TW201815983A - Coloring composition - Google Patents

Abstract

The present invention relates to a coloring composition comprising a compound represented by formula (I) and a resin. (In the formula (I), R<SP>N1</SP> and R<SP>N2</SP> are each independently represents an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. R<SP>N3</SP> represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. R1 to R8 are each independently represents a hydrogen atom, -CO-R102, -COO-R101, -OCO-R102, -O-R102, -SO2-R101, -SO2N(R102)2, -CON (R102)2, -N(R102)2, -NHCO-R102, a halogen atom, a cyano group, a nitro group, -SO3M, -CO2M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. R101 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. R102 represents a hydrogen atom, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent. M represents a hydrogen atom or an alkali metal atom. When there are a plurality of R101, R102 and M, they may be the same or different. Ag- represents a g valent anion. g represents an integer of 1 to 14.).

Description

   Coloring composition   

The present invention relates to a compound and a coloring composition useful as a colorant.

Dyes are used in fields such as fiber materials, liquid crystal display devices, and inkjet to display colors using reflected light or transmitted light. As such a dye, coumarin 6 represented by the following formula is known (Japanese Patent Application Laid-Open No. 2006-154740).

The present invention includes the following inventions.

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

[In formula (I), R ^N1 and R ^N2 each independently represent an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, and R ^N3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or may be A heterocyclic group having a substituent, R ¹ to R ⁸ each 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} , can be a hydrocarbon group having a carbon number of 1 to 40 substituted or unsubstituted heterocyclic group may have a group of R ¹⁰¹ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group having substituents, and R ¹⁰² represents a hydrogen atom, a hydrocarbon group which may have 1 to 40 carbon atoms in which a substituent may be substituted Heterocyclic group of the group, M represents a hydrogen atom or an alkali metal atom, and when there are a plurality of R ¹⁰¹ , R ¹⁰² and M, these may be the same or different. A ^g- represents an anion having a valence of g and g represents Integer 1 to 14].

[2] The 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 an essential element , Or a fluorine-containing anion.

[3] The 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 an essential element, Or fluoride anions.

[4] The coloring composition according to any one of [1] to [3], wherein A ^g contains at least one element selected from the group consisting of tungsten and phosphorus and oxygen as an essential element Of anion.

[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 containing a solvent.

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

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

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

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

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

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

[In formula (IB), R ^N1 and R ^N2 each independently represent an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, and R ^N3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or may be A heterocyclic group having a substituent, R ¹ to R ⁸ each 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} , can be a hydrocarbon group having a carbon number of 1 to 40 substituted or unsubstituted heterocyclic group may have a group of R ¹⁰¹ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group having substituents, and R ¹⁰² represents a hydrogen atom, a hydrocarbon group which may have 1 to 40 carbon atoms in which a substituent may be substituted Heterocyclic group of the group, M represents a hydrogen atom or an alkali metal atom, and when there are a plurality of R ¹⁰¹ , R ¹⁰² and M, these may be the same or different, and B ^h- represents a group selected from tungsten, molybdenum, silicon And at least one element of the group consisting of phosphorus and oxygen as essential elements For h-valent anions, h is an integer of 1 to 14].

[13] The 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 each independently represent an alkyl group having 1 to 10 carbon atoms which may have a substituent.

The coloring composition of the present invention contains a compound represented by formula (I) (hereinafter, referred to as a compound (I)) and a resin (hereinafter referred to as a resin (B)).

The compound (I) includes tautomers, and salts thereof.

The compound (I) can be used as a colorant.

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

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

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

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). In addition, the compound (I) and the coloring agent (A1) are collectively referred to as "coloring" Agent (A) ".

The colorant (A1) may contain one or more colorants.

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

The colored curable composition of the present invention contains at least one of a compound (I), a resin (B), and a solvent (E), and a 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 formula (I), R ^N1 and R ^N2 each independently represent an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent.

R ^N3 represents a hydrocarbon group having 1 to 40 carbons which may have a substituent or a heterocyclic group which may have a substituent.

R ¹ to R ⁸ are each independently 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 carbons which may have a substituent, or a heterocyclic group which may have a substituent.

R ¹⁰¹ represents a hydrocarbon group having 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 having 1 to 40 carbons 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 there is a plurality of R ¹⁰¹ , R ¹⁰² and M, these may be the same or different.

A ^g- system represents g-valent anions.

g is an integer of 1 to 14].

The carbon number 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, more preferably 1 to 15, and particularly preferably 1 to 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, nonyl, decyl, and deca Linear alkyl groups such as mono, dodecyl, heptyl, octadecyl, and icosyl; etc .; isopropyl, isobutyl, second butyl, third butyl, (2-ethyl ) Butyl, isopentyl, neopentyl, third pentyl, (1-methyl) pentyl, (2-methyl) pentyl, (1-ethyl) pentyl, (3-ethyl) Branched chain alkyl groups such as pentyl, isohexyl, (5-methyl) hexyl, (2-ethyl) hexyl and (3-ethyl) heptyl; etc .; vinyl, 1-propenyl, 2-propylene (Allyl), (1-methyl) vinyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1- (2-propenyl)) vinyl, Alkenyl groups such as (1,2-dimethyl) propenyl and 2-pentenyl. The carbon number of the saturated or unsaturated chain hydrocarbon group is preferably from 1 to 30, more preferably from 1 to 20, more preferably from 1 to 15, particularly preferably from 1 to 10, even more preferably from 1 to 8. Further particularly preferred are 1 to 5. Among them, a linear or branched alkyl group having 1 to 10 carbon atoms, and preferably 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, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and 1-methyl. Cyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-bis Methylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-di Methylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4,4-dimethylcyclohexyl, cyclooctyl, 2 , 4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl, 4-pentylcyclohexyl, 4-octyl Cycloalkyl groups such as cyclohexyl, 4-cyclohexylcyclohexyl; cyclohexenyl (such as cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, cyclooctenyl and other cycloalkenyl groups; Fluorenyl, adamantyl, bicyclic [2.2.2] octane, etc. The carbon number of the saturated or unsaturated alicyclic hydrocarbon group is preferably from 3 to 30, more preferably from 3 to 20, more preferably from 4 to 20, even more preferably from 4 to 15, even more preferably from 5 to 15, The best is 5 to 10. Among them, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl are particularly preferred.

The aliphatic hydrocarbon group represented by R ^N1 and R ^N2 may be an aliphatic hydrocarbon group listed above and an 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). Group of hydrocarbon groups).

Examples of such aromatic hydrocarbon groups include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, and 2,5-dimethyl. Phenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 4-vinylphenyl, o-isopropylphenyl, m-iso Propylphenyl, p-isopropylphenyl, o-thirdbutylphenyl, m-thirdbutylphenyl, p-thirdbutylphenyl, 2,4,6-trisyl (mesityl), 4 -Ethylphenyl, 4-butylphenyl, 4-pentylphenyl, 2,6-bis (2-propyl) phenyl, 4-cyclohexylphenyl, 2,4,6-trimethyl Phenyl, 4-octylphenyl, 4-vinylphenyl, 1-naphthyl, 2-naphthyl, 5,6,7,8-tetrahydro-1-naphthyl, 5,6,7,8 -Aromatic hydrocarbon groups such as tetrahydro-2-naphthyl, fluorenyl, phenanthryl, anthracenyl, and fluorenyl. The carbon number of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15.

Examples of the combination of the above-mentioned aliphatic hydrocarbon group and an 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 Aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenethyl; arylalkenyl groups such as phenylvinyl; arylalkynyl groups such as phenylethynyl; biphenyl, bitriphenyl, etc. A phenyl group having one or more phenyl groups bonded thereto; cyclohexylmethylphenyl, benzylphenyl, (dimethyl (phenyl) methyl) phenyl, and the like. The group represented by R ^N1 and R ^N2 may be, for example, a cyclopropylmethyl group or a cyclopropylethyl group as a group obtained by combining the above-mentioned hydrocarbon groups (for example, a chain hydrocarbon group and an alicyclic hydrocarbon group). , Cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylcyclohexylmethyl, cyclohexylethyl, adamantylmethyl, etc. An alkyl group having more than one alicyclic hydrocarbon group.

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

The carbon number 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, more preferably 1 to 15, 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. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be chain-like. 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 , Nonyl, decyl, undecyl, dodecyl, heptyl, octadecyl, and icosyl, etc .; linear isopropyl, isopropyl, isobutyl, second butyl, third Butyl, (2-ethyl) butyl, isopentyl, neopentyl, third pentyl, (1-methyl) pentyl, (2-methyl) pentyl, (1-ethyl) pentyl , Branched chain alkyl groups such as (3-ethyl) pentyl, isohexyl, (5-methyl) hexyl, (2-ethyl) hexyl and (3-ethyl) heptyl; etc .; vinyl, 1-propenyl, 2-propenyl (allyl), (1-methyl) vinyl, 2-butenyl, 3-butenyl, 1,3-butadienyl, (1- (2 -Propenyl)) vinyl, alkenyl such as (1,2-dimethyl) propenyl and 2-pentenyl, and the like. The carbon number of the saturated or unsaturated chain hydrocarbon group is preferably from 1 to 30, more preferably from 1 to 20, more preferably from 1 to 15, particularly preferably from 1 to 10, even more preferably from 1 to 8. Among them, a linear or branched alkyl group having 1 to 10 carbon atoms, preferably 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 cyclopropyl, 1-methylcyclopropyl, cyclobutyl, cyclopentyl, and cyclo Hexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1,2-dimethylcyclohexyl, 1,3-dimethyl Cyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2,5-dimethylcyclohexyl, 2,6-dimethyl Cyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3,3-dimethylcyclohexyl, 4,4-dimethyl Cyclohexyl, cyclooctyl, 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl, 4- Cycloalkyl such as pentylcyclohexyl, 4-octylcyclohexyl, 4-cyclohexylcyclohexyl; cyclohexenyl (e.g. cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl, cyclo Cycloalkenyl such as octenyl; norbornyl, adamantyl, bicyclic [2.2.2] octane, etc. The carbon number of the saturated or unsaturated alicyclic hydrocarbon group is preferably from 3 to 30, more preferably from 3 to 20, more preferably from 4 to 20, even more preferably from 4 to 15, even more preferably from 5 to 15 , Preferably 5 to 10. Among them, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl are particularly preferred.

^Examples of the aromatic hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include phenyl, o-tolyl, m-tolyl, p-tolyl, 2,3-dimethylphenyl, 2 4,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 4 -Vinylphenyl, o-isopropylphenyl, m-isopropylphenyl, p-isopropylphenyl, o-third butylphenyl, m-third butylphenyl, p-third butylphenyl , 2,4,6-trimethylphenyl, 4-ethylphenyl, 4-butylphenyl, 4-pentylphenyl, 2,6-bis (2-propyl) phenyl, 4-cyclohexyl Phenyl, 2,4,6-trimethylphenyl, 4-octylphenyl, 4-vinylphenyl, 1-naphthyl, 2-naphthyl, 5,6,7,8-tetrahydro- Aromatic hydrocarbon groups such as 1-naphthyl, 5,6,7,8-tetrahydro-2-naphthyl, fluorenyl, phenanthryl, anthracenyl, fluorenyl and the like. The carbon number of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15.

The hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² may be a combination of the hydrocarbon groups listed above (for example, an aromatic hydrocarbon group, at least one of a chain hydrocarbon group and an alicyclic hydrocarbon group). Examples of the base include aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenethyl; arylalkenyl such as phenylvinyl; arylalkynyl such as phenylethynyl; biphenyl , Triphenyl, and the like are bonded to one or more phenyl groups; cyclohexylmethylphenyl, benzylphenyl, (dimethyl (phenyl) methyl) phenyl, and the like.

The group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² , and a group obtained by combining the above-mentioned hydrocarbon groups (for example, a chain hydrocarbon group and an alicyclic hydrocarbon group) may be cyclopropyl, for example. Methyl, cyclopropylethyl, cyclobutylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, 2-methylcyclohexylmethyl, cyclohexylethyl An alkyl group having one or more alicyclic hydrocarbon groups, such as adamantylmethyl, and the like.

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

The aliphatic 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 monovalent or bivalent. It is preferable that two linking bonds of a divalent substituent are bonded to the same carbon atom to form a double bond.

Examples of the monovalent substituent include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, third butoxy, and pentyloxy. Hexyl, hexyloxy, (2-ethyl) hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, (2-ethyl) Hexyloxy, eicosyloxy, 1-phenylethoxy, 1-methyl-1-phenylethoxy, phenoxy, o-tolyloxy, 2,3-dimethylphenoxy Group, 2,4-dimethylphenoxy, 2,5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5- Dimethylphenoxy, 2,2-dicyanophenoxy, 2,3-dicyanophenoxy, 2,4-dicyanophenoxy, 2,5-dicyanophenoxy , 2,6-dicyanophenoxy, 3,4-dicyanophenoxy, 3,5-dicyanophenoxy, 4-methoxyphenoxy, 2-methoxyphenoxy Group, 3-methoxyphenoxy group, 4-ethoxyphenoxy group, 2-ethoxyphenoxy group, 3-ethoxyphenoxy group, etc., and the group represented by the following formula is on one side Hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) or a derivatized group thereof (e.g., carboxyl group, sulfonic acid group) , Nitro, hydroxy, halogen (preferably chlorine atom), alkylaminesulfonyl group (preferably octylaminesulfonyl group) derived from 1 to 10 carbon atoms;

Methylthio, ethylthio, propylthio, butylthio, tertiary butylthio, pentylthio, hexylthio, (2-ethyl) hexylthio, heptylthio, octylthio, nonanthio Group, decylthio group, undecylthio group, dodecylthio group, eicosylthio group, phenylthio group and o-tolylthio group, etc. have a carbon number of 1 to 20 (preferably a carbon number of 1 to 10) The thio group of the hydrocarbon group; epoxy group, oxetanyl group, tetrahydrofuryl group, tetrahydropyranyl group; methyl amidino group; ethyl amidino group, propionyl group, butanyl group, 2,2-dimethylpropane Fluorenyl, pentyl, hexyl, (2-ethyl) hexanyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and twenty-one , Benzamidine and the like, and the group represented by the following formula are bonded to a hydrocarbon group having a carbon number of 1 to 20 (preferably a carbon number of 1 to 11) or a derivatized group thereof (e.g., a carboxyl group, a sulfonic acid group , Nitro, hydroxyl, halogen (preferably chlorine atom), alkylaminesulfonyl group (preferably octylaminesulfonyl group) having 1 to 10 carbon atoms, etc. In the case where the carbonyl group is an alkanoyl group, the carbon number is preferably 2 to 12);

Methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, tertiary butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, (2-ethyl) hexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, nonyloxy Carbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, eicosyloxycarbonyl, phenoxycarbonyl, o-tolyloxycarbonyl, etc., and the group represented by the following formula are bonded to carbon A hydrocarbon group of 1 to 20 (preferably carbon number of 1 to 10) or a derivative thereof (e.g., by a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), a carbon number of 1 to 10, Oxycarbonyl group derived from alkyl amine sulfonyl (preferably octylamine sulfonyl) and the like);

