KR20170091525A - Compound and coloring composition - Google Patents

Abstract

Provided is a novel coloring composition used in color filters. To this end, the coloring composition contains a compound represented by chemical formula (I) and a resin.

Description

COMPOUND AND COLORING COMPOSITION [0001]

The present invention relates to compounds and coloring compositions.

As yellow pigments, for example, C.I. Pigment Yellow 139 and the like are known, and they are used for color display by using reflected light or transmitted light in the fields of printing ink, paint and the like.

The gist of the present invention is as follows:

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

[In the formula (I), L ¹ represents -CO- or -SO ₂ -.

R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , _{^{SO 2 N (R 102) 2}} , -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102 ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ independently represent 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 of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

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

The broken line represents E-form or Z-form.]

[2] The coloring composition according to [1], wherein the compound represented by formula (I) is a compound represented by formula (I-a).

[In the formula (Ia), L ¹ , R ¹¹ , R ¹ to R ⁵ and the broken line have the same meanings as defined above.

L ² represents -CO- or -SO ₂ -.

R ¹⁴ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

[3] The coloring composition according to [2], wherein R ¹¹ and R ¹⁴ are the same group, and L ¹ and L ² are the same group.

[4] The compound according to [1], wherein R ¹¹ and R ¹⁴ are each independently selected from the group consisting of an alkyl group having 1 to 40 carbon atoms which may have a substituent, a phenyl group which may have a substituent, a naphthyl group which may have a substituent or a tetrahydronaphthyl group , A thienyl group optionally having a substituent, a furyl group optionally having a substituent or a pyridinyl group optionally having a substituent (s).

[5] The coloring composition according to [1], wherein the compound represented by formula (I) is a compound represented by formula (I-b).

[In the formula (Ib), L ¹ , R ¹¹ , R ¹ to R ⁵ and the broken line have the same meanings as defined above.

R < ²⁰ > and R < ³⁰ > are combined to form a ring Q.

The ring Q may have a substituent, is a ring having 5 to 7 constituent atoms of the ring, and the ring Q may be a hydrocarbon ring or a heterocyclic ring. The ring Q may be bonded to a monocyclic ring having 5 to 7 ring atoms constituting a ring or condensed with a monocyclic ring thereof selected from a hydrocarbon ring and a heterocyclic ring.]

[6] The coloring composition according to [5], wherein the compound represented by formula (I) is a compound represented by formula (I-c).

[In the formula (Ic), L ¹ , R ¹¹ , R ¹ to R ⁵ and the broken line have the same meanings as defined above.

R ⁶ and R ⁷ are, independently, a hydrogen ^{atom, -CO-R 102, -COO-} R 101, -OCO-R 102, -OR 102, -SO 2 -R 101, -SO 2 N (R 102 together ^{_{) 2, -CON (R 102)}} 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102) 2, a halogen atom, A cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

R ¹⁰¹ , R ¹⁰² and M have the same meanings as defined above.

[7] The coloring composition according to any one of [1] to [6], wherein R ¹ is a hydrogen atom and R ² to R ⁵ are each independently a hydrogen atom or a nitro group.

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

[9] A color filter formed from the colored curable resin composition according to [8].

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

[11] A compound represented by the formula (II).

Wherein R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-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} , which may have a substituent may have a hydrocarbon group or substituent of 1 to 40 carbon atoms which heterocyclic group .

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ independently represent 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 of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

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

The broken line represents E-form or Z-form.]

[12] A compound represented by the formula (II-a1).

Wherein R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ - _{^{R 101, -SO 2 N (R}} 102) 2, -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, - OCON (R ¹⁰² ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

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

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

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹¹ represents a heterocyclic ring which may have a substituent or a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent. However, R ¹¹¹ is a carbon number of 1 to 40 hydrocarbon group which may have a substituent, R ¹² and R ¹³ is either one of the -SO ₂ -R ^111, also R ¹² and R ¹³ of the another one cyano group , At least one of R ² to R ⁵ is -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-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 Nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

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

The broken line represents E-form or Z-form.]

[13] The compound according to [12], wherein R ¹¹¹ is a heterocyclic ring which may have a substituent.

[14] A compound represented by the formula (I-b).

[In the formula (Ib), L ¹ represents -CO- or -SO ₂ -.

R < ²⁰ > and R < ³⁰ > are combined to form a ring Q.

The ring Q may have a substituent, is a ring having 5 to 7 constituent atoms of the ring, and the ring Q may be a hydrocarbon ring or a heterocyclic ring. The ring Q may be bonded to a monocyclic ring having 5 to 7 constituent atoms of the ring, or a condensed ring thereof, selected from a hydrocarbon ring and a heterocyclic ring.

R ¹ ~ R ⁵ are, independently, a hydrogen ^{atom, -CO-R 102, -COO-} R 101, -OCO-R 102, -OR 102, -SO 2 -R 101, -SO 2 N (R 102 together ^{_{) 2, -CON (R 102)}} 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102) 2, a halogen atom, A cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

R ² and R ³ , R ³ and R ^4, and R ⁴ and R ⁵ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ independently represent a hydrocarbon ring of 1 to 40 carbon atoms which may have a substituent or a heterocyclic ring which may have a substituent.

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

M represents a hydrogen atom or an alkali metal atom.

When a plurality of R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different. The broken line represents E-form or Z-form.]

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

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

The compound (I) can be used as a coloring agent.

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

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

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

The colorant (A1) preferably contains a yellow colorant or a green colorant.

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

The colored curable resin composition of the present invention includes a polymerizable compound (C) and a polymerization initiator (D) in addition to the compound represented by the formula (I) and the resin.

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

The coloring composition and the colored curable resin composition of the present invention may further contain a leveling material (F) and an antioxidant.

The coloring composition and the colored curable resin composition of the present invention can produce a color filter having a low retardation value from the color filter formed from the colored curable resin composition containing C.I. Pigment Yellow 185. [

≪ Compound (I) >

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

[In the formula (I), L ¹ represents -CO- or -SO ₂ -.

R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , _{^{SO 2 N (R 102) 2}} , -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102 ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.

R ¹¹ and R ¹⁰¹ independently represent 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 of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

M represents a hydrogen atom or an alkali metal atom.

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

The broken line represents E-form or Z-form.]

L ¹ is preferably -CO-.

In the compound ^{(I), R 1 ~ R} 5 and R ¹² ~ R ^13, independently, a hydrogen ^{atom, -CO-R 102, -COO-} R 101, -OCO-R 102, -OR 102 with each other, - _{^{SO 2 -R 101, -SO 2 N}} (R 102) 2, -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

The number of carbon atoms of the hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² is 1 to 40, preferably 1 to 30, more preferably 1 to 20, Is from 1 to 15, more preferably from 1 to 10.

The hydrocarbon group having 1 to 40 carbon atoms represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may} be an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and the aliphatic hydrocarbon group may be saturated or unsaturated, Chain or alicyclic.

^Examples of the saturated or unsaturated chain hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, (2-methyl) propyl group, isobutyl group, sec-butyl group, sec-butyl group, sec-butyl group, sec-butyl group, sec-butyl group, sec-butyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, heptadecyl group, octadecyl group and eicosyl group; (1-methyl) pentyl group, (2-methyl) pentyl group, (1-ethylbutyl group), Branched chain alkyl group such as pentyl group, (3-ethyl) pentyl group, isohexyl group, (5-methyl) hexyl group, (1- (2-butenyl), 1-propenyl, 2-propenyl (allyl), isopropenyl, Propenyl)) ethenyl group, (1,2-dimethyl) propenyl group and 2-pentenyl group, etc .; Can. The number of carbon atoms of the saturated or unsaturated chain hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, still more preferably 1 to 15, still more preferably 1 to 10, Preferably 1 to 8, and particularly preferably 1 to 5. Among them, a linear or branched alkyl group having 1 to 8 carbon atoms is particularly preferable.

^Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² include a cyclopropyl group, a 1-methylcyclopropyl group, a cyclobutyl group, Cyclohexyl group, cyclohexyl group, cycloheptyl group, 1-methylcyclohexyl group, 2-methylcyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 1,2-dimethylcyclohexyl group, A cyclohexyl group, a 1,4-dimethylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 2,4-dimethylcyclohexyl group, a 2,5-dimethylcyclohexyl group, a 2,6-dimethylcyclohexyl group, Dimethyl cyclohexyl group, 3,5-dimethylcyclohexyl group, 2,2-dimethylcyclohexyl group, 3,3-dimethylcyclohexyl group, 4,4-dimethylcyclohexyl group, cyclooctyl group, 4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group and 3,3,5,5-tetramethylcyclohexyl group, 4-pentylcyclohexyl group, 4-octylcyclohexyl group , 4-cyclohexenedicyclohexyl Cycloalkyl group such as a group; Cycloalkenyl groups such as cyclohexenyl group (for example, cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl group and cyclooctenyl group; Norbornane group, adamantyl group, bicyclo [2.2.2] octane, and the like. The number of carbon atoms of the alicyclic hydrocarbon group is preferably from 3 to 30, more preferably from 3 to 20, still more preferably from 4 to 20, still more preferably from 4 to 15, 5 to 15, and particularly preferably 5 to 10. Among them, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group are particularly preferable.

The saturated or unsaturated hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may} be a combination of the above-described hydrocarbon groups, and examples thereof include a cyclopropylmethyl group, , An alkyl group having at least one alicyclic hydrocarbon group bonded thereto such as a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, and a cyclohexylethyl group, and the number of carbon atoms thereof is preferably 4 to 30 More preferably 4 to 20, and even more preferably 4 to 15.

^Examples of the aromatic hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² include a phenyl group, o-tolyl group, m-tolyl group, p- , 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 4-vinylphenyl, o- Propylphenyl group, a 4-pentylphenyl group, a 2-ethylphenyl group, a 2-methylphenyl group, a 2-methylphenyl group, a 2-methylphenyl group, A 4-vinylphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 5,6,7-cyclohexylphenyl group, a 2,4,6-trimethylphenyl group, , Aromatic hydrocarbon groups such as 8-tetrahydro-1-naphthyl group, 5,6,7,8-tetrahydro-2-naphthyl group, fluorenyl group, phenanthryl group and anthryl group.

The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 15.

The aromatic hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ^{102 may} be a combination of the above-described hydrocarbon groups and may be a benzyl group, a phenethyl group, a 1-methyl- Aralkyl groups such as methyl group; An arylalkenyl group such as a phenylethynyl group, a phenyl group to which at least one phenyl group is bonded, such as a biphenylyl group or a terphenyl group, a cyclohexylmethylphenyl group, a benzylphenyl group, (Dimethyl (phenyl) methyl) phenyl group; , And the number of carbon atoms thereof is preferably from 4 to 30, more preferably from 4 to 20, and still more preferably from 4 to 15.

The hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have a substituent. The substituent may be monovalent or divalent. It is preferable that the divalent substituent binds two carbon atoms to the same carbon atom to form a double bond.

As the monovalent substituent,

Butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, (2-ethyl) hexyloxy group, heptyloxy group, heptyloxy group, isobutyloxy group, An oxy group bonded to one side of a hydrocarbon group having 1 to 10 carbon atoms such as a methoxy group, an isopropoxy group, a heptyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a phenyloxy group, and an o-tolyloxy group;

An alkylsulfanyl group having 1 to 10 carbon atoms such as methylthio group, ethylthio group, propylthio group and butylthio group;

Formyl group;

The number of carbon atoms in the alkyl group is preferably 1 or less, more preferably 1 to 3, more preferably 1 to 3, more preferably 1 to 3, more preferably 1 to 3, more preferably 1 to 3, more preferably 1 to 3, and most preferably 1 to 3, A carbonyl group bonded with a hydrocarbon group having 1 to 12 carbon atoms;

(2-ethyl) hexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, nonyloxycarbonyl group, octyloxycarbonyl group, butoxycarbonyl group, butoxycarbonyl group, butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group, , An oxycarbonyl group to which a hydrocarbon group having 1 to 10 carbon atoms such as a phenyloxycarbonyl group and an o-tolyloxycarbonyl group is bonded;

An amino group;

N, N-diisopropylamino, N, N-diisopropylamino, N, N-diisopropylamino, N, N-diisopropylamino, N, Butylamino group, an N, N-di-sec-butylamino group, an N, N-diisobutylamino group, (1-ethylpropyl) amino group, N, N-di (1-ethylpropyl) amino group , N-heptylamino group, N, N-dihexylamino group, N, N-dihexylamino group, An N, N-dimethylamino group, an N, N-ethylmethylamino group, an N, N-dimethylamino group, an N, N-dialkylamino group, -Propylmethylamino group, N, N-isopropylmethylamino group, N, N-butylmethyl Amino group, N, N-tert- butyl-methyl-amino group and N, N- phenyl by one or two of 1 to 10 carbon atoms substituted with an amino group of a hydrocarbon group such as a methyl group;

Sulfamoyl group;

An N, N-dimethylsulfamoyl group, an N, N-dimethylsulfamoyl group, an N, N-dimethylsulfamoyl group, An N, N-diisopropylsulfamoyl group, an N, N-diisopropylsulfamoyl group, an N-butylsulfamoyl group, an N, Butylsulfamoyl group, N, N-di-tert-butylsulfamoyl group, N-sec-butylsulfamoyl group, N, N, N-di (1-ethylpropyl) sulfamoyl group, N-hexylsulfamoyl group, N, N-diphenylsulfamoyl group, N- (2-ethyl) hexylsulfamoyl group, N-heptylsulfamoyl group, N, N-diheptylsulfamoyl group, N An N, N-dinoylsulfamoyl group, an N-phenylsulfamoyl group, an N, N-dioctylsulfamoyl group, an N, N-octylsulfamoyl group, N-diphenylsulfone N, N-tert-butylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-diethylsulfamoyl group, A sulfamoyl group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms such as a butylmethylsulfamoyl group and an N, N-phenylmethylsulfamoyl group;

Formylamino group; (2-ethyl) hexanoylamino group, heptanoylamino group, octanoylamino group, octanoylamino group, octanoylamino group, octanoylamino group, acetylamino group, propanoylamino group, butanoylamino group, 2,2-dimethylpropanoylamino group, pentanoylamino group, hexanoylamino group, An amino group substituted with a carbonyl group in which a hydrocarbon group having 1 to 12 carbon atoms is bonded such as an amino group, a decanoylamino group, an undecanoylamino group, a dodecanoylamino group, a hecinoconoylamino group, or a benzoylamino group;

A hydroxyl group;

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

A carboxyl group, a sulfo group, a nitro group, a cyano group, -SO ₃ M, -CO ₂ M;

Formyloxy group; (2-ethyl) hexanoyloxy group, heptanoyloxy group, octanoyloxy group, naphthoyloxy group, propanoyloxy group, butanoyloxy group, 2,2- A carbonyloxy group bonded with a hydrocarbon group having 1 to 10 carbon atoms such as a nioyloxy group and a benzoyloxy group;

(2-ethyl) hexylsulfonyl, heptylsulfonyl, octylsulfonyl, nonylsulfonyl, decylsulfonyl, phenylsulfonyl, phenylsulfonyl, A sulfonyl group substituted with a hydrocarbon group having 1 to 10 carbon atoms such as a sulfonyl group and a p-tolylsulfonyl group;

Carbamoyl group;

An N, N-dimethylcarbamoyl group, an N-ethylcarbamoyl group, an N, N-diethylcarbamoyl group, an N-propylcarbamoyl group, An N, N-diisopropylcarbamoyl group, an N, N-diisopropylcarbamoyl group, an N, N-dibutylcarbamoyl group, Butylcarbamoyl group, N, N-di-tert-butylcarbamoyl group, N-sec-butylcarbamoyl group, N, (1-ethylpropyl) carbamoyl group, an N-hexylcarbamoyl group, an N, N-diethylcarbamoyl group, (2-ethyl) hexylcarbamoyl group, an N-heptylcarbamoyl group, an N, N-diheptylcarbamoyl group, An N-octylcarbamoyl group, an N, N-dioctylcarbamoyl group, an N-nonylcarbamoyl group, an N, A carbamoyl group, a carbamoyl group, a carbamoyl group, a carbamoyl group, a carbamoyl group, a carbamoyl group, a carbamoyl group, a carbamoyl group, a carbamoyl group, , Carbamoyl groups substituted with one or two hydrocarbon groups of 1 to 10 carbon atoms such as N, N-butylmethylcarbamoyl, N, N-tert-butylmethylcarbamoyl and N, diary;

A perfluorohexyl group, a perfluoroheptyl group, a perfluorohexyl group, a perfluorohexyl group, a perfluorohexyl group, a perfluorohexyl group, a perfluorohexyl group, a perfluorohexyl group, An octyl group, a perfluorononyl group, a perfluorodecyl group, a perfluorocyclohexyl group, a perfluorophenyl group,

A perfluorohexylmethyl group, a perfluorooctylmethyl group, a perfluorooctylmethyl group, a perfluorohexylmethyl group, a perfluorohexylmethyl group, a perfluorohexylmethyl group, a perfluorohexylmethyl group, a perfluorohexylmethyl group, a perfluorohexylmethyl group, A rurononylmethyl group;

A fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms such as a 2-fluorophenyl group, a 3-fluorophenyl group, a 4-fluorophenyl group, and a 2,4,6-trifluorophenyl group;

-CO-SH, -CO-S- CH 3, -CO-S-CH 2 CH 3, -CO-S-CH 2 -CH 2 -CH 3, -CO-S-CH 2 -CH 2 -CH 2 and the like; in combination with a sulfur atom bonded with an alkyl group having 2 to 10 carbon atoms, such as -CH ₃ group, -CO-SC ₆ H _5, such as a carbonyl group bonded with an aryl group and a sulfur atom bonded with a carbon number of 7-20.

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

As the substituent of the hydrocarbon group having 1 to 40 carbon atoms,

An oxy group bonded to one side by a hydrocarbon group having 1 to 10 carbon atoms;

A carbonyl group bonded with a hydrocarbon group having 1 to 12 carbon atoms;

An oxycarbonyl group bonded with a hydrocarbon group of 1 to 10 carbon atoms;

An amino group;

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

Sulfamoyl group;

A sulfamoyl group substituted with one or two hydrocarbon groups having 1 to 10 carbon atoms;

An amino group substituted with a carbonyl group bonded with a hydrocarbon group having 1 to 12 carbon atoms;

A hydroxyl group;

Fluorine atom, chlorine atom, bromine atom;

A carboxy group;

Sulfo group;

A nitro group;

Cyano;

A carbonyloxy group bonded with a hydrocarbon group of 1 to 10 carbon atoms;

A sulfonyl group bonded with a hydrocarbon group of 1 to 10 carbon atoms;

Carbamoyl group;

A carbamoyl group substituted with one or two hydrocarbon groups of 1 to 10 carbon atoms;

A fluorine-substituted hydrocarbon group having 1 to 10 carbon atoms;

An oxo group;

-SO ₃ M;

-CO ₂ M;

.

The heterocyclic group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may be either monocyclic or multicyclic, preferably a heterocyclic ring containing a hetero atom to be. Examples of the heteroatom include a nitrogen atom, an oxygen atom and a sulfur atom. Specific examples of the heterocyclic group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² include rings represented by the following formulas. The carbon number of the heterocyclic group is preferably 3 to 30, more preferably 3 to 22, still more preferably 3 to 20, still more preferably 3 to 18, still more preferably 3 To 15, particularly preferably from 3 to 14.

