KR20180027371A - Colored composition - Google Patents

Abstract

The present invention relates to a colored composition comprising a compound represented by the formula (I) and a resin. R_N1 and R_N2 independently represent an aliphatic hydrocarbon group of 1 to 40 carbons, which may have a substituent. RN3 represents a hydrocarbon group of 1 to 40 carbons, which may have a substituent, or a heterocyclic group which may have a substituent.

Description

[0001] COLORED COMPOSITION [0002]

The present invention relates to compounds and coloring compositions useful as colorants.

Dyes are used for color display by using reflected light or transmitted light in the fields of, for example, textile materials, liquid crystal display devices, inkjet, and the like. As such a dye, coumarin 6 represented by the following formula is known (Japanese Unexamined Patent Application Publication No. 2006-154740).

The present invention includes the following inventions.

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

[In the formula (I), R ^N1 and R ^N2 represent, independently of each other, an aliphatic hydrocarbon group of 1 to 40 carbon atoms which may have a substituent.

R ^N3 represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹ to R ⁸ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , _{^{SO 2 N (R 102) 2}} , -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102 ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

R ¹⁰¹ represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹⁰² represents a hydrogen atom, a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

When a plurality of R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.

A ^{g -} represents anion of g. and g represents an integer of 1 to 14.]

[2] A coloring composition according to [1], wherein A ^{g -} is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, or a fluorinated anion.

[3] A coloring composition according to [1] or [2], wherein A ^{g -} is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements, or a fluorinated anion.

[4] A coloring composition according to any one of [1] to [3], wherein A ^{g -} is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements.

[5] The coloring composition according to any one of [1] to [4], wherein R ^N1 and R ^N2 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.

[6] The coloring composition according to any one of [1] to [5], further comprising a solvent.

[7] The coloring composition according to any one of [1] to [6], further comprising a yellow colorant, an orange colorant or a red colorant.

[8] A colored curable composition comprising the coloring composition according to any one of [1] to [7], and a polymerizable compound.

[9] The colored curable composition according to [8], further comprising a polymerization initiator.

[10] A color filter formed from the coloring composition according to any one of [1] to [7] or the coloring and curing composition according to [8] or [9].

[11] A liquid crystal display device comprising a color filter according to [10].

[12] A compound represented by the formula (I-B).

[In the formula (I-B), R ^N1 and R ^N2 represent, independently of each other, an aliphatic hydrocarbon group of 1 to 40 carbon atoms which may have a substituent.

R ^N3 represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹ to R ⁸ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , _{^{SO 2 N (R 102) 2}} , -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102 ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

R ¹⁰¹ represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹⁰² represents a hydrogen atom, a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

When a plurality of R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.

B ^{h -} represents at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and h anion containing oxygen as an essential element.

and h represents an integer of 1 to 14.]

[13] A compound according to [12], wherein B ^{h -} is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements.

[14] The compound according to [12] or [13], wherein R ^N1 and R ^N2 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent.

The coloring composition of the present invention includes a compound represented by the formula (I) (hereinafter sometimes referred to as a compound (I)) and a resin (hereinafter referred to as a resin (B) in some cases).

Compound (I) also includes tautomers or salts thereof.

Compound (I) can be used as a coloring agent.

The coloring composition of the present invention may contain one or more compounds (I).

The coloring composition of the present invention may contain a solvent (hereinafter sometimes referred to as solvent (E)).

The compound (I) is preferably dispersed in the solvent (E).

The coloring composition of the present invention is a colorant other than the compound (I) (hereinafter sometimes referred to as a colorant (A1)). Hereinafter, the compound (I) and the colorant (A1) May be included).

The colorant (A1) may contain one or more coloring agents.

The colorant (A1) preferably contains a yellow colorant, an orange colorant or a red colorant.

The colored curable composition of the present invention comprises at least one of the compound (I), the resin (B) and the solvent (E), and the polymerizable compound (C).

The colored curable composition of the present invention may contain a polymerization initiator (D).

The colored curable composition of the present invention may contain a polymerization initiator (D1).

The coloring composition of the present invention may further contain a leveling agent (F) and an antioxidant.

≪ Compound (I) >

The compound (I) is a compound represented by the formula (I).

[In the formula (I), R ^N1 and R ^N2 represent, independently of each other, an aliphatic hydrocarbon group of 1 to 40 carbon atoms which may have a substituent.

R ^N3 represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹ to R ⁸ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , _{^{SO 2 N (R 102) 2}} , -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102 ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

R ¹⁰¹ represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ¹⁰² represents a hydrogen atom, a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

When a plurality of R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.

A ^g- represents anion of g.

and g represents an integer of 1 to 14.]

The number of carbon atoms of the aliphatic hydrocarbon group represented by R ^N1 and R ^N2 is 1 to 40, preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 ~ 10.

The aliphatic hydrocarbon group represented by R ^N1 and R ^N2 may be saturated or unsaturated, and may be chain or alicyclic.

Examples of the saturated or unsaturated chain aliphatic hydrocarbon group represented by R ^N1 and R ^N2 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, A straight chain alkyl group such as a heptadecyl group, an octadecyl group and an icosyl group; (2-ethyl) butyl group, isopentyl group, neopentyl group, tert-pentyl group, (1-methyl) pentyl group, (3-ethyl) pentyl group, a (3-ethyl) pentyl group, an isohexyl group, a Branched alkyl group and the like; (1- (2-propenyl) propyl group, 1-propenyl group, 2-propenyl group (allyl group) Phenyl)) ethenyl group, (1,2-dimethyl) propenyl group and 2-pentenyl group; And the like. The number of carbon atoms of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 10, still more preferably 1 ~ 8. Still more preferably from 1 to 5. Of these, a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms is particularly preferable, and a methyl group or an ethyl group is particularly preferable.

Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ^N1 and R ^N2 include cyclopropyl group, 1-methylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group, Dimethyl cyclohexyl group, 1, 3-dimethylcyclohexyl group, 1, 4-dimethylcyclohexyl group, 2-methylcyclohexyl group, 2-methylcyclohexyl group, Dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl group, 3,5-dimethylcyclohexyl Dimethylcyclopentyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclohexyl group, A cycloalkyl group such as a 6-tetramethylcyclohexyl group, a 3,3,5,5-tetramethylcyclohexyl group, a 4-pentylcyclohexyl group, a 4-octylcyclohexyl group, and a 4-cyclohexylcyclohexyl group; Cycloalkenyl groups such as cyclohexenyl group (for example, cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl group and cyclooctenyl group; Norbornane, adamantyl, bicyclo [2,2,2] octane, and the like. The number of carbon atoms of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, even more preferably 4 to 20, still more preferably 4 to 15, Preferably from 5 to 15, and most preferably from 5 to 10. Of these, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are particularly preferable.

The aliphatic hydrocarbon group represented by R ^N1 and R ^N2 is preferably a combination of the aliphatic hydrocarbon group and the aromatic hydrocarbon group having 1 to 40 carbon atoms (for example, at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group and an aromatic hydrocarbon group) It is also a contribution.

Examples of the aromatic hydrocarbon group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,3-dimethylphenyl group, a 2,4-dimethylphenyl group, a 2,5- An isopropylphenyl group, an o-tert-butylphenyl group, an m-tert-butylphenyl group, an isopropylphenyl group, an n- (2-propyl) phenyl group, a 4-cyclohexylphenyl group, a 2,4,6-trimethylphenyl group, a p-tert-butylphenyl group, a mesityl group, 4-vinylphenyl group, 1-naphthyl group, 2-naphthyl group, 5,6,7,8-tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro- An aromatic hydrocarbon group such as a 2-naphthyl group, a fluorenyl group, a phenanthryl group, an anthryl group, and a pyrenyl group; And the like. The carbon number of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 15.

Examples of the group of the aliphatic hydrocarbon group and the aromatic hydrocarbon group having 1 to 40 carbon atoms (for example, at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group and an aromatic hydrocarbon group) include a benzyl group, a phenethyl group, An aralkyl group such as a 1-phenylethyl group; An arylalkenyl group such as a phenylethenyl group (phenylvinyl group); An arylalkynyl group such as a phenylethynyl group; A phenyl group to which at least one phenyl group such as a biphenylyl group or a terphenyl group is bonded; A cyclohexylmethylphenyl group, a benzylphenyl group, and a (dimethyl (phenyl) methyl) phenyl group. The groups represented by R ^N1 and R ^N2 are groups obtained by combining the above hydrocarbon groups (for example, a chain hydrocarbon group and an alicyclic hydrocarbon group), and examples thereof include a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, An alkyl group in which at least one alicyclic hydrocarbon group such as an ethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, a cyclohexylethyl group, or an adamantylmethyl group may be bonded.

The number of carbon atoms in the hydrocarbon group is preferably 4 to 30, more preferably 6 to 30, even more preferably 6 to 20, even more preferably 4 to 20, , And particularly preferably from 6 to 15.

The number of carbon atoms of the hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² is 1 to 40, preferably 1 to 30, more preferably 1 to 20, 15, and particularly preferably 1 to 10.

The hydrocarbon group having 1 to 40 carbon atoms represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ^{102 may} be an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated, or may be linear or alicyclic.

Examples of the saturated or unsaturated chain hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, A straight chain alkyl group such as an acyl group, an undecyl group, a dodecyl group, a heptadecyl group, an octadecyl group and an eicosyl group; (2-ethyl) butyl group, isopentyl group, neopentyl group, tert-pentyl group, (1-methyl) pentyl group, (3-ethyl) pentyl group, a (3-ethyl) pentyl group, an isohexyl group, a Branched alkyl group and the like; (1- (2-propenyl) propyl group, 1-propenyl group, 2-propenyl group (allyl group) Phenyl)) ethenyl group, (1,2-dimethyl) propenyl group and 2-pentenyl group; And the like. The number of carbon atoms of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, still more preferably 1 to 10, 1 to 8. Of these, a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 8 carbon atoms is particularly preferable, and a methyl group or an ethyl group is particularly preferable.

Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include a cyclopropyl group, a 1-methylcyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, 1-methylcyclohexyl group, 1-methylcyclohexyl group, 1-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, Dimethylcyclohexyl group, 2,3-dimethylcyclohexyl group, 2,4-dimethylcyclohexyl group, 2,5-dimethylcyclohexyl group, 2,6-dimethylcyclohexyl group, 3,4-dimethylcyclohexyl Dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 2,4,6-trimethylcyclo Hexyl group, 2,2,6,6-tetramethylcyclohexyl group, 3,3,5,5-tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group, 4-cyclohexyl group Chlorhexyl group, etc. Cycloalkyl group; Cycloalkenyl groups such as cyclohexenyl group (for example, cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl group and cyclooctenyl group; Norbornane group, adamantyl group, bicyclo [2.2.2] octane, and the like. The number of carbon atoms of the saturated or unsaturated alicyclic hydrocarbon group is preferably 3 to 30, more preferably 3 to 20, even more preferably 4 to 20, still more preferably 4 to 15, Still more preferably from 5 to 15, and most preferably from 5 to 10. Of these, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are particularly preferable.

Examples of the aromatic hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include a phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 2,3-dimethylphenyl group, Isopropylphenyl group, m-isopropylphenyl group, p-iso-propylphenyl group, n-butylphenyl group, Propylphenyl group, a 4-pentylphenyl group, a 2,6-bis (2-tert-butylphenyl) phenyl group, an isopropylphenyl group, Propyl) phenyl group, 4-cyclohexylphenyl group, 2,4,6-trimethylphenyl group, 4-octylphenyl group, 4-vinylphenyl group, 1-naphthyl group, 2-naphthyl group, 5,6,7,8-tetrahydro- Aromatic hydrocarbon groups such as a 1-naphthyl group, a 5,6,7,8-tetrahydro-2-naphthyl group, a fluorenyl group, a phenanthryl group, an anthryl group and a pyrenyl group; And the like. The carbon number of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 15.

The hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² is preferably a hydrocarbon group having at least one of a hydrocarbon group (for example, an aromatic hydrocarbon group and at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group) An aralkyl group such as a benzyl group, a phenethyl group and a 1-methyl-1-phenylethyl group; An arylalkenyl group such as a phenylethenyl group (phenylvinyl group); An arylalkynyl group such as a phenylethynyl group; A phenyl group to which at least one phenyl group such as a biphenylyl group or a terphenyl group is bonded; A cyclohexylmethylphenyl group, a benzylphenyl group, and a (dimethyl (phenyl) methyl) phenyl group.

The group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² is a group obtained by combining the above hydrocarbon group (for example, a chain hydrocarbon group and an alicyclic hydrocarbon group), and examples thereof include a cyclopropylmethyl group, An alkyl group in which at least one alicyclic hydrocarbon group such as a cyclohexylmethyl group, a cyclohexylmethyl group, a cyclohexylethyl group, an adamantylmethyl group and the like is bonded, do.

The carbon number of the hydrocarbon group is preferably 4 to 30, more preferably 6 to 30, even more preferably 6 to 20, still more preferably 4 to 20, and still more preferably 4 to 15 And particularly preferably from 6 to 15.

The hydrocarbon group represented by R ^N1 and R ^N2 , the hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may have a substituent. The substituent may be either 1 or 2. It is preferable that the divalent substituent binds two carbon atoms to the same carbon atom to form a double bond.

