TWI554509B - Compound for dye - Google Patents

Description

Dye compound

The present invention relates to a compound which can be used as a dye or the like.

The dye is used for color display using, for example, reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, and inkjet. As the dye, coumarin 6 (a compound represented by the following formula) is known (JP2006-154740-A Example 8).

In terms of thermal stability, the above-mentioned compound is not sufficiently satisfied as a dye used for a color filter of a display device such as a liquid crystal display device.

The invention includes the following invention.

[1] a compound represented by the formula (I), [In the formula (1), L represents a divalent hydrocarbon group having 1 to 20 carbon atoms; and the methylene group constituting the divalent hydrocarbon group may also be through an oxygen atom, a sulfur atom, -N(R ¹⁰ )-, a sulfonyl group or a carbonyl group. Substituting, the hydrogen atom contained in the divalent hydrocarbon group may also be through a cyano group, a nitro group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group, a chlorine atom, a bromine atom, an imidazol-1-yl group or Amine substituted; X represents an oxygen atom, a sulfur atom or -N(R ¹⁰ )-; A represents an aromatic group having 6 to 20 carbon atoms; and a hydrogen atom contained in the aromatic group may also pass through a halogen atom or a cyano group. , a nitro group, an aminomethyl sulfhydryl group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group, an imidazol-1-yl group, an amine group or a carbon number of 1 to 20 one-valent hydrocarbon group; a methylene group constituting the monovalent hydrocarbon group; It may also be substituted by an oxygen atom, a sulfur atom, a -N(R ¹⁰ )-, a sulfonyl group or a carbonyl group, and the hydrogen atom contained in the monovalent hydrocarbon group may also pass through a halogen atom, a cyano group, a nitro group or an amine group. , sulfonyl, sulfo, carboxy, hydroxy, imidazol-1-yl or amine substituted; R ¹ to R ⁴ each independently represent a hydrogen atom or a carbon number of 1 to 20, or R ¹ and R ³ bonded to the carbon atom on the adjacent benzene ring and Adjacent nitrogen atoms form a ring together, or R ² and R ^{4 are} bonded to form a ring together with a carbon atom on the adjacent benzene ring and an adjacent nitrogen atom; the methylene group constituting the monovalent hydrocarbon group may also be oxygenated. Substituting an atom, a sulfur atom, a -N(R ¹⁰ )-, a sulfonyl group or a carbonyl group, the hydrogen atom contained in the monovalent hydrocarbon group may also pass through a halogen atom, a cyano group, a nitro group, an amine carbaryl group, an amine sulfonium group a group, a sulfo group, a carboxyl group, a hydroxyl group, an imidazol-1-yl group or an amine group; and R ⁵ to R ⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group, an amine group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, R ⁵ and R ^{6 are} bonded to form a ring together with an adjacent carbon atom, or R ⁷ and R ^{8 are} bonded to each other and adjacent thereto. The carbon atoms form a ring together; the methylene group constituting the monovalent hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, a -N(R ¹⁰ )-, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the monovalent hydrocarbon group It may also be substituted by a halogen atom, a cyano group, a nitro group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group, an imidazol-1-yl group or an amine group; R ¹⁰ represents a hydrogen atom or a carbon number of 1 to 20 one a valence hydrocarbon group; when a plurality of R ¹⁰ are present, they are the same or different from each other].

[2] a compound represented by the formula (I'), [In the formula (I'), R ¹ to R ⁹ , X and L each have the same meaning as described above].

[3] The compound according to [1] or [2] above, wherein X is an oxygen atom or a nitrogen atom.

[4] The compound according to any one of the above [1] to [3] wherein X is an oxygen atom.

[5] The compound according to any one of the above [1] to [4] wherein L is a methylene group or a sulfonyl group which may have a substituent.

[6] The compound according to any one of the above [1] to [5] wherein L is a dimethylmethylene group or a sulfonyl group.

[7] The compound according to any one of the above [1] to [6] wherein R ⁵ to R ⁹ are each a hydrogen atom.

[8] A dye comprising the compound according to any one of [1] to [7] above.

[9] A colored curable resin composition comprising the dye according to [8] above, a resin, a polymerizable compound, and a polymerization initiator.

[10] A colored curable resin composition comprising: a coloring agent containing a compound represented by the formula (I) or the formula (I'), a resin, a polymerizable compound, and a polymerization initiator.

[11] The colored curable resin composition according to [10] above, wherein the colorant further contains a pigment.

[12] The colored curable resin composition according to [11] above, wherein the pigment is at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment.

[13] The colored curable resin composition according to [11] or [12] above, wherein the pigment is selected from the group consisting of copper chloride phthalocyanine pigment, copper bromide phthalocyanine pigment, and zinc bromide phthalocyanine pigment. At least one of them.

[14] The colored curable resin composition according to any one of [11] to [13] wherein the pigment is a green pigment.

[15] The colored curable resin composition according to any one of [11] to [14] wherein the pigment is at least selected from the group consisting of CI Pigment Green 7, CI Pigment Green 36, and CI Pigment Green 58. One.

[16] The colored curable resin composition according to any one of [11] to [15] wherein the pigment is C.I. Pigment Green 7.

[17] A color filter comprising the color-curable resin composition according to any one of the above [9] to [16].

[18] A liquid crystal display device comprising the color filter of [17] above.

Since the compound of the present invention has high thermal stability, it is excellent as a dye used for a color filter of a display device such as a liquid crystal display device.

The compound of the present invention is a compound represented by the formula (I) or the formula (I') (hereinafter, sometimes referred to as a compound (I) or a compound (I'), respectively). Salts of the tautomers and the like can also be included in the compounds of the present invention.

In the formulae (I) and (I'), R ¹ to R ⁹ , L, X and A each have the same meaning as described above.

The sulfo group represents a group represented by -SO ₃ M. M represents a hydrogen atom or an alkali metal atom.

Carboxyl group represents a group represented by -CO ₂ M.

M represents a hydrogen atom or an alkali metal atom, preferably a hydrogen atom, a sodium atom or a potassium atom, more preferably a hydrogen atom.

Examples of the group represented by L include a group represented by the formula (L1) to the formula (L29), and a hydrogen atom contained in the group via a cyano group. A group substituted with a nitro group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group, a chlorine atom, a bromine atom, an imidazol-1-yl group or an amine group. In the formula (L1) to the formula (L29), ● indicates a bond key.

L is preferably a methylene group or a sulfonyl group which may have a substituent. Specific examples of the preferred L include a group represented by the formula (L1) and the formula (L3) to the formula (L14). More preferably, it is a group represented by the formula (L1), the formula (L3), the formula (L10), the formula (L13), and the formula (L14), and more preferably a formula (L1) or a formula. (L3), the formula (L13) and the formula (L14). If L is the basis of these, it is easy to obtain raw materials.

X represents an oxygen atom, a sulfur atom or -N(R ¹⁰ )-, preferably an oxygen atom and a sulfur atom. Among them, an oxygen atom is more preferred. If X is an oxygen atom, there is a tendency that the luminance of the green color filter is high.

Examples of the aromatic group having 6 to 20 carbon atoms represented by A include a group represented by the formula (A1) to the formula (A12), and a hydrogen atom contained in the group via a halogen atom. A group formed by substituting a cyano group, a nitro group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group, an imidazol-1-yl group, an amine group or a monovalent hydrocarbon group having 1 to 20 carbon atoms. The methylene group constituting the monovalent hydrocarbon group may be substituted by an oxygen atom, a sulfur atom, a -N(R ¹⁰ )-, a sulfonyl group or a carboxyl group, and the hydrogen atom contained in the monovalent hydrocarbon group may also pass through a halogen atom or a cyanogen. Substituted by a nitro group, an amide group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group, an imidazol-1-yl group or an amine group. Among them, a group represented by the formula (A12) is preferred. When A is a group represented by the formula (A12), the thermal decomposition temperature tends to be higher. Moreover, there is a tendency to sublimate.

[In the formulae (A1) to (A12), R ¹ to R ⁹ and X are respectively the same as described above, and ● represents a bonding bond with L].

Examples of the halogen atom in R ¹ to R ⁹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the one-valent hydrocarbon group having 1 to 20 carbon atoms in R ¹ to R ⁹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, and a butyl group. Base, isobutyl, t-butyl, tert-butyl, (2-ethyl)butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, 3-pentyl Base, neopentyl, third amyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, (3-ethyl)pentyl, hexyl, isohexyl, 5-methylhexyl , an aliphatic hydrocarbon group such as (2-ethyl)hexyl, heptyl, (3-ethyl)heptyl, octyl, decyl, decyl, undecyl, dodecyl, octadecyl; Propyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl 1,2-dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl , 2,5-Dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl , 3,3-dimethylcyclohexyl, 4,4-dimethyl ring An alicyclic hydrocarbon group such as 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl; phenyl, O-tolyl, m-tolyl, p-tolyl, xylyl, An aromatic hydrocarbon group such as isopropylidene, m-isopropylidene, p-cumylphenyl, benzyl, phenethyl, biphenyl, 1-naphthyl or 2-naphthyl; and combinations thereof The foundation of the foundation.

a group in which a methylene group constituting the monovalent hydrocarbon group is substituted with an oxygen atom, a sulfur atom, a -N(R ¹⁰ )-, a sulfonyl group or a carbonyl group; and a hydrogen atom contained in the monovalent hydrocarbon group passes through a halogen atom a group obtained by substituting a cyano group, a nitro group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group or an amine group, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropyl group. An alkoxy group such as an oxy group, a butoxy group, an isobutoxy group, a second butoxy group, a third butoxy group, a pentyloxy group or a (2-ethyl)hexyloxy group; an aryloxy group such as a phenoxy group; An aralkoxy group such as a benzyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group or a propoxycarbonyl group; a decyloxy group such as an ethoxycarbonyl group or a benzhydryloxy group; and an N-methylamine group; Indenyl, N-ethylamine, mercapto, N-propylamine, mercapto, N-isopropylamine, N-butylamine, N-isobutylamine, N-isobutylamine N-tert-butylamine-methyl sulfhydryl, N-t-butylamine, decyl, N-pentylamine, fluorenyl, N-(1-ethylpropyl)amine, fluorenyl, N-(1 ,1-dimethylpropyl)aminecarboxymethyl, N-(1,2-dimethylpropyl)aminecarbamyl, N-(2,2-dimethylpropyl)aminecarbamyl, N-(1- Methyl butyl) amine methyl sulfhydryl, N-(2-methylbutyl) amine methyl sulfhydryl, N-(3-methylbutyl) amine methyl sulfhydryl, N-cyclopentylamine methyl sulfhydryl, N-hexylamine methyl sulfhydryl, N-(1,3-dimethylbutyl)amine methyl sulfhydryl, N-(3,3-dimethylbutyl)amine carbhydryl, N-heptylamine A Indenyl, N-(1-methylhexyl)amine, mercapto, N-(1,4-dimethylpentyl)amine, mercapto, N-octylamine, N-(2-B N-1 such as hexylaminoamine, N-(1,5-dimethyl)hexylaminecarbamyl, N-(1,1,2,2-tetramethylbutyl)carbamyl Substituted aminemethanyl; N,N-dimethylaminecarbamyl, N,N-ethylmethylaminecarbamyl, N,N-diethylaminemethylhydrazine, N,N-propyl Base amine, N,N-isopropylmethylamine, mercapto, N,N-t-butylmethylamine, mercapto, N,N-butylethylamine, N,N- N,N-2 substitution such as bis(1-methylpropyl)aminecarbamyl, N,N-heptylmethylaminecarbamyl, N,N-bis(2-ethylhexyl)aminecarbamyl Aminomethyl sulfhydryl; N-methylamine sulfonyl, N-ethylamine sulfonyl, N-propylamine sulfonyl, N-isopropylamine sulfonyl, N-butylamine sulfonyl , N-isobutylamine sulfonyl, N-butylbutylsulfonyl, N -T-butylamine sulfonyl, N-pentylamine sulfonyl, N-(1-ethylpropyl)amine sulfonyl, N-(1,1-dimethylpropyl)amine sulfonate , N-(1,2-dimethylpropyl)aminesulfonyl, N-(2,2-dimethylpropyl)aminesulfonyl, N-(1-methylbutyl)amine sulfonate Mercapto, N-(2-methylbutyl)amine sulfonyl, N-(3-methylbutyl)amine sulfonyl, N-cyclopentylamine sulfonyl, N-hexylamine sulfonyl , N-(1,3-dimethylbutyl)amine sulfonyl, N-(3,3-dimethylbutyl)amine sulfonyl, N-heptylamine sulfonyl, N-(1 -Methylhexyl)aminesulfonyl, N-(1,4-dimethylpentyl)aminesulfonyl, N-octylaminesulfonyl, N-(2-ethylhexyl)aminesulfonyl N-substituted aminesulfonyl group such as N-(1,5-dimethyl)hexylaminesulfonyl, N-(1,1,2,2-tetramethylbutyl)aminesulfonyl; N , N-dimethylamine sulfonyl, N,N-ethylmethylamine sulfonyl, N,N-diethylamine sulfonyl, N,N-propylmethylamine sulfonyl, N , N-isopropylmethylamine sulfonyl, N,N-t-butylmethylamine sulfonyl, N,N-butylethylamine sulfonyl, N,N-bis(1-methylpropane Amine sulfonyl, N,N-heptylmethylamine sulfonyl, N,N-bis(2-ethylhexyl)amine sulfonyl N,N-2 substituted amine sulfonyl; N-methylamino, N-ethylamino, N-propylamino, N-isopropylamino, N-butylamino, N- Isobutylamino, N-second butylamino, N-tert-butylamino, N-pentylamino, N-(1-ethylpropyl)amino, N-(1,1 - dimethylpropyl)amino, N-(1,2-dimethylpropyl)amino, N-(2,2-dimethylpropyl)amino, N-(1-methylbutyl Amino group, N-(2-methylbutyl)amino group, N-(3-methylbutyl)amino group, N-cyclopentylamino group, N-hexylamino group, N-(1, 3-dimethylbutyl)amine, N-(3,3-dimethylbutyl)amine, N-heptylamino, N-(1-methylhexyl)amine, N-(1 ,4-dimethylpentyl)amino, N-octylamino, N-(2-ethylhexyl)amino, N-(1,5-dimethyl)hexylamino, N-(1 N-alkylamino group such as 1,2,2-tetramethylbutyl)amine; N,N-dimethylamino, N,N-ethylmethylamino, N,N-diethyl Amino, N,N-propylmethylamino, N,N-isopropylmethylamino, N,N-tert-butylmethylamino, N,N-butylethylamino, N N,N-dialkylamino group such as N-bis(1-methylpropyl)amino, N,N-heptylmethylamino, N,N-bis(2-ethylhexyl)amine ;N -methylaminomethyl, N-ethylaminomethyl, N-propylaminomethyl, N-isopropylaminomethyl, N-butylaminomethyl, N-isobutyl Aminomethyl, N-second butylaminomethyl, N-tert-butylaminomethyl, N-pentylaminomethyl, N-(1-ethylpropyl)aminomethyl , N-(1,1-dimethylpropyl)aminomethyl, N-(1,2-dimethylpropyl)aminomethyl, N-(2,2-dimethylpropyl) Aminomethyl, N-(1-methylbutyl)aminomethyl, N-(2-methylbutyl)aminomethyl, N-(3-methylbutyl)aminomethyl, N-cyclopentylaminomethyl, N-hexylaminomethyl, N-(1,3-dimethylbutyl)aminomethyl, N-(3,3-dimethylbutyl)amine Methyl, N-heptylaminomethyl, N-(1-methylhexyl)aminomethyl, N-(1,4-dimethylpentyl)aminomethyl, N-octylamine Methyl, N-(2-ethylhexyl)aminomethyl, N-(1,5-dimethyl)hexylaminomethyl, N-(1,1,2,2-tetramethylbutene N-alkylaminomethyl group such as aminomethyl; N,N-dimethylaminomethyl, N,N-ethylmethylaminomethyl, N,N-diethylamino Methyl, N,N-propylmethylaminomethyl, N,N-isopropylmethylaminomethyl, N,N-T-butylmethylaminomethyl, N,N-butylethylaminomethyl, N,N-bis(1-methylpropyl)aminomethyl, N,N-heptyl N,N-dialkylaminomethyl group such as methylaminomethyl, N,N-bis(2-ethylhexyl)aminomethyl; trifluoromethyl, perfluoroethyl, perfluoropropyl , perfluoroisopropyl, perfluoroisopropenyl, perfluoro(1-propenyl), perfluoro(2-propenyl), perfluorobutyl, perfluoroisobutyl, perfluoro(second butyl) , perfluoro(tert-butyl), perfluoro(2-butenyl), perfluoro(1,3-butadienyl), perfluoropentyl, perfluoro(isopentyl), perfluoro(3) -pentyl), perfluoro neopentyl, perfluoro(third amyl), perfluoro(1-methylpentyl), perfluoro(2-methylpentyl), perfluoro(2-pentenyl) ), perfluorohexyl, perfluoroisohexyl, perfluoro(5-methylhexyl), perfluoro(2-ethylhexyl), perfluoroheptyl, perfluorooctyl, perfluorodecyl, perfluorodecyl An aliphatic hydrocarbon group having a fluorine atom such as perfluoroundecyl group, perfluorododecyl group or perfluorooctadecyl group; perfluorocyclopropyl group, perfluorocyclobutyl group, perfluorocyclopentyl group, perfluoro group Cyclohexyl, perfluorocyclohexenyl, perfluorocycloheptyl, perfluoro(1-methylcyclohexane Perfluoro) (2-methylcyclohexyl), perfluoro(3-methylcyclohexyl), perfluoro(4-methylcyclohexyl), perfluoro(1,2-dimethylcyclohexyl), Perfluoro(1,3-dimethylcyclohexyl), perfluoro(1,4-dimethylcyclohexyl), perfluoro(2,3-dimethylcyclohexyl), perfluoro(2,4-di) Methylcyclohexyl), perfluoro(2,5-dimethylcyclohexyl), perfluoro(2,6-dimethylcyclohexyl), perfluoro(3,4-dimethylcyclohexyl), perfluoro (3,5-Dimethylcyclohexyl), perfluoro(2,2-dimethylcyclohexyl), perfluoro(3,3-dimethylcyclohexyl), perfluoro(4,4-dimethyl) Cyclohexyl), perfluoro(2,4,6-trimethylcyclohexyl), perfluoro(2,2,6,6-tetramethylcyclohexyl), perfluoro(3,3,5,5-four An alicyclic hydrocarbon group having a fluorine atom such as methylcyclohexyl); a perfluorophenyl group, a perfluoro(o-tolyl) group, a perfluoro(m-tolyl group), a perfluoro(p-tolyl group), a perfluorodimethylbenzene group, Perfluoro Base, perfluoro(o-isopropylphenyl), perfluoro(p-isopropylphenyl), perfluoro(p-isopropylphenyl), perfluorobenzyl, perfluorophenethyl, perfluorobiphenyl, all Fluorine (1-naphthyl), perfluoro(2-naphthyl), 1-trifluoromethylphenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethyl An aromatic hydrocarbon group having a fluorine atom such as a phenyl group; perfluoromethoxy group, perfluoroethoxy group, perfluoropropoxy group, perfluoro(isopropoxy group), perfluorobutoxy group, perfluoro(isobutoxide) Base), perfluoro(second butoxy), perfluoro(t-butoxy), perfluoropentyloxy, perfluorophenoxy, perfluorobenzyloxy, 2,2,2-trifluoroethyl Oxyl, (perfluoroethyl)methoxy, (perfluoropropyl)methoxy, (perfluoro(isopropyl))methoxy, (perfluoro(isopropenyl))methoxy, ( Perfluoro(1-propenyl))methoxy, (perfluoro(2-propenyl))methoxy, (perfluorobutyl)methoxy, (perfluoro(isobutyl))methoxy, (perfluoro(t-butyl))methoxy, (perfluoro(t-butyl))methoxy, (perfluoro(2-butenyl))methoxy, (perfluoro (1,3) -butadienyl)) methoxy, (perfluoropentyl)methoxy, (perfluoro(isopentyl))methoxy, (perfluoro (3-pentyl) )) methoxy, (perfluoro(neopentyl))methoxy, (perfluoro(tripentyl))methoxy, (perfluoro(1-methylpentyl))methoxy, ( Perfluoro(2-methylpentyl))methoxy, (perfluoro(2-pentenyl))methoxy, (perfluorohexyl)methoxy, (perfluoro(isohexyl))methoxy , (perfluoro(5-methylhexyl))methoxy, (perfluoro((2-ethyl)hexyl))methoxy, (perfluoroheptyl)methoxy, (perfluorooctyl) A) Oxylate, (perfluorodecyl)methoxy, (perfluorodecyl)methoxy, (perfluoroundecyl)methoxy, (perfluorododecyl)methoxy, (perfluoro) a substituted oxy group having a fluorine atom such as octadecyl) methoxy; 2,3-bis(trifluoromethyl)phenylmethyl, 2,4-bis(trifluoromethyl)phenylmethyl, 2 ,5-bis(trifluoromethyl)phenylmethyl, 2,6-bis(trifluoromethyl)phenylmethyl, 3,4-bis(trifluoromethyl)phenylmethyl, 3,5 - bis(trifluoromethyl)phenylmethyl and the like.