Examples of the heterocyclic ring containing a nitrogen atom include monocyclic saturated heterocyclic rings such as aziridine, azetidine, pyrrolidine, piperidine and piperazine;

Pyrazole such as pyrrole such as 2,5-dimethylpyrrole, 2-methylpyrazole and 3-methylpyrazole, imidazole, 1,2,3-triazole, 1,2,4- Cyclic unsaturated heterocyclic rings, pyrimidines such as pyridine, pyridazine and 6-methylpyrimidine, 6-membered cyclic unsaturated heterocyclic rings such as pyrazine and 1,3,5-triazine, imidazole, indoline, isoindoline , Quinoxaline such as indole, indolizine, benzoimidazole, quinoline, isoquinoline, 5,6,7,8-tetrahydro (3-methyl) quinoxaline and 3-methylquinoxaline, quinazoline, Condensed bicyclic heterocyclic rings such as benzothiazole, thiazolidinedione, thiazolidinedione, thiazolidinediones, thiazines, thiazines, thiazines, thiazines, .

Examples of the heterocycle containing an oxygen atom include oxirane, oxetane, tetrahydrofuran, tetrahydropyran, monocyclic saturated complexes such as 1,3-dioxane, 1,4-dioxane and 1-cyclopentyldioxolane A bicyclic saturated heterocyclic ring such as 1,4-dioxaspiro [4.5] decane or 1,4-dioxaspiro [4.5] nonane; lactone-based heterocyclic rings such as? -acetolactone,? -propiolactone,? -butyrolactone,? -valerolactone and? -valerolactone; ketones such as 2,3-dimethylfuran and 2,5- A 5-membered cyclic unsaturated heterocyclic ring such as furan, a 6-membered cyclic unsaturated heterocyclic ring such as 2H-pyran or 4H-pyran, benzopyran such as 1-benzofuran or 4-methylbenzopyran, benzodioxole, Condensed bicyclic heterocyclic rings such as isochroman, condensed tricyclic heterocyclic rings such as xanthene and dibenzofuran, and the like.

Examples of the heterocyclic ring containing a sulfur atom include a 5-membered cyclic unsaturated heterocyclic ring such as dithiolane; Thiophene such as 3-methylthiophene, 2-carboxythiophene, 4H-thiophene, benzoquinone, 5-membered cyclic unsaturated heterocyclic rings such as tetrahydrothiopyran and tetrahydrothiopyran, condensed two-ring heterocyclic rings such as benzothiophene, and condensed tricyclic heterocyclic rings such as thianthrene and dibenzothiophene; .

Examples of the heterocyclic ring containing a nitrogen atom and an oxygen atom include monocyclic saturated rings such as morpholine, 2-pyrrolidone, 2-methyl-2-pyrrolidone, 2-piperidone, Monocyclic unsaturated heterocyclic rings such as oxazole, 4-methyloxazole and the like, isoxazole such as 2-methylisoxazole and 3-methylisoxazole, benzooxazole, benzoisoxazole, benzoxazine, Condensed bicyclic heterocyclic rings such as dioxane and benzimidazoline, and condensed tricyclic heterocyclic rings such as phenoxazine, and the like.

Examples of the heterocyclic ring containing a nitrogen atom and a sulfur atom include monocyclic heterocyclic rings such as 3-methylthiazole and 2,4-dimethylthiazole, benzothiazole and the like condensed dicyclic heterocyclic rings such as benzothiazole, And condensed tri-cyclic heterocyclic rings such as n-butadiene and n-butadiene.

The heterocycle may be a combination of the hydrocarbon groups described above, and examples thereof include a tetrahydrofurylmethyl group.

Other heterocyclic rings may be represented by the following groups.

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

The bonding position of the heterocyclic ring is a structure in which any hydrogen atom contained in each ring is eliminated.

The heterocyclic group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have a substituent. The substituent may be the same as the substituent which the hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have. When the heterocyclic ring contains a nitrogen atom as a constituent element, the hydrocarbon group exemplified above may be bonded to the nitrogen atom as a substituent.

-CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R of R ¹ to R ⁵ , R ⁶ , R ⁷ , R ¹¹ , R ¹² and R ^{13 _{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, will be described halogen _{atom, -SO 3 M, -CO 2 M} .

Examples of -CO-R ¹⁰² include a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a 2,2-dimethylpropanoyl group, a pentanoyl group, a hexanoyl group, a (2-ethyl) hexanoyl group, a heptanoyl group, A carbonyl group in which a hydrocarbon group having 1 to 41 carbon atoms is bonded such as a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, a naphthyl group, Carbonyl group.

Examples of -COO-R ¹⁰¹ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, An oxycarbonyl group in which a hydrocarbon group having 1 to 40 carbon atoms is bonded such as an octyloxycarbonyl group, a nonyloxycarbonyl group, a decyloxycarbonyl group, an undecyloxycarbonyl group, a dodecyloxycarbonyl group, a phenyloxycarbonyl group and an icosyloxycarbonyl group, And an oxycarbonyl group in which a hydrocarbon group having 1 to 10 carbon atoms is bonded.

Examples of -OCO-R ¹⁰² include a formyloxy group, an acetoxy group, a propanoyloxy group, a butanoyloxy group, a 2,2-dimethylpropanoyloxy group, a pentanoyloxy group, a hexanoyloxy group, A carboxy group having 1 to 41 carbon atoms, such as a heptanoyloxy group, an octanoyloxy group, a nonanoyloxy group, a decanoyloxy group, an undecanoyloxy group, a dodecanoyloxy group, a hecinocanoyloxy group and a benzoyloxy group And a carbonyloxy group in which a hydrocarbon group having 1 to 12 carbon atoms is bonded may, for example, be mentioned.

Examples of -OR ¹⁰² include a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert- Ethylhexyloxy group, icosyloxy group, 1-phenylethoxy group, 1-methyl-1-phenyl (2-ethylhexyloxy) group, Dimethylphenyloxy group, 2,4-dimethylphenyloxy group, 2,5-dimethylphenyloxy group, 2,6-dimethylphenyloxy group, 3,4-dimethylphenyl An alkoxycarbonyloxy group, an oxy group, a 3,5-dimethylphenyloxy group, a 2,2-dicyanophenyloxy group, a 2,3-dicyanophenyloxy group, a 2,4- A 4-methoxyphenyloxy group, a 2-methoxyphenyloxy group, a 3-methoxyphenyloxy group, a 3-methoxyphenyloxy group, Methoxyphenyloxy group, 4-ethoxyphenyloxy group, 2-ethoxyphenyloxy group, 3-ethoxyphenyl And an oxy group in which a hydrocarbon group having 1 to 40 carbon atoms such as a nitro group or the like is bonded, and an oxy group bonded with a hydrocarbon group having 1 to 10 carbon atoms.

Examples of -SO ₂ -R ¹⁰¹ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, a pentylsulfonyl group, a hexylsulfonyl group, a (2-ethyl) hexylsulfonyl group, a heptylsulfonyl group, And a sulfonyl group having a hydrocarbon group bonded with 1 to 40 carbon atoms such as a sulfonyl group, a decyl sulfonyl group, an undecyl sulfonyl group, a dodecyl sulfonyl group, an icosyl sulfonyl group, a phenylsulfonyl group and a p-tolylsulfonyl group, Include a sulfonyl group bonded with a hydrocarbon group having 1 to 10 carbon atoms.

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

N-isopropylsulfamoyl group, N-methylsulfamoyl group, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-hexylsulfamoyl group, N- (2-ethyl) hexylsulfamoyl group, N-heptylsulfamoyl group, N-heptylsulfamoyl group, N- Heptylsulfamoyl group, N-octylsulfamoyl group, N-nonylsulfamoyl group, N-desilsulfamoyl group, N-undecylsulfamoyl group, N-dodecylsulfamoyl group, N- A sulfamoyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms such as a phenylsulfamoyl group and the like;

N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, , N, N-diisopropylsulfamoyl group, N, N-diisopropylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-dipentylsulfamoyl group, N, N-dibutylsulfamoyl group, Di (2-ethyl) hexylsulfamoyl group, N, N-diheptylsulfamoyl group, N, N-octyl Methylsulfamoyl group, N, N-dioctylsulfamoyl group, N, N-dinylsulfamoyl group, N, N-decyl methyl sulfamoyl group, N, N-undecyl methyl sulfamoyl group, N, A sulfamoyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms such as a methylsulfamoyl group, an N, N-eicosylmethylsulfamoyl group, an N, N-phenylmethylsulfamoyl group and an N, It can be given, and so on may be made of, preferably one or two of 1 to 10 carbon atoms such as a sulfamoyl group substituted with a hydrocarbon group.

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

N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-isopropylcarbamoyl group, N-butylcarbamoyl group, N-isobutylcarbamoyl group, N-sec- (1-ethylpropyl) carbamoyl group, an N-hexylcarbamoyl group, an N- (2-ethyl) hexylcarbamoyl group, an N-butylcarbamoyl group, Heptylcarbamoyl group, N-heptylcarbamoyl group, N-octylcarbamoyl group, N-nonylcarbamoyl group, N-decylcarbamoyl group, N- A carbamoyl group substituted with a hydrocarbon group having 1 to 40 carbon atoms such as a nitro group and an N-phenylcarbamoyl group;

An N, N-dimethylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-ethylmethylcarbamoyl group, N, N-diisopropylcarbamoyl group, N, N-diisopropylcarbamoyl group, N, N-diisopropylcarbamoyl group, An N, N-dibutylcarbamoyl group, an N, N-butyloctylcarbamoyl group, an N, N-dibutylcarbamoyl group, N-di (2-ethyl) hexylcarbamoyl group, N, N-di (1-ethylpropyl) carbamoyl group, N, N-dodecylcarbamoyl, N, N-dodecylcarbamoyl, N, N-dodecylcarbamoyl, N, N-octylmethylcarbamoyl, N, N-dodecylmethylcarbamoyl, N, N-eicosylmethylcarbamoyl, N, N-phenylmethylcarbamoyl And a carbamoyl group substituted with two hydrocarbon groups having 1 to 40 carbon atoms, such as an N, N-diphenylcarbamoyl group, and the like, preferably 1 or 2 carbon atoms substituted with a hydrocarbon group having 1 to 10 carbon atoms Bamboo shoots, and the like.

Examples of -N (R ¹⁰² ) ₂ include an amino group;

N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-isobutylamino group, N-sec-butylamino group, , N-hexylamino group, N- (2-ethyl) hexylamino group, N-heptylamino group, N-octylamino group, N-nonylamino group, N-decylamino group, N-undecylamino group, An amino group substituted with a hydrocarbon group having 1 to 40 carbon atoms such as an isocylamino group and an N-phenylamino group;

N, N-dimethylamino group, N, N-ethylmethylamino group, N, N-diethylamino group, N, N-propylmethylamino group, Diisopropylamino group, N, N-tert-butylmethylamino group, N, N-diisobutylamino group, N, Diethylamino group, N, N-diethylamino group, N, N-di (2-ethyl N-dodecylamino group, N, N-dodecylmethylamino group, N, N-undecylmethylamino group, N, N-dodecylamino group, An amino group substituted with two hydrocarbon groups having 1 to 40 carbon atoms such as a methylmethyl group, N, N-eicosylmethylamino group, N, N-phenylmethylamino group and N, N-diphenylamino group, Is one or two hydrocarbon groups of 1 to 10 carbon atoms There may be mentioned substituted amino group or the like.

Examples of -NHCO-R ¹⁰² include a formylamino group, an acetylamino group, a propanoylamino group, a butanoylamino group, a 2,2-dimethylpropanoylamino group, a pentanoylamino group, a hexanoylamino group, a (2- A carbonylamino group in which a hydrocarbon group having 1 to 40 carbon atoms such as a heptanoylamino group, an octanoylamino group, a nonanoylamino group, a decanoylamino group, an undecanoylamino group, a dodecanoylamino group, a heptachinoylamino group, And a carbonylamino group to which a hydrocarbon group having 1 to 10 carbon atoms is bonded may, for example, be mentioned.

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom are preferable.

Examples of M of -SO ₃ M and -CO ₂ M include a hydrogen atom, an alkali metal atom such as a lithium atom, a sodium atom and a potassium atom, preferably a hydrogen atom, a sodium atom and a potassium atom .

The rings formed by R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ are condensed with the benzene ring of the isoindoline skeleton of formula (I). Examples of the condensed ring structure of the ring formed by R ² and R ³ , R ³ and R ⁴ , or R ⁴ and R ⁵ and the benzene ring include indene, naphthalene, biphenylene, indacene, acenaphthylene, fluorene , Phenanthrene, phenanthrene, anthracene, fluoranthene, acenaphthylene, asanthrylene, triphenylene, pyrene, chrysene, N-methylphthalimide, N- (1-phenylethyl) (For example, 9,10-dihydroanthracene, 1,2,3,4-tetrahydronaphthalene, etc.), indole, isoindole, indazole, quinoline, Condensation heterocyclic rings such as isoquinoline, phthalazine, quinoxaline, quinazoline, cinnoline, carbazole, carbolin, phenanthridine, acridine, perimidine, phenanthroline, Oxygen-condensed heterocyclic rings such as 3-hydrobenzofuran-2-one, and the partially reduced form thereof.

When R ² and R ³ , R ³ and R ⁴ , and R ⁴ and R ⁵ form a ring, the ring may have a substituent. The substituent may be the same as the substituent which the hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have. Preferable examples of the substituent include the same ones as those preferred for the substituent which the hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have.

Ring wherein the R ¹² and R ¹³ has the formula (I) of isophthalic in and bonded turned and exo-methylene (C = CH ₂₎ skeleton, R ¹² and R ¹³ form ring the exo-methylene (C = a CH ₂ ), for example, a structure in which a carbonyl group such as the following group A and an exomethylene and a carbonyl group are arranged in this order can be exemplified. ** represents the binding hand of the isoindoline skeleton.

[A]

R ¹⁰⁴ and R ¹⁰⁵ are, independently, a hydrogen ^{atom, -CO-R 102, -COO-} R 101, -OCO-R 102, -OR 102, -SO 2 -R 101, -SO 2 N (R 102 together ^{_{) 2, -CON (R 102)}} 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102) 2, a halogen atom, A cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

R ¹⁰⁴ and R ¹⁰⁵ are each independently selected from the group consisting of methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, A nonyl group, a cyclohexyl group, and a phenyl group, or a hydrogen atom.

In the groups exemplified in group A, hydrogen atoms bonded to the ring structure may be substituted with substituents. The substituent may be the same as the substituent which the hydrocarbon group represented by R ¹ to R ⁵ , R ¹¹ , R ¹² , R ¹³ , R ¹⁰¹ and R ¹⁰² may have.

When R ¹² and R ¹³ do not form a ring, the compound (I) is a compound represented by the formula (Ia) (hereinafter sometimes referred to as a compound (Ia)) and a compound represented by the formula (II) , The compound (II-a1)), and the compound represented by the formula (II-a1) (hereinafter sometimes referred to as the compound (II-a1)).

[In the formula (Ia), L ¹ , R ¹¹ , R ¹ to R ⁵ and the broken line have the same meanings as defined above.

L ² represents -CO- or -SO ₂ -.

R ¹⁴ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.

Examples of the hydrocarbon group having 1 to 40 carbon atoms which may have a substituent represented by R ¹⁴ or the heterocyclic group which may have a substituent include a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent represented by R ¹¹ and R ¹⁰¹ , Which may be the same as the heterocyclic group which may be present.

In the compound (Ia), R ¹¹ and R ¹⁴ are preferably the same group. It is preferable that L ¹ and L ² are the same group.

R ¹¹ and R ¹⁴ independently represent a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a tetrahydronaphthyl group which may have a substituent, a pyridinyl group which may have a substituent, A thienyl group which may be present, a furyl group which may have a substituent or an alkyl group which may have a substituent. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 8.

The substituent of the phenyl group, the naphthyl group, the tetrahydronaphthyl group, the thienyl group, the furyl group and the pyridinyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a trifluoromethyl group; a trifluoromethyl group; An oxycarbonyl group bonded with a hydrocarbon group of 1 to 10 carbon atoms; A nitro group; A hydroxyl group; Sulfamoyl group; -SO ₃ M; preferably a -CO ₂ M.

Examples of the substituent of the alkyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; -SO ₃ M; preferably a -CO ₂ M.

L ¹ is preferably -CO-.

L ² is preferably -CO-.

R ¹ is preferably a hydrogen atom.

It is preferable that R ² to R ⁵ independently represent a hydrogen atom, a halogen atom or a nitro group. The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

[In the formula (II), R ¹ to R ⁵ and R ¹¹ to R ¹³ each have the same meaning as defined above.]

R ¹¹ represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a tetrahydronaphthyl group which may have a substituent, a pyridinyl group which may have a substituent, a thienyl group which may have a substituent, Or an alkyl group which may have a substituent. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 8.

The substituent of the phenyl group, the naphthyl group, the tetrahydronaphthyl group, the thienyl group, the furyl group and the pyridinyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a trifluoromethyl group; a trifluoromethyl group; An oxycarbonyl group bonded with a hydrocarbon group of 1 to 10 carbon atoms; A nitro group; A hydroxyl group; Sulfamoyl group; -SO ₃ M; preferably a -CO ₂ M.

Examples of the substituent of the alkyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; -SO ₃ M; preferably a -CO ₂ M.

R ¹ is preferably a hydrogen atom.

It is preferable that R ² to R ⁵ independently represent a hydrogen atom, a halogen atom or a nitro group. The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

R ¹² is preferably -CO-R ¹⁰² or -SO ₂ -R ¹⁰¹ . R ¹² is more preferably -CO-R ¹⁰² .

It is more preferable that R ¹³ is a cyano group.

R ¹⁰¹ and R ¹⁰² each have the same meaning as defined above.

[In the formula (II-a1), R ¹ to R ⁵ , R ¹² to R ¹³ and the broken line each have the same meaning as defined above. R ¹¹¹ represents a heterocyclic ring R ¹¹¹ which may have a substituent, a heterocyclic ring which may have a substituent or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent. However, R ¹¹¹ and the carbon number of 1 to 40 hydrocarbon group which may have a substituent, and R ¹² and R ¹³ is either -SO ₂ -R ¹¹¹ wherein also R ¹² and R ¹³ is another one of a cyano group , At least one of R ² to R ⁵ is -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , -SO ₂ N (R ^{102 _{) 2, -CON (R 102)}} 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102) 2, a halogen atom, A cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.

The heterocyclic group which may have a substituent represented by R < ¹¹¹ &^gt; includes the same heterocyclic group which may have a substituent represented by R < ¹¹ >.

R ¹¹¹ is preferably a pyridinyl group, a thienyl group or a furyl group which may have a substituent.

Examples of the substituent of the thienyl group, furyl group and pyridinyl group include groups having 1 to 20 carbon atoms such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, tert-butyl group, hexyl group, A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a trifluoromethyl group; An oxycarbonyl group bonded with a hydrocarbon group of 1 to 10 carbon atoms; A nitro group; A hydroxyl group; Sulfamoyl group; -SO ₃ M; preferably a -CO ₂ M.

R ¹² is preferably -CO-R ¹⁰² or -SO ₂ -R ¹⁰¹ . R ¹² is more preferably -SO ₂ -R ¹⁰¹ . R ¹⁰¹ and R ¹⁰² each have the same meaning as defined above.

R ¹³ is preferably a cyano group.

R ¹ is preferably a hydrogen atom.

It is preferable that R ² to R ⁵ independently represent a hydrogen atom, a halogen atom or a nitro group. The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

In the compound (II-a1), examples of the hydrocarbon group include a hydrocarbon group exemplified for R < ¹¹ >.

When R ¹² and R ¹³ form a ring, the compound (I) is preferably a compound represented by the formula (Ib) (hereinafter sometimes referred to as a compound (Ib)).

[In the formula (Ib), L ¹ , R ¹¹ , R ¹ to R ⁵ and the broken line have the same meanings as defined above.

R < ²⁰ > and R < ³⁰ > are combined to form a ring Q.