As the monovalent substituent,

Butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, (2-ethyl) hexyloxy group, heptyloxy group, heptyloxy group, isobutyloxy group, Ethylhexyloxy group, icosyloxy group, 1-phenylethoxy group, 1-methyl-1-phenyl (2-ethylhexyloxy) group, An alkoxy group, an ethoxy group, a phenyloxy group, an o-tolyloxy group, a 2,3-dimethylphenyloxy group, a 2,4-dimethylphenyloxy group, a 2,5- 2, 4-dimethylphenyloxy group, 3,5-dimethylphenyloxy group, 2,2-dicyanophenyloxy group, 2,3-dicyanophenyloxy group, 2,4- A 4-methoxyphenyloxy group, a 2-methoxyphenyloxy group, a 3-methoxyphenyloxy group, a 5-dicyanophenyloxy group, a 2,6-dicyanophenyloxy group, Phenyloxy group, 3-methoxyphenyloxy group, 4-ethoxyphenyloxy group, 2-ethoxyphenyloxy group, 3- (Such as a carboxy group, a sulfo group, a nitro group, a hydroxy group, an alkoxy group, an alkoxy group, an alkoxy group, An oxy group bonded on one side with a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group) or the like);

A methylthio group, an ethylthio group, a propylthio group, a butylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a (2-ethylhexylthio group, a heptylthio group, an octylthio group, , A decanyl group, a decylthio group, an undecylthio group, a dodecylthio group, an eicosylthio group, a phenylthio group, and an o-tolylthio group;

An epoxy group, an oxetanyl group, a tetrahydrofuryl group, and a tetrahydropyranyl group;

Formyl group; (2-ethyl) hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, an undecanoyl group, an acetyl group, an acetyl group, a propanoyl group, a butanoyl group, a 2,2-dimethylpropanoyl group, a pentanoyl group, a hexanoyl group, , A dodecanoyl group, a hecinocanoyl group, a benzoyl group, etc., and a group represented by the following formula such as a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 11 carbon atoms) (A carbonyl group in which a carbonyl group, a sulfo group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkyl sulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group) When the alkanoyl group is used, the number of carbon atoms is preferably 2 to 12;

(2-ethyl) hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxycarbonyl, butoxycarbonyl, butoxycarbonyl, (Preferably having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-propyl group, an isopropyl group, A halogen atom (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an alkylsulfamoyl group having 1 to 10 carbon atoms, preferably an octylsulfamoyl group having 1 to 10 carbon atoms, Diacyl) or the like) bonded to each other;

An amino group; N, N-diisopropylamino, N, N-diisopropylamino, N, N-diisopropylamino, N, N-diisopropylamino, N, Butylamino group, an N, N-di-sec-butylamino group, an N, N-diisobutylamino group, (1-ethylpropyl) amino group, N, N-di (1-ethylpropyl) amino group , N-heptylamino group, N, N-dihexylamino group, N, N-dihexylamino group, An N, N-dimethylamino group, an N, N-ethylmethylamino group, an N, N-dimethylamino group, an N, N-dialkylamino group, -Propylmethylamino group, N, N-isopropylmethylamino group, N, N-butylmethyl An amino group, an amino group, an N-decylamino group, an N, N-dodecylmethylamino group, an N-undecylamino group, , N, N-diethylamino group, N, N-eicosylmethylamino group, N, N-tert-butylmethylamino group, N, N-phenylmethylamino group, and groups represented by the following formulas A halogen group (preferably a chlorine atom), an alkylsulfamoyl group having a carbon number of 1 to 10 (preferably a carboxyl group, a sulfo group, a nitro group, a hydroxy group, An octylsulfamoyl group) or the like);

Sulfamoyl group; An N, N-dimethylsulfamoyl group, an N, N-dimethylsulfamoyl group, an N, N-dimethylsulfamoyl group, An N, N-diisopropylsulfamoyl group, an N, N-diisopropylsulfamoyl group, an N-butylsulfamoyl group, an N, Butylsulfamoyl group, N, N-di-tert-butylsulfamoyl group, N-sec-butylsulfamoyl group, N, N, N-di (1-ethylpropyl) sulfamoyl group, N-hexylsulfamoyl group, N, N-diphenylsulfamoyl group, N- (2-ethyl) hexylsulfamoyl group, N-heptylsulfamoyl group, N, N-diheptylsulfamoyl group, N An N, N-dinoylsulfamoyl group, an N-phenylsulfamoyl group, an N, N-dioctylsulfamoyl group, an N, N-octylsulfamoyl group, N-diphenylsulfone An N, N-dimethylamino sulfamoyl group, an N, N-dimethylamino sulfamoyl group, an N, N-dimethylamino sulfamoyl group, , N, N-dodecylsulfamoyl, N, N-dodecylsulfamoyl, N, N-dodecylsulfamoyl, N-decylsulfamoyl, N, N-tert-butylmethylsulfamoyl group, N, N-phenylmethylsulfamoyl group, etc., and a group represented by the following formula Or a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) or an inducible group thereof (e.g., a carboxy group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom) A sulfamoyl group substituted with an alkylsulfamoyl group (preferably an octylsulfamoyl group) or the like);

Formylamino group; (2-ethyl) hexanoylamino group, heptanoylamino group, octanoylamino group, octanoylamino group, octanoylamino group, octanoylamino group, acetylamino group, propanoylamino group, butanoylamino group, 2,2-dimethylpropanoylamino group, pentanoylamino group, hexanoylamino group, (Preferably having 1 to 12 carbon atoms) such as an amino group, a decanoylamino group, an undecanoylamino group, a dodecanoylamino group, a hecinocanoylamino group, a benzoylamino group and the like and a group represented by the following formula A carboxyl group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having a carbon number of 1 to 10 (preferably an octylsulfamoyl group) (When the carbonylamino group is an alkanoylamino group, the number of carbon atoms is preferably 1 to 12) substituted with a carbonyl group bonded to the carbonyl group;

A hydroxy group; A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom;

A carboxyl group, -CO ₂ M ² (M ² is an alkali metal, preferably lithium, sodium, potassium); Sulfo group, -SO ₃ M ² (M ² is an alkali metal, preferably lithium, sodium, potassium); A nitro group; Cyano; Formyloxy group; (2-ethyl) hexanoyloxy group, heptanoyloxy group, octanoyloxy group, naphthoyloxy group, propanoyloxy group, butanoyloxy group, 2,2- (Preferably having 1 to 20 carbon atoms, such as 1 to 20 carbon atoms, such as a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, (Preferably a carboxyl group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group ) Or the like) bonded to the carbonyloxy group (when the carbonyloxy group is an alkanoyloxy group, the number of carbon atoms is preferably 1 to 10);

(2-ethyl) hexylsulfonyl group, a heptylsulfonyl group, an octylsulfonyl group, a nonylsulfonyl group, a decylsulfonyl group, an undecylsulfonyl group, an isopropylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, a pentylsulfonyl group, (Preferably having 1 to 10 carbon atoms) hydrocarbon group such as a sulfonyl group, a dodecylsulfonyl group, an icosylsulfonyl group, a phenylsulfonyl group and a p-tolylsulfonyl group, and a group represented by the following formula (Preferably an alkylsulfamoyl group having 1 to 10 carbon atoms, preferably an octylsulfamoyl group), or the like, which is derivatized with a carboxyl group, a carboxyl group, a sulfo group, a nitro group, a hydroxy group, a halogen A sulfonyl group to which a group is bonded;

Carbamoyl group; An N, N-dimethylcarbamoyl group, an N-ethylcarbamoyl group, an N, N-diethylcarbamoyl group, an N-propylcarbamoyl group, An N, N-diisopropylcarbamoyl group, an N, N-diisopropylcarbamoyl group, an N, N-dibutylcarbamoyl group, Butylcarbamoyl group, N, N-di-tert-butylcarbamoyl group, N-sec-butylcarbamoyl group, N, (1-ethylpropyl) carbamoyl group, an N-hexylcarbamoyl group, an N, N-diethylcarbamoyl group, (2-ethyl) hexylcarbamoyl group, an N-heptylcarbamoyl group, an N, N-diheptylcarbamoyl group, An N-octylcarbamoyl group, an N, N-dioctylcarbamoyl group, an N-nonylcarbamoyl group, an N, An N, N-diphenylcarbamoyl group, an N, N-ethylmethylcarbamoyl group, an N, N-diethylcarbamoyl group, , N, N-isopropylmethylcarbamoyl, N, N-butylmethylcarbamoyl, N-decylcarbamoyl, N, N-decylmethylcarbamoyl, N N-dodecylcarbamoyl group, N-eicosylcarbamoyl group, N, N-eicosylcarbamoyl group, N, N-dodecylcarbamoyl group, An N, N-tert-butylmethylcarbamoyl group, a N, N-phenylmethylcarbamoyl group and the like, and groups represented by the following formulas: A halogen group (preferably a chlorine atom), an alkylsulfamoyl group having a carbon number of 1 to 10 (preferably a hydrocarbon group having a carbon number of 1 to 10), or a group derived therefrom (for example, a carboxyl group, a sulfo group, a nitro group, It is a carbamoyl group substituted with a group) derivatized with such oxide tilsul sulfamoyl group);

A perfluorohexyl group, a perfluoroheptyl group, a perfluorohexyl group, a perfluorohexyl group, a perfluorohexyl group, a perfluorohexyl group, a perfluorohexyl group, a perfluorohexyl group, And all of the hydrogen atoms of the perfluoroalkyl group, the perfluoroalkyl group, the perfluoroalkyl group, the perfluoroalkyl group, the perfluoroalkyl group, the perfluoroalkyl group, A hydrocarbon group of 1 to 20 carbon atoms substituted with a fluorine atom;

A perfluorohexylmethyl group, a perfluorooctylmethyl group, a perfluorooctylmethyl group, a perfluorohexylmethyl group, a perfluorohexylmethyl group, a perfluorohexylmethyl group, a perfluorohexylmethyl group, a perfluorohexylmethyl group, a perfluorohexylmethyl group, A straight chain or branched chain having 1 to 20 carbon atoms in which all the hydrogen atoms of the perfluorodecylmethyl group, the perfluorododecylmethyl group, the perfluorodecylmethyl group, etc., are substituted with a fluorine atom, such as a perfluorodecylmethyl group, a perfluorodecylmethyl group, A hydrocarbon group of 1 to 20 carbon atoms substituted with an alkyl group of 1 to 20 carbon atoms;

(Preferably having 1 to 20 carbon atoms) substituted with fluorine in a part of hydrogen atoms such as 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl and 2,4,6- 10) hydrocarbon group;

-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 thiocarbonyl group bonded with an aryl group having 6 to 20 carbon atoms such as a thiocarbonyl group bonded with an alkyl group having 1 to 20 carbon atoms (preferably 2 to 10 carbon atoms) such as -CH ₃ , -CO-SC ₆ H ₅ or the like;

(Wherein R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, those having 1 to 20 carbon atoms in the above-mentioned hydrocarbon group), or a group represented by the following formula: --COCO - R A group derivatized with an inducible group such as a carboxyl group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkyl sulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group) );

-NRCONR ₂ (wherein R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, one having 1 to 20 carbon atoms in the above-mentioned hydrocarbon group), or a derivative thereof A halogen atom (preferably a chlorine atom), an alkylsulfamoyl group (preferably an octylsulfamoyl group) having 1 to 10 carbon atoms, and the like), a halogen atom (e.g., a carboxyl group, a sulfo group, a nitro group, And R may be the same or different and may be bonded to each other to form a ring;

-OCONR ₂ (wherein R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, those having 1 to 20 carbon atoms in the above-mentioned hydrocarbon group), or a derivative thereof A halogen atom (preferably a chlorine atom), an alkylsulfamoyl group (preferably an octylsulfamoyl group) having 1 to 10 carbon atoms, and the like), a halogen atom (e.g., a carboxyl group, a sulfo group, a nitro group, And R may be the same or different and may be bonded to each other to form a ring;

-NRCOOR (wherein R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, those having 1 to 20 carbon atoms in the above-described hydrocarbon groups), or an induction group (For example, a group induced by a carboxyl group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkyl sulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group) R may be the same or different and may be bonded to each other to form a ring;

_{* -OP (O) (OCH 3} ) 2 , etc. * -OP (O) (OR) 2 ( wherein, R is a hydrocarbon group that is included in the example (for example, a hydrogen atom, a hydrocarbon group of 1 to 20 carbon atoms A halogen atom (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an alkylsulfamoyl group having 1 to 10 carbon atoms) Octylsulfamoyl group, etc.), which may be the same or different and may be bonded to each other to form a ring;

_{* -Si (CH 3) 3,} * - Si (CH 2 CH 3) 3, * - Si (C 6 H 5) 3 and _{* -Si (CH (CH 3)} 2) , such as ₃ * -SiR ₃ ( In the formula, R represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, those having 1 to 20 carbon atoms in the above-mentioned hydrocarbon groups), or an inducible group thereof (e.g., a carboxy group, A halogen atom (preferably a chlorine atom), an alkylsulfamoyl group having a carbon number of 1 to 10 (preferably octylsulfamoyl group), and the like, which may be the same or different, And they may be bonded to each other to form a ring; And the like.

Examples of the divalent substituent include an oxo group, a thioxo 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 have. Examples of the imino group substituted with an alkyl group include CH ₃ -N═, CH ₃ -CH ₂ -N═, CH ₃ - (CH ₂ ) ₂ -N═, CH ₃ - (CH ₂ ) ₃ -N═ and the like . Examples of the imino group substituted with an aryl group include C ₆ H ₅ -N═.

The substituent of the hydrocarbon group of 1 to 40 carbon atoms is preferably a substituent of the group s1. The following inducer is preferably a group induced by a carboxyl group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkyl sulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group) Do.

[Group s1]

An oxy group in which a hydrocarbon group of 1 to 20 carbon atoms or an inducing group thereof is bound on one side;

A carbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms or an inducible group thereof is bonded;

An oxycarbonyl group to which a hydrocarbon group having 1 to 20 carbon atoms or an inducible group thereof is bonded;

An amino group; An amino group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or an inducible group thereof; Sulfamoyl group; A sulfamoyl group substituted with one or two hydrocarbon groups having 1 to 20 carbon atoms or an inducible group thereof;

A carbonylamino group to which a hydrocarbon group having 1 to 20 carbon atoms or an inducible group thereof is bonded;

A hydroxy group; A halogen atom; -CO ₂ M (preferably a carboxyl group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); -SO ₃ M (preferably a sulfo group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom);

A nitro group; Cyano; A carbonyloxy group bonded with a hydrocarbon group of 1 to 20 carbon atoms or an inducible group thereof; A sulfonyl group to which a hydrocarbon group having 1 to 20 carbon atoms or an inducible group thereof is bonded; Carbamoyl group; A carbamoyl group substituted with one or two hydrocarbon groups of 1 to 20 carbon atoms or its derivatizing group; A hydrocarbon group of 1 to 20 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms;

A hydrocarbon group of 1 to 20 carbon atoms substituted with a linear or branched alkyl group having 1 to 20 carbon atoms in which all of the hydrogen atoms are substituted with fluorine atoms; A hydrocarbon group of 1 to 20 carbon atoms in which a part of the hydrogen atoms are substituted with fluorine; Oxo group.