Amino groups; N-methylamino, N, N-dimethylamino, N-ethylamino, N, N-diethylamino, N-propylamino, N, N-dipropyl Amino, N-isopropylamino, N, N-diisopropylamino, N-butylamino, N, N-dibutylamino, N-isobutylamino, N, N-diisobutylamino, N-second butylamino, N, N-disecond butylamino, N-third butylamino, N, N-dithird butylamino , N-pentylamino, N, N-dipentylamino, N- (1-ethylpropyl) amino, N, N-bis (1-ethylpropyl) amino, N-hexyl Amine, N, N-dihexylamino, N- (2-ethyl) hexylamino, N, N-di (2-ethyl) hexylamino, N-heptylamino, N, N- Diheptylamino, N-octylamino, N, N-dioctylamino, N-nonylamino, N, N-dinonylamino, N-phenylamino, N, N -Diphenylamino, N, N-ethylmethylamino, N, N-propylmethylamino, N, N-isopropylmethylamino, N, N-butylmethylamino, N-decylamino, N, N-decylmethylamino, N-undecylamino, N, N-undecylmethylamino, N-dodecylamino, N, N- Dodecylmethylamino, N-icosylamino, N, N-icosylmethylamino, N, N-third butylmethylamino group, N, N-phenylmethylamino group, and the like represented by the following formula are 1 or 2 carbon numbers 1 to 20 (preferably carbon number 1 to 10) Hydrocarbyl or derivative thereof (e.g. carboxyl, sulfo, nitro, hydroxy, halogen (preferably chlorine atom), alkylaminesulfonyl group having 1 to 10 carbon atoms (preferably octylaminosulfone Fluorenyl) and other derivatized groups) substituted amino groups;

Aminosulfonyl; N-methylaminesulfonyl, N, N-dimethylaminesulfonyl, N-ethylaminesulfonyl, N, N-diethylaminesulfonyl, N-propyl Aminosulfonyl, N, N-dipropylaminesulfonyl, N-isopropylaminesulfonyl, N, N-diisopropylaminesulfonyl, N-butylaminesulfonyl, N, N-dibutylaminosulfonyl, N-isobutylaminesulfonyl, N, N-diisobutylaminesulfonyl, N-second butylaminesulfonyl, N, N- Di-second butylaminosulfonyl, N-third butylaminesulfonyl, N, N-di-third butylaminesulfonyl, N-pentylaminesulfonyl, N, N-dipentyl N- (1-ethylpropyl) aminosulfonyl, N, N-bis (1-ethylpropyl) aminosulfonyl, N-hexylaminosulfonyl, N, N -Dihexylaminesulfonyl, N- (2-ethyl) hexylaminesulfonyl, N, N-di (2-ethyl) hexylaminesulfonyl, N-heptylaminesulfonyl, N, N-diheptylaminesulfonyl, N-octylaminesulfonyl, N, N-dioctylaminesulfonyl, N, N-octylmethylaminesulfonyl, N-nonylaminesulfonyl Fluorenyl, N, N-dinonylaminesulfonyl, N-phenylaminesulfonyl, N, N-diphenylaminesulfonyl, N, N-ethylmethylaminesulfonyl, N , N-propylmethylaminosulfonyl N, N-isopropylmethylaminesulfonyl, N, N-butylmethylaminesulfonyl, N-decylaminesulfonyl, N, N-decylmethylaminesulfonyl, N-deca Monomethylaminosulfonyl, N, N-undecylmethylaminesulfonyl, N-dodecylaminesulfonyl, N, N-dodecylmethylaminesulfonyl, N-icosyl Aminosulfonyl, N, N-icosylmethylaminesulfonyl, N, N-tert-butylmethylaminesulfonyl, N, N-phenylmethylaminesulfonyl and the like, and the following formula Represented groups such as 1 or 2 carbons having 1 to 20 carbons (preferably 1 to 10 carbons) or their derivatized groups (e.g., carboxyl, sulfonic acid, nitro, hydroxyl, halogen (preferably Is a chlorine atom), an alkylaminesulfonyl group having a carbon number of 1 to 10 (preferably an octylaminesulfonyl group), and the like) substituted aminesulfonyl group;

Formamylamino; ethamylamino, propylamylamino, butylamylamino, 2,2-dimethylpropylamylamino, pentamylamino, hexamylamino, (2- (Ethyl) hexylamino, heptylamino, octylamino, nonylamino, decylamino, undecylamino, dodecylamino, dodecylamino Amino groups, benzamidine amino groups, and the like, and groups represented by the following formula are bonded to a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 12 carbon atoms) or a derivative thereof (for example, by a carboxyl group, Sulfonate, nitro, hydroxyl, halogen (preferably chlorine atom), alkyl amine sulfonyl group (preferably octylamine sulfonyl group) having 1 to 10 carbon atoms) Carbonyl-substituted amino group (in the case where the carbonylamino group is an alkylamino group, the carbon number is preferably 1 to 12);

Hydroxyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; carboxyl group, -CO ₂ M ² (M ² is an alkali metal, preferably lithium, sodium, potassium); sulfonic acid group, -SO ₃ M ² (M ² is an alkali metal, preferably lithium, sodium, potassium); nitro; cyano; formamyloxy; acetamyloxy, propylammonyloxy, butanyloxy, 2,2-dimethyl Propionyloxy, pentyloxy, hexamethyloxy, (2-ethyl) hexanoyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy A group having a carbon number of 1 to 20 (preferably a carbon number of 1 to 10), a dodecyloxy group, a twenty-one alkoxy group, a benzamyloxy group, and the like represented by the following formula Hydrocarbyl or derivative thereof (e.g. carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkylaminesulfonyl group having 1 to 10 carbon atoms (preferably octylaminesulfonyl) ), Such as a derivatized carbonyl group (in the case where the carbonyloxy group is an alkanoyloxy group, the carbon number is preferably 1 to 10);

Methanesulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, (2-ethyl) hexylsulfonyl, heptylsulfonyl Base, octylsulfonyl, nonylsulfonyl, decylsulfonyl, undecylsulfonyl, dodecylsulfonyl, eicosylsulfonyl, phenylsulfonyl, p-tolyl A sulfonyl group and the like, and a group represented by the following formula are bonded to a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) or a derivatized group thereof (e.g., carboxyl group, sulfonic acid group, nitro group, A sulfonyl group derived from a hydroxy group, a halogen (preferably a chlorine atom), an alkylaminesulfonyl group having a carbon number of 1 to 10 (preferably an octylaminesulfonyl group), and the like;

Aminoformyl; N-methylaminoformyl, N, N-dimethylaminoformyl, N-ethylaminoformyl, N, N-diethylaminoformyl Methyl, N-propylaminomethylmethyl, N, N-dipropylaminomethylmethyl, N-isopropylaminomethylmethyl, N, N-diisopropylaminomethylmethyl, N-butylaminomethane, N, N-dibutylaminomethane, N-isobutylaminomethane, N, N-diisobutylaminomethane, N- Second butylaminomethylammonium, N, N-disecond butylaminomethylammonyl, N-third butylaminomethylammonyl, N, N-dithird butylaminomethylammonium Methyl, N-pentylaminomethylmethyl, N, N-dipentylaminomethylmethyl, N- (1-ethylpropyl) aminomethylmethyl, N, N-bis (1-ethyl Propyl) aminomethylmethyl, N-hexylaminomethylmethyl, N, N-dihexylaminomethylmethyl, N- (2-ethyl) hexylaminomethylmethyl, N, N- Di (2-ethyl) hexylaminomethane, N-heptylaminomethane, N, N-diheptylaminomethane, N-octylaminomethane, N, N -Dioctylaminomethylamidino, N-nonylaminomethylamidino, N, N-octylmethylaminomethylamidino, N, N-octylbutylaminomethylamidino, N, N-Dinonyl Methylformyl, N-phenylaminomethylformyl, N, N-diphenylaminomethylformyl, N, N-ethylmethylaminomethylformyl, N, N-propylmethyl Aminoformyl, N, N-isopropylmethylaminoformyl, N, N-butylmethylaminoformyl, N-decylaminoformyl, N, N-decylformyl Aminoaminomethylamido, N-undecylaminomethylamido, N, N-undecylmethylaminomethylamido, N-dodecylaminomethylamido, N, N-dodecyl Methylmethylaminomethylamidino, N-icosylaminomethylamidino, N, N-icosylmethylaminomethylamidino, N, N-third butylmethylaminomethylamidino, N , N-phenylmethylaminomethyl and the like, and the group represented by the following formula are each a hydrocarbon group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms) or a derivative thereof (E.g., derivatized with a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylaminesulfonyl group having a carbon number of 1 to 10 (preferably an octylaminesulfonyl group), and Into a base) substituted aminomethylformyl;

Trifluoromethyl, perfluoroethyl, perfluoropropyl, perfluoroisopropyl, perfluorobutyl, perfluoropentyl, perfluorohexyl, perfluoroheptyl, perfluorooctyl, perfluorononyl, Perfluorodecyl, perfluoroundecyl, perfluorododecyl, perfluoroicosyl, perfluorocyclohexyl, perfluorophenyl and other hydrocarbon groups having 1 to 20 carbon atoms in which all hydrogen atoms are replaced by fluorine atoms; Perfluoroethylmethyl, perfluoropropylmethyl, perfluoroisopropylmethyl, perfluorobutylmethyl, perfluoropentylmethyl, perfluorohexylmethyl, perfluoroheptylmethyl, perfluorooctyl Methyl, perfluorononylmethyl, perfluorodecylmethyl, perfluoroundecylmethyl, perfluorododecylmethyl, perfluoroicosylmethyl, etc. Substituted 1 to 20 straight or branched chain alkyl groups substituted with 1 to 20 carbon hydrocarbon groups; 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl and 2,4, 6-trifluorophenyl and a part of hydrogen atoms with a fluorine atom substituted with a carbon atom having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms); -CO-SH, -CO-S-CH ₃ , -CO- _{S-CH 2 CH 3, -CO} -S-CH 2 -CH 2 -CH 3, -CO-S-CH 2 -CH 2 -CH 2 -CH 3 and the like have 1 to 20 carbon atoms (preferably Thiocarbonyl group having a carbon number 2 to 10) bonded to the alkyl group, -CO-SC ₆ H _5, etc., have thiocarbonyl group bonded to the aromatic group of 6 to 20 carbon atoms; and represented by the following formula * -COCO-R (formula In the formula, R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, the hydrocarbon groups listed above satisfying 1 to 20 carbon atoms), or a derivative group thereof (for example, a carboxyl group, a sulfonic acid group, a nitro group, or a hydroxyl group , A halogen (preferably a chlorine atom), a radical derived from an alkylaminesulfonyl group (preferably an octylaminesulfonyl group) having a carbon number of 1 to 10));

* -NRCONR ₂ represented by the following formula (wherein R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, the hydrocarbon groups listed above satisfying 1 to 20 carbon atoms), or a derivatized group thereof (such as Derivatives derived from carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkylaminesulfonyl groups (preferably octylaminesulfonyl) having 1 to 10 carbon atoms ), The R may be the same as or different from each other, or may be bonded to each other to form a ring);

* -OCONR ₂ represented by the following formula (wherein R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, the hydrocarbon groups listed above satisfying 1 to 20 carbon atoms), or a derivatized group thereof (such as Derivatives derived from carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkylaminesulfonyl groups (preferably octylaminesulfonyl) having 1 to 10 carbon atoms ), The R may be the same as or different from each other, or may be bonded to each other to form a ring);

* -NRCOOR represented by the following formula (where R is a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms (for example, the hydrocarbon groups listed above satisfying 1 to 20 carbon atoms), or a derivative thereof (for example, a carboxyl group) Sulfonate, nitro, hydroxyl, halogen (preferably chlorine atom), alkylamine sulfonyl group (preferably octylaminesulfonyl group) having 1 to 10 carbon atoms) , The R may be the same as or different from each other, or may be bonded to each other to form a ring);

* -OP (O) (OCH ₃ ) ₂ etc. * -OP (O) (OR) ₂ (where R is a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms (for example, among the above-listed hydrocarbon groups, the carbon number is satisfied) 1 to 20), or a derivative thereof (e.g., by a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylaminesulfonyl group having a carbon number of 1 to 10 (preferably Octylaminesulfonyl) and other derivatized groups), the R may be the same as or different from each other, or 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 ) _3, etc. * -SiR ₃ (where R is a hydrogen atom and 1 to 20 carbon atoms) Hydrocarbon group (such as those listed above satisfying carbon number 1 to 20), or its derivatization group (such as carboxyl, sulfonic acid, nitro, hydroxyl, halogen (preferably chlorine atom), carbon number 1 To 10 alkylaminesulfonyl (preferably octylaminesulfonyl) and other derivatized groups), the R may be the same or different from each other, or may be bonded to each other to form a ring) .

Examples of the divalent substituent include a pendant oxygen group, a thioxo group, an imine group, an imine group substituted with an alkyl group having 1 to 20 carbon atoms (preferably 1 to 10 carbon atoms), 6 to 20 carbon substituted aryl groups and the like. Examples of the imino group substituted with an alkyl group include CH ₃ -N =, CH ₃ -CH ₂ -N =, CH _3- (CH ₂ ) ₂ -N =, and CH _3- (CH ₂ ) ₃ -N = Wait. Examples of the imino group substituted with an aryl group include C ₆ H ₅ -N =.

The substituent of the hydrocarbon group having 1 to 40 carbon atoms is preferably a substituent of group s1. The derivatization group disclosed below is a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), and an alkylaminesulfonyl group (preferably an octylaminosulfonyl group) having 1 to 10 carbon atoms A base derived from fluorene) is preferred.

[群 s1]

An oxy group having a hydrocarbon group of 1 to 20 carbons or a derivative thereof is bonded to one side; a carbonyl group having a hydrocarbon group of 1 to 20 carbons or a derivative thereof; a hydrocarbon group having 1 to 20 carbon atoms is bonded Or its derivatized oxycarbonyl group; amine group; amine group substituted by 1 or 2 hydrocarbon groups having 1 to 20 carbon atoms or derivatized group thereof; amine sulfonyl group; 1 or 2 carbon numbers of 1 to Hydrocarbyl group substituted by a hydrocarbyl group of 20 or a derivatized group thereof; carbonylamino group bonded with a hydrocarbyl group of 1 to 20 or a derivatized group thereof; a hydroxyl 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 sulfonic acid group) (M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom); Nitro group; cyano group; carbonyloxy group having a hydrocarbon group of 1 to 20 carbons or a derivative thereof; sulfonyl group having a hydrocarbon group of 1 to 20 carbons or a derivative thereof; aminoformamidine Radicals; aminoformyl groups substituted with 1 or 2 hydrocarbon groups of 1 to 20 carbons or derivatized groups thereof; hydrocarbon groups of 1 to 20 carbons in which all hydrogen atoms are replaced by fluorine atoms; hydrogen atoms in all Number of carbons substituted by fluorine atom 1 to 20 A straight or branched alkyl group is substituted with a hydrocarbon group having 1 to 20 carbon atoms; a part of hydrogen atoms is substituted with a fluorine-containing hydrocarbon group having 1 to 20 carbon atoms; and a pendant oxygen group.

