CN105732604B

CN105732604B - Compounds useful as dyes

Info

Publication number: CN105732604B
Application number: CN201510979743.2A
Authority: CN
Inventors: 织田胜成
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2014-12-26
Filing date: 2015-12-23
Publication date: 2020-12-29
Anticipated expiration: 2035-12-23
Also published as: KR20160079692A; CN105732604A; KR102407625B1; TW201629052A; JP6480728B2; TWI694997B; JP2016124970A

Abstract

The subject of the invention is: provided is an excellent compound as a dye for a color filter of a display device such as a liquid crystal display device. The solution is as follows: a compound represented by the formula (I).

Description

Compounds useful as dyes

Technical Field

The present invention relates to a novel compound useful as a dye (for example, a colorant, a colored curable resin composition, a color filter, and a liquid crystal display device containing the same).

Background

Dyes are used for displaying colors by reflected light or transmitted light in the fields of fiber materials, liquid crystal display devices, ink jet, and the like. Coumarin 6 is known as the dye (patent document 1).

Prior Art

Patent document

Patent document 1 Japanese patent laid-open No. 2006-154740 (example 8)

Disclosure of Invention

Problems to be solved by the invention

The subject of the invention is: provided is an excellent compound used as a dye in a color filter of a display device such as a liquid crystal display device. The present invention also addresses the problem of providing an intermediate for the above compound, a colorant comprising the above compound, a colored curable resin composition, a color filter, and a liquid crystal display device.

Means for solving the problems

The present invention includes the following inventions.

[1] A compound represented by the formula (I).

[ CHEM 1]

(wherein L represents a C1-20 hydrocarbon group having a valence of 2 or a sulfonyl group.

X represents an oxygen atom or a sulfur atom.

R¹Represents an optionally substituted alkenyl group having 2 to 20 carbon atoms or an optionally substituted cycloalkenyl group having 3 to 20 carbon atoms, -CH constituting the alkenyl group or cycloalkenyl group₂Can be substituted by an oxygen atom, -N (R)¹⁰) -, or carbonyl substitution.

R²Represents a hydrogen atom or a 1-valent hydrocarbon group having 1 to 20 carbon atoms.

R³～R⁹Each independently represents a hydrogen atom, a C1-20 hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, or-SO₃M、-CO₂M, hydroxy, formyl or amino.

R²～R⁹In the aforementioned hydrocarbon group represented by the formula, -CH₂May be substituted by oxygen, sulfur, -N (R)¹¹) -, sulfonyl or carbonyl, the hydrogen atom being optionally substituted by halogen, cyano, nitro, carbamoyl, sulfamoyl, -SO₃M、-CO₂M, hydroxy, formyl, or amino.

R¹⁰And R¹¹Each independently represents a hydrogen atom or a 1-valent hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R are present¹⁰And R¹¹When they are the same or different from each other.

M represents a hydrogen atom or an alkali metal atom. )

[2]Such as [1]]The compound of (A), R¹The alkenyl group may have a substituent(s) and has 2 to 16 carbon atoms, or the cycloalkenyl group may have a substituent(s) and has 3 to 16 carbon atoms.

[3]Such as [1]]Or [ 2]]The compound of (A), R¹The alkenyl group may have a substituent(s) and has 2 to 10 carbon atoms or the cycloalkenyl group may have a substituent(s) and has 3 to 10 carbon atoms.

[4]Such as [1]]～[3]The compound of any one of (1), R²Is alkenyl of 2-10 carbon atoms, alkyl of 3-10 carbon atoms, cycloalkenyl of 3-10 carbon atoms or carbon atomAryl groups having a seed number of 6 to 15.

[5] A colorant comprising the compound according to any one of [1] to [4 ].

[6] The colorant according to [5], which further comprises a pigment.

[7] A colored curable resin composition comprising the colorant according to [5] or [6], a resin, a polymerizable compound, a polymerization initiator and a solvent.

[8] A color filter comprising the colored curable resin composition according to [7 ].

[9] A liquid crystal display device comprising the color filter of [8 ].

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

[ CHEM 2]

(in the formula, R¹An optionally substituted alkenyl group having 2 to 20 carbon atoms or an optionally substituted cycloalkenyl group having 3 to 20 carbon atoms, -CH constituting the alkenyl group or cycloalkenyl group₂Can be substituted by an oxygen atom, -N (R)¹⁰) -, or carbonyl substitution.

R³～R⁵Each independently represents a hydrogen atom, a C1-20 hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, or-SO₃M、-CO₂M, hydroxy, formyl or amino.

R²～R⁵In the aforementioned hydrocarbon group represented by the formula, -CH₂May be substituted by oxygen, sulfur, -N (R)¹¹) -, sulfonyl or carbonyl, the hydrogen atom being optionally substituted by halogen, cyano, nitro, carbamoyl, sulfamoyl, -SO₃M、-CO₂M, hydroxy, formyl, or amino.

R¹⁰And R¹¹Each independent earth surfaceA hydrogen atom or a C1-20 valent hydrocarbon group, each of which has a plurality of R¹⁰And R¹¹When they are the same or different from each other.

M represents a hydrogen atom or an alkali metal atom. )

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

[ CHEM 3]

M represents a hydrogen atom or an alkali metal atom. )

Effects of the invention

Even when a colored coating film produced using the above compound is immersed in NMP, the amount of the colorant dissolved in NMP from the colored coating film is small, and therefore the compound of the present invention is excellent as a dye for a color filter of a display device such as a liquid crystal display device.

Detailed Description

The compound of the present invention is a compound represented by formula (I) (hereinafter, sometimes referred to as compound (I)). The compound (I) also includes tautomers thereof and salts thereof.

[ CHEM 4]

X represents an oxygen atom or a sulfur atom.

M represents a hydrogen atom or an alkali metal atom. )

In the formula (I), L represents a C1-20 2-valent hydrocarbon group or a sulfonyl group.

Examples of the 2-valent hydrocarbon group having 1 to 20 carbon atoms include aliphatic saturated hydrocarbon groups such as methylene, dimethylene, trimethylene, tetramethylene, 1-ethylene (i.e., ethane-1, 1-diyl), 2-propylene (i.e., propane-2, 2-diyl), and the like; alicyclic saturated hydrocarbon groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group; and aromatic hydrocarbon groups such as fluorene-9, 9-diyl.

L is preferably a C1-16 valent hydrocarbon group, more preferably a C1-14 valent hydrocarbon group. The 2-valent hydrocarbon group may be the above-mentioned aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group, or may be a combination thereof.

From the viewpoint of obtaining a raw material, L is more preferably a group represented by any one of the following formulae (L1) to (L4), even more preferably a group represented by any one of formulae (L1) to (L3), particularly preferably a group represented by formula (L1) or formula (L2), and most preferably a group represented by formula (L1). In the following formula, ● represents a bonding position.

[ CHEM 5]

In the formula (I), X represents an oxygen atom or a sulfur atom, preferably an oxygen atom. A color filter formed from a colored curable resin composition containing a colorant containing a compound (I) in which X is an oxygen atom tends to have high lightness.

R in the formula (I)¹Represents an optionally substituted alkenyl group having 2 to 20 carbon atoms or an optionally substituted cycloalkenyl group having 3 to 20 carbon atoms (hereinafter, these groups may be collectively referred to as "optionally substituted alkenyl group having 2 to 20 carbon atoms or cycloalkenyl group having 3 to 20 carbon atoms"), or a group-CH constituting the alkenyl group or cycloalkenyl group₂Can be substituted by an oxygen atom, -N (R)¹⁰) -, or carbonyl substitution.

R¹Examples of the alkenyl group having 2 to 20 carbon atoms include: linear alkenyl groups such as vinyl (ethenyl, vinyl), propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, and eicosenyl; branched alkenyl groups such as isopropenyl, 1-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 1, 2-dimethyl-1-propenyl, and 1-methyl-1-butenyl. Wherein R is¹The C2-20 linear alkenyl group is preferable.

R¹Examples of the cycloalkenyl group having 3 to 20 carbon atoms include: cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, and the like.