The substituent of the hydrocarbon group of 1 to 40 carbon atoms is more preferably a substituent of the group s2.

[Group s2]

An oxy group in which a hydrocarbon group of 1 to 10 carbon atoms or its derivatized group is bound to one side;

A carbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or an inducible group thereof is bonded;

An oxycarbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or an inducible group thereof is bonded;

An amino group; An amino group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms;

Sulfamoyl group; A sulfamoyl group substituted with one or two hydrocarbon groups of 1 to 10 carbon atoms or its derivatizing group; A carbonylamino group to which a hydrocarbon group having 1 to 10 carbon atoms or an inducible group thereof is bonded; A hydroxy group; Fluorine atom, chlorine atom, bromine atom;

-CO ₂ M (preferably a carboxyl group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); -SO ₃ M (preferably a sulfo group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); A nitro group; Cyano; A carbonyloxy group bonded with a hydrocarbon group having 1 to 10 carbon atoms or an inducible group thereof; A sulfonyl group to which a hydrocarbon group having 1 to 10 carbon atoms or an inducible group thereof is bonded; Carbamoyl group; A carbamoyl group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms or an inducible group thereof; A hydrocarbon group of 1 to 10 carbon atoms in which all hydrogen atoms are substituted with fluorine atoms; A hydrocarbon group of 1 to 10 carbon atoms substituted with a linear or branched alkyl group having 1 to 10 carbon atoms in which all of the hydrogen atoms are substituted with fluorine atoms; A hydrocarbon group having 1 to 10 carbon atoms in which a part of the hydrogen atoms are substituted with fluorine; Oxo group.

Examples of the hydrocarbon group having 1 to 40 carbon atoms and having a substituent represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include a hydrocarbon group having 1 to 40 carbon atoms and having a monovalent or divalent substituent, Is a saturated or unsaturated chain hydrocarbon group having 1 to 30 carbon atoms and a monovalent or divalent substituent, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 30 carbon atoms and having a monovalent or divalent substituent, a monovalent or divalent alicyclic hydrocarbon group having a monovalent or divalent substituent An aromatic hydrocarbon group having 6 to 30 carbon atoms or a combination of a hydrocarbon group and a group having 1 to 30 carbon atoms and having a monovalent or divalent substituent,

More preferably, a saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms having a substituent group of the group s1, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 20 carbon atoms having a substituent group of the group s1, An aromatic hydrocarbon group or a hydrocarbon group having from 1 to 20 carbon atoms,

Particularly preferably, a saturated or unsaturated chain hydrocarbon group having 1 to 15 carbon atoms having a substituent group of the group s2, a saturated or unsaturated alicyclic hydrocarbon group having 3 to 15 carbon atoms having a substituent group of the group s2, A group having a substituent of the group s2 and a group having a carbon number of 1 to 15, which is a group obtained by combining an aromatic hydrocarbon group or a hydrocarbon group of 1 to 15 carbon atoms.

The heterocyclic group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may be a monocyclic ring or a polycyclic ring, preferably a heterocyclic ring containing a hetero atom as a constituent of the ring. Examples of the hetero atom include a nitrogen atom, an oxygen atom and a sulfur atom.

The carbon number of the heterocyclic group is preferably 3 to 30, more preferably 3 to 22, still more preferably 3 to 20, still more preferably 3 to 18, still more preferably 3 to 15 , And particularly preferably from 3 to 14.

As the heterocyclic ring containing a nitrogen atom,

Monocyclic saturated heterocyclic rings such as aziridine, azetidine, pyrrolidine, piperidine and piperazine;

A pyrazole such as pyrrole such as 2,5-dimethylpyrrole, 2-methylpyrazole or 3-methylpyrazole, a 5-membered ring such as imidazole, 1,2,3-triazole or 1,2,4- A systematic unsaturated heterocyclic ring;

6-membered cyclic unsaturated heterocyclic rings such as pyridine, pyridazine, pyridazine, 6-methylpyrimidine and the like, pyrazine and 1,3,5-triazine;

There can be mentioned quinone such as indazole, indoline, isoindoline, indole, indolidine, benzoimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro (3-methyl) quinoxaline, Condensed divalent heterocyclic rings such as salin, quinazoline, cinnoline, phthalazine, naphthyridine, purine, pteridine, benzopyrazole, and benzopiperidine;

Condensed tricyclic heterocyclic rings such as carbazole, acridine and phenazine; And the like.

Examples of the heterocyclic ring containing an oxygen atom include monocyclic saturated heterocyclic rings such as oxylane, oxetane, tetrahydrofuran, tetrahydropyran, 1,3-dioxane, 1,4-dioxane, and 1-cyclopentyldioxolane; Bicyclic saturated heterocyclic rings such as 1,4-dioxaspiro [4.5] decane and 1,4-dioxaspiro [4.5] nonane;

lactone type heterocyclic rings such as? -acetolactone,? -propiolactone,? -butyrolactone,? -valerolactone and? -valerolactone;

5-membered cyclic unsaturated heterocyclic rings such as 2,3-dimethyl furan and furan such as 2,5-dimethyl furan;

6-membered cyclic unsaturated heterocyclic rings such as 2H-pyran and 4H-pyran;

Condensed divalent heterocyclic rings such as benzopyran, benzodioxole, chroman, isochromane such as 1-benzofuran and 4-methylbenzopyran;

Condensed tricyclic heterocyclic rings such as xanthene and dibenzofuran; And the like.

Examples of the heterocyclic ring containing a sulfur atom include a 5-membered ring saturated hetero ring such as dithiolane; 6-membered cyclic saturated heterocyclic rings such as thian, 1,3-dithiane, and 2-methyl 1,3-dithiane; 5-membered cyclic unsaturated heterocyclic rings such as thiophene such as 3-methylthiophene or 2-carboxythiophene, benzothiopyrane such as 4H-thiopyran or benzotetrahydrothiopyran; Condensed divalent heterocyclic rings such as benzothiophene and the like; Condensed tricyclic heterocyclic rings such as thianthrene, dibenzothiophene and the like; And the like.

Examples of the heterocyclic ring containing a nitrogen atom and an oxygen atom include monocyclic saturated heterocyclic rings such as morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, Summons;

Oxazole such as 4-methyloxazole, isooxazole such as 2-methylisooxazole and 3-methylisoxazole, and other monocyclic unsaturated heterocyclic rings;

Condensed divalent heterocyclic rings such as benzooxazole, benzoisoxazole, benzoxazine, benzodioxane, and benzoimidazoline; Condensed tricyclic heterocyclic rings such as phenoxazin; And the like.

Examples of the heterocyclic ring containing a nitrogen atom and a sulfur atom include monocyclic heterocyclic rings such as thiols such as 3-methylthiazole and 2,4-dimethylthiazole; Condensed divalent heterocyclic rings such as benzothiazole;

Condensed tricyclic heterocyclic rings such as phenothiazine; And the like.

The heterocyclic ring may be a combination of the above-mentioned hydrocarbon groups, for example, tetrahydrofurylmethyl group.

The heterocyclic ring may be represented by the following formula.

The heterocyclic group may be a heterocyclic group formed by combining two or more of R ¹ to R ³ and R ⁵ to R ⁸ . Such a heterocyclic group has two or more ring structures together with a benzene ring to which R ¹ to R ³ and R ⁵ to R ⁸ are bonded. As the ring structure of two or more rings, for example, the following structure can be given.

The bonding position of the above-mentioned heterocyclic ring is a portion in which any hydrogen atom contained in each ring is eliminated.

The heterocyclic group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may have a substituent. Examples of the substituent include the same aliphatic hydrocarbon group represented by R ^N1 and R ^N2 , and the same substituent group that the hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may have. When the heterocyclic ring contains a nitrogen atom as a constituent element, the hydrocarbon atom may be bonded to the nitrogen atom as a substituent.

Preferable examples of the substituent include the same ones as those of the aliphatic hydrocarbon group represented by R ^N1 and R ^N2 , the substituents which the hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may have .

Examples of the heterocyclic group having a substituent represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include a monovalent or divalent heterocyclic group having a substituent, preferably a heterocyclic group having a substituent of the group s 1 , And more preferably a heterocyclic group having a substituent of the group s2.

The substituent (first substituent) which the hydrocarbon group or heterocyclic group may have may be one or more than two, and two or more substituents may be the same or different from each other. The first substituent may be bonded to a hydrocarbon group contained in a part thereof with another substituent (second substituent). The second substituent may be selected from the same group as the first substituent.

Or less, R ¹ ~R ⁸ of ^{-CO-R 102, -COO-R} 101, -OCO-R 102, -COCO-R 102, -OR 102, -SO 2 -R 101, -SO 2 N (R 102 ^{_{) 2, -CON (R 102)}} 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102) 2, a halogen atom, -SO ₃ M, and -CO ₂ M will be described.

-CO-R ^{102 is preferably} formyl group; (2-ethyl) hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, an undecanoyl group, an acetyl group, an acetyl group, a propanoyl group, a butanoyl group, a 2,2-dimethylpropanoyl group, a pentanoyl group, a hexanoyl group, , A dodecanoyl group, a hecinocanoyl group, a benzoyl group, and the like, and a group represented by the above formula, such as a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or an inducible group thereof such as a carboxy group, A group derived from a sulfone group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group), or the like) Include a carbonyl group in which a hydrocarbon group having 1 to 10 carbon atoms is bonded (when the carbonyl group is an acyl group, the number of carbon atoms is 2 to 41), and the like. Preferably a hydrocarbon group having 1 to 11 carbon atoms (more preferably 1 to 10 carbon atoms) or a carbonyl group to which the inducible group is bonded (more preferably 2 to 12 carbon atoms when the carbonyl group is an alkanoyl group) And the like.

Examples of -COO-R ¹⁰¹ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, (Preferably having 1 to 20 carbon atoms, such as a carbonyl group, an alkoxycarbonyl group, an octyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, an undecyloxycarbonyl group, a dodecyloxycarbonyl group, a phenyloxycarbonyl group and an icosyloxycarbonyl group, (For example, a carboxyl group, a sulfo group, a nitro group, a hydroxy group, a halogen atom (preferably a chlorine atom (preferably a chlorine atom), a bromine atom or an iodine atom), or an oxycarbonyl group to which a hydrocarbon group ), An alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group), or the like) An oxycarbonyl group and the like.

Preferably a hydrocarbon group of 1 to 10 carbon atoms or an oxycarbonyl group to which an inducible group thereof is bonded.

Examples of -OCO-R ¹⁰² include a formyloxy group; (2-ethyl) hexanoyloxy group, heptanoyloxy group, octanoyloxy group, naphthoyloxy group, propanoyloxy group, butanoyloxy group, 2,2- (Preferably one having 1 to 40 carbon atoms such as a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, More preferably a hydrocarbon group having 1 to 10 carbon atoms or an inducible group thereof such as a carboxy group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably, a halogen atom A carbonyloxy group in which a carbonyloxy group bonded with a carbonyloxy group), an alkylsulfamoyl group (preferably an octylsulfamoyl group), or the like) bonded with a carbonyloxy group (in which the carbonyloxy group is bonded to an acyloxy group , The number of carbon atoms is in the range of 2 to 41), preferably a hydrocarbon group having 1 to 11 carbon atoms (more preferably 1 to 10 carbon atoms) or a carbonyloxy group And when the oxy group is an acyloxy group, the number of carbon atoms is more preferably from 2 to 12).

Examples of -COCO-R ¹⁰² include a methyloxyl group, an ethyloxyl group, a propyloxyl group, a butyloxyl group, a pentyloxyl group, a hexyloxyl group, a (2-ethyl) hexyloxyl group, An octyloxyl group, a cyclopentyloxyl group, a cyclohexyloxyl group, a phenyloxyl group, a phenyloxycarbonyl group, a p-toluenesulfonyl group, a p-toluenesulfonyl group, (E.g., a carboxy group, a sulfo group, a nitro group, a hydroxy group, a hydroxyl group, a hydroxyl group, a hydroxyl group, , A halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group)), and the like.

-OR ¹⁰² includes a hydroxy group; Butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, 2-ethylhexyloxy group, icosyloxy group, 1-phenylethoxy group, 1-methyl-1-phenylethoxy group, phenyloxy group, 2-ethylhexyloxy group, Dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyloxy group, An alkoxycarbonyloxy group, an oxy group, a 2,2-dicyanophenyloxy group, a 2,3-dicyanophenyloxy group, a 2,4-dicyanophenyloxy group, a 2,5- A 3-methoxyphenyloxy group, a 3-methoxyphenyloxy group, a 4-methoxyphenyloxy group, a 4-methoxyphenyloxy group, 2-ethoxyphenyloxy group, 3-ethoxyphenyloxy group, etc., and the above-mentioned formula (Such as a carboxyl group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), a halogen atom (preferably a chlorine atom) A group derived from an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group)), and an oxy group bonded with a hydrocarbon group having 1 to 10 carbon atoms, and the like.

Preferably a hydrocarbon group having 1 to 10 carbon atoms or an oxy group bonded with an inducing group thereof.

Examples of -SO ₂ -R ¹⁰¹ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, a pentylsulfonyl group, a hexylsulfonyl group, a (2-ethyl) hexylsulfonyl group, a heptylsulfonyl group, (Preferably having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an ethyl group, an ethyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a heptyl group, A halogen atom (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an alkylsulfamoyl group having 1 to 10 carbon atoms, preferably an alkylsulfamoyl group having 1 to 10 carbon atoms, A pyrazolyl group, a pyrazolyl group, a pamoyl group), and the like, preferably a hydrocarbon group having 1 to 10 carbon atoms or a sulfonyl group bonded with its induction group.

