fused tricyclic heterocyclic groups such as carbazole, aclysine, and phenazine; heterocyclic groups represented by the following formulas can be mentioned.

（式中、＊は結合手を表す）

(In the formula, * represents a bond)

Examples of the heterocyclic group containing only an oxygen atom as a hetero atom include a monocyclic saturated heterocyclic group such as oxylane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, and 1-cyclopentyldioxolane; , 4-Dioxaspiro [4.5] decane, 1,4-dioxaspiro [4.5] nonane and other bicyclic saturated heterocyclic groups; α-acetlactone, β-propiolactone, γ-butyrolactone, δ-valero Lactone-based heterocyclic groups such as lactone; 5-membered ring-based unsaturated heterocyclic groups such as furan, 2,3-dimethylfuran, 2,5-dimethylfuran and the like; 3,4-dihydro-2H-pyran, 3 , 6-membered ring-based unsaturated heterocyclic group such as 6-dihydro-2H-pyran; benzopyrane such as 1-benzofuran, isobenzofuran, 4-methylbenzopyran, fused bicyclic group such as benzodioxol, chroman, isochroman and the like. Heterocyclic groups; fused tricyclic heterocyclic groups such as xanthene and dibenzofuran; and the like.

Examples of the heterocyclic group containing only a sulfur atom as a hetero atom include a 5-membered ring-based saturated heterocyclic group such as dithiolane; a 6-membered ring-based saturated heterocyclic group such as thian, 1,3-dithian, and 2-methyl1,3-dithian. Ring groups; thiophenes such as thiophene, 3-methylthiophene, 2-carboxythiophene, thiophene 1-oxide, thiophene 1,1-dioxide, etc., and 5-membered ring-based unsaturated heterocyclic groups such as 4H-thiopyran; benzothiophene, benzothiophene. Fused bicyclic heterocyclic groups such as oxides, benzotetrahydrothiopyrans and benzothiophene dioxides; fused tricyclic heterocyclic groups such as thiantolen and dibenzothiophene; and the like.

Heterocyclic groups containing a nitrogen atom and an oxygen atom as heteroatoms include monocyclic saturated heterocyclic groups such as morpholin, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, and 2-methyl-2-piperidone. Oxazole, 4-methyloxazole and the like, isooxazole, 2-methylisoxazole, 3-methylisoxazole and the like, monocyclic unsaturated heterocyclic groups such as 1,2,4-oxadiazole; Fused bicyclic heterocyclic groups such as benzoxazole, benzoisoxazole and benzoxazole; condensed tricyclic heterocyclic groups such as phenoxazine; and the like can be mentioned.

Examples of the heterocyclic group containing a nitrogen atom and a sulfur atom as heteroatoms include monocyclic heterocyclic groups such as thiazole, 3-methylthiazole, and 2,4-dimethylthiazole; benzothiazole, benzoisothiazole, and benzothiathiazole. Such as fused bicyclic heterocyclic groups; fused tricyclic heterocyclic groups such as phenothiazine; and the like.

The heterocyclic group represented by R ¹ to R ⁷ and R ²⁰ may be a group in which the above-mentioned heterocyclic group and a hydrocarbon group are combined, and may be, for example, a tetrahydrofurylmethyl group or a methyltetrahydrofuryl group. And so on.
The bond position of the above heterocyclic group is a portion where an arbitrary hydrogen atom contained in each ring is eliminated.

The heterocyclic group represented by R ¹ to R ⁷ and R ²⁰ may have a substituent. Examples of the substituent include the same as the monovalent substituent described as the substituent that the hydrocarbon group represented by R ¹ to R ⁷ and R ²⁰ may have. When the heterocyclic group contains a nitrogen atom as a constituent element thereof, the hydrocarbon group mentioned above 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 independent of each other and may be the same. It may be different.

When the heterocyclic group represented by R ¹ to R ⁷ contains -CH _2- , which does not form a ring, the -CH _2- is -O-, -CO-, -S (O) _2- , or. It may be replaced with -NR ^20- . However, the replacement of -CH _2- does not form -CO ₂ H and -S (O) ₂ OH. When —CH ₂ − is replaced with —O— or the like, the heterocyclic group represented by R ¹ to R ⁷ may have the above group (Z1).

When R ² and R ³ , R ³ and R ⁴ or R ⁴ and R ⁵ are bonded to form a ring, the ring may be a hydrocarbon ring or a heterocycle. Examples of the hydrocarbon ring include an aliphatic hydrocarbon ring and an aromatic hydrocarbon ring.

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

Examples of the aromatic hydrocarbon ring include benzene, naphthalene, 1,2,3,4-tetrahydronaphthalene, fluorene, phenanthrene, anthracene; and the like. The number of carbon atoms in 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 ² and R ³ , R ³ and R ⁴ or R ⁴ and R ⁵ are combined to form a heterocycle, the heterocycle is represented by the above R ¹ to R ⁷ and R ²⁰ . A ring similar to the heterocycle in the group may be formed.

When R ² and R ³ , R ³ and R ⁴ , or R ⁴ and R ⁵ are combined to form a heterocycle, the heterocycle is composed of two or more rings together with the benzene ring to which R ² to R ⁵ are bonded. Form a ring structure. Examples of the ring structure having two or more rings include a heterocycle having the structure of the following formula.

（式中のベンゼン環は、化合物（１）が有するイソインドリン構造中のベンゼン環に相当する）

(The benzene ring in the formula corresponds to the benzene ring in the isoindoline structure of compound (1)).

When R ² and R ³ , R ³ and R ⁴ and R ⁴ and R ⁵ combine to form a ring, the ring may have a substituent. Examples of the substituent include the same as the monovalent substituent described as the substituent that the hydrocarbon group represented by R ¹ to R ⁷ and R ²⁰ may have.

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

The ring formed by bonding R ² and R ³ , R ³ and R ⁴ and R ⁴ and R ⁵ may have the above group (Z1).

Examples of the halogen atom represented by R ² to R ⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom, a chlorine atom and a bromine atom, and more preferably a fluorine atom. It is 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 a hydrogen atom is more preferable.

When a plurality of R ²⁰ and M are present in compound (1), they may be the same or different.