R ¹ and R ^{2 are} preferably an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

The hydrogen atom contained in the alicyclic hydrocarbon group may be substituted with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

The hydrogen atom contained in the aromatic hydrocarbon group may be substituted with an aliphatic hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

R ^{1 is} preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. Among them, preferred are ethyl, butyl, hexyl, (2-ethyl)hexyl and octyl, and more preferred are: ethyl, butyl, hexyl and (2-ethyl)hexyl, and further preferably Is (2-ethyl)hexyl. When R ^{1 is} such a group, it is excellent in solubility in a solvent.

R ^{2 is} preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms. More preferably, it is ethyl, butyl, hexyl, (2-ethyl)hexyl and octyl, and further preferably: ethyl, butyl, hexyl and (2-ethyl)hexyl, particularly preferably It is a hexyl group and a (2-ethyl)hexyl group. When R ^{2 is} such a group, it is excellent in solubility in a solvent.

R ³ to R ^{9 are} preferably all hydrogen atoms.

Examples of the monovalent hydrocarbon group having 1 to 20 carbon atoms in R ¹⁰ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 2-propenyl group, a butyl group, and a different one. Butyl, t-butyl, tert-butyl, (2-ethyl)butyl, 2-butenyl, 1,3-butadienyl, pentyl, isopentyl, 3-pentyl, new Pentyl, third amyl, 1-methylpentyl, 2-methylpentyl, 2-pentenyl, (3-ethyl)pentyl, hexyl, isohexyl, 5-methylhexyl, (2 An aliphatic hydrocarbon group such as -ethyl)hexyl, heptyl, (3-ethyl)heptyl, octyl, nonyl, decyl, undecyl, dodecyl, octadecyl; cyclopropyl, Cyclobutyl, cyclopentyl, cyclohexyl, cyclohexenyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1, 2-Dimethylcyclohexyl, 1,3-dimethylcyclohexyl, 1,4-dimethylcyclohexyl, 2,3-dimethylcyclohexyl, 2,4-dimethylcyclohexyl, 2, 5-dimethylcyclohexyl, 2,6-dimethylcyclohexyl, 3,4-dimethylcyclohexyl, 3,5-dimethylcyclohexyl, 2,2-dimethylcyclohexyl, 3, 3-dimethylcyclohexyl, 4,4-dimethylcyclohexyl , 2,4,6-trimethylcyclohexyl, 2,2,6,6-tetramethylcyclohexyl, 3,3,5,5-tetramethylcyclohexyl and other alicyclic hydrocarbon groups; phenyl, adjacent Tolyl, m-tolyl, p-tolyl, xylyl, An aromatic hydrocarbon group such as isopropylidene, m-isopropylidene, p-cumylphenyl, benzyl, phenethyl, biphenyl, 1-naphthyl or 2-naphthyl; and combinations thereof The foundation of the foundation.

In the compound (I)

As "F", will

In the case where the compound (I) is represented by F-G as "G", examples of F include, for example, the groups represented by the formulae (F1) to (F20). In the formula, ● indicates a bond key.

Examples of G include a group represented by the formula (G1) to the formula (G109), respectively.

The compound (1) is exemplified in Tables 1 to 5 by the combination of F and G described above. In Tables 1 to 5, the F column and the G column respectively indicate the numbers of the formulas exemplified above.

Then, in the above formula (I), A is a compound of A12, that is, formula (I')

In the formula (I'), R ¹ to R ⁹ , X and L each represent a compound represented by the same meaning as described above (hereinafter sometimes referred to as a compound (I')).

In the case of the compound (I'), the compound represented by the above formula (F1) to the formula (F20) is exemplified as the "H", and the group represented by the above formula (F1) to the formula (F20), and H, for example, (H1)~ The base represented by the formula (H93). In the formula, ● indicates a bond key.

The compound (I') is exemplified in Tables 6 to 22 by the combination of F and H described above. In Tables 6 to 22, the F and H columns respectively indicate the numbers of the formulas exemplified above.

From the viewpoint of obtaining a raw material, the compound (I) is preferably a compound represented by Tables 23 to 27, and more preferably a compound represented by Tables 28 to 29.

The method for producing the compound (I) of the present invention can be produced, for example, according to the method described in Dyes and Pigments 2008, 77, 556. Specifically, it can be produced by subjecting a compound represented by the formula (pa1), a compound represented by the formula (pa2), and ethyl cyanoacetate to a cyclization reaction in the presence of benzoic acid and a solvent. The reaction temperature is preferably from 0 ° C to 200 ° C, more preferably from 100 ° C to 150 ° C. The reaction time is preferably from 1 hour to 24 hours, more preferably from 8 hours to 18 hours, and still more preferably from 8 to 16 hours. The solvent may, for example, be methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol or N-methylpyrrolidone, and is preferably 1-pentanol.

[In the formula (Pa1) and the formula (pa2), R ¹ to R ⁵ , R ⁷ to R ⁹ , A, X and L respectively have the same meanings as described above].

In the production of the compound (I), the compound represented by the formula (pa1) is used in an amount of from 1 mol to 10 mol, preferably from 1 to 2, per mol of the compound represented by the formula (pa2). Moor, more preferably 1 mole.

In the production of the compound (I), the ethyl cyanoacetate is used in an amount of from 1 mol to 10 mol, preferably from 1 mol to 10 mol, based on the compound represented by the formula (pa2). It is 1~2 moles, more preferably 1 mole.

In the production of the compound (I), the amount of the benzoic acid used is usually from 0.3 mol to 3 mol, preferably from 0.3 to 0.6 mol, based on the compound of the formula (Pa2). It is 0.3~0.4 m.

Further, the compound (I') is produced by subjecting a compound represented by the formula (Pa1), a compound represented by the formula (pa3), and ethyl cyanoacetate to cyclization in the presence of benzoic acid and a solvent. . The reaction temperature is preferably from 0 ° C to 200 ° C, more preferably from 100 ° C to 150 ° C. The reaction time is preferably from 1 hour to 24 hours, more preferably from 8 hours to 18 hours, and still more preferably from 8 to 16 hours. The solvent may, for example, be methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol or N-methylpyrrolidone, and is preferably 1-pentanol.

[In the formula (pa3), R ⁷ to R ⁹ , X and L have the same meanings as described above].

In the production of the compound (I'), the compound represented by the formula (pa1) is used in an amount of 2 mol or more and 20 mol or less, preferably 2 mol or less, based on the compound 1 represented by the formula (pa3). 2 to 4 moles, more preferably 2 moles.

In the production of the compound (I'), the ethyl cyanoacetate is used in an amount of 2 moles to 20 moles, preferably 2 to 4 moles, per mole of the compound represented by the formula (pa3). More preferably 2 moles.

In the production of the compound (I'), the amount of benzoic acid used is usually from 0.6 mol to 6 mol, preferably from 0.6 to 1.2 mol, relative to the compound 1 represented by the formula (pa3). Good for 0.6~0.7 moles.

The method of obtaining the compound (I) or the compound (I') of the present invention as the objective compound according to the reaction mixture is not particularly limited, and various known methods can be employed. For example, it is preferred to appropriately adjust the temperature of the column chromatography or the reaction mixture to precipitate crystals, thereby filtering the crystals. The crystals to be filtered are preferably washed by a solvent such as water, acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, tetrahydrofuran, acetone, acetic acid, A mixture of ethyl acetate, hexane, toluene or the like is then dried. Further, if necessary, purification may be carried out by a known method such as dissolving in acetonitrile, methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol or tetrahydrofuran. A method in which a solvent such as acetone, acetic acid, ethyl acetate, ethyl acetate, hexane, toluene, chloroform or the like is washed with an aqueous sodium hydroxide solution, followed by drying; column chromatography or recrystallization.

The dye of the present invention contains the compound (I) or the compound (I') as an active ingredient. The dye of the present invention may be a dye containing only the compound (I) or the compound (I'), and may further contain the following dye. The dye of the present invention preferably contains the compound (I) or the compound (I') in a proportion of 70 to 100% by mass, and more preferably contains the compound (I) or the compound (I') in a ratio of 80 to 100% by mass.

The dye of the present invention can be used as a dye contained in a colored curable resin composition used for a color filter of a display device such as a liquid crystal display device.

The color-curable resin composition of the present invention comprises a colorant (AA), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).

The colorant (AA) comprises the compound (I) or the compound (I').

The colored curable resin composition of the present invention preferably further contains at least one selected from the group consisting of a solvent (E) and a leveling agent (FF).

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

In the present specification, the compounds exemplified as the respective components may be used singly or in combination of plural kinds unless otherwise specified.

<Colorant (AA)>

The colorant (AA) may contain, in addition to the compound (I) or the compound (I'), a dye and/or a pigment different from the compound (I) or the compound (I').

As the dye other than the compound (I) or the compound (I'), it can be exemplified as a solvent (Solvent) in the Colour Index (published by The Society of Dyers and Colourists) (Solvent) ), an acid, a basic, a reactive, a direct, a disperse, or a reduced (Vat) compound. More specifically, the dye index (C.I.) numbered dyes described below are exemplified, but are not limited thereto.

CI Solvent Yellow 25, 79, 81, 82, 83, 89; CI Acid Yellow 7, 23, 25, 42, 65, 76; CI Reactive Yellow 2, 76, 116; CI Direct Yellow 4, 28, 44, 86 , 132; CI disperse yellow 54, 76; CI solvent orange 41, 54, 56, 99; CI acid orange 56, 74, 95, 108, 149, 162; CI reactive orange 16; CI direct orange 26; CI Solvent Red 24, 49, 90, 91, 118, 119, 122, 124, 125, 127, 130, 132, 160, 218; CI Acid Red 73, 91, 92, 97, 138, 151, 211, 274, 289; CI Acid Violet 102; CI Solvent Green 1, 5; CI Acid Green 3, 5, 9, 25, 28; CI Alkaline Green 1; CI Reducing Green 1 and the like.

The colorant (AA) contains the compound (I) or the compound (I'), and preferably further contains a pigment (P).

The pigment (P) is not particularly limited, and a known pigment can be used, and examples thereof include a pigment classified as a pigment in a dye index (published by the British Society of Coloring and Colorists).

As the pigment, for example, CI Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, Yellow pigments such as 128, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214; CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, Orange pigments such as 59, 61, 64, 65, 71, 73; CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments; C.I. Pigment blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments; CI pigment purple 1,19,23,29,32,36,38 and other purple pigments; CI pigment green 7,36,58 and other green pigments; CI pigment brown 23,25 and other brown pigments; CI pigment black 1,7 and other black Pigments, etc.

The pigment (P) is preferably a phthalocyanine pigment, more preferably at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment, and further preferably selected from CI Pigment Green 7, 36 and 58. At least one of the group consisting of. The above pigment can be preferably used for a green pigment, and by including the above pigment, it is easy to optimize the transmission spectrum, and the color filter is excellent in light resistance and chemical resistance.

The pigment may be subjected to treatment such as rosin treatment, surface treatment using a pigment derivative into which an acidic group or a basic group is introduced, or the like, and graft treatment on the surface of the pigment by using a polymer compound or the like; The micronization treatment such as the sulfuric acid micronization method; the cleaning treatment using an organic solvent for removing impurities and water; and the removal treatment by an ion exchange method using ionic impurities. The particle size of the pigment is preferably uniform.

The pigment contains a pigment dispersant and is subjected to a dispersion treatment, whereby the pigment dispersion liquid can be uniformly dispersed in the pigment dispersant solution. The pigments may be separately subjected to dispersion treatment, or may be mixed and mixed to carry out dispersion treatment.

Examples of the pigment dispersant include pigment dispersants such as cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic. These pigment dispersants may be used singly or in combination of two Used on. Examples of the pigment dispersant include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), and Solsperse (manufactured by Zeneca Co., Ltd.). EFKA (manufactured by CIBA Co., Ltd.), Ajisper (manufactured by Ajinomoto Fine-Techno Co., Ltd.), Disperbyk (manufactured by BYK-Chemie Co., Ltd.), and the like.