Examples of -SO ₂ N (R ¹⁰² ) ₂ include a sulfamoyl group;

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-hexylsulfamoyl group, N- (2-ethyl) hexylsulfamoyl group, N-heptylsulfamoyl group, N-heptylsulfamoyl group, N- N-heptylsulfamoyl group, N-octylsulfamoyl group, N-nonylsulfamoyl group, N-desilsulfamoyl group, N-undecylsulfamoyl group, N-dodecylsulfamoyl group, N-icosylsulfamoyl group, N (For example, a carboxy group, a sulfo group, a nitro group (for example, a carboxy group, a sulfo group or a nitro group) having 1 to 40 (preferably 1 to 20) carbon atoms such as a group represented by the above formula , A sulfamoyl group substituted with a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group), etc.);

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, , N, N-diisopropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-dipentylsulfamoyl group, N, N-dibutylsulfamoyl group, Di (2-ethyl) hexylsulfamoyl group, N, N-diheptylsulfamoyl group, N, N-octyl Methylsulfamoyl group, N, N-dioctylsulfamoyl group, N, N-dinylsulfamoyl group, N, N-decyl methyl sulfamoyl group, N, N-undecyl methyl sulfamoyl group, N, A methylsulfamoyl group, an N, N-eicosylmethylsulfamoyl group, an N, N-phenylmethylsulfamoyl group, an N, N-diphenylsulfamoyl group and the like, 1-4 A halogen atom (preferably a chlorine atom), an alkylsulfamoyl group (having a carbon number of 1 to 10), a halogen atom (preferably a chlorine atom) Preferably an octylsulfamoyl group), and the like, and the like.

Preferably 1 or 2 hydrocarbon groups having 1 to 10 carbon atoms or a sulfamoyl group substituted with an inducing group thereof.

Examples of -CON (R ¹⁰² ) ₂ include a carbamoyl group;

N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-isopropylcarbamoyl group, N-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec- (1-ethylpropyl) carbamoyl group, an N-hexylcarbamoyl group, an N- (2-ethyl) hexylcarbamoyl group, an N-butylcarbamoyl group, Heptylcarbamoyl group, N-heptylcarbamoyl group, N-octylcarbamoyl group, N-nonylcarbamoyl group, N-decylcarbamoyl group, N- An alkyl group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) such as a halogen atom, a hydroxyl group, a nitro group, an N-phenylcarbamoyl group, and the group represented by the above formula, , A nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably an octylsulfamoyl group) A carbamoyl group substituted with a halogen atom);

An N, N-dimethylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-ethylmethylcarbamoyl group, N, N-diisopropylcarbamoyl group, N, N-diisopropylcarbamoyl group, N, N-diisopropylcarbamoyl group, An N, N-dibutylcarbamoyl group, an N, N-butyloctylcarbamoyl group, an N, N-dibutylcarbamoyl group, N-di (2-ethyl) hexylcarbamoyl group, N, N-di (1-ethylpropyl) carbamoyl group, N, N-dodecylcarbamoyl, N, N-dodecylcarbamoyl, N, N-dodecylcarbamoyl, N, N-octylmethylcarbamoyl, N, N-dodecylmethylcarbamoyl, N, N-eicosylmethylcarbamoyl, N, N-phenylmethylcarbamoyl , An N, N-diphenylcarbamoyl group, and the like, and groups represented by the above formulas, or an inducible group thereof (e.g., a carboxy group, A carbamoyl group substituted with a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having a carbon number of 1 to 10 (preferably octylsulfamoyl group) Can,

Preferably one or two hydrocarbon groups of 1 to 10 carbon atoms or a carbamoyl group substituted by an inducible group thereof.

Examples of -N (R ¹⁰² ) ₂ include an amino group; N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, , N-hexylamino group, N- (2-ethyl) hexylamino group, N-heptylamino group, N-octylamino group, N-nonylamino group, N-decylamino group, N-undecylamino group, (Preferably having 1 to 20 carbon atoms) such as an isocyanic acid group, an isocyanic acid group, an isocyanic acid group, an isosylamino group, an N-phenylamino group, An amino group substituted with a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having 1 to 10 carbon atoms (preferably octylsulfamoyl group), etc.);

N, N-dimethylamino group, N, N-ethylmethylamino group, N, N-diethylamino group, N, N-propylmethylamino group, Diisopropylamino group, N, N-tert-butylmethylamino group, N, N-diisobutylamino group, N, Diethylamino group, N, N-diethylamino group, N, N-di (2-ethyl N-dodecylamino group, N, N-dodecylmethylamino group, N, N-undecylmethylamino group, N, N-dodecylamino group, (Preferably having 1 to 20 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, n-butyl, isobutyl, A hydrocarbon group of 1 to 20 carbon atoms) or an induction group thereof (e.g., a carboxyl group , An amino group substituted with a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having a carbon number of 1 to 10 (preferably octylsulfamoyl group) Can,

Preferably 1 or 2 hydrocarbon groups having 1 to 10 carbon atoms or amino groups substituted with an inducing group thereof.

-NHCO-R ^{102 is preferably a} formylamino group; (2-ethyl) hexanoylamino group, heptanoylamino group, octanoylamino group, octanoylamino group, octanoylamino group, octanoylamino group, acetylamino group, propanoylamino group, butanoylamino group, 2,2-dimethylpropanoylamino group, pentanoylamino group, hexanoylamino group, (Preferably having 1 to 20 carbon atoms) such as an amino group, a decanoylamino group, an undecanoylamino group, a dodecanoylamino group, a hecinocanoylamino group, a benzoylamino group, etc., A carboxyl group, a sulfo group, a nitro group, a hydroxy group, a halogen (preferably a chlorine atom), an alkylsulfamoyl group having a carbon number of 1 to 10 (preferably an octylsulfamoyl group) (When the carbonylamino group is an acylamino group, the number of carbon atoms is 1 to 40), and the like,

Preferably a hydrocarbon group having 1 to 10 carbon atoms or a carbonylamino group to which an inducible group thereof is bonded (when the carbonylamino group is an alkanoylamino group, the number of carbon atoms is more preferably 1 to 10).

Examples of -NHCON (R ¹⁰² ) ₂ include the above groups and the like.

Examples of -NHCOOR ¹⁰² include the above groups.

Examples of -OCON (R ¹⁰² ) ₂ include the above groups.

The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

As M of -SO ₃ M and -CO ₂ M, a hydrogen atom; And alkali metal atoms such as lithium atom, sodium atom and potassium atom, preferably hydrogen atom, sodium atom and potassium atom.

-CO-R ¹⁰² , -COO-R ¹⁰² , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰² , -SO ₂ N (R ¹⁰² ) ₂ , -CON _{^{102) 2, -N (R 102}} ) 2, -NHCO-R 102, -NHCON (R 102) 2, -NHCOOR 102, -OCON (R 102) substituents included in the _second (first substituent) is one or And two or more substituents may be independently the same or different.

The first substituent may be bonded to a hydrocarbon group contained in a part thereof with another substituent (second substituent). The second substituent may be selected from the same group as the first substituent.

The compound represented by the formula (I) may have the following partial structure in addition to the above-mentioned groups.

R ^N1 and R ^N2 are preferably an aliphatic hydrocarbon group, an aralkyl group, a (cycloalkyl) alkyl group, an aliphatic hydrocarbon group substituted with a hydroxy group, or an aliphatic hydrocarbon group substituted with an oxy group bonded to a hydrocarbon group having 1 to 20 carbon atoms, More preferably a linear or branched alkyl group substituted with a linear or branched alkyl group, a linear or branched alkenyl group, a cycloalkyl group, an aralkyl group, a (cycloalkyl) alkyl group, a hydroxyl group-substituted linear or branched alkyl group or an alkoxy group Do.

R ^N1 and R ^N2 may be the same or different.

R ^N3 is preferably an aliphatic hydrocarbon group, more preferably a straight-chain or branched-chain alkyl group, and more preferably a straight-chain alkyl group.

R ⁴ is preferably a hydrogen atom, and R ¹ to R ⁸ are more preferably a hydrogen atom.

In the compound represented by the formula (I), A ^{g -} represents anion of g. g represents an integer of 1 to 14, preferably an integer of 1 to 10, more preferably an integer of 1 to 8, still more preferably an integer of 1 to 6, particularly preferably 1 Represents an integer of 4.

A ^{g- is a} known anion. Specifically, as A ^g- ,

Halide ions such as fluoride ion, chloride ion, bromide ion, and iodide ion;

OH ^- ; CN ^- ; NO ₃ ^- ; NO ₂ ^- ; ClO ^- ; ClO ₂ ^- ; ClO ₃ ^- ; ClO ₄ ^-; MnO ₄ ^- ; CH ₃ CO ₂ ^- , C ₆ H ₅ CO ₂ ^- ; Tosylate anion; HCO ₃ ^- ; H ₂ PO ₄ ^- ; HSO ₄ ^- ; HS ^- ; SCN ^- ; H (COO) ₂ ^- ; ^{_{[Al (OH) 4] -}} , [Al (OH) 4 (H 2 O) 2] -; [Ag (CN) ₂ ] ^- ; [Cr (OH) ₄ ] ^- ; [AuCl _4] ^-; O ^2- ; S ^2- ; O ₂ ^2- ; SO ₄ ^2- , HSO ₄ ^- ; SO ₃ ^2- ; S ₂ O ₃ ^2- ; CO ₃ ^2- ; CrO ₄ ^2-; Cr ₂ O ₇ ^2- ; (COO) ₂ ^2- ; HPO ₄ ^2- ; [Zn (OH) ₄ ] ^2- ; [Zn (CN) ₄ ] ^2- ; [CuCl ₄ ] ^2- ; PO ₄ ^3- ; [Fe (CN) ₆ ] ^3- ; [Ag (S ₂ O ₃ ) ₂ ] ^3- ; [Fe (CN) ₆ ] ^4- ; _{^{CH 3 O -, CH 3 CH}} 2 O -, (CH 3) 3 CO - ions such as alkoxy, C ₆ H ₅ O of 1 to 20 carbon atoms ^- such as of aryloxy ion of 6 to 20 carbon atoms;

It is not fluorine; Tungsten, molybdenum, silicon and phosphorus, and an anion containing oxygen as an essential element.

From the viewpoint of improving the heat resistance and reducing the sublimation property, A ^{g -} is an element which contains no element which contains fluorine or at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and an anion which contains oxygen as an essential element More preferably an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements, or an anion containing at least one element selected from the group consisting of tungsten and phosphorus And more preferably anion containing an element and oxygen as essential elements.

Examples of fluorine atoms include CF ₃ CO ₂ ^- and groups represented by the following formulas (III), (IV), (V) and (VI).

Wherein W ³ and W ⁴ independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms or W ³ and W ⁴ together form a fluorinated alkyl group having 1 to 4 carbon atoms Indicates candidiasis.]

[In the formula (IV), W ^{5 to} W ⁷ independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms.]

[In the formula (V), Y ¹ represents a fluorinated alkanediyl group having 1 to 4 carbon atoms.]

[In the formula (VI), Y ² represents an alkyl fluoride group having 1 to 4 carbon atoms.]

In the formulas (III), (IV) and (VI), the fluoroalkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. Examples of the perfluoroalkyl group include -CF ₃ , -CF ₂ CF ₃ , -CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) _2, and the like -C (CF _{3) 3.}

In the formulas (III) and (V), as the fluorinated alkanediyl group having 1 to 4 carbon atoms, a perfluoroalkanediyl group is preferable, and -CF ₂ -, -CF ₂ CF ₂ -, -CF ₂ CF ₂ CF ₂ - , -C (CF ₃ ) ₂ -, -CF ₂ CF ₂ CF ₂ CF ₂ - and the like.

Anion represented by the formula (III) (hereinafter sometimes referred to as "anion (III)") is an anion represented by the formulas (III-1) to (III-6) Quot; on (III-1) " to " anion (III-6) "

Anion (IV-1) represented by the formula (IV-1) is an example of an anion represented by the formula (IV) (hereinafter sometimes referred to as "anion (IV)").

Anion represented by the formula (V) (hereinafter sometimes referred to as "anion (V)") includes anions represented by the formulas (V-1) to (V-4) (V-1) "to" Anion (V-4) ".

Anion represented by the formula (VI) (hereinafter sometimes referred to as "anion (VI)") is an anion represented by the formulas (VI-1) to (VI- (VI-1) "to" Anon (VI-4) ".

The fluorine anion may be at least one anion selected from the group consisting of CF ₃ CO ₂ ^- , anion (III), anion (IV), anion (V) and anion (VI). Among them, anions such as CF ₃ CO ₂ ^- , anion (III-1), anion (III-2), anion (III-6), anion (IV- (VI-1), anion (VI-2) and anion (VI-3) are preferred and CF ₃ CO ₂ ^- , anion (III-2), anion VI-1) is more preferable.

As anions there may be mentioned anions containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements. Anions of heteropoly acid or isopoly acid containing tungsten as an essential element are preferable, and anions of tungstic acid, tungstic acid and tungsten-based isopoly acid are more preferable. Such anion is used for a coloring compound represented by the formula (I) having, for example, fluorine atom (preferably anion (VI-1)), and anion exchange contributes to improvement in heat resistance .

Examples of anions of heteropoly acid or isopoly acid containing tungsten as an essential element include tungstate ion α- [PW ₁₂ O ₄₀ ] ^3- , tungsten type tungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , quasic type tungstate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , ^{_{γ- [SiW 12 O 40] 4-}} , also as other example _{[P 2 W 17 O 61]} 10-, [P 2 W 15 O 56] 12-, [H 2 P 2 W 12 O 48] 12-, _{[NaP 5 W 30 O 110]} 14-, α- [SiW 9 O 34] 10-, γ- [SiW 10 O 36] 8-, α- [SiW 11 O 39] 8-, β- [SiW 11 O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- and the like. Among them, it is more preferred cake ginhyeong of tungstate ion ^{_{α- [PW 12 O 40] 3-}} .

The compound (I) is preferably a compound represented by the formula (I-B) (hereinafter sometimes referred to as a compound (I-B)). If the compound (I) is the compound (I-B), the heat resistance is excellent.

In the formula (I-B), R ^N1 , R ^N2 , R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ , R ¹⁰² and M have the same meanings as defined above.

B ^{h -} represents at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and h anion containing oxygen as an essential element.

and h represents an integer of 1 to 14.]

In the formula (I-B), B ^{h -} may be the same as the anion of g having tungsten, molybdenum or the like contained as A ^{g -} in the formula (I).

Preferable B ^{h - in the} formula (I-B) includes at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus contained as A ^{g -} in the formula (I) The same as the preferable one among the anions of g.

Examples of the compound (I) include the compounds shown in Tables 1 to 10 or their alkali metal salts.