The naphthyl group which may have a substituent represented by R ⁸ and R ⁹ has at least one −CO ₂ M in any of R ⁸ and R ⁹ , and is preferably R ⁸ and R ⁹ . Both have at least one -CO ₂ M. Further, the naphthyl groups which may have the substituents represented by R ⁸ and R ⁹ may have one or more substituents other than -CO ₂ M independently of each other. When having _two or more substituents other than —CO 2M, the substituents may be the same or different. As substituents other than -CO ₂ M, -CO ₂ M is excluded from the monovalent substituents described as substituents that the hydrocarbon groups represented by R ¹ to R ⁷ and R ²⁰ may have. Can be mentioned. Further, a hydrocarbon group having 1 to 20 carbon atoms, a heterocyclic group and the like are also included in the substituent of the naphthyl group. When -CH _2- and the heterocyclic group do not form a ring-CH _2- contained in the hydrocarbon group, the -CH _2- is -O-, -CO-, -S (O) ₂ . -, -NR ²⁰ -may be replaced with. However, the replacement of -CH _2- does not form -CO ₂ H and -S (O) ₂ OH. M and R ²⁰ have the same meanings as described above. Examples of the hydrocarbon group having 1 to 20 carbon atoms and the heterocyclic group as the substituent include those similar to R ¹ except that the example having 21 or more carbon atoms is not included.

Among these, the substituents other _than -CO 2M of the naphthyl group represented by R ⁸ and R ⁹ are halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; hydrocarbons having 1 to 3 carbon atoms. A hydrogen group and a group in which -CH _2- contained in the hydrocarbon group is replaced with -O-, -CO-, -S (O) _2- , -NR ^20- are preferable, and chlorine atom, bromine atom; methyl. An alkyl group having 1 to 3 carbon atoms such as a group and an ethyl group; an amino group; and a hydroxy group are more preferable.

The number of substituents of the naphthyl group which may have the substituents represented by R ⁸ and R ⁹ is preferably 1 to 7, and more preferably 1 to 3.
The number of substituents contained in the naphthyl group is the number per naphthyl group.

The number of -CO ₂ M contained in the naphthyl group represented by R ⁸ and R ⁹ is that the total of -CO ₂ M contained in the naphthyl group represented by R ⁸ and R ⁹ is 1 to 6. It is preferably 1 to 4, more preferably 1 to 2, and further preferably each of the naphthyl groups represented by R ⁸ and R ⁹ has one -CO ₂ M. More preferred. When each of the naphthyl groups represented by R ⁸ and R ⁹ has one -CO ₂ M, the bond position of the -CO ₂ M is on the same six-membered ring side as the bond of R ⁸ and R ⁹ below. The structure of the formula (2a) may be used, or the structure of the following formula (2b) having different six-membered ring sides may be used.

（式中、＊は結合手を表す）

(In the formula, * represents a bond)

As the compound (1), those in which R ¹ to R ⁹ and M are as follows are preferable.
As R ¹ , a hydrogen atom is preferable.
As R ² to R ⁵ , they are independent of each other.
Hydrogen atom; 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 an alkyl group which may have a substituent); An alkoxy group having 1 to 10 carbon atoms such as a methoxy group and butoxy; an alkanoyl group having 2 to 6 carbon atoms such as an acetyl group; a substituent such as a 3,4-kisilyloxy group and an α, α, α-trifluorotoluyloxy group. An aryloxy group having 6 to 10 carbon atoms (preferably a phenyloxy group which may have a substituent); a halogen atom such as a fluorine atom and a chlorine atom; a nitro group; a cyano group; It is preferably one selected from the group consisting of an amino group; a hydroxy group; a formyl group; a sulfamoyl group; a carboxy group; a sulfone group and the like, and preferably one selected from a hydrogen atom; a halogen atom such as a fluorine atom and a chlorine atom. It is more preferable to have a hydrogen atom; it is further preferable to be one selected from a chlorine atom.
When R ² and R ³ , R ³ and R ⁴ or R ⁴ and R ⁵ are bonded to form a ring together with the carbon atoms to which they are bonded, an aromatic having 6 to 10 carbon atoms such as benzene is used. It is preferably a group hydrocarbon ring, and more preferably formed naphthalene together with a benzene ring in the isoindoline structure.
It is preferable that R ² to R ⁵ do not form a ring.
R ⁶ and R ⁷ are preferably one selected from the group consisting of a hydrogen atom, a cyano group, a nitro group, and a halogen atom independently of each other, and are preferably a group consisting of a cyano group, a nitro group, and a chlorine atom. It is more preferably one selected from the above, more preferably a cyano group or a nitro group, and even more preferably a cyano group. Further, it is preferable that R ⁶ and R ⁷ have the same group.
R ⁸ and R ⁹ have one -CO ₂ H independently of each other, a halogen atom such as a chlorine atom and a bromine atom; an alkyl group having 1 to 3 carbon atoms such as a methyl group and an ethyl group; a carboxy group. Amino group; A naphthyl group which may have 0 to 3 substituents independently selected from the hydroxy group is preferable, and it has one -CO ₂ H and has a bromine atom; a methyl group; a carboxy group; an amino group; A naphthyl group which may have 0 to 1 substituent independently selected from the hydroxy group is more preferable, and a naphthyl group which has one —CO ₂ H and no other substituent is further preferable. The binding position of the -CO ₂ H may be any binding position corresponding to any of the above formulas (2a) and (2b), and is a position represented by the following formulas (na1) and (na2). It is preferable that it is bound to. When -CO ₂ H is bonded to the positions represented by the formulas (na1) and (na2), it is preferable that R ⁸ and R ⁹ are the same group.
When M is present in compound (1), a hydrogen atom is preferable as M.

As a specific example of the compound (1), for example, in the compound represented by the formula (1a), the combinations of R ¹ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and B ¹ B ² are shown in Tables 1 to 1. Examples thereof include compound numbers 1 to 1071 which are substituents shown in any one of 15. In Tables 1 to 15, H represents a hydrogen atom, CN represents a cyano group, NO ₂ represents a nitro group, and Cl represents a chlorine atom. R ⁸ and R ⁹ represent any of the partial structures represented by the equations (na1) to (na17). B ¹ B ² represents any of the partial structures represented by the equations (be1) to (be21). Further, in the formulas (na1) to (na17) and the formulas (be1) to (be21), * and B ¹ B ² mean a bond, respectively.