In the case of using a pigment dispersant, the amount thereof is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less based on 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion liquid having a more uniform dispersed state can be obtained.

In the case where the colorant (AA) contains a dye and/or a pigment different from the compound (I) or the compound (I') in addition to the compound (I) or the compound (I'), the compound (I) or the compound The content of (I') is preferably 1% by mass or more and 100% by mass or less, more preferably 3% by mass or more and 100% by mass or less, and further preferably 3% by mass based on the total amount of the coloring agent (AA). % or more and 70% by mass or less, and particularly preferably 3% by mass or more and 60% by mass or less.

When the pigment (P) is contained, the content of the pigment (P) is preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 97% based on the total amount of the coloring agent (AA). The mass% or less is more preferably 30% by mass or more and 97% by mass or less, and particularly preferably 40% by mass or more and 97% by mass or less.

The content of the coloring agent (AA) is preferably 1% by mass or more and 70% by mass or less, more preferably 1% by mass or more and 60% by mass or less, and still more preferably 5% by mass based on the total amount of the solid content component. The above is 60% by mass or less, and particularly preferably 5% by mass or more and 50% by mass or less. If the content of the colorant (AA) is Within the above range, it is easier to obtain the desired spectral and color density.

In the present specification, the "total amount of the solid content component" means the total amount of the components obtained by removing the solvent (E) from the colored curable resin composition of the present invention. The total amount of the solid content component and the content of each component relative thereto can be measured by a known analytical method such as liquid chromatography or gas chromatography.

<Resin (B)>

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, more preferably an addition polymer having a structural unit derived from at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides. . Examples of such a resin include the following resins [K1] to [K6].

The resin [K1] is at least one selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (a) (hereinafter sometimes referred to as "(a)") and a cyclic ether structure having a carbon number of 2 to 4. a copolymer of a monomer (b) having an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)"); a resin [K2] (a), (b) and a monomer copolymerizable with (a) ( c) (wherein, different from (a) and (b)) (hereinafter sometimes referred to as "(c)"); copolymer [K3] (a) and (c); resin [K4] a resin obtained by reacting the copolymer of (a) and (c) with (b); a resin obtained by reacting the copolymer of (b) and (c) with (a); resin [ K6] A resin obtained by reacting the copolymer of (b) and (c) with (a) and further reacting a carboxylic anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, and p-vinylbenzoic acid; Aenedioic acid, fumaric acid, methyl maleic acid, methyl fumaric acid, itaconic acid, 3-vinyl phthalic acid, 4-vinyl phthalic acid, 3, 4, 5, 6- Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexene dicarboxylic acid; Base-5-down Alkene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5 -Methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2. 1] a bicyclic unsaturated compound having a carboxyl group such as hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; maleic anhydride, methyl-n-butene Diacid anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride , dimethyltetrahydrophthalic anhydride, unsaturated dicarboxylic anhydride such as 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride; succinic acid mono [2-(methyl) propylene Unsaturated mono[(meth)acryloxyalkylene group of divalent or higher polycarboxylic acid such as methoxyethyl]ester or phthalic acid mono [2-(methyl) propylene oxyethyl] ester An ester; an unsaturated acrylic acid having a hydroxyl group and a carboxyl group in the same molecule as α-(hydroxymethyl)acrylic acid.

Among these, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferable in terms of copolymerization reactivity and solubility of the obtained resin to an alkaline aqueous solution.

(b) means a cyclic ether structure having, for example, a carbon number of 2 to 4 (for example, at least one selected from the group consisting of an oxirane ring, a propylene oxide ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Polymeric compound. (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloxy group.

In the present specification, "(meth)acrylic acid" means at least one selected from the group consisting of acrylic acid and methacrylic acid. The notation of "(meth)acrylonitrile" and "(meth)acrylate" has the same meaning.

(b), for example, a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"); having an oxypropylene group and an ethylenic unsaturated group The monomer (b2) of the bond (hereinafter sometimes referred to as "(b2)"); and the monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)")).

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

Examples of (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, and glycidylvinyl Ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-inter-ethylene Glycidyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidoxymethyl)styrene, 2,4-bis(glycidoxymethyl) Phenylene Alkene, 2,5-bis(glycidoxymethyl)styrene, 2,6-bis(glycidoxymethyl)styrene, 2,3,4-tris(glycidoxymethyl)benzene Ethylene, 2,3,5-tris(glycidoxymethyl)styrene, 2,3,6-tris(glycidoxymethyl)styrene, 3,4,5-tris(glycidyloxy) Methyl)styrene, 2,4,6-tris(glycidoxymethyl)styrene, and the like.

Examples of (b1-2) include vinylcyclohexene oxide, 1,2-epoxy-4-vinylcyclohexane, and 3,4-epoxycyclohexylmethyl (meth)acrylate. 3,4-epoxycyclohexylmethyl methacrylate, a compound represented by the formula (1), a compound represented by the formula (2), and the like.

In the formulae (1) and (2), R ^a and R ^{b each} represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and a hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group.

X ^a and X ^b 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 key with O.].

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, and a third butyl group.

Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxyl group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, and a 1-hydroxy group. 1-methylethyl, 2-hydroxy-1-methylethyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, and the like.

R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylidene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. - Diyl, hexane-1,6-diyl and the like.

As X ^a and X ^b , a single bond, a methylene group, an ethylidene group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O- are preferably exemplified, and a single bond and more preferably * -CH ₂ CH ₂ -O- (* indicates the bond with O).

The compound represented by the formula (1), a compound represented by any one of the formulae (1-1) to (1-15), and the like can be given. Among them, preferred are formula (1-1), formula (1-3), formula (1-5), formula (1-7), formula (1-9) or formula (1-11) to formula (1). The compound represented by -15) is more preferably a compound represented by the formula (1-1), the formula (1-7), the formula (1-9) or the formula (1-15).

Examples of the compound represented by the formula (2) include a compound represented by any one of the formulae (2-1) to (2-15). Among them, preferred are formula (2-1), formula (2-3), formula (2-5), formula (2-7), formula (2-9) or formula (2-11) to formula (2). The compound represented by -15) is more preferably a compound represented by the formula (2-1), the formula (2-7), the formula (2-9) or the formula (2-15).

The compound represented by the formula (1) and the compound represented by the formula (2) may be used singly or in combination with the compound represented by the formula (1) and the compound represented by the formula (2). In the case where they are used in combination, the content ratio of the compound represented by the formula (1) and the compound represented by the formula (2) is expressed by the molar standard, preferably 5:95 to 95:5, more preferably 10: 90~90:10, and further preferably 20:80~80:20.

As (b2), a monomer having an oxypropylene group and a (meth) propylene methoxy group is more preferable. Examples of (b2) include 3-methyl-3-methylpropenyloxymethyl propylene oxide, 3-methyl-3-propenyloxymethyl propylene oxide, and 3-ethyl-3. -Methacryloxymethoxymethyl propylene oxide, 3-ethyl-3-propenyloxymethyl propylene oxide, 3-methyl-3-methylpropenyloxyethyl propylene oxide, 3 -methyl-3-propenyloxyethyl propylene oxide, 3-ethyl-3-methylpropenyloxyethyl propylene oxide, 3-ethyl-3-acryloxyethyl epoxide Propane, etc.

As (b3), a monomer having a tetrahydrofuranyl group and a (meth)acryloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate. (For example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

(b) is preferably (b1) in terms of further improving the reliability of heat resistance and chemical resistance of the obtained color filter. Further, in terms of excellent storage stability of the colored curable resin composition, (b1-2) is more preferable.

Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, second butyl (meth)acrylate, and (meth)acrylic acid. Tributyl ester, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, (meth)acrylic acid Cyclopentyl ester, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decane-8-yl (meth)acrylate In the technical field, it is called "dicyclopentanyl (meth) acrylate" as a conventional name. Further, it is sometimes called "tricyclodecyl (meth) acrylate) or tricyclo(meth) acrylate [ 5.2.1.0 ^2,5 ]decene-8-yl ester (referred to as "dicyclopentenyl (meth) acrylate) in the technical field), dicyclopentyl (meth) acrylate Oxyethyl ester, (meth)acrylic acid Base ester, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, (methyl) (meth)acrylates such as benzyl acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate; (meth)acrylates having hydroxyl groups; Dicarboxylic acid diesters such as diethyl acid diethyl ester, diethyl fumarate, diethyl iconate; bicyclo [2.2.1] hept-2-ene, 5-methyl bicyclo [2.2.1 Hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2. 1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5 -ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2 .1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1] Hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5- Hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl -5-Methylbicyclo[2.2.1]hept-2-ene, 5-t-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2 .1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(t-butoxycarbonyl)bicyclo[2.2.1]heptane- a bicyclic unsaturated compound such as 2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; N-phenyl maleimide, N- Cyclohexyl maleimide, N-benzyl maleimide, N-butylenediamine-3-butyleneimine benzoate, N-butane Imino-4-butylindoleimine butyrate, N-butanediamine-6-m-butyleneimine hexanoate, N-butanediamine-3- Dicarbonyl quinone imine derivatives such as maleimide propionate, N-(9-acridinyl) maleimide, styrene, α-methylstyrene, m-methyl Styrene, p-methylstyrene, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.

Among these, in terms of copolymerization reactivity and heat resistance, styrene, vinyl toluene, benzyl (meth)acrylate, and trimethyl (meth)acrylate [5.2.1.0 ^{2, 6 are} preferred. ] decane-8-yl ester, N-phenyl maleimide, N-cyclohexyl maleimide, N-benzyl maleimide and bicyclo [2.2. 1] Hept-2-ene.

In the resin [K1], in the entire structural unit constituting the resin [K1], the ratio of the structural unit derived from each is preferably: the structural unit derived from (a): 2 to 60 mol% derived from ( b) The structural unit: 40 to 98 mol%, more preferably: the structural unit derived from (a): 10 to 50 mol% derived from the structural unit of (b): 50 to 90 mol%.

When the ratio of the structural unit of the resin [K1] is in the above range, the storage stability of the colored curable resin composition, the developability in forming a colored pattern, and the solvent resistance of the obtained color filter are more excellent. tendency.

Resin [K1] can be referred to, for example, in the literature "Experimental method for polymer synthesis" (Dazu Takashi, the Institute of Chemicals (company), the first edition of the first edition, issued on March 1, 1972) It is produced by the method described and the cited documents described in the literature.

Specifically, a method in which a specific amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction container, for example, by replacing oxygen with nitrogen, thereby deoxidizing the environment Stir, heat and keep warm. again The polymerization initiator, solvent and the like used herein are not particularly limited, and those generally used in the field can be used. For example, examples of the polymerization initiator include an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic The solvent (E) which is a solvent (E) of the colored curable resin composition of the present invention is exemplified as the solvent (E).

Further, the obtained copolymer may be directly used as a solution after the reaction, or may be a solution obtained by concentration or dilution, or may be extracted as a solid (powder) by a method such as reprecipitation. In particular, in the polymerization, the solvent contained in the colored curable resin composition of the present invention can be used as a solvent, and the solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention. The production steps of the color hardening resin composition of the present invention can be simplified.

In the resin [K2], in the entire structural unit constituting the resin [K2], the ratio of the structural unit derived from each is preferably: the structural unit derived from (a): 2 to 45 mol% is derived from ( b) The structural unit: 2~95 mol% derived from the structural unit of (c): 1~65 mol%, more preferably: the structural unit derived from (a): 5~40 mol% from ( b) The structural unit: 5 to 80 mol% derived from the structural unit of (c): 5 to 60 mol%.

When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition and the development of the colored pattern are formed. The color filter obtained has a tendency to be more excellent in solvent resistance, heat resistance and mechanical strength.

The resin [K2] can be produced in the same manner as the method described in the method for producing the resin [K1].

In the resin [K3], in the entire structural unit constituting the resin [K3], the ratio of the structural unit derived from each is preferably: the structural unit derived from (a): 2 to 60 mol% derived from ( c) The structural unit: 40~98 mol%, more preferably: the structural unit derived from (a): 10~50 mol% derived from the structural unit of (c): 50-90 mol%.

The resin [K3] can be produced in the same manner as the method described in the production method of the resin [K1].

The resin [K4] can be produced by obtaining a copolymer of (a) and (c), and (b) having a cyclic ether having 2 to 4 carbon atoms and (a) having a carboxyl group. Acid and / or carboxylic anhydride addition.

First, a copolymer of (a) and (c) is produced in the same manner as the method described in the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same ratio as those listed in the resin [K3].

Then, a part of the carboxylic acid and/or carboxylic anhydride derived from (a) in the above copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms which is contained in (b).

Following the manufacture of the copolymers of (a) and (c), the resin [K4] can be produced by replacing the environment in the flask with nitrogen from air, and (b), carboxylic acid or carboxylic anhydride with Reaction catalyst for cyclic ethers (eg tris(dimethylamino) A phenol or the like, and a polymerization inhibitor (for example, hydroquinone) are placed in a flask, for example, at 60 to 130 ° C for 1 to 10 hours.

The amount of use of (b) is preferably from 5 to 80 moles, more preferably from 10 to 75 moles, relative to (a) 100 moles. When it is in this range, the storage stability of the colored curable resin composition, the developability at the time of pattern formation, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern are better. Propensity. Since the reactivity of the cyclic ether is high and it is difficult to remain unreacted (b), it is preferably (b1), more preferably (b1-1), as the resin (K4).

The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c). The amount of the polymerization inhibitor to be used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of (a), (b) and (c).

The reaction conditions such as the addition method, the reaction temperature, and the time can be appropriately adjusted in consideration of the production equipment, the calorific value of the polymerization, and the like. Further, in the same manner as the polymerization conditions, the addition method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value of the polymerization, and the like.

The resin [K5] was used as the first stage, and the copolymers of (b) and (c) were obtained in the same manner as in the above-mentioned production method of the resin [K1]. The copolymer obtained in the same manner as described above may be used as it is, or may be a solution obtained by concentration or dilution, or may be extracted as a solid (powder) by a method such as reprecipitation.

The ratio of the structural units derived from (b) and (c) to the total number of moles of the entire structural unit constituting the above copolymer is preferably: The structural unit derived from (b): 5 to 95 mol% derived from the structural unit of (c): 5 to 95 mol%, more preferably: the structural unit derived from (b): 10 to 90 mol% The structural unit derived from (c): 10 to 90 mol%.

Further, the resin [K5] can be obtained by subjecting the copolymer of (b) and (c) to the ring derived from (b) under the same conditions as the method for producing the resin [K4]. The ether is reacted with the carboxylic acid or carboxylic acid anhydride (a).

The amount of (a) used for the reaction in the above copolymer is preferably from 5 to 80 moles per 100 moles of (b). Since the cyclic ether has high reactivity and does not easily remain unreacted (b), it is preferably (b1), more preferably (b1-1), as the resin (K5).

The resin [K6] is a resin obtained by further reacting a resin [K5] with a carboxylic acid anhydride. The hydroxyl group produced by the reaction of a cyclic ether with a carboxylic acid or a carboxylic anhydride is reacted with a carboxylic acid anhydride.

Examples of the carboxylic acid anhydride include maleic anhydride, methyl maleic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, and 3,4,5,6-tetrahydroortylene. Formic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. . The amount of the carboxylic anhydride used is 1 mole based on the amount used in (a), preferably 0.5 to 1 mole.

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth)acrylate/(meth)acrylic acid copolymer and 3,4-epoxy tricyclo(meth)acrylate. [5.2.1.0 ^2,6 ] Resin such as oxime ester/(meth)acrylic acid copolymer [K1]; glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, ( Glycidyl methacrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.4.1.0 ^2,6 ]decyl methacrylate/(meth)acrylic acid/N -cyclohexylmethyleneimine copolymer, 3,4-epoxytricyclo(5.4-diethyl)[5.2.1.0 ^2,6 ]decyl ester / (meth)acrylic / vinyl toluene copolymer, 3 -Methyl-3-(meth)acryloxymethyl propylene oxide / (meth)acrylic acid / styrene copolymer resin [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer Resin, styrene/(meth)acrylic acid copolymer, benzyl (meth)acrylate/tricyclodecyl (meth)acrylate/(meth)acrylic acid copolymer [K3]; benzyl (meth)acrylate Ester/resin obtained by adding (meth)acrylic acid copolymer and glycidyl (meth)acrylate, (methyl) Tricyclodecyl acrylate/styrene/resin obtained by adding (meth)acrylic acid copolymer and glycidyl (meth)acrylate, tricyclodecyl (meth)acrylate/benzyl (meth)acrylate a resin such as a resin obtained by adding a (meth)acrylic copolymer and a glycidyl (meth)acrylate [K4]; tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate A resin obtained by reacting a copolymer with (meth)acrylic acid, a tricyclodecyl (meth)acrylate/styrene/copolymer of glycidyl (meth)acrylate and (meth)acrylic acid Resin such as resin [K5]; tricyclodecyl (meth) acrylate / resin such as resin obtained by further reacting the following resin with tetrahydrophthalic anhydride, etc., that is, (methyl) A resin obtained by reacting a copolymer of glycidyl acrylate with (meth)acrylic acid.