In the Tables 1 to 10, "Me" represents a methyl group, "Et" represents an ethyl group, "Bu" represents a butyl group, "TBu" represents a tert-butyl group, "Hex""CH" represents a cyclohexyl group, "PH" represents a phenyl group, "BZ" represents an octyl group, "Oct" represents an octyl group, "2EH" represents a 2-ethylhexyl group, "CHM" represents a cyclohexylmethyl group, Represents a benzyl group, "NPR" represents a propyl group, "IPR" represents an isopropyl group, "IBu" represents an isobutyl group, "EOE" represents -CH ₂ CH ₂ OCH ₂ CH ₃ , &Quot; represents an allyl group, " HYE " represents a 2-hydroxyethyl group,

"COM" represents -CO-CH ₃ , "COE" represents -COO-CH ₂ CH ₃ , "OCM" represents -OCO-CH ₃ , "OME" represents -O-CH ₃ ,

"SOT" represents a tosyl group, "SNH" is _{-SO 2 NH-CH 2 CH (} CH 2 CH 3) ((CH 2) 3 CH 3) represents a, "SN2" is -SO ₂ N (CH _{3 ) ((CH 2) 7 CH} 3) represents a, "CNM" represents -CONHCH _3, "CN2" is -CON (CH ₃₎ represents a C ₆ H _5, a is -NHC ₆ H _5, "NPH" shows, "NOT" is _{-N ((CH 2) 7 CH} 3) denotes _2, the "NCO" is _{-NHCO ((CH 2) 4 CH} 3) represents a, "F" denotes a fluorine atom, "Cl "Represents a chlorine atom," Br "represents a bromine atom," CN "represents a cyano group,

"NO2" represents a nitro group, "SUA" represents -SO ₃ H, "CBA" represents -CO ₂ H, "CHO" represents -CHO,

"OCH" represents -OCOH, "OH" represents -OH, "SFM" represents -SO ₂ NH ₂ , "CBM" represents -CONH ₂ ,

"NH2" represents an -NH _2, "NCH" denotes a -NHCOH, "Ⅲ-1" - "Ⅲ-6" represents an anionic (Ⅲ-1) ~ anionic (Ⅲ-6),

V-1 "represents anion (IV-1)," V-1 "to" V-4 "represent anion (V-1) (VI-4) represents anion (VI-1) to anion (VI-4).

The compound (I-1) is, for example, a compound represented by the formula (I-1).

The compound (I-1) to the compound (I-312) are more preferable, and the compound (I-1) to the compound (I- To (I-24) are more preferable, and compounds (I-13) to (I-24) are particularly preferable.

Among them, the compound (I) of the present invention is particularly preferably the compound (I-14).

The compound (I) of the present invention can be produced by reacting a compound represented by the formula (II) (hereinafter sometimes referred to as a compound (II)) and a compound represented by the formula (II- 1). Alternatively, a compound containing at least one element selected from the group consisting of tungsten, silicon, and phosphorus and oxygen as essential elements may be further added to the obtained compound Or the like.

Equation (Ⅱ) and formula (Ⅱ-1) ^{of, R 1 ~R 8, R N1} , R N2, R N3 , and g have the same meanings as defined above, A 'is the A ^{g -} e g in the dog Quot;

The compound represented by the formula (II-1) includes an alkylating agent. The alkylating agent is preferably a halogenated alkyl (such as methyl chloride, methyl bromide or methyl iodide) having 1 to 10 carbon atoms, more preferably 1 to 3 carbon atoms, such as halogenated alkyl; Preferably a dialkyl carbonate having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and still more preferably 2 to 4 carbon atoms (e.g., dimethyl carbonate or diethyl carbonate); Preferably a dialkyl sulfuric acid (such as dimethyl sulfate or diethyl sulfate) having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms; Preferably an alkylsulfonyl group having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, and more preferably 2 to 4 carbon atoms, such as methyl methanesulfonate, ethyl ethanesulfonate, ethyl methanesulfonate, methyl ethanesulfonate, trifluoromethane Methyl sulfonate, ethyl trifluoromethanesulfonate, etc.).

The alkylating agent is preferably a methylating agent, an ethylating agent, a propylating agent, a butylating agent and the like, more preferably a methylating agent.

The amount of the alkylating agent to be used is preferably 1 mol or more and 20 mol or less, and more preferably 1 mol or more and 10 mol or less, relative to 1 mol of the compound (II).

The reaction temperature is preferably 0 to 150 캜, more preferably 10 to 100 캜. In order to make the solubility of the coloring compound precursor represented by the formula (I) satisfactory, it may be premixed with a predetermined organic solvent at about 70 to 100 ° C. The reaction time is preferably 10 minutes to 24 hours, more preferably 1 hour to 12 hours.

From the viewpoint of the yield, it is preferable that the reaction is carried out in an organic solvent. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; Aliphatic hydrocarbon solvents such as hexane; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, methylene chloride and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol and butanol; A nitrohydrocarbon solvent such as nitrobenzene; Ketone solvents such as acetone and methyl isobutyl ketone; Ester solvents such as ethyl acetate; Ether solvents such as diethyl ether and tetrahydrofuran; Nitrile solvents such as acetonitrile; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone; , And aromatic hydrocarbon solvents are preferable, and toluene and xylene are more preferable. The amount of the organic solvent to be used is preferably 1 part by mass or more and 300 parts by mass or less, and more preferably 1 part by mass or more and 100 parts by mass or less, relative to 1 part by mass of compound (II).

The method for obtaining the compound from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture may be filtered, washed with a solvent such as an aromatic hydrocarbon solvent such as toluene, and the obtained residue may be dried. If necessary, it may be further purified by recrystallization using a solvent or by silica gel column chromatography. The resulting compound is, for example, a compound represented by the formula (I).

Next, a method of exchanging the anion of the compound represented by the formula (I) may be employed. As the method, there is a method in which at least one element selected from the group consisting of tungsten, silicon and phosphorus and oxygen And a method of adding a compound or the like.

(Hereinafter, also referred to as an anion exchange agent in the present specification) containing at least one element selected from the group consisting of tungsten, silicon and phosphorus and oxygen as essential elements can be produced by a publicly known method, May be used as it is. Examples of such a compound include a corresponding heteropoly acid salt, an isophosphate salt, a silicate, a phosphate, and the like, and it may be a tungstic acid, a silicotungstic acid, an phospholybdic acid, a silicomolybdic acid or the like.

The amount of the anion exchanger to be used is preferably 0.01 mol or more and 5 mol or less, and more preferably 0.01 mol or more and 1 mol or less based on 1 mol of the compound represented by the formula (I).

The reaction temperature is preferably 0 to 150 占 폚, more preferably 10 to 100 占 폚. The reaction time is preferably 10 minutes to 36 hours, more preferably 10 minutes to 24 hours.

This reaction is preferably carried out in water, an organic solvent or a mixture thereof from the viewpoint of the yield. Examples of the organic solvent include aromatic hydrocarbon solvents such as toluene and xylene; Aliphatic hydrocarbon solvents such as hexane; Halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, methylene chloride and chloroform; Alcohol solvents such as methanol, ethanol, isopropanol and butanol; A nitrohydrocarbon solvent such as nitrobenzene; Ketone solvents such as acetone and methyl isobutyl ketone; Ester solvents such as ethyl acetate; Ether solvents such as diethyl ether and tetrahydrofuran; Nitrile solvents such as acetonitrile; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and 1-methyl-2-pyrrolidone; And the like. Examples of the solvent to be used for the above reaction include water, an alcohol solvent, a ketone solvent, an ether solvent, a nitrile solvent, an amide solvent or a mixture thereof, more preferably water, an alcohol solvent, a ketone solvent, a nitrile solvent, Or a mixture thereof, more preferably water, an alcohol solvent or a mixture thereof, particularly preferably water, methanol or a mixture thereof.

The amount of the organic solvent to be used is preferably 1 part by mass or more and 1000 parts by mass or less, and more preferably 10 parts by mass or more and 500 parts by mass or less, based on 1 part by mass of the compound represented by formula (I).

By employing such a method, when the anion of the compound represented by the formula (I) is exchanged, a compound suitable for improving the heat resistance and reducing the sublimation property can be obtained.

The compound (II) is a compound represented by the formula (VII) (hereinafter sometimes referred to as a compound (VII)) and a compound represented by the formula (VIII) ) ≪ / RTI > in the presence of a base.

[Wherein R ¹ to R ³ , R ⁵ to R ⁸ , R ^N1 and R ^N2 have the same meanings as defined above, and R ⁹ represents an alkyl group having 1 to 20 carbon atoms]

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ⁹ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert- An alkyl group having 1 to 6 carbon atoms.

As the base, organic bases such as triethylamine, piperidine and the like can be mentioned, and the amount of the base is usually 0.05 to 20 mol based on 1 mol of the compound (VII).

The amount of the compound (VIII) to be used is usually 1 to 10 moles, preferably 1 to 4 moles, per 1 mole of the compound (II).

The reaction between the compound (VII) and the compound (VIII) is usually carried out in the presence of a solvent, and examples of the solvent include nitrile solvents such as acetonitrile, alcohols such as methanol, ethanol, 2-propanol, An aliphatic hydrocarbon solvent such as hexane; an aromatic hydrocarbon solvent such as toluene; a halogenated hydrocarbon such as methylene chloride or chloroform; a halogenated hydrocarbon such as methylene chloride or chloroform; And amide solvents such as N, N-dimethylformaldehyde and N-methylpyrrolidone. Preferred are nitrile solvents, alcohol solvents and aromatic hydrocarbon solvents. More preferred are acetonitrile, methanol And toluene. The amount to be used is usually 1 to 100 parts by mass based on 1 part by mass of the compound (VII).

The reaction temperature is usually 0 to 200 캜, preferably 0 to 150 캜. The reaction time is usually 0.5 to 36 hours.

After completion of the reaction, the compound (II) can be taken out by, for example, mixing a reaction mixture in which the compound (II) is difficult to dissolve with the obtained reaction mixture and filtering. If necessary, it may be purified by a method of recrystallization using a solvent or a silica gel column chromatography.

The compound (VII) may be referred to as a compound represented by the formula (IX) (hereinafter sometimes referred to as the compound (IX)) and a compound represented by the formula (X) ) In a solvent.

[Wherein R ⁵ to R ⁹ have the same meanings as defined above, and R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms.] [In the formulas (IX) and (X)

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹⁰ include a methyl group, an ethyl group, a propyl group and a butyl group.

The amount of the compound (X) to be used is usually 1 to 5 moles, preferably 1 to 3 moles, per 1 mole of the compound (IX).

As the solvent, an alcohol solvent such as methanol can be used. The amount of the solvent to be used is usually 1 to 200 parts by mass based on 1 part by mass of the compound (IX).

The reaction temperature is usually -20 to 100 占 폚, and the reaction time is usually 1 to 72 hours.

After completion of the reaction, the compound (VII) can be taken out, for example, by mixing the reaction mixture with water or methanol as required, followed by filtration. After the completion of the reaction, the compound (VII) can be taken out, for example, by mixing the reaction mixture and water as needed, followed by extraction with an insoluble organic solvent such as ethyl acetate and concentration of the obtained organic layer have. If necessary, it may be purified by a method of recrystallization using a solvent or a silica gel column chromatography.

Compound (X) can be prepared, for example, in J. Med. Chem. 2012, 55, 3398-3413, and the like.

The coloring composition of the present invention may contain two or more compounds (I). The compound (I) can be used as a colorant (A) together with a dye or a pigment other than the compound (I) (colorant (A1)), if necessary.

The coloring composition of the present invention comprises at least one of the compound (I), the resin (B) and the solvent (E) and contains both the compound (I), the resin (B) .

≪ Resin (B) >

The resin (B) is preferably an alkali-soluble resin, and is derived from at least one kind of monomer (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride More preferably a polymer having a structural unit derived from

The resin (B) is preferably a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond (hereinafter also referred to as "(b)") Is a copolymer having a structural unit of < RTI ID = 0.0 >

As the other structural unit, a structural unit derived from a monomer (c) copolymerizable with the monomer (a) (provided that the monomer (a) and the monomer (b) , Structural units having an ethylenic unsaturated bond, and the like.

(a) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and 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, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Carboxybicyclo [2.2.1] hept-2-ene, 5,6-carboxybicyclo [2.2.1] hept-2-ene, A bicyclo-unsaturated compound containing a carboxy group such as 5-carboxymethylbicyclo [2.2.1] hept-2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;

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

Unsaturated mono [(meth) acryloyloxyalkyl] polyvalent carboxylic acid such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Esters;

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

Of these, acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and the solubility of the resulting resin in an aqueous alkali solution.

(b) refers to a polymerizable compound having an ethylenic unsaturated bond with a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one member selected from the group consisting of oxirane rings, oxetane rings, and tetrahydrofuran rings) . (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

(b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter may be referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond, (Hereinafter sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter occasionally referred to as "(b3)").

(b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-1)") and alicyclic unsaturated And a monomer (b1-2) having a structure in which a hydrocarbon is epoxidized (hereinafter sometimes referred to as "(b1-2)").

(b1-1) is preferably a monomer having a glycidyl group and an ethylenic unsaturated bond. (meth) acrylate,? -methyl glycidyl (meth) acrylate,? -ethyl glycidyl (meth) acrylate, glycidyl vinyl ether, vinyl Benzyl glycidyl ether,? -Methyl vinyl benzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene, 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (Glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene, 2,3,5- Methyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene and 2,4,6-tris (glycidyloxymethyl) Styrene, and the like.

(b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celloxide (registered trademark) 2000; Cyclohexylmethyl (meth) acrylate (for example, cyclomer (registered trademark) A400 manufactured by Daicel Chemical Industries, Ltd.), 3,4-epoxycyclohexylmethyl (meth) (Registered trademark) M100 manufactured by Daicel Chemical Industries, Ltd.), a compound represented by formula (BI) and a compound represented by formula (BII).

[Wherein R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group .

X ^a and X ^b independently represent a single bond, * -R ^c -, * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-.

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

* Stands for a binding hand with O.]

Examples of the compound represented by the formula (BI) include compounds represented by any one of the formulas (BI-1) to (BI-15), preferably the compounds represented by the formulas (BI- , A compound represented by the formula (BI-5), a compound represented by the formula (BI-7), a compound represented by the formula (BI-9) and a compound represented by the formula (BI- -1), formula (BI-7), formula (BI-9) and formula (BI-15).