Among the compounds shown in Tables 1 to 15, compound (1) is
It is preferably a compound represented by compound numbers 1 to 630, and is preferably a compound.
More preferably, it is a compound represented by compound numbers 1 to 126, and is
More preferably, the compounds are represented by compound numbers 1 to 3, 13 to 15, 64-66 and 76 to 78.

Hereinafter, a method for producing the compound (1) will be described. In the following, in compound (1), a compound in which R ¹ is a hydrogen atom is referred to as "compound (1-H)", and in compound (1), a compound in which R ¹ is other than a hydrogen atom is referred to as "compound". (1-R) ".
The compound (1-H) is a compound represented by the formula (pt1) (hereinafter, may be referred to as a phthalonitrile compound) and a compound represented by the formula (pt2) (hereinafter, may be referred to as an alkoxide compound). After the reaction, the compound represented by the formula (pt3) (hereinafter, may be referred to as compound (pt3)) and the compound represented by the formula (pt4) (hereinafter, may be referred to as compound (pt4)) are combined. It can be produced by further reacting in the presence of an acid.
Further, the compound (1-H) reacts with a compound represented by the formula (pt5) (hereinafter, may be referred to as a 1,3-diiminoisoindoline compound), a compound (pt3) and a compound (pt4). It can be manufactured by letting it.
The compound (1-R) can be produced by reacting compound (1-H) with a compound represented by the formula (pt6) (hereinafter, may be referred to as compound (pt6)).

[In the formula (pt1) to the formula (pt6), the formula (1-H) and the formula (1-R),
R ¹ to R ⁹ have the same meanings as described above.
R ³³ 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 ³³ 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, which are preferable. 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 used is usually 0.1 to 10 mol, preferably 0.2 to 5 mol, and more preferably 0.3 to 3 mol, based on 1 mol of the phthalonitrile compound. More preferably, it is 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, relative to 1 mol of the phthalonitrile compound. It is 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 tartrate acid, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and Carous acid is mentioned, more preferably acetic acid.
The amount of the acid used is usually 1 to 20 mol, preferably 1 to 10 mol, more preferably 1 to 8 mol, still more preferably 1 to 6 mol, relative to 1 mol of the phthalonitrile compound. be.

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

The reaction solvent includes 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; a ketone solvent such as acetone. Ester solvent such as ethyl acetate; aliphatic hydrocarbon solvent such as hexane; aromatic hydrocarbon solvent such as toluene; halogenated hydrocarbon solvent such as methylene chloride and chloroform; N, N-dimethylformamide and N-methylpyrrolidone etc. Amid solvent; examples thereof include sulfoxide solvents such as dimethyl sulfoxide, preferably water, nitrile solvent, alcohol solvent, ether solvent, ketone solvent, ester solvent, aromatic hydrocarbon solvent, halogenated hydrocarbon solvent, amide solvent and sulfoxide solvent. 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 More preferably, water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N, N-dimethylformamide, N-dimethylacetamide. , 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone N-methylpyrrolidone and dimethylsulfoxide, even more preferably. Examples include water, acetonitrile, methanol, ethanol, 2-propanol, N-methylpyrrolidone and dimethylsulfoxide.

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, and more preferably 0 to 50 ° C. The reaction time is usually 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. The reaction solvent includes 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; a ketone solvent such as acetone. Ester solvent such as ethyl acetate; aliphatic hydrocarbon solvent such as hexane; aromatic hydrocarbon solvent such as toluene; halogenated hydrocarbon solvent such as methylene chloride and chloroform; N, N-dimethylformamide and N-methylpyrrolidone etc. Amid solvent; examples include a sulfoxide solvent such as dimethyl sulfoxide, 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. More preferably, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, ethyl acetate, toluene, methylene chloride, chloroform, N, N-dimethylformamide, N. , N-dimethylacetamide, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone and dimethylsulfoxide. More preferably, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N, N-dimethylformamide, N, N-dimethylacetamide, N. -Methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and 1,3-dimethyl-3,4,5,6-tetrahydro-2 (1H) -pyrimidinone and dimethylsulfoxide are mentioned, and 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 can be mentioned.

The amount of the reaction solvent used 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, the compound (pt3) and the compound (pt4) is usually 0 to 200 ° C, preferably 0 to 100 ° C, and more preferably 0 to 80 ° C. .. The reaction time is usually 0.5 to 300 hours.

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

Further, 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 methoxydo, sodium ethoxydo, sodium tert-butoxide and potassium tert-butoxide, and butyl lithium. , Tart-organic metal compounds such as butyl lithium and phenyl lithium; inorganic bases such as lithium hydroxide, sodium hydroxide and potassium hydroxide.

The amount of the base used is usually 1 to 10 mol, preferably 1 to 5 mol, more preferably 1 to 3 mol, still more preferably 1 to 2 mol, relative to 1 mol of compound (1-H). It 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.

The amount of the reaction solvent used is usually 1 to 1,000 parts by mass with respect to 1 part by mass of the compound (1-R). The reaction temperature of the compound (pt6) is usually −90 to 200 ° C., preferably −80 to 100 ° C., and more preferably 0 to 50 ° C. The reaction time is usually 0.5 to 300 hours.

The method for extracting the compound (1) from the reaction mixture is not particularly limited, and the compound (1) can be extracted by various known methods. For example, after the reaction is completed, the compound (1) can be taken out by filtering the reaction mixture. Further, after filtering, the obtained residue may be washed with a washing solvent. Further, after filtration, column chromatography, vacuum drying, recrystallization, sublimation purification and the like may be performed.

The cleaning solvent can be selected from the above-mentioned reaction solvent and an acid such as acetic acid.

<Coloring composition>
The coloring composition of the present invention contains the compound (1) and the resin (B).
The coloring composition of the present invention may further contain a solvent (E).
The colored curable resin composition of the present invention contains the colored composition of the present invention, the polymerizable compound (C), and the polymerization initiator (D).
The colored curable resin composition of the present invention may contain a polymerization initiation aid (D1).
The colored curable resin composition of the present invention may further contain a leveling agent (F) and an antioxidant.
The coloring curable resin composition may further contain a resin in addition to the resin (B) contained in the coloring composition. The resin which may be further contained may be the same as or different from the resin (B) contained in the coloring composition.
In the present specification, the compounds exemplified as each component may be used alone or in combination of a plurality of kinds unless otherwise specified.