The resin (B) is preferably one selected from the group consisting of a resin [K1], a resin [K2], and a resin [K3], and more preferably selected from the group consisting of a resin [K2] and a resin [K3]. One of the group consisting of. When it is such a resin, the coloring curable resin composition is excellent in developability. From the viewpoint of the adhesion between the colored pattern and the substrate, the resin [K2] is further preferable.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, still more preferably 5,000 to 35,000, still more preferably 5,000 to 30,000, still more preferably 6,000 to 30,000. When the molecular weight is in the above range, the coating film has a high hardness and a high residual film ratio, and the solubility of the unexposed portion in the developer is good, and the resolution of the colored pattern is improved.

The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably from 1.1 to 6, more preferably from 1.2 to 4.

The acid value of the resin (B) is usually from 20 to 170 mg-KOH/g, preferably from 30 to 170 mg-KOH/g, further preferably from 40 to 170 mg-KOH/g, more preferably from 50 to 150 mg. The KOH/g is further preferably 60 to 150 mg-KOH/g, more preferably 60 to 135 mg-KOH/g, and particularly preferably 70 to 135 mg-KOH/g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained, for example, by titration with an aqueous potassium hydroxide solution.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 10 to 60% by mass, still more preferably 13 to 60% by mass, and particularly preferably 17 to 55% by mass based on the total amount of the solid content component. %. When the content of the resin (B) is in the above range, there is a tendency that the coloring pattern is easily formed, and the resolution of the colored pattern and the residual film ratio are improved.

<Polymerizable compound (C)>

The polymerizable compound (C) is a compound which is polymerized by an active radical and/or an acid which is produced by polymerizing the initiator (D), and examples thereof include a polymerizable compound having an ethylenically unsaturated bond. A good (meth) acrylate compound.

Examples of the polymerizable compound having one ethylenically unsaturated bond include mercaptophenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-ethylhexyl carbitol acrylic acid. Ester, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, etc., (a), (b) and (c) above.

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

Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol penta(meth)acrylic acid. Ester, dipentaerythritol hexa(meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, pentaerythritol deca (meth) acrylate, pentaerythritol nin (meth) acrylate Ester, tris(2-(meth)acryloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate Ester, propylene glycol modified pentaerythritol tetra(meth) acrylate, propylene glycol modified dipentaerythritol hexa(meth) acrylate, caprolactone modification Pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like.

Among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, more preferably 150 or more and 1,500 or less, still more preferably 150 or more and 800 or less, and still more preferably 190 or more and 700 or less.

The content of the polymerizable compound (C) is usually 7 to 65% by mass, preferably 7 to 65% by mass, more preferably 10 to 60% by mass, and still more preferably 13%, based on the total amount of the solid content component. 60% by mass, particularly preferably 17 to 55% by mass.

Further, the content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is represented by a mass standard, preferably 20:80 to 80:20, more preferably 35. : 65~80:20.

When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>

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

As the polymerization initiator (D), a phenylalkyl ketone compound, three a compound, a mercaptophosphine oxide compound, an o-nonylphosphonium compound, a biimidazole compound, and the like.

The above ortho-indenyl ruthenium compound has a partial structure represented by the formula (d1) Compound. Hereinafter, * indicates a keying key.

Examples of the above o-nonyl fluorene compound include N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine and N-benzylformamide. 1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclo Pentylpropan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzhydryl)-9H-indazol-3-yl] Ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-di Cyclopentylmethoxy)benzylidene}-9H-indazol-3-yl]ethane-1-imine, N-ethyloxy-1-[9-ethyl-6-(2- Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzylidene-1-(9-ethyl-6-(2) -Methylbenzylidene)-9H-indazol-3-yl]-3-cyclopentylpropan-1-one-2-imine. Commercial products such as Irgacure OXE01, OXE02 (above, BASF) and N-1919 (made by ADEKA) can also be used. Wherein, the orthoquinone-based oxime compound is preferably selected from the group consisting of N-benzylideneoxy-1-(4-phenylthiophenyl)butan-1-one-2-imine, N-benzyl hydrazine 1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzylideneoxy-1-(4-phenylthiophenyl)-3-cyclo At least one of the group consisting of pentylpropan-1-one-2-imine, more preferably N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one -2-imine.

The phenylalkyl ketone compound is a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In some of the structures, the benzene ring may have a substituent.

As a compound having a partial structure represented by the formula (d2), for example, 2-methyl-2- Lolinyl-1-(4-methylthiophenyl)propan-1-one, 2-dimethylamino-1-(4- Phenylphenyl)-2-benzylbutan-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4- Polinyl)phenyl]butan-1-one and the like. Commercial products such as Irgacure 369, 907, and 379 (manufactured by BASF Corporation) can also be used.

Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1-[4] -(2-hydroxyethoxy)phenyl]propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1 a ketone oligomer, α,α-diethoxyacetophenone, benzoin dimethyl ketal or the like.

In terms of sensitivity, the phenylalkyl ketone compound is preferably a compound having a partial structure represented by the formula (d2).

The biimidazole compound is, for example, a compound represented by the formula (d5).

[In the formula (d5), R ⁵¹ to R ⁵⁵ represent an aryl group having 6 to 10 carbon atoms which may have a substituent].

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolylmethyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferred.

Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and is preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferred.

Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(2,3- Dichlorophenyl)-4,4',5,5',-tetraphenylbiimidazole (for example, refer to JPH06-75372-A, JPH06-75373-A, etc.), 2,2'-bis(2-chlorobenzene) -4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetrakis(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chloro Phenyl)-4,4',5,5'-tetrakis(trialkoxyphenyl)biimidazole (for example, refer to JPS48-38403-B, JPS62-174204-A, etc.), 4,4'5,5' An imidazole compound in which a phenyl group is substituted with an alkoxycarbonyl group (for example, refer to JPH07-10913-A, etc.) and the like. Among them, preferred are compounds represented by the following formulas and mixtures thereof.

As the above three The compound may, for example, be 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-tri , 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-sunflower-1,3,5-three 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-[5-methylfuran-2-yl)vinyl]- 1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-three , 2,4-bis(trichloromethyl)-6-[2-(3,4[dimethoxyphenyl)vinyl]-1,3,5-three Wait.

The above fluorenylphosphine oxide compound may, for example, be 2,4,6-trimethylbenzimidyldiphenylphosphine oxide.

Further, examples of the polymerization initiator (D) include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone, benzamidine benzoic acid methyl ester, and 4 -phenyldiphenyl ketone, 4-benzylidene-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(t-butylperoxycarbonyl)diphenyl ketone, a diphenyl ketone compound such as 2,4,6-trimethyldiphenyl ketone; an anthracene compound such as 9,10-phenanthrenequinone, 2-ethylhydrazine, camphorquinone; 10-butyl-2-chloroacridine Ketone, benzyl, methyl benzhydrazinecarboxylate, titanium titanate compound, and the like. These are preferably used in combination with the following polymerization starting assistant (D1) (especially an amine).

The polymerization initiator (D) preferably comprises a compound selected from the group consisting of a phenylalkyl ketone compound, three A polymerization initiator which is at least one of a group consisting of a compound, a mercaptophosphine oxide compound, an o-nonylphosphonium compound and a biimidazole compound is more preferably a polymerization initiator containing an orthoquinone-based compound.

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). It is 1~30 mass, especially preferably 1~20 mass parts.

<Polymerization starter (D1)>

The polymerization initiation aid (D1) is used to promote the polymerization by the polymerization initiator A compound which is polymerized with a polymerizable compound or a sensitizer. In the case where the polymerization initiator (D1) is contained, the polymerization initiator (D) is usually used in combination.

Examples of the polymerization initiation assistant (D1) include an amine compound, an alkoxy fluorene compound, and 9-oxosulfuric acid. Compounds, carboxylic acid compounds, and the like.

The amine compound may, for example, be triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate or 4-dimethyl Isoamyl benzoate benzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4, 4'-bis(dimethylamino)diphenyl ketone (commonly known as mickleone), 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-double (B The methylamino)diphenyl ketone or the like is preferably 4,4'-bis(diethylamino)diphenyl ketone. Commercial products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) can also be used.

The above alkoxy fluorene compound may, for example, be 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene or 2-ethyl -9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, and the like.

As the above 9-oxygen sulfur Compounds can be exemplified by 2-isopropyl 9-oxosulfur 4-isopropyl 9-oxosulfur 2,4-diethyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 1-chloro-4-propoxy 9-oxosulfur Wait.

Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, and dimethylphenylthioacetic acid. Methoxyphenylthioacetic acid, dimethoxy Phenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthyloxyacetic acid Wait.

When the polymerization initiator (D1) is used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, the coloring pattern can be formed with high sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>

The solvent (E) is not particularly limited, and a solvent generally used in the field can be used. For example, an ester solvent (a solvent having -COO- in the molecule and having no -O-), an ether solvent (a solvent having -O- in the molecule and having no -COO-), an ether ester solvent (in the molecule) a solvent having -COO- and -O-), a ketone solvent (a solvent having -CO- in the molecule and having no -COO-), an alcohol solvent (having OH in the molecule and having no -O-, -CO) - and -COO-solvent), aromatic hydrocarbon solvent, guanamine solvent, dimethyl hydrazine, and the like.

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

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

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, and 3-methoxypropionic acid. Methyl ester, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, 2-methoxypropionic acid Ethyl ester, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, 2- Ethoxyethyl 2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether Acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate Ester, dipropylene glycol methyl ether acetate, and the like.

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

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

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

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

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

Among them, preferred are propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol. Monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3-methoxy-1-butanol, 4-hydroxy-9-methyl-2-pentanone, N, N - dimethylformamide and N-methylpyrrolidone, more preferably propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, dipropylene glycol methyl ether acetate, lactate B Ester, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and N-methylpyrrolidone.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, still more preferably 75 to 90% by mass, based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably from 5 to 30% by mass, more preferably from 8 to 25% by mass, even more preferably from 10 to 25% by mass. When the content of the solvent (E) is in the above range, there is a tendency that the flatness at the time of application is good, and the color density is not insufficient when the color filter is formed, so that the display characteristics are good.

<Leveling agent (FF)>

Examples of the leveling agent (FF) include a polyfluorene-based surfactant, a fluorine-based surfactant, and a polyfluorene-based surfactant having a fluorine atom. These may also have a polymerizable group in the branch.

Examples of the polyoxymethylene surfactant include a surfactant having a oxime bond in the molecule. Specifically, it can be cited as: Toray Silicone DC3PA, same as SH7PA, same DC11PA, same SH21PA, same SH28PA, same SH29PA, same SH30PA, same SH8400 (trade name, manufactured by Toray Dow Corning Co., Ltd.); KP321, KP322, KP323, KP324, KP326, KP340, KP341 (Manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF-4446, TSF4452, and TSF4460 (made by Momentive Advanced Materials Japan Co., Ltd.).

The fluorine-based surfactant may, for example, be a surfactant having a fluorocarbon chain in a molecule. Specifically, Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M (company)); MEGAFAC (registered trademark) F142D, same as F171, same as F172, same as F173, same as F177, same as F183, the same F554, the same R30, the same RS-718-K (made by DIC (company)); Eftop (registered trademark) EF301, the same EF303, the same EF351, the same EF352 (manufactured by Mitsubishi Materials Electronic Co., Ltd.); Surflon (registered trademark) S381, the same as S382, the same SC101, the same SC105 (made by Asahi Glass Co., Ltd.); E5844 (manufactured by Daikin Precision Chemical Research Institute Co., Ltd.).

The polyfluorene-based surfactant having a fluorine atom as described above may be a surfactant having a oxime bond or a fluorocarbon chain in the molecule. Specific examples include MEGAFAC (registered trademark) R08, the same BL20, the same F475, the same F477, and the same F443 (manufactured by DIC Co., Ltd.).

The content of the leveling agent (FF) is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002% by mass or more and 0.1% by mass or less, based on the total amount of the coloring curable resin composition, and further preferably 0.005 mass% The above is 0.07 mass% or less. When the content of the leveling agent (FF) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>

The colored curable resin composition of the present invention may further contain additives such as a filler, another polymer compound, an adhesion promoter, an antioxidant, a light stabilizer, and a chain transfer agent, which are known in the art.

<Method for Producing Colored Curable Resin Composition>

The colored curable resin composition of the present invention can be prepared by mixing, for example, a coloring agent (AA), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and optionally Solvent (E), leveling agent (FF), polymerization starting aid (D1) and other ingredients used.

The pigment in the case where the pigment (P) is contained is preferably a part or all of the premixed solvent (E), and is dispersed by a bead mill or the like to have an average particle diameter of the pigment of about 0.2 μm or less. At this time, part or all of the above pigment dispersant and resin (B) may be blended as needed. The coloring resin composition for the purpose can be prepared by mixing the remaining components in a pigment dispersion liquid obtained as described above so as to have a specific concentration.

The compound (I) is preferably prepared by partially or completely dissolving a part or all of the solvent (E) in advance. Preferably, the solution is filtered by a filter having a pore diameter of about 0.01 to 1 μm.

It is preferred to filter and mix the colored curable resin composition by a filter having a pore diameter of about 0.01 to 10 μm.

<Method of Manufacturing Color Filter>

A coloring pattern is produced by the colored curable resin composition of the present invention The method of the case includes a photolithography method, an inkjet method, a printing method, and the like. Among them, photolithography is preferred. The photolithography method is a method in which the colored curable resin composition is applied onto a substrate and dried to form a colored composition layer, and the colored composition layer is exposed through a photomask to be developed. In the photolithography method, a coloring coating film which is a cured product of the coloring composition layer can be formed by not using a photomask during exposure and/or without developing. The colored pattern and the colored coating film formed in the above manner are the color filters of the present invention.

The film thickness of the produced color filter is not particularly limited, and may be appropriately adjusted depending on the purpose, use, and the like, and is, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda lime glass coated with cerium oxide, polycarbonate, polymethyl methacrylate, and polyterephthalic acid can be used. A resin plate such as ethylene glycol or a polyfluorene oxide is formed on the substrate, and an aluminum, silver, silver/copper/palladium alloy film or the like is formed on the substrate. Other color filter layers, resin layers, transistors, circuits, and the like may be formed on the substrates.

The formation of the respective color pixels by the photolithography method can be carried out by well-known or conventional devices and conditions. For example, it can be produced in the following manner.

First, the colored curable resin composition is applied onto a substrate, and dried by heating (pre-baked) and/or dried under reduced pressure to remove volatile components such as a solvent and dried, thereby obtaining a smooth color combination. Layer of matter.

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

The temperature at the time of heat drying is preferably from 30 to 120 ° C, more preferably from 50 to 110 ° C. Further, the heating time is preferably from 10 seconds to 60 minutes, more preferably from 30 seconds to 30 minutes.

In the case of drying under reduced pressure, it is preferably carried out at a temperature of from 20 to 25 ° C under a pressure of from 50 to 150 Pa.

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

The colored composition layer is then exposed through a reticle that forms the desired color pattern. The pattern on the photomask is not particularly limited, and a pattern can be used depending on the intended use.

As the light source for exposure, a light source that generates light of a wavelength of 250 to 450 nm is preferable. For example, a filter that cuts the wavelength region can be used to cut off light of less than 350 mn, or a band pass filter that draws the wavelength regions can be used to selectively draw near 436 nm, near 408 nm, and 365 nm. Nearby light. Specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. are mentioned.

In order to uniformly illuminate the parallel light to the entire exposed surface, or to accurately align the reticle with the substrate on which the colored composition layer is formed, it is preferred to use a reticle alignment machine and a stepper Equal exposure device.

The exposed coloring composition layer is brought into contact with the developing solution to be developed, thereby forming a colored pattern on the substrate. The unexposed portion of the coloring composition layer by development is dissolved in the developer to be removed. As the developer, for example, an aqueous solution of a basic compound such as potassium hydroxide, sodium hydrogencarbonate, sodium carbonate or tetramethylammonium hydroxide is preferred. The concentration in the aqueous solution of the basic compounds is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass. Further, the developer may also contain a surfactant.