R¹The alkenyl group having 2 to 16 carbon atoms or the cycloalkenyl group having 3 to 16 carbon atoms, which may have a substituent, is preferable, the alkenyl group having 2 to 10 carbon atoms or the cycloalkenyl group having 3 to 10 carbon atoms, which may have a substituent, is more preferable, and the alkenyl group having 2 to 8 carbon atoms or the cycloalkenyl group having 3 to 8 carbon atoms is even more preferable.

The number of the ethylenically unsaturated bond contained in the alkenyl group or cycloalkenyl group may be 1 (e.g., AE-1 to 99, 101 to 105, 107 to 114 described later), 2 (e.g., AE-100, AE-106 described later), or 3 or more. The number of the ethylenically unsaturated bonds contained in the above alkenyl group or cycloalkenyl group is preferably 1.

The ethylenically unsaturated bond may be present at the terminal end (free end side) of the alkenyl group, or may be present in a portion other than the terminal end of the alkenyl group. When present in a moiety other than the terminal of the alkenyl group, the isomer may be either cis or trans. The aforementioned ethylenically unsaturated bond may be, for example, -CH-, -CH-CH₂Such unsubstituted ethylenically unsaturated bond may be-CH ═ CR^c- (e.g. R)^cAlkyl group having 1 to 10 carbon atoms), -CR^c＝CR^d- (e.g. R)^c、R^dAlkyl groups having 1 to 10 carbon atoms, which may be the same or different), or-CR^c＝CH₂(e.g. R)^cAlkyl group having 1 to 10 carbon atoms) or the like^c、R^dOf (a) an ethylenically unsaturated bond.

R mentioned above^c、R^dPreferred is an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group (particularly, a t-butyl group), a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, or the like.

The hydrogen atom contained in the aforementioned alkenyl group or cycloalkenyl group may be substituted with a substituent.

Examples of the substituent include aromatic groups such as phenyl group and toluyl group; halogen atoms such as fluorine atom, chlorine atom, and bromine atom; alkoxy groups having 1 to 10 carbon atoms such as methoxy, ethoxy, propoxy and butoxy; alkoxycarbonyl groups having 2 to 10 carbon atoms such as methoxycarbonyl group and ethoxycarbonyl group; a hydroxyl group; a carboxylic acid group; nitrile groups, and the like. When 2 or more substituents are bonded to the alkenyl group or cycloalkenyl group, they may be bonded to the same carbon atom.

The substituent may be bonded to a carbon atom constituting the ethylenically unsaturated bond or may be bonded to a carbon atom not constituting the ethylenically unsaturated bond. When the substituent is a carboxyl group, an alkoxy group, an aromatic group or the like, it is often bonded to a carbon atom constituting the ethylenically unsaturated bond.

Further, the aforementioned alkenyl or cycloalkenyl group which may have a substituent(s) contains-CH therein as long as it has an ethylenically unsaturated bond₂May be substituted by oxygen atoms, -N (R)¹⁰) -or carbonyl substitution.

R mentioned above¹⁰Represents a hydrogen atom or a 1-valent hydrocarbon group having 1 to 20 carbon atoms. R¹⁰Examples of the hydrocarbon group of (b) include alkyl groups having 1 to 10 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl and hexyl; alkenyl groups having 2 to 10 carbon atoms such as vinyl, propenyl, butenyl, pentenyl, hexenyl, hexadienyl and the like; and cycloalkenyl groups having 3 to 10 carbon atoms such as cyclobutenyl, cyclopentenyl, cyclohexenyl and cyclohexadienyl.

-CH₂In the case of substitution with a carbonyl group, the position of the carbonyl group is not particularly limited,preferably the carbonyl group has the formula (I) -NR¹R²The position of the N bond.

In addition, -CH₂-CH adjacent to a carbonyl group, in case of substitution by said carbonyl group₂May be substituted by oxygen atoms and-N (R)¹⁰) -1 or more substitutions in (a). Namely, -CH₂-CH₂-may be substituted by carboxyl or-C (═ O) -N (R)¹⁰) -substitution.

Examples of the alkenyl group or cycloalkenyl group which may have a substituent(s) include groups represented by the following formulae (AE-1) to (AE-114). In the following formula, ● represents a group represented by the formula-NR¹R²The position of the N bond.

[ CHEM 6]

[ CHEM 7]

[ CHEM 8]

[ CHEM 9]

[ CHEM 10]

[ CHEM 11]

[ CHEM 12 ]

[ CHEM 13 ]

[ CHEM 14 ]

[ CHEM 15 ]

From the viewpoint of solubility in the solvent of the compound (I), R¹The group represented by any one of the formulae (AE-1) to (AE-25), the formulae (AE-38) to (AE-44), the formulae (AE-61) to (AE-64), or the formulae (AE-80) to (AE-81) is preferable, the group represented by any one of the formulae (AE-1) to (AE-25), the formulae (AE-61) to (AE-64), or the formulae (AE-80) to (AE-81) is more preferable, and the group represented by any one of the formulae (AE-1) to (AE-19), or the formulae (AE-80) to (AE-81) is particularly preferable.

R²～R⁹Examples of the hydrocarbon group in (1) include: an alkenyl group represented by the above-mentioned formula (AE-1) to formula (AE-25), formula (AE-38) to formula (AE-44) or formula (AE-61) to formula (AE-63); methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, (2-ethyl) butyl, 1, 3-butadienyl, tert-butyl,an aliphatic hydrocarbon group such as an alkyl group including an pentyl group, an isopentyl group, a 3-pentyl group, a neopentyl group, a tert-pentyl group, a 1-methylpentyl group, a 2-pentenyl group, a (3-ethyl) pentyl group, a hexyl group, an isohexyl group, a 5-methylhexyl group, a (2-ethyl) hexyl group, a heptyl group, a (3-ethyl) heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, and an octadecyl group;

cycloalkenyl groups such as cyclopentenyl, cyclohexenyl (e.g., a compound represented by the formula (AE-64)), cycloheptenyl, and cyclooctenyl; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, 1-methylcyclohexyl, 2-methylcyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 1, 2-dimethylcyclohexyl, 1, 3-dimethylcyclohexyl, 1, 4-dimethylcyclohexyl, cycloalkyl groups such as 2, 3-dimethylcyclohexyl, 2, 4-dimethylcyclohexyl, 2, 5-dimethylcyclohexyl, 2, 6-dimethylcyclohexyl, 3, 4-dimethylcyclohexyl, 3, 5-dimethylcyclohexyl, 2-dimethylcyclohexyl, 3-dimethylcyclohexyl, 4-dimethylcyclohexyl, 2, 4, 6-trimethylcyclohexyl, 2, 6, 6-tetramethylcyclohexyl, and 3, 3, 5, 5-tetramethylcyclohexyl; alicyclic hydrocarbon groups;

monocyclic aromatic hydrocarbon groups such as phenyl, o-tolyl, m-tolyl, p-tolyl, 2, 3-dimethylphenyl, 2, 4-dimethylphenyl, 2, 5-dimethylphenyl, 2, 6-dimethylphenyl, 3, 4-dimethylphenyl, 3, 5-dimethylphenyl, mesityl (メシチル -yl), o-cumenyl, m-cumenyl, p-cumenyl, and 2, 6-bis (2-propyl) phenyl; polycyclic aromatic hydrocarbon groups such as 1-naphthyl, 2-naphthyl and biphenyl groups; and the like. Further, there may be mentioned a group formed by combining the above groups such as cyclohexylmethyl group, benzyl group and phenethyl group.

R²～R⁹In the (C1-C20) hydrocarbon group, the C1-valent aliphatic hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group is preferably C1-C10.

The aliphatic hydrocarbon group is preferably a saturated or unsaturated aliphatic hydrocarbon group, and more preferably an alkenyl group, an alkyl group or the like.

The alicyclic hydrocarbon group is preferably a monocyclic or polycyclic alicyclic hydrocarbon group, and more preferably a cycloalkenyl group or a cycloalkyl group.

The aromatic hydrocarbon group is preferably a monocyclic or polycyclic aromatic hydrocarbon group.