The ring Q may have a substituent, is a ring having 5 to 7 constituent atoms of the ring, and the ring Q may be a hydrocarbon ring or a heterocyclic ring. The ring Q may be bonded to a monocyclic ring having 5 to 7 ring atoms constituting a ring or condensed with a monocyclic ring thereof selected from a hydrocarbon ring and a heterocyclic ring.]

The number of constituent atoms of the ring is preferably 5 to 6 rings.

It is preferable that these mono rings or annular rings are combined with the ring Q at two points to constitute a ring.

The ring Q and the ring in which the monocyclic ring or the ring ring is bonded are the same as those in the above group A, and the formulas (QQ1) to (QQ25).

Among them, preferably the formula (Q1), the formula (Q4), the formula (Q7), the formula (Q8), the formula (Q18), the formula (QQ5), the formula (QQ9) Are the equations (Q8), (Q18), (QQ9), and (QQ25).

The compound (I-b) is more preferably a compound represented by the formula (I-c) (hereinafter sometimes referred to as a compound (I-c)).

[In the formula (Ic), L ¹ , R ¹¹ , R ¹ to R ⁵ and the broken line have the same meanings as defined above.

R ⁶ and R ⁷ are, independently, a hydrogen ^{atom, -CO-R 102, -COO-} R 101, -OCO-R 102, -OR 102, -SO 2 -R 101, -SO 2 N (R 102 together ^{_{) 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, or a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic ring which may have a substituent.

R ¹⁰¹ , R ¹⁰² and M have the same meanings as defined above.

In the compounds (Ib) and (Ic), R ¹¹ represents a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a tetrahydronaphthyl group which may have a substituent, a pyridinyl group which may have a substituent, A thienyl group which may have a substituent, a furyl group which may have a substituent, or an alkyl group which may have a substituent.

When R ¹¹ is an alkyl group which may have a substituent, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 8 carbon atoms.

The substituent of the phenyl group, the naphthyl group, the tetrahydronaphthyl group, the thienyl group, the furyl group and the pyridinyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, A halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a trifluoromethyl group; a trifluoromethyl group; An oxycarbonyl group bonded with a hydrocarbon group of 1 to 10 carbon atoms; A nitro group; A hydroxyl group; Sulfamoyl group; -SO ₃ M; preferably a -CO ₂ M.

Examples of the substituent of the alkyl group include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; -SO ₃ M; preferably a -CO ₂ M.

R ¹ is preferably a hydrogen atom. L ¹ is preferably -CO-.

It is preferable that R ² to R ⁵ independently represent a hydrogen atom, a halogen atom or a nitro group. The halogen atom is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom. The number of halogen atoms is preferably 1 to 4, more preferably 1 or 2. R ³ or R ⁴ is preferably a halogen atom. The number of nitro groups is preferably 0 to 2, more preferably 0 or 1. R ³ or R ⁴ is preferably a nitro group.

R ⁶ and R ⁷ each independently represent a group having 1 to 10 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, hexyl, An alkyl group, a cyclohexyl group, a phenyl group or a hydrogen atom.

Specific examples of the compound (I) include compounds having a substituent shown in Tables 1 to 4 and 9 (a) (compound 1 to 360 and compounds 725 to 745 in the formula (I-aa) ). B ¹ B ² represents a partial structure of any of the formulas (BB1) to (BB60). R ¹¹ and R ¹⁴ represent partial structures of any of the formulas (HH1) to (HH89).

[Table 1]

[Table 2]

[Table 3]

[Table 4]

Specific examples of the compound (I) include compounds having a substituent shown in Tables 5 to 8 and 9 (b) (compounds 361 to 724 and compounds 746 to 759). B ¹ B ² represents a structure of any of the formulas (BB1) to (BB60). QQ represents the structure of any of the expressions (QQ1) to (QQ25). R ¹¹ represents a structure of any of the formulas (HH1) to (HH89).

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9 (a)]

[Table 9 (b)]

Specific examples of the compound (I) include compounds in which one to three -SO ₃ M or -CO ₂ M are bonded to the compounds shown in Tables 1 to 9 (a) and 9 (b) . For example, a compound in which one to three sulfo groups are bonded to the compound 102 of Table 2 shows the following structure.

From the viewpoint that the degree of difficulty of synthesis is low, one to three -SO ₃ M is added to any of Compound 1 to Compound 12, Compound 100 to Compound 273, Compound 448 to Compound 637, Compound 725 to Compound 759, A compound in which -CO ₂ M is bonded is preferable,

Compound 1 to Compound 12, Compound 100 to Compound 168, Compound 186 to Compound 255, Compound 273, Compound 448 to Compound 532, Compound 550 to Compound 619, Compound 637, Compound 725 to Compound 726, Compound 732 to Compound 733, Compounds wherein 1 to 3 -SO ₃ M or -CO ₂ M are bonded to any of compounds 740 to 747, 753 to 754, and compounds thereof are more preferable, and compounds 100 to 168, Compound 186 to Compound 255, Compound 273, Compound 464 to Compound 532, Compound 550 to Compound 619, Compound 637, Compound 732 to Compound 733, Compound 739 to Compound 740, Compound 746 to Compound 747, Compound 753 to Compound 754, and the combinations thereof that any 1 to 3 -SO ₃ M, -CO ₂ M, or a combination of the compound being especially preferred.

Each symbol in Tables 1 to 9 (b) represents the following structure. In the following structures, Me represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. *, B ¹ , B ^2, and ** denote binding hands, respectively.

As the compound (I), L ¹ is -CO- or -SO ₂ -, preferably -CO-, R ¹ is a hydrogen atom or -SO ₃ M, and R ² to R ⁵ -SO ₃ M or a halogen atom, and R ¹¹ is -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -SO ₃ M, -CO ₂ M, -OR ¹⁰² , - SO ₂ N (R ¹⁰² ) ₂ , an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent selected from a halogen atom, a cyano group and a nitro group, one of R ¹² and R ¹³ is a cyano group and R ¹² And R ¹³ is another group represented by -CO-R ¹¹ or -SO ₂ -R ¹¹ , preferably -CO-R ¹¹ , and R ¹⁰¹ and R ¹⁰² each represent a hydrogen atom or a group of 1 to 8 carbon atoms An aliphatic hydrocarbon group, and M is a hydrogen atom or an alkali metal atom,

L ¹ is -CO- or -SO ₂ -, preferably -CO-, R ¹ is a hydrogen atom or -SO ₃ M, R ² to R ⁵ are each independently a hydrogen atom, a nitro group, -SO ₃ M or a halogen atom, and R ¹¹ is -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -SO ₃ M, -CO ₂ M, -OR ¹⁰² , -SO ₂ N (R ¹⁰² ) ₂ , R ¹² and R ¹³ is a cyano group, and another of R ¹² and R ¹³ is -CO-R ¹¹ or -SO ₂ -R ¹¹ , Preferably -CO-R ¹¹ , R ¹⁰¹ and R ¹⁰² are each a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and M is a hydrogen atom or an alkali metal atom.

(Ic), L ¹ is -CO- or -SO ₂ -, preferably -CO-, and R ¹ is a hydrogen atom or - SO ₃ M, R ² to R ⁵ are each independently a hydrogen atom, a nitro group, -SO ₃ M or a halogen atom, and R ⁶ to R ⁷ are each independently a hydrogen atom, -SO ₃ M, An alkyl group having 1 to 4 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group,

R ¹¹ is selected from -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -SO ₃ M, -CO ₂ M, -OR ¹⁰² , -SO ₂ N (R ¹⁰² ) ₂ , a halogen atom, a cyano group and a nitro group An aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and M is a hydrogen atom or an alkali metal atom.

Compound (I), R ¹ is when the hydrogen atom, the formula (in some cases referred to as phthalonitrile compound) (pt1) represents a compound in the formula for said compound (hereinafter referred to as the alkoxide compound represented by the formula (pt2) , And then reacting the compound represented by formula (pt3) with the compound represented by formula (pt4) in the presence of an acid. When R ¹ is other than a hydrogen atom, the compound (I) can also be produced by reacting it with a compound represented by the formula (pt5).

[In the formulas (pt1) to (pt5) and (I), R ¹ to R ⁵ and R ¹¹ to R ¹³ have the same meanings as defined above. R ¹⁴ represents an alkyl group having 1 to 20 carbon atoms.

M ¹ represents an alkali metal atom. LG represents a halogen atom, a methanesulfonyloxy group, a toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group.

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹⁴ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert- An alkyl group having 1 to 6 carbon atoms.

Examples of the alkali metal atom represented by M ¹ include a lithium atom, a sodium atom and a potassium atom.

The amount of the alkoxide compound to be used is usually 0.1 to 10 moles, preferably 0.2 to 5 moles, more preferably 0.3 to 3 moles, and still more preferably 0.4 to 2 moles per 1 mole of the phthalonitrile compound It is mall.

The amount of the compound (pt3) to be used is usually 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 3 moles, and still more preferably 1 to 3 moles, per 1 mole of the phthalonitrile compound. 2 moles.

The amount of the compound (pt4) to be used is usually 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 3 moles, and still more preferably 1 to 3 moles, per 1 mole of the phthalonitrile compound. 2 moles.

Examples of the acid include inorganic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, fluorosulfonic acid and phosphoric acid; sulfonic acids such as methanesulfonic acid, trifluoromethanesulfonic acid and p-toluenesulfonic acid; acetic acid, citric acid, formic acid, , And carboxylic acids such as lactic acid, oxalic acid and tartaric acid. Preferred examples thereof include hydrochloric acid, hydrobromic acid, sulfuric acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid and carboxylic acid, Acetic acid can be exemplified.

The amount of the acid to be used is usually 1 to 20 moles, preferably 1 to 10 moles, more preferably 1 to 8 moles, and still more preferably 1 to 6 moles, per 1 mole of the phthalonitrile compound .

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

Examples of the solvent include water, nitrile solvents such as acetonitrile, alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol and 1-octanol, ether solvents such as tetrahydrofuran, Ketone solvents, ester solvents such as ethyl acetate, aliphatic hydrocarbon solvents such as hexane, aromatic hydrocarbon solvents such as toluene, halogenated hydrocarbon solvents such as methylene chloride and chloroform, N, N-dimethylformaldehyde and N-methylpyrrolidone An ether solvent, a ketone solvent, an ester solvent, an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, an amide solvent and a sulfoxide solvent, for example, water, a nitrile solvent, an alcohol solvent, More preferably water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, N, N-dimethylformaldehyde, N-methylpyrrolidone and dimethylsulfoxide, and more preferably water, acetonitrile, methanol, acetonitrile, Butanol, 1-pentanol, 1-octanol, acetone, methylene chloride, chloroform, N, N-dimethylformaldehyde, N-methylpyrrolidone and dimethylsulfoxide, Particularly preferred are water, acetonitrile, methanol, ethanol and 2-propanol.

The amount of the solvent to be used is usually 1 to 1000 parts by mass based on 1 part by mass of the phthalonitrile compound.

The reaction temperature is usually 0 to 200 ° C, preferably 0 to 100 ° C, and more preferably 0 to 50 ° C. The reaction time is usually from 0.5 to 300 hours.

The amount of the compound (pt5) to be used is usually 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 3 moles per 1 mole of the compound (I) in which R ¹ is a hydrogen atom, More preferably 1 to 2 moles.

When the compound (pt5) is reacted, it is preferable that a base coexists. Examples of the base include organic bases such as triethylamine, 4- (N, N-dimethylamino) pyridine, pyridine, piperidine and the like, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert- And organic metal compounds such as lithium, lithium, sodium hydroxide, potassium hydroxide, and the like.

The amount of the base to be used is usually from 1 to 10 moles, preferably from 1 to 5 moles, more preferably from 1 to 3 moles, per mole of the compound (I) in which R ¹ is a hydrogen atom, Is 1 to 2 moles.

The reaction of the compound (pt5) is usually carried out in the presence of a solvent. The solvent can be selected in the same range as described above.

The amount of the solvent to be used is usually 1 to 1000 parts by mass based on 1 part by mass of the compound (I) in which R ¹ is not a hydrogen atom. The reaction temperature of the compound (pt5) is usually -90 to 200 占 폚, preferably -80 to 100 占 폚, and more preferably 0 to 50 占 폚. The reaction time is usually from 0.5 to 300 hours.

When the compound (I) does not have a sulfo group, the sulfo group can be introduced by reacting the compound (I) with a sulfonating agent such as fuming sulfuric acid or chlorosulfonic acid.

The amount of SO ₃ to be used in fuming sulfuric acid is usually 1 to 50 moles, preferably 5 to 40 moles, more preferably 5 to 30 moles, and still more preferably 5 moles per mole of the compound (I) ~ 25 moles.

The amount of sulfuric acid to be used in fuming sulfuric acid is usually 1 to 200 moles, preferably 10 to 100 moles, more preferably 10 to 75 moles, and still more preferably 10 to 100 moles, per 1 mole of compound (I) 50 moles.

The amount of chlorosulfonic acid to be used is usually 1 to 500 moles, preferably 10 to 300 moles, more preferably 10 to 200 moles, and still more preferably 10 to 150 moles, relative to 1 mole of compound (I) to be.

The reaction temperature for the sulphurization is usually -20 to 200 占 폚, preferably -10 to 100 占 폚, and more preferably 0 to 50 占 폚. The reaction time is usually from 0.5 to 300 hours.

The method of extracting the compound (I) from the reaction mixture is not particularly limited, and can be taken out by various known methods. For example, after completion of the reaction, the reaction mixture may be filtered to remove the compound (I). After filtration, the obtained residue may be subjected to column chromatography or recrystallization. After completion of the reaction, the solvent of the reaction mixture may be distilled off and then purified by column chromatography.

The coloring composition of the present invention may contain two or more compounds (I). Compound (I) can be used as a coloring agent.

≪ Resin (B) >

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

The resin (B) is preferably a copolymer comprising a structural unit derived from a cyclic ether structure having 2 to 4 carbon atoms and a monomer (b) having an ethylenic unsaturated bond (hereinafter also referred to as "(b)") Units are preferable.

The other structural unit is derived from a monomer (c) copolymerizable with the monomer (a) (note that the monomer (a) and the monomer (b) A structural unit, and a structural unit having an ethylenic unsaturated bond.

(a) include, for example, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and o-, m-, p-vinylbenzoic acid;

Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, Unsaturated dicarboxylic acids such as tetrahydrophthalic acid and 1,4-cyclohexene dicarboxylic acid;

Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hepto-2- A non-cyclodecanedic compound containing a carboxyl group such as 5-carboxymethylbicyclo [2.2.1] hepto-2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;

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

(Meth) acryloyloxyalkyl (meth) acrylate of a divalent or higher polyvalent carboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- ] Esters;

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

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

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

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

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

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

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

[Wherein, in formula (BI) and formula (BII), R ^a and R ^b independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxyl group . X ^a and X ^b independently represent a single bond, * -R ^c -, * -R ^c -O-, * -R ^c -S- or * -R ^c -NH-. R ^c represents an alkanediyl group having 1 to 6 carbon atoms. * Indicates the binding hand with O.]

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

Examples of the compound represented by the formula (BII-1) include compounds represented by any one of the formulas (BII-1) to (BII-15) 3), a compound represented by formula (BII-5), a compound represented by formula (BII-7), a compound represented by formula (BII-9), and a compound represented by formula (BII- Compounds represented by formulas (BII-1), (BII-7), (BII-9) and (BII-15).

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

(meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, (Meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6} ] decane-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-9-yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-8- (Meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decen-9- (Meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, (Meth) acrylic acid ester of acrylate and the like;

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

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

2,2-hept-2-ene, 5-methylbicyclo [2.2.1] hepto-2-ene, 5-ethylbicyclo [2.2.1] 2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] 2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2.1] 2,6-di (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5,6-di (2'- hydroxyethyl) bicyclo [2.2.1] 2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept- 2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept- 2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept- Cycarbonylbicyclo [ 2.2.1] hepto-2-ene, 5,6-bis (tert-butoxycarbonyl) Cyclo [2.2.1] hepto-2-ene;

N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-4-maleimide butyrate, N- Dicarbonylimide derivatives such as 6-maleimidocaproate, N-succinimidyl-3-maleimidepropionate and N- (9-acridinyl) maleimide;

(Meth) acrylonitrile and the like, vinyl halide-containing nitriles such as vinyl chloride and vinylidene chloride, (meth) acrylonitrile, and the like; Acrylamide and the like; esters such as vinyl acetate; dienes such as 1,3-butadiene, isoprene and 2,3-dimethyl-1,3-butadiene;

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

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

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

The polymer having a structural unit derived from the structural unit (a) can be produced, for example, by polymerizing a monomer constituting the structural unit of the polymer in a solvent in the presence of a polymerization initiator. The polymerization initiator, the solvent and the like are not particularly limited, and those conventionally used in the art can be used. Examples of the polymerization initiator include azo compounds (2,2'-azobisisobutylonitrile, 2,2'-azobis (2,4-dimethylvaleronitrile) and the like) and organic peroxides (benzoyl peroxide Etc.), and the solvent may be one which dissolves each monomer. Further, as the obtained polymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or a solid (powder) obtained by re-precipitation or the like may be used.

(Such as tris (dimethylaminomethyl) phenol and the like) and a polymerization inhibitor (e.g., hydroquinone, etc.) may be used, if necessary, in the presence of a catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether do.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) (Meth) acrylate / glycidyl (meth) acrylate / glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl 3,4-epoxy-tricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^2,6 ] Decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide acid / 2-hydroxyethyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (Meth) acrylate / (meth) acrylate / vinyltoluene copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / (Meth) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / tricyclo [5.2.1.0 ^2,6 ] (Meth) acryloyloxymethyl oxetane / (meth) acrylic acid / styrene copolymer, benzyl (meth) acrylate / methacrylic acid / (Meth) acrylic acid copolymers, styrene / (meth) acrylic acid copolymers, and copolymers disclosed in JP-A Nos. 9-106071, 2004-29518 and 2004-361455 Resins and the like.

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

The resin (B) may be used in combination of two or more. In this case, the resin (B) is preferably at least one selected from the group consisting of 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate / acrylic acid copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / N- cyclohexyl maleimide / 2-hydroxyethyl (meth) acrylate copolymer , 3,4-epoxy-tricyclo [5.2.1.0 ^2,6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, the resin composition comprising 3,4-tricyclo [5.2.1.0 ^2,6] decyl ( (Meth) acrylate / (meth) acrylic acid / 2-ethylhexyl (meth) acrylate copolymer.

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

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

The content of the resin (B) in the coloring composition is preferably not less than 3% by mass, more preferably not less than 5% by mass, further preferably not less than 7% by mass and not more than 99% by mass, based on the total amount of the solid matter By mass to 13% by mass to 99% by mass, and particularly preferably from 17% by mass to 95% by mass.

In the present specification, the "total amount of solids" refers to the total amount of components excluding the solvent (E) from the coloring composition of the present invention. The total amount of solids and the content of each component in the solution can be measured by known analytical means such as liquid chromatography or gas chromatography.

≪ Colorant (A1) >

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 two or more coloring agents. The colorant (A1) preferably contains a yellow colorant or a green colorant.

The colorant (A1) may be a dye or a pigment. Examples of the dyes include known dyes described in Color Index (published by The Society of Dyers and Colourists) and dyeing notes (Shikisensa). According to the chemical structure, azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes and phthalocyanine dyes can be mentioned. These dyes may be used in combination of two or more.

Specifically, dyes having the following color index (CI) numbers can be mentioned.