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

[群 s2]

An alkyloxy group having a carbon number of 1 to 10 or a derivatized group thereof is bonded to one side; a carbonyl group of a hydrocarbon group having a carbon number of 1 to 10 or a derivative thereof is bonded; a hydrocarbon group having a carbon number of 1 to 10 is bonded to one side Or its derivatized oxycarbonyl group; amine group; amine group substituted by 1 or 2 hydrocarbon groups having 1 to 10 carbons; sulfamoyl group; 1 or 2 hydrocarbon groups having 1 to 10 carbons or Derivative-substituted aminesulfonyl groups; carbonylamino groups bonded to hydrocarbon groups of 1 to 10 carbons or derivatized groups thereof; hydroxyl groups; fluorine atoms, chlorine atoms, bromine atoms; -CO ₂ M (preferably carboxyl group) ) (M represents hydrogen atom or alkali metal atom, preferably hydrogen atom); -SO ₃ M (preferably sulfonic acid group) (M represents hydrogen atom or alkali metal atom, preferably hydrogen atom) Nitro group; cyano group; carbonyloxy group having a carbon group of 1 to 10 or a derivative thereof; sulfonyl group having a hydrocarbon group of 1 to 10 or a derivative thereof; aminomethyl Fluorenyl groups; aminomethyl fluorenyl groups substituted by 1 or 2 hydrocarbon groups of 1 to 10 carbons or derivatized groups thereof; hydrocarbon groups of 1 to 10 carbons having all hydrogen atoms replaced by fluorine atoms; replaced by all hydrogens Number of carbon atoms substituted with fluorine atom 1 The hydrocarbyl substituted straight chain or branched chain alkyl group having 1 to 10 carbon 10; a part of hydrogen atoms of the fluorine-substituted hydrocarbon group having 1 to 10 carbons; oxo.

^Examples of the hydrocarbon group having 1 to 40 carbon atoms 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 having a monovalent or divalent substituent, Preferable examples include saturated or unsaturated chain hydrocarbon groups having 1 to 30 carbon atoms having monovalent or divalent substituents, and 3 to 30 carbon atoms having monovalent or divalent substituents. It is an unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 30 carbon atoms having a monovalent or divalent substituent, or a combination of hydrocarbon groups, and has a monovalent or divalent substituent. The group having 1 to 30 carbon atoms is more preferably a saturated or unsaturated chain hydrocarbon group having 1 to 20 carbon atoms having a substituent of group s1, and a saturated group having 3 to 20 carbon atoms having a substituent of group s1. Or an unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group having 6 to 20 carbons of a substituent of group s1, or a combination of hydrocarbon groups, and a group of 1 to 20 carbons of a substituent of group s1, Particularly preferred examples include saturated or unsaturated chain hydrocarbon groups having 1 to 15 carbon atoms having a substituent of group s2, and saturated or unsaturated alicyclic hydrocarbon groups having 3 to 15 carbon atoms having a substituent of group s2. A formula hydrocarbon group, an aromatic hydrocarbon group having 6 to 15 carbons of a substituent of group s2, or a combination of hydrocarbon groups, and a group of 1 to 15 carbons of a substituent of group s2.

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, and is preferably a heterocyclic ring containing a hetero atom as a constituent element 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 from 3 to 30, more preferably from 3 to 22, more preferably from 3 to 20, more preferably from 3 to 18, even more preferably from 3 to 15, particularly preferably from 3 to 14.

Examples of the heterocyclic ring containing a nitrogen atom include acridine, azetidine, pyrrolidine, piperidine, and piperidine. Isomonocyclic saturated heterocyclic ring; pyrrole such as 2,5-dimethylpyrrole, pyrazole such as 2-methylpyrazole, 3-methylpyrazole, imidazole, 1,2,3-triazole, 1,2 , 4-triazole and other 5-membered ring system unsaturated heterocyclic ring; pyridine, da , 6-methylpyrimidine and other pyrimidines, pyridine , 1,3,5-three 6-membered ring system unsaturated heterocyclic ring; indazole, indolin, isoindolin, indole, indole , Benzimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro (3-methyl) quine Quinoline, 3-methylquine Quinoline Quinoline, quinazoline, Cinnoline, pyrene , Condensed bicyclic heterocycles such as pyridine, purine, pteridine, benzopyrazole, and benzopiperidine; carbazole, acridine, brown Isocondensation tricyclic heterocycles and the like.

Examples of the hetero ring containing an oxygen atom include ethylene oxide, oxetane, tetrahydrofuran, tetrahydropyran, and 1,3-dioxane. Alkane, 1,4-di Monocyclic saturated heterocyclic rings such as alkane, 1-cyclopentyl dioxolane; bicyclic rings such as 1,4-dioxaspiro [4.5] decane, 1,4-dioxaspiro [4.5] nonane Saturated heterocyclic rings; lactone heterocyclic rings such as α-glycolide, β-propiolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone; 2,3-dimethylfuran, 5-membered ring system unsaturated heterocyclic rings such as 2,5-dimethylfuran and other furans; 6-membered ring system unsaturated heterocyclic rings such as 2H-pyran and 4H-pyran; 1-benzofuran, 4-methylbenzene Benzopyran and benzobis Uh (benzodioxole), Chrom (chroman), iso Condensed bicyclic heterocyclic rings such as alkane; condensed tricyclic heterocyclic rings such as dibenzopiperan (xanthene) and dibenzofuran.

Examples of the heterocyclic ring containing a sulfur atom include saturated 5-membered ring heterocyclic rings such as dithiocyclopentane; thiane, 1,3-dithiocyclohexane, and 2-methyl 6-membered ring system saturated heterocyclic rings such as 1,3-dithiocyclohexane; thiophenes such as 3-methylthiophene and 2-carboxythiophene; benzothioans such as 4H-thiothio and benzotetrahydrothio; Member ring systems are unsaturated heterocyclic rings; condensed bicyclic system heterocycles, such as benzothiophene; condensed tricyclic system heterocycles, such as thioanthracene and dibenzothiophene.

Examples of the heterocyclic ring containing a nitrogen atom and an oxygen atom include morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, and 2-methyl-2-piperidone Isomonocyclic saturated heterocyclic ring; 4-methyl Azole Azole, 2-methyliso Azole, 3-methyliso Isoxazole Unsaturated heterocyclic rings such as azole; benzo Azole, benzo Azole, benzo Benzodi Condensed bicyclic heterocyclic rings such as alkane and benzimidazoline; (phenoxazine) and other condensed tricyclic heterocycles.

Examples of the heterocyclic ring containing a nitrogen atom and a sulfur atom include monocyclic heterocyclic rings such as thiazole such as 3-methylthiazole and 2,4-dimethylthiazole; condensed bicyclic heterocyclic rings such as benzothiazole; phenothiazine Isocondensation tricyclic heterocycles and the like.

The heterocyclic ring may be a group obtained by combining the hydrocarbon groups listed above, and examples thereof include a tetrahydrofurylmethyl group.

The heterocyclic ring may be one represented by the following formula.

The heterocyclic group may be a heterocyclic group formed by bonding two or more R ¹ to R ³ and R ⁵ to R ⁸ . Such a heterocyclic group has a ring structure having two or more rings together with a benzene ring to which R ¹ to R ³ and R ⁵ to R ^{8 are} bonded. Examples of the ring structure having two or more rings include a structure of the following formula.

The above-mentioned heterocyclic bond position is a portion where any hydrogen atom contained in each ring is removed.

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 an aliphatic hydrocarbon group represented by R ^N1 and R ^N2 and a hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² which may have the same substituent. When the heterocyclic system contains a nitrogen atom as a constituent element, the nitrogen atom may be bonded to the above-mentioned hydrocarbon group as a substituent.

Preferable examples of the substituent include those which may be substituted with the aliphatic hydrocarbon group represented by R ^N1 and R ^N2 , and the hydrocarbon group represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² . Those who are the same.

^Examples of the heterocyclic group having a substituent represented by R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ and R ¹⁰² include a heterocyclic group having a monovalent or divalent substituent, and preferably a group having s1 As the heterocyclic group of the substituent, a heterocyclic group having a substituent of the group s2 is more preferable.

The substituent (first substituent) that the hydrocarbon group or heterocyclic group may have is one or two or more, and the two or more substituents are independent of each other and may be the same or different. Further, the aforementioned first substituent may have another substituent (second substituent) bonded to a hydrocarbon group contained in a part thereof. The second substituent can be selected from the same groups as the first substituent.

Hereinafter, R ¹ to R -CO-R ⁸ to ^{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 , halogen atom , -SO ₃ M, -CO ₂ M.

Examples of -CO-R ¹⁰² include methyl amidino; ethyl amidino, propyl amidino, butyl amidino, 2,2-dimethylpropyl amidino, pentyl amidino, hexamethylene, and (2-ethyl) Hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, twenty-one, benzyl, and the like represented by the above formula are bonded Hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivative thereof (for example, carboxyl group, sulfonic acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), 1 to 10 carbon atoms Alkylaminosulfonyl (preferably octylaminesulfonyl) and other derivatized carbonyl groups), preferably carbonyl groups having a hydrocarbon group having 1 to 10 carbon atoms (the carbonyl group is In the case of fluorenyl, the carbon number is 2 to 41) and the like. Preferred examples include a carbonyl group having a hydrocarbon group having 1 to 11 carbon atoms (more preferably, 1 to 10 carbon atoms) or a derivatized carbonyl group thereof (in the case where the carbonyl group is an alkyl group, the carbon number is more preferable). 2 to 12) and so on.

Examples of -COO-R ¹⁰¹ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a third butoxycarbonyl group, a butoxycarbonyl group, a pentoxycarbonyl group, a hexyloxycarbonyl group, and a (2-ethyl) hexyloxycarbonyl group. , Heptyloxycarbonyl, octyloxycarbonyl, nonoxycarbonyl, decyloxycarbonyl, undecyloxycarbonyl, dodecyloxycarbonyl, phenoxycarbonyl, eicosyloxycarbonyl, etc., and the groups represented by the above formulas, etc. As the oxycarbonyl group having a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms), a hydrocarbon group having 1 to 10 carbon atoms or a derivative thereof (for example, Oxygen, nitro, hydroxyl, halogen (preferably chlorine atom), alkyl amine sulfonyl (preferably octylamine sulfonyl) derived from 1 to 10 carbon atoms) oxygen Carbonyl, etc.

Preferable examples include an oxycarbonyl group having a carbon group of 1 to 10 or a derivatized group thereof.

Examples of -OCO-R ¹⁰² include methyloxy, ethoxy, propyloxy, butyloxy, 2,2-dimethylpropyloxy, pentyloxy, and hexane. Oxy, (2-ethyl) hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, twenty-one An oxy group such as an oxy group, a benzamyloxy group, and the group represented by the above formula are bonded to a carbonyl group of a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms). Examples include a hydrocarbon group having a carbon number of 1 to 10 or a derivative thereof (e.g., a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylamine sulfonyl group (preferably a Octylaminesulfonyl) and other derivatized groups) carbonyloxy (when this carbonyloxy group is fluorenyloxy, the carbon number is 2 to 41), etc., preferably, the number of carbon atoms is 1 The carbonyloxy group of a hydrocarbon group of 11 to 11 (more preferably, carbon number of 1 to 10) or a derivative thereof (when the carbonyloxy group is a fluorenyloxy group, the carbon number is preferably 2 to 12), and the like.

Examples of -COCO-R ¹⁰² include methyloxanthenyl, ethyloxanthenyl, propyloxanthenyl, butyloxanthenyl, pentyloxanthenyl, hexyloxanthenyl, (2-ethyl Base) Hexyl, pentyl, octyl, octyl, nonyl, decyl, nondecyl Base, cyclopentylcurcumenyl, cyclohexylcurcumenyl, phenylcurcumenyl, p-tolylcuroxenyl, etc., and the base represented by the above formula are bonded with a carbon number of 1 to 40 (preferably a carbon number) 1 to 20) of a hydrocarbon group or a derivative thereof (e.g., by a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylaminesulfonyl group having a carbon number of 1 to 10 (preferably Octylaminosulfonyl) and other derivatized bases) such as arsenyl.

Examples of -OR ¹⁰² include a hydroxyl group; methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, second butoxy, third butoxy, pentyl Oxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, (2-ethyl) hexyloxy, eicosyloxy , 1-phenylethoxy, 1-methyl-1-phenylethoxy, phenoxy, 2,3-dimethylphenoxy, 2,4-dimethylphenoxy, 2, 5-dimethylphenoxy, 2,6-dimethylphenoxy, 3,4-dimethylphenoxy, 3,5-dimethylphenoxy, 2,2-dicyanobenzene Oxy, 2,3-dicyanophenoxy, 2,4-dicyanophenoxy, 2,5-dicyanophenoxy, 2,6-dicyanophenoxy, 3,4 -Dicyanophenoxy, 3,5-dicyanophenoxy, 4-methoxyphenoxy, 2-methoxyphenoxy, 3-methoxyphenoxy, 4-ethoxy Phenylphenoxy, 2-ethoxyphenoxy, 3-ethoxyphenoxy, etc., and the groups represented by the above formula are bonded with 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) Hydrocarbyl or its derivative (e.g. carboxyl, sulfonic, nitro, hydroxyl, halogen (preferably chlorine atom) The alkoxy group having a carbon number of 1 to 10 (derived from an alkylaminosulfonyl group (preferably an octylaminesulfonyl group)) is preferably an alkyl group having a carbon number of 1 to 10 Of oxygen and so on.

Preferable examples include an oxy group having a hydrocarbon group having 1 to 10 carbon atoms or a derivatized group thereof.

Examples of -SO ₂ -R ¹⁰¹ include methylsulfonyl, ethylsulfonyl, propylsulfonyl, butylsulfonyl, pentylsulfonyl, hexylsulfonyl, (2- (Ethyl) hexylsulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, undecylsulfonyl, dodecylsulfonyl, eicosylsulfonyl A fluorenyl group, a phenylsulfonyl group, a p-tolylsulfonyl group, and the like represented by the above formula are bonded to a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivative thereof ( Derived from carboxyl, sulfo, nitro, hydroxyl, halogen (preferably chlorine atom), alkylaminesulfonyl group (preferably octylaminesulfonyl group) having 1 to 10 carbon atoms, etc. Examples of the sulfofluorenyl group and the like include a sulfofluorenyl group having a hydrocarbon group having 1 to 10 carbon atoms or a derivatized group thereof.

Examples of -SO ₂ N (R ¹⁰² ) ₂ include aminesulfonyl; N-methylaminesulfonyl, N-ethylaminesulfonyl, N-propylaminesulfonyl, N-iso Propylaminesulfonyl, N-butylaminesulfonyl, N-isobutylaminesulfonyl, N-second butylaminesulfonyl, N-thirdbutylaminesulfonyl, N- Amylaminosulfonyl, N- (1-ethylpropyl) aminosulfonyl, N-hexylaminesulfonyl, N- (2-ethyl) hexylaminesulfonyl, N-heptylaminesulfonyl Fluorenyl, N-octylaminesulfonyl, N-nonylaminesulfonyl, N-decylaminesulfonyl, N-undecylaminesulfonyl, N-dodecylaminesulfonyl, N-eicosylaminesulfonyl, N-phenylaminesulfonyl and the like, and the groups represented by the above formula are each a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivative thereof (E.g., derived from a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), an alkylaminesulfonyl group having a carbon number of 1 to 10 (preferably an octylaminesulfonyl group), etc. (Formed groups) substituted aminesulfonyl groups, etc .; N, N-dimethylaminesulfonyl, N, N-ethylmethylaminesulfonyl, N, N-diethylaminesulfonyl , N, N-propylmethylaminesulfonyl, N, N-dipropylaminesulfonyl, N, N -Isopropylmethylaminesulfonyl, N, N-diisopropylaminesulfonyl, N, N-tert-butylmethylaminesulfonyl, N, N-diisobutylaminesulfonyl, N, N-di-second butylaminosulfonyl, N, N-di-third butylaminesulfonyl, N, N-butylmethylaminesulfonyl, N, N-dibutylaminesulfonyl , N, N-dipentylaminesulfonyl, N, N-di (1-ethylpropyl) aminesulfonyl, N, N-dihexylaminesulfonyl, N, N-di (2- (Ethyl) hexylaminesulfonyl, N, N-diheptylaminesulfonyl, N, N-octylmethylaminesulfonyl, N, N-dioctylaminesulfonyl, N, N- Dinonylaminosulfonyl, N, N-decylmethylaminesulfonyl, N, N-undecylmethylaminesulfonyl, N, N-dodecylmethylaminesulfonyl, N , N-eicosylmethylaminesulfonyl, N, N-phenylmethylaminesulfonyl and N, N-diphenylaminesulfonyl, etc., and the groups represented by the above formula are 2 Hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivative thereof (for example, carboxyl group, sulfonic acid group, nitro group, hydroxyl group, halogen (preferably chlorine atom), 1 to 10 carbon atoms Alkylaminesulfonyl (preferably octylaminesulfonyl) and other derivatized groups) substituted aminesulfonyl and the like, preferably Out with 1 or 2 carbon atoms or a hydrocarbon group substituted with the amine derivatized sulfo acyl having 1 to 10.