R¹¹Represents a hydrogen atom or a 1-valent hydrocarbon group having 1 to 20 carbon atoms. In the presence of a plurality of R¹¹When they are the same or different from each other. R¹¹And the aforementioned R¹⁰The same meaning is indicated.

Form R²～R⁹Of the 1-valent hydrocarbon group of (1) — CH₂By an oxygen atom, a sulfur atom, -N (R)¹¹) A group in which a hydrogen atom contained in the 1-valent hydrocarbon group is substituted with a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO₃M、-CO₂Examples of the group substituted with M, hydroxyl, formyl or amino include:

alkoxy groups such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, and (2-ethyl) hexyloxy;

aryloxy groups such as phenoxy group;

aralkyloxy such as benzyloxy;

linear alkylcarbonyl such as acetyl, ethylcarbonyl, propylcarbonyl, butylcarbonyl, pentylcarbonyl, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, nonylcarbonyl, decylcarbonyl, undecylcarbonyl, dodecylcarbonyl, butylcarbonyl and the like; an alkylcarbonyl group having a branch such as an isopropylcarbonyl group, an isobutylcarbonyl group, a sec-butylcarbonyl group, a tert-butylcarbonyl group, a (1-ethyl) butylcarbonyl group, a (2-ethyl) butylcarbonyl group, an isopentylcarbonyl group, a neopentylcarbonyl group, a tert-pentylcarbonyl group, a 1-methylpentylcarbonyl group, a 2-methylpentylcarbonyl group, a (1-ethyl) pentylcarbonyl group, a (3-ethyl) pentylcarbonyl group, an isohexylcarbonyl group, a 5-methylhexylcarbonyl group, a (2-ethyl) hexylcarbonyl group, or a (3-ethyl) hept; an alkenylcarbonyl group such as an isopropenylcarbonyl group, a 1-propenylcarbonyl group, a 2-butenylcarbonyl group, a 1, 3-butadienylcarbonyl group, or a 2-pentenylcarbonyl group; an acyl group such as a cycloalkylcarbonyl group including a cyclohexylmethylcarbonyl group, a cyclopropylcarbonyl group, a cyclobutylcarbonyl group, a cyclopentylcarbonyl group, and a cyclohexylcarbonyl group;

acyloxy groups such as acetoxy and benzoyloxy;

alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl and propoxycarbonyl;

an alkenyl group represented by the above-mentioned formula (AE-26) to formula (AE-37), formula (AE-45) to formula (AE-60) or formula (AE-65) to formula (AE-102);

n-linear alkylcarbamoyl groups such as N-methylcarbamoyl, N-ethylcarbamoyl, N-propylcarbamoyl, N-butylcarbamoyl, N-pentylcarbamoyl, N-hexylcarbamoyl, N-heptylcarbamoyl and N-octylcarbamoyl; n-isopropylcarbamoyl, N-isobutylcarbamoyl, N-sec-butylcarbamoyl, N-tert-butylcarbamoyl, N- (1-ethylpropyl) carbamoyl, N- (1, 1-dimethylpropyl) carbamoyl, N- (1, 2-dimethylpropyl) carbamoyl, N- (2, 2-dimethylpropyl) carbamoyl, N- (1-methylbutyl) carbamoyl, N- (2-methylbutyl) carbamoyl, N- (3-methylbutyl) carbamoyl, N- (1, 3-dimethylbutyl) carbamoyl, N- (3, 3-dimethylbutyl) carbamoyl, N- (1-methylhexyl) carbamoyl, N-tert-butylcarbamoyl, N- (1-ethylhexyl) carbamoyl, N-isopropylcarbamoyl, N-isobutylcarbamoyl, N-sec-butylcarbamoyl, N-tert-butylcarbamoyl, N- (1, 2-dimethylpropyl) carbamoyl, N- (1-methylbutyl) carbamoyl, N- (, N-branched alkylcarbamoyl groups such as N- (1, 4-dimethylpentyl) carbamoyl group, N- (2-ethylhexyl) carbamoyl group, N- (1, 5-dimethyl) hexylcarbamoyl group, and N- (1, 1, 2, 2-tetramethylbutyl) carbamoyl group; a mono-substituted carbamoyl group such as an N-cycloalkylcarbamoyl group such as an N-cyclopentylcarbamoyl group;

n, N-linear alkyl linear alkylcarbamoyl groups such as N, N-dimethylcarbamoyl group, N-ethylmethylcarbamoyl group, N-diethylcarbamoyl group, N-propylmethylcarbamoyl group, N-butylethylcarbamoyl group, and N, N-heptylmethylcarbamoyl group; n, N-branched alkyl-containing linear alkylcarbamoyl such as N, N-isopropylmethylcarbamoyl or N, N-t-butylmethylcarbamoyl; n, N-disubstituted carbamoyl groups such as N, N-bis (1-methylpropyl) carbamoyl group and N, N-bis (2-ethylhexyl) carbamoyl group, wherein the branched alkyl group is a branched alkyl group;

n-linear alkylsulfamoyl groups such as N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-butylsulfamoyl, N-pentylsulfamoyl, N-hexylsulfamoyl, N-heptylsulfamoyl and N-octylsulfamoyl; n-isopropylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N- (1-ethylpropyl) sulfamoyl, N- (1, 1-dimethylpropyl) sulfamoyl, N- (1, 2-dimethylpropyl) sulfamoyl, N- (2, 2-dimethylpropyl) sulfamoyl, N- (1-methylbutyl) sulfamoyl, N- (2-methylbutyl) sulfamoyl, N- (3-methylbutyl) sulfamoyl, N- (1, 3-dimethylbutyl) sulfamoyl, N- (3, 3-dimethylbutyl) sulfamoyl, N- (1-methylhexyl) sulfamoyl, N- (1, a mono-substituted sulfamoyl group such as an N-branched alkyl-containing sulfamoyl group (e.g., a 4-dimethylpentyl) sulfamoyl group, an N- (2-ethylhexyl) sulfamoyl group, an N- (1, 5-dimethyl) hexylsulfamoyl group, an N- (1, 1, 2, 2-tetramethylbutyl) sulfamoyl group, and an N-cycloalkylsulfamoyl group (e.g., an N-cyclopentylsulfamoyl group);

n, N-linear alkyl straight chain alkylsulfamoyl groups such as N, N-dimethylsulfamoyl, N-ethylmethylsulfamoyl, N-diethylsulfamoyl, N-propylmethylsulfamoyl, N-butylethylsulfamoyl and N, N-heptylmethylsulfamoyl; n, N-branched alkyl-containing linear alkylsulfamoyl group such as N, N-isopropylmethylsulfamoyl group and N, N-t-butylmethylsulfamoyl group; n, N-disubstituted sulfamoyl groups such as N, N-bis (1-methylpropyl) sulfamoyl groups and N, N-bis (2-ethylhexyl) sulfamoyl groups, wherein the branched alkyl group is a branched alkyl group-containing sulfamoyl group;

n-linear alkylamino, such as N-methylamino, N-ethylamino, N-propylamino, N-butylamino, N-hexylamino, N-heptylamino, N-octylamino, etc.; n-isopropylamino, N-isobutylamino, N-sec-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, N- (2-methylbutyl) amino, N- (3-methylbutyl) amino, N- (1, 3-dimethylbutyl) amino, N- (3, 3-dimethylbutyl) amino, N- (1-methylhexyl) amino, N- (1, 4-dimethylpentyl) amino, N- (2-ethylhexyl) amino, N-tert-butylamino, N-pentylamino, N- (1-ethylpropyl) amino, N- (1-methylbutyl) amino, N- (3-dimethylbutyl) amino, an N-branched alkylamino group such as an N- (1, 5-dimethyl) hexylamino group or an N- (1, 1, 2, 2-tetramethylbutyl) amino group; an N-alkylamino group such as an N-cycloalkylamino group such as an N-cyclopentylamino group;