C.I. Solvent Yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 , 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;

C.I. Reactive Yellow 2, 76, 116;

C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 108, 109, 129, 132, 136, 138, 141;

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

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

C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

C.I. Reactive Orange 16;

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

C.I. Solvent Red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 181, 207, 218, 222, 227, 230, 245, 247;

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

C.I. Acid violet 34, 102;

C.I. Disperse Violet 26, 27;

C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

C.I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 112, 122, 128, 132, 136, 139;

C.I. Acid Blue 25, 27, 40, 45, 78, 80, 112;

C.I. Direct Blue 40;

C.I. Disperse Blue 1, 14, 56, 60;

C.I. Solvent Green 1, 3, 5, 28, 29, 32, 33;

C.I. Acid Green 3, 5, 9, 25, 27, 28, 41;

C.I. Basic Green 1;

C.I. Bat Green 1st.

As the pigment, known pigments can be used, for example, pigments classified as pigments in the color index (published by The Society of Dyers and Colourists). Two or more species may be used in combination.

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

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

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

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

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

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

Examples of the colorant (A1) include yellow dyes and yellow pigments (hereinafter collectively referred to as " yellow coloring agents "), green dyes and green pigments (hereinafter collectively referred to as "green coloring agents" More preferably yellow pigments and green pigments, and even more preferably green pigments.

Examples of the yellow dye include dyes in which the hue is classified into yellow, and yellow pigments include pigments in which the hue is classified into yellow.

Of the yellow pigments, quinophthalone yellow pigments, metal-containing yellow pigments and isoindoline yellow pigments are preferred.

Examples of the green dye include dyes in which the hue is classified as green, and the green pigment is a pigment in which the hue is classified as green.

Among the green pigments, phthalocyanine pigments are preferable, and at least one kind selected from the group consisting of halogenated copper phthalocyanine pigments and halogenated zinc phthalocyanine pigments is more preferable, and C.I. Pigment Green 7, 36, 58 and 59 are more preferable.

≪ Solvent (E) >

The coloring composition may contain a solvent (E). The solvent (E) is, for example, an ester solvent (a solvent containing -COO- in a molecule and not containing -O-), an ether solvent (containing -O- in the molecule and containing -COO- (Solvent containing -COO- and -O- in the molecule), ketone solvent (solvent containing -CO- in the molecule and not including -COO-), alcohol solvent (in the molecule), ether ester solvent OH, and not containing -O-, -CO- and -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethylsulfoxide.

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

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

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, Ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-methoxypropionate, Methyl propionate, methyl propionate, methyl 2-ethoxy-2-methyl propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate , Di, and the like ethylene 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- Cyclopentanone, cyclohexanone, isophorone, and the like.

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

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

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

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

The content of the solvent (E) is preferably 40 to 99% by mass, more preferably 50 to 95% by mass, still more preferably 70 to 95% by mass, By mass to 75% by mass to 90% by mass.

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

The coloring composition is prepared by mixing a coloring agent (A1) -containing liquid containing the compound represented by the formula (I), the resin (B), the solvent (E) to be used if necessary, and the colorant (A1) . In the above production method, the compound represented by the formula (I), the resin (B) and the solvent (E) to be used are mixed by a bead mill or the like, and the resulting mixture is mixed with the colorant (A1) Is mixed with a liquid containing the colorant (A1).

The colorant (A1) is preferably a colorant comprising at least one selected from a green colorant and a yellow colorant.

The colorant such as the compound (I) may be subjected to a surface treatment using a rosin treatment, an acidic group or a colorant derivative into which a basic group is introduced, graft treatment on the surface of a colorant with a polymer compound or the like, an atomization treatment using a sulfuric acid atomization method, A cleaning treatment with an organic solvent or water to remove impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. The particle size of the colorant is preferably substantially uniform. The colorant may be a state in which the colorant is uniformly dispersed in the dispersion by adding a dispersant and carrying out a dispersion treatment. Each of the coloring agents may be dispersed singly or plural kinds of dispersing agents may be mixed and dispersed.

Examples of the dispersing agent include surfactants, and surfactants such as cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants. Specific examples thereof include surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants. These dispersants may be used alone or in combination of two or more. Examples of the dispersing agent which can be used as the dispersing agent include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyowa Chemical Industry Co., Ltd.), Solsperse (manufactured by Zeneca), EFKA ) And Disperbyk (trade name, manufactured by Big Cakes Co., Ltd.) and BYK (trade name, manufactured by Big Cakes Co., Ltd.) .

When a dispersant is used to prepare the colorant-containing liquid, the amount of the dispersing agent (solid content) to be used is preferably 300 parts by mass or less, more preferably 100 parts by mass or less based on 100 parts by mass of the colorant, More preferably 5 parts by mass or more and 100 parts by mass or less, still more preferably 5 parts by mass or more and 50 parts by mass or less. When the amount of the dispersing agent is in the above range, there is a tendency to obtain a coloring agent-containing liquid in a more uniformly dispersed state.

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

The content of the colorant in the colorant-containing liquid is usually 1% by mass or more and 90% by mass or less, preferably 1% by mass or more and 80% by mass or less, more preferably 2% Mass% or less, and more preferably 5 mass% or more and 75 mass% or less.

When the coloring composition of the present invention is prepared using the coloring composition after preparing the coloring agent-containing liquid containing the coloring agent and the solvent (E) in advance, the coloring composition may be a part or all of the resin (B) , Preferably a part of them may be included in advance. By containing the resin (B) in advance, the dispersion stability of the colorant-containing liquid can be further improved.

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

In the coloring composition, the content of the colorant (A) including the compound (I) and the colorant (A1) is usually 1% by mass or more and 90% by mass or less based on the total amount of the solid matter, preferably 1% By mass or less, more preferably 2% by mass or more and 75% by mass or less, and still more preferably 5% by mass or more and 75% by mass or less.

The content of the compound (I) is usually 0.001% by mass or more, preferably 0.003% by mass or more, more preferably 0.005% by mass or more, still more preferably 1% by mass or more in the total amount of the colorant (A) , And the upper limit is 100 mass% or less, preferably 99.999 mass% or less, more preferably 99.997 mass% or less, further preferably 70 mass% or less, and even more preferably 50 mass% or less.

The content of the compound (I) is usually 0.001% by mass or more, preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 60% by mass or more in the total amount of the yellow colorant Particularly preferably 70% by mass or more, and the upper limit is 100% by mass or less, preferably 99.999% by mass or less, and more preferably 99.997% by mass or less.

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

The colored curable resin composition of the present invention includes a compound (I), a resin (B), a polymerizable compound (C) and a polymerization initiator (D).

≪ Polymerizable compound (C) >

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

The polymerizable compound having one ethylenically unsaturated bond includes, for example, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, (A), the monomer (b) and the monomer (c) described above, and the like.

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenic unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol Ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, Acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate (Meth) acrylate, caprolactone-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate. Preferred examples thereof include dipentaerythritol penta And erythritol 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 resin composition is preferably 1% by mass, more preferably 3% by mass, and still more preferably 5% by mass, based on the total solid content, More preferably 65% by mass, still more preferably 3% by mass to 60% by mass, and particularly preferably 7% by mass to 55% by mass.

≪ Polymerization initiator (D) >

The polymerization initiator (D) may be any known polymerization initiator without particular limitation as long as it is a compound capable of generating an active radical, an acid, or the like by the action of light or heat and capable of initiating polymerization.

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

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

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

Examples of the alkylphenone compound include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl- 1- [4- (2-hydroxyethoxy) phenyl] 1-on, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan- Dimethyl ketal.

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

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) 2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (Trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine and 2,4- 6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like.

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

Examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, Benzoquinone such as benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3'4,4'-tetra (tert-butylperoxycarbonyl) benzophenone and 2,4,6- Phenol compounds, quinone compounds such as 9,10-phenanthrenequinone, 2-ethyl anthraquinone and camphorquinone, 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate and titanocene compounds have.

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

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

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C).

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

≪ Polymerization Initiator (D1) >

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

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

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethyl para-toluidine, 4,4'-bis (dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'-bis (diethylamino) benzophenone and 4 , 4'-bis (ethylmethylamino) benzophenone, and the like, preferably 4,4'-bis (diethylamino) benzophenone. As the amine compound, commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

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

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

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, Chlorophenylsulfanylacetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

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

When the polymerization initiator (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 part by mass, per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C) To 20 parts by mass.

≪ Solvent (E) >

As the solvent (E), the same solvent as the solvent exemplified in the above coloring composition can be mentioned.

The content of the solvent (E) is preferably 70 to 95% by mass, and more preferably 75 to 90% by mass, based on the total amount of the colored curable resin composition.

≪ Leveling agent (F) >

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

Examples of the silicone surfactant include a surfactant having a siloxane bond in the molecule. Concretely, it is preferable to use a silicone resin such as Torensilicon DC3PA, Copper SH7PA, Copper DC11PA, Copper SH21PA, Copper SH28PA, Copper SH29PA, Copper SH30PA, Copper SH8400 (trade name: Toray Dow Corning Co., Ltd.), KP321, KP322, KP324, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan Joint- .

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

Examples of the silicon-based surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples thereof include Megapac (registered trademark) R08, B20, B475, B477 and F443 (manufactured by DIC).

When the leveling agent (F) is contained, the content thereof is usually from 0.0005 mass% to 1 mass%, preferably from 0.001 mass% to 0.5 mass%, based on the total amount of the coloring composition or the colored curable resin composition, More preferably, it is 0.001 mass% or more and 0.2 mass% or less, still 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 improved.

<Antioxidant>

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

Examples of the phenolic antioxidant include Irganox 1010 (pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (Irganox 1076: octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, BASF), Irgas (Irganox 1330: 3,3 ', 3 ", 5,5', 5" -hexa-tert-butyl-a, a ', a " Tris (3,5-di-tert-butyl-4-hydroxybenzyl) -1, (1H, 3H, 5H) -triene, manufactured by BASF Co., Irganox 3790: 1,3,5-tris ((4-tert Methyl-1,3,5-triazine-2,4,6 (1H, 3H, 5H) -thione, produced by BASF Co., (Irganox 1035: thiodiethylene bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], BASF Co., ), Irganox 1135 (benzene propanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, BASF) Irganox 3525 (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF), Irganox 3125 (manufactured by BASF), Irganox 565 : 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ', 5'-di-tert-butyl anilino) -1,3,5-triazine, , Adecastab AO-80 (adecastab AO-80: 3,9-bis (2- (3- (tert- butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1 -Dimethylethyl) -2,4,8,10-tetraoxaspiro (5,5 undecane, manufactured by ADEKA), water mill Riser BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), water mill Riser GA- Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, manufactured by Cytec Co., Ltd.), and vitamins (manufactured by Sumitomo Chemical Industries, Ltd.) E (manufactured by Eizoi Co., Ltd.) and the like.

Examples of the phosphorus antioxidant include Irgafos 168 (tris (2,4-di-tert-butylphenyl) phosphite, BASF), Irgafos 12 Butyl] dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, BASF ( (Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphoric acid, manufactured by BASF), Adekastab 329K Adekastab PEP36 (manufactured by ADEKA), Adecastab PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (manufactured by ADEKA) Hydrogen 626 (manufactured by GE) and Sumilizer GP: 6- [3- (3-tert-butyl-4-hydroxycyclohexyl) Methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1.3.2] dioxaphosphepin) (Sumitomo Chemical Co., It can be given.

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

<Other ingredients>

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

As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidoxy Propylmethyldimethoxysilane, 3-chloropropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxy Silane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-sulfanylpropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, N-2- N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N- (aminoethyl) -3-aminopropyltrimethoxysilane, N- Aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3- Phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.

<Color filter>

A color filter can be formed from the colored curable resin composition of the present invention. Examples of the method of forming a coloring pattern include a photolithographic method, an inkjet method, and a printing method. Among them, a photolithographic method is preferable. In the photolithographic method, the above-mentioned colored curable resin composition is applied to a substrate, followed by drying to form a colored curable resin composition layer, and the colored curable resin composition layer is exposed and developed through a photomask. In the photolithographic method, a colored coating film which is a cured product of the colored curable resin composition layer can be formed by not using a photomask at the time of exposure and / or not developing it. The coloring pattern or colored coating film thus formed is the color filter of the present invention.

The thickness of the color filter to be produced is not particularly limited and may be appropriately adjusted depending on the purpose and application, and is, for example, 0.1 to 30 탆, preferably 0.1 to 20 탆, more preferably 0.5 to 6 Mu m.

As the substrate, a glass plate, a resin plate, silicon, and an aluminum, silver or silver / copper / palladium alloy thin film formed on the substrate are used. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

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

First, a colored curable resin composition is coated on a substrate, followed by drying by heating (prebaking) and / or drying under reduced pressure to remove volatile components such as a solvent and drying to obtain a smooth colored curable resin composition layer.

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

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

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

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

The developing method may be any of a paddle method, a dipping method and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development.

The substrate after development is preferably washed with water.

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

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

Example

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited by the following Examples.

In the following synthesis examples and examples, the structure of the compound was determined by NMR (JMM-ECA-500, manufactured by Nippon Denshoku KK) or mass spectrometry (LC: Agilent 1200 type, MASS; Respectively.

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

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

Column: TSK-GELG2000HXL

Column temperature: 40 DEG C

Solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

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

Injection amount: 50 μl

Detector: RI

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

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

Example 1

11.0 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 91.5 parts of methanol were mixed. While maintaining the temperature of the obtained mixture at 2 占 폚, a mixture of 8.59 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 77.6 parts of methanol was added dropwise over 1 hour and 45 minutes, And stirred for 40 minutes. To the resulting mixture was added 4.18 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was stirred at 2 ° C for 1 hour and 45 minutes. 17.0 parts of acetic acid was added while maintaining the temperature of the obtained mixture at 4 占 폚 or lower. To the resulting mixture, 23.9 parts of pivaloylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 87 hours. 10.8 parts of pivaloylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.40 parts of acetic acid were added to the obtained mixture, followed by stirring at 40 占 폚 for 4 hours and 30 minutes. The resulting mixture was filtered, and the residue was washed with 360 parts of methanol. The obtained residue was dried under reduced pressure at 60 캜 to obtain 22.8 parts of a compound represented by the formula (I-1).

<Identification of Compound Represented by Formula (I-1)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 362

                          Exact Mass: 361

Example 2

2.59 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 24.1 parts of methanol were mixed. A mixture of 1.50 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 23.2 parts of methanol was added dropwise to this mixture over 1 hour and 10 minutes while maintaining the temperature of the obtained mixture at 2 캜. The resulting mixture was stirred at 2 캜 for 2 hours and 20 minutes. 2.35 parts of acetic acid was added while keeping the temperature of the obtained mixture at 3 占 폚 or lower, and 4.13 parts of pivaloylacetonitrile (manufactured by TOKYO FUSCHI CO., LTD.) Was further added. The resulting mixture was stirred at room temperature for 3 hours and 35 minutes, and then stirred at 40 ° C for 1 hour and 45 minutes. To the obtained mixture was added 4.16 parts of pivaloylacetonitrile (manufactured by TOKYO FUJI KOGYO CO., LTD.), And the mixture was stirred at 40 ° C for 1.5 hours. The resulting mixture was stirred at room temperature for 37 hours. 1.89 parts of pivaloylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.24 parts of acetic acid were added to the obtained mixture, followed by stirring at 40 占 폚 for 5 hours and 15 minutes. The resulting mixture was filtered, and the residue was washed with 198 parts of methanol. The obtained residue was dried under reduced pressure at 60 ° C to obtain 5.58 parts of a compound represented by the formula (I-2).

&Lt; Identification of compound represented by formula (I-2) &gt;

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 407

                          Exact Mass: 406

Example 3

7.02 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 61.6 parts of methanol were mixed. While maintaining the temperature of the obtained mixture at 2 占 폚, a mixture of 8.20 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 74.6 parts of methanol was added dropwise over 1 hour and 30 minutes. The resulting mixture was stirred at 2 캜 for 6 hours and 15 minutes. 10.7 parts of acetic acid was added while maintaining the temperature of the resulting mixture at 4 占 폚 or lower. To the resulting mixture, 17.6 parts of benzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) was added, and the mixture was stirred at room temperature for 44 hours. The resulting mixture was filtered, and the residue was washed with 800 parts of methanol. The obtained residue was dried under reduced pressure at 60 ° C to obtain 18.0 parts of a compound represented by the formula (I-3).

<Identification of Compound Represented by Formula (I-3)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 402

                          Exact Mass: 401

Example 4

4.12 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 37.2 parts of methanol were mixed. A mixture of 4.82 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 45.2 parts of methanol was added dropwise to the mixture over 1 hour while maintaining the temperature of the mixture at 2 캜. The resulting mixture was stirred at 2 캜 for 6 hours. 6.29 parts of acetic acid was added while maintaining the temperature of the obtained mixture at 4 占 폚 or lower. To the resulting mixture was added 12.7 parts of 2-chlorobenzoyl acetonitrile (manufactured by TOKYO CHEMICAL INDUSTRY CO., LTD.), And the mixture was stirred at 2 占 폚 for 1 hour and at room temperature for 20 minutes. The resulting mixture was stirred at 40 캜 for 2 hours, and then at room temperature for 11 hours, and further at 40 캜 for 5 hours and 40 minutes. To the obtained mixture, 3.18 parts of acetic acid and 6.45 parts of 2-chlorobenzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The resulting mixture was stirred at 40 占 폚 for 4 hours and then at room temperature for 62 hours. The resulting mixture was filtered and the residue was washed three times with methanol in the same volume as the residue. The resulting residue was recrystallized from N, N-dimethylformamide. The obtained crystals were dried under reduced pressure at 60 ° C to obtain 9.99 parts of a compound represented by the formula (I-4).

<Identification of Compound Represented by Formula (I-4)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 470

                          Exact Mass: 469

Example 5

4.07 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 36.0 parts of methanol were mixed. While maintaining the temperature of the obtained mixture at 2 占 폚, a mixture of 4.76 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 44.3 parts of methanol was added dropwise over 1 hour and 10 minutes. The resulting mixture was stirred at 2 캜 for 5 hours and 25 minutes. 6.23 parts of acetic acid was added while maintaining the resultant mixture at 3 占 폚 or lower. To the resulting mixture was added 12.6 parts of 4-chlorobenzoyl acetonitrile (manufactured by TOKYO FUSCHI CO., LTD.), And the mixture was stirred at 40 ° C for 40 minutes. To the resultant mixture was added 456 parts of methanol, and the mixture was stirred at 40 ° C for 3 hours and then at room temperature for 37 hours. To the resulting mixture was added 3.14 parts of acetic acid, 6.31 parts of 4-chlorobenzoyl acetonitrile (manufactured by TOKYO HOSUNG KOGYO CO., LTD.) And 124 parts of methanol, and the mixture was stirred at 40 ° C for 6 hours and 40 minutes. The resulting mixture was stirred at room temperature for 18 hours. The resulting mixture was filtered, and the residue was washed with 554 parts of methanol. To the obtained residue was added 1740 parts of N, N-dimethylformamide, and the mixture was stirred at 80 DEG C and then filtered while being kept at 80 DEG C. [ To obtain a residue and a filtrate (ROE-1). The obtained residue was washed with 150 parts of N, N-dimethylformamide. To obtain a residue and a cleaning liquid (SEN-1). The obtained residue was dried under reduced pressure at 60 ° C to obtain 4.88 parts of a compound represented by the formula (I-5). The obtained filtrate (ROE-1) and the washing liquid (SEN-1) were combined and allowed to stand at room temperature for 12 hours. The resulting mixture was filtered, and the residue was washed three times with N, N-dimethylformamide in the same volume as the residue. The obtained residue was dried under reduced pressure at 60 ° C to obtain 5.16 parts of a compound represented by the formula (I-5).