The development method may be any of a liquid coating method, a immersion plating method, and a spray method. Further, the substrate can be tilted at an arbitrary angle during development.

It is preferred to carry out water washing after development.

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

According to the colored curable resin composition of the present invention, in particular, a high-intensity color filter can be produced. The color filter can be used as a color filter for display devices (for example, liquid crystal display devices, organic EL (Electro Luminescence) devices, electronic paper, etc.) and solid-state imaging devices.

Example

Next, the embodiments will be described, and the present invention will be specifically described. The "%" and "parts" in the examples are all % by mass and parts by mass unless otherwise stated.

In the following synthesis examples, the structure of the compound is by NMR (JMM-ECA-500, manufactured by JEOL Ltd.) or mass spectrometry (LC, Model 1200 manufactured by Agilent, MASS, LC/MSD type manufactured by Agilent). ) and confirm.

The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene of the resin was carried out by GPC (chromatography) under the following conditions.

Device: HLC-8120GPC (manufactured by Tosoh Co., Ltd.)

Column: TSK-GELG2000HXL

Column temperature: 40 ° C

Solvent: THF (tetrahydrofuran, tetrahydrofuran)

Flow rate: 1.0 mL/min

The concentration of the solid content of the test liquid: 0.001~0.01% by mass

Injection volume: 50 μL

Detector: RI

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

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

Synthesis Example 1

The following were mixed: bis(3-amino-4-hydroxyphenyl)anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.6 parts, 4-(diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd. Ltd.) 14.6 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.17 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 183 parts and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) 8.61 parts and stirred at 120 ° C for 3 hours. 14.6 parts of 4-(diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.17 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and cyanoacetic acid were added to the reaction solution. Ethyl ester (manufactured by Tokyo Chemical Industry Co., Ltd.) was 8.61 parts and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, precipitated crystals were obtained as a residue for suction filtration. 236 parts of acetonitrile and 234 parts of isopropyl alcohol were added to the residue, and after stirring, an insoluble matter was obtained as a residue for suction filtration. 236 parts of acetonitrile and 234 parts of isopropyl alcohol were added to the residue, and after stirring, an insoluble matter was obtained as a residue for suction filtration. 2,220 parts of chloroform was added to the residue, and the mixture was stirred and filtered. To the filtrate, 530 parts of a 5% aqueous sodium hydroxide solution was added and stirred to extract a chloroform solution layer. To the chloroform solution, 610 parts of an 18% aqueous sodium chloride solution was added and stirred, and a chloroform solution layer was extracted. To the chloroform solution, 10 parts of magnesium sulfate was added, and after stirring, filtration was carried out. The filtrate solvent was distilled off by a rotary evaporator, and dried under reduced pressure at 60 ° C to obtain 19.5 parts of the compound of the formula (I-148). The structure was confirmed by ¹ H-NMR.

<Identification of the compound represented by formula (I-148)>

¹ H-NMR (500 MHz, DMSO-d ₆ ): 1.14 (12H, t), 3.50 (8H, q), 6.61 (2H, d), 6.82 (2H, dd), 7.71 (2H, d), 7.95 (2H, d), 8.04 (2H, dd), 8.43 (2H, d), 8.83 (2H, s).

Synthesis Example 2

The following materials were mixed: bis(3-amino-4-hydroxyphenyl)dimethylmethane (manufactured by Changzhou Sunshine Pharmaceutical Materials Co., Ltd.) 10.1 parts, 4-(diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) 15.2 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 3.26 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 191 parts and ethyl cyanoacetate (Tokyo) 8.89 parts manufactured by Huacheng Industrial Co., Ltd., and stirred at 120 ° C for 3 hours. To the reaction solution, 8.39 parts of 4-(diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.80 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 8.00 parts of amyl alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.91 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, precipitated crystals were obtained as a residue for suction filtration. 332 parts of acetonitrile was added to the residue, and after stirring, an insoluble matter was obtained as a residue for suction filtration. To the residue, 315 parts of acetonitrile was added, and after stirring, an insoluble matter was obtained as a residue for suction filtration. The residue was dried under reduced pressure at 60 ° C to obtain 23.6 parts of the compound of formula (I-169). The structure was confirmed by ¹ H-NMR.

<Identification of the compound represented by formula (I-169)>

¹ H-NMR (500 MHz, DMSO-d ₆ ): 1.14 (12H, t), 1.80 (6H, s), 3.49 (8H, q), 6.60 (2H, d), 6.81 (2H, dd), 7.19 (2H, dd), 7.59 (2H, d), 7.67 (2H, d), 7.68 (2H, d), 8.75 (2H, s).

Synthesis Example 3

The following were mixed: bis(3-amino-4-hydroxyphenyl)indole (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.57 parts, 4-(dibutylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd. Ltd.) 9.89 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.67 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 96.0 parts and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) 4.52 parts, and stirred at 120 ° C for 3 hours. To the reaction solution, 9.97 parts of 4-(dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.71 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were added. 20 parts of pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.52 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, precipitated crystals were obtained as a residue for suction filtration. 600 parts of isopropyl alcohol was added to the residue, and after stirring, an insoluble matter was obtained as a residue for suction filtration. The residue was dried under reduced pressure at 60 ° C to obtain 14.2 parts of the compound of formula (I-149). The structure was confirmed by ¹ H-NMR.

<Identification of the compound represented by formula (I-149)>

¹ H-NMR (500 MHz, CDCl ₃ ): 0.98 (12H, t), 1.39 (8H, qt), 1.62 (8H, tt), 3.37 (8H, t), 6.50 (2H, d), 6.63 (2H) , dd), 7.41 (2H, d), 7.67 (2H, d), 7.96 (2H, dd), 8.39 (2H, d), 8.62 (2H, s).

Synthesis Example 4

The following were mixed: bis(3-amino-4-hydroxyphenyl)anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.29 parts, 4-(bis(2-ethylhexyl)amino) salicylaldehyde ( 3.31 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.385 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 22.3, synthesized according to the method described in Japanese Patent Laid-Open Publication No. 2007-508275 1.0 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 3 hours. To the reaction solution, 4-(bis(2-ethylhexyl)amino)salicylaldehyde (synthesized according to the method described in Japanese Patent Laid-Open Publication No. 2007-508275), 3.29 parts, benzoic acid (Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution. Ltd.) 0.406 parts, 11.9 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.04 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C 12 hours. After cooling the above reaction liquid to room temperature, it was added to 450 parts of methanol, and a precipitate was obtained by removing the supernatant. To the precipitate, 5.00 parts of acetone was added, and the mixture was stirred at 55 ° C to prepare a solution. 50.1 parts of methanol was added to the solution, and the mixture was stirred at 55 °C. After the mixture was cooled to room temperature, a precipitate was obtained by removing the supernatant. To the precipitate, 5.00 parts of acetone was added, and the mixture was stirred at 55 ° C to prepare a solution. 50.0 parts of methanol was added to the solution, and the mixture was stirred at 55 °C. After the mixture was cooled to room temperature, a precipitate was obtained by removing the supernatant. To the precipitate, 23.0 parts of N,N-dimethylformaldehyde was added to prepare a solution. This solution was added to 281 parts of 18% saline and stirred to obtain precipitated crystals as a residue for suction filtration. To the residue, 200 parts of water was added and stirred to obtain an insoluble matter as a residue for suction filtration. The residue was dried under reduced pressure at 60 ° C to obtain 3.00 parts of the compound of formula (I-156). The structure was confirmed by ¹ H-NMR.

<Identification of the compound represented by formula (I-156)>

¹ H-NMR (500 MHz, DMSO-d ₆ ): 0.83 (12H, t), 0.83 (12H, t), 1.22 (8H, qt), 1.22 (8H, tt), 1.27 (8H, td), 1.28 (8H, qd), 1.74 (4H, ttt), 3.37 (8H, d), 6.55 (2H, d), 6.79 (2H, dd), 7.67 (2H, d), 7.93 (2H, d), 8.03 ( 2H, dd), 8.41 (2H, d), 8.79 (2H, s).

Synthesis Example 5

The following substances were mixed: bis(3-amino-4-hydroxyphenyl)dimethylmethane (manufactured by Changzhou Sunshine Pharmaceutical Materials Co., Ltd.) 5.96 parts, 4-(dibutylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) 11.6 parts, 1.97 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 114 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyl cyanoacetate (Tokyo) 5.24 parts manufactured by Chemical Industry Co., Ltd., and stirred at 120 ° C for 3 hours. To the reaction solution, 5.67 parts of 4-(dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.988 parts of benzoic acid (manufactured by Tokyo Seisakusho Co., Ltd.), and cyanoacetic acid were added. Ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was 2.59 parts, and stirred at 120 ° C for 12 hours. After cooling the reaction liquid to room temperature, it was added to 1750 parts of hexane, and the precipitated crystal was obtained as a residue of suction filtration. 413 parts of tetrahydrofuran was added to the residue, and the mixture was stirred at 60 ° C, and after cooling to room temperature, precipitated crystals were obtained as a residue for suction filtration. 308 parts of acetonitrile was added to the residue, and the mixture was stirred at 80 ° C, and after cooling to room temperature, precipitated crystals were obtained as a residue for suction filtration. The residue was dried under reduced pressure at 60 ° C to obtain 14.5 parts of the compound of formula (I-170). The structure was confirmed by ¹ H-NMR.

<Identification of the compound represented by formula (I-170)>

¹ H-NMR (500 MHz, CDCl ₃ ): 0.98 (12H, t), 1.37 (8H, qt), 1.61 (8H, tt), 1.80 (6H, s), 3.35 (8H, t), 6.50 (2H) , d), 6.63 (2H, dd), 7.11 (2H, dd), 7.39 (2H, d), 7.42 (2H, d), 7.81 (2H, d), 8.59 (2H, s).

Synthesis Example 6

275 parts of resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 101 parts of n-hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed, and the generated water was removed at 150 to 155 ° C. Stir for 20 hours. After standing to cool, the reaction mixture was dissolved in 433 parts of toluene, and the toluene solution was washed three times with 1000 parts of warm water of 40 °C. 50 parts of anhydrous magnesium sulfate was added to this toluene solution, stirred, and it filtered. Distillate filtrate The solvent was used to obtain a crude product. This crude product was dissolved in 234 parts of toluene, and stirred at 0 ° C or lower to collect crystallization. The crystallization product was dried under reduced pressure at 50 ° C to obtain 95.7 parts of the compound of formula (pt1).

<Identification of the compound represented by formula (pt1)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 194.2

Exact Mass: 193.2

95.3 parts of the compound represented by the mixed formula (pt1) and 48.0 parts of water were mixed and stirred at 80 °C. Then, 107 parts of 1-bromo-2-ethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added thereto, and the mixture was stirred at 80 ° C for 3 hours, and then 22.4 parts of a 48% aqueous sodium hydroxide solution was added. The mixture was stirred at 110 ° C for 18 hours. After standing to cool, the pH of the reaction mixture was adjusted to 5 using a 10% aqueous sodium hydroxide solution, and 130 parts of toluene was added thereto and stirred to extract a toluene layer. The toluene extract was washed twice with 500 parts of warm water, and 25 parts of anhydrous magnesium sulfate was added thereto, stirred and filtered. The solvent of the filtrate was distilled off to obtain 154 parts of a residue containing a compound represented by the formula (pt2) as a main component.

<Identification of the compound represented by formula (pt2)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 306.3

Exact Mass: 305.3

154 parts of a residue containing a compound represented by the formula (pt2) as a main component and 597 parts of N,N-dimethylformamide were mixed and stirred at -6 ° C to 3 ° C. Further, 258 parts of phosphonium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added while maintaining the liquid temperature at -6 ° C to 3 ° C. After the mixture was stirred at room temperature for 1 hour, it was stirred at 60 ° C for 4 hours. After standing to cool, the reaction mixture was added to 1500 parts of ice and neutralized using a 48% aqueous sodium hydroxide solution. To the mixture was added 867 parts of toluene, and the toluene layer was extracted. The toluene extract was washed twice with 1200 parts of a 15% aqueous sodium chloride solution. 60 parts of anhydrous magnesium sulfate was added to the toluene extract, and the mixture was stirred, followed by filtration. The solvent of the filtrate was distilled off to obtain a residue. This residue was purified by column chromatography to give 94.4 parts of the compound of formula (pt3).

<Identification of the compound represented by formula (pt3)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 334.3

Exact Mass: 333.3

The following were mixed: bis(3-amino-4-hydroxyphenyl)indole (manufactured by Tokyo Chemical Industry Co., Ltd.) 10.6 parts, 25.3 parts of the compound represented by the formula (pt3), benzoic acid (Tokyo Chemical Industry Co., Ltd. ( Co., Ltd.) 3.20 parts, 184 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.59 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) at 120 ° C Stir for 3 hours. 25.4 parts of the compound represented by the formula (pt3), 3.21 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 90.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the reaction solution. And 8.59 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, it was added to 1800 parts of methanol to obtain precipitated crystals as a residue for suction filtration. This residue was purified by column chromatography to obtain 20.6 parts of the compound of formula (I-157). The structure was confirmed by ¹ H-NMR.

<Identification of the compound represented by formula (I-157)>

¹ H-NMR (500 MHz, DMSO-d ₆ ): 0.85 (6H, t), 0.87 (6H, t), 0.87 (6H, t), 1.20 to 1.40 (28H), 1.56 (4H, tt), 1.75 (2H, ttt), 3.34 (4H, d), 3.43 (4H, t), 6.55 (2H, d), 6.79 (2H, dd), 7.64 (2H, d), 7.91 (2H, d), 8.01 ( 2H, dd), 8.36 (2H, d), 8.73 (2H, s).

Synthesis Example 7

The following were mixed: 1.94 parts of bis(3-amino-4-hydroxyphenyl)dimethylmethane (manufactured by Changzhou Sunshine Pharmaceutical Materials Co., Ltd.), 5.03 parts of the compound represented by formula (pt3), and benzoic acid (Tokyo Chemicals Co., Ltd.) (manufactured by Industrial Co., Ltd.), 0.65 parts, 10.000 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1.74 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and at 120 Stir at ° C for 3 hours. 2.52 parts of the compound represented by the formula (pt3), 0.325 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 5.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were added to the solution. Ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was 0.865 parts, and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, it was added to 603 parts of methanol. A precipitate was obtained by removing the supernatant. To the precipitate, 7.10 parts of acetone was added, and the mixture was stirred at 55 ° C to prepare a solution. 73.6 parts of methanol was added to the solution, and the mixture was stirred at 55 °C. After the mixture was cooled to room temperature, a precipitate was obtained by removing the supernatant. To the precipitate, 6.20 parts of acetone was added, and the mixture was stirred at 55 ° C to prepare a solution. 65.2 parts of methanol was added to the solution, and the mixture was stirred at 55 °C. After the mixture was cooled to room temperature, a precipitate was obtained by removing the supernatant. To the precipitate, 30.1 parts of N,N-dimethylformamide was added and dissolved. This solution was added to 360 parts of 18% saline and stirred to obtain precipitated crystals as a residue for suction filtration. 350 parts of water was added to the residue and stirred to obtain an insoluble matter as a residue for suction filtration. The residue was dried under reduced pressure at 60 ° C to give 4.10 parts of the compound of formula (I-178). The structure was confirmed by ¹ H-NMR.

<Identification of the compound represented by formula (I-178)>

¹ H-NMR (500 MHz, DMSO-d ₆ ): 0.86 (6H, t), 0.87 (6H, t), 0.88 (6H, t), 1.20 to 1.40 (28H), 1.57 (4H, tt), 1.76 (2H, ttt), 1.81 (6H, s), 3.34 (4H, d), 3.43 (4H, t), 6.55 (2H, d), 6.78 (2H, dd), 7.22 (2H, dd), 7.56 ( 2H, d), 7.62 (2H, d), 7.65 (2H, d), 8.67 (2H, s).

Synthesis Example 8

64.5 parts of 2-ethylhexylamine was added to 138 parts of resorcin, and the produced water was removed at 150 to 155 ° C, and the mixture was stirred for 18 hours. After standing to cool, 250 parts of toluene was added to the reaction mixture, and washed three times with 500 parts of warm water. To the toluene solution, 20.0 parts of anhydrous magnesium sulfate was added and stirred, followed by filtration. The solvent of the filtrate was distilled off to obtain 113 parts of a residue containing a compound represented by the formula (pt4) as a main component.