<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 acid anhydrides (hereinafter referred to as "monomer (a)"). It is preferably a polymer having a structural unit derived from (in some cases).
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, may be referred to as “monomer (b)”), and others. It is preferably a copolymer having the structural unit of.
The other structural unit is a monomer copolymerizable with the monomer (a) (however, it is different from the monomer (a) and the monomer (b); hereinafter, “monomer (c)”. Examples thereof include structural units derived from (may be referred to as), structural units 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-cyclohexendicarboxylic 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, Bicyclounsaturated compounds containing carboxy groups such as 5-carboxymethylbicyclo [2.2.1] hept-2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;
Carboxylic acid anhydrides such as the above unsaturated dicarboxylic acid anhydrides excluding fumaric acid and mesaconic acid;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as monosuccinic acid mono [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerizability and solubility of the obtained resin in an alkaline aqueous 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 oxylan ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. To 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 oxylanyl group and an ethylenically unsaturated bond (hereinafter, may be referred to as “monomer (b1)”), an oxetanyl group and an ethylenically unsaturated bond. (Hereinafter referred to as "monomer (b2)") and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "monomer (b3)"). ) Etc. can be mentioned.

The monomer (b1) is, 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)”). There is) and a monomer having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter, may be 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, and 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 Examples thereof include 5-tris (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) styrene.

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

[In the formula (BI) and the formula (BII ^{), Ra 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. It may be replaced with.
X ^a and X ^b independently represent a single bond, * -R ^{c-, * -R c-O-, * -R c-S- or * -R c - NH- .}
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

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

Examples of the compound represented by the formula (BII) include compounds represented by any of the formulas (BII-1) to (BII-15), and among them, the formula (BII-1) and the formula are preferable. (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) and compounds represented by formulas (BII-11) to formula (BII-15) can be mentioned. Preferred examples thereof include compounds represented by the formula (BII-1), the formula (BII-7), the formula (BII-9) and the 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). You may. When these are used in combination, the content ratios of the compound represented by the formula (BI) and the compound represented by the formula (BII) are based on a molar basis, preferably 5:95 to 95: 5, and more preferably 10: It is 90 to 90:10, 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. (Meta) 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, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, (Meta) acrylic acid esters such as propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate and benzyl (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconic acid;
Bicyclo [2.2.1] 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, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyl) Oxycarbonyl) bicyclounsaturated compounds such as bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide 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. Such as vinyl group-containing amides; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; and the like.
Of these, from the viewpoint of copolymerization reactivity and heat resistance, styrene, vinyltoluene, 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, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene, benzyl (meth) acrylate and the like are preferable.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group. A resin having such a structural unit is a polymer having a structural unit derived from the monomer (a) or the monomer (b), and 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 and an ethylenically unsaturated bond.
Such structural units include a structural unit in which glycidyl (meth) acrylate is added to a (meth) acrylic acid unit, a structural unit in which 2-hydroxyethyl (meth) acrylate is added to a maleic anhydride unit, and glycidyl (meth). ) A structural unit in which (meth) acrylic acid is added to the acrylate unit can be mentioned. When these structural units have a hydroxy group, a structural unit to which a carboxylic acid anhydride is further added can also be mentioned as a structural unit having an ethylenically unsaturated bond.

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

As the obtained polymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the polymer is taken out as a solid (powder) by a method such as reprecipitation. May be used.
If necessary, a reaction catalyst of a carboxylic acid or carboxylic acid anhydride and a cyclic ether (for example, tris (dimethylaminomethyl) phenol, etc.), a polymerization inhibitor (for example, hydroquinone, etc.) and the like may be used.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, 1 , 2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride and 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride and the like.

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-cyclohexylmaleimide 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) ) Acrylic / (meth) acrylic acid / 2-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) acrylic loyloxymethyloxetane / (meth) acrylic acid / styrene Copolymers, benzyl (meth) acrylate / (meth) acrylic acid copolymers, styrene / (meth) acrylic acid copolymers, JP-A-9-106071, JP-A-2004-29518 and JP-A-2004- Examples thereof include the resins described in each publication of the publication No. 361455.
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, in which case the resin (B) is at least 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate. / (Meta) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (Meta) Acrylate Copolymer, 3,4-Epoxytricyclo [5.2.1.0 ^2,6 ] Decyl (meth) Acrylate / (Meta) Acrylic Acid / Vinyl Toluene Copolymer, 3,4-Epoxy It is preferable to contain 1 or more selected from the tricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylate / 2-ethylhexyl (meth) acrylate copolymer.

The polystyrene-equivalent weight average molecular weight (Mw) of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 30, It is 000. The dispersity [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

The acid value (solid content conversion value) of the resin (B) is preferably 10 to 300 mg-KOH / g, more preferably 20 to 250 mg-KOH / g, still more preferably 20 to 200 mg-KOH / g, and even more preferably. Is 20 to 170 mg-KOH / g, more preferably 30 to 170 mg-KOH / g, even more preferably 50 to 150 mg-KOH / g, particularly preferably 60 to 140 mg-KOH / g, and 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 obtained by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) in the coloring composition is, for example, 1 to 1200 parts by mass, preferably 30 to 1000 parts by mass, and more preferably 50 to 50 parts by mass with respect to 100 parts by mass of the compound (1). It is 800 parts by mass.
The content of the resin (B) in the coloring composition is preferably 3% by mass or more, more preferably 5% by mass or more, still more preferably 7 to 99% by mass, based on the total amount of solid content. Even more preferably, it is 13 to 99% by mass, and particularly preferably 17 to 95% by mass.
As used herein, the term "total amount of solids" refers to the total amount of the components of the coloring composition or the coloring curable resin composition of the present invention excluding the solvent (E). The total amount of solid content and the content of each component relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

<Solvent (E)>
The solvent (E) is, for example, an ester solvent (solvent containing -COO- in the molecule and not containing -O-), an ether solvent (solvent containing -O- in the molecule and not containing -COO-), and the like. Ether ester solvent (solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule) , -O-, -CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, 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, γ-butyrolactone and the like.