<Identification of Compound Represented by Formula (I-5)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 470

                          Exact Mass: 469

Example 6

10.0 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 93 parts of methanol were mixed. A mixture of 11.7 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 110 parts of methanol was added dropwise to the resulting mixture over 1 hour and 15 minutes. The resulting mixture was stirred at 5 캜 for 3 hours. To the resulting mixture, while maintaining the temperature below 5 占 폚, 7.71 parts of acetic acid and 8 parts of methanol were added. To the resulting mixture was added 11.4 parts of benzoyl acetonitrile (manufactured by TOKYO HOSUNG KOGYO CO., LTD.). The resulting mixture was stirred at 2 캜 for 40 minutes and then stirred at room temperature for 17 hours and 40 minutes. 109 parts of methanol was added to the resulting mixture, and the mixture was stirred at room temperature for 1 hour and 20 minutes. To the obtained mixture, 6.41 parts of acetic acid, 10.1 parts of barbituric acid and 16.0 parts of methanol were added. The resulting mixture was stirred at room temperature for 5 hours and then at 40 ° C for 2 hours. To the resultant mixture was added 344 parts of water. The obtained mixture was stirred at 40 캜 for 3 hours and 25 minutes, and then stirred at room temperature for 16 hours. The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 1.55 parts of a compound represented by the formula (I-6).

<Identification of Compound Represented by Formula (I-6)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 385

                          Exact Mass: 384

Example 7

5.00 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 42.0 parts of methanol were mixed. A mixture of 5.83 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 52.5 parts of methanol was added dropwise to the obtained mixture over 1 hour and 30 minutes while maintaining the temperature below 2 캜. The resulting mixture was stirred at 2 캜 for 6 hours. To the obtained mixture was added 7.59 parts of acetic acid while maintaining the temperature at 4 캜 or lower, 17.4 parts of methyl 4-cyanoacetylbenzoate (synthesized in accordance with the method described in JP-A No. 8-176154) and 682 parts of methanol were added Respectively. The resulting mixture was stirred at room temperature for 4 hours and then at 40 ° C for 48 hours. The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 2.21 parts of a compound represented by the formula (I-7).

&Lt; Identification of compound represented by formula (I-7) &gt;

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 518

                          Exact Mass: 517

Example 8

8.10 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 69.0 parts of methanol were mixed. A mixture of 4.68 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 45.0 parts of methanol was added dropwise to the obtained mixture over 50 minutes while the temperature was maintained at 2 캜. The obtained mixture was stirred at 2 캜 for 2 hours and 30 minutes. 7.35 parts of acetic acid and 18.7 parts of phenylsulfonylacetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the resulting mixture while keeping the temperature below 2 占 폚. The resulting mixture was stirred at room temperature for 15 hours and then at 40 ° C for 50 hours. The obtained mixture was divided in half to obtain Mixture 1 and Mixture 2.

The mixture 1 was subjected to solvent distillation using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.0273 part of a compound represented by the formula (I-8).

2.00 parts of acetic acid, 3.02 parts of barbituric acid, 50 parts of methanol and 102 parts of water were added to the mixture 2, and the mixture was stirred at 40 占 폚 for 12 hours. The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.0313 part of a compound represented by the formula (I-9).

&Lt; Identification of compound represented by formula (I-8)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 519

                          Exact Mass: 518

&Lt; Identification of compound represented by formula (I-9) &gt;

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 466

                          Exact Mass: 465

Example 9

(I-10) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 3-chlorobenzoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio .

<Identification of Compound Represented by Formula (I-10)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 470

                          Exact Mass: 469

Example 10

Compound (I-11) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was used in place of methyl 3-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-11)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 518

                          Exact Mass: 517

Synthesis Example 1

(I-12) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with phenylsulfonylacetonitrile (manufactured by TOKYO HOSUNG KOGYO Co., Ltd.) while maintaining the molar ratio Compound.

<Identification of Compound Represented by Formula (I-12)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 474

                          Exact Mass: 473

Example 11

(I-13) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 2-methylbenzoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio .

<Identification of Compound Represented by Formula (I-13)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 430

                          Exact Mass: 429

Example 12

(I-14) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 3-methylbenzoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio .

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

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 430

                          Exact Mass: 429

Example 13

(I-15) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 4-methylbenzoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio .

<Identification of Compound Represented by Formula (I-15)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 430

                          Exact Mass: 429

Example 14

Compound (I-16) was obtained in the same manner as in Example 7 except that 2-nitrobenzoyl acetonitrile was used in place of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

&Lt; Identification of compound represented by formula (I-16) &gt;

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 492

                          Exact Mass: 491

Example 15

Compound (I-17) was obtained in the same manner as in Example 7 except that 3-nitrobenzoyl acetonitrile was used in place of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-17)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 492

                          Exact Mass: 491

Example 16

Compound (I-18) was obtained in the same manner as in Example 7 except that 4-nitrobenzoyl acetonitrile was used in place of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of compound represented by formula (I-18)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 492

                          Exact Mass: 491

Example 17

Compound (I-19) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was used in place of 4-cyanobenzoyl acetonitrile while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-19)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 452

                          Exact Mass: 451

Example 18

A compound represented by the formula (I-20) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with 3-dimethylaminobenzoyl acetonitrile while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-20)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 488

                          Exact Mass: 487

Example 19

Compound (I-21) was obtained in the same manner as in Example 7 except that 1-naphthoyl acetonitrile was used in place of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-21)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 502

                          Exact Mass: 501

Example 20

Compound (I-22) was obtained in the same manner as in Example 7 except that 2-naphthoyl acetonitrile was used in place of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-22)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 502

                          Exact Mass: 501

Example 21

Compound (I-23) was obtained in the same manner as in Example 7 except that 2-trifluoromethylbenzoyl acetonitrile was used in place of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-23)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 538

                          Exact Mass: 537

Example 22

(I-1) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 3-trifluoromethylbenzoyl acetonitrile (Sigma Aldrich Japan KK) 24) was obtained.

<Identification of Compound Represented by Formula (I-24)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 538

                          Exact Mass: 537

Example 23

(I-1) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 4-trifluoromethylbenzoyl acetonitrile (Sigma Aldrich Japan KK) 25) was obtained.

<Identification of Compound Represented by Formula (I-25)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 538

                          Exact Mass: 537

Example 24

(I-26) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 2-fluorobenzoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio. Was obtained.

<Identification of Compound Represented by Formula (I-26)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 438

                          Exact Mass: 437

Example 25

A compound represented by the formula (I-27) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with 3-fluorobenzoyl acetonitrile while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-27)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 438

                          Exact Mass: 437

Example 26

(I-28) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 4-fluorobenzoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio. Was obtained.

<Identification of Compound Represented by Formula (I-28)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 438

                          Exact Mass: 437

Example 27

A compound represented by the formula (I-29) was obtained in the same manner as in Example 7 except that 2-bromobenzoyl acetonitrile was used in place of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-29)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 558

                          Exact Mass: 557

Example 28

Compound (I-30) was obtained in the same manner as in Example 7 except that 3-bromobenzoyl acetonitrile was used instead of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-30)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 558

                          Exact Mass: 557

Example 29

(I-31) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 4-bromobenzoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio. Was obtained.

<Identification of Compound Represented by Formula (I-31)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 558

                          Exact Mass: 557

Example 30

Compound (I-32) was obtained in the same manner as in Example 7 except that 2-methoxybenzoyl acetonitrile was used in place of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-32)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 462

                          Exact Mass: 461

Example 31

Compound (I-33) was obtained in the same manner as in Example 7 except that 3-methoxybenzoyl acetonitrile was used in place of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-33)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 462

                          Exact Mass: 461

Example 32

(I-34) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 4-methoxybenzoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio. Was obtained.

&Lt; Identification of compound represented by formula (I-34)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 462

                          Exact Mass: 461

Example 33

13.8 parts of 4-nitrophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 115 parts of methanol were mixed. A mixture of 7.94 parts of 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 74.0 parts of methanol was added dropwise to the resulting mixture while maintaining the temperature below 2 to 3 占 폚 over 40 minutes. The resulting mixture was stirred at 2 to 3 占 폚 for 4 hours. While maintaining the resultant mixture at 3 占 폚 or lower, 12.5 parts of acetic acid was added, followed by addition of 25.4 parts of benzoyl acetonitrile (TOKYO CHEMICAL INDUSTRY CO., LTD.) And 150 parts of methanol. The resulting mixture was stirred at room temperature for 18 hours and then at 43 ° C for 5 hours. The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 1.02 parts of a compound represented by the formula (I-35).

<Identification of Compound Represented by Formula (I-35)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 447

                          Exact Mass: 446

Example 34

(I-36) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 3,4-dichlorobenzoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio ) Was obtained.

<Identification of Compound Represented by Formula (I-36)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 538

                          Exact Mass: 537

Example 35

Except that methyl 4-cyanoacetylbenzoate was replaced with (5,6,7,8-tetrahydro-2-naphthoyl) acetonitrile (Sigma Aldrich Japan Co., Ltd.) while maintaining the molar ratio, 7, a compound represented by the formula (I-37) was obtained.

<Identification of Compound Represented by Formula (I-37)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 510

                          Exact Mass: 509

Example 36

(I-38) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 4-dimethylaminobenzoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio. Was obtained.

&Lt; Identification of compound represented by formula (I-38)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 488

                          Exact Mass: 487

Synthesis Example 2

(I-39) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with methylsulfonylacetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio. Compound.

&Lt; Identification of compound represented by formula (I-39)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 350

                          Exact Mass: 349

Synthesis Example 3

Was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with (4-bromophenylsulfonyl) acetonitrile (Sigma Aldrich Japan Co., Ltd.) I-40) was obtained.

<Identification of Compound Represented by Formula (I-40)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 630

                          Exact Mass: 629

Example 37

A compound represented by the formula (I-41) was obtained in the same manner as in Example 7 except that the methyl 4-cyanoacetylbenzoate was replaced with methyl 2-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-41)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 518

                          Exact Mass: 517

Example 38

Compound (I-42) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with 4-sulfamoylbenzoyl acetonitrile while maintaining the molar ratio.

Example 39

A compound represented by the formula (I-43) was obtained in the same manner as in Example 7 except that the methyl 4-cyanoacetylbenzoate was replaced with 2-cyanoacetylbenzoic acid while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-43)

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ^- 488

                          Exact Mass: 489

Example 40

A compound represented by the formula (I-44) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with 3-cyanoacetylbenzoic acid while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-44)

(Mass spectrometry) Ionization mode = ESI-: m / z = [M-H] ^- 488

                                Exact Mass: 489

Example 41

A compound represented by the formula (I-45) was obtained in the same manner as in Example 7 except that the methyl 4-cyanoacetylbenzoate was replaced with 4-cyanoacetylbenzoic acid while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-45)

(Mass spectrometry) Ionization mode = ESI-: m / z = [M-H] ^- 488

                                Exact Mass: 489

Example 42

The compound represented by the formula (I-46) was obtained in the same manner as in Example 7 except that the methyl 4-cyanoacetylbenzoate was replaced with 3-cyanoacetylbenzoic acid while maintaining the molar ratio.

Example 43

A compound represented by the formula (I-47) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with 2-hydroxybenzoyl acetonitrile while maintaining the molar ratio.

&Lt; Identification of compound represented by formula (I-47)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 434

                          Exact Mass: 433

Example 44

A compound represented by the formula (I-48) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced by 3-hydroxybenzoyl acetonitrile while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-48)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 434

                          Exact Mass: 433

Example 45

A compound represented by the formula (I-49) was obtained in the same manner as in Example 7 except that the methyl 4-cyanoacetylbenzoate was replaced by 4-hydroxybenzoyl acetonitrile while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-49)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 434

                          Exact Mass: 433

Example 46

A compound represented by the formula (I-50) was obtained in the same manner as in Example 7 except that the methyl 4-cyanoacetylbenzoate was replaced by 2-aminobenzoyl acetonitrile while maintaining the molar ratio.

Example 47

(I-51) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with 3-aminobenzoyl acetonitrile while maintaining the molar ratio.

Example 48

Compound (I-52) was obtained in the same manner as in Example 7 except that the methyl 4-cyanoacetylbenzoate was replaced with 4-aminobenzoyl acetonitrile while maintaining the molar ratio.

Example 49

(I-53) was obtained in the same manner as in Example 7 except that 4-acetylbenzoyl acetonitrile was used in place of methyl 4-cyanoacetylbenzoate while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-53)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 486

                          Exact Mass: 485

Example 50

The compound represented by the formula (I-54) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with 4-diethylaminobenzoyl acetonitrile while maintaining the molar ratio.

Example 51

The compound represented by the formula (I-55) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with 4-methylthiobenzoyl acetonitrile while maintaining the molar ratio.

Synthesis Example 4

(I-56) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with (4-acetylaminophenylsulfonyl) acetonitrile while maintaining the molar ratio of .

Example 52

Compound (I-57) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced by (2-pyridylsulfonyl) acetonitrile while maintaining the molar ratio.

Example 53

(I-58) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was used in place of N-octyl- ((4-cyanoacetyl) ) Is obtained.

Example 54

(4-cyanoacetyl) phenyl) sulfonamide was used instead of N, N-dibutyl- (4-cyanoacetyl) phenyl) sulfonamide while maintaining the molar ratio, I-59).

Example 55

(I-60) was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was replaced with N, N-diphenyl- ((4-cyanoacetyl) .

Example 56

0.513 part of the compound represented by the formula (I-3) obtained in Example 3 was added while stirring 7.6 parts of fuming sulfuric acid (25%) at 3 占 폚 (manufactured by Wako Pure Chemical Industries, Ltd.). To the resulting mixture, 3.8 parts of fuming sulfuric acid (25%) (manufactured by Wako Pure Chemical Industries, Ltd.) was added. The resulting mixture was heated to 15 캜 over 3 hours and 30 minutes while stirring. 139 parts of ice water was added to the obtained mixture, and further 38.2 parts of sodium chloride was added. The resulting mixture was filtered, and the obtained residue was washed with 64 parts of a 21.5% aqueous sodium chloride solution. The obtained residue was dried under reduced pressure at 60 ° C to obtain 1.02 parts of a compound represented by the formula (I-61).

<Identification of Compound Represented by Formula (I-61)

(Mass analysis) Ionization mode = ESI-: m / z = [M-H] ^- 560

                                Exact Mass: 561

Example 57

12.2 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 103 parts of methanol were mixed. A mixture of 14.3 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 130 parts of methanol was added dropwise to the resulting mixture over 2 hours and 10 minutes while maintaining the temperature at 4 to 6 占 폚. The resulting mixture was stirred at 4 to 6 캜 for 6 hours. 9.37 parts of acetic acid and 13.8 parts of benzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the resulting mixture while keeping the temperature below 5 占 폚. The resulting mixture was stirred at room temperature for 15 hours. 1.00 parts of acetic acid and 1.39 parts of benzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture, and the mixture was stirred at room temperature for 3 hours and at 40 占 폚 for 2 hours and 30 minutes. To the resulting mixture was added 1.44 parts of acetic acid and 2.13 parts of benzoyl acetonitrile (manufactured by Tokyosho Kagaku Kogyo K.K.), followed by stirring at 40 ° C for 3 hours. 0.985 parts of acetic acid, 1.46 parts of benzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 170 parts of methanol were added to the obtained mixture, followed by stirring at 40 ° C for 2 hours. 9.29 parts of acetic acid, 12.2 parts of barbituric acid and 17 parts of methanol were added to the obtained mixture, followed by stirring at 40 占 폚 for 20 hours. 9.29 parts of acetic acid, 14.4 parts of barbituric acid and 14 parts of methanol were added to the obtained mixture, followed by stirring at 40 占 폚 for 18 hours. The resulting mixture was filtered. The obtained residue was washed twice with a mixture of 200 parts of water and 200 parts of methanol once with a mixture of 219 parts of water and 219 parts of methanol and once with 500 parts of water. The obtained residue was dried under reduced pressure at 60 ° C to obtain 31.3 parts of a mixture containing a compound represented by the formula (I-3) and a compound represented by the formula (I-6).

<Identification of Compound Represented by Formula (I-3)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 402

                           Exact Mass: 401

<Identification of Compound Represented by Formula (I-6)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 385

                          Exact Mass: 384

Example 58

11.5 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 136 parts of methanol were mixed. A mixture of 13.5 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 101 parts of methanol was added dropwise to the resulting mixture while keeping the temperature below 2 to 4 캜 over one hour. The resulting mixture was stirred for 6 hours while keeping the temperature below 5 캜. To the resulting mixture was added 8.88 parts of acetic acid, 3.2 parts of methanol and 16.3 parts of 2-chlorobenzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) while maintaining the temperature at 4 to 8 占 폚. The resulting mixture was stirred at room temperature for 16 hours. 1.02 parts of acetic acid, 1.64 parts of 2-chlorobenzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 parts of methanol were added to the obtained mixture, followed by stirring at room temperature for 1.5 hours and at 40 占 폚 for 6 hours. 1.35 parts of acetic acid, 2.44 parts of 2-chlorobenzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 10 parts of methanol were added to the obtained mixture, followed by stirring at 40 占 폚 for 3 hours. To the resulting mixture was added 1.16 parts of acetic acid, 2.03 parts of 2-chlorobenzoyl acetonitrile (manufactured by TOKYO HOSAG KOGYO CO., LTD.) And 10 parts of methanol, followed by stirring at 40 ° C for 17 hours. 8.83 parts of acetic acid, 12.6 parts of barbituric acid and 14 parts of methanol were added to the obtained mixture, followed by stirring at 40 占 폚 for 22 hours. 4.40 parts of acetic acid, 5.75 parts of barbituric acid and 14 parts of methanol were added to the obtained mixture, and the mixture was stirred at 40 占 폚 for 9 hours and then at room temperature for 4 hours. The resulting mixture was filtered. The obtained residue was washed with 393 parts of methanol once, once with a mixture of 393 parts of water and 393 parts of methanol. 800 parts of methanol was added to the obtained residue, and the mixture was stirred at 40 占 폚 for 2 hours. The resulting mixture was filtered. The obtained residue was dried under reduced pressure at 40 ° C to obtain 40.7 parts of a mixture containing the compound represented by the formula (I-4) and the compound represented by the formula (I-63).

<Identification of Compound Represented by Formula (I-4)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 470

                          Exact Mass: 469

<Identification of Compound Represented by Formula (I-63)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 419

                          Exact Mass: 418

Example 59

(I-5) and (I-64) were obtained in the same manner as in Example 58, except that 2-chlorobenzoyl acetonitrile was used in place of 4-chlorobenzoyl acetonitrile while maintaining the molar ratio. &Lt; / RTI &gt; was obtained.

<Identification of Compound Represented by Formula (I-5)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 470

                          Exact Mass: 469

&Lt; Identification of compound represented by formula (I-64)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 419

                          Exact Mass: 418

Example 60

(I-1) and a compound represented by the formula (I-65) were obtained in the same manner as in Example 58, except that 2-chlorobenzoyl acetonitrile was used instead of pivaloylacetonitrile while maintaining the molar ratio Lt; / RTI &gt;

<Identification of Compound Represented by Formula (I-1)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 362

                          Exact Mass: 361

<Identification of Compound Represented by Formula (I-65)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 365

                          Exact Mass: 364

Example 61

(I-66) and the compound represented by the formula (I-67) were obtained in the same manner as in Example 58 except that the phthalonitrile was replaced with 4-nitropthalonitrile while maintaining the molar ratio. To obtain a mixture containing the compound.

<Identification of Compound Represented by Formula (I-66)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 515

                          Exact Mass: 514

&Lt; Identification of compound represented by formula (I-67)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 464

                          Exact Mass: 463

Example 62

In the same manner as in Example 58 except that 4-nitrophthalonitrile was used instead of phthalonitrile while maintaining the molar ratio and 2-chlorobenzoyl acetonitrile was used in place of 4-chlorobenzoyl acetonitrile while maintaining the molar ratio To obtain a mixture containing the compound represented by the formula (I-68) and the compound represented by the formula (I-69).