Examples of -CON (R ¹⁰² ) ₂ include aminomethylamido; N-methylaminomethylamido, N-ethylaminomethylamido, N-propylaminomethylamido, N -Isopropylaminomethylamido, N-butylaminomethylamido, N-isobutylaminomethylamido, N-second butylaminomethylamido, N-third butylamine Methylformyl, N-pentylaminoformyl, N- (1-ethylpropyl) aminoformyl, N-hexylaminoformyl, N- (2-ethyl) hexylamine Methylformyl, N-heptylaminoformyl, N-octylaminoformyl, N-nonylaminoformyl, N-decylaminoformyl, N-undecyl Aminomethylamidino, N-dodecylaminomethylamidino, N-icosylaminomethylamidino, N-phenylaminomethylamidino, etc., and the bases and the like represented by the above formula are represented by 1 carbon. A hydrocarbon group of 1 to 40 (preferably carbon number of 1 to 20) or a derivative thereof (e.g., by a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, a halogen (preferably a chlorine atom), a carbon number of 1 to 10 Derivatives such as alkylaminosulfonyl (preferably octylaminosulfonyl) and the like) substituted aminomethylsulfonyl and the like; N, N-dimethylaminomethylsulfanyl, N, N -Ethylmethylaminomethane, N, N-diethylamino Fluorenyl, N, N-propylmethylaminomethylmethyl, N, N-dipropylaminomethylmethyl, N, N-isopropylmethylaminomethylmethyl, N, N-dimethyl Isopropylaminomethane, N, N-tert-butylmethylaminomethane, N, N-diisobutylaminomethane, N, N-disecondbutylaminomethane Methyl, N, N-di-tert-butylaminomethylmethyl, N, N-butylmethylaminomethylmethyl, N, N-dibutylaminomethylmethyl, N, N-butyloctyl Aminoformyl, N, N-dipentylaminoformyl, N, N-bis (1-ethylpropyl) aminoformyl, N, N-dihexylaminoformyl, N, N-bis (2-ethyl) hexylaminomethane, N, N-diheptylaminomethane, N, N-octylmethylaminomethane, N, N-di Octylaminomethane, N, N-dinonylaminomethane, N, N-decylmethylaminomethane, N, N-undecylmethylaminomethane, N, N-dodecylmethylaminomethylmethyl, N, N-icosylmethylaminomethylmethyl, N, N-phenylmethylaminomethylmethyl, N, N-diphenyl And the like represented by the above formula are each a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivative thereof (for example, a carboxyl group, a sulfonic acid group) , Nitro, hydroxyl, halogen (preferably chlorine atom), alkyl amine sulfonyl group (preferably octylamine sulfonyl group) having 1 to 10 carbon atoms) substituted amine group Formamyl and the like are preferably exemplified by an aminoformamyl group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms or a derivative thereof.

Examples of -N (R ¹⁰² ) ₂ include amino groups; N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, and N-butylamine. Group, N-isobutylamino group, N-second butylamino group, N-third butylamino group, N-pentylamino group, N-hexylamino group, N- (2-ethyl) hexyl group Amino, N-heptylamino, N-octylamino, N-nonylamino, N-decylamino, N-undecylamino, N-dodecylamino, N-di Decylamino group, N-phenylamino group, etc., and the group represented by the above formula are each a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivative thereof (for example, a carboxyl group, Sulfonate, nitro, hydroxyl, halogen (preferably chlorine atom), alkylamine sulfonyl group (preferably octylaminesulfonyl group) having 1 to 10 carbon atoms) Amine groups, etc .; N, N-dimethylamino, N, N-ethylmethylamino, N, N-diethylamino, N, N-propylmethylamino, N, N -Dipropylamino, N, N-isopropylmethylamino, N, N-diisopropylamino, N, N-third butylmethylamino, N, N-diisobutylamine N, N-di-second butylamino, N, N-di-third butylamino, N, N-butylmethylamino, N, N-di Butylamino, N, N-dipentylamino, N, N-di (1-ethylpropyl) amino, N, N-dihexylamino, N, N-di (2-ethyl ) Hexylamino, N, N-diheptylamino, N, N-dioctylamino, N, N-dinonylamino, N, N-decylmethylamino, N, N- Undecylmethylamino, N, N-dodecylmethylamino, N, N-icosylmethylamino, N, N-phenylmethylamino, N, N-diphenyl Amine groups, etc., and the groups represented by the above formula are substituted by a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or a derivative thereof (for example, a carboxyl group, a sulfonic acid group, a nitro group, a hydroxyl group, Halogen (preferably a chlorine atom), alkylaminesulfonyl group (preferably octylaminesulfonyl group) derived from 1 to 10 carbon atoms) substituted amine group, etc .; preferably, Amino groups substituted with 1 or 2 hydrocarbon groups having 1 to 10 carbon atoms or derivatized groups thereof, etc.

Examples of -NHCO-R ¹⁰² include methylamidoamino; ethylamidoamino, propylamidoamino, butylamidoamino, 2,2-dimethylpropylamidoamine, and pentamylamine Hexylamino, hexylamino, hexylamino, heptylamino, octylamino, nonylamino, decylamino, undecylamino, Dialkylamino, behenylamino, benzamidinylamino and the like, and the group represented by the above formula are bonded to a hydrocarbon group having 1 to 40 carbon atoms (preferably 1 to 20 carbon atoms) or Its derivatized group (e.g. carboxyl, sulfonate, nitro, hydroxyl, halogen (preferably chlorine atom), alkylaminesulfonyl group having 1 to 10 carbon atoms (preferably octylaminesulfonyl group) Carbonyl groups (such as derivatized groups) (such as when the carbonylamino group is a fluorenyl group, carbon number is 1 to 40), etc., preferably, a hydrocarbon group having 1 to 10 carbon atoms is bonded. Or a carbonylamino group derived therefrom (in the case where the carbonylamino group is an alkylamino group, the number of carbons is preferably 1 to 10) and the like.

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

Examples of -NHCOOR ¹⁰² include the groups mentioned above.

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

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

Examples of M of -SO ₃ M and -CO ₂ M include a hydrogen atom; alkali metal atoms such as a lithium atom, a sodium atom, and a potassium atom, and preferably a hydrogen atom, a sodium atom, and a 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 (R ¹⁰² ) ₂ , -N (R ¹⁰² ) ₂ , -NHCO-R ¹⁰² , -NHCON (R ¹⁰² ) ₂ , -NHCOOR ¹⁰² , -OCON (R ¹⁰² ) ₂ The substituent (first substituent) contained in may be One or two or more substituents are independent of each other and may be the same or different.

The first substituent may have another substituent (second substituent) bonded to a hydrocarbon group contained in a part of the first substituent. The second substituent can be selected from the same groups as the first substituent.

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

R ^N1 and R ^N2 are substituted with an aliphatic hydrocarbon group, an aralkyl group, a (cycloalkyl) alkyl group, an aliphatic hydrocarbon group substituted with a hydroxyl group, and an oxy group having a hydrocarbon group of 1 to 20 carbon atoms bonded to one side. Aliphatic hydrocarbon groups are preferred, with linear or branched chain alkyl groups, linear or branched chain alkenyl groups, cycloalkyl groups, aralkyl groups, (cycloalkyl) alkyl groups, A chain-like or branched-chain alkyl group or a linear or branched-chain alkyl group substituted with an alkoxy group is preferred.

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

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

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

A ^{g- in} the compound represented by the formula (I) represents a g-valent anion. g is an integer of 1 to 14, preferably an integer of 1 to 10, more preferably an integer of 1 to 8, more preferably an integer of 1 to 6, and particularly preferably an integer of 1 to 4.

^Examples of A ^g- include well-known anions. A ^g- are as specifically include: halide ions fluoride ion, chloride ion, bromide ion, iodide ^{ion; OH -; CN -; NO} 3 -; NO 2 -; ClO -; _{^{ClO 2 -; ClO3 -; ClO4}} -; MnO 4 -; CH 3 CO 2 -, C 6 H 5 CO 2 -; toluenesulfonate _{^{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 ^- like ions alkoxy having from 1 to 20, C ₆ H ₅ O ^- ions and the like having a carbon number of 6 to 20 aryloxy group; a fluorine-containing anion; and selected from the group consisting of tungsten, molybdenum, silicon and phosphorus by At least one element constituting the group, an anion, etc., which oxygen contains as an essential element.

In terms of improvement in heat resistance and reduction in sublimation, A ^g- is an anion containing a fluorine-containing anion, or at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen as an essential element. Preferably, at least one element selected from the group consisting of tungsten and phosphorus, and anion or fluorine-containing anion containing oxygen as an essential element is more preferable, and the group selected from the group consisting of tungsten and phosphorus is more preferable. An anion containing at least one element and oxygen as an essential element is more preferred.

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

[In the formula (III), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ together represent a fluorinated alkyl group having 1 to 4 carbon atoms二 基],

[In the formula (IV), W ⁵ to W ⁷ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms],

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

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

In the formulae (III), (IV), and (VI), the fluorinated alkyl 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 , -C (CF ₃ ) ₃ and the like.

In formulae (III) and (V), the fluorinated alkanediyl group having 1 to 4 carbon atoms is preferably a perfluoroalkanediyl group, and examples thereof include -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 so on.

Examples of the anion represented by the formula (III) (hereinafter referred to as "anion (III)") include anions each represented by the formula (III-1) to the formula (III-6) (hereinafter referred to as "anions"). "Anion (III-1)" to "anion (III-6)").

Examples of the anion represented by the formula (IV) (hereinafter referred to as "anion (IV)") include the anion (IV-1) represented by the formula (IV-1).

Examples of the anion represented by the formula (V) (hereinafter referred to as "anion (V)") include anions each represented by the formula (V-1) to the formula (V-4) (hereinafter, referred to as "Anion (V-1)" to "Anion (V-4)").

Examples of the anion represented by the formula (VI) (hereinafter referred to as "anion (VI)") include anions each represented by the formula (VI-1) to the formula (VI-4) (hereinafter, referred to as "Anion (VI-1)" to "Anion (VI-4)").

May be selected from the group consisting of fluorinated anionic CF ₃ CO ₂ ^-, an anion (III), anions (IV), anions (V) and an anion (VI) by a group of at least one anion. Among them, CF ₃ CO ₂ ^-, an anion (III-1), anionic (III-2), anionic (III-6), anionic (IV-1), anionic (V-1), anionic (VI-1) anionic (VI-2), anionic (VI-3) is preferable, and CF ₃ CO ₂ ^-, an anion (III-2), anionic (IV-1), anionic (VI-1) is preferred.

Examples of the anion include an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen as an essential element. An anion of a heteropolymeric acid or a homopolymeric acid containing tungsten as an essential element is preferable, and anions of phosphotungstic acid, silicotungstic acid, and a tungsten-based isomeric polymer acid are more preferable. Such an anion system is used, for example, in a coloring compound represented by formula (I) having a fluorine-containing anion (preferably an anion (VI-1)) and when anion exchange is performed, which contributes to improvement of heat resistance.

An anion of a heteropoly acid or isopoly acid containing tungsten as an essential element, such as a Keggin type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ^{3 -} , Dawson type phosphotungstic acid ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Kejin type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^4- , and other examples include [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- [SiW1 ₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W ₆ O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2- Wait. Among them, a Kejin-type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ^3- is preferred.

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

[In formula (IB), R ^N1 , R ^N2 , R ^N3 , R ¹ to R ⁸ , R ¹⁰¹ , R ¹⁰² and M represent the same meanings as described above.

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

h is an integer from 1 to 14]

In the formula (IB), as the B ^h- , the same as those having the g-valent anions of tungsten, molybdenum, and the like as A ^{g- in} the formula (I) can be mentioned.

In formula (IB), preferable B ^h- may include at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus as A ^g- as listed in formula (I). Among the anions having a g-valent anion in which oxygen is contained as an essential element, the same is preferred.

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

In Tables 1 to 10, "Me" means methyl, "Et" means ethyl, "Bu" means butyl, "TBu" means third butyl, "Hex" means hexyl, “Oc” means octyl, “2EH” means 2-ethylhexyl, “CHM” means cyclohexylmethyl, “CH” means cyclohexyl, “PH” means phenyl, and “BZ” means benzene Methyl, "NPR" means propyl, "IPR" means isopropyl, "IBu" means isobutyl, "EOE" means -CH ₂ CH ₂ OCH ₂ CH ₃ , and "ALL" means olefin propyl, "HYE" line represents a 2-hydroxyethyl, "COM" line represents -CO-CH _3, "COE" line represents -COO-CH ₂ CH _3, "OCM" line represents -OCO-CH _3, " OME "are diagrams -O-CH _3," SOT "line represents toluenesulfonic acyl," SNH "line represents _{-SO 2 NH-CH 2 CH (} CH 2 CH 3) ((CH 2) 3 CH 3), ""SN2" means -SO ₂ N (CH ₃ ) ((CH ₂ ) ₇ CH ₃ ), "CNM" means -CONHCH ₃ , "CN2" means -CON (CH ₃ ) C ₆ H ₅ , "NPH" line represents -NHC ₆ H _5, "NOT" line represents _{-N ((CH 2) 7 CH} 3) 2, "NCO" line represents _{-NHCO ((CH 2) 4 CH} 3) "F" line represents a fluorine atom, "Cl" represents a chlorine atom based, "Br" represents a bromine atom based, "CN" represents a cyano group-based, "NO2" represents a nitro-based, "SUA" line represents -SO ₃ H, "CBA" means -CO ₂ H, "CHO" means -CHO, "OCH" means -OCOH, "OH" means -OH, "SFM" means -SO ₂ NH ₂ , and "CBM" means -CONH ₂ , "NH2" means -NH ₂ , "NCH" means -NHCOH, "III-1" to "III-6" means anions (III-1) to anions (III-6), "IV "-1" means anion (IV-1), "V-1" to "V-4" means anion (V-1) to anion (V-4), "VI-1" to "VI-4" System represents anion (VI-1) to anion (VI-4).

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

From the viewpoint of easy synthesis, the compound (I-1) to the compound (I-312) is preferable, the compound (I-1) to the compound (I-156) is more preferable, and the compound (I-1 ) To compound (I-24) are more preferred, and compound (I-13) to compound (I-24) are particularly preferred.

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 a compound represented by formula (II) (hereinafter, referred to as a compound (II)) and a compound represented by formula (II-1) (hereinafter, referred to as a compound (hereinafter II-1), and can be obtained by reacting a compound containing at least one element selected from the group consisting of tungsten, silicon, and phosphorus and oxygen as essential elements. The compound is further reacted to obtain it.