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, diethylene glycol methyl ethyl Examples thereof include ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyletol, methyl anisol and the like.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 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 ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl Examples thereof include ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

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 so on.

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

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

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

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

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

In the coloring composition of the present invention, the compound (1) is preferably dispersed in the solvent (E).

When the compound (1) is dispersed in the solvent (E) to prepare a coloring composition, by including the resin (B), the dispersion stability when the coloring composition is prepared can be further improved, and the storage stability can be further improved. It is possible to create a color filter with excellent properties.
The content of the resin (B) in the coloring composition (for example, the coloring composition does not contain a polymerizable compound or a polymerization initiator) is, for example, 1 to 500 parts by mass with respect to 100 parts by mass of the compound (1). It is preferably 5 to 200 parts by mass, and more preferably 10 to 100 parts by mass.

The compound (1) is treated with a rosin, a surface treatment using a derivative having an acidic group or a basic group introduced therein, a graft treatment on the surface of the compound (1) with a polymer compound or the like, and sulfuric acid atomization, if necessary. It may be subjected to atomization treatment by a method or the like, cleaning treatment with an organic solvent or water for removing impurities, removal treatment of ionic impurities by an ion exchange method or the like. The particle size of compound (1) is preferably substantially uniform. The compound (1) can be uniformly dispersed in the dispersion liquid by containing a dispersant and performing a dispersion treatment.

Examples of the dispersant include a surfactant and the like, and any of a cationic, anionic, nonionic and amphoteric surfactants may be used. Specific examples thereof include polyester-based, polyamine-based and acrylic-based surfactants. These dispersants may be used alone or in combination of two or more. Dispersants include KP (manufactured by Shin-Etsu Chemical Industry Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Co., Ltd.), and EFKA (registered trademark). (BASF Co., Ltd.), Azisper (registered trademark) (Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (registered trademark) (Big Chemie Co., Ltd.), BYK (registered trademark) (Big Chemie Co., Ltd.), etc. Can be mentioned.

When a dispersant is used, the amount of the dispersant (solid content) used is preferably 400 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 200 parts by mass, based on 100 parts by mass of the compound (1). It is 5 parts by mass or more and 200 parts by mass or less, and more preferably 5 parts by mass or more and 150 parts by mass or less. When the amount of the dispersant used is in the above range, a colored composition in a more uniform dispersed state tends to be obtained.

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

The content of the compound (1) in the coloring composition is usually 1% by mass or more and 90% by mass or less, preferably 1% by mass or more and 80% by mass or less, more preferably, with respect to the total amount of solid content. It is 2% by mass or more and 75% by mass or less, and more preferably 5% by mass or more and 75% by mass or less.

The coloring composition of the present invention may contain a coloring agent other than the compound (1) (hereinafter, may be referred to as a coloring agent (A1)). In the following, the compound (1) and the colorant (A1) may be collectively referred to as "colorant (A)". The colorant (A1) may contain one kind or two or more kinds of colorants.

<Colorant (A1)>
The colorant (A1) may be a dye or a pigment. Examples of the dye include known dyes described in Color Index (The Society of Dyers and Colorists Publishing) and Dyeing Note (Color Dyeing Co., Ltd.). Also, according to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, cyanine dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridin dyes, styryl dyes, coumarin dyes, quinoline. Examples thereof include dyes, nitro dyes and phthalocyanine dyes. Of these, organic solvent-soluble dyes are preferable. Two or more of these dyes may be used in combination.

Specific examples thereof 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 and 243, 246, 250;
C. I. Modant tread 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 1st prize.

As the pigment, known pigments can be used, and examples thereof include pigments classified as pigments in the Color Index (The Society of Dyers and Colorists Publishing). 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. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 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 and 273;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Examples thereof include green pigments such as Pigment Green 7, 36, 58 and 59.

When the coloring composition of the present invention contains a colorant (A1) and a solvent (E), a colorant (A1) -containing liquid containing the colorant (A1) and the solvent (E) is prepared in advance, and then the coloring is performed. A coloring composition may be prepared using the agent (A1) -containing liquid. When the colorant (A1) is insoluble in the solvent (E), the colorant (A1) -containing liquid can be prepared by dispersing the colorant (A1) in the solvent (E) and mixing. The colorant (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) used is preferably 400 parts by mass or less with respect to 100 parts by mass of the colorant (A1). Yes, more preferably 200 parts by mass or less, further preferably 5 parts by mass or more and 200 parts by mass or less, and even 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, there is a tendency to obtain a colorant (A1) -containing liquid in a more uniform dispersed state.

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 liquid. It is more preferably 1 to 40% by mass.

The content of the colorant (A1) in the colorant (A1) -containing liquid is usually 1% by mass or more and 90% by mass or less, preferably 1% by mass or more and 80% by mass or less, based on the total amount of solid content. It is more preferably 2% by mass or more and 75% by mass or less, and further preferably 5% by mass or more and 75% by mass or less.

When a colorant (A1) -containing liquid containing a colorant (A1) and a solvent is prepared in advance and then the coloring composition of the present invention is prepared using the colorant (A1) -containing liquid, the colorant (A1) is used. ) The 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 colorant (A1) -containing liquid can be further improved.
The content of the resin (B) in the colorant (A1) -containing liquid is, for example, 1 to 500 parts by mass, preferably 5 to 200 parts by mass with respect to 100 parts by mass of the colorant (A1). More preferably, it is 10 to 100 parts by mass.

The content of the colorant (A), which is a combination of the compound (1) and the colorant (A1), in the coloring composition is usually 1% by mass or more and 90% by mass or less, preferably 90% by mass or less, based on the total amount of solids. It is 1% by mass or more and 80% by mass or less, more preferably 2% by mass or more and 75% by mass or less, and further preferably 5% by mass or more and 75% by mass or less.

When the colorant (A1) is contained, the content of the colorant (A1) is preferably 0.1 part by mass or more, and more preferably 0.5 part by mass or more with respect to 100 parts by mass of the compound (1). It is more preferably 1 part by mass or more, preferably 10000 parts by mass or less, and more preferably 5000 parts by mass or less.