n, N-linear alkyl alkylamino such as N, N-dimethylamino, N-ethylmethylamino, N-diethylamino, N-propylmethylamino, N-butylethylamino, and N, N-heptylmethylamino; n, N-branched alkyl-containing linear alkylamino such as N, N-isopropylmethylamino or N, N-t-butylmethylamino; n, N-dialkylamino such as N, N-branched alkyl group-containing branched alkylamino group (e.g., N-bis (1-methylpropyl) amino group, N-bis (2-ethylhexyl) amino group, etc.);

n-linear alkylaminomethyl groups such as N-methylaminomethyl group, N-ethylaminomethyl group, N-propylaminomethyl group, N-pentylaminomethyl group, N-hexylaminomethyl group, N-heptylaminomethyl group, and N-octylaminomethyl group; n-isopropylaminomethyl, N-isobutylaminomethyl, N-sec-butylaminomethyl, N-tert-butylaminomethyl, 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- (1, 3-dimethylbutyl) aminomethyl, N- (3, 3-dimethylbutyl) aminomethyl, N- (1-methylhexyl) aminomethyl, N- (1, an N-branched alkyl-containing aminomethyl group such as a 4-dimethylpentyl) aminomethyl group, an N- (2-ethylhexyl) aminomethyl group, an N- (1, 5-dimethyl) hexylaminomethyl group, or an N- (1, 1, 2, 2-tetramethylbutyl) aminomethyl group; an N-alkylaminomethyl group such as an N-cycloalkylaminomethyl group such as an N-cyclopentylaminomethyl group;

n, N-linear alkyl aminomethyl groups such as N, N-dimethylaminomethyl group, N-ethylmethylaminomethyl group, N-diethylaminomethyl group, N-propylmethylaminomethyl group, N-butylethylaminomethyl group, and N, N-heptylmethylaminomethyl group; n, N-branched alkyl-containing linear alkyl aminomethyl such as N, N-isopropylmethylaminomethyl and N, N-t-butylmethylaminomethyl; an N, N-dialkylaminomethyl group such as an N, N-branched alkyl group-containing branched alkylaminomethyl group, e.g., an N, N-bis (1-methylpropyl) aminomethyl group, an N, N-bis (2-ethylhexyl) aminomethyl group, etc.;

a perfluoroalkyl group such as a trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluorobutyl group, perfluoropentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononyl group, perfluorodecyl group, perfluoroundecyl group, perfluorododecyl group, and perfluorooctadecyl group; perfluoro branched alkyl groups such as perfluoro isopropyl group, perfluoro isobutyl group, perfluoro sec-butyl group, perfluoro tert-butyl group, perfluoro isopentyl group, perfluoro (3-pentyl) group, perfluoro neopentyl group, perfluoro tert-pentyl group, perfluoro (1-methylpentyl) group, perfluoro (2-methylpentyl) group, perfluoro isohexyl group, perfluoro (5-methylhexyl) group, and perfluoro (2-ethylhexyl) group; an aliphatic hydrocarbon group having a fluorine atom such as a perfluoroalkenyl group such as a perfluoroisopropenyl group, a perfluoro (1-propenyl) group, a perfluoro (2-butenyl) group, a perfluoro (1, 3-butadienyl) group, or a perfluoro (2-pentenyl) group;

perfluorocycloalkyl groups such as perfluorocyclopropyl, perfluorocyclobutyl, perfluorocyclopentyl, perfluorocyclohexyl, and perfluorocycloheptyl; perfluoro (1-methylcyclohexyl) group, perfluoro (2-methylcyclohexyl) group, perfluoro (3-methylcyclohexyl) group, perfluoro (4-methylcyclohexyl) group, perfluoro (1, 2-dimethylcyclohexyl) group, perfluoro (1, 3-dimethylcyclohexyl) group, perfluoro (1, 4-dimethylcyclohexyl) group, perfluoro (2, 3-dimethylcyclohexyl) group, perfluoro (2, 4-dimethylcyclohexyl), perfluoro (2, 5-dimethylcyclohexyl) group, perfluoro (2, 6-methylcyclohexyl) group, perfluoro (3, 4-dimethylcyclohexyl) group, perfluoro (3, 5-dimethylcyclohexyl) group, perfluoro (2, 2-dimethylcyclohexyl) group, perfluoro (3, 3-dimethylcyclohexyl) group, perfluoro (4), perfluoro-substituted cycloalkyl groups such as a 4-dimethylcyclohexyl) group, a perfluoro (2, 4, 6-trimethylcyclohexyl) group, a perfluoro (2, 2, 6, 6-tetramethylcyclohexyl) group, and a perfluoro (3, 3, 5, 5-tetramethylcyclohexyl) group; alicyclic hydrocarbon groups having a fluorine atom such as perfluorocycloalkenyl groups such as perfluorocyclohexenyl groups;

perfluorophenyl group, perfluoroo-tolyl group, perfluorom-tolyl group, perfluorop-tolyl group, perfluoroxylyl group, perfluoromesityl group, perfluoroo-cumenyl group, perfluorom-cumenyl group, perfluorop-cumenyl group, perfluorobenzyl group, perfluorophenethyl group, perfluorobiphenyl group, an aromatic hydrocarbon group having a fluorine atom such as a perfluoro (1-naphthyl) group, a perfluoro (2-naphthyl) group, a 1-trifluoromethylphenyl group, a 2-trifluoromethylphenyl group, a 3-trifluoromethylphenyl group, a 4-trifluoromethylphenyl group, a 2, 3-bis (trifluoromethyl) phenylmethyl group, a 2, 4-bis (trifluoromethyl) phenylmethyl group, a 2, 5-bis (trifluoromethyl) phenylmethyl group, a 2, 6-bis (trifluoromethyl) phenylmethyl group, a 3, 4-bis (trifluoromethyl) phenylmethyl group, a 3, 5-bis (trifluoromethyl) phenylmethyl group, etc.;

perfluoroalkoxy groups such as perfluoromethoxy, perfluoroethoxy, perfluoropropoxy, perfluorobutoxy, and perfluoropentoxy groups; a perfluoroalkyl alkoxy group such as perfluoroisopropoxy, perfluoroisobutoxy, perfluoro-sec-butoxy, perfluoro-tert-butoxy, (perfluoroethyl) methoxy, (perfluoropropyl) methoxy, (perfluorobutyl) methoxy, (perfluoropentyl) methoxy, (perfluorohexyl) methoxy, (perfluoroheptyl) methoxy, (perfluorooctyl) methoxy, (perfluorononyl) methoxy, (perfluorodecyl) methoxy, (perfluoroundecyl) methoxy, (perfluorododecyl) methoxy, or perfluorooctadecyl) methoxy; a perfluoro (branched alkyl) alkoxy group such as a (perfluoroisopropyl) methoxy group, a (perfluoroisobutyl) methoxy group, a (perfluorosec-butyl) methoxy group, a (perfluorotert-butyl) methoxy group, a (perfluoroisopentyl) methoxy group, a (perfluoro (3-pentyl)) methoxy group, a (perfluoroneopentyl) methoxy group, a (perfluorotert-pentyl) methoxy group, a (perfluoro (1-methylpentyl) methoxy group, a (perfluoro (2-methylpentyl)) methoxy group, a (perfluoroisohexyl) methoxy group, a (perfluoro (5-methylhexyl) methoxy group, a (perfluoro ((2-ethylhexyl)) methoxy group, a (perfluoroaryloxy) group such as a perfluorophenoxy group, a (perfluoroaralkyloxy) group such as a perfluorobenzyloxy group, a (perfluoroisopropenyl) methoxy group, a (1-propenyl, Perfluoroalkylalkoxy groups such as a (perfluoro (2-butenyl)) methoxy group, a (perfluoro (1, 3-butadienyl) methoxy group, and a (perfluoro (2-pentenyl)) methoxy group, and substituted oxy groups having a fluorine atom such as a 2, 2, 2-trifluoroethoxy group, and the like.

M represents a hydrogen atom or an alkali metal atom. Examples of the alkali metal atom include a sodium atom and a potassium atom. M is preferably a hydrogen atom.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

R³～R⁹Hydrogen atoms are particularly preferred.