[In formulae (II) and (II-1), R ¹ to R ⁸ , R ^N1 , R ^N2 , R ^N3, and g represent the same meanings as above, and A ′ represents the supply of g electrons to the A ^g- By]

Examples of the compound represented by the formula (II-1) include an alkylating agent. Examples of the alkylating agent include halogenated alkyl groups (such as methylene chloride, methyl bromide, or methyl iodide), such as halogenated alkyl groups having 1 to 10 carbon atoms, and more preferably 1 to 3 carbon atoms. ; Preferably 2 to 10 carbons, more preferably 2 to 6 carbons, and still more preferably 2 to 4 carbon dialkyl carbonates (dimethyl carbonate or diethyl carbonate, etc.); more preferably Dialkyl sulfuric acid (dimethyl sulfuric acid or diethyl sulfuric acid, etc.) having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms; preferably 2 to 10 carbon atoms 10. More preferred are alkane sulfonates having 2 to 6 carbon atoms, and even more preferably having 2 to 4 carbon alkyl esters (methyl methanesulfonate, ethyl ethanesulfonate, ethyl methanesulfonate, methyl ethanesulfonate). , Methyl triflate, ethyl triflate, etc.).

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

The use amount of the alkylating agent is preferably 1 mol or more and 20 mol or less with respect to 1 mol of the compound (II), and more preferably 1 mol or more and 10 mol or less.

The reaction temperature is preferably 0 to 150 ° C, and more preferably 10 to 100 ° C. In order to make the solubility of the colored compound precursor represented by the formula (I) sufficient, a predetermined organic solvent may be mixed in advance at about 70 to 100 ° C. The reaction time is preferably 10 minutes to 24 hours, and more preferably 1 hour to 12 hours.

In terms of yield, the reaction is preferably performed 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, dichloromethane, and chloroform; methanol, ethanol, and isopropanol Alcohol solvents such as butanol; nitro hydrocarbon solvents 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; N, Amine solvents such as N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, etc., preferably aromatic hydrocarbon solvents, and toluene and xylene as Better. The used amount of the organic solvent is preferably 1 part by mass or more and 300 parts by mass or less with respect to 1 part by mass of the compound (II), and more preferably 1 part by mass or more and 100 parts by mass or less.

The method for obtaining the compound from the reaction mixture is not particularly limited, and various known methods can be used. Examples thereof include a method of filtering the reaction mixture, washing the solvent with an aromatic hydrocarbon solvent such as toluene, and drying the obtained residue. If necessary, it can be purified by further recrystallization using a solvent or by silica gel column chromatography. The obtained compound is, for example, a compound represented by formula (I).

Next, a method of exchanging the anions of the compound represented by the formula (I) may be adopted. Examples of the method include adding at least one element selected from the group consisting of tungsten, silicon, and phosphorus, and oxygen. Methods and the like of compounds and the like contained as essential elements.

A compound containing at least one element selected from the group consisting of tungsten, silicon, and phosphorus, and oxygen as an essential element (in this specification, hereinafter also referred to as an anion exchanger), a well-known and commonly used method can be used. To manufacture, but it is also possible to use a commercially available product directly. Examples of such compounds include corresponding heteropolymeric acid salts, homopolymeric acid salts, or silicates, phosphates, and the like. Phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, and silicomolybdic acid can also be mentioned.

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

The reaction temperature is preferably 0 to 150 ° C, and more preferably 10 to 100 ° C. The reaction time is preferably 10 minutes to 36 hours, and more preferably 10 minutes to 24 hours.

In terms of yield, the reaction is preferably performed in water, an organic solvent, or a mixture thereof. 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, dichloromethane, and chloroform; methanol, ethanol, and isopropanol Alcohol solvents such as butanol; nitro hydrocarbon solvents 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; N, Solvents such as N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, and the like. Examples of the solvent that can be used for the reaction include water, alcohol solvents, ketone solvents, ether solvents, nitrile solvents, amidine solvents, and mixtures thereof. Preferable examples include water, alcohol solvents, ketone solvents, nitrile solvents, and amidine. An amine solvent or a mixture of these is more preferably water, an alcohol solvent or a mixture of these, and particularly preferred is water, methanol or a mixture of these.

The used amount of the organic solvent is preferably 1 part by mass or more and 1,000 parts by mass or less with respect to 1 part by mass of the compound represented by the formula (I), and more preferably 10 parts by mass or more and 500 parts by mass or less.

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

The compound (II) is a compound represented by the formula (VII) (hereinafter, referred to as the compound (VII)) and a compound represented by the formula (VIII) (hereinafter, referred to as the compound (VIII)). It is produced by reacting in the presence of a base.

[In formula (VII) and formula (VIII), R ¹ to R ³ , R ⁵ to R ⁸ , R ^N1 and R ^N2 represent the same meanings as 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, second butyl, and third butyl. Examples thereof include an alkyl group having 1 to 6 carbon atoms.

Examples of the base include organic bases such as triethylamine and piperidine, and the amount used 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, relative to 1 mole of the compound (II).

The reaction of the compound (VII) and the compound (VIII) is usually carried out in the presence of a solvent. Examples of the solvent include a nitrile solvent such as acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, and 1-pentane. Alcohol solvents such as alcohols and 1-octanol; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbons such as dichloromethane and chloroform Solvents and ammonium solvents such as N, N-dimethylformaldehyde and N-methylpyrrolidone are preferably nitrile solvents, alcohol solvents, and aromatic hydrocarbon solvents, and preferably include acetonitrile, methanol, and toluene. The amount of the compound (VII) to be used is generally 1 to 100 parts by mass.

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

After completion of the reaction, the compound (II) can be taken out, for example, by mixing and filtering the solvent in which the compound (II) is not easily dissolved, and the obtained reaction mixture. If necessary, a solvent may be used for recrystallization or a silica gel column chromatography may be used for purification.

The compound (VII) can be a compound represented by the formula (IX) (hereinafter, referred to as the compound (IX)) and a compound represented by the formula (X) (hereinafter, referred to as the compound (X)). It is produced by reacting in a solvent.

[In formula (IX) and formula (X), R ⁵ to R ⁹ represent the same meaning as above, and R ¹⁰ represents an alkyl group having 1 to 4 carbon atoms]

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

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

Examples of the solvent include alcohol solvents such as methanol, and the amount 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 ° C, and the reaction time is usually 1 to 72 hours.

After completion of the reaction, for example, the reaction mixture can be mixed with water or methanol as necessary, and then the compound (VII) can be taken out by filtration. After the reaction is completed, for example, the reaction mixture can be mixed with water, if necessary, and then the resulting organic layer can be extracted by using an insoluble organic solvent such as ethyl acetate to concentrate the compound (VII). take out. If necessary, a method of recrystallization using a solvent or a silica gel column chromatography may be used for purification.

The compound (X) can be produced, for example, according to a known method such as the method described in J. Med. Chem. 2012, 55, 3398-3413.

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 pigment (colorant A1) other than the compound (I), if necessary.

The coloring composition of the present invention contains at least one of the compound (1), the resin (B), and the solvent (E), and includes both the compound (1), the resin (B), and the solvent (E) as good.

    <Resin (B)>    

The resin (B) is preferably an alkali-soluble resin, and has at least one monomer (a) (hereinafter referred to as "(a)") derived from a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. In the case of) a polymer of a structural unit is preferred.

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

Examples of the other structural unit include a monomer (c) derived from the monomer (a) that can be copolymerized with the monomer (a) (however, it is different from the monomer (a) and the monomer (b). It is hereinafter referred to as "(c ) "), Structural units with ethylenically unsaturated bonds, etc.

Examples of (a) include 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-vinyl phthalic acid, 4-vinyl phthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3 Unsaturated dicarboxylic acids such as 1,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; methyl-5-norbornene-2,3- Dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxymethylbicyclo [2.2.1] heptane- 2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene and other bicyclic unsaturated compounds containing a carboxyl group; anhydrides of the aforementioned unsaturated dicarboxylic acids except fumaric acid and mesaconic acid, etc. Carboxylic acid anhydride; succinic acid mono [2- (meth) acryloxyethyl] and phthalic acid mono [2- (meth) acryloxyethyl]; Saturated mono [(meth) acrylic alkoxyalkyl] esters; such as α- (hydroxymethyl) acrylic acid, etc. unsaturated acrylates containing hydroxyl and carboxyl groups in the same molecule.

Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the point of copolymerization reactivity and the solubility of the obtained resin with respect to an alkali aqueous solution.

(b) means a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an ethylene oxide ring, an oxetane ring, and a tetrahydrofuran ring) and ethylenic unsaturation Bondable polymerizable compound. (b) A monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acrylfluorenyloxy group is preferred.

Examples of (b) include a monomer (b1) having an ethylene oxide group and an ethylenically unsaturated bond (hereinafter referred to as "(b1)"), an oxetanyl group, and Ethylene unsaturated bond monomer (b2) (hereinafter referred to as "(b2)"), and monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter referred to as "(b3) ") And so on.

(B1) includes, for example, a monomer (b1-1) having a structure obtained by epoxidizing a linear or branched chain aliphatic unsaturated hydrocarbon (hereinafter referred to as "(b1-1) "(B1-2)" (hereinafter referred to as "(b1-2)") and a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

As (b1-1), a monomer having an epoxypropyl group and an ethylenically unsaturated bond is preferred. Specific examples of (b1-1) include epoxypropyl (meth) acrylate, β-methylepoxypropyl (meth) acrylate, and β-ethyl (meth) acrylate Glycidyl Ester, Glycidyl Ether, Glycidyl Glycidyl Ether, Alpha-Methylvinyl Glycidyl Glycidyl Ether, 2,3-Bis (Glycidyloxy (Meth) styrene, 2,4-bis (glycidoxymethyl) styrene, 2,5-bis (glycidoxymethyl) styrene, 2,6-bis (glycidoxy) Methylmethyl) styrene, 2,3,4-ginsyl (glycidoxymethyl) styrene, 2,3,5-ginseng (glycidyloxymethyl) styrene, 2,3,6 -Ginseng (glycidoxymethyl) styrene, 3,4,5-ginseng (glycidoxymethyl) styrene and 2,4,6-ginseng (glycidoxymethyl) benzene Ethylene, etc.

Examples of (b1-2) include vinylcyclohexene monooxide and 1,2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE (registered trademark) 2000; manufactured by Daicel) ), 3,4-epoxycyclohexyl methyl (meth) acrylate (for example, CYCLOMER (registered trademark) A400; manufactured by Daicel (Stock)), 3,4-epoxy cyclohexyl methyl (meth) acrylate Esters (for example, CYCLOMER (registered trademark) M100; Daicel (product)), compounds represented by formula (BI), compounds represented by formula (BII), and the like.

[Formula (BI) and the formula (BII), R ^a is and R ^b each independently represent a line a hydrogen atom, or an alkyl group having 1 to 4 carbon atoms, the hydrogen atoms contained in the alkyl group may be substituted with hydroxy.

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

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

* Indicates a link key with O].

Examples of the compound represented by the formula (BI) include compounds represented by any one of the formula (BI-1) to (BI-15). Preferred examples include the formula (BI-1) and (BI- 3) Compounds represented by formula (BI-5), formula (BI-7), formula (BI-9), and formula (BI-11) to formula (BI-15), more preferably, formula (BI- 1) Compounds represented by 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 formula (BII-1) to (BII-15). Preferred examples include the formula (BII-1) and (BII-3). ), Formula (BII-5), formula (BII-7), formula (BII-9), and compounds represented by formula (BII-11) to formula (BII-15), more preferably, formula (BII-1) ), A compound represented by formula (BII-7), formula (BII-9) and formula (BII-15).

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

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, second butyl (meth) acrylate, and (meth) acrylic acid. Third butyl ester, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate Ester, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-9-yl (meth) acrylate, (formaldehyde (Triyl) acrylic tricyclic [5.2.1.0 ^2,6 ] decene-8-yl ester, (meth) acrylic tricyclic [5.2.1.0 ^2,6 ] decene-9-yl ester, (meth) acrylic acid di Cyclopentyloxyethyl, isoamyl (meth) acrylate, adamantane (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, benzene (meth) acrylate (Meth) acrylates such as esters, naphthyl (meth) acrylate and benzyl (meth) acrylate; hydroxyl-containing groups such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate (Meth) acrylates; dicarboxylic acids such as diethyl maleate, diethyl fumarate, and diethyl iconate Esters; bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] hept-2-ene Ene, 5,6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (2'-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5 , 6-Dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2 .1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene , 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] heptane -2-ene, 5,6-bis (third butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5,6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2- Bicyclic unsaturated compounds such as alkene; N-phenylcis butene difluorene imide, N-cyclohexyl cis butene difluorene imine, N-benzyl cis butene difluorene imine, N-succinimide Base-3- Butene difluorenimide benzoate, N-succinimide imino-4-cis butylene diimide butyrate, N-succinimide imino-6-cis butene diimide Esters, N-succinylideneimide-3-cis butylene diimide propionate, and N- (9-acridyl) cis butylene diimide derivatives, such as dicarbonylamine imine derivatives; benzene Vinyl-containing aromatic compounds such as ethylene, α-methylstyrene, vinyltoluene, and p-methoxystyrene; vinyl-containing nitriles such as (meth) acrylonitrile; halogenated vinyl chloride and vinylidene chloride Hydrocarbons; vinylamines such as (meth) acrylamide; esters such as vinyl acetate; 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butane Diene, etc.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyltoluene, (cyclo) (meth) acrylic acid [5.2.1.0 ^2,6 ] decane-8-yl ester, Tricyclo [5.2.1.0 ^2,6 ] decane-9-yl (meth) acrylate, Tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, (methyl) Acrylic tricyclo [5.2.1.0 ^2,6 ] decene-9-yl ester, N-phenylcis butene difluorene imide, N-cyclohexyl cis butylene diimide, N-benzyl cis Dieneimine, 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) acrylfluorenyl group. The resin having such a structural unit can be added to a monomer having an ethylenically unsaturated bond in a group capable of reacting with a group possessed by (a) and (b), and added to a monomer derived from (a), ( b) a polymer of structural units.

Examples of such a structural unit include a structural unit obtained by adding glycidyl (meth) acrylate to a (meth) acrylic unit, and adding 2-hydroxyethyl (meth) acrylate to cis-butyl. A structural unit composed of an oxalic anhydride unit, a structural unit obtained by adding (meth) acrylic acid to a glycidyl (meth) acrylate unit, and the like. When the structural unit has a hydroxyl group, a structural unit obtained by further adding a carboxylic acid anhydride may be cited as a structural unit having an ethylenically unsaturated bond.

A polymer having a structural unit derived from (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, solvent, and the like are not particularly limited, and those commonly used in this field can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.), The organic peroxide (such as benzamidine peroxide) may be any solvent as long as it dissolves each monomer.

Further, the obtained polymer may be a solution after the reaction, a solution after concentration or dilution, or a substance taken out as a solid (powder) by a method such as reprecipitation.