<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 preferable. It is a (meth) acrylic acid ester compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Etc., as well as the above-mentioned monomers (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. Examples thereof include (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate.

Above all, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (dipentaerythritol hexa (). Meta) 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, Examples thereof include caprolactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, preferably dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

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

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

<Polymer Initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light or heat, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include O-acyloxygen compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, acylphosphine oxide compounds and the like.

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-. 1-on-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-on-2-imin, N-acetoxy-1- (4-phenylsulfanylphenyl)- 3-Cyclopentylpropane-1-on-2-imine, N-acetoxy-1- (4-phenylsulfanylphenyl) -3-cyclohexylpropane-1-on-2-imine, N-acetoxy-1- [9-ethyl -6- (2-Methylbenzoyl) -9H-carbazole-3-yl] ethane-1-imine, 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-carbazole-3-yl] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3- Cyclopentylpropane-1-on-2-imine and the like can be mentioned. Further, as the O-acyloxime compound, commercially available products such as Irgacure OXE01, OXE02 (all manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may be used. Among them, the O-acyloxym compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-. At least one selected from the group consisting of 1-on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-on-2-imine is preferable, and N-benzoyl is preferable. Oxy-1- (4-phenylsulfanylphenyl) octane-1-on-2-imine is more preferred.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane-1-. On and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one, 2-hydroxy-2-methyl-1-phenyl Propane-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- Examples thereof include (4-isopropenylphenyl) propan-1-one oligomers, α, α-diethoxyacetophenone, benzyldimethylketal 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 (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2' -Bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxyphenyl) biimidazole (see, for example, Japanese Patent Publication No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.) and Examples thereof include 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).

Examples of the triazine compound 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- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methyl) Phenyl) ethenyl] -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like can be mentioned. ..

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

Further, the polymerization initiator (D) is a benzophenone compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl O-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-. Benzophenone compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6-trimethylbenzophenone; 9,10-phenanthlenquinone, Kinone compounds such as 2-ethylanthraquinone and benzophenone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycoxylate and titanosen compounds.
These are preferably used in combination with the polymerization initiation aid (D1) (particularly amines) described later.

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

The content of the polymerization initiator (D) is preferably 0.001 to 40% by mass, 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 0.1 to 40 parts by mass, and more preferably 1 to 35 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is a mass part.

<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 started by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D). Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4-. 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, preferably 4,4'-bis (diethylamino) benzophenone and the like. Further, as the amine compound, a commercially available product such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

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. Examples thereof include anthracene and 2-ethyl-9,10-dibutoxyanthracene.

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, and N. -Phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

When these polymerization initiation aids (D1) are used, the content thereof is preferably 0.001 to 30% by mass, more preferably 0.01, 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 with respect to 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.

<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, Torre Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, Examples thereof include 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).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554. R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

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 thereof include Megafuck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

When the leveling agent (F) is contained, the content thereof is usually 0.0005% by mass or more and 1% by mass or less, preferably 0.001% by mass or more and 0, based on the total amount of the colored curable resin composition. It is 0.5% by mass, more preferably 0.001% by mass or more and 0.2% by mass or less, still more preferably 0.002% by mass or more and 0.1% by mass or less, and even more preferably 0.005. It is mass% or more and 0.1 mass% or less. 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 the antioxidant alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an industrially generally used antioxidant, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant and the like can be used.

Examples of the phenolic antioxidant include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Co., Ltd.). Irganox 1076 (Irganox 1076: Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Co., Ltd.), Irganox 1330 (Irganox 1330: 3,3', 3', ', 5,5', 5''-Hexa-tert-butyl-a, a', a''-(methicylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Co., Ltd., Irganox 3114 (Irganox 3114: 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) )-Trion, manufactured by BASF Co., Ltd., Irganox 3790 (Irganox 3790: 1,3,5-tris ((4-tert-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3 5-Triazine-2,4,6 (1H, 3H, 5H) -Torion, manufactured by BASF Co., Ltd., Irganox 1035: Thiodiethylenebis [3- (3,5-di-tert-butyl-) 4-Hydroxyphenyl) propionate], BASF Co., Ltd.), Irganox 1135: benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl Ester, manufactured by BASF Co., Ltd., Irganox 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF Co., Ltd.), Irganox 3125 (Irganox 3125, manufactured by BASF Co., Ltd.) ), Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxy 3', 5'-di-tert-butylanilino) -1,3,5-triazine, BASF (strain) ), Adecastab AO-80 (Adecastab AO-80: 3,9-bis (2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethyl) Ethyl) -2,4,8,10-tetraoxaspiro (5, 5) Undecan, manufactured by ADEKA Corporation, Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), Sumitomo GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumitomo GS (Sumilizer GS, Sumitomo Chemical Co., Ltd.) Examples thereof include Cyanox 1790 (manufactured by Cyanox 1790, manufactured by Cytec Co., Ltd.) and Vitamin E (manufactured by Eisai Corporation).

Examples of the phosphorus-based antioxidant include Irgafos 168 (Irgafos 168: Tris (2,4-di-tert-butylphenyl) phosfite, manufactured by BASF Co., Ltd.), Irgafos 12: Tris [2- [[2,4,8,10-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, manufactured by BASF Co., Ltd.), Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphite, BASF Co., Ltd.), Adecastab 329K (ADEKA Co., Ltd.), Adecastab PEP36 (manufactured by ADEKA Co., Ltd.), Adecastab PEP-8 (manufactured by ADEKA Co., Ltd.), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (manufactured by Weston 618, GE), Weston 619G (Weston 619G, GE) , Ultraknox 626 (Ultranox 626, manufactured by GE) and Sumilizer GP: 6- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4 8,10-Tetra-tert-butyldibenz [d, f] [1.3.2] dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.) and the like can be mentioned.

Examples of the sulfur-based antioxidant include β-alkyl mercaptopropion of a dialkylthiodipropionate compound such as dilauryl thiodipropionate, dimyristyl or distearyl, and a polyol such as tetrakis [methylene (3-dodecylthio) propionate] methane. Examples thereof include acid ester compounds.