Examples of the compound represented by the formula (BII) include compounds represented by any one of the formulas (BII-1) to (BII-15) , Compounds represented by the following formulas (II-5), (II-7), (II-9) and (II-11) to (II-15) (BII-1), (BII-7), (BII-9) and (BII-15).

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

(meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert- (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 ] decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8- Acrylate, dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamanthyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-9- (Meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate, (Meth) acrylic acid ester of acrylate and the like;

(Meth) acrylic acid esters having a hydroxy group such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

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

2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] hept- Ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 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- Cyclohexyl [2.2.1] hept-2-ene, 5,6-bis (Tertiary butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept- Cyclounsaturated compounds;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

Vinyl group-containing aromatic compounds such as styrene,? -Methylstyrene, vinyltoluene and p-methoxystyrene; Vinyl group-containing nitriles such as (meth) acrylonitrile; Halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; Vinyl group-containing amides such as (meth) acrylamide; Esters such as vinyl acetate; Dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene; And the like.

Of these, styrene, vinyltoluene, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-9 (Meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-9- N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and benzyl (meth) acrylate are preferred.

The structural unit having an ethylenically unsaturated bond is preferably a structural unit having a (meth) acryloyl group. The resin having such a structural unit is obtained by adding a monomer having an ethylenically unsaturated bond to a group capable of reacting with a group of (a) or (b) to a polymer having a structural unit derived from (a) or (b) .

Examples of such structural units include structural units obtained by adding glycidyl (meth) acrylate to a (meth) acrylic acid unit, structural units obtained by adding 2-hydroxyethyl (meth) acrylate to a maleic anhydride unit and glycidyl (Meth) acrylate units, and structural units obtained by adding (meth) acrylic acid to (meth) acrylate units. When such a structural unit has a hydroxyl group, the structural unit to which the carboxylic acid anhydride is further added may be a structural unit having an ethylenically unsaturated bond.

The polymer having a structural unit derived from the structural unit (a) can be produced, for example, by polymerizing a monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator and the solvent are not particularly limited, and those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), organic peroxides (such as benzoyl peroxide) And the solvent may be any one that dissolves the respective monomers.

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

If necessary, a reaction catalyst of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (e.g., hydroquinone) may be used.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) (Meth) acrylate / glycidyl (meth) acrylate / glycidyl (meth) acrylate / benzyl (meth) acrylate / , 4-epoxy-tricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^2,6] (Meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl Acrylate / (meth) acrylic acid / vinyltoluene copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (Meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / tricyclo [5.2.1.0 ^2,6 ] decenyl (meth) acrylate / (Meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer, benzyl Styrene / (meth) acrylic acid copolymers, resins disclosed in the respective publications of Japanese Patent Application Laid-Open Nos. 9-106071, 2004-29518 and 2004-361455, .

Among them, as the resin (B), a copolymer containing a structural unit derived from (a) and a structural unit derived from (b) is preferable.

The resin (B) may be used in combination of two or more. In this case, the resin (B) is at least 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) (Meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth) acrylate copolymer, 3-epoxytricyclo [5.2.1.0 ^2,6 ] decyl , 4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (meth) acrylic acid / vinyltoluene copolymer and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ) Acrylate / (meth) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer.

The weight average molecular weight (Mw) of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. The degree of dispersion (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 (in terms of solid content) of the resin (B) is preferably 10 to 300 mg-KOH / g, more preferably 20 to 250 mg-KOH / g, and still more preferably 30 to 200 mg-KOH / g. The acid value is a value measured as an amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the resin (B), and can be determined by titration using, for example, an aqueous potassium hydroxide solution.

The content of the resin (B) in the coloring composition is preferably 3 to 99% by mass, more preferably 5 to 99% by mass, and further preferably 7 to 95% by mass, based on the total solid content.

≪ Solvent (E) >

The solvent (E) is, for example, an ester solvent (a solvent containing -COO- in a molecule and not containing -O-), an ether solvent (containing -O- in the molecule and not containing -COO- (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (OH in the molecule), ether ester solvent A solvent containing no -O-, -CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, and dimethylsulfoxide.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol 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 ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole and methyl anisole .

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, Methoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, ethyl propionate, propyleneglycol monomethyl ether acetate, Ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether And the like Le acetate, diethylene glycol monobutyl ether acetate and dipropylene glycol methyl ether acetate.

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

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

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

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

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

The content of the solvent (E) is preferably 40 to 99% by mass, more preferably 50 to 95% by mass with respect to the total amount of the coloring composition.

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

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

As the dispersing agent, a surfactant and the like can be mentioned, and a surfactant such as cationic, anionic, nonionic or amphoteric surfactant may be used. Specific examples thereof include surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants. These dispersants may be used alone or in combination of two or more. As the dispersing agent, there may be mentioned a dispersant such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), fluorene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca) (Manufactured by BASF), Aji Spa (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemical Co., Ltd.), BYK (registered trademark) ) And the like.

When a dispersant is used, the amount of the dispersant (solid content) to be used is preferably 300 parts by mass or less, more preferably 5 parts by mass or more and 100 parts by mass or less, based on 100 parts by mass of the compound (I). When the amount of the dispersing agent is in the above range, a colored composition in a more uniform dispersion state tends to be obtained.

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

The content of the compound (I) 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 2% Or more and 75 mass% or less.

The coloring composition of the present invention may contain a coloring agent other than the compound (I) (hereinafter sometimes referred to as a coloring agent (A1)). The colorant (A1) may contain one or more coloring agents. The colorant (A1) preferably contains a yellow colorant, an orange colorant or a red colorant.

≪ Colorant (A1) >

The colorant (A1) may be either a dye or a pigment. As the dyes, known dyes can be used, and dyes described in the color index (published by The Society of Dyers and Colourists) and dyeing notes (Shisensha) can be mentioned. According to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes and phthalocyanine dyes can be cited. These dyes may be used singly or in combination of two or more.

Specifically, dyes having the following color index (CI) numbers can be mentioned. C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

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, 112, 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. Reactive Yellow 2, 76, 116;

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, 108, 109, 129, 132, 136, 138, 141;

C.I. Disperse Yellow 51, 54, 76;

C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

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. Reactive Orange 16;

C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

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, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. Acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Acid Violet 34, 102;

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, 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.

As the pigment, a known pigment can be used, and for example, a pigment classified as a pigment in the color index (The Society of Dyers and Colourists) can be mentioned. These may be used alone or in combination of two or more.

Specifically, C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 185, 194 and 214;

C.I. Orange pigments such as Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266 , 268, 269, 273 and the like;

C.I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, and 60;

C.I. Violet pigments such as Pigment Violet 1, 19, 23, 29, 32, 36, 38;

C.I. Pigment Green 7, 36, 58, 59 and the like.

The colorant (A1) is preferably a colorant comprising at least one color selected from a yellow colorant, an orange colorant and a red colorant.

As the yellow colorant, the above-mentioned C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; 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, 112, 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. Reactive Yellow 2, 76, 116;

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, 108, 109, 129, 132, 136, 138, 141;

C.I. Yellow dyes such as Disperse Yellow 51, 54, and 76;

C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138 , 139, 147, 148, 150, 153, 154, 166, 173, 185, 194 and 214;

May be selected from among them.

As the yellow colorant, yellow dyes and yellow pigments are preferable, yellow pigments are more preferable, quinophthalone yellow pigments, metal containing yellow pigments and isoindoline yellow pigments are more preferable, and C.I. Pigment Yellow 129, 138, 139, 150 and 185 are particularly preferred.

The orange colorant is the above-mentioned C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

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. Reactive Orange 16;

C.I. Orange dyes such as Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106 and 107;

C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

May be selected from among them.

The orange colorant is preferably an orange colorant and an orange colorant, more preferably an orange colorant, and C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71,

The red colorant is the above-mentioned 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, 181, 207, 218, 222, 227, 230, 245, 247;

C.I. Red dyes such as Acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;

C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 179, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266 , 268, 269, 273 and the like;

May be selected from among them.

As the red colorant, red dyes and red dyes are preferable, and azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, perylene dyes, azo pigments, diketopyrrolopyrrole pigments, anthraquinone pigments, xanthine pigments, More preferred are rylene pigments, and CI Acid Red 52, C.I. Pigment Red 144, 177, 179, 242, 254, and 269 are more preferable.

As the yellow colorant, the orange colorant or the red colorant, the xanthene compound described in JP-A-2013-235257 may be used.

When the coloring composition of the present invention contains the colorant (A1) and the solvent (E), the liquid containing the colorant (A1) containing the colorant (A1) and the solvent (E) May be used to prepare the coloring composition. When the colorant (A1) is not dissolved in the solvent (E), the liquid containing the colorant (A1) can be prepared by dispersing and mixing the colorant (A1) in the solvent (E). The liquid containing the colorant (A1) may contain a part or all of the solvent (E) contained in the coloring composition.

The coloring composition of the present invention is produced by mixing a liquid containing a coloring agent (A1) comprising a compound represented by the formula (I), a resin, a solvent (E), and a colorant (A1) . As the above-mentioned production method, a coloring composition is prepared by mixing a compound represented by the formula (I), a resin and a solvent (E) with a bead mill or the like to prepare a coloring composition and the colorant (A1) A method of mixing the liquid containing the colorant (A1) is preferable.

The colorant (A1) may be subjected to surface treatment using a rosin treatment, a coloring agent derivative into which an acidic group or a basic group is introduced, graft treatment with a polymer compound or the like on the surface of the colorant (A1), atomization treatment with a sulfuric acid atomization method, A cleaning treatment with an organic solvent or water to remove impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. The particle diameter of the colorant (A1) is preferably substantially uniform. The colorant (A1) can be made to be uniformly dispersed in the colorant (A1) -containing liquid by containing the dispersant and performing the dispersion treatment. Each of the colorants (A1) may be dispersed singly or plural kinds thereof may be mixed and dispersed.

As the dispersing agent, a surfactant and the like can be mentioned, and a surfactant such as cationic, anionic, nonionic or amphoteric surfactant may be used. Specific examples thereof include surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants. These dispersants may be used alone or in combination of two or more. As the dispersing agent, there may be mentioned a dispersant such as KP (manufactured by Shin-Etsu Chemical Co., Ltd.), fluorene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca) (Manufactured by BASF), Aji Spa (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemical Co., Ltd.), BYK (registered trademark) ) And the like.

When a dispersing agent is used to prepare the liquid containing the colorant (A1), the amount of the dispersing agent (solid content) to be used is preferably 300 parts by mass or less, more preferably 5 parts by mass or less per 100 parts by mass of the colorant (A1) And not more than 100 parts by mass. When the amount of the dispersant is within the above range, there is a tendency that a liquid containing the colorant (A1) in a more uniform dispersion state is obtained.

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

The content of the coloring agent (A1) in the liquid containing the coloring agent (A1) 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 matter, more preferably 2% % Or more and 75 mass% or less.

When the coloring composition of the present invention is prepared using the liquid containing the coloring agent (A1) after preparing the liquid containing the coloring agent (A1) containing the coloring agent (A1) and the solvent (E) in advance, , And a part or all, preferably a part of the resin (B) contained in the coloring composition. By including the resin (B) in advance, the dispersion stability of the liquid containing the coloring agent (A1) can be further improved.

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

The content of the colorant (A) containing the compound (I) and the colorant (A1) 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% , More preferably 2 mass% or more and 75 mass% or less.

The content of the compound (I) is usually 0.001% by mass or more, preferably 0.003% by mass or more, more preferably 0.005% by mass or more, and the upper limit is 100% by mass or less in the total amount of the colorant (A) 99.999 mass% or less, and more preferably 99.997 mass% or less.

When the colorant (A1) is contained, the content of the colorant (A1) is preferably at least 0.1 part by mass, more preferably at least 0.5 part by mass, and most preferably at least 1 part by mass with respect to 100 parts by mass of the compound (I) More preferably 10,000 parts by mass or less, and most preferably 5,000 parts by mass or less.

The colored curable composition of the present invention comprises at least one of the compound (I), the resin (B) and the solvent (E) and the polymerizable compound (C).

≪ Polymerizable compound (C) >

The polymerizable compound (C) is a compound capable of polymerizing with an active radical and / or an acid generated from the polymerization initiator (D), for example, a compound having a polymerizable ethylenically unsaturated bond, Methacrylate ester compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxy Ethyl acrylate, N-vinyl pyrrolidone, and the above-mentioned monomers (a), (b) and (c).

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, pentaerythritol hexa (meth) acrylate, tripentaerythritol octa (metha) acrylate, tripentaerythritol hepta (metha) acrylate, tetrapentaerythritol deca (Meth) acrylate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (metha) ) Acrylate, propylene glycol-modified dipentaerythritol hexa (metha) arc Caprolactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (metha) acrylate. Of these, preferred are dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa Metha) 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 from 1 to 65% by mass, more preferably from 3 to 60% by mass, and still more preferably from 5 to 55% by mass, based on the total solid content in the colored curable composition .

The colored curable composition of the present invention may contain a polymerization initiator (D).

≪ Polymerization initiator (D) >

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

Examples of the polymerization initiator (D) include O-acyloxime compounds, alkylphenone compounds, imidazole compounds, triazine compounds and acylphosphine oxide compounds.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetoxy- , 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethan- 1-imine, N-acetoxy- - {2-methyl-4- (3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3- yl] ethan- 1- Yl] -3-cyclopentylpropan-1-imine and N-benzoyloxy-1- [9-ethyl-6- ( 2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine. As the O-acyloxime compound, commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF Corporation) and N-1919 (manufactured by ADEKA Corporation) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy- 1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan- N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine is more preferable.

Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan- -1-one and 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. As the alkylphenone compounds, commercially available products such as Irgacure 369, 907 and 379 (manufactured by BASF) may be used.

Examples of the alkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2- Oligomers of 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one,?,? -Diethoxyacetophenone and benzyldimethylketal .

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole (see, for example, JP-A 6-75372 and JP-A 6-75373) Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis Bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole (for example, Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open No. 62-174204 (See, for example, JP-A-7-10913, etc.) in which the phenyl group at the 4,4 ', 5,5'-position is substituted by a carboalkoxy group, And the like.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Methyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2, Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- - [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (tert- butylperoxycarbonyl) benzophenone And benzophenone compounds such as 2,4,6-trimethylbenzophenone; Quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone and camphorquinone; Butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate and titanocene compounds.