<Identification of the compound represented by formula (pt4)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 222.2

Exact Mass: 221.2

The above-mentioned residue containing the compound represented by the formula (pt4) as a main component To 58.5 parts, 23.0 parts of water was added, and while stirring, the liquid temperature was 60 °C. At this temperature, 39.3 parts of diethyl sulfate and 10.6 parts of a 48% aqueous sodium hydroxide solution were added, and the mixture was stirred for 9 hours. Thereafter, the mixture was stirred at 60 ° C for 5 hours. After standing to cool, the reaction mixture was neutralized by a 10% aqueous sodium hydroxide solution, and 300 parts of toluene was added. The toluene solution was washed three times with 500 parts of warm water. To the toluene solution, 20.0 parts of anhydrous magnesium sulfate was added and stirred, followed by filtration. The solvent of the filtrate was distilled off to obtain 67.5 parts of a residue containing a compound represented by the formula (pt5) as a main component.

<Identification of the compound represented by formula (pt5)>

(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] + 250.2

Exact Mass: 249.2

To 67.5 parts of the residue containing the compound represented by the formula (pt5) as a main component, 323 parts of N,N-dimethylformamide was added. While maintaining the temperature of the mixed solution at -6 ° C to 4 ° C, 105 parts of phosphorus oxychloride was added thereto. After the temperature of the reaction mixture was returned to room temperature and stirred for 1 hour, the temperature of the reaction liquid was raised to 60 ° C and stirred for 3 hours. After standing to cool, the reaction mixture was added to 1,500 parts of ice water, and while stirring, a 48% aqueous sodium hydroxide solution was added thereto to carry out neutralization. 500 parts of toluene was added thereto, and a toluene layer was extracted. The toluene solution was washed by 1000 parts of water. Then, the toluene solution was washed by 1500 parts of a saturated aqueous solution of sodium chloride. To the toluene solution, 25.0 parts of anhydrous magnesium sulfate was added and stirred, followed by filtration. The solvent of the filtrate was distilled off to obtain a residue. Pure residue by column chromatography Further, 36.7 parts of the compound represented by the formula (pt6) was obtained.

<Identification of the compound represented by formula (pt6)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 278.2

Exact Mass: 277.2

The following were mixed: 15.7 parts of bis(3-amino-4-hydroxyphenyl)anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.), 31.0 parts of the compound represented by formula (pt6), and benzoic acid (Tokyo Chemical Industry Co., Ltd.) Co., Ltd.) 4.6 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 12.6 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) at 120 ° C Stir for 3 hours. 31.1 parts of the compound represented by the formula (pt6), 4.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 20.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the reaction solution. And 12.6 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, it was added to 2100 parts of methanol to obtain precipitated crystals as a residue for suction filtration. This residue was purified by column chromatography to obtain 26.6 parts of the compound of formula (I-158).

<Identification of the compound represented by formula (I-158)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 899.4

Exact Mass: 898.4

Synthesis Example 9

The following were mixed: 9,9-bis(3-amino-4-hydroxyphenyl)anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.), 8.56 parts, 15.0 parts of the compound represented by the formula (pt3), benzoic acid ( (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.87 parts, 108 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 5.09 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and Stir at 120 ° C for 3 hours. 15.0 parts of the compound represented by the formula (pt3), 1.88 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the reaction solution. 5.09 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, it was added to 860 parts of methanol to obtain precipitated crystals as a residue for suction filtration. This residue was purified by column chromatography to obtain 13.7 parts of the compound of formula (I-242).

<Identification of the compound represented by formula (I-242)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 1111.6

Exact Mass: 1110.6

Synthesis Example 10

103 parts of bis(3-aminophenyl) fluorene (manufactured by Tokyo Chemical Industry Co., Ltd.) and 208 parts of potassium thiocyanate (manufactured by Sigma-Aldrich Japan Co., Ltd.) were dissolved in 510 parts of glacial acetic acid. In the solution prepared in the middle, a solution obtained by dissolving 160 parts of bromine in 27.1 parts of glacial acetic acid was added dropwise under stirring for 1 hour. After the completion of the dropwise addition, the stirring was further continued for 2 hours, and then left overnight. After adding 1740 parts of water thereto and heating to the boiling point, it was cooled and filtered. Sodium hydrogencarbonate was added to the filtrate, and the resulting precipitate was filtered, washed with water, and dried. This precipitate was purified by column chromatography to obtain 30.1 parts of a compound represented by formula (pt7).

<Identification of the compound represented by formula (pt7)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 363.0

Exact Mass: 362.0

To a solution of 60.0 parts of the compound represented by the formula (pt7), an aqueous solution of 3.00 M of potassium hydroxide was added to an average of 1.00 g of the compound represented by the formula (pt7) in an argon atmosphere. 141 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with the mixture, and the mixture was stirred for 30 hours while refluxing. After cooling the reaction solution to room temperature, it was neutralized using 2.00 N hydrochloric acid. Thereto was added 1740 parts of ethyl acetate, and the ethyl acetate layer was extracted. The solvent was distilled off to obtain a residue. To the residue, 688 parts of N,N-dimethylformamide was added to obtain a solution. Add to the solution A solution obtained by dissolving 64.2 parts of DL-dithiothreitol in 729 parts of water was stirred at room temperature for 2 hours. In the reaction solution, a volume of 1:2 in a volume ratio of 0.500 M acetic acid aqueous solution and 0.500 M sodium acetate aqueous solution was added in the same volume as the previously added N,N-dimethylformamide. Aqueous solution. Then, 1310 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. To the aqueous layer, 1310 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. The ethyl acetate layer was mixed, and the solvent of the solution was distilled off to obtain a residue. The residue was purified by column chromatography to give 5.04 parts of the compound of formula (pt8).

<Identification of the compound represented by formula (pt8)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 313.0

Exact Mass: 312.0

The following were mixed: 6.56 parts of the compound represented by the formula (pt8), 14.0 parts of the compound represented by the formula (pt3), 1.75 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-pentanol (Tokyo Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) 101 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 4.75 parts, and stirred at 120 ° C for 3 hours. 14.1 parts of the compound represented by the formula (pt3), 1.75 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the reaction solution. And 4.74 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. Column chromatography The residue was purified to obtain 1.75 parts of the compound represented by formula (I-320).

<Identification of the compound represented by formula (I-320)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 1043.5

Exact Mass: 1042.5

Synthesis Example 11

For the preparation of 2,2-bis(3-aminophenyl)propane (synthesized according to the method described in Justus Liebigs Analen der Chemie 1933, 507, 14. or Bulletin de la Societe Chimique de France 1974, 641) and 224 parts of potassium thiocyanate (manufactured by Sigma-Aldrich Japan Co., Ltd.) dissolved in 549 parts of glacial acetic acid, and stirred for 1 hour under stirring to dissolve 173 parts of bromine in 29.2 parts of glacial acetic acid. a solution made in the middle. After the completion of the dropwise addition, the stirring was further continued for 2 hours, and then left overnight. After adding 1870 parts of water thereto and heating to the boiling point, it was cooled and filtered. Sodium hydrogencarbonate was added to the filtrate, and the resulting precipitate was filtered, washed with water, and dried. This precipitate was purified by column chromatography to obtain 22.0 parts of a compound represented by formula (pt9).

<Identification of the compound represented by formula (pt9)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 341.1

Exact Mass: 340.1

To a solution of 35.0 parts of the compound represented by the formula (pt9), an aqueous solution of 3.00 M of potassium hydroxide was added to an average of 1.00 g of the compound represented by the formula (pt9) in an argon atmosphere to an extent of 57.3 mL. 87.3 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with the mixture, and the mixture was stirred for 34 hours while refluxing. After cooling the reaction solution to room temperature, it was neutralized using 2.00 N hydrochloric acid. To this was added 1080 parts of ethyl acetate, and the ethyl acetate layer was extracted. The solvent was distilled off to obtain a residue. To the residue, 427 parts of N,N-dimethylformamide was added to obtain a solution. A solution obtained by dissolving 39.8 parts of DL-dithiothreitol in 453 parts of water was added to the solution, and the mixture was stirred at room temperature for 2 hours. In the reaction solution, a volume of 1:2 in a volume ratio of 0.500 M acetic acid aqueous solution and 0.500 M sodium acetate aqueous solution was added in the same volume as the previously added N,N-dimethylformamide. Aqueous solution. Then, 812 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. 812 parts of ethyl acetate was added to the aqueous layer, and the ethyl acetate layer was extracted. The ethyl acetate layer was mixed, and the solvent of the solution was distilled off to obtain a residue. This residue was purified by column chromatography to give 3.43 parts of the compound of formula (pt10).

<Identification of the compound represented by formula (pt10)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 291.1

Exact Mass: 290.1

The following were mixed: 6.53 parts of the compound represented by the formula (pt10), 15.0 parts of the compound represented by the formula (pt3), 1.87 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-pentanol (Tokyo Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) 108 parts and 5.09 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 3 hours. In the reaction solution, 15.0 parts of the compound represented by the formula (pt3), 1.90 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-pentanol (manufactured by Jingjing Chemical Industry Co., Ltd.) 9.00 were mixed. 5.10 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 2.53 parts of the compound of formula (I-341).

<Identification of the compound represented by formula (I-341)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 1021.6

Exact Mass: 1020.6

Synthesis Example 12

100 parts of 3,3'-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and potassium thiocyanate (Sigma-Aldrich Japan) Manufactured by a solution of 253 parts dissolved in 620 parts of glacial acetic acid, a solution obtained by dissolving 195 parts of bromine in 33.0 parts of glacial acetic acid was added dropwise under stirring for 1 hour. After the completion of the dropwise addition, the stirring was further continued for 2 hours, and then left overnight. After 2110 parts of water was added thereto and heated to the boiling point, it was cooled and filtered. Sodium hydrogencarbonate was added to the filtrate, and the resulting precipitate was filtered, washed with water, and dried. This precipitate was purified by column chromatography to obtain 20.1 parts of a compound represented by formula (pt11).

<Identification of the compound represented by formula (pt11)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 313.1

Exact Mass: 312.1

To a solution of 35.0 parts of the compound represented by the formula (pt11), an aqueous solution of 3.00 M of potassium hydroxide was added to an average of 1.00 g of the compound represented by the formula (pt11) in an argon atmosphere. 95.1 parts of diethylene glycol (manufactured by Tokyo Chemical Industry Co., Ltd.) was mixed with the mixture, and the mixture was stirred for 36 hours while being refluxed. After cooling the reaction solution to room temperature, it was neutralized using 2.00 N hydrochloric acid. 1180 parts of ethyl acetate was added thereto, and the ethyl acetate layer was extracted. The solvent was distilled off to obtain a residue. To the residue, 466 parts of N,N-dimethylformamide was added to obtain a solution. A solution obtained by dissolving 43.4 parts of DL-dithiothreitol in 493 parts of water was added to the solution, and the mixture was stirred at room temperature for 2 hours. To the reaction solution, a 0.500 M aqueous acetic acid solution and a 0.500 M sodium acetate aqueous solution were mixed at a volume ratio of 1:2 in the same volume as the previously added N,N-dimethylformamide. Into the aqueous solution. Then, 885 parts of ethyl acetate was added, and the ethyl acetate layer was extracted. 885 parts of ethyl acetate was added to the aqueous layer, and the ethyl acetate layer was extracted. The ethyl acetate layer was mixed, and the solvent of the solution was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 2.43 parts of the compound of formula (pt12).

<Identification of the compound represented by formula (pt12)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 263.1

Exact Mass: 262.1

The following were mixed: 3.93 parts of the compound represented by the formula (pt12), 10.1 parts of the compound represented by the formula (pt3), 1.25 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-pentanol (Tokyo Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) 80.0 parts and 3.79 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 3 hours. 10.0 parts of the compound represented by the formula (pt3), 1.30 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 10.0 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the reaction solution. 3.40 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to give 1.34 parts of the compound of formula (I-448).

<Identification of the compound represented by formula (I-448)>

(mass analysis) ionization mode = ESI +: m / z = [M + H] ⁺ 993.5

Exact Mass: 992.5

[Heat resistance evaluation]

The compound obtained by the synthesis examples 1 to 12 and the coumarin 6 (Tokyo Chemical Industry Co., Ltd.) were subjected to the use of the thermogravimetric thermal synchronization measuring apparatus (TG/DTA6200R manufactured by Seiko Instruments Inc.). Manufacturing) differential scanning calorimetry. The amount of sample used in one measurement was 5 mg. The measurement temperature was initially started at 25 ° C, and the temperature was raised at a rate of 10 ° C in 毎 minutes, and measured to 600 ° C. Find: Temperature T ₅ (under air) with a weight reduction rate of 5% in air, temperature T ₁₀ (under air) with a weight reduction rate of 10% in air, and a weight reduction rate of 5 in a nitrogen atmosphere % of the temperature T ₅ (under nitrogen), and the weight reduction ratio to 10% under a nitrogen atmosphere temperature T ₁₀ (under nitrogen). The results are shown in Table 30.

From the results of Table 30, it is understood that the compound of the present invention has high thermal stability.

Synthesis Example 13

The following materials were mixed: o-amino-p-benzylphenol (refer to Journal of the American Chemical Society (1935), 57, 1697-8.) 10.3 parts, 4-(diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd. ( Co., Ltd.) 10.0 parts, 2.16 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 125 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyl cyanoacetate Industrial Co., Ltd. manufactured 5.85 parts and stirred at 120 ° C for 3 hours. In this solution, 10.0 parts of 4-(diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.16 parts, 1-penta Alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.5 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.85 parts, and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-1).

Synthesis Example 14

The following substances are mixed: o-amino-p-phenylsulfonate phenol (refer to Japanese Patent Laid-Open Publication No. SHO-49-126979), 12.9 parts, 4-(diethylamino) salicylaldehyde (Tokyo Chemical Industry Co., Ltd.) Manufactured) 10.0 parts, 2.16 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 125 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd. The company) manufactured 5.85 parts and stirred at 120 ° C for 3 hours. In this solution, 10.0 parts of 4-(diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.16 parts, 1-penta 12.5 parts of an alcohol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.85 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-60).

Synthesis Example 15

The following materials were mixed: bis(3-amino-9-hydroxyphenyl)dimethylmethane (manufactured by Changzhou Sunshine Pharmaceutical Materials Co., Ltd.) 3.57 parts, 4-(bis(2-ethylhexyl)amino)salicylide Aldehyde (synthesized according to the method described in JP-A-2007-508275), 10.0 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.15 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 66.7 parts and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 120 ° C for 3 hours. To the reaction solution, 4-(bis(2-ethylhexyl)amino)salicylaldehyde (synthesized according to the method described in JP-A-2007-508275) was mixed with 10.0 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.) Ltd.) 1.15 parts, 1.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-177).

Synthesis Example 16

The following substances were mixed: bis(3-amino-4-hydroxyphenyl)dimethylmethane (manufactured by Changzhou Sunshine Pharmaceutical Materials Co., Ltd.): 4.66 parts, represented by formula (pt6) 10.0 parts, 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 86.9 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd. The company) made 4.08 parts and stirred at 120 ° C for 3 hours. 10.0 parts of the compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 9.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the reaction solution. And 4.08 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-179).

Synthesis Example 17

The following were mixed: 9,9-bis(3-amino-4-hydroxyphenyl)anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.), 9.84 parts, 4-(diethylamino) salicylaldehyde (Tokyo) Chemicals (manufactured by Chemical Industry Co., Ltd.) 10.0 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 2.16 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 125 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.86 parts, and stirred at 120 ° C for 3 hours. 10.0 parts of 4-(diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.16 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed with the reaction solution. Pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) 12.5 parts and ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd. (manufactured by the company) 5.86 parts and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off by a rotary evaporator to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-233).

Synthesis Example 18

The following were mixed: 9,9-bis(3-amino-4-hydroxyphenyl)anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.), 7.63 parts, 4-(dibutylamino) salicylaldehyde (Tokyo) 10.0 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.67 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.54 parts, and stirred at 120 ° C for 3 hours. 10.0 parts of 4-(dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed with the reaction solution. 10.0 parts of pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.54 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-234).

Synthesis Example 19

The following were mixed: 9,9-bis(3-amino-9-hydroxyphenyl)anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.) 5.26 parts, 4-(bis(2-ethylhexyl)amino) Salicylaldehyde (synthesized according to the method described in Japanese Patent Publication No. 2007-508275) 10.0 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.15 parts, 1-pentanol (Tokyo Chemical Industry Co., Ltd. (manufactured) 66.7 parts and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 3 hours. To the reaction solution, 4-(bis(2-ethylhexyl)amino)salicylaldehyde (synthesized according to the method described in JP-A-2007-508275) was mixed with 10.0 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.) Ltd.) 1.15 parts, 1.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-241).