If necessary, reaction catalysts of carboxylic acid or carboxylic anhydride and cyclic ether (for example, (dimethylaminomethyl) phenol) and polymerization inhibitors (for example, hydroquinone) may be used.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexyl methyl (meth) acrylate / (meth) acrylic copolymer and 3,4-epoxy (meth) acrylate. Tricyclic [5.2.1.0 ^2,6 ] decyl / (meth) acrylic copolymer, glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic copolymer, (formyl Base) glycidyl acrylate / styrene / (meth) acrylic acid copolymer, (meth) acrylic 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl cis-butene difluorene imine copolymer, 3,4-epoxy tricyclic (meth) acrylic acid [5.2.1.0 ^2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl cis Copolymer of butene difluorene imine / 2-hydroxyethyl (meth) acrylate, 3,4-epoxy tricyclo [5.2.1.0 ^2,6 ] decyl / (meth) acrylic acid / Vinyltoluene copolymer, (meth) acrylic 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl / (meth) acrylic acid / (meth) acrylic acid 2-ethylhexyl copolymer thereof, (meth) acrylate, 3,4-epoxy-tricyclo [5.2.1.0 ^2,6] decyl acrylate / (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decene acrylate / (meth) Acrylic acid / N-cyclohexyl maleic acid Copolymer, 3-methyl-3- (meth) acryloxymethyloxetane / (meth) acrylic acid / styrene copolymer, benzyl (meth) acrylate / (meth) Acrylic copolymers, styrene / (meth) acrylic copolymers, and resins described in JP-A-9-106071, JP-A-2004-29518, and JP-A-2004-361455.

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

The resin (B) may be used in combination of two or more kinds. In this case, the resin (B) contains at least 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ester selected from (meth) acrylic acid / ( (Meth) acrylic acid copolymer, (meth) acrylic 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ester / (meth) acrylic acid / N-cyclohexyl maleimide diimide / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl / (meth) acrylic acid / vinyl toluene copolymer, And (meth) acrylic 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl / (meth) acrylic acid / (meth) acrylic acid 2-ethylhexyl copolymer is one or more kinds good.

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

The acid value (solid content conversion value) of the resin (B) is preferably from 10 to 300 mg-KOH / g, more preferably from 20 to 250 mg-KOH / g, more preferably from 30 to 200 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined by, for example, titration with 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 even more preferably 7 to 95% by mass with respect to the total amount of the solid content.

    <Solvent (E)>    

Examples of the solvent (E) include an ester solvent (a solvent containing -COO- and no -O- in the molecule), an ether solvent (a solvent containing -O- and no -COO- in the molecule), and an ether Ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and -COO- not contained in the molecule), alcohol solvents (containing OH and no- O-, -CO- and -COO- solvents), aromatic hydrocarbon solvents, amidine solvents and dimethyl sulfene.

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

Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, Diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol , Tetrahydrofuran, tetrahydropyran, 1,4-di Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenyl ether and Methyl anisole and so on.

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxy Methyl propionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxy Ethyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2-ethoxy-2-methylpropanoic acid ethyl ester, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether ethyl Acid esters, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate And dipropylene glycol methyl ether acetate.

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

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 amine solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

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

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

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

Compound (I) may be subjected to rosin treatment, surface treatment using a derivative in which an acidic group or a basic group is introduced, and graft treatment on the surface of compound (I) using a polymer compound or the like, if necessary. Micronization treatment using a sulfuric acid micronization method or the like, washing treatment using an organic solvent, water, or the like to remove impurities, removal treatment using an ion exchange method using an ionic impurity, or the like. The particle diameter of the compound (I) is preferably approximately uniform. The compound (I) is dispersed in a dispersing agent, so that the compound (I) can be uniformly dispersed in the dispersion liquid.

Examples of the dispersant include a surfactant, and may be any of a cationic, anionic, nonionic, and amphoteric surfactant. Specific examples include polyester-based, polyamine-based, and acrylic-based surfactants. These dispersants can be used alone or in combination of two or more. As a dispersant, when it is represented by a trade name, KP (Shin-Etsu Chemical Industry Co., Ltd.), FLOWLEN (Kyoeisha Chemical Co., Ltd.), SOLSPERSE (registered trademark) (ZENECA (Co., Ltd.)), EFKA (registered trademark) (BASF (share) system), AJISPER (registered trademark) (Ajinomoto Fine-Techno (share) system), Disperbyk (registered trademark) (BYK-Chemie (share) system), BYK (registered trademark) ( BYK-Chemie (stock)).

When a dispersant is used, the amount of the dispersant (solid content) used is preferably 300 parts by mass or less, and more preferably 5 parts by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the compound (I). When the amount of the dispersant used is in the aforementioned range, there is a tendency that a colored composition in a relatively uniform dispersed state can be obtained.

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

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

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

    <Colorant (A1)>    

The colorant (A1) may be a dye or a pigment. As the dye person, well-known dyes can be used, and examples include dyes described in the Color Index (published by The Society of Dyers and Colourists) and dyeing notes (color dyeing company). Examples of the chemical structure include azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopiperan dyes, and phthalocyanine dyes. These dyes can be used individually or in combination of 2 or more types.

Specific examples include dyes having the following color index (C.I.) numbers. CI solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162; CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI Reactive Yellow 2, 76, 116; CI Direct Yellow 2 , 4, 28, 33, 34, 35, 38, 39, 43, 44, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109 , 129, 132, 136, 138, 141; CI disperse yellow 51, 54, 76; CI solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99; CI 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; CI reactive orange 16; CI direct orange 26 , 34, 39, 41, 46 , 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; CI Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Acid Red 52, 73 , 80, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 34, 102; CI Disperse Violet 26, 27; CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; CI Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97 , 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; CI Acid Blue 25, 27, 40, 45, 78, 80, 112; CI Direct Blue 40; CI Disperse Blue 1, 14, 56, 60; CI Solvent Green 1, 3, 5, 28, 29, 32, 33; CI Acid Green 3, 5, 9, 25, 27, 28, 41; CI Basic Green 1; CI reduced vat green 1 and the like.

As a pigmenter, a well-known pigment can be used, For example, the pigment classified as a pigment by the color index (published by The Society of Dyers and Colourists) is mentioned. These can be used individually or in combination of 2 or more types.

Specific examples include CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214 and other yellow pigments; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments; CI 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 other red pigments; CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other cyan pigments ; CI Pigment Purple 1, 19, 23, 29, 32, 36, 38 and other purple pigments; CI Pigment Green 7, 36, 58, 59 and other green pigments.

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

The yellow colorant can be selected from the following: the above-mentioned CI solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162 ; CI Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; CI response Sex Yellow 2, 76, 116; CI Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93 , 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; CI Disperse Yellow 51, 54, 76 and other yellow dyes; and CI Pigment Yellow 1, 3, 12, 13, 14, 15 , 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166 , 173, 185, 194, 214 and other yellow pigments.

Yellow colorants are preferably yellow dyes and yellow pigments, and yellow pigments are more preferred. Quinophthalone yellow pigments, metal-containing yellow pigments, and isoindoline yellow pigments are more preferred. CI pigments are preferred. Huang 129, 138, 139, 150, and 185 are particularly good.

The orange colorant can be selected from the following: CI solvent orange 2, 7, 11, 15, 15, 26, 41, 54, 56, 99; CI 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; CI reactive orange 16; CI direct orange 26, 34, 39, 41, 46 , 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107 and other orange dyes; and CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments.

Orange colorants are preferably orange dyes and orange pigments, preferably orange pigments, and CI pigment oranges 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65 , 71, 73 are more preferred.

The red colorant can be selected from the following: CI solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151 , 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; CI Acid Red 52, 73, 80, 91, 92, 97, 138, 151, 211, 274, 289 and other red dyes; and CI 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 other red pigments.

Red colorants are preferably red dyes and red pigments. Azo dyes, anthraquinone dyes, triphenylmethane dyes, dibenzopiperan dyes, perylene dyes, azo pigments, diketopyrrolopyrrole pigments, Anthraquinone pigments, dibenzopiperan pigments, and fluorene pigments are preferred, and CI Acid Red 52 and CI Pigment Red 144, 177, 179, 242, 254, and 269 are more preferred.

Moreover, as a yellow coloring agent, an orange coloring agent, or a red coloring agent, the dibenzopiperan compound etc. which were described in Unexamined-Japanese-Patent No. 2013-235257 can also be used.

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

The coloring composition of the present invention is produced by mixing a compound represented by formula (I), a resin, a solvent (E), and a coloring agent (A1) -containing liquid containing a colorant (A1) and a solvent (E). Better. The production method is a method in which a coloring composition is prepared by mixing a compound represented by formula (I), a resin, and a solvent (E) using a bead mill or the like, and the obtained coloring composition and a colorant (A1) and The method of mixing the solvent (E) -containing coloring agent (A1) is preferred.

The colorant (A1) may also be subjected to rosin treatment, surface treatment using a coloring agent derivative introduced with an acidic group or a basic group, etc., and grafting treatment on the surface of the colorant (A1) using a polymer compound, etc. as necessary. , A micronization treatment using a sulfuric acid micronization method, a cleaning treatment using an organic solvent, water, etc. to remove impurities, a removal treatment using an ion exchange method using ionic impurities, and the like. The particle size of the colorant (A1) is preferably approximately uniform. The colorant (A1) can be dispersed by containing a dispersant, and the colorant (A1) can be uniformly dispersed in the colorant (A1) -containing liquid. Each of the colorants (A1) may be separately subjected to a dispersion treatment, or a plurality of types may be mixed to perform a dispersion treatment.

Examples of the dispersant include a surfactant, and may be any of a cationic, anionic, nonionic, and amphoteric surfactant. Specific examples include polyester-based, polyamine-based, and acrylic-based surfactants. These dispersants can be used alone or in combination of two or more. As a dispersant, when it is represented by a trade name, KP (Shin-Etsu Chemical Industry Co., Ltd.), FLOWLEN (Kyoeisha Chemical Co., Ltd.), SOLSPERSE (registered trademark) (ZENECA (Co., Ltd.)), EFKA (registered trademark) (BASF (share) system), AJISPER (registered trademark) (Ajinomoto Fine-Techno (share) system), Disperbyk (registered trademark) (BYK-Chemie (share) system), BYK (registered trademark) ( BYK-Chemie (stock)).

When a dispersant is used to prepare the colorant (A1) -containing liquid, the dispersant (solid content) is preferably used in an amount of 300 parts by mass or less with respect to 100 parts by mass of the colorant (A1), and more preferably 5 At least 100 parts by mass. When the usage-amount of this dispersing agent is the said range, there exists a tendency for the coloring agent (A1) containing liquid to be obtained in a relatively uniform dispersion state.

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

In the colorant (A1) containing liquid, the content of the colorant (A1) is usually 1 mass% or more and 90 mass% or less, and preferably 1 mass% or more and 80 mass% or less with respect to the total amount of the solid content. It is preferably 2% by mass or more and 75% by mass or less.

When the coloring agent (A1) containing liquid containing the colorant (A1) and the solvent (E) is prepared in advance, the coloring composition of the present invention may be prepared by using the coloring agent (A1) containing liquid to prepare the coloring composition of the present invention. A part or all of the resin (B) contained in the coloring composition is contained in advance, and it is preferably a part. By containing the resin (B) in advance, the dispersion stability of the colorant (A1) -containing liquid can be further improved.

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

The content of the coloring agent (A) in which the compound (I) and the coloring agent (A1) are combined with respect to the total amount of the solid content in the coloring composition is usually 1% by mass or more and 90% by mass or less. 1 mass% or more and 80 mass% or less is preferable, and 2 mass% or more and 75 mass% or less is more preferable.

In the total amount of the colorant (A), the content rate 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 being 100% by mass or less, and 99.999%. The content is preferably not more than mass%, and more preferably not more than 99.997 mass%.

When the colorant (A1) is contained, the content of the colorant (A1) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and more preferably 1 part by mass or more based on 100 parts by mass of the compound (I). It is preferably 10,000 parts by mass or less, and more preferably 5,000 parts by mass or less.

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

    <Polymerizable compound (C)>    

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

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

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, neopentaerythritol tri (meth) acrylate, neopentaerythritol tetra (meth) acrylate, and dineopentyl. Tetraol penta (meth) acrylate, dinepentaerythritol hexa (meth) acrylate, trinepentaerythritol octa (meth) acrylate, trinepentaerythritol hepta (meth) acrylate, tetra Neopentaerythritol deca (meth) acrylate, tetranepentaerythritol nona (meth) acrylate, ginseng (2- (meth) propenyloxyethyl) isotricyanate, ethylene glycol Modified neopentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol hexa (meth) acrylate, propylene glycol modified neopentaerythritol tetra (meth) acrylate, propylene glycol modified Dipentaerythritol hexa (meth) acrylate, caprolactone-modified neopentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate, etc. Preferred examples include dipentaerythritol penta (meth) acrylate and dinepentaerythritol hexa (meth) acrylate.

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

The content of the polymerizable compound (C) in the colored curable composition is preferably 1 to 65% by mass, more preferably 3 to 60% by mass, and 5 to 55% by mass relative to the total amount of the solid content. % Is better.

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 long as it is a compound capable of generating living radicals, acids, and the like by the action of light and heat, and starting polymerization, and a well-known polymerization initiator can be used.

Examples of the polymerization initiator (D) include an O-fluorenyl oxime compound, an alkylphenone compound, a biimidazole compound, and a triimide Compounds and fluorenyl phosphine oxide compounds.

Examples of the O-fluorenyl oxime compound include N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine and N-benzyloxy 1- (4-phenylthiophenyl) octane-1-one-2-imine, N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentyl Propane-1-one-2-imine, N-acetoxy-1- (4-phenylthiophenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetamidine Oxy-1- (4-phenylthiophenyl) -3-cyclohexylpropane-1-one-2-imine, N-ethoxyl-1- [9-ethyl-6- (2- Methylbenzyl) -9H-carbazol-3-yl] ethane-1-imine, N-ethoxy-1--1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,4-dioxolylmethoxy) benzylidene} -9H-carbazol-3-yl] ethane-1-imine, N-acetamidine Oxy-1--1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine and N-benzyl Phenoxy-1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-one-2-imine Wait. As the O-fluorenyl oxime compound, commercially available products such as IRGACURE OXE01, OXE02 (above, manufactured by BASF (stock)), and N-1919 (made by ADEKA (stock)) can also be used. Among them, the O-fluorenyl oxime compound is selected from the group consisting of N-benzyloxy-1- (4-phenylthiophenyl) butane-1-one-2-imine and N-benzyloxy 1- (4-phenylthiophenyl) octane-1-one-2-imine and N-benzyloxy-1- (4-phenylthiophenyl) -3-cyclopentyl At least one of the group consisting of propane-1-one-2-imine is preferred, and N-benzyloxy-1- (4-phenylthiophenyl) octan-1-one-2- Imines are preferred.

Examples of the alkyl phenone compound include 2-methyl-2-morpholinyl-1- (4-methylthiophenyl) propane-1-one and 2-dimethylamino-1- ( 4-morpholinylphenyl) -2-benzylbutane-1-one and 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one and the like. As the alkyl phenone compound, commercially available products such as IRGACURE 369, 907, and 379 (above, manufactured by BASF) can also be used.

Examples of the alkyl phenone compound include 2-hydroxy-2-methyl-1-phenylpropane-1-one and 2-hydroxy-2-methyl-1- [4- (2-hydroxyethyl (Oxy) phenyl] propane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propane-1-one oligomer , Α, α-diethoxyacetophenone and benzyldimethylketal.

Examples of the bisimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole and 2,2'-bis (2,3 -Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (for example, refer to Japanese Patent Application Laid-Open No. 6-75372, Japanese Patent Application Laid-Open No. 6-75373, etc.), 2,2' -Bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'- Tetrakis (alkoxyphenyl) bisimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (dialkoxyphenyl) bisimidazole, 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetrakis (trialkoxyphenyl) bisimidazole (for example, refer to Japanese Patent Publication No. 48-38403, Japanese Patent Publication No. 62 -174204, etc.) and imidazole compounds in which the 4,4 ', 5,5'-position phenyl group is substituted with a carboalkoxy group (for example, refer to Japanese Patent Application Laid-Open No. 7-10913).