&Lt; Identification of compound represented by formula (I-68)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 515

                          Exact Mass: 514

&Lt; Identification of compound represented by formula (I-69)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 464

                          Exact Mass: 463

Example 63

In the same manner as in Example 58 except that the molar ratio was maintained instead of 4-nitropthalonitrile in place of phthalonitrile, and 2-chlorobenzoyl acetonitrile was replaced with pivaloyl acetonitrile while maintaining the molar ratio To obtain a mixture containing the compound represented by formula (I-2) and the compound represented by formula (I-70).

&Lt; Identification of compound represented by formula (I-2) &gt;

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 407

                          Exact Mass: 406

<Identification of Compound Represented by Formula (I-70)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 410

                          Exact Mass: 409

Example 64

The procedure of Example 58 was repeated except that 2-chlorobenzoyl acetonitrile was replaced with benzoyl acetonitrile while maintaining the molar ratio and replacing the phthalonitrile with 4-nitropthalonitrile and maintaining the molar ratio thereof , A mixture containing a compound represented by the formula (I-35) and a compound represented by the formula (I-72) was obtained.

<Identification of Compound Represented by Formula (I-35)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 447

                          Exact Mass: 446

<Identification of Compound Represented by Formula (I-72)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 430

                          Exact Mass: 429

Example 65

A mixture containing a compound represented by the formula (I-4) and a compound represented by the formula (I-73) was obtained in the same manner as in Example 58 except that benzoyl acetonitrile was used instead of barbituric acid while maintaining the molar ratio &Lt; / RTI &gt;

<Identification of Compound Represented by Formula (I-4)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 470

                          Exact Mass: 469

<Identification of Compound Represented by Formula (I-73)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 436

                          Exact Mass: 435

Example 66

(I-5) was obtained in the same manner as in Example 58 except that 2-chlorobenzoyl acetonitrile was replaced with 4-chloroacetonitrile and barbituric acid was replaced with benzoyl acetonitrile while maintaining the molar ratio And a compound represented by the formula (I-74) was obtained.

<Identification of Compound Represented by Formula (I-5)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 470

                          Exact Mass: 469

<Identification of Compound Represented by Formula (I-74)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 436

                          Exact Mass: 435

Example 67

Was obtained in the same manner as in Example 58, except that 4-nitropthalonitrile was used instead of phthalonitrile while benzoyl acetonitrile was used instead of benzoyl acetonitrile while maintaining the molar ratio, -66) and a compound represented by the formula (I-75) were obtained.

<Identification of Compound Represented by Formula (I-66)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 515

                          Exact Mass: 514

<Identification of Compound Represented by Formula (I-75)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 481

                          Exact Mass: 480

Example 68

2-chlorobenzoyl acetonitrile was replaced by 4-chlorobenzoyl acetonitrile while maintaining the molar ratio and phthalonitrile was replaced by 4-nitropthalonitrile while keeping the molar ratio, and the barbituric acid was dissolved in benzoyl acetonitrile , A mixture containing a compound represented by the formula (I-68) and a compound represented by the formula (I-76) was obtained in the same manner as in Example 58.

&Lt; Identification of compound represented by formula (I-68)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 515

                          Exact Mass: 514

<Identification of Compound Represented by Formula (I-76)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 481

                          Exact Mass: 480

Example 69

(I-3) and a compound represented by the formula (I-3) were obtained in the same manner as in Example 57 except that barbituric acid was replaced with dimedone (manufactured by Tokyo Chemical Industry Co., -77) was obtained.

<Identification of Compound Represented by Formula (I-3)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 402

                          Exact Mass: 401

&Lt; Identification of compound represented by formula (I-77)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 397

                          Exact Mass: 396

Example 70

Was obtained in the same manner as in Example 7 except that methyl 4-cyanoacetylbenzoate was used in place of 3-oxo-3- (2-thienyl) propionitrile (Sigma Aldrich Japan) To obtain a compound represented by the formula (I-78).

Example 71

(I-79) was obtained in the same manner as in Example 7, except that methyl 4-cyanoacetylbenzoate was replaced with 2-furoyl acetonitrile (Sigma Aldrich Japan KK) while maintaining the molar ratio &Lt; / RTI &gt;

<Identification of Compound Represented by Formula (I-79)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 382

                          Exact Mass: 381

Example 72

(I-44) and the compound represented by the formula (I-80) were obtained in the same manner as in Example 58, except that 2-chlorobenzoyl acetonitrile was replaced with 3-cyanoacetylbenzoic acid while maintaining the molar ratio Lt; / RTI &gt;

<Identification of Compound Represented by Formula (I-44)

(Mass spectrometry) Ionization mode = ESI-: m / z = [M-H] ^- 488

                                Exact Mass: 489

<Identification of Compound Represented by Formula (I-80)

(Mass spectrometry) Ionization mode = ESI-: m / z = [M-H] ^- 427

                                Exact Mass: 428

Example 73

(I-45) and the compound represented by the formula (I-81) were obtained in the same manner as in Example 58 except that 2-chlorobenzoyl acetonitrile was replaced with 4-cyanoacetylbenzoic acid while maintaining the molar ratio Lt; / RTI &gt;

<Identification of Compound Represented by Formula (I-45)

(Mass spectrometry) Ionization mode = ESI-: m / z = [M-H] ^- 488

                               Exact Mass: 489

&Lt; Identification of compound represented by formula (I-81)

(Mass spectrometry) Ionization mode = ESI-: m / z = [M-H] ^- 427

                                Exact Mass: 428

Example 74

The same procedure as in Example 58 was followed except that 2-chlorobenzoyl acetonitrile was replaced with 3-cyano acetyl benzoic acid while maintaining the molar ratio and replacing the phthalonitrile with 4-nitropthalonitrile and maintaining the molar ratio To obtain a mixture containing the compound represented by the formula (I-82) and the compound represented by the formula (I-83).

<Identification of Compound Represented by Formula (I-82)

(Mass spectrometry) Ionization mode = ESI-: m / z = [M-H] ^- 533

                                Exact Mass: 534

&Lt; Identification of compound represented by formula (I-83)

(Mass spectrometry) Ionization mode = ESI-: m / z = [M-H] ^- 472

                                Exact Mass: 473

Example 75

The procedure of Example 58 was repeated except that 4-nitrophthalonitrile was used instead of phthalonitrile while maintaining the molar ratio and 2-chlorobenzoyl acetonitrile was replaced with 4-cyanoacetylbenzoic acid while maintaining the molar ratio. To obtain a mixture containing the compound represented by the formula (I-84) and the compound represented by the formula (I-85).

&Lt; Identification of compound represented by formula (I-84)

(Mass spectrometry) Ionization mode = ESI-: m / z = [M-H] ^- 533

                                Exact Mass: 534

<Identification of Compound Represented by Formula (I-85)

(Mass spectrometry) Ionization mode = ESI-: m / z = [M-H] ^- 472

                                Exact Mass: 473

Example 76

The compound represented by the formula (I-43) and the compound represented by the formula (I-86) were obtained in the same manner as in Example 58 except that 2-chlorobenzoyl acetonitrile was replaced with 2-cyanoacetylbenzoic acid while maintaining the molar ratio Lt; / RTI &gt;

<Identification of Compound Represented by Formula (I-43)

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ^- 488

                          Exact Mass: 489

<Identification of Compound Represented by Formula (I-86)

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ^- 427

                          Exact Mass: 428

Example 77

In the same manner as in Example 58 except that 2-chlorobenzoyl acetonitrile was replaced with 2-cyano acetyl benzoic acid while maintaining the molar ratio and replacing the phthalonitrile with 4-nitropthalonitrile and maintaining the molar ratio To obtain a mixture containing the compound represented by the formula (I-87) and the compound represented by the formula (I-88).

<Identification of Compound (Compound 221) Represented by Formula (I-87)> [

(Mass spectrometry) Ionization mode = ESI +: m / z = [M + H] ^- 533

                          Exact Mass: 534

<Identification of Compound (Compound 585) Represented by Formula (I-88)> [

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ^- 472

                          Exact Mass: 473

Synthesis Example 5

In a one liter flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was appropriately poured into the flask and the flask was purged with nitrogen. 280 parts of propylene glycol monomethyl ether acetate was added and heated to 80 DEG C with stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan- (289 parts) and propylene glycol monomethyl ether acetate (125 parts) was added dropwise over 5 hours.

On the other hand, a mixed solution obtained by dissolving 33 parts of 2,2-azobis (2,4-dimethylvaleronitrile) in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin B1) having a solid content of 35.0%. The resin B1 thus obtained had a weight average molecular weight of 8800, a degree of dispersion of 2.1, and a solution acidity of 28 mg-KOH / g.

Synthesis Example 6

In a one liter flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was poured in a nitrogen stream, 371 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 DEG C with stirring. Then, 54 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan- , 81 parts of vinyl toluene (isomer mixture) and 80 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, a solution prepared by dissolving 30 parts of polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the addition of the initiator solution was completed, the mixture was maintained at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin B2) having a solid content of 37.5%. The resin B2 thus obtained had a weight-average molecular weight of 10600, a degree of dispersion of 2.01, and a solution acid value of 43 mg-KOH / g.

Example 78

Colorant (A): 18 parts of the compound (I-2) obtained in Example 2;

Resin (B): Resin B1 solution 465 parts;

Solvent (E): 6.24 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 510 parts of N-methyl-2-pyrrolidone and

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

To obtain a coloring composition.

Example 79

Colorant (A): 10 parts of the compound (I-3) obtained in Example 3;

7 parts of a dispersing agent (DISPERBYK-2155; manufactured by VICK Chemie Japan KK);

Resin (B): 18.6 parts of Resin B2 solution;

Solvent (E): 154 parts of propylene glycol monomethyl ether acetate;

Solvent (E): 10 parts of 4-hydroxy-4-methyl-2-pentanone;

And the compound represented by the formula (I-3) was dispersed using a bead mill to obtain a colored dispersion.

Example 80

Pigment: C.I. Pigment Green 7 27 parts;

12.2 parts of an acrylic pigment dispersant;

Resin (B): 25.2 parts of Resin B2 solution;

Solvent (E): 161 parts of propylene glycol monomethyl ether acetate;

A pigment dispersion in which a pigment is dispersed using a bead mill;

60 parts of the colored dispersion obtained in Example 79;

Resin (B): Resin B2 solution 97.2 parts;

Polymerizable compound (C): 48 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.);

Polymerization initiator (D): 9.6 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01;

Solvent (E): 560 parts of propylene glycol monomethyl ether acetate; and

Leveling agent: 0.15 part of a polyether-modified silicone oil (Toresilicon SH8400; manufactured by Toray Dow Corning Incorporated);

Were mixed to obtain a colored curable resin composition.

Example 81

Pigment: C.I. Pigment Green 58 27 parts;

12.2 parts of an acrylic pigment dispersant;

Resin (B): 25.2 parts of Resin B2 solution;

Solvent (E): 161 parts of propylene glycol monomethyl ether acetate;

A pigment dispersion in which a pigment is dispersed using a bead mill;

60 parts of the colored dispersion obtained in Example 79;

Resin (B): Resin B2 solution 97.2 parts;

Polymerizable compound (C): 48 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.);

Polymerization initiator (D): 9.6 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01;

Solvent (E): 560 parts of propylene glycol monomethyl ether acetate; and

Leveling agent: 0.15 part of a polyether-modified silicone oil (Toresilicon SH8400; manufactured by Toray Dow Corning Incorporated);

Were mixed to obtain a colored curable resin composition.

Example 82

Pigment: C.I. Pigment Green 59 27 parts;

12.2 parts of an acrylic pigment dispersant;

Resin (B): 25.2 parts of Resin B2 solution;

Solvent (E): 161 parts of propylene glycol monomethyl ether acetate;

A pigment dispersion in which a pigment is dispersed using a bead mill;

60 parts of the colored dispersion obtained in Example 79;

Resin (B): Resin B2 solution 97.2 parts;

Polymerizable compound (C): 48 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.);

Polymerization initiator (D): 9.6 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01;

Solvent (E): 560 parts of propylene glycol monomethyl ether acetate; and

Leveling agent: 0.15 part of a polyether-modified silicone oil (Toresilicon SH8400; manufactured by Toray Dow Corning Incorporated);

Were mixed to obtain a colored curable resin composition.

Example 83

Pigment: C.I. Pigment Green 36 27 parts;

12.2 parts of an acrylic pigment dispersant;

Resin (B): 25.2 parts of Resin B2 solution;

Solvent (E): 161 parts of propylene glycol monomethyl ether acetate;

A pigment dispersion in which a pigment is dispersed using a bead mill;

60 parts of the colored dispersion obtained in Example 79;

Resin (B): Resin B2 solution 97.2 parts;

Polymerizable compound (C): 48 parts of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.);

Polymerization initiator (D): 9.6 parts of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01;

Solvent (E): 560 parts of propylene glycol monomethyl ether acetate; and

Leveling agent: 0.15 part of a polyether-modified silicone oil (Toresilicon SH8400; manufactured by Toray Dow Corning Incorporated);

Were mixed to obtain a colored curable resin composition.

Example 84

[Production of coloring pattern]

The colored curable resin composition obtained in Example 80 was applied on a glass substrate (Eagle XG; Corning) having a size of 2 inches and a width of 2 inches by a spin coat method, and then prebaked at 100 캜 for 3 minutes to form a coloring composition layer. After cooling, an exposure amount (365 nm) of 80 mJ / cm &lt; 2 &gt; in an atmospheric environment was measured using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) at a distance of 200 mu m between the substrate on which the colored composition layer was formed and the quartz glass photomask. Nm). As the photomask, a 100 μm line and space pattern was formed. The colored 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 캜 for 70 seconds to develop and wash.

This colored coating film was post-baked at 230 캜 for 30 minutes to obtain a colored pattern.

Example 85

A colored pattern was obtained in the same manner as in Example 84 except that the colored curable resin composition obtained in Example 80 was replaced with the colored curable resin composition obtained in Example 81.

Example 86

A colored pattern was obtained in the same manner as in Example 84 except that the colored curable resin composition obtained in Example 80 was replaced with the colored curable resin composition obtained in Example 82. [

Example 87

A colored pattern was obtained in the same manner as in Example 84 except that the colored curable resin composition obtained in Example 80 was replaced with the colored curable resin composition obtained in Example 83.

Synthesis Example 7

(Trimethylsilyl) amide in a molar ratio of three times the molar number of moles of acetonitrile, 4- (carboxymethyl) benzoate and 10 parts of methyl 4- (carboxymethyl) benzoate at a molar ratio of 4 times the number of moles of methyl, A mixture of 130 parts of tetrahydrofuran was obtained.

To this mixture was added a mixture of 10 parts of methyl 4- (carboxymethyl) benzoate and 90 parts of tetrahydrofuran, and the mixture was stirred at -78 캜 for 16 hours at room temperature.

The obtained mixture was purified to obtain 8 parts of 4- (carboxymethyl) -1- (cyanomethylcarbonyl) benzene.

<Identification of 4- (carboxymethyl) -1- (cyanomethylcarbonyl) benzene>

(Mass analysis) Ionization mode = ESI-: m / z = [MH] ^- 202

   Exact Mass: 203

Synthesis Example 8

A solution of lithium bis (trimethyl (trimethylsilyl) trimethylsilyl) diborate in a molar ratio of 5.5 times the number of moles of acetonitrile and methyl 4- (2-carboxyethyl) benzoate in a molar ratio of 6 times the number of moles of methyl 4- Silyl) amide and 890 parts of tetrahydrofuran.

To this mixture was added 33 parts of methyl 4- (2-carboxyethyl) benzoate, and the mixture was stirred at -78 ° C for 30 minutes. The resulting mixture was purified to obtain 29 parts of 4- (2-carboxyethyl) -1- (cyanomethylcarbonyl) benzene.

<Identification of 4- (2-carboxyethyl) -1- (cyanomethylcarbonyl) benzene>

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 216

   Exact Mass: 217

Synthesis Example 9

(Trimethylsilyl) amide having a molar number of 3 times the number of moles of acetonitrile and 30 parts of methyl methyl 2- (carboxymethyl) benzoate in a molar amount of 4 times the number of moles of 30 parts of methyl 2- (carboxymethyl) benzoate and A mixture of 270 parts of tetrahydrofuran was obtained. To this mixture was added a mixture of 30 parts of methyl 2- (carboxymethyl) benzoate and 270 parts of tetrahydrofuran, and the mixture was stirred at -78 占 폚 for 3 hours at room temperature. The resulting mixture was purified to obtain 27 parts of 2- (carboxymethyl) -1- (cyanomethylcarbonyl) benzene.

<Identification of 2- (carboxymethyl) -1- (cyanomethylcarbonyl) benzene>

(Mass analysis) Ionization mode = ESI-: m / z = [MH] ^- 202

   Exact Mass: 203

Synthesis Example 10

The molar number of moles of 34 parts of acetonitrile and 4- (2- (methoxycarbonyl) ethyl) benzoic acid in the molar amount of 6 times the number of moles of 4- (2- (methoxycarbonyl) ethyl) To obtain a mixture of lithium bis (trimethylsilyl) amide and 1200 parts of tetrahydrofuran.

To this mixture was added 34 parts of 4- (2- (methoxycarbonyl) ethyl) benzoic acid, and the mixture was stirred at -78 ° C for 1 hour. The resulting mixture was purified by recrystallization using ethyl acetate and hexane to obtain 30 parts of 4- (2- (cyanomethylcarbonyl) ethyl) benzoic acid.

<Identification of 4- (2- (cyanomethylcarbonyl) ethyl) benzoic acid>

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 216

   Exact Mass: 217

Synthesis Example 11

Butyllithium at a molar ratio of 5 times the number of moles of acetonitrile and 4- (methoxycarbonylmethyl) benzoic acid in a molar number of 5.5 times the molar number of moles of 4- (methoxycarbonylmethyl) benzoic acid, 28 parts of 4- And 1100 parts of tetrahydrofuran.

To the mixture was added 28 parts of 4- (methoxycarbonylmethyl) benzoic acid, and the mixture was stirred at -78 ° C for 15 minutes. The resulting mixture was purified by column chromatography to obtain 22 parts of 4- (cyanomethylcarbonylmethyl) benzoic acid.

<Identification of 4- (cyanomethylcarbonylmethyl) benzoic acid>

(Mass analysis) Ionization mode = ESI-: m / z = [MH] ^- 202

   Exact Mass: 203

Synthesis Example 12

To a solution of 18 parts of 4- (methoxycarbonyl) -3-methoxybenzoic acid and 18 parts of 4- (methoxycarbonyl) -3-methoxybenzoic acid under the condition of 3 To obtain a mixture of lithium bis (trimethylsilyl) amide and 160 parts of tetrahydrofuran.

To this mixture was added a mixture of 18 parts of 4- (methoxycarbonyl) -3-methoxybenzoic acid and 160 parts of tetrahydrofuran, and the mixture was stirred at -78 캜 for 16 hours at room temperature.

The resulting mixture was purified to obtain 15 parts of 4- (cyanomethylcarbonyl) -3-methoxybenzoic acid.

<Identification of 4- (cyanomethylcarbonyl) -3-methoxybenzoic acid>

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 218

   Exact Mass: 219

Synthesis Example 13

A solution of 3 parts of the number of moles of acetonitrile and 14 parts of 4- (methoxycarbonyl) -2-methoxybenzoic acid, which is four times the number of moles of 4- (methoxycarbonyl) -2-methoxybenzoic acid, To obtain a mixture of lithium bis (trimethylsilyl) amide and 120 parts of tetrahydrofuran in a molar ratio of 2: 1.

To the mixture was added a mixture of 14 parts of 4- (methoxycarbonyl) -2-methoxybenzoic acid and 120 parts of tetrahydrofuran, and the mixture was stirred at -78 캜 for 16 hours at room temperature.