These are preferably used in combination with the polymerization initiator D1 (particularly amines) to be described later.

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

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

The colored curable composition of the present invention may contain a polymerization initiator (D1).

≪ Polymerization initiator (D1) >

The polymerization initiator (D1) is a compound or a sensitizer used for promoting polymerization of a polymerizable compound initiated by polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator (D1) include an amine compound, an alkoxyanthracene compound, a thioxanthone compound, and a carboxylic acid compound.

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

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

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

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

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

The coloring composition of the present invention may further contain a leveling agent (F) and an antioxidant.

≪ Leveling agent (F) >

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

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Concretely, TORAY Silicon DC3PA, copper SH7PA, copper DC11PA, copper SH21PA, copper SH28PA, copper SH29PA, copper SH30PA, copper SH8400 (manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, (Manufactured by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (made by Momentive Performance Materials Japan Joint- have.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Concretely, it is possible to use a flour (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Corporation), Megapack (registered trademark) F142D, copper F171, copper F172, copper F173, copper F177 copper copper F554 copper R30, RS-718-K (manufactured by DIC Corporation), EFTOT (registered trademark) EF301, EF303, EF351 and EF352 (manufactured by Mitsubishi Materials Electronic Gaskets Co., Ltd.) , S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Research Co., Ltd.).

Examples of the silicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, Copolymer BL20, Copolymer F475, Copolymer F477 and Copolymer F443 (manufactured by DIC Corporation).

When the leveling agent (F) is contained, the content thereof is usually from 0.0005 mass% to 1 mass%, preferably from 0.001 mass% to 0.5 mass%, more preferably from 0.001 mass% Or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, and particularly preferably 0.005 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 standpoint 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 antioxidant generally used industrially, and phenol antioxidants, phosphorus antioxidants and sulfur antioxidants can be used.

Examples of the phenolic antioxidant include Irganox 1010 (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF (Irganox 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate manufactured by BASF Corporation), Irganox 1330 (Irganox 1330: 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a " Tri-p-cresol, manufactured by BASF), Irganox 3114 (1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) (1H, 3H, 5H) -triene, manufactured by BASF, Irganox 3790: 1,3,5-tris ((4-tert-butyl Triazine-2,4,6 (1H, 3H, 5H) -thione, manufactured by BASF Corporation), Irgas (Irganox 1135, manufactured by BASF), Irganox 1035 (thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] benzene (1,1-dimethylethyl) -4-hydroxy, C7-C9 branched alkyl ester, manufactured by BASF), Irganox 1520L (4,6-bis (Irganox 3125, manufactured by BASF), Irganox 565 (2,4-bis (n-octylthio) (Adekastab AO-80 (adecastab AO-80, manufactured by BASF), 6- (4-hydroxy-3 ', 5'- -80: 3,9-bis (2- (3- (tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1- dimethylethyl) -2,4,8,10 Sumilizer BHT (Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), tetraoxazospiro (5,5 undecane, manufactured by ADEKA) Ltd.), Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (manufactured by Cytec), and vitamin E (manufactured by Aisai Corporation).

Examples of the phosphorus antioxidant include Irgafos 168 (tris (2,4-di-tert-butylphenyl) phosphite, manufactured by BASF), Irgafos 12 Butyl] dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, BASF (Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphoric acid, produced by BASF Co., Ltd., Adekastab 329K (ADEKA), Adecastab PEP36 (ADEKA), Adecastab PEP-8 (ADEKA), Sandstab P-EPQ (Clariant), Weston 618 (Manufactured by GE), Sumilizer GP: 6- [3- (3-tert-butyl-4-hydroxyphenyl) Butyl dibenz [d, f] [1.3. 2] dioxaphosphperin) (manufactured by Sumitomo Chemical Co., Ltd.) .

Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl and distearyl, and tetrakis [methylene (3-dodecylthio) propionate] methane And? -Alkylmercaptopropionic acid ester compounds of polyols such as?

<Other ingredients>

The coloring 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.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxypropyl Methyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane , 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2- N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropylmethyldimethoxysilane, N-2- Aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl 3-aminopropyltriethoxysilane, and the like.

<Color filter>

A color filter can be formed with the coloring composition or the color-curing composition of the present invention. Examples of the method of forming the color pattern include a photolithography method, an inkjet method, a printing method, and the like, and a photolithographic method is preferably used. The photolithography method is a method in which the above-mentioned colored curable composition is applied to a substrate, followed by drying to form a colored curable composition layer, and then the colored curable composition layer is exposed and developed through a photomask. In the photolithographic method, the colored curable composition preferably contains a polymerization initiator (D). In the photolithographic method, a colored coating film which is a cured product of the colored curable composition layer can be formed by not using a photomask and / or not developing it at the time of exposure. The coloring pattern or colored coating film thus formed can be used as the color filter of the present invention.

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

As the substrate, a glass plate, a resin plate, silicon, and an aluminum, silver, silver / copper / palladium alloy thin film formed on the substrate are used. A separate color filter layer, a resin layer, a transistor, a circuit, and the like may be formed on such a substrate.

The formation of each color pixel by a photolithographic method can be carried out under a known or common apparatus or condition. For example, it can be manufactured as follows.

First, a colored curable composition is applied on a substrate, and the mixture is dried by heating (prebaking) and / or reduced-pressure drying to remove volatile components such as a solvent and dried to obtain a smooth colored curable composition layer.

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

Next, the colored curable composition layer is exposed through a photomask for forming a desired colored pattern. It is preferable to use an exposure apparatus such as a mask aligner and a stepper because uniform alignment of the parallel light ray over the entire exposure surface or accurate positioning between the photomask and the substrate on which the colored curable composition layer is formed .

The coloring curable composition layer after exposure is brought into contact with a developing solution to develop a colored pattern on the substrate. By the development, the unexposed portion of the colored curable composition layer is dissolved and removed in the developer.

As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate and tetramethylammonium hydroxide is preferable.

The developing method may be any of paddle method, dipping method and spray method. In addition, the substrate may be inclined at an arbitrary angle at the time of development.

The substrate after development is preferably washed with water.

In addition, post-baking is preferably performed on the obtained coloring pattern.

The color filter is useful as a color filter used in a liquid crystal display device, particularly as a color filter used in a display device (e.g., a liquid crystal display device, an organic EL device, an electronic paper and the like) and a solid-state image pickup device.

(Example)

Hereinafter, the present invention will be described in more detail with reference to Examples. However, it is needless to say that the present invention is not limited by the following Examples, but the present invention can be carried out by modifying it appropriately within a range suitable for the purpose Of course, all of which are within the technical scope of the present invention.

In the examples, &quot;% &quot; and &quot; part &quot; indicate mass% and mass part, respectively, unless otherwise specified.

In the following synthesis example, the structure of the compound was determined by NMR (JMM-ECA-500, manufactured by Japan Electronics Co., Ltd.) or mass spectrometry (LC: Agilent 1200 type, MASS; ).

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

Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)

Column: TSK-GELG2000HXL

Column temperature: 40 DEG C

Solvent: tetrahydrofuran

Flow rate: 1.0 mL / min

Solid content concentration of analytical sample: 0.001 to 0.01 mass%

Injection volume: 50 μL

Detector: RI

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

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

Example 1

14.4 parts of coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.) and 737 parts of toluene were mixed and stirred at 87 占 폚. To this mixture was added 10.1 parts of methyl trifluoromethanesulfonate. This mixture was stirred at 87 占 폚 for 3 hours. The mixture was stirred at 10 占 폚. The mixture was filtered, and the obtained residue was washed with 433 parts of toluene six times. The residue was dried under reduced pressure at 60 ° C to obtain 20.8 parts of a compound represented by the formula (I-2).

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

(Mass Spec.) Ionization mode = ESI +: m / z = 365 [M-CF 3 SO 3] +

Exact Mass: 514

5.00 parts of the compound represented by the formula (I-2) and 1500 parts of methanol were mixed. To this mixture was added a mixture of 10.4 parts of phosphotungstic acid hydrate (Sigma Aldrich Japan K.K.) and 104 parts of methanol. The mixture was filtered, and the obtained residue was washed with 500 parts of methanol. The residue was dried under reduced pressure at 60 ° C to obtain 12.4 parts of a compound represented by the formula (I-14).

&Lt; Identification of compound represented by formula (I-14) >

(Mass analysis) Ionization mode = ESI +: m / z = 365 [(M-PW ₁₂ O ₄₀ ) / 3] ⁺

Exact Mass: 3974

[Heat resistance evaluation]

Differential scanning calorimetry of the compound obtained in Example 1 was carried out by using a differential thermal thermogravimetry (TG / DTA 6200, manufactured by SIEI NANO TECHNOLOGY Co., Ltd.). The amount of sample used for one measurement was 5 mg. The measurement temperature was first started at 45 ° C, the temperature was raised at a rate of 5 ° C per minute, and the temperature was measured up to 550 ° C. And a temperature T ₅ (under nitrogen) at which the weight loss rate was 5% in a nitrogen atmosphere was determined. The results are shown in Table 11.

From the results shown in Table 11, it can be seen that the compound of the present invention has a high heat resistance.

Synthetic Example 1

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, a nitrogen stream was appropriately purged and replaced with a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80 DEG C with stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan- (289 parts) and propylene glycol monomethyl ether acetate (125 parts) was added dropwise over 5 hours. On the other hand, a mixed solution obtained by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (B1)) having a solid content of 35.0%. The obtained resin (B1) had a weight average molecular weight (Mw) of 8800, a degree of dispersion of 2.1, and a solution acid value of 28 mg-KOH / g.

Synthetic Example 2

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was poured in an appropriate amount and the flask was purged with a nitrogen atmosphere. 257 parts of ethyl lactate was added and heated to 75 캜 with stirring. Then, 81 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan- 369 parts of a mixture of ethyl acrylate and 25 parts of ethyl lactate was added dropwise over 5 hours. On the other hand, a mixed solution obtained by dissolving 11 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 162 parts of ethyl lactate was added dropwise over 5 hours. After completion of the dropwise addition, the mixture was maintained at the same temperature for 5 hours, 95 parts of ethyl lactate was added, and the mixture was cooled to room temperature to obtain a solution of a copolymer (resin (B2)) having a solid content of 47.7%. The obtained resin (B2) had a weight average molecular weight (Mw) of 8100, a degree of dispersion of 1.9, and a solution acid value of 53 mg-KOH / g.

Synthetic Example 3

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, a nitrogen stream was poured in a nitrogen atmosphere, 371 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 DEG C with stirring. Then, 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan- , 81 parts of vinyl toluene (isomer mixture) and 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the addition of the initiator solution was completed, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (B3)) having a solid content of 37.5%. The obtained resin (B3) had a weight-average molecular weight (Mw) of 10600, a degree of dispersion of 2.01, and a solution acid value of 43 mg-KOH / g.

Synthetic Example 4

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, a nitrogen stream was poured in a nitrogen atmosphere and 54 parts of ethyl lactate and 141 parts of propyleneglycol monomethylether acetate were added and heated to 85 캜 with stirring. Then 35 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan- , Cyclohexyl maleimide (161 parts), 2-hydroxyethyl methacrylate (12 parts) and propylene glycol monomethyl ether acetate (493 parts) was added dropwise over 5 hours. Meanwhile, a mixed solution obtained by dissolving 3 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 78 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin (B4)) having a solid content of 24.4%. The obtained resin (B4) had a weight average molecular weight (Mw) of 8400, a dispersion degree of 2.1, and a solution acid value of 26 mg-KOH / g.

[Measurement of film thickness]

The film thickness was DEKTAK3; And measured using a vacuum cleaner manufactured by Nippon Vacuum Technology Co., Ltd.

[Preparation of resin composition for sublimation test (SJS)] [

Resin: Methacrylic acid / benzyl methacrylate (molar ratio: 30/70) Copolymer (weight average molecular weight (Mw) 10700, acid value 70 mg-KOH / g, manufactured by Daoka Chemical Industry Co., Ltd.) 33.8% Propylene glycol monomethyl Ether acetate solution 40 parts;

Polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.)      5.8 parts;

Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE01, manufactured by BASF Japan)     0.58 parts;

Leveling agent: Polyether-modified silicone oil (TORAYI Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.)    0.010 part;

Solvent: Propylene glycol monomethyl ether 47 parts;

Solvent: Propylene glycol monomethyl ether acetate 6.8 part

To obtain a resin composition for sublimation test (SJS).

[Formation of resin coating film (SJSM) for sublimation test]

The above-obtained resin composition for sublimation test (SJS) was coated on a glass substrate (Eagle XG; manufactured by Corning) having a width of 2 inches by spin coating, and the volatile components were volatilized at 100 ° C for 3 minutes. After cooling, the substrate was irradiated with light at an exposure dose (based on 365 nm) of 150 mJ / cm 2 using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) in an air atmosphere. And heated in an oven at 220 DEG C for 2 hours to form a sublimation test resin coating film (SJSM) (film thickness 2.2 mu m).

Example 2

Colorant (A): A compound represented by the formula (I-2)    14 parts;

Resin (B): Resin (B1) solution   480 parts;

Solvent (E): Propylene glycol monomethyl ether acetate   6.2 parts;

Solvent (E): N-methyl-2-pyrrolidone   500 parts; And

Surfactant: polyether-modified silicone oil (TORAYI Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.063 part

To obtain Coloring Composition 1.

Example 3

Colorant (A): A compound represented by the formula (I-14)    36 parts;

Resin (B): Resin (B1) solution   410 parts;

Solvent (E): Propylene glycol monomethyl ether acetate   6.2 parts;

Solvent (E): N-methyl-2-pyrrolidone   540 parts; And

Surfactant: polyether-modified silicone oil (TORAYI Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.063 part

Were mixed to obtain Coloring Composition 2.

Example 4

Colorant (A): A compound represented by the formula (I-14)    10 parts;

Resin (B): Resin (B2) solution    97 parts;

Solvent (E): N-methyl-2-pyrrolidone   180 parts;

Solvent (E): 4-hydroxy-4-methyl-2-pentanone    26 parts;

Solvent (E): Propylene glycol monomethyl ether acetate   2.0 parts; And

Surfactant: polyether-modified silicone oil (TORAYI Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)       0.020 part

Were mixed to obtain Coloring Composition 3.