As three As a compound, 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-tri , 2,4-bis (trichloromethyl) -6-piperyl-1,3,5-tri , 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl] -1,3,5-tris , 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl] -13,5-tris , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl] -1,3,5-tris And 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) vinyl] -1,3,5-tris Wait.

Examples of the fluorenylphosphine oxide compound include 2,4,6-trimethylbenzylidenediphenylphosphine 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; Phenyl ketone, methyl o-benzoyl benzoate, 4-phenyl diphenyl ketone, 4-benzyl phenyl-4'-methyldiphenyl sulfide, 3,3 ', 4,4' -Tetrakis (third butylperoxycarbonyl) diphenyl ketone and diphenyl ketone compounds such as 2,4,6-trimethyldiphenyl ketone; 9,10-phenanthrenequinone, 2-ethylanthraquinone and Quinone compounds such as camphor quinone; 10-butyl-2-chloroacridone, diphenylbenzil, methyl phenylglyoxylate, and titanocene compounds.

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

The polymerization initiator (D) preferably contains a compound selected from the group consisting of The polymerization initiator of at least one of the group consisting of the compound, the fluorenylphosphine oxide compound, the O-fluorenyl oxime compound, and the bisimidazole compound is preferably a polymerization initiator containing an O-fluorenyl oxime compound.

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

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

    <Polymerization starter (D1)>    

The polymerization initiation aid (D1) is a compound or a sensitizer used to promote polymerization of a polymerizable compound in which polymerization is started by a polymerization initiator. When a polymerization initiator (D1) is contained, it is usually used in combination with a polymerization initiator (D).

Examples of the polymerization initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine, 4, 4'-bis (dimethylamino) diphenyl ketone (commonly known as Michelin), 4,4'-bis (diethylamino) diphenyl ketone, and 4,4'-bis (ethyl) Methylamino) diphenyl ketone and the like are preferably 4,4'-bis (diethylamino) diphenyl ketone. As the amine compound, commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

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

Examples of the thioanthrone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorosulfan Heteranthrone and 1-chloro-4-propoxythioanthrone, etc.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, and methoxyphenylthio Acetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioglycolic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycolic acid And naphthyloxyacetic acid.

When such a polymerization initiation aid (D1) is used, the content of the polymerization initiation aid (D1) in the total amount of the solid components in the color-hardening composition is preferably 0.001 to 30% by mass, more preferably It is 0.01 to 20% by mass.

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-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in a side chain.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (TORAY.DOW CORNING (Co., Ltd.)), KP321 , KP322, KP323, KP324, KP326, KP340, KP341 (made by Shin-Etsu Chemical Industry Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (made by Momentive Performance Materials Japan), etc.

Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples include FLUORAD (registered trademark) FC430, FLUORAD FC431 (made by Sumitomo 3M, Ltd.), MEGAFAC (registered trademark) F142D, MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F177, MEGAFAC F183, MEGAFAC F554, MEGAFAC R30, MEGAFAC RS-718-K (in DIC), EFTOP (registered trademark) EF301, EFTOP EF303, EFTOP EF351, EFTOP EF352 (Mitsubishi Material Electronic Co., Ltd.), SURFLON (registered trademark) S381, SURFLON S382, SURFLON SC101, SURFLON SC105 (made by Asahi Glass), and E5844 (made by DAIKIN FINECHEMICAL Institute).

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

When the leveling agent (F) is contained, its content ratio is usually 0.0005 mass% or more and 1 mass% or less, preferably 0.001 mass% or more and 0.5 mass% or less, and more preferably 0.001 with respect to the total amount of the coloring composition. Mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, 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 made good.

    <Antioxidant>    

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

Examples of the phenol-based antioxidant include IRGANOX 1010 (Irganox 1010: neopentaerythritol [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], BASF ( Stock)), IRGANOX 1076 (Irganox 1076: octadecyl-3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate, BASF (stock)), IRGANOX 1330 (Irganox 1330: 3,3 ', 3 ”, 5,5', 5” -hexa-third-butyl-a, a ', a ”-(mesitylene-2,4,6-triyl) tri-p-cresol , Made by BASF), IRGANOX 3114 (Irganox 3114: 1,3,5-ginseng (3,5-di-third-butyl-4-hydroxybenzyl) -1,3,5-tris -2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF (stock), IRGANOX3790 (Irganox 3790: 1,3,5-ginseng ((4-thirdbutyl-3-hydroxy-2 , 6-xylyl) methyl) -1,3,5-tri -2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF (shares), IRGANOX1035 (Irganox 1035: thiodiethylene ethylbis [3- (3,5-di-third-butyl- 4-hydroxyphenyl) propionate], manufactured by BASF (stock)), IRGANOX1135 (Irganox 1135: phenylpropionic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7- C9 side chain alkyl ester, made from BASF (stock)), IRGANOX 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, made from BASF (stock)), IRGANOX3125 (Irganox 3125, BASF (stock) )), IRGANOX565 (Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ', 5'-di-tert-butylaniline) -1,3,5-tri , Made by BASF), Adekastab AO-80 (Adekastab AO-80: 3,9-bis (2- (3- (3-third-butyl-4-hydroxy-5-methylphenyl)) (Oxy) -1,1-dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, manufactured by ADEKA Co., Ltd.), Sumilizer BHT (Sumilizer BHT, Sumitomo Chemical (stock) system, Sumilizer GA-80 (Sumilizer GA-80, Sumitomo Chemical (stock) system), Sumilizer GS (Sumilizer GS, Sumitomo Chemical (stock) system), Cyanox1790 (Cyanox 1790, CYTEC (stock) system) And VITAMIN E (EISAI (shares) system).

Examples of the phosphorus-based antioxidant include IRGAFOS 168 (Irgafos 168: Phosphite (2,4-di-third-butylphenyl) ester, manufactured by BASF (Stock)), and IRGAFOS 12 (Irgafos 12: See [2-[[2,4,8,10-Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] Amine, made by BASF (stock)), IRGAFOS 38 (Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, BASF (stock )), Adekastab 329K (ADEKA (stock)), Adekastab PEP36 (ADEKA (stock)), Adekastab PEP-8 (ADEKA (stock)), Sandstab P-EPQ (CLARIANT), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (Ultranox 626, manufactured by GE), and Sumilizer GP (Sumilizer GP: 6- [3- (3-third butyl-4- (Hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenzo [d, f] [1.3.2] dioxaphosphacycloheptane) (Sumitomo Chemical Co., Ltd.) and so on.

Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl, and distearyl esters, and [[methylene (3- Dodecylthio) propionate] β-alkyl mercaptopropionate compounds of polyols such as methane.

    <Other ingredients>    

The coloring composition of the present invention may also contain fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and other well-known additives in the technical field as required.

Examples of adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl ginseng (2-methoxyethoxy) silane, and 3-glycidoxypropyl Trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxy ring Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto Propyltrimethoxysilane, 3-hydrothiopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethyl Oxysilane, N-2- (aminoethyl) -3-aminopropylmethyldiethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-amine Propyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.

    <Color filter>    

A color filter can be formed from the colored composition or colored curable composition of the present invention. Examples of the method for forming a colored pattern include a lithography method, an inkjet method, and a printing method. Preferably, a lithography method is used. The lithography method is a method in which the colored curable composition is coated on a substrate and dried to form a colored curable composition layer, and the colored curable composition layer is exposed and developed through a photomask. . In the lithography method, it is preferable that the color-hardening composition contains a polymerization initiator (D). In the lithography method, a colored coating film of a cured product of the colored curable composition layer can be formed without using a photomask and / or without development during exposure. The colored pattern and colored coating film thus formed can be used as the color filter of the present invention.

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

As the substrate, a glass plate, a resin plate, silicon, or an aluminum, silver, silver / copper / palladium alloy thin film, or the like formed on the substrate can be used. On these substrates, another color filter layer, a resin layer, a transistor, and a circuit may be formed.

The formation of pixels of various colors by lithography can be performed under well-known or customary devices and conditions. For example, it can be manufactured as follows.

First, a colored hardening composition is coated on a substrate, and a volatile component such as a solvent is removed by drying (pre-baking) and / or drying under reduced pressure and dried to obtain a smooth colored hardening composition. Floor.

Examples of the coating 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 mask for forming a desired colored pattern. In order to uniformly irradiate the entire exposure surface with parallel light rays and accurately position the photomask and the substrate on which the colored hardening composition layer is formed, a mask aligner and stepper are used. Other exposure devices are preferred.

A colored pattern can be formed on a board | substrate by making a coloring curable composition layer after exposure contact a developing solution and developing. The unexposed portion of the colored curable composition layer can be dissolved in a developing solution and removed by development.

As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide is preferred.

The development method may be any of a puddle method, a dipping method, and a spray method. Furthermore, the substrate can be tilted at any angle during development.

The substrate after development is preferably washed with water.

Further, it is preferable to post-bake the obtained colored pattern.

The aforementioned color filters are used as color filters used in display devices (such as liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging devices, and are particularly used as liquid crystal display devices. Color filters.

[Example]

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and it is needless to say that the present invention can be appropriately modified and implemented within a range suitable for the purpose described above. Any of these is included in the technical scope of the present invention.

In the examples, "%" and "part" indicate mass% and mass parts unless otherwise specified.

In the following synthesis examples, the structure of the compound was confirmed by NMR (JMM-ECA-500; manufactured by JEOL Ltd.) or mass analysis (LC; Model 1200 by Agilent, MASS; Model LC / MSD6130 by Agilent).

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured using the GPC method under the following conditions.

Device: HLC-8120GPC (TOSOH (stock) system)

Column: TSK-GELG2000HXL

Column temperature: 40 ℃

Solvent: Tetrahydrofuran

Flow rate: 1.0mL / min

Analysis sample solid content concentration: 0.001 to 0.01% by mass

Injection volume: 50 μL

Detector: RI

Calibration Standards: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (made by TOSOH)

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

    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 ° C. To this mixture was added 10.1 parts of methyl triflate. The mixture was stirred at 87 ° C for 3 hours. The mixture was stirred at 10 ° C. This mixture was filtered, and the obtained residue was washed 6 times with 433 parts of toluene. This residue was dried under reduced pressure at 60 ° C to obtain 20.8 parts of a compound represented by the formula (I-2).

    <Identification of compound represented by formula (I-2)>    

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

Exact Mass: 514

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

    <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

    [Evaluation of heat resistance]    

The differential scanning calorimetry of the compound obtained in Example 1 was performed using a differential thermogravimetric simultaneous measurement device (TG / DTA6200 manufactured by SII Nano Technology). The amount of sample used for one measurement was 5 mg. The measurement temperature was first started at 45 ° C, and the temperature was raised at a rate of 5 ° C per minute, and the measurement was performed up to 550 ° C. The temperature T ₅ (under nitrogen) at which the weight reduction rate was 5% was obtained in a nitrogen environment. The results are shown in Table 11.

From the results in Table 11, it was found that the compound system of the present invention has high heat resistance.

    Synthesis Example 1    

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen was allowed to flow in an appropriate amount and replaced with a nitrogen atmosphere. 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80 ° C. with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester of acrylic acid, and 3,4-epoxytricycloacrylic acid [5.2.1.0 ^2,6 The mixed solution of 289 parts of decane-9-yl ester and 125 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. On the other hand, a mixed solution prepared by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After the completion of the dropping, the solution was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a 35.0% copolymer (resin B1) solution having a solid content. The weight average molecular weight (Mw) of the obtained resin B1 was 8,800, the degree of dispersion was 2.1, and the solution acid value was 28 mg-KOH / g.

    Synthesis Example 2    

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen was allowed to flow in an appropriate amount and replaced with a nitrogen atmosphere. 257 parts of ethyl lactate was added and heated to 75 ° C while stirring. Next, 81 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, and 3,4-epoxytricyclo acrylate [5.2.1.0 ^{2 , 6]} dec-9-yl ester of 369 parts, 25 parts of ethyl lactate was mixed dropwise spending 5 hours. On the other hand, a mixed solution prepared by dissolving 11 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 162 parts of ethyl lactate was dropped over 5 hours. After the completion of the dropping, after maintaining the same temperature for 5 hours, 95 parts of ethyl lactate was added and cooled to room temperature to obtain a 47.7% copolymer (resin B2) solution with a solid content. The weight average molecular weight (Mw) of the obtained resin B2 was 8100, the degree of dispersion was 1.9, and the acid value of the solution was 53 mg-KOH / g.

    Synthesis Example 3    

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, a suitable amount of nitrogen was allowed to flow and replaced with a nitrogen atmosphere. 371 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ° C. while stirring. Next, 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate, and 3,4-epoxytricycloacrylic acid [5.2.1.0 ^2,6 The mixed solution of 225 parts of a decane-9-yl ester, 81 parts of vinyl toluene (isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate was dropped over 4 hours. On the other hand, a solution obtained by dissolving 30 parts of a polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was dropped over 5 hours. . After the dropping of the initiator solution was completed, the solution was kept at the same temperature for 4 hours, and then cooled to room temperature to obtain a 37.5% copolymer (resin B3) solution with a solid content. The weight average molecular weight (Mw) of the obtained resin B3 was 10600, the degree of dispersion was 2.01, and the solution acid value was 43 mg-KOH / g.

    Synthesis Example 4    

In a flask equipped with a reflux cooler, a dropping funnel, and a stirrer, nitrogen was flowed in an appropriate amount and replaced with a nitrogen atmosphere. 54 parts of ethyl lactate and 141 parts of propylene glycol monomethyl ether acetate were added, and heated to 85 ° C while stirring. until. Next, 35 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl ester of acrylic acid, and 3,4-epoxytricyclic acrylic acid [5.2.1.0 ^2,6 ] A mixed solution of 23 parts of a mixture of decane-9-yl esters, 161 parts of cyclohexyl cis butene diimide, 12 parts of 2-hydroxyethyl methacrylate, and 493 parts of propylene glycol monomethyl ether acetate costs 5 Hours dripping. On the other hand, a solution prepared by dissolving 3 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 78 parts of propylene glycol monomethyl ether acetate was dropped over 6 hours. After completion of the dropping, the solution was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a 24.4% copolymer (resin B4) solution with a solid content. The weight average molecular weight (Mw) of the obtained resin B4 was 8,400, the degree of dispersion was 2.1, and the solution acid value was 26 mg-KOH / g.

    [Measurement of film thickness]    

The film thickness was measured using DEKTAK3 (manufactured by Japan Vacuum Technology Co., Ltd.).

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

Resin: methacrylic acid / benzyl methacrylate (molar ratio: 30/70) copolymer (manufactured by Taoka Chemical Industry Co., Ltd., weight average molecular weight)

(Mw) 10700, acid value 70-mgKOH / g) 40 parts of 33.8% propylene glycol monomethyl ether acetate solution; polymerizable compound: dineopentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; Japanese chemical medicine ( Stock)) 5.8 parts; polymerization initiator: N-benzyloxy-1- (4-phenylthiophenyl) octane-1-one-2-imine (IRGACURE (registered trademark) OXE01; 0.58 parts by BASF Japan; leveling agent: 0.010 parts of polyether modified silicone oil (Toray Silicone SH8400; manufactured by TORAY. DOW CORNING); solvent: 47 parts of propylene glycol monomethyl ether; solvent: propylene glycol monomethyl ether 6.8 parts of ether acetate was mixed to obtain a sublimation test resin composition (SJS).