The resulting mixture was purified to obtain 13 parts of 4- (cyanomethylcarbonyl) -2-methoxybenzoic acid.

<Identification of 4- (cyanomethylcarbonyl) -2-methoxybenzoic acid>

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 218

   Exact Mass: 219

Example 88

5 parts of 4-aminophthalonitrile and 40 parts of methanol were mixed.

To the resulting mixture was added a 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 0.5 times the number of moles of 4-aminopthalonitrile while keeping the temperature below 5 占 폚. This mixture was stirred at 5 캜 for 3 hours and then at room temperature for 16 hours.

Benzoyl acetonitrile having a molar number of 2.2 times the number of moles of 5-aminopthalonitrile and 5.3 parts of acetic acid were added to the resulting mixture. This mixture was stirred at room temperature for 32 hours. The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.3 part of a compound represented by the formula (I-89).

&Lt; Identification of compound represented by formula (I-89)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 417

   Exact Mass: 416

Example 89

5 parts of 4- (N-acetylamino) phthalonitrile and 40 parts of methanol were mixed.

A 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 0.5 times the number of moles of 4- (N-acetylamino) phthalonitrile was added to the resulting mixture while keeping the temperature below 5 占 폚.

This mixture was stirred at 5 캜 for 3 hours and then at room temperature for 16 hours.

Benzoyl acetonitrile having a molar number of 2.2 times the number of moles of 4- (N-acetylamino) phthalonitrile and 5.3 parts of acetic acid was added to the resulting mixture.

This mixture was stirred at room temperature for 16 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.2 part of a compound represented by the formula (I-90).

<Identification of Compound Represented by Formula (I-90)

(Mass analysis) Ionization mode = ESI +: m / z = [MH] ⁺ 459

   Exact Mass: 458

Example 90

3 parts of 4-carboxyphthalonitrile and 32 parts of ethanol were mixed.

To the resulting mixture was added a 21% sodium ethoxide ethanol solution containing sodium ethoxide at a molar ratio of 2.1 times the number of moles of 3-carboxy phthalonitrile at room temperature.

This mixture was stirred at 60 캜 for 16 hours.

Benzoyl acetonitrile having a molar number of 2.3 times the number of moles of 3-carboxy phthalonitrile and 9.4 parts of acetic acid were added to the obtained mixture. This mixture was stirred at 90 캜 for 20 hours. To the obtained mixture, 9.4 parts of acetic acid was added.

This mixture was stirred at 90 캜 for 72 hours. The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.5 part of a compound represented by the formula (I-91).

&Lt; Identification of compound represented by formula (I-91)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 444

   Exact Mass: 445

Example 91

3 parts of 4-carboxyphthalonitrile and 47 parts of ethanol were mixed. To the resulting mixture was added a 25% sodium methoxide methanol solution containing sodium methoxide in a molar amount twice that of 3 parts of 4-carboxyphthalonitrile at room temperature.

This mixture was stirred at 60 캜 for 16 hours.

To the obtained mixture, 4-cyanoacetylbenzoic acid having a molar number of 2.3 times the number of moles of acetic acid and 3 parts of 4-carboxyphthalonitrile and 120 parts of methanol was added.

This mixture was stirred at 70 캜 for 96 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.2 part of a compound represented by the formula (I-92).

<Identification of Compound Represented by Formula (I-92)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 532

   Exact Mass: 533

Example 92

3 parts of 4,5-dichlorophthalonitrile and 48 parts of methanol were mixed.

To the resulting mixture was added a 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 1 mole of 3 parts of 4,5-dichloro phthalonitrile while maintaining the temperature at 0 占 폚.

This mixture was stirred at room temperature for 16 hours.

To the obtained mixture, 4-cyanoacetylbenzoic acid having a molar number of 2.2 times the number of moles of acetic acid and 3 parts of 4,5-dichlorophthalonitrile and 160 parts of methanol was added.

This mixture was stirred at room temperature for 48 hours, and then stirred at 50 ° C for 16 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.6 part of a compound represented by the formula (I-93).

&Lt; Identification of compound represented by formula (I-93)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 556

   Exact Mass: 557

Example 93

5 parts of 4-methoxyphthalonitrile and 79 parts of methanol were mixed.

A 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 2.5 times the number of moles of 4-methoxyphthalonitrile was added to the resulting mixture while keeping the temperature at 0 占 폚.

This mixture was stirred at room temperature for 3 hours, and then stirred at 65 ° C for 3 hours.

To the obtained mixture, 4-cyanoacetylbenzoic acid having a molar number of 2.2 times the number of moles of 4-methoxyphthalonitrile, 160 parts of methanol and 21 parts of acetic acid were added.

This mixture was stirred at room temperature for 64 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.6 part of a compound represented by the formula (I-94).

&Lt; Identification of compound represented by formula (I-94)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 518

   Exact Mass: 519

Example 94

5 parts of 4-methoxyphthalonitrile and 79 parts of methanol were mixed.

To the resulting mixture was added a 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of twice the mole number of 5-methoxyphthalonitrile while maintaining the temperature at 0 占 폚. This mixture was stirred at 70 캜 for 5 hours.

3-cyanoacetylbenzoic acid having a molar number of 2.5 times the number of moles of 4-methoxyphthalonitrile, 160 parts of methanol and 21 parts of acetic acid were added to the obtained mixture.

This mixture was stirred at room temperature for 68 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.6 part of a compound represented by the formula (I-95).

<Identification of compound (Compound 21-168) represented by formula (I-95)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 518

   Exact Mass: 519

Example 95

8 parts of 4-methoxyphthalonitrile and 95 parts of methanol were mixed.

At room temperature, 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 2.5 times the number of moles of 4-methoxyphthalonitrile was added to the resulting mixture.

The mixture was stirred at 65 캜 for 3 hours.

To the resulting mixture, 2-cyanoacetylbenzoic acid and 34 parts of acetic acid in a molar ratio of 2.2 times the number of moles of 4-methoxyphthalonitrile were added.

This mixture was stirred at room temperature for 16 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.4 part of a compound represented by the formula (I-96).

<Identification of the compound represented by the formula (I-96) (Compound 21-167)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 518

   Exact Mass: 519

Example 96

2 parts of 4-carboxyphthalonitrile and 32 parts of methanol were mixed.

To the resulting mixture was added a 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of twice the mole number of 4-carboxyphthalonitrile while maintaining the temperature at 0 占 폚.

This mixture was stirred at 60 캜 for 6 hours.

To the resulting mixture, 4.2 parts of acetic acid, 4- (carboxymethyl) -1- (cyanomethylcarbonyl) benzene having a molar number of 2.2 times the number of moles of 2-carboxyphthalonitrile and 95 parts of methanol were added.

This mixture was stirred at 70 캜 for 16 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.3 part of a compound represented by the formula (I-97).

&Lt; Identification of compound represented by formula (I-97)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 560

   Exact Mass: 561

Example 97

6.51 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 58 parts of methanol were mixed.

A mixture of 7.61 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 71 parts of methanol was added dropwise to the obtained mixture over 1 hour and 30 minutes while maintaining the temperature at 5 ° C or lower. The resulting mixture was stirred at 5 占 폚 or lower for 12 hours. 15.0 parts of acetic acid was added to the resulting mixture while keeping the temperature below 5 占 폚, and then 30.2 parts of 2-chlorobenzoyl acetonitrile (manufactured by TOKYO HOSUNG KOGYO CO., LTD.) And 927 parts of methanol were added.

The resulting mixture was stirred at room temperature for 4 hours and then at 40 ° C for 96 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.882 part of a compound represented by the formula (I-4).

<Identification of Compound Represented by Formula (I-4)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 470

   Exact Mass: 469

Example 98

5.44 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 64 parts of methanol were mixed.

A mixture of 6.37 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 48 parts of methanol was added dropwise to the resulting mixture while keeping the temperature at 5 占 폚 or lower for 1 hour and 30 minutes. The resulting mixture was stirred for 12 hours while keeping the temperature below 5 캜. 4.20 parts of acetic acid, 742 parts of methanol and 7.69 parts of 2-chlorobenzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the resulting mixture while keeping the temperature at 5 占 폚 or lower. The resulting mixture was stirred at room temperature for 36 hours.

0.482 parts of acetic acid and 0.775 parts of 2-chlorobenzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the resulting mixture, and the mixture was stirred at room temperature for 3 hours and then at 40 占 폚 for 12 hours.

0.638 parts of acetic acid and 1.15 parts of 2-chlorobenzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the obtained mixture, followed by stirring at 40 占 폚 for 6 hours. 0.549 parts of acetic acid and 0.958 parts of 2-chlorobenzoyl acetonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the resulting mixture, and the mixture was stirred at 40 占 폚 for 36 hours. To the resulting mixture was added 4.17 parts of acetic acid and 5.96 parts of barbituric acid, and the mixture was stirred at 40 占 폚 for 48 hours. 2.08 parts of acetic acid and 2.72 parts of barbituric acid were added to the obtained mixture, and the mixture was stirred at 40 占 폚 for 24 hours. The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.283 parts of a compound represented by the formula (I-63).

<Identification of Compound Represented by Formula (I-63)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 419

   Exact Mass: 418

Example 99

7.51 parts of 4,5-dichlorophthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 130 parts of methanol were mixed.

7.41 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the obtained mixture while maintaining the temperature at 0 占 폚 for 1 hour and 30 minutes.

The resulting mixture was stirred at room temperature for 16 hours.

At room temperature, 16.0 parts of acetic acid, 670 parts of methanol and 7.27 parts of 4-cyanoacetylbenzoic acid were added to the resulting mixture.

The resulting mixture was stirred at room temperature for 12 hours and then at 50 ° C for 12 hours.

To the resultant mixture was added 0.433 part of acetic acid and 0.733 part of 4-cyanoacetylbenzoic acid, followed by stirring at 50 ° C for 6 hours. To the resulting mixture was added 0.573 part of acetic acid and 1.09 part of 4-cyanoacetylbenzoic acid, and the mixture was stirred at 50 ° C for 6 hours. 0.493 parts of acetic acid and 0.906 parts of 4-cyanoacetylbenzoic acid were added to the resulting mixture, and the mixture was stirred at 50 캜 for 12 hours. To the obtained mixture, 3.75 parts of acetic acid and 5.35 parts of barbituric acid were added, and the mixture was stirred at 50 占 폚 for 24 hours. 1.87 parts of acetic acid and 2.44 parts of barbituric acid were added to the obtained mixture, and the mixture was stirred at 50 占 폚 for 24 hours. The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.252 part of a compound represented by the formula (I-98).

&Lt; Identification of compound represented by formula (I-98)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 495

   Exact Mass: 496

Example 100

In the same manner as in Example 98 except that 2-chlorobenzoyl acetonitrile was replaced with 4-cyanoacetylbenzoic acid while the molar ratio was maintained, and benzoyl acetonitrile was used instead of barbituric acid, To obtain a compound represented by the formula (I-99).

<Identification of Compound Represented by Formula (I-99)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 444

   Exact Mass: 445

Example 101

2-chlorobenzoyl acetonitrile was replaced with 4-cyano acetyl benzoic acid while the molar ratio was maintained, while 4-nitrophthalonitrile was used instead of the phthalonitrile, and while maintaining the molar ratio, A compound represented by the formula (I-100) was obtained in the same manner as in Example 98 except that benzoyl acetonitrile was used instead of benzoyl acetonitrile.

<Identification of Compound Represented by Formula (I-100)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 489

   Exact Mass: 490

Example 102

A compound represented by the formula (I-101) was obtained in the same manner as in Example 99 except that benzoyl acetonitrile was used instead of benzoyl peroxide while maintaining the molar ratio.

&Lt; Identification of compound represented by formula (I-101)

(Mass analysis) Ionization mode = ESI-: m / z = [MH] ^- 512

   Exact Mass: 513

Example 103

In the same manner as in Example 98 except that 2-chlorobenzoyl acetonitrile was replaced with 2-cyano acetyl benzoic acid while the molar ratio was maintained, and benzoyl acetonitrile was used instead of barbituric acid while maintaining the molar ratio, A compound represented by the formula (I-102) was obtained.

<Identification of Compound Represented by Formula (I-102)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 444

   Exact Mass: 445

Example 104

While keeping the molar ratio, the substitution of 4-nitropthalonitrile for phthalonitrile, 2-cyanoacetylbenzoic acid for 2-chlorobenzoyl acetonitrile, and maintaining the molar ratio of bovisulfic acid to benzoyl acetonitrile , A compound represented by the formula (I-103) was obtained in the same manner as in Example 98.

<Identification of Compound Represented by Formula (I-103)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 489

   Exact Mass: 490

Example 105

Was obtained in the same manner as in Example 99 except that 4-cyanoacetylbenzoic acid was replaced with 2-cyanoacetylbenzoic acid while the molar ratio was maintained, and benzoyl acetonitrile was used instead of barbituric acid, To obtain a compound represented by the formula (I-104).

<Identification of the compound represented by the formula (I-104) (01-151)

(Mass analysis) Ionization mode = ESI-: m / z = [MH] ^- 512

   Exact Mass: 513

Example 106

3 parts of 4-bromophthalonitrile and 24 parts of methanol were mixed.

To the obtained mixture was added a 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 0.5 times the molar amount of 3 parts of 4-bromophthalonitrile while maintaining the temperature at 0 占 폚.

This mixture was stirred for 3 hours at 0 ° C.

To the resulting mixture, 4-cyanoacetylbenzoic acid and 3.1 parts of acetic acid in a molar ratio of 2.2 times the number of moles of 3-bromomethanitrile were added.

This mixture was stirred at room temperature for 16 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.3 part of a compound represented by the formula (I-105).

&Lt; Identification of compound represented by formula (I-105)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 566

   Exact Mass: 567

Example 107

5 parts of 3,4-dicyanobenzenesulfonic acid and 79 parts of methanol were mixed.

A 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 0.5 times the number of moles of 3,4-dicyanobenzenesulfonic acid was added to the resulting mixture while keeping the temperature at 0 占 폚.

This mixture was stirred for 6 hours at 0 ° C.

To the resulting mixture was added 5.2 parts of 4-cyanoacetylbenzoic acid and acetic acid in a molar ratio of 2.2 times the number of moles of 3,4-dicyanobenzenesulfonic acid.

This mixture was stirred at room temperature for 16 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.4 part of a compound represented by the formula (I-106).

<Identification of Compound Represented by Formula (I-106)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 568

   Exact Mass: 569

Example 108

2 parts of phthalonitrile and 16 parts of methanol were mixed.

A 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 0.5 times the number of moles of phthalonitrile was added to the resulting mixture while keeping the temperature at 5 캜.

This mixture was stirred at 5 캜 for 3 hours.

To the obtained mixture, N-acetyl-4- (cyanoacetyl) aniline and 2.2 parts of acetic acid in a molar ratio of 2.2 times the number of moles of phthalonitrile were added.

This mixture was stirred at room temperature for 16 hours.

To the obtained mixture, N-acetyl-4- (cyanoacetyl) aniline in a molar ratio of 1.1 times the molar amount of 2 parts of phthalonitrile was added.

This mixture was stirred at room temperature for 16 hours, and then stirred at 50 ° C for 48 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.3 part of a compound represented by the formula (I-107).

&Lt; Identification of compound represented by formula (I-107)

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

   Exact Mass: 515

Example 109

2 parts of 4- (trifluoromethyl) phthalonitrile and 32 parts of methanol were mixed.

A 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 0.8 times the number of moles of 4- (trifluoromethyl) phthalonitrile was added to the resulting mixture while maintaining the temperature at 0 占 폚.

This mixture was stirred at 10 캜 for 2 hours.

To the resulting mixture was added 4-cyanoacetylbenzoic acid in a molar ratio of 2.2 times the number of moles of the acetic acid and 4.4 parts of 4- (trifluoromethyl) phthalonitrile.

This mixture was stirred at room temperature for 16 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.3 part of a compound represented by the formula (I-108).

<Identification of Compound Represented by Formula (I-108)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 556

   Exact Mass: 557

Example 110

4 parts of 4- (trifluoromethyl) phthalonitrile and 32 parts of methanol were mixed.

A 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 0.5 times the number of moles of 4- (trifluoromethyl) phthalonitrile was added to the resulting mixture while maintaining the temperature at 0 占 폚.

This mixture was stirred for 3 hours at 0 ° C.

To the obtained mixture, 3-cyanoacetylbenzoic acid and 4.4 parts of acetic acid in a molar ratio of 2.2 times the number of moles of 4- (trifluoromethyl) phthalonitrile were added.

This mixture was stirred at room temperature for 16 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.3 part of a compound represented by the formula (I-109).

<Identification of Compound Represented by Formula (I-109)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 556

   Exact Mass: 557

Example 111

2.5 parts of 4- (trifluoromethyl) phthalonitrile and 79 parts of methanol were mixed.

To the obtained mixture was added a 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 0.5 times the molar amount of 2.5 parts of 4- (trifluoromethyl) phthalonitrile while maintaining the temperature at 0 占 폚.

This mixture was stirred for 3 hours at 0 ° C.

To the obtained mixture, 2.2 parts of moles of 2-cyanoacetylbenzoic acid and 3 parts of acetic acid were added to 2.5 parts of 4- (trifluoromethyl) phthalonitrile.

This mixture was stirred at room temperature for 16 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.1 part of a compound represented by the formula (I-110).

<Identification of Compound Represented by Formula (I-110)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 556

   Exact Mass: 557

Example 112

2 parts of phthalonitrile and 16 parts of methanol were mixed.

A 25% sodium methoxide methanol solution containing sodium methoxide in a molar ratio of 0.5 times the number of moles of phthalonitrile was added to the resulting mixture while keeping the temperature at 5 캜.

This mixture was stirred at 5 캜 for 3 hours and then at room temperature for 16 hours.

To the resulting mixture was added 2.2 parts of 4-sulfamoylbenzoyl acetonitrile and 2.2 parts of acetic acid in a molar ratio of 2.2 times the number of moles of phthalonitrile.

This mixture was stirred at room temperature for 16 hours.

The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.3 part of a compound represented by the formula (I-42).

<Identification of Compound Represented by Formula (I-42)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 560

   Exact Mass: 559

Example 113 Synthesis of

4.1 parts of phthalonitrile (manufactured by Tokyo Chemical Industry Co., Ltd.) and 48 parts of methanol were mixed.

A mixture of 4.8 parts of a 28% sodium methoxide methanol solution (manufactured by Wako Pure Chemical Industries, Ltd.) and 36 parts of methanol was added dropwise to the obtained mixture while keeping the temperature at 5 占 폚 or lower for 1 hour and 30 minutes. The resulting mixture was stirred for 12 hours while keeping the temperature below 5 캜.

To the resulting mixture was added 5.1 parts of acetic acid, 750 parts of methanol and 7.2 parts of 4-sulfamoyl benzoyl acetonitrile while keeping the temperature below 5 占 폚.

The resulting mixture was stirred at room temperature for 36 hours. 0.56 parts of acetic acid and 0.73 part of 4-sulfamoyl benzoyl acetonitrile were added to the obtained mixture, and the mixture was stirred at room temperature for 3 hours and then at 40 占 폚 for 12 hours. 0.77 parts of acetic acid and 1.1 parts of 4-sulfamoylbenzoyl acetonitrile were added to the obtained mixture, and the mixture was stirred at 40 占 폚 for 6 hours.

0.66 part of acetic acid and 0.90 part of 4-sulfamoyl benzoyl acetonitrile were added to the resulting mixture, and the mixture was stirred at 40 占 폚 for 36 hours. 3.1 parts of acetic acid and 4.5 parts of barbituric acid were added to the obtained mixture, and the mixture was stirred at 40 占 폚 for 48 hours.