Synthesis Example 20

The following were mixed: 9,9-bis(3-amino-4-hydroxyphenyl)anthracene (manufactured by Tokyo Chemical Industry Co., Ltd.), 6.86 parts, 10.0 parts of the compound represented by the formula (pt6), benzoic acid ( Manufactured by Tokyo Chemical Industry Co., Ltd., 1.00 parts, 86.9 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and 4.08 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and Stir at 120 ° C for 3 hours. 10.0 parts of the compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 9.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the reaction solution. And 4.08 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-243).

Synthesis Example 21

The following were mixed: 8.08 parts of the compound represented by the formula (pt8), 10.0 parts of 4-(diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and benzoic acid (Tokyo Chemical Industry Co., Ltd. (manufactured by the company) 2.16 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 125 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.85 parts, and stirred at 120 ° C hour. Mixing 4-(diethylamino) salicylaldehyde in the reaction solution (10.00 parts, benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.16 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 12.5 parts and cyanoacetic acid, manufactured by Tokyo Chemical Industry Co., Ltd. Ethyl acetate (manufactured by Tokyo Chemical Industry Co., Ltd.) was 5.85 parts, and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-311).

Synthesis Example 22

The following were mixed: 6.26 parts of the compound represented by the formula (pt8), 10.0 parts of 4-(dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and benzoic acid (Tokyo Chemical Industry Co., Ltd. (manufactured by the company) 1.67 parts, 96.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.54 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 °C 3 hour. 10.0 parts of 4-(dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed with the reaction solution. 10.0 parts of pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.54 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. The residue is purified by column chromatography to obtain the formula (I-312) The compound represented.

Synthesis Example 23

The following were mixed: 4.32 parts of the compound represented by the formula (pt8), 4-(bis(2-ethylhexyl)amino) salicylaldehyde (synthesized according to the method described in JP-A-2007-508275) 10.0 parts , 1.75 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 66.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.13 parts and stirred at 120 ° C for 3 hours. To the reaction solution, 4-(bis(2-ethylhexyl)amino)salicylaldehyde (synthesized according to the method described in JP-A-2007-508275) was mixed with 10.0 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.) Ltd.) 1.15 parts, 1.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue is purified by column chromatography to obtain a compound represented by the formula (I-319).

Synthesis Example 24

The following were mixed: 5.63 parts of the compound represented by the formula (pt8), 10.0 parts of the compound represented by the formula (pt6), 1.00 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-pentanol (Tokyo Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) 86.9 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.08 parts, and stirred at 120 ° C for 3 hours. 10.0 parts of the compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 9.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the reaction solution. And 4.08 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. The residue is purified by column chromatography to obtain a compound represented by the formula (I-321).

Synthesis Example 25

The following were mixed: 7.52 parts of the compound represented by the formula (pt10), 10.0 parts of 4-(diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and benzoic acid (Tokyo Chemical Industry Co., Ltd. (manufactured by the company) 2.16 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 125 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.85 parts, and stirred at 120 ° C hour. To the reaction solution, 10.0 parts of 4-(diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and benzoic acid (Tokyo) were mixed. Chemical Manufacturing Co., Ltd. manufactured by 2.16 parts, 12.5 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 5.85 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) Stir at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-332).

Synthesis Example 26

The following were mixed: 5.82 parts of the compound represented by the formula (pt10), 10.0 parts of 4-(dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and benzoic acid (Tokyo Chemical Industry Co., Ltd. (manufactured by the company) 1.67 parts, 96.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.54 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 °C 3 hour. 10.0 parts of 4-(dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed with the reaction solution. 10.0 parts of pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.54 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-333).

Synthesis Example 27

The following were mixed: 4.02 parts of the compound represented by the formula (pt10), 4-(bis(2-ethylhexyl)amino) salicylaldehyde (synthesized according to the method described in JP-A-2007-508275) 10.0 parts , 1.75 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 66.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.13 parts and stirred at 120 ° C for 3 hours. To the reaction solution, 4-(bis(2-ethylhexyl)amino)salicylaldehyde (synthesized according to the method described in JP-A-2007-508275) was mixed with 10.0 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.) Ltd.) 1.15 parts, 1.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-340).

Synthesis Example 28

The following were mixed: 5.24 parts of the compound represented by the formula (pt10), 10.0 parts of the compound represented by the formula (pt6), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 1.50 parts, 1-pentanol (Tokyo Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) 86.9 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.08 parts, and stirred at 120 ° C for 3 hours. 10.0 parts of the compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 9.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the reaction solution. And 4.08 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-342).

Synthesis Example 29

The following were mixed: 6.79 parts of the compound represented by the formula (pt12), 10.0 parts of 4-(diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), and benzoic acid (Tokyo Chemical Industry Co., Ltd. (manufactured by the company) 2.16 parts, 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), 125 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.85 parts, and stirred at 120 ° C hour. 10.0 parts of 4-(diethylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.) and 2.16 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed with the reaction solution. Pentanol (Tokyo Chemical Industry) 12.5 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.85 parts, and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-439).

Synthesis Example 30

The following were mixed: 5.26 parts of the compound represented by the formula (pt12), 1 (10 parts) of 4-(dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), benzoic acid (Tokyo Chemical Industry Co., Ltd. (manufactured by the company) 1.67 parts, 96.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 4.54 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 °C 3 hour. 10.0 parts of 4-(dibutylamino) salicylaldehyde (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.67 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-pentanol ( 10.0 parts and 4.54 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were produced by Tokyo Chemical Industry Co., Ltd., and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-440).

Synthesis Example 31

The following were mixed: 3.63 parts of the compound represented by the formula (pt12), 4-(bis(2-ethylhexyl)amino)salicylaldehyde (synthesized according to the method described in JP-A-2007-508275) 10.0 parts , 1.75 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 66.7 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.), and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 3.13 parts and stirred at 120 ° C for 3 hours. To the reaction solution, 4-(bis(2-ethylhexyl)amino)salicylaldehyde (synthesized according to the method described in JP-A-2007-508275) was mixed with 10.0 parts of benzoic acid (Tokyo Chemical Industry Co., Ltd.) Ltd.) 1.15 parts, 1.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.13 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-447).

Synthesis Example 32

The following were mixed: 4.73 parts of the compound represented by the formula (pt12), 10.0 parts of the compound represented by the formula (pt6), 1.00 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 1-pentanol (Tokyo Chemical Industry Co., Ltd.) (manufactured by Co., Ltd.) 86.9 parts and ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) 4.08 parts, and stirred at 120 ° C for 3 hours. 10.0 parts of the compound represented by the formula (pt6), 1.50 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), and 9.00 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed in the reaction solution. And 4.08 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and stirred at 120 ° C for 12 hours. After cooling the above reaction liquid to room temperature, the solvent was distilled off to obtain a residue. This residue was purified by column chromatography to obtain a compound represented by the formula (I-449).

Synthesis Example 33

An appropriate amount of nitrogen was introduced into a flask including a reflux condenser, a dropping funnel, and a stirrer to make a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was placed, and the mixture was heated to 85 ° C while stirring. Then, in the flask, 19 parts of methacrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-8-yl acrylate and 3 were added dropwise using a drip pump for about 5 hours. , a mixture of 4-epoxytricyclo[5.2.1.0 ^2,6 ]decane-9-yl acrylate (containing 50:50 in molar ratio) 171 parts dissolved in propylene glycol monomethyl ether acetate 40 The solution is divided into parts. On the other hand, it takes about 5 hours to use another drip pump, and 26 parts of the polymerization initiator 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in propylene glycol monomethyl ether acetate. A solution of 120 parts was added dropwise to the flask. After completion of the dropwise addition of the polymerization initiator, the mixture was kept at the same temperature for about 3 hours, and then cooled to room temperature to obtain a solution of a copolymer (resin B1) having a solid content of 43.5%. The obtained resin B1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value of 53 mgKOH/g in terms of solid content.

[Preparation of Colored Curable Resin Composition] Example 1

A coloring curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: coloring agent (A): CI pigment green 7 (pigment) 53 parts, acrylic pigment dispersing agent 24 parts, resin (B): resin B1 (solid content conversion) 19 parts, and solvent (E): 350 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 148) 10 parts of the compound represented; resin (B): resin B1 (in terms of solid content) 10 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Limited) Manufacturing) 29 copies; Polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01, BASF 5.7 parts by the company, o-mercaptopurine compound; solvent (E): 13 parts of propylene glycol monomethyl ether acetate; solvent (E): 490 parts of N-methylpyrrolidone; and leveling agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 2

A coloring curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: coloring agent (A): CI pigment green 7 (pigment) 37 parts, acrylic pigment dispersing agent 17 parts, resin (B): resin B1 (converted solid content conversion) 13 parts, and solvent (E): 240 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 169) Compound represented by 26 parts; Resin (B): Resin B1 (converted solid content) 19 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 32 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure ( Registered trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 6.4 parts; solvent (E): propylene glycol monomethyl ether acetate 24 parts; Solvent (E): N-methylpyrrolidone 580 parts; and leveling agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 3

A colored curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: colorant (A): 52 parts of CI Pigment Green 7 (pigment), 23 parts of acrylic pigment dispersant, and resin (B): resin B1 (solid content conversion) 18 parts, and solvent (E): 340 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 149) 11 parts of the compound represented; resin (B): resin B1 (converted solid content) 11 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 29 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure ( Registered trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 5.8 parts; solvent (E): propylene glycol monomethyl ether acetate 14 parts; solvent (E): N-methylpyrrolidone 500 parts; And leveling agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 4

A colored curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: colorant (A): CI pigment green 7 (pigment) 49 parts, acrylic pigment dispersant 22 parts, resin (B): resin B1 (converted solid content conversion) 17 parts, and solvent (E): 320 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 156) 14 parts of the compound represented; resin (B): resin B1 (in terms of solid content) 12 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 29 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure ( Registered trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 5.9 parts; solvent (E): 530 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether modified polyoxyl Oil (Toray Silicone SH8400, manufactured by Toray Silicon Corning Co., Ltd.) 0.50 parts.

Example 5

A colored curable resin composition: a pigment dispersion liquid mixed with a coloring agent (A): 60 parts of CI Pigment Green 36 (pigment), 27 parts of an acrylic pigment dispersant, and a resin (B): resin were obtained by mixing the following: B1 (solid content conversion) 21 copies, and Solvent (E): 390 parts of propylene glycol monomethyl ether acetate, and fully dispersed by using a bead mill; coloring agent (A); compound of formula (I-148): 2.9 parts; resin ( B): Resin B1 (converted in solid content) 6.0 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 27 parts; polymerization initiation Agent (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corporation, O-indenyl hydrazine compound) 5.4 parts; solvent (E): propylene glycol monomethyl ether acetate 7.8 parts; solvent (E): N-methylpyrrolidone 450 parts; and leveling agent (F): polyether modified Toray Silicone SH8400 (manufactured by Toray Silicone Co., Ltd.) 0.50 parts.

Example 6

A coloring curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: coloring agent (A): CI pigment green 36 (pigment) 54 parts, acrylic pigment dispersing agent 24 parts, resin (B): resin B1 (solid content conversion) 19 parts, and solvent (E): 350 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 169) 9.1 parts of the compound represented; resin (B): resin B1 (solid content conversion) 9.4 parts; Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 28 parts; polymerization initiator (D): N-benzylideneoxy-1 -(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corporation, o-mercaptopurine compound) 5.7 parts; solvent (E): 12 parts of propylene glycol monomethyl ether acetate; solvent (E): 490 parts of N-methylpyrrolidone; and leveling agent (F): polyether modified polyoxygenated oil (Toray Silicone SH8400, Toray Dow Corning ( Co., Ltd.) Manufacturing) 0.50 parts.

Example 7

A colored curable resin composition: a pigment dispersion liquid mixed with a coloring agent (A): 60 parts of CI Pigment Green 36 (pigment), 27 parts of an acrylic pigment dispersant, and a resin (B): resin were obtained by mixing the following: B1 (converted solid content conversion) 21 parts, and solvent (E): 390 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 149) 3.3 parts of the compound represented; resin (B): resin B1 (converted solid content) 6.2 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 27 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl) octyl Alkan-1-one-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corporation, o-nonyl hydrazine compound) 5.4 parts; solvent (E): propylene glycol monomethyl ether acetate 8.1 parts; solvent ( E): 450 parts of N-methylpyrrolidone; and leveling agent (F): Polyether modified polysiloxane (Toray Silicone SHB400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 8

A colored curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: colorant (A): CI pigment green 36 (pigment) 59 parts, acrylic pigment dispersant 27 parts, resin (B): resin B1 (converted solid content conversion) 21 parts, and solvent (E): 380 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill; coloring agent (A): formula (I- 156) Compound represented by 4.1 parts; Resin (B): Resin B1 (converted solid content) 6.7 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 27 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure ( Registered trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 5.5 parts; solvent (E): 470 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether modified polyoxyl Oil (Toray Silicone SH8400; manufactured by Toray Road Corning Co., Ltd.) 0.50 parts.

Example 9

A colored curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: colorant (A): CI pigment green 58 (pigment) 61 parts, acrylic pigment dispersant 28 parts, resin (B): resin B1 (converted solid content conversion) 21 parts, and solvent (E): 400 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 148) 1.7 parts of the compound represented; resin (B): resin B1 (in terms of solid content) 5.3 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 27 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure ( Registered trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 5.4 parts; solvent (E): 6.4 parts of propylene glycol monomethyl ether acetate; solvent (E): 440 parts of N-methylpyrrolidone; And leveling agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 10

A coloring curable resin composition is obtained by mixing the following: a pigment dispersion liquid, which is mixed: Colorant (A): 58 parts of CI Pigment Green 58 (pigment), 26 parts of acrylic pigment dispersant, resin (B): Resin B1 (in terms of solid content) 20 parts, and solvent (E): propylene glycol monomethyl ether 380 parts of acetate and using a bead mill to sufficiently disperse the pigment; coloring agent (A): 5.2 parts of the compound represented by the formula (I-169); resin (B): resin B1 (solid content Conversion) 7.2 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 27 parts; polymerization initiator (D): N-benzene醯oxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark)) OXE-01, manufactured by BASF Corporation, o-mercaptopurine compound) 5.5 parts Solvent (E): 9.4 parts of propylene glycol monomethyl ether acetate; solvent (E): 460 parts of N-methylpyrrolidone; and leveling agent (F): polyether modified polysiloxane (Toray Silicone) SH8400, manufactured by Toray Road Corning Co., Ltd.) 0.50 parts.

Example 11

A colored curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: colorant (A): CI pigment green 58 (pigment) 61 parts, acrylic pigment dispersant 27 parts, resin (B): resin B1 (converted solid content conversion) 21 parts, and solvent (E): 400 parts of propylene glycol monomethyl ether acetate, And using a bead mill to sufficiently disperse the pigment; the colorant (A): 2.0 parts of the compound represented by the formula (I-149); the resin (B): the resin B1 (in terms of solid content) 5.5 parts; Compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 27 parts; polymerization initiator (D): N-benzylideneoxy-1- (4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corporation, o-nonyl fluorene compound) 5.4 parts; solvent (E): propylene glycol 7.1 parts of monomethyl ether acetate; solvent (E): 440 parts of N-methylpyrrolidone; and leveling agent (F): polyether modified polysiloxane (Toray Silicone SH8400; Toray Dow Corning (share Ltd.) manufactured) 0.50 parts.

Example 12

A colored curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: colorant (A): CI pigment green 58 (pigment) 61 parts, acrylic pigment dispersant 27 parts, resin (B): resin B1 (converted solid content conversion) 21 parts, and solvent (E): 400 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 156) The compound represented by 2.5 parts; Resin (B): Resin B1 (in terms of solid content) 5.8 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 27 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl) octyl Alkan-1-one-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corporation, o-mercaptopurine compound) 5.4 parts; solvent (E): propylene glycol monomethyl ether acetate 450 parts; Flat agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 13

A coloring curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: coloring agent (A): CI pigment green 7 (pigment) 35 parts, acrylic pigment dispersing agent 16 parts, resin (B): resin B1 (converted solid content conversion) 12 parts, and solvent (E): 230 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 170) 28 parts of the compound represented; resin (B): resin B1 (in terms of solid content) 20 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 32 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure ( Registered trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 6.4 parts; Solvent (E): propylene glycol monomethyl ether acetate 26 parts; solvent (E): N-methylpyrrolidone 600 parts; and leveling agent (F): polyether modified polyoxygenated oil (Toray Silicone SH8400 , manufactured by Toray Road Corning Co., Ltd.) 0.50 parts.