Example 5

Colorant (A): A compound represented by the formula (I-14)    10 parts,

Dispersant (BYK-LPN 21324, manufactured by Big Chem Japan Co., Ltd.)    10 parts,

Resin (B): Resin (B1) solution    11 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate   160 parts

And a coloring composition in which a compound represented by the formula (I-14) is dispersed using a bead mill  100 parts;

Resin (B): Resin (B1) solution   55 parts;

Solvent (E): Propylene glycol monomethyl ether acetate  3.6 parts; And

Surfactant: polyether-modified silicone oil (TORAYI Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)      0.010 part

Were mixed to obtain Coloring Composition 4.

Comparative Example 1

Colorant (A): Coumarin 6   11 parts;

Resin (B): Resin (B2) solution  350 parts;

Solvent (E): Propylene glycol monomethyl ether acetate  6.2 parts;

Solvent (E): N, N-dimethylformamide  630 parts; And

Surfactant: polyether-modified silicone oil (TORAYI Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)      0.063 part

Were mixed to obtain Coloring Composition 5.

[Sublimation evaluation]

Example 6

The coloring composition 1 was coated on a glass substrate (Eagle XG; manufactured by Corning) having an aspect ratio of 2 inches by a spin coating method, and then prebaked at 100 캜 for 3 minutes to form a coloring composition layer. The film thickness was measured by DEKTAK 3; And measured using a vacuum cleaner manufactured by Nippon Vacuum Technology Co., Ltd. This colored coating film and the resin coating film for sublimability test (SJSM) obtained above were opposed to each other with an interval of 70 mu m therebetween, and post-baking was performed at 220 DEG C for 40 minutes. The color difference (? Eab *) before and after heating of the resin coating film for sublimation test (SJSM) was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). When the color difference (DELTA Eab *) is 5.0 or more, it indicates that the colorant has sublimation properties. The results are shown in Table 12. In Table 12, &amp; cir &amp; indicates that the colorant has no sublimation property, and X indicates that the colorant has sublimation properties.

Example 7

The sublimation property was evaluated in the same manner as in Example 6 except that the coloring composition 1 was changed to the coloring composition 2. The results are shown in Table 12.

Example 8

The sublimation property was evaluated in the same manner as in Example 6 except that the coloring composition 1 was changed to the coloring composition 3. The results are shown in Table 12.

Example 9

The sublimation property was evaluated in the same manner as in Example 6 except that the coloring composition 1 was changed to the coloring composition 4. The results are shown in Table 12.

Comparative Example 2

Sublimation evaluation was carried out in the same manner as in Example 6 except that the coloring composition 1 was changed to the coloring composition 5. The results are shown in Table 12.

From the above results, it was found that the coloring composition containing the compound of the present invention reduced the sublimation of the coloring agent.

Example 10

Colorant (A): A compound represented by the formula (I-14)   100 parts,

Dispersant (BYK-LPN 21324, manufactured by BICKEMI Japan Co., Ltd.)   130 parts,

Resin (B): Resin (B4) solution   170 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate   610 part

And a coloring composition in which a compound represented by the formula (I-14) is dispersed using a bead mill   380 parts;

Colorant (A): C.I. Pigment Yellow 138 (pigment)    18 parts,

Dispersant   7.6 parts,

Suzy   7.6 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate   120 parts

And the total amount of the pigment dispersion in which the pigment was dispersed using a bead mill;

Colorant (A): A compound represented by the following formula (manufactured by the method described in JP-A-2013-235257)   4.2 parts;

Resin (B): Resin (B3) solution    21 parts;

Polymerizable compound (C): Polymerizable compound (A9550; manufactured by Shin-Nakamura Chemical Co., Ltd.)

   25 parts;

Polymerization initiator (D): A compound represented by the following formula (manufactured by Changzhou Power Electronics Co., Ltd.)   6.6 parts;

Solvent (E): 4-Hydroxy-4-methyl-2-pentanone   170 parts;

Solvent (E): Propylene glycol monomethyl ether acetate   250 parts; And

Surfactant: polyether-modified silicone oil (TORAYI Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)       0.075 part

To obtain a colored curable composition 1.

[Production of coloring pattern]

The colored curable composition 1 was applied on a glass substrate (Eagle XG; Corning) having a size of 2 inches by 2 inches by spin coating, and then pre-baked at 100 ° C for 3 minutes to form a colored curable composition layer. After cooling, an exposure amount (365 nm (nm)) of 80 mJ / cm &lt; 2 &gt; was formed in an atmospheric environment using an exposure machine (TME-150RSK manufactured by Topcon Co., Ltd.) with a distance of 200 mu m between the substrate on which the colored curable composition layer was formed and the quartz glass photomask. Standard). A photomask having a line and space pattern of 100 mu m was used. The exposed layer of the colored curable composition was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 캜 for 70 seconds to develop and wash. This colored coating film was post-baked at 230 캜 for 30 minutes to obtain a colored pattern.

[Sublimation evaluation]

The colored curable composition 1 was applied on a glass substrate (Eagle XG; Corning) having a size of 2 inches by 2 inches by spin coating, and then pre-baked at 100 ° C for 3 minutes to form a colored curable composition layer. After cooling, the substrate on which the colored curable composition layer was formed was exposed using an exposure apparatus (TME-150RSK; manufactured by Topcon Co., Ltd.) at an exposure amount of 80 mJ / cm 2 (365 nm standard) in an air atmosphere. The exposed layer of the colored curable composition was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 캜 for 70 seconds to develop and wash.

The film thickness was measured by DEKTAK3; And measured using a vacuum cleaner manufactured by Nippon Vacuum Technology Co., Ltd.

The colored coating film and the resin coating film for sublimability test (SJSM) obtained above were opposed to each other with an interval of 70 mu m, and post-baking was performed at 220 DEG C for 40 minutes.

The color difference (? Eab *) before and after heating of the resin coating film for sublimation test (SJSM) was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). When the color difference (DELTA Eab *) is 5.0 or more, it indicates that the colorant has sublimation properties. The results are shown in Table 13. In Table 13, &amp; cir &amp; indicates that the colorant has no sublimation property, and X indicates that the colorant has sublimation properties.

Example 11

Colorant (A): A compound represented by the formula (I-14)   100 parts,

Dispersant (BYK-LPN 21324, manufactured by BICKEMI Japan Co., Ltd.)   130 parts,

Resin (B): Resin (B4) solution   170 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate   610 part

And a coloring composition in which a compound represented by the formula (I-14) is dispersed using a bead mill   340 parts;

Colorant (A): C.I. Pigment Yellow 138 (pigment)    18 parts,

Dispersant   7.6 parts,

Suzy   7.6 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate   120 parts

And the total amount of the pigment dispersion in which the pigment was dispersed using a bead mill;

Colorant (A): A compound represented by the following formula (manufactured by the method described in JP-A-2013-235257)   7.8 parts;

Resin (B): Resin (B3) solution    27 parts;

Polymerizable compound (C): Polymerizable compound (A9550; manufactured by Shin-Nakamura Chemical Co., Ltd.)

   26 parts;

Polymerization initiator (D): A compound represented by the following formula (manufactured by Changzhou Power Electronics Co., Ltd.)   6.8 parts;

Solvent (E): 4-Hydroxy-4-methyl-2-pentanone   170 parts;

Solvent (E): Propylene glycol monomethyl ether acetate   270 parts; And

Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.075 part

To obtain a colored curable composition 2.

The procedure of Example 10 was repeated except that the color-curable composition 1 was changed to the color-curable composition 2 to prepare a coloring pattern and perform sublimation evaluation. Table 13 shows the results of the sublimation evaluation.

Example 12

Colorant (A): A compound represented by the formula (I-14)   100 parts,

Dispersant (BYK-LPN 21324, manufactured by BICKEMI Japan Co., Ltd.)   130 parts,

Resin (B): Resin (B4) solution   170 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate   610 part

And a coloring composition in which a compound represented by the formula (I-14) is dispersed using a bead mill   290 parts;

Colorant (A): C.I. Pigment Yellow 138 (pigment)    23 parts,

Dispersant   9.6 parts,

Suzy   9.6 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate   150 parts

And the total amount of the pigment dispersion in which the pigment was dispersed using a bead mill;

Colorant (A): A compound represented by the following formula (manufactured by the method described in JP-A-2013-235257)   5.1 parts;

Resin (B): Resin (B3) solution    31 parts;

Polymerizable compound (C): Polymerizable compound (A9550; manufactured by Shin-Nakamura Chemical Co., Ltd.)

   27 parts;

Polymerization initiator (D): A compound represented by the following formula (manufactured by Changzhou Power Electronics Co., Ltd.)   7.2 parts;

Solvent (E): 4-Hydroxy-4-methyl-2-pentanone   170 parts;

Solvent (E): Propylene glycol monomethyl ether acetate   280 parts; And

Surfactant: polyether-modified silicone oil (TORAYI Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.075 part

To obtain a colored curable composition 3.

The procedure of Example 10 was repeated except that the color-curable composition 1 was changed to the color-curable composition 3, and a coloring pattern and a sublimation property were evaluated. Table 13 shows the results of the sublimation evaluation.

Example 13

Colorant (A): A compound represented by the formula (I-14)   100 parts,

Dispersant (BYK-LPN 21324, manufactured by BICKEMI Japan Co., Ltd.)   130 parts,

Resin (B): Resin (B4) solution   170 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate   610 part

And a coloring composition in which a compound represented by the formula (I-14) is dispersed using a bead mill   270 parts;

Colorant (A): C.I. Pigment Yellow 138 (pigment)    23 parts,

Dispersant   9.6 parts,

Suzy   9.6 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate   150 parts

And the total amount of the pigment dispersion in which the pigment was dispersed using a bead mill;

Colorant (A): A compound represented by the following formula (manufactured by the method described in JP-A-2013-235257)   7.4 parts;

Resin (B): Resin (B3) solution    35 parts;

Polymerizable compound (C): Polymerizable compound (A9550; manufactured by Shin-Nakamura Chemical Co., Ltd.)

   27 parts;

Polymerization initiator (D): A compound represented by the following formula (manufactured by Changzhou Power Electronics Co., Ltd.)   7.3 parts;

Solvent (E): 4-Hydroxy-4-methyl-2-pentanone   170 parts;

Solvent (E): Propylene glycol monomethyl ether acetate   290 parts; And

Surfactant: polyether-modified silicone oil (TORAYI Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.075 part

Were mixed to obtain a colored curable composition 4.

The procedure of Example 10 was repeated except that the color-curable composition 1 was changed to the color-curable composition 4 to prepare a coloring pattern and evaluate the sublimation properties. Table 13 shows the results of the sublimation evaluation.

Example 14

A colored curable composition 5 was obtained in the same manner as in Example 10, except that the compound represented by the formula (I-14) was changed to a compound represented by the formula (I-2) . Table 13 shows the results of the sublimation evaluation.

Example 15

A colored curable composition 6 was obtained in the same manner as in Example 13, except that the compound represented by the formula (I-14) was changed to the compound represented by the formula (I-2) . Table 13 shows the results of the sublimation evaluation.

Comparative Example 3

A colored curable composition 7 was obtained in the same manner as in Example 10, except that the compound represented by the formula (I-14) was changed to coumarin 6 to prepare a coloring pattern and perform sublimation evaluation. Table 13 shows the results of the sublimation evaluation.

Comparative Example 4

A colored curable composition 8 was obtained in the same manner as in Example 13 except that the compound represented by the formula (I-14) was changed to coumarin 6 to prepare a colored pattern and to evaluate the sublimation property. Table 13 shows the results of the sublimation evaluation.

From the above results, it was found that the sublimation of the coloring agent was reduced in the color-curing composition containing the compound of the present invention.

The coloring composition or the color-curing composition of the present invention can reduce the sublimation property of a colorant and is suitably used for a display device such as a color filter or a liquid crystal display device.

Claims (14)

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

[In the formula (I), R ^N1 and R ^N2 represent, independently of each other, an aliphatic hydrocarbon group of 1 to 40 carbon atoms which may have a substituent.
R ^N3 represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.
R ¹ to R ⁸ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , _{^{SO 2 N (R 102) 2}} , -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102 ) ₂ , A halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
R ¹⁰¹ represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. R ¹⁰² represents a hydrogen atom, a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent. M represents a hydrogen atom or an alkali metal atom.
When a plurality of R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.
A ^{g -} represents anion of g. and g represents an integer of 1 to 14.] The method according to claim 1,
Wherein A ^{g -} is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and oxygen as essential elements, or fluorinated anion. 3. The method according to claim 1 or 2,
Wherein A ^{g -} is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements, or fluorinated anion. 4. The method according to any one of claims 1 to 3,
A ^{g -} is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements. 5. The method according to any one of claims 1 to 4,
And R ^N1 and R ^N2 are each independently an alkyl group having 1 to 10 carbon atoms which may have a substituent. 6. The method according to any one of claims 1 to 5,
Further comprising a solvent. 7. The method according to any one of claims 1 to 6,
Further comprising a yellow colorant, an orange colorant or a red colorant. A colored curable composition comprising the coloring composition according to any one of claims 1 to 7 and a polymerizable compound. 9. The method of claim 8,
Further comprising a polymerization initiator. A color filter formed by the coloring composition according to any one of claims 1 to 7 or the coloring curable composition according to claim 8 or 9. A liquid crystal display device comprising the color filter according to claim 10. A compound represented by the formula (I-B).

[In the formula (I-B), R ^N1 and R ^N2 represent, independently of each other, an aliphatic hydrocarbon group of 1 to 40 carbon atoms which may have a substituent.
R ^N3 represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.
R ¹ to R ⁸ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -COCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , _{^{SO 2 N (R 102) 2}} , -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102 ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
R ¹⁰¹ represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.
R ¹⁰² represents a hydrogen atom, a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
M represents a hydrogen atom or an alkali metal atom.
When a plurality of R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.
B ^{h -} represents at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus, and h anion containing oxygen as an essential element.
and h represents an integer of 1 to 14.] 13. The method of claim 12,
B ^{h -} is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as essential elements. The method according to claim 12 or 13,
R ^N1 and R ^N2 are independently of each other an alkyl group having 1 to 10 carbon atoms which may have a substituent.