<Other ingredients>
The color curable resin composition of the present invention may contain additives known in the art such as fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents and the like, if necessary. ..

<Color filter>
A coloring pattern can be formed from the coloring curable resin composition of the present invention. Examples of the method for forming the colored pattern include a photolithography method, an inkjet method, a printing method and the like. Of these, the photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a colored composition layer, and the colored composition layer is exposed and developed through a photomask. In the photolithography 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 photomask. The colored pattern and the colored coating film thus formed are the color filters of the present invention.

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

The substrate includes a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or on the substrate. Aluminum, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit and the like may be formed on these substrates.

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

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

When drying under reduced pressure, it is preferable to carry out drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C.

The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.

The coloring composition layer is then exposed via a photomask to form the desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.

As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps and the like.

An exposure device such as a mask aligner and a stepper should be used because it is possible to uniformly irradiate the entire exposed surface with parallel rays and to accurately align the photomask with the substrate on which the coloring composition layer is formed. Is preferable.

A coloring pattern is formed on the substrate by bringing the exposed coloring composition layer into contact with a developing solution for development. By development, the unexposed portion of the coloring composition layer is dissolved in a developing solution and removed.

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

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

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

According to the coloring composition of the present invention, a color filter having excellent light resistance and heat resistance can be produced. Further, the coloring composition of the present invention has high storage stability, and the color filter formed from the coloring curable resin composition of the present invention includes a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, etc.) and a color filter. It is useful as a color filter used in solid-state imaging devices.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can meet the purposes of the preceding and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

In the following examples, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200, MASS; Agilent LC / MSD6130).

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.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40 ° C
Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Solid content concentration of analytical sample: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was defined as the degree of dispersion.

Example 1
6.0 parts of dimethyl 2,6-naphthalenedicarboxylic acid (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-butoxysodium (manufactured by Kanto Chemical Co., Inc.) was added over 1 minute, and the mixture was stirred for 90 minutes. While keeping the temperature below 5 ° C., 2.2 parts of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Inc.) 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 obtained mixture was filtered, the filtered residue was washed with 30 parts of water and 10 parts of methanol, and the obtained residue was dried under reduced pressure at 60 ° C. to 6- (2-cyanoacetyl) -2-. 3.7 parts of methyl naphthalenecarboxylate was obtained (yield 60%).

3.7 parts of methyl 6- (2-cyanoacetyl) -2-naphthalene carboxylate was suspended in 15 parts of water. While keeping the temperature of the obtained mixture at 80 ° C., 0.88 part of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and the mixture was stirred for 25 minutes. While keeping the temperature below 5 ° C., 2.8 parts of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Inc.) was added dropwise over 30 minutes, the temperature was raised to 25 ° C., and the mixture was stirred at 25 ° C. for 1 hour. The obtained mixture was filtered, the filtered residue was washed with 30 parts of water and 10 parts of methanol, and the obtained residue was dried under reduced pressure at 60 ° C. to 6- (2-cyanoacetyl) -2-. 2.6 parts of naphthalene carboxylic acid was obtained (yield 75%).

6.0 parts of 1,3-diiminoisoindoline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 300 parts of N, N-dimethylformamide were mixed. To the obtained mixture, 30 parts of 6- (2-cyanoacetyl) -2-naphthalenecarboxylic acid was added, 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. 15 parts of N, N-dimethylformamide was added to the residue after washing, and the mixture was stirred at 80 ° C. for 2 hours. The mixture was cooled to 0 ° C. and stirred for 2 hours. The obtained mixture is filtered, washed with 60 parts of methanol, and the obtained residue is dried under reduced pressure at 60 ° C. to form a compound represented by the formula (1-1) (Compound No. 1, hereinafter, compound). 18 parts of the compound (also referred to as (1-1)) was obtained (yield 76%). The wavy line indicates that an E-form, a Z-form or a mixture thereof is included (in the examples, the same applies hereinafter).

<Identification of compound (1-1)>
(Mass spectrometry) Ionization mode = ESI- ^: m / z = [MH ^] --588
Exact Mass: 589

Example 2
8.1 parts of 4,5-dichlorophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 244 parts of methanol were mixed. While keeping the temperature of the obtained mixture at 5 ° C or lower, 4.8 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise over 30 minutes, and the mixture was stirred at 5 ° C for 6 hours. did. 11 parts of acetic acid was added while keeping the temperature of the obtained mixture below 5 ° C. To the obtained mixture, 30 parts of 6- (2-cyanoacetyl) -2-naphthalenecarboxylic acid was added, and the mixture was stirred at 45 ° C. for 18 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. 15 parts of N, N-dimethylformamide was added to the residue after washing, and the mixture was stirred at 80 ° C. for 2 hours. The mixture was cooled to 0 ° C. and stirred for 2 hours. The obtained mixture is filtered, washed with 60 parts of methanol, and the obtained residue is dried under reduced pressure at 60 ° C. to form a compound represented by the formula (1-2) (Compound No. 13, hereinafter, compound). Fifteen parts of the compound (also referred to as (1-2)) was obtained (yield 55%).

<Identification of compound (1-2)>
(Mass spectrometry) Ionization mode = ESI- ^: m / z = [MH ^] -656
Exact Mass: 657

Example 3
6.0 parts of 1,4-naphthalenedicarboxylic acid dimethyl (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-butoxysodium (manufactured by Kanto Chemical Co., Inc.) was added over 1 minute, and the mixture was stirred for 90 minutes. While keeping the temperature below 5 ° C., 2.2 parts of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Inc.) 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 obtained mixture was filtered, the filtered residue was washed with 30 parts of water and 10 parts of methanol, and the obtained residue was dried under reduced pressure at 60 ° C. to 4- (2-cyanoacetyl) -1-. 2.8 parts of methyl naphthalenecarboxylate was obtained (yield 45%).

2.8 parts of methyl 4- (2-cyanoacetyl) -1-naphthalene carboxylate was suspended in 11 parts of water. While maintaining the temperature of the obtained mixture at 80 ° C., 0.67 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 below 5 ° C., 2.1 parts of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Inc.) was added dropwise over 30 minutes, the temperature was raised to 25 ° C., and the mixture was stirred at 25 ° C. for 1 hour. The obtained mixture was filtered, the filtered residue was washed with 25 parts of water and 9 parts of methanol, and the obtained residue was dried under reduced pressure at 60 ° C. to 4- (2-cyanoacetyl) -1-. 1.9 parts of naphthalene carboxylic acid was obtained (yield 72%).