R mentioned above²Examples of the hydrocarbon group of (A) include: alkenyl groups represented by the above-mentioned formulae (AE-1) to (AE-14), formulae (AE-20) to (AE-25), formulae (AE-38) to (AE-44), formulae (AE-61) to (AE-63), 1, 3-butadienyl group and 2-pentenyl group; alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, (2-ethyl) butyl, pentyl, isopentyl, 3-pentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, (3-ethyl) pentyl, hexyl, isohexyl, 5-methylhexyl, (2-ethyl) hexyl, heptyl, (3-ethyl) heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like; aliphatic hydrocarbon groups such as aliphatic hydrocarbon groups;

and aromatic hydrocarbon groups such as an aryl group, for example, a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2, 3-dimethylphenyl group, a 2, 4-dimethylphenyl group, a 2, 5-dimethylphenyl group, a 2, 6-dimethylphenyl group, a 3, 4-dimethylphenyl group, a 3, 5-dimethylphenyl group, a mesityl group, an o-cumenyl group, a m-cumenyl group, a p-cumenyl group, and a 2, 6-bis (2-propyl) phenyl group.

Among them, particularly preferred are alkyl groups having 1 to 10 carbon atoms such as a group represented by the above formulae (AE-1) to (AE-10), methyl group, ethyl group, propyl group, isopropyl group, 2-propenyl group, butyl group, pentyl group, hexyl group, (2-ethyl) hexyl group, heptyl group, octyl group, nonyl group, decyl group, etc.; and (b) an aromatic group having 1 to 10 carbon atoms such as a phenyl group, an o-tolyl group, a p-tolyl group, a 2, 3-dimethylphenyl group, a 2, 4-dimethylphenyl group, a 2, 5-dimethylphenyl group, a 2, 6-dimethylphenyl group, a mesityl group, an o-cumenyl group, or the like.

R²The compounds of the present invention having these groups are excellent in solubility in a solvent.

From the viewpoint of solubility of the compound (I) in a solvent, R²Preferably a C1-15 hydrocarbon group, more preferably a C1-15 aliphatic, alicyclic or aromatic hydrocarbon group, more preferably a C2-10 alkenyl, C3-10 alkylA cycloalkenyl group having 3 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 3 to 8 carbon atoms or an aryl group having 6 to 10 carbon atoms.

R³The aliphatic hydrocarbon group, alicyclic hydrocarbon group and aromatic hydrocarbon may be a combination of 1 or more.

In the formula (I), R¹～R⁹There are 2 each, and 2 may be the same or different from each other.

Specific examples of the compound (I) include compounds having a basic structure represented by the formula (IA) shown in tables 1 to 16 below.

[ CHEM 16 ]

In tables 1 to 16 below,

"L1" represents a group represented by the formula (L1), "L2" represents a group represented by the formula (L2), "L3" represents a group represented by the formula (L3), "L4" represents a group represented by the formula (L4), "O" represents an oxygen atom, "S" represents a sulfur atom,

"AE 2" represents a group represented by the formula (AE-2),

"AE 3" represents a group represented by the formula (AE-3),

"AE 4" represents a group represented by the formula (AE-4),

"AE 5" represents a group represented by the formula (AE-5),

"AE 7" represents a group represented by the formula (AE-7),

"AE 9" represents a group represented by the formula (AE-9),

"AE 10" represents a group represented by the formula (AE-10),

"AE 17" represents a group represented by the formula (AE-17),

"EHx" represents 2-ethyl-1-hexyl,

"Oct" means an octyl group,

"Ph" represents a phenyl group,

"Tol" means an o-tolyl group,

"DMP" means 2, 4-dimethylphenyl,

"MES" represents mesityl.

[ TABLE 1]

	X^A	L^A	R^1A	R^2A
					I-1	O	L1	AE2	AE2
I-2	O	L1	AE2	EHx
					I-3	O	L1	AE2	Oct
I-4	O	L1	AE2	Ph
					I-5	O	L1	AE2	Tol
I-6	O	L1	AE2	DMP
					I-7	O	L1	AE2	MES
I-8	O	L1	AE3	AE3
					I-9	O	L1	AE3	EHx
I-10	O	L1	AE3	Oct
					I-11	O	L1	AE3	Ph
I-12	O	L1	AE3	Tol
					I-13	O	L1	AE3	DMP
I-14	O	L1	AE3	MES
					I-15	O	L1	AE4	AE4
I-16	O	L1	AE4	EHx
					I-17	O	L1	AE4	Oct
I-18	O	L1	AE4	Ph
					I-19	O	L1	AE4	Tol
I-20	O	L1	AE4	DMP
					I-21	O	L1	AE4	MES
I-22	O	L1	AE5	AE5
					I-23	O	L1	AE5	EHx
I-24	O	L1	AE5	Oct
					I-25	O	L1	AE5	Ph
I-26	O	L1	AE5	Tol
					I-27	O	L1	AE5	DMP
I-28	O	L1	AE5	MES

[ TABLE 2]

	X^A	L^A	R^1A	R^2A
					I-29	O	L1	AE7	AE7
I-30	O	L1	AE7	EHx
					I-31	O	L1	AE7	Oct
I-32	O	L1	AE7	Ph
					I-33	O	L1	AE7	Tol
I-34	O	L1	AE7	DMP
					I-35	O	L1	AE7	MES
I-36	O	L1	AE9	AE9
					I-37	O	L1	AE9	EHx
I-38	O	L1	AE9	Oct
					I-39	O	L1	AE9	Ph
I-40	O	L1	AE9	Tol
					I-41	O	L1	AE9	DMP
I-42	O	L1	AE9	MES
					I-43	O	L1	AE10	AE10
I-44	O	L1	AE10	EHx
					I-45	O	L1	AE10	Oct
I-46	O	L1	AE10	Ph
					I-47	O	L1	AE10	Tol
I-48	O	L1	AE10	DMP
					I-49	O	L1	AE10	MES
I-50	O	L1	AE17	AE17
					I-51	O	L1	AE17	EHx
I-52	O	L1	AE17	Oct
					I-53	O	L1	AE17	Ph
I-54	O	L1	AE17	Tol
					I-55	O	L1	AE17	DMP
I-56	O	L1	AE17	MES

[ TABLE 3]

	X^A	L^A	R^1A	R^2A
					I-57	O	L2	AE2	AE2
I-58	O	L2	AE2	EHx
					I-59	O	L2	AE2	Oct
I-60	O	L2	AE2	Ph
					I-61	O	L2	AE2	Tol
I-62	O	L2	AE2	DMP
					I-63	O	L2	AE2	MES
I-64	O	L2	AE3	AE3
					I-65	O	L2	AE3	EHx
I-66	O	L2	AE3	Oct
					I-67	O	L2	AE3	Ph
I-68	O	L2	AE3	Tol
					I-69	O	L2	AE3	DMP
I-70	O	L2	AE3	MES
					I-71	O	L2	AE4	AE4
I-72	O	L2	AE4	EHx
					I-73	O	L2	AE4	Oct
I-74	O	L2	AE4	Ph
					I-75	O	L2	AE4	Tol
I-76	O	L2	AE4	DMP
					I-77	O	L2	AE4	MES
I-78	O	L2	AE5	AE5
					I-79	O	L2	AE5	EHx
I-80	O	L2	AE5	Oct
					I-81	O	L2	AE5	Ph
I-82	O	L2	AE5	Tol
					I-83	O	L2	AE5	DMP
I-84	O	L2	AE5	MES

[ TABLE 4]