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

The resin composition (SJS) for a sublimation test obtained as described above was applied to a 2-inch-square glass substrate (EAGLE XG; manufactured by Corning) using a spin coating method, and the conditions were applied at 100 ° C for 3 minutes. Volatile components are volatile. After cooling, light was irradiated using an exposure machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) under an atmospheric environment at an exposure amount of 150 mJ / cm ² (based on a 365 nm). It heated at 220 degreeC in the oven for 2 hours, and formed the resin coating film (SJSM) for sublimation test (film thickness 2.2 micrometers).

    Example 2    

Colorant (A): 14 parts of the compound represented by formula (I-2); resin (B): 480 parts of resin B1 solution; solvent (E): 6.2 parts of propylene glycol monomethyl ether acetate; solvent (E): 500 parts of N-methyl-2-pyrrolidone; and 0.063 parts of a surfactant: polyether-modified silicone oil (Toray Silicone SH8400; manufactured by TORAY. DOW CORNING) were mixed to obtain a coloring composition 1.

    Example 3    

Colorant (A): 36 parts of the compound represented by formula (I-14); resin (B): 410 parts of resin B1 solution; solvent (E): 6.2 parts of propylene glycol monomethyl ether acetate; solvent (E): 540 parts of N-methyl-2-pyrrolidone; and a surfactant: 0.063 parts of polyether-modified silicone oil (Toray Silicone SH8400; manufactured by TORAY. DOW CORNING) were mixed to obtain a coloring composition 2.

    Example 4    

Colorant (A): 10 parts of the compound represented by formula (I-14); resin (B): 97 parts of resin B2 solution; solvent (E): 180 parts of N-methyl-2-pyrrolidone; solvent ( E): 26 parts of 4-hydroxy-4-methyl-2-pentanone; solvent (E): 2.0 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether-modified silicone oil (Toray Silicone SH8400 ; TORAY.DOW CORNING (products) 0.020 parts were mixed to obtain a colored composition 3.

    Example 5    

Colorant (A): 10 parts of the compound represented by formula (I-14), 10 parts of dispersant (BYK-LPN21324; manufactured by BYK-Chemie. Japan Co., Ltd.), and resin (B): 11 parts of resin B1 solution And solvent (E): 100 parts of a coloring composition obtained by mixing 160 parts of propylene glycol monomethyl ether acetate and dispersing the compound represented by formula (I-14) using a bead mill; resin (B): resin 55 parts of B1 solution; solvent (E): 3.6 parts of propylene glycol monomethyl ether acetate; and surfactant: polyether modified silicone oil (Toray Silicone SH8400; TORAY. DOW CORNING (shares)) 0.010 parts mixed and mixed A colored composition 4 was obtained.

    Comparative Example 1    

Colorant (A): 611 parts of coumarin; resin (B): 350 parts of resin B2 solution; solvent (E): 6.2 parts of propylene glycol monomethyl ether acetate; solvent (E): N, N-dimethylformate 630 parts of methylformamide; and 0.063 parts of a surfactant: polyether-modified silicone oil (Toray Silicone SH8400; manufactured by TORAY. DOW CORNING (stock)) were mixed to obtain a colored composition 5.

    [Sublimation Assessment]         Example 6    

The colored composition 1 was applied on a 2-inch square glass substrate (EAGLE XG; manufactured by Corning) using a spin coating method, and then prebaked at 100 ° C for 3 minutes to form a colored composition layer. The film thickness was measured using DEKTAK3 (manufactured by Japan Vacuum Technology Co., Ltd.). This colored coating film and the resin coating film for sublimation test (SJSM) obtained above were opposed to each other with a space of 70 μm, and post-baked at 220 ° C. for 40 minutes. The color difference (ΔEab *) before and after heating of the resin coating film (SJSM) for sublimation test was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). When the color difference (ΔEab *) is 5.0 or more, it means that the colorant has sublimability. The results are shown in Table 12. In Table 12, ○ indicates that the colorant does not have sublimability, and X indicates that the colorant has sublimability.

    Example 7    

Sublimation properties were 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    

Sublimation properties were 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    

Sublimation properties were 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 properties were evaluated 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 can reduce the sublimation of the colorant.

    Example 10    

Colorant (A): 100 parts of the compound represented by the formula (I-14), 130 parts of a dispersant (BYK-LPN21324; BYK-Chemie. Japan Co., Ltd.), and 170 parts of resin (B): resin B4 solution And solvent (E): 380 parts of a coloring composition obtained by mixing 610 parts of propylene glycol monomethyl ether acetate and dispersing the compound represented by formula (I-14) using a bead mill; colorant (A) : 18 parts of CI Pigment Yellow 138 (pigment), 7.6 parts of dispersant, 7.6 parts of resin, and solvent (E): 120 parts of propylene glycol monomethyl ether acetate mixed and pigment dispersed using a bead mill Total amount; colorant (A): 4.2 parts of a compound represented by the following formula (manufactured using the method described in Japanese Patent Application Laid-Open No. 2013-235257);

Resin (B): 21 parts of resin B3 solution; Polymerizable compound (C): Polymerizable compound (A9550; Shin Nakamura Chemical Industry Co., Ltd.) 25 parts; Polymerization initiator (D): Compound represented by the following formula (Changzhou Qiangli Electronic New Material Co., Ltd.) 6.6 copies;

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone; Solvent (E): 250 parts of propylene glycol monomethyl ether acetate; and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; TORAY. DOW CORNING (made by Co., Ltd.) 0.075 parts were mixed to obtain a colored hardening composition 1.

    [Manufacture of colored patterns]    

The colored curable composition 1 was applied on a 2-inch square glass substrate (EAGLE XG; manufactured by Corning) using a spin coating method, and then prebaked at 100 ° C for 3 minutes to form a colored curable composition layer. After cooling, the distance between the substrate on which the color-hardening composition layer was formed and the mask made of quartz glass was set to 200 μm, and an exposure machine (TME-150RSK; manufactured by TOPCON) was used at 80 mJ / cm in an atmospheric environment. Exposure was performed at an exposure amount of ² (based on 365 nm). As the photomask, a 100 μm line and gap pattern was used. The colored hardening composition layer after exposure was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for 70 seconds for development, and washed with water. This colored coating film was post-baked at 230 ° C for 30 minutes to obtain a colored pattern.

    [Sublimation Assessment]    

The colored curable composition 1 was applied on a 2-inch square glass substrate (EAGLE XG; manufactured by Corning) using a spin coating method, and then prebaked 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 machine (TME-150RSK; manufactured by TOPCON Co., Ltd.) at an exposure amount (based on 365 nm) of 80 mJ / cm ² in an atmospheric environment. The colored hardening composition layer after exposure was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C for 70 seconds to develop, and washed with water. The film thickness was measured using DEKTAK3 (manufactured by Japan Vacuum Technology Co., Ltd.).

This colored coating film and the resin coating film for sublimation test (SJSM) obtained above were opposed to each other with a space of 70 μm, and post-baked at 220 ° C. for 40 minutes.

The color difference (ΔEab *) before and after heating of the resin coating film (SJSM) for sublimation test was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS). When the color difference (ΔEab *) is 5.0 or more, it means that the colorant has sublimability. The results are shown in Table 13. In Table 13, ○ indicates that the colorant does not have sublimability, and X indicates that the colorant has sublimability.

    Example 11    

Colorant (A): 100 parts of the compound represented by the formula (I-14), 130 parts of a dispersant (BYK-LPN21324; BYK-Chemie. Japan), resin (B): 170 parts of resin B4 solution And solvent (E): 340 parts of a coloring composition obtained by mixing 610 parts of propylene glycol monomethyl ether acetate and dispersing the compound represented by formula (I-14) using a bead mill; colorant (A) : 18 parts of CI Pigment Yellow 138 (pigment), 7.6 parts of dispersant, 7.6 parts of resin, and solvent (E): 120 parts of propylene glycol monomethyl ether acetate mixed and pigment dispersed using a bead mill The total amount of colorant (A): 7.8 parts of a compound represented by the following formula (made using the method described in Japanese Patent Application Laid-Open No. 2013-235257);

Resin (B): 27 parts of resin B3 solution; polymerizable compound (C): polymerizable compound (A9550; Shin Nakamura Chemical Industry Co., Ltd.) 26 parts; polymerization initiator (D): compound represented by the following formula (Changzhou Qiangli Electronic New Material Co., Ltd.) 6.8 copies;

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone; Solvent (E): 270 parts of propylene glycol monomethyl ether acetate; and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; TORAY.DOW CORNING (made by Co., Ltd.) 0.075 parts were mixed to obtain a colored hardening composition 2.

Except having changed the coloring curable composition 1 into the coloring curable composition 2, it carried out similarly to Example 10, and produced the coloring pattern and evaluated the sublimability. The results of the sublimation evaluation are shown in Table 13.

    Example 12    

Colorant (A): 100 parts of the compound represented by the formula (I-14), 130 parts of a dispersant (BYK-LPN21324; BYK-Chemie. Japan Co., Ltd.), and 170 parts of resin (B): resin B4 solution And solvent (E): 290 parts of a coloring composition obtained by mixing 610 parts of propylene glycol monomethyl ether acetate and dispersing the compound represented by formula (I-14) using a bead mill; colorant (A) : 23 parts of CI Pigment Yellow 138 (pigment), 9.6 parts of dispersant, 9.6 parts of resin, and solvent (E): 150 parts of propylene glycol monomethyl ether acetate mixed and pigment dispersed using a bead mill The total amount of colorant (A): 5.1 parts of a compound represented by the following formula (made using the method described in Japanese Patent Application Laid-Open No. 2013-235257);

Resin (B): 31 parts of resin B3 solution; polymerizable compound (C): polymerizable compound (A9550; Shin Nakamura Chemical Industry Co., Ltd.) 27 parts; polymerization initiator (D): compound represented by the following formula (Changzhou Qiangli Electronic New Materials Co., Ltd.) 7.2 copies;

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone; Solvent (E): 280 parts of propylene glycol monomethyl ether acetate; and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; TORAY. DOW CORNING (made by Co., Ltd.) 0.075 parts were mixed to obtain a colored hardening composition 3.

Except having changed the coloring curable composition 1 into the coloring curable composition 3, it carried out similarly to Example 10, and produced the coloring pattern and evaluated the sublimability. The results of the sublimation evaluation are shown in Table 13.

    Example 13    

Colorant (A): 100 parts of the compound represented by the formula (I-14), 130 parts of a dispersant (BYK-LPN21324; BYK-Chemie. Japan), resin (B): 170 parts of resin B4 solution And solvent (E): 270 parts of a coloring composition obtained by mixing 610 parts of propylene glycol monomethyl ether acetate and dispersing the compound represented by formula (I-14) using a bead mill; colorant (A) : 23 parts of CI Pigment Yellow 138 (pigment), 9.6 parts of dispersant, 9.6 parts of resin, and solvent (E): 150 parts of propylene glycol monomethyl ether acetate mixed and pigment dispersed using a bead mill 7.4 parts of a compound represented by the following formula (made using the method described in Japanese Patent Application Laid-Open No. 2013-235257);

Resin (B): 35 parts of resin B3 solution; polymerizable compound (C): polymerizable compound (A9550; Shin Nakamura Chemical Industry Co., Ltd.) 27 parts; polymerization initiator (D): compound represented by the following formula (Changzhou Qiangli Electronic New Materials Co., Ltd.) 7.3 copies;

Solvent (E): 170 parts of 4-hydroxy-4-methyl-2-pentanone; Solvent (E): 290 parts of propylene glycol monomethyl ether acetate; and Surfactant: Polyether-modified silicone oil (Toray Silicone SH8400; TORAY. DOW CORNING (manufactured) 0.075 parts were mixed to obtain a colored hardening composition 4.

Except having changed the coloring curable composition 1 into the coloring curable composition 4, it carried out similarly to Example 10, and produced the coloring pattern and evaluated the sublimability. The results of the sublimation evaluation are shown in Table 13.

    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), and a colored pattern was produced and evaluated for sublimation properties . The results of the sublimation evaluation are shown in Table 13.

    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 a compound represented by the formula (I-2), and a colored pattern was produced and evaluated for sublimability. . The results of the sublimation evaluation are shown in Table 13.

    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, and a colored pattern was produced and evaluated for sublimability. The results of the sublimation evaluation are shown in Table 13.

    Comparative Example 4    

A colored curable composition 8 was obtained in the same manner as in Example 13 except that the compound represented by formula (I-14) was changed to coumarin 6, and a colored pattern was produced and evaluated for sublimability. The results of the sublimation evaluation are shown in Table 13.

From the results described above, it was found that the colored curable composition containing the compound of the present invention reduces the sublimation of the colorant.

    [Possibility of industrial use]    

The colored composition and colored curable composition of the present invention can reduce the sublimability of the colorant, and are suitable for use in display devices such as color filters and liquid crystal display devices.

Claims (14)

A coloring composition containing a compound represented by formula (I) and a resin, In formula (I), R ^N1 and R ^N2 each independently represent an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, and R ^N3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or may have A heterocyclic group of a substituent, R ¹ to R ⁸ each 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 carbons which may have a substituent, or a heterocyclic group which may have a substituent, R ¹⁰¹ represents a hydrocarbon group having 1 to 40 carbons which may have a substituent or a heterocyclic group having substituents, and R ¹⁰² represents a hydrogen atom, a hydrocarbon group which may have 1 to 40 carbons which may have a substituent or may have a substituent For heterocyclic groups, M represents a hydrogen atom or an alkali metal atom, and when there are a plurality of R ¹⁰¹ , R ¹⁰² and M, these may be the same or different. A ^g- represents an anion having a valence of g and g represents 1 Integer to 14. The coloring composition according to item 1 of the scope of patent application, 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 an essential element , Or a fluorine-containing anion. The colored composition according to item 1 or 2 of the scope of patent application, wherein A ^g- is an anion containing at least one element selected from the group consisting of tungsten and phosphorus and oxygen as an essential element, or Fluoride anion. The coloring composition according to any one of claims 1 to 3, wherein A ^g- is a component containing at least one element selected from the group consisting of tungsten and phosphorus, and oxygen as essential elements. Anion. The coloring composition according to any one of claims 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.     The coloring composition according to any one of claims 1 to 5, further comprising a solvent.         The coloring composition according to any one of claims 1 to 6 of the scope of patent application, further comprising a yellow colorant, an orange colorant, or a red colorant.         A coloring curable composition containing the coloring composition according to any one of claims 1 to 7 and a polymerizable compound.         The colored hardening composition as described in claim 8 of the patent application range further contains a polymerization initiator.         A color filter is formed of the coloring composition described in any one of claims 1 to 7 or the color-curing composition described in any one of claims 8 or 9.         A liquid crystal display device includes a color filter as described in claim 10 of the scope of patent application.     A compound represented by formula (IB), In formula (IB), R ^N1 and R ^N2 each independently represent an aliphatic hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, and R ^N3 represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or may have A heterocyclic group of a substituent, R ¹ to R ⁸ each 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 carbons which may have a substituent, or a heterocyclic group which may have a substituent, R ¹⁰¹ represents a hydrocarbon group having 1 to 40 carbons which may have a substituent or a heterocyclic group having substituents, and R ¹⁰² represents a hydrogen atom, a hydrocarbon group which may have 1 to 40 carbons which may have a substituent or may have a substituent In the heterocyclic group, M represents a hydrogen atom or an alkali metal atom, and when there are a plurality of R ¹⁰¹ , R ¹⁰² and M, these may be the same or different. B ^h- represents that it will be selected from tungsten, molybdenum, silicon, And at least one element of the group consisting of phosphorus and oxygen as essential elements Containing monovalent anion of h, h represents an integer of lines 1 to 14. The compound according to item 12 of the scope of patent application, 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. The compound according to claim 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.