Synthesis was carried out in the same manner as in Example 1 except that the 6- (2-cyanoacetyl) -2-naphthalene carboxylic acid of Example 1 was changed to 4- (2-cyanoacetyl) -1-naphthalene carboxylic acid. 14 parts of a compound composed of the compound represented by the formula (1-3) (compound number 64, hereinafter also referred to as compound (1-3)) was obtained (yield 59%).

<Identification of compound (1-3)>
(Mass spectrometry) Ionization mode = ESI- ^: m / z = [MH ^] --588
Exact Mass: 589

Example 4
Synthesis was carried out in the same manner as in Example 2 except that the 6- (2-cyanoacetyl) -2-naphthalene carboxylic acid of Example 2 was changed to 4- (2-cyanoacetyl) -1-naphthalene carboxylic acid. Twenty-two parts of a compound composed of the compound represented by the formula (1-4) (compound number 76, hereinafter also referred to as compound (1-4)) was obtained (yield 81%).

<Identification of compound (1-4)>
(Mass spectrometry) Ionization mode = ESI- ^: m / z = [MH ^] -656
Exact Mass: 657

Comparative 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 obtained mixture, 23 parts of 4- (2-cyanoacetyl) benzoic acid (synthesized according to the method described in US2680731) was added, and the mixture was stirred at 45 ° C. and 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 the residue. 15 parts of N, N-dimethylformamide was added to 9.5 parts of the residue after washing, and the mixture was stirred at 80 ° C. for 2 hours. The mixture was cooled to 0 ° C. and stirred for 2 hours. The obtained mixture is filtered, washed with 60 parts of methanol, and then the obtained residue is dried under reduced pressure at 60 ° C. to form a compound represented by the formula (ii) (hereinafter, also referred to as compound (ii)). 16 parts of the compound consisting of the above was obtained (yield 77%).

<Identification of compound (ii)>
(Mass spectrometry) Ionization mode = ESI- ^: m / z = [MH ^] --488
Exact Mass: 489

Comparative Example 2
A compound of the following formula (i) (hereinafter, also referred to as compound (i)) was produced according to the description of Example 39 of JP-A-2017-137490.

Synthesis example 1
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 ° C. with stirring. Then 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.2.10 ^{2, 6} ] A mixed solution of 289 parts of a mixture of decane-9-ylacrylate (content ratio: 1: 1 in molar ratio) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. On the other hand, a solution prepared by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropping, the mixture was kept at 80 ° C. for 4 hours, 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 with a B-type viscometer (23 ° C.). Got The weight average molecular weight Mw of the produced copolymer was 9.2 × 103 ^, the dispersity was 2.08, and the acid value in terms of solid content was 77 mg-KOH / g. Resin B1 has the following structural units.

Example 5
(1) Preparation of coloring composition Compound (1): Compound (1-1) 50 parts;
Dispersant (BYK-LPN6919; manufactured by Big Chemie Japan Co., Ltd.) 58 copies;
Resin (B): 93 parts of resin B1 solution;
And the solvent (E): 800 parts of propylene glycol monomethyl ether acetate; were mixed, and the compound (1-1) was dispersed using a bead mill to obtain a colored composition 1. The coloring composition 1 was allowed to stand at 23 ° C. for 14 hours. The viscosity of the coloring composition 1 did not increase with time, and the storage stability was high.
Then
Coloring composition 1: 400 parts;
Resin (B): 45 parts of resin B1 solution;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 25 parts;
Polymerization Initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-on-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation) 15 parts;
Solvent (E): 86 parts of propylene glycol monomethyl ether acetate;
And a leveling agent: 0.12 parts of a polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.); were mixed to obtain a colored curable resin composition 1.

(2) Preparation of Colored Coating Film A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle XG; manufactured by Corning Inc.) by a spin coating method so that the film thickness after post-baking was 2 μm. Then, it was prebaked at 100 ° C. for 3 minutes to form a colored composition layer. After allowing to cool, the colored composition layer formed on the substrate was exposed to light at an exposure amount of 80 mJ / cm ² (365 nm standard) under an atmospheric atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). Irradiated. After light irradiation, post-baking was performed at 230 ° C. for 30 minutes in an oven to obtain a colored coating film.

(3) Heat resistance test The absorption of the obtained color curable resin composition film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The obtained colored curable resin composition film was further heated at 230 ° C. for 120 minutes in an oven and in an air atmosphere, and then absorption was measured with a colorimeter. The absorbance retention rate was determined from the change in absorbance at the maximum absorption wavelength of the colored curable resin composition film before and after the test.

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

Example 6 and Comparative Examples 3 and 4
Instead of compound (1-1) as the colorant (A),
In Example 6, compound (1-2),
In Comparative Example 3, compound (ii),
In Comparative Example 4, compound (i)
Was the same as in Example 5 except that The results are shown in Table 16. In each case, the storage stability of the coloring composition was high.

Claims (7)

A compound represented by the formula (1).

[In equation (1),
R ¹ represents a hydrogen atom .
R ² to R ⁵ represent hydrogen or halogen atoms independently of each other .
R ⁶ and R ⁷ represent a cyano group.
R ⁸ and R ⁹ represent naphthyl groups which may have substituents independently of each other. Both R ⁸ and R ⁹ have at least one -CO ₂ M.
M represents a hydrogen atom or an alkali metal atom.
When there are a plurality of M's, they may be the same or different.
Wavy lines indicate that E-forms, Z-forms or mixtures thereof are included. ] The compound according to claim 1 , wherein R ⁸ and R ⁹ are the same group. A coloring composition containing a coloring agent containing the compound according to claim 1 or 2 and a resin. The coloring composition according to claim 3 , further comprising a solvent. A coloring curable resin composition containing the coloring composition according to claim 4 , a polymerizable compound, and a polymerization initiator. A color filter formed from the colored curable resin composition according to claim 5 . A display device including the color filter according to claim 6 .