	X^A	L^A	R^1A	R^2A
					I-85	O	L2	AE7	AE7
I-86	O	L2	AE7	EHx
					I-87	O	L2	AE7	Oct
I-88	O	L2	AE7	Ph
					I-89	O	L2	AE7	Tol
I-90	O	L2	AE7	DMP
					I-91	O	L2	AE7	MES
I-92	O	L2	AE9	AE9
					I-93	O	L2	AE9	EHx
I-94	O	L2	AE9	Oct
					I-95	O	L2	AE9	Ph
I-96	O	L2	AE9	Tol
					I-97	O	L2	AE9	DMP
I-98	O	L2	AE9	MES
					I-99	O	L2	AE10	AE10
I-100	O	L2	AE10	EHx
					I-101	O	L2	AE10	Oct
I-102	O	L2	AE10	Ph
					I-103	O	L2	AE10	Tol
I-104	O	L2	AE10	DMP
					I-105	O	L2	AE10	MES
I-106	O	L2	AE17	AE17
					I-107	O	L2	AE17	EHx
I-108	O	L2	AE17	Oct
					I-109	O	L2	AE17	Ph
I-110	O	L2	AE17	Tol
					I-111	O	L2	AE17	DMP
I-112	O	L2	AE17	MES

[ TABLE 5]

	X^A	L^A	R^1A	R^2A
					I-113	O	L3	AE2	AE2
I-114	O	L3	AE2	EHx
					I-115	O	L3	AE2	Oct
I-116	O	L3	AE2	Ph
					I-117	O	L3	AE2	Tol
I-118	O	L3	AE2	DMP
					I-119	O	L3	AE2	MES
I-120	O	L3	AE3	AE3
					I-121	O	L3	AE3	EHx
I-122	O	L3	AE3	Oct
					I-123	O	L3	AE3	Ph
I-124	O	L3	AE3	Tol
					I-125	O	L3	AE3	DMP
I-126	O	L3	AE3	MES
					I-127	O	L3	AE4	AE4
I-128	O	L3	AE4	EHx
					I-129	O	L3	AE4	Oct
I-130	O	L3	AE4	Ph
					I-131	O	L3	AE4	Tol
I-132	O	L3	AE4	DMP
					I-133	O	L3	AE4	MES
I-134	O	L3	AE5	AE5
					I-135	O	L3	AE5	EHx
I-136	O	L3	AE5	Oct
					I-137	O	L3	AE5	Ph
I-138	O	L3	AE5	Tol
					I-139	O	L3	AE5	DMP
I-140	O	L3	AE5	MES

[ TABLE 6]

	X^A	L^A	R^1A	R^2A
					I-141	O	L3	AE7	AE7
I-142	O	L3	AE7	EHx
					I-143	O	L3	AE7	Oct
I-144	O	L3	AE7	Ph
					I-145	O	L3	AE7	Tol
I-146	O	L3	AE7	DMP
					I-147	O	L3	AE7	MES
I-148	O	L3	AE9	AE9
					I-149	O	L3	AE9	EHx
I-150	O	L3	AE9	Oct
					I-151	O	L3	AE9	Ph
I-152	O	L3	AE9	Tol
					I-153	O	L3	AE9	DMP
I-154	O	L3	AE9	MES
					I-155	O	L3	AE10	AE10
I-156	O	L3	AE10	EHx
					I-157	O	L3	AE10	Oct
I-158	O	L3	AE10	Ph
					I-159	O	L3	AE10	Tol
I-160	O	L3	AE10	DMP
					I-161	O	L3	AE10	MES
I-162	O	L3	AE17	AE17
					I-163	O	L3	AE17	EHx
I-164	O	L3	AE17	Oct
					I-165	O	L3	AE17	Ph
I-166	O	L3	AE17	Tol
					I-167	O	L3	AE17	DMP
I-168	O	L3	AE17	MES

[ TABLE 7]

	X^A	L^A	R^1A	R^2A
					I-169	O	L4	AE2	AE2
I-170	O	L4	AE2	EHx
					I-171	O	L4	AE2	Oct
I-172	O	L4	AE2	Ph
					I-173	O	L4	AE2	Tol
I-174	O	L4	AE2	DMP
					I-175	O	L4	AE2	MES
I-176	O	L4	AE3	AE3
					I-177	O	L4	AE3	EHx
I-178	O	L4	AE3	Oct
					I-179	O	L4	AE3	Ph
I-180	O	L4	AE3	Tol
					I-181	O	L4	AE3	DMP
I-182	O	L4	AE3	MES
					I-183	O	L4	AE4	AE4
I-184	O	L4	AE4	EHx
					I-185	O	L4	AE4	Oct
I-186	O	L4	AE4	Ph
					I-187	O	L4	AE4	Tol
I-188	O	L4	AE4	DMP
					I-189	O	L4	AE4	MES
I-190	O	L4	AE5	AE5
					I-191	O	L4	AE5	EHx
I-192	O	L4	AE5	Oct
					I-193	O	L4	AE5	Ph
I-194	O	L4	AE5	Tol
					I-195	O	L4	AE5	DMP
I-196	O	L4	AE5	MES

[ TABLE 8]

	X^A	L^A	R^1A	R^2A
					I-197	O	L4	AE7	AE7
I-198	O	L4	AE7	EHx
					I-199	O	L4	AE7	Oct
I-200	O	L4	AE7	Ph
					I-201	O	L4	AE7	Tol
I-202	O	L4	AE7	DMP
					I-203	O	L4	AE7	MES
I-204	O	L4	AE9	AE9
					I-205	O	L4	AE9	EHx
I-206	O	L4	AE9	Oct
					I-207	O	L4	AE9	Ph
I-208	O	L4	AE9	Tol
					I-209	O	L4	AE9	DMP
I-210	O	L4	AE9	MES
					I-211	O	L4	AE10	AE10
I-212	O	L4	AE10	EHx
					I-213	O	L4	AE10	Oct
I-214	O	L4	AE10	Ph
					I-215	O	L4	AE10	Tol
I-216	O	L4	AE10	DMP
					I-217	O	L4	AE10	MES
I-218	O	L4	AE17	AE17
					I-219	O	L4	AE17	EHx
I-220	O	L4	AE17	Oct
					I-221	O	L4	AE17	Ph
I-222	O	L4	AE17	Tol
					I-223	O	L4	AE17	DMP
I-224	O	L4	AE17	MES

[ TABLE 9]

	X^A	L^A	R^1A	R^2A
					I-225	S	L1	AE2	AE2
I-226	S	L1	AE2	EHx
					I-227	S	L1	AE2	Oct
I-228	S	L1	AE2	Ph
					I-229	S	L1	AE2	Tol
I-230	S	L1	AE2	DMP
					I-231	S	L1	AE2	MES
I-232	S	L1	AE3	AE3
					I-233	S	L1	AE3	EHx
I-234	S	L1	AE3	Oct
					I-235	S	L1	AE3	Ph
I-236	S	L1	AE3	Tol
					I-237	S	L1	AE3	DMP
I-238	S	L1	AE3	MES
					I-239	S	L1	AE4	AE4
I-240	S	L1	AE4	EHx
					I-241	S	L1	AE4	Oct
I-242	S	L1	AE4	Ph
					I-243	S	L1	AE4	Tol
I-244	S	L1	AE4	DMP
					I-245	S	L1	AE4	MES
I-246	S	L1	AE5	AE5
					I-247	S	L1	AE5	EHx
I-248	S	L1	AE5	Oct
					I-249	S	L1	AE5	Ph
I-250	S	L1	AE5	Tol
					I-251	S	L1	AE5	DMP
I-252	S	L1	AE5	MES

[ TABLE 10]

	X^A	L^A	R^1A	R^2A
					I-253	S	L1	AE7	AE7
I-254	S	L1	AE7	EHx
					I-255	S	L1	AE7	Oct
I-256	S	L1	AE7	Ph
					I-257	S	L1	AE7	Tol
I-258	S	L1	AE7	DMP
					I-259	S	L1	AE7	MES
I-260	S	L1	AE9	AE9
					I-261	S	L1	AE9	EHx
I-262	S	L1	AE9	Oct
					I-263	S	L1	AE9	Ph
I-264	S	L1	AE9	Tol
					I-265	S	L1	AE9	DMP
I-266	S	L1	AE9	MES
					I-267	S	L1	AE10	AE10
I-268	S	L1	AE10	EHx
					I-269	S	L1	AE10	Oct
I-270	S	L1	AE10	Ph
					I-271	S	L1	AE10	Tol
I-272	S	L1	AE10	DMP
					I-273	S	L1	AE10	MES
I-274	S	L1	AE17	AE17
					I-275	S	L1	AE17	EHx
I-276	S	L1	AE17	Oct
					I-277	S	L1	AE17	Ph
I-278	S	L1	AE17	Tol
					I-279	S	L1	AE17	DMP
I-280	S	L1	AE17	MES