1.6 parts of acetic acid and 2.0 parts of barbituric acid were added to the obtained mixture, and the mixture was stirred at 40 占 폚 for 24 hours. The solvent was distilled off using a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 0.21 part of a compound represented by the formula (I-111).

&Lt; Identification of compound represented by formula (I-111)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 464

   Exact Mass: 463

Example 114

A compound represented by the formula (I-112) was obtained in the same manner as in Example 113 except that the phthalonitrile was replaced with 4-nitropthalonitrile while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-112)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 509

   Exact Mass: 508

Example 115

A compound represented by the formula (I-113) was obtained in the same manner as in Example 108 except that the phthalonitrile was replaced with 4-nitropthalonitrile while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-113)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 561

   Exact Mass: 560

Example 116

Compound (I-114) was obtained in the same manner as in Example 112 except that 4-nitropthalonitrile was used instead of phthalonitrile while maintaining the molar ratio.

&Lt; Identification of compound represented by formula (I-114)

(Mass analysis) Ionization mode = ESI +: m / z = [M + H] ⁺ 605

   Exact Mass: 604

Example 117

Compound (I-115) was obtained in the same manner as in Example 106 except that 2-cyanoacetylbenzoic acid was used instead of 4-cyanoacetylbenzoic acid while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-115)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 566

   Exact Mass: 567

Example 118

Compound (I-116) was obtained in the same manner as in Example 106 except that 3-cyanoacetylbenzoic acid was used instead of 4-cyanoacetylbenzoic acid while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-116)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 566

   Exact Mass: 567

Example 119

The compound represented by the formula (I-117) was obtained in the same manner as in Example 99 except that the barbituric acid was replaced with dimedone (manufactured by Tokyo Chemical Industry Co., Ltd.) while maintaining the molar ratio.

<Identification of Compound Represented by Formula (I-117)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 507

   Exact Mass: 508

Examples 120 to 171

Phthalonitrile was changed to a compound represented by the formula (PPA-1) having the group shown in the column of &quot; B1B2 &quot; in Table 10, and 2-chlorobenzoyl acetonitrile was changed to a compound represented by the formula (PPA-3) having the substituent described in each of the above columns was obtained in the same manner as in Example 97 except that the compound represented by the formula (PPA-2) having the group represented by the formula

The identity of the compounds was determined by mass spectrometry. The value detected in the (mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ is shown in the "detection value" column for the embodiment in which "1" is described in the "ionization mode" column. For the embodiment described a "-1" in the table "ionization mode" column of the next page example, (Mass Spec.) Ionization mode = ESI-: m / z = [ MH] - of the values detected in, Table 10. " Detection value &quot;&Quot; Exact. In the column "Exact. Mass. Respectively.

[Table 10]

In Table 10, symbols (HH35, BB19, etc.) described in the column "B1B2" and "Hd" are defined in the same manner as the symbols in Tables 1 to 9 (b) do.

(HHJ5), HHJ6, HHJ7, HHJ10, HHJ14, HHJ6, HHJ7, HHJ10, HHJ14, HHJ15, HHk5, HHk6 and HHk7, , The formula (HHJ15), the formula (HHk5), the formula (HHk6) and the formula (HHk7).

Examples 172 to 187

4-cyanoacetylbenzoic acid was replaced with a compound represented by the formula (PPA-2) having a group represented by the "Lk" column and the "Hd" column in Table 11, in the same manner as in Example 92, To obtain a compound represented by the formula (I-93a) having a substituent described in the above.

The identity of the compounds was determined by mass spectrometry. The results of the mass spectrometric analysis are shown in Table 11 in the same manner as in Examples 120 to 171.

[Table 11]

In Table 11, the symbols (HH35 and the like) described in the column "Hd" are defined in the same manner as the symbols in Tables 1 to 9 (b) of the present specification. HHk7 represents a group represented by the above formula (HHk7).

Examples 188 to 229

Phthalonitrile was changed to a compound represented by the formula (PPA-1) having the group shown in the column of &quot; B1B2 &quot; in Table 12 and 2-chlorobenzoyl acetonitrile was added to the column of &quot; Lk &quot; (PPA-2) having the group represented by the formula (I-63) shown above, the compound represented by the formula (I-63a) having the substituents described in the above columns was obtained in the same manner as in Example 98.

The identity of the compounds was determined by mass spectrometry. The results of the mass spectrometric analyzes are shown in Table 12 in the same manner as in Examples 120 to 171.

[Table 12]

In Table 12, the symbols in the column "B1B2" and the column "Hd" are defined in the same manner as the symbols in Tables 1 to 9 (b) of this specification except for the following symbols. HHk7 represents a group represented by the above formula (HHk7).

Examples 230 to 243

4-cyanoacetylbenzoic acid was replaced with a compound represented by the formula (PPA-2) having a group represented by the "Lk" column and the "Hd" column in Table 13, in the same manner as in Example 99, A compound represented by the formula (I-98a) having a substituent described in (1) above was obtained.

The identity of the compounds was determined by mass spectrometry. The results of the mass spectrometric analysis are shown in Table 13 in the same manner as in Examples 120 to 171.

[Table 13]

In Table 13, the symbols in the column "Hd" are defined in the same manner as the symbols in Tables 1 to 9 (b) of this specification except for the following symbols. HHk7 represents a group represented by the above formula (HHk7).

Examples 244 to 246

Phthalonitrile was changed to a compound represented by the formula (PPA-1) having the group shown in the column of &quot; B1B2 &quot; in Table 14 and 2-chlorobenzoyl acetonitrile was added to the compound represented by the column &quot; Lk &quot; (I-63b) having a substituent described in each of the above columns was obtained in the same manner as in Example 98, except that the compound represented by the formula (PPA-2) was changed to the compound represented by the formula (PPA-2), and further the barbituric acid was changed to dimedone. Was obtained.

The identity of the compounds was determined by mass spectrometry. The results of the mass spectrometric analysis are shown in Table 14 in the same manner as in Examples 120 to 171.

[Table 14]

In Table 14, the symbols in the column "B1B2" and the column "Hd" are defined in the same way as the symbols in Tables 1 to 9 (b) of the present specification.

Example 247

In the same manner as in Example 98 except that 2-chlorobenzoyl acetonitrile was replaced with 3-cyanoacetylbenzoic acid while the molar ratio was maintained and benzoyl acetonitrile was used instead of barbituric acid, To obtain a compound represented by the formula (I-118).

&Lt; Identification of compound represented by formula (I-118)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 444

   Exact Mass: 445

Example 248

2-chlorobenzoyl acetonitrile was replaced by 3-cyanoacetyl benzoic acid while maintaining the molar ratio, while replacing the phthalonitrile with 4-nitrophthalonitrile, and while maintaining the molar ratio, A compound represented by the formula (I-119) was obtained in the same manner as in Example 98 except that benzoyl acetonitrile was used instead of benzoyl acetonitrile.

&Lt; Identification of compound represented by formula (I-119)

(Mass spectrometry) Ionization mode = ESI-: m / z = [MH] ^- 489

   Exact Mass: 490

Example 249

In the same manner as in Example 99 except that 4-cyanoacetylbenzoic acid was replaced with 3-cyanoacetylbenzoic acid while the molar ratio was maintained and benzoyl acetonitrile was used instead of barbituric acid while the molar ratio was maintained, To obtain a compound represented by the formula (I-120).

<Identification of Compound Represented by Formula (I-120)

(Mass analysis) Ionization mode = ESI-: m / z = [MH] ^- 512

   Exact Mass: 513

Synthesis Example 14

An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the flask was purged with a nitrogen atmosphere. Then, 350 parts of propylene glycol monomethyl ether acetate was added and heated to 85 DEG C with stirring. Subsequently, 70 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate or / and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan- (Meth) acrylate, 78 parts of vinyl toluene (isomer mixture) and 100 parts of propylene glycol monomethyl ether acetate was added dropwise over 4 hours. On the other hand, a solution obtained by dissolving 33 parts of polymerization initiator 2,2-azobis (2,4-dimethylvaleronitrile) in 167 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After completion of the dropwise addition of the initiator solution, the mixture was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a solution of a copolymer (resin B5) having a solid content of 38.1%. The obtained resin B5 had a weight average molecular weight (Mw) of 10,400, a degree of dispersion of 2.03, and a solution acid value of 53 mg-KOH / g.

Example 250

Pigment: C.I. Pigment Green 58 60 parts,

Acrylic pigment dispersant 8.1 parts,

Resin (B): Resin B5 solution 73 parts, and

Solvent (E): Propylene glycol monomethyl ether acetate 290 pts

, And a pigment dispersion (liquid containing colorant (A1)) in which the pigment was dispersed using a bead mill was prepared. Separately

Colorant (A): The compound of the formula (I-45) 50 parts,

Dispersant 58 parts,

Resin (B): resin B2 solution 93 parts, and

Solvent (E): 800 parts of propylene glycol monomethyl ether acetate was mixed and the compound of formula (I-45) was dispersed using a bead mill to obtain a coloring composition.

next,

The total amount of the obtained pigment dispersion (liquid containing colorant (A1));

The obtained coloring composition 400 parts;

Resin (B): Resin B1 solution  45 parts;

Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Yakuza Co., Ltd.) 25 parts;

Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE- 15 parts;

Solvent (E): Propylene glycol monomethyl ether acetate 86 parts;

Leveling agent: polyether-modified silicone oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.12 parts;

To obtain a colored curable resin composition 1.

[Production of coloring pattern]

The colored curable resin composition 1 was applied on a glass substrate (Eagle XG; manufactured by Corning) having an aspect ratio of 2 inches by a spin coat method, and then prebaked at 100 ° C for 3 minutes to form a colored curable resin composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) with an interval of 200 mu m between the substrate on which the colored curable resin composition layer was formed and the quartz glass photomask, exposure amount of 80 mJ / (Based on 365 nm). As the photomask, a 100 μm line and space pattern was formed. The colored curable resin 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 캜 for 70 seconds to develop and wash. This colored curable resin composition layer was post-baked at 230 캜 for 30 minutes to obtain a colored pattern.

[Measurement of phase difference value]

The colored curable resin composition 1 was applied on a glass substrate (Eagle XG; manufactured by Corning) having an aspect ratio of 2 inches by a spin coat method, and then prebaked at 100 ° C for 3 minutes to form a colored curable resin composition layer. After cooling, the colored curable resin composition layer was exposed to light at an exposure amount of 80 mJ / cm 2 (based on 365 nm) in an air atmosphere using an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.). The colored curable resin 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 캜 for 70 seconds to develop and wash. This colored curable resin composition layer was post-baked at 230 캜 for 30 minutes to obtain a colored coating film.

The film thickness of the resulting colored coating film was measured using DEKTAK3 (manufactured by Nippon Vacuum Technology Co., Ltd.). The retardation value of this colored coating film at an oblique angle of 45 was measured using an ellipsometer (M-220 type spectroscopic ellipsometer; manufactured by Nippon Bunko K.K.). For measurement of the retardation value, light having a wavelength of 550 nm was used. The results are shown in Table 15.

Examples 251 to 480

Except that the compound represented by the formula (I-45) was replaced with the compound shown in the column of &quot; compound &quot; in Table 15, the color-curable resin A composition was obtained to obtain a colored pattern. Further, a colored coating film was obtained in the same manner as in Example 250, and the film thickness measurement and the retardation value measurement were carried out. The results are shown in Table 15.

[Table 15]

Examples 481 to 711

The compound represented by the formula (I-45) was replaced with the compound shown in the column of &quot; compound &quot; Pigment Green 58 was prepared according to the procedure of C.I. Pigment Green 7, a colored curable resin composition shown in the column of &quot; colored curable resin composition &quot; in Table 16 was obtained in the same procedure as in Example 250 to obtain a colored pattern. Further, a colored coating film was obtained in the same procedure as in Example 250, and the film thickness measurement and the retardation value measurement were carried out. The results are shown in Table 16.

[Table 16]

Examples 712 to 942

The compound represented by the formula (I-45) was replaced with the compound shown in the column of &quot; compound &quot; Pigment Green 58 was prepared according to the procedure of C.I. Pigment Green 59, a colored curable resin composition shown in the column of &quot; color curable resin composition &quot; in Table 17 was obtained in the same procedure as in Example 250 to obtain a colored pattern. In the same manner as in Example 250, a colored coating film was obtained, and the film thickness and the retardation value were measured. The results are shown in Table 17.

[Table 17]

Comparative Examples 1 to 3

The compound represented by the formula (I-45) is referred to as C.I. Pigment Yellow 185, and the dispersing agent for the coloring composition was replaced with a dispersant (BYK-LPN6919; manufactured by Big Chem Japan Co., Ltd.). Pigment Green 58 was replaced with the pigment shown in the column of &quot; Pigment &quot; in Table 18, the colored curable resin composition shown in the column of &quot; Coloring curable resin composition &quot; in Table 18 was obtained in the same procedure as in Example 250, &Lt; / RTI &gt; Further, a colored coating film was obtained in the same procedure as in Example 250, and the film thickness measurement and the retardation value measurement were carried out. The results are shown in Table 18.

[Table 18]

From the above results, it was confirmed that in the colored coating film formed from the colored curable resin composition containing the compound of the present invention, C.I. It was found that the retardation value was smaller than that of the colored coating film formed of the colored curable resin composition containing Pigment Yellow 185.

Industrial availability

The coloring composition and the compound of the present invention are preferably used for display devices such as color filters and liquid crystal display devices.

Claims (14)

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

[In the formula (I), L ¹ represents -CO- or -SO ₂ -.
R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ -R ¹⁰¹ , _{^{SO 2 N (R 102) 2}} , -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102 ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.
R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.
R ¹¹ and R ¹⁰¹ independently represent 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 of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
M represents a hydrogen atom or an alkali metal atom.
When a plurality of R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.
The broken line represents E-form or Z-form.] The method according to claim 1,
Wherein the compound represented by formula (I) is a compound represented by formula (Ia).

[In the formula (Ia), L ¹ , R ¹¹ , R ¹ to R ⁵ and the broken line have the same meanings as in the above-mentioned formula ( ¹ ).
L ² represents -CO- or -SO ₂ -.
R ¹⁴ represents a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent. 3. The method of claim 2,
R ¹¹ and R ¹⁴ are the same group, and L ¹ and L ² are the same group. The method according to claim 2 or 3,
R ¹¹ and R ¹⁴ are, independently of each other, an alkyl group having 1 to 40 carbon atoms which may have a substituent, a phenyl group which may have a substituent, a naphthyl group which may have a substituent, a tetrahydronaphthyl group which may have a substituent, A thienyl group which may be present, a furyl group which may have a substituent or a pyridinyl group which may have a substituent. The method according to claim 1,
Wherein the compound represented by formula (I) is a compound represented by formula (Ib).

[In the formula (Ib), L ¹ , R ¹¹ , R ¹ to R ⁵ and the broken line have the same meanings as those of the above-mentioned formula ( ¹ ).
R &lt; ²⁰ &gt; and R &lt; ³⁰ &gt; are combined to form a ring Q.
The ring Q may have a substituent, is a ring having 5 to 7 constituent atoms of the ring, and the ring Q may be a hydrocarbon ring or a heterocyclic ring. The ring Q may be bonded to a monocyclic ring having 5 to 7 ring atoms constituting a ring or condensed with a monocyclic ring thereof selected from a hydrocarbon ring and a heterocyclic ring.] 6. The method of claim 5,
Wherein the compound represented by the formula (I) is a compound represented by the formula (Ic).

[In the formula (Ic), L ¹ , R ¹¹ , R ¹ to R ⁵ and the broken line have the same meanings as in the above-mentioned formula ( ¹ ).
R ⁶ and R ⁷ are, independently, a hydrogen ^{atom, -CO-R 102, -COO-} R 101, -OCO-R 102, -OR 102, -SO 2 -R 101, -SO 2 N (R 102 together ^{_{) 2, -CON (R 102)}} 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102) 2, a halogen atom, A cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent. R ¹⁰¹ , R ¹⁰² and M have the same meanings as defined above. 7. The method according to any one of claims 1 to 6,
R ¹ is a hydrogen atom, and R ² to R ⁵ are independently of each other a hydrogen atom or a nitro group. A colored curable resin composition comprising the coloring composition according to any one of claims 1 to 7, a polymerizable compound and a polymerization initiator. 9. A color filter formed from the colored curable resin composition according to claim 8. A liquid crystal display device comprising the color filter according to claim 9. A compound represented by formula (II).

Wherein R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-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} , which may have a substituent may have a hydrocarbon group or substituent of 1 to 40 carbon atoms which heterocyclic group .
R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.
R ¹¹ and R ¹⁰¹ independently represent 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 of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
M represents a hydrogen atom or an alkali metal atom.
When a plurality of R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.
The broken line represents E-form or Z-form.] A compound represented by the formula (II-a1).

Wherein R ¹ to R ⁵ and R ¹² to R ¹³ independently represent a hydrogen atom, -CO-R ¹⁰² , -COO-R ¹⁰¹ , -OCO-R ¹⁰² , -OR ¹⁰² , -SO ₂ - _{^{R 101, -SO 2 N (R}} 102) 2, -CON (R 102) 2, -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, - OCON (R ¹⁰² ) ₂ , a halogen atom, a cyano group, a nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.
R ¹⁰¹ represents a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent or a heterocyclic group which may have a substituent.
R ¹⁰² represents a hydrogen atom, a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ^5, and R ¹² and R ¹³ may be bonded to each other to form a ring.
R ¹¹¹ represents a heterocyclic ring which may have a substituent or a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent. Provided that when R ¹¹¹ is a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, and either one of R ¹² and R ¹³ is -SO ₂ -R ¹¹¹ , and the other one of R ¹² and R ¹³ is a cyano group , at least one of R ² ~ R ^{5 are, -CO-R 102, -COO-} R 101, -OCO-R 102, -OR 102, -SO 2 -R 101, -SO 2 N (R 102) 2 _{^{, -CON (R 102) 2,}} -N (R 102) 2, -NHCO-R 102, -NHCO-N (R 102) 2, -NHCOOR 102, -OCON (R 102) 2, a halogen atom, a cyano group, , A nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
M represents a hydrogen atom or an alkali metal atom.
When a plurality of R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.
The broken line represents E-form or Z-form.] 13. The method of claim 12,
R ¹¹¹ is a heterocyclic ring which may have a substituent, A compound represented by formula (Ib).

[In the formula (Ib), L ¹ represents -CO- or -SO ₂ -.
R &lt; ²⁰ &gt; and R &lt; ³⁰ &gt; are combined to form a ring Q.
The ring Q may have a substituent, is a ring having 5 to 7 constituent atoms of the ring, and the ring Q may be a hydrocarbon ring or a heterocyclic ring. The ring Q may be bonded to a monocyclic ring having 5 to 7 constituent atoms of the ring, or a condensed ring thereof, selected from a hydrocarbon ring and a heterocyclic ring.
R ¹ ~ R ⁵ are, independently, a hydrogen ^{atom, -CO-R 102, -COO-} R 101, -OCO-R 102, -OR 102, -SO 2 -R 101, -SO 2 N (R 102 together ^{_{) 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 Nitro group, -SO ₃ M, -CO ₂ M, a hydrocarbon group having 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
R ² and R ³ , R ³ and R ^4, and R ⁴ and R ⁵ may be bonded to each other to form a ring.
R ¹¹ and R ¹⁰¹ independently represent a hydrocarbon ring of 1 to 40 carbon atoms which may have a substituent or a heterocyclic ring which may have a substituent.
R ¹⁰² represents a hydrogen atom, a hydrocarbon group of 1 to 40 carbon atoms which may have a substituent, or a heterocyclic group which may have a substituent.
M represents a hydrogen atom or an alkali metal atom.
When a plurality of R ¹⁰¹ , R ¹⁰² and M exist, they may be the same or different.
The broken line represents E-form or Z-form.]