Example 14

A coloring curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: coloring agent (A): CI pigment green 36 (pigment) 53 parts, acrylic pigment dispersant 24 parts, resin (B): resin B1 (solid content conversion) 18 parts, and solvent (E): 340 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 170) 10 parts of the compound represented; resin (B): resin B1 (in terms of solid content) 10 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 29 parts; start of polymerization (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered Trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 5.7 parts; solvent (E): propylene glycol monomethyl ether acetate 13 parts; solvent (E): N-methylpyrrolidone 490 parts; Leveling agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 15

A colored curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: colorant (A): CI pigment green 58 (pigment) 57 parts, acrylic pigment dispersant 26 parts, resin (B): resin B1 (converted solid content conversion) 20 parts, and solvent (E): 370 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 170) Compound represented by 5.9 parts; Resin (B): Resin B1 (in terms of solid content) 7.7 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 28 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure ( Registered trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 5.5 parts; solvent (E): 9.9 parts of propylene glycol monomethyl ether acetate; solvent (E): 470 parts of N-methylpyrrolidone; And leveling agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 16

A coloring curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: a coloring agent (A): C.I. Pigment Green 7 (pigment) 49 parts, 22 parts of acrylic-based frequency material dispersing agent, resin (B): resin B1 (converted solid content) 17 parts, and solvent (E): 320 parts of propylene glycol monomethyl ether acetate, and using a bead mill to make the pigment sufficient Dispersion; coloring agent (A): 14 parts of the compound represented by the formula (I-157); resin (B): resin B1 (in terms of solid content) 12 parts; polymerizable compound (C): dipentaerythritol Acrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 29 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl) Octane-1-one-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corporation, o-mercaptopurine compound) 5.9 parts; solvent (E): 530 parts of propylene glycol monomethyl ether acetate; And leveling agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 17

A coloring curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: coloring agent (A): CI pigment green 36 (pigment) 59 parts, acrylic pigment dispersing agent 26 parts, resin (B): resin B1 (converted solid content conversion) 21 parts, and solvent (E): 380 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed using a bead mill; coloring agent (A): formula (I- 157) the indicated compound is 4.3 parts; Resin (B): Resin B1 (converted in terms of solid content) 6.7 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 27 parts; Starting agent (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01, BASF Corporation Manufacture, o-mercaptopurine compound) 5.5 parts; solvent (E): 470 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether modified polysiloxane (Toray Silicone SH8400, Toray Silicone) (Manufacturer) Co., Ltd.) 0.50 parts.

Example 18

A colored curable resin composition is obtained by mixing the following: a pigment dispersion liquid, which is mixed: colorant (A): 60 parts of CI Pigment Green 58 (pigment), 27 parts of acrylic pigment dispersant, and resin (B): resin B1 (converted solid content conversion) 21 parts, and solvent (E): 390 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 157) The compound represented by 2.6 parts; Resin (B): Resin B1 (in terms of solid content) 5.8 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 27 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl) octyl Alkan-1-one-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corporation, o-mercaptopurine compound) 5.4 parts; solvent (E): propylene glycol monomethyl ether acetate 460 parts; Flat agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 19

A coloring curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: coloring agent (A): CI pigment green 7 (pigment) 43 parts, acrylic pigment dispersing agent 19 parts, resin (B): resin B1 (converted solid content conversion) 15 parts, and solvent (E): 280 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 178) 20 parts of the compound represented; resin (B): resin B1 (converted solid content) 16 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 31 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure ( Registered trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 6.1 parts; solvent (E): 570 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether modified polyoxyl Oil (Toray Silicone SH8400, manufactured by Toray Silicon Corning Co., Ltd.) 0.50 parts.

Example 20

A coloring curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: coloring agent (A): CI pigment green 36 (pigment) 56 parts, acrylic pigment dispersing agent 25 parts, resin (B): resin B1 (converted solid content conversion) 20 parts, and solvent (E): 370 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 178) The compound represented by 6.8 parts; Resin (B): Resin B1 (in terms of solid content) 8.2 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 28 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure ( Registered trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 5.6 parts; solvent (E): 480 parts of propylene glycol monomethyl ether acetate; and leveling agent (F): polyether modified polyoxyl Oil (Toray Silicone SH8400, manufactured by Toray Silicon Corning Co., Ltd.) 0.50 parts.

Example 21

A colored curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: a colorant (A): C.I. Pigment Green 58 (pigment) 59 parts, and an acrylic pigment dispersant 27 parts, Resin (B): Resin B1 (converted solid content) 21 parts, and solvent (E): 390 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed by using a bead mill; coloring agent (A) ): 4.0 parts of the compound represented by the formula (I-178); Resin (B): Resin B1 (converted solid content) 6.6 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA , manufactured by Nippon Kayaku Co., Ltd.) 27 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2 -imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corporation, o-quinone hydrazine compound) 5.5 parts; solvent (E): propylene glycol monomethyl ether acetate 460 parts; and leveling agent (F): poly Ether-modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 22

A colored curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: a coloring agent (A): 51 parts of CI Pigment Green 7 (pigment), 23 parts of an acrylic pigment dispersant, and a resin (B): resin B1 (converted solid content conversion) 18 parts, and solvent (E): 330 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 158) 12 parts of the compound represented; resin (B): resin B1 (converted in solid content) 11 parts; Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 29 parts; polymerization initiator (D): N-benzylideneoxy-1 -(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF Corporation, o-nonyl fluorene compound) 5.8 parts; solvent (E): 14 parts of propylene glycol monomethyl ether acetate; solvent (E): 500 parts of N-methylpyrrolidone; and leveling agent (F): polyether modified polyoxygenated oil (Toray Silicone SH8400; Toray Dow Corning ( Co., Ltd.) Manufacturing) 0.50 parts.

Example 23

A colored curable resin composition: a pigment dispersion liquid mixed with a coloring agent (A): 60 parts of CI Pigment Green 36 (pigment), 27 parts of an acrylic pigment dispersant, and a resin (B): resin were obtained by mixing the following: B1 (converted solid content conversion) 21 parts, and solvent (E): 390 parts of propylene glycol monomethyl ether acetate, and the pigment was sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 158) The compound represented by 3.5 parts; Resin (B): Resin B1 (in terms of solid content) 6.3 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 27 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl) octyl Alkan-1-one-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corporation, o-mercaptopurine compound) 5.4 parts; solvent (E): propylene glycol monomethyl ether acetate 8.2 parts; solvent ( E): 450 parts of N-methylpyrrolidone; and leveling agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

Example 24

A colored curable resin composition was obtained by mixing the following: a pigment dispersion liquid, which was mixed: colorant (A): CI pigment green 58 (pigment) 61 parts, acrylic pigment dispersant 27 parts, resin (B): resin B1 (converted solid content conversion) 21 parts, and solvent (E): 400 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): formula (I- 158) 2.1 parts of the compound represented; resin (B): resin B1 (in terms of solid content) 5.5 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, Nippon Chemical Co., Ltd. Co., Ltd.) 27 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure ( Registered trademark) OXE-01, manufactured by BASF, o-mercaptopurine compound) 5.4 parts; solvent (E): 7.2 parts of propylene glycol monomethyl ether acetate; solvent (E): 440 parts of N-methylpyrrolidone; and Leveling agent (F): Polyether modified polyoxyxide oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.50 parts.

[Production of coloring patterns]

The colored curable resin composition was applied onto a 2 inch square glass substrate (Eagle XG, manufactured by Corning Incorporated) by a spin coating method, and then prebaked at 100 ° C for 3 minutes to form a colored composition. Floor. After cooling, the distance between the substrate on which the colored composition layer was formed and the mask made of quartz glass was 200 μm, and it was exposed to an atmospheric environment at 80 mJ/ using an exposure machine (TME-150RSK, manufactured by TOPCON Co., Ltd.). Exposure of cm ² (365 nm standard) exposure. Further, as the photomask, a line and a gap pattern formed with 100 μm were used. The exposed coloring composition layer was immersed in an aqueous solution containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide for 70 seconds at 25 ° C to carry out development, and after washing with water, it was carried out in an oven at 230 ° C. Bake after 20 minutes, thereby obtaining a colored pattern.

[Measurement of film thickness]

The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3, manufactured by Nippon Vacuum Technology Co., Ltd.). The results are shown in Table 31.

[Color Evaluation]

For the obtained color pattern, the color measurement was measured using a color measuring machine (OSP-SP-200, manufactured by Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was measured using the characteristic function of the C light source. (x, y). The results are shown in Table 31.

[Preparation of colored curable resin composition for sublimation test] Comparative example 1

A colored curable resin composition for sublimation test was obtained by mixing the following: a pigment dispersion liquid: coloring agent (A): 50 parts of CI Pigment Green 7 (pigment), 22 parts of acrylic pigment dispersant, and resin ( B): Resin B1 (converted in solid content) 17 parts, and solvent (E): 320 parts of propylene glycol monomethyl ether acetate, and the pigment is sufficiently dispersed by using a bead mill; coloring agent (A): Coumarin 6 (manufactured by Tokyo Chemical Industry Co., Ltd.) 13 parts; resin (B): resin B1 (converted solid content) 12 parts; polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered) Trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 29 parts; polymerization initiator (D): N-benzylideneoxy-1-(4-phenylthiophenyl)octane-1- Keto-2-imine (Irgacure (registered trademark) OXE-01, manufactured by BASF Corporation, o-nonyl hydrazine compound) 5.8 parts; solvent (E): propylene glycol monomethyl ether acetate 15 parts; solvent (E): N - 510 parts of methylpyrrolidone; and leveling agent (F): polyether modified polyoxyxide oil (Toray Silicone SH8400, Toray Dow Corning (股份有限公司) Made) 0.50 parts.

[Preparation of resin composition for sublimation test]

A sublimation test resin composition was obtained by mixing the following materials: Resin: methacrylic acid / benzyl methacrylate (Morby: 30/70) copolymer (manufactured by Tajika Chemical Industry Co., Ltd., average molecular weight 10700, acid value 70 mgKOH/g) 33.8% propylene glycol single 40.2 parts of methyl ether acetate solution; polymerizable compound: dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd.) 5.8 parts; polymerization initiator: N-benzonitrile 1-(4-phenylthiophenyl)octane-1-one-2-imine (Irgacure (registered trademark) OXE01, manufactured by BASF, Japan) 0.58 parts; leveling agent: polyether modified poly Toray Silicone SH8400 (manufactured by Toray Silicone Co., Ltd.) 0.01 parts; solvent: 46.6 parts of propylene glycol monomethyl ether; and solvent: 6.8 parts of propylene glycol monomethyl ether acetate.

[Formation of Colored Coating Film for Sublimation Test]

The colored curable resin composition obtained in Example 1 to Example 24 or Comparative Example 1 was applied to a glass substrate of 2 inches square (Eagle XG, manufactured by Corning Incorporated) by a spin coating method. The volatile component was volatilized at 100 ° C for 3 minutes to obtain a colored coating film for sublimation test.

[Formation of resin coating film for sublimation test]

The resin composition for sublimation test obtained by the above was applied to a glass substrate (Eaglexc, manufactured by Corning Co., Ltd.) of 2 inches square by a spin coating method, and volatile components were volatilized at 100 ° C. 3 minutes. After cooling, an exposure machine (TME-150RSK, manufactured by TOPCON Co., Ltd.) was used, and light irradiation was performed at an exposure amount (365 nm standard) of 150 mJ/cm ² in an atmosphere. The film was heated at 220 ° C for 2 hours in an oven to form a resin coating film for a sublimation test (film thickness: 2.2 μm).

[sublimation evaluation]

The coloring coating film for sublimation test and the resin coating film for sublimation test were opposed to each other while leaving a gap of 70 μm, and heated at 220 ° C for 40 minutes. The color difference (ΔEab*) before and after heating of the resin coating film for sublimation test was measured using a color measuring machine (OSP-SP-200, manufactured by OLYMPUS Co., Ltd.). When the color difference (ΔEab*) is 5.0 or more, sublimation is indicated. The results are shown in Table 31. In Table 31, in each of the examples, when the colorant was not sublimed, it was represented by ○, and when the colorant was sublimated, it was represented by ×.

Example 25 to Example 90

A colored curable resin composition and a color filter were obtained in the same manner as in the example YYY except that the compound XXX was used instead of the compound synthesized in the synthesis example 1. The above compound XXX or the example YYY represents the compound XXX shown in Tables 32 to 34 or the example YYY, respectively.

Since the compound of the present invention has high thermal stability, it can be used as a dye used for a color filter of a display device such as a liquid crystal display device.

Claims (17)

a compound represented by the formula (I'): [In the formula (I'), L represents a divalent hydrocarbon group having 1 to 20 carbon atoms; and the methylene group constituting the divalent hydrocarbon group may also be through an oxygen atom, a sulfur atom, -N(R ¹⁰ )-, a sulfonyl group or The carbonyl group may be substituted, and the hydrogen atom contained in the divalent hydrocarbon group may also be a cyano group, a nitro group, an amine methyl sulfonyl group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group, a chlorine atom, a bromine atom, or an imidazol-1-yl group. Or an amine group; X represents an oxygen atom, a sulfur atom or -N(R ¹⁰ )-; and R ¹ to R ⁴ each independently represent a hydrogen atom or a carbon number of 1 to 20, or a R ¹ and R ³ bond. And forming a ring together with the carbon atom on the adjacent benzene ring and the adjacent nitrogen atom, or R ² and R ^{4 are} bonded to form a ring together with the carbon atom on the adjacent benzene ring and the adjacent nitrogen atom; The methylene group of the monovalent hydrocarbon group may be substituted by an oxygen atom, a sulfur atom, a -N(R ¹⁰ )-, a sulfonyl group or a carbonyl group, and a hydrogen atom contained in the monovalent hydrocarbon group may also pass through a halogen atom or a cyano group. a nitro group, an amine carbaryl group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group, an imidazol-1-yl group or an amine group; and R ⁵ to R ⁹ each independently represent a hydrogen atom, a halogen atom, a cyano group, or a nitrate Base, amine methyl sulfhydryl, amine sulfonate a mercapto group, a sulfo group, a carboxyl group, a hydroxyl group, an amine group or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and R ⁵ and R ^{6 are} bonded to form a ring together with an adjacent carbon atom, or R ⁷ and R ^{8 are} bonded to each other. a ring is formed together with an adjacent carbon atom; the methylene group constituting the monovalent hydrocarbon group may be substituted by an oxygen atom, a sulfur atom, a -N(R ¹⁰ )-, a sulfonyl group or a carbonyl group, and the monovalent hydrocarbon group is contained The hydrogen atom may also be substituted by a halogen atom, a cyano group, a nitro group, an amine carbenyl group, an amine sulfonyl group, a sulfo group, a carboxyl group, a hydroxyl group, an imidazol-1-yl group or an amine group; and R ¹⁰ represents a hydrogen atom or a carbon number. 1 to 20 a monovalent hydrocarbon group; when a plurality of R ¹⁰ are present, they are the same or different from each other]. The compound of claim 1, wherein X is an oxygen atom or a nitrogen atom. The compound of claim 2, wherein X is an oxygen atom. The compound of claim 1, wherein L is a methylene or sulfonyl group which may also have a substituent. The compound of claim 4, wherein L is dimethylmethylene or sulfonyl. The compound of claim 1, wherein R ⁵ to R ⁹ are each a hydrogen atom. A dye comprising the compound of claim 1. A colored curable resin composition comprising the dye according to claim 7, a resin, a polymerizable compound, and a polymerization initiator. A colored curable resin composition comprising a coloring agent containing a compound represented by the formula (I') of claim 1 , a resin, a polymerizable compound, and a polymerization initiator. The colored curable resin composition of claim 9, wherein the colorant further comprises a pigment. The colored curable resin composition of claim 10, wherein the pigment is selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment. One less. The colored curable resin composition of claim 10 or 11, wherein the pigment is at least one selected from the group consisting of copper chloride phthalocyanine pigment, copper bromide phthalocyanine pigment, and zinc bromide phthalocyanine pigment. The colored curable resin composition of claim 10, wherein the pigment is a green pigment. The colored curable resin composition of claim 10, wherein the pigment is at least one selected from the group consisting of C.I. Pigment Green 7, C.I. Pigment Green 36, and C.I. Pigment Green 58. The colored curable resin composition of claim 10, wherein the pigment is C.I. Pigment Green 7. A color filter formed of the colored curable resin composition of claim 8. A liquid crystal display device comprising the color filter of claim 16.