[ TABLE 11]

	X^A	L^A	R^1A	R^2A
					I-281	S	L2	AE2	AE2
I-282	S	L2	AE2	EHx
					I-283	S	L2	AE2	Oct
I-284	S	L2	AE2	Ph
					1-285	S	L2	AE2	Tol
I-286	S	L2	AE2	DMP
					I-287	S	L2	AE2	MES
I-288	S	L2	AE3	AE3
					I-289	S	L2	AE3	EHx
I-290	S	L2	AE3	Oct
					I-291	S	L2	AE3	Ph
I-292	S	L2	AE3	Tol
					I-293	S	L2	AE3	DMP
I-294	S	L2	AE3	MES
					I-295	S	L2	AE4	AE4
I-296	S	L2	AE4	EHx
					I-297	S	L2	AE4	Oct
I-298	S	L2	AE4	Ph
					I-299	S	I2	AE4	Tol
I-300	S	L2	AE4	DMP
					I-301	S	L2	AE4	MES
I-302	S	L2	AE5	AE5
					I-303	S	L2	AE5	EHx
I-304	S	L2	AE5	Oct
					I-305	S	L2	AE5	Ph
I-306	S	L2	AE5	Tol
					I-307	S	L2	AE5	DMP
I-308	S	L2	AE5	MES

[ TABLE 12 ]

	X^A	L^A	R^1A	R^2A
					I-309	S	L2	AE7	AE7
I-310	S	L2	AE7	EHx
					I-311	S	L2	AE7	Oct
I-312	S	L2	AE7	Ph
					I-313	S	L2	AE7	Tol
I-314	S	L2	AE7	DMP
					I-315	S	L2	AE7	MES
I-316	S	L2	AE9	AE9
					I-317	S	L2	AE9	EHx
I-318	S	L2	AE9	Oct
					I-319	S	L2	AE9	Ph
I-320	S	L2	AE9	TOl
					I-321	S	L2	AE9	DMP
I-322	S	L2	AE9	MES
					I-323	S	L2	AE10	AE10
I-324	S	L2	AE10	EHx
					I-325	S	L2	AE10	Oct
I-326	S	L2	AE10	Ph
					I-327	S	L2	AE10	Tol
I-328	S	L2	AE10	DMP
					I-329	S	L2	AE10	MES
I-330	S	L2	AE17	AE17
					I-331	S	L2	AE17	EHx
I-332	S	L2	AE17	Oct
					I-333	S	L2	AE17	Ph
I-334	S	L2	AE17	Tol
					I-335	S	L2	AE17	DMP
I-336	S	L2	AE17	MES

[ TABLE 13 ]

	X^A	L^A	R^1A	R^2A
					I-337	S	L3	AE2	AE2
I-338	S	L3	AE2	EHx
					I-339	S	L3	AE2	Oct
I-340	S	L3	AE2	Ph
					I-341	S	L3	AE2	Tol
I-342	S	L3	AE2	DMP
					I-343	S	L3	AE2	MES
I-344	S	L3	AE3	AE3
					I-345	S	L3	AE3	EHx
I-346	S	L3	AE3	Oct
					I-347	S	L3	AE3	Ph
I-348	S	L3	AE3	Tol
					I-349	S	L3	AE3	DMP
I-350	S	L3	AE3	MES
					I-351	S	L3	AE4	AE4
I-352	S	L3	AE4	EHx
					I-353	S	L3	AE4	Oct
I-354	S	L3	AE4	Ph
					I-355	S	L3	AE4	Tol
I-356	S	L3	AE4	DMP
					I-357	S	L3	AE4	MES
I-358	S	L3	AE5	AE5
					I-359	S	L3	AE5	EHx
I-360	S	L3	AE5	Oct
					I-361	S	L3	AE5	Ph
I-362	S	L3	AE5	Tol
					I-363	S	L3	AE5	DMP
I-364	S	L3	AE5	MES

[ TABLE 14 ]

	X^A	L^A	R^1A	R^2A
					I-365	S	L3	AE7	AE7
I-366	S	L3	AE7	EHx
					I-367	S	L3	AE7	Oct
I-368	S	L3	AE7	Ph
					I-369	S	L3	AE7	Tol
I-370	S	L3	AE7	DMP
					I-371	S	L3	AE7	MES
I-372	S	L3	AE9	AE9
					I-373	S	L3	AE9	EHx
I-374	S	L3	AE9	Oct
					I-375	S	L3	AE9	Ph
I-376	S	L3	AE9	Tol
					I-377	S	L3	AE9	DMP
I-378	S	L3	AE9	MES
					I-379	S	L3	AE10	AE10
I-380	S	L3	AE10	EHx
					I-381	S	L3	AE10	Oct
I-382	S	L3	AE10	Ph
					I-383	S	L3	AE10	Tol
I-384	S	L3	AE10	DMP
					I-385	S	L3	AE10	MES
I-386	S	L3	AE17	AE17
					I-387	S	L3	AE17	EHx
I-388	S	L3	AE17	Oct
					I-389	S	L3	AE17	Ph
I-390	S	L3	AE17	Tol
					I-391	S	L3	AE17	DMP
I-392	S	L3	AE17	MES

[ TABLE 15 ]

	X^A	L^A	R^1A	R^2A
					I-393	S	L4	AE2	AE2
I-394	S	L4	AE2	EHx
					I-395	S	L4	AE2	Oct
I-396	S	L4	AE2	Ph
					I-397	S	L4	AE2	Tol
I-398	S	L4	AE2	DMP
					I-399	S	L4	AE2	MES
I-400	S	L4	AE3	AE3
					I-401	S	L4	AE3	EHx
I-402	S	L4	AE3	Oct
					I-403	S	L4	AE3	Ph
I-404	S	L4	AE3	Tol
					I-405	S	L4	AE3	DMP
I-406	S	L4	AE3	MES
					I-407	S	L4	AE4	AE4
I-408	S	L4	AE4	EHx
					I-409	S	L4	AE4	Oct
I-410	S	L4	AE4	Ph
					I-411	S	L4	AE4	Tol
I-412	S	L4	AE4	DMP
					I-413	S	L4	AE4	MES
I-414	S	L4	AE5	AE5
					I-415	S	L4	AE5	EHx
I-416	S	L4	AE5	Oct
					I-417	S	L4	AE5	Ph
I-418	S	L4	AE5	Tol
					I-419	S	L4	AE5	DMP
I-420	S	L4	AE5	MES

[ TABLE 16 ]

	X^A	L^A	R^1A	R^2A
					I-421	S	L4	AE7	AE7
I-422	S	L4	AE7	EHx
					I-423	S	L4	AE7	Oct
I-424	S	L4	AE7	Ph
					I-425	S	L4	AE7	Tol
I-426	S	L4	AE7	DMP
					I-427	S	L4	AE7	MES
I-428	S	L4	AE9	AE9
					I-429	S	L4	AE9	EHx
I-430	S	L4	AE9	Oct
					I-431	S	L4	AE9	Ph
I-432	S	L4	AE9	Tol
					I-433	S	L4	AE9	DMP
I-434	S	L4	AE9	MES
					I-435	S	L4	AE10	AE10
I-436	S	L4	AE10	EHx
					I-437	S	L4	AE10	Oct
I-438	S	L4	AE10	Ph
					I-439	S	L4	AE10	Tol
I-440	S	L4	AE10	DMP
					I-441	S	L4	AE10	MES
I-442	S	L4	AE17	AE17
					I-443	S	L4	AE17	EHx
I-444	S	L4	AE17	Oct
					I-445	S	L4	AE17	Ph
I-446	S	L4	AE17	Tol
					I-447	S	L4	AE17	DMP
I-448	S	L4	AE17	MES

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

[ CHEM 17 ]

From the viewpoints of solubility in a solvent and brightness of a color filter formed from the colored curable resin composition, the composition is preferably used

Compounds (I-1) to (I-42),

Compounds (I-57) to (I-98),

Compounds (I-113) to (I-154),

Compounds (I-169) to (I-210),

Compounds (I-225) to (I-266),

Compounds (I-281) to (I-322),

Compounds (I-337) to (I-378), and

compounds (I-393) to (I-434),

more preferably

Compounds (I-1) to (I-42),

Compounds (I-57) to (I-98),

Compounds (I-113) to (I-154),

Compounds (I-169) to (I-210),

Compounds (I-225) to (I-266), and

compounds (I-281) to (I-322),

is particularly preferred

Compounds (I-1) to (I-42)

Compounds (I-57) to (I-98)

Compounds (I-113) to (I-154), and

compound (I-169) to Compound (I-210). Most preferred are compounds (I-1), (I-2), (I-6), (I-8), (I-34), (I-57), (I-58), (I-62), (I-64), (I-90), (I-113), (I-114), (I-118), (I-120), (I-146), (I-169), (I-170), (I-174), (I-176), and (I-202).

The compound (I) can be produced by reacting a compound represented by the formula (IV) (hereinafter, sometimes referred to as a compound (IV)) with a compound represented by the formula (II) (hereinafter, sometimes referred to as a compound (II)) in the presence of a base.

[ CHEM 18 ]

(in the formula, L, X, R¹～R⁵And R⁷～R⁹The same meanings as above, R¹²Represents an alkyl group having 1 to 20 carbon atoms. )

R¹²Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like. Among them, preferred is an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, etc.

Examples of the base include organic bases such as triethylamine and piperidine, and the amount of the base to be used is usually 0.1 to 20 mol based on 1 mol of the compound (IV).

The amount of the compound (II) to be used is preferably 2 to 10 moles, more preferably 2 to 4 moles, based on 1 mole of the compound (IV).

The reaction of the compound (IV) with the compound (II) is usually carried out in the presence of a solvent, and examples of the solvent include nitrile solvents such as acetonitrile; alcohol solvents such as methanol, ethanol, 2-propanol, 1-butanol, 1-pentanol, 1-octanol, and the like; ether solvents such as tetrahydrofuran; ketone solvents such as acetone; ester solvents such as ethyl acetate; aliphatic hydrocarbon solvents such as hexane; aromatic hydrocarbon solvents such as toluene; halogenated hydrocarbon solvents such as methylene chloride and chloroform, and amide solvents such as N, N-dimethylformaldehyde and N-methylpyrrolidone. Preferred are nitrile solvents, alcohol solvents and aromatic hydrocarbon solvents, and more preferred are acetonitrile, methanol and toluene. The amount thereof is usually 1 to 50 parts by mass per 1 part by mass of the compound (IV).

The reaction temperature is usually from 0 ℃ to 200 ℃ and preferably from 0 ℃ to 150 ℃. The reaction time is usually 0.5 to 36 hours.

After the reaction is completed, for example, a solvent in which the compound (I) is hardly soluble is mixed with the obtained reaction mixture and filtered, whereby the compound (I) can be obtained.

The compound (II) is a novel compound, and can be produced by reacting a compound represented by the formula (III) (hereinafter, sometimes referred to as compound (III)) with a formylating agent.

[ CHEM 19 ]

(in the formula, R¹～R⁵The same meanings as described above are given. )

Examples of the formylating agent include phosphorus oxychloride. The amount thereof to be used is usually 1 to 5 moles based on 1 mole of the compound (III).

The reaction of the compound (III) with the formylating agent is usually carried out in the presence of a solvent, and N, N-dimethylformamide is exemplified as the solvent. The amount thereof is usually 1 to 10 parts by mass per 1 part by mass of the compound (III).

The reaction temperature is usually 0 to 100 ℃ and the reaction time is usually 0.5 to 24 hours.

After the reaction is completed, for example, the reaction mixture is mixed with water, neutralized, extracted with a water-insoluble organic solvent such as ethyl acetate, and the resulting organic layer is concentrated to obtain compound (II).

Compound (III) is also a novel compound, which can be produced by reacting a compound represented by formula (VI) (hereinafter sometimes referred to as compound (VI)) with boron tribromide, followed by hydrolysis.

[ CHEM 20 ]

(in the formula, R¹～R⁵Represents the same meaning as described above, R¹²Represents an alkyl group having 1 to 4 carbon atoms. )

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

The amount of boron tribromide to be used is usually 1 to 5 moles per 1 mole of the compound (VI).

The reaction of compound (VI) with boron tribromide is usually carried out in a solvent, and examples of the solvent include halogenated hydrocarbon solvents such as dichloromethane. The amount of the solvent used is usually 1 to 50 parts by mass per 1 part by mass of the compound (VI).

The reaction temperature is usually-78-50 ℃, and the reaction time is usually 1-24 hours.

After the reaction is completed, for example, the reaction mixture and water are mixed, followed by liquid separation, and the obtained organic layer is concentrated to obtain compound (III).

The compound (VI) can be produced, for example, by reacting a compound represented by the formula (VII) (hereinafter, sometimes referred to as the compound (VII)) with a compound represented by the formula (VIII) (hereinafter, sometimes referred to as the compound (VIII)) in the presence of a palladium catalyst and a base. The compound (VI) can also be produced, for example, by reacting a compound represented by the formula (IX) (hereinafter, sometimes referred to as compound (IX)) with a compound represented by the formula (X) (hereinafter, sometimes referred to as compound (X)) in the presence of a base.

[ CHEM 21 ]

(in the formula, R¹～R⁵And R¹²Denotes the same meaning as above, X²And X³Each independently represents a halogen atom, a methanesulfonyloxy group, a toluenesulfonyloxy group or a trifluoromethanesulfonyloxy group. )

X²And X³Examples of the halogen atom include a chlorine atom, a bromine atom and an iodine atom.

The reaction of the compound (VII) and the compound (VIII) can be carried out according to a known method for aminating an aromatic halide (for example, J. org. chem.2003, 68, 1163-1164, etc.). Specifically, the reaction can be carried out by mixing a palladium catalyst such as palladium (II) acetate, a phosphine ligand such as 2, 8, 9-triisopropyl-2, 5, 8, 9-tetraaza-1-phosphabicyclo [3.3.3] undecane, a base such as potassium tert-butoxide, a compound (VII), a compound (VIII), and a solvent such as toluene. The reaction temperature is usually 50 ℃ to 150 ℃, and the reaction time is usually 0.5 to 24 hours. After the reaction is completed, for example, the reaction mixture and water are mixed, an organic layer is separated, and the obtained organic layer is concentrated to obtain compound (VI).

The reaction of the compound (IX) and the compound (X) can be carried out according to a known method for alkylating an amine compound (e.g., J.org.chem.2011, 76, 8015-8021, etc.). Specifically, a base such as triethylamine, sodium hydride, sodium methoxide, potassium hydroxide, sodium hydroxide, or potassium tert-butoxide; compound (IX); a compound (X); and a solvent such as dimethyl sulfoxide, to carry out the reaction. The reaction temperature is usually 0-100 ℃, and the reaction time is usually 0.5-72 hours. After the reaction is completed, for example, the compound (VI) can be obtained by mixing the reaction mixture with water, if necessary, mixing a water-insoluble organic solvent with water, separating an organic layer, and concentrating the obtained organic layer.

The compound (IV) is a novel compound, and can be produced by reacting a compound represented by the formula (XI) (hereinafter, sometimes referred to as a compound (XI)) with a compound represented by the formula (XII) (hereinafter, sometimes referred to as a compound (XII)) in a solvent.

[ CHEM 22 ]

(in the formula, R⁷～R⁹、R¹¹L and X are as defined above, and R is¹³Represents an alkyl group having 1 to 4 carbon atoms. )

R¹³Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, a propyl group and a butyl group.

The amount of the compound (XII) to be used is preferably 2 to 5 moles, more preferably 2 to 3 moles, based on 1 mole of the compound (XI).

The solvent may be an alcohol solvent such as methanol, and the amount thereof to be used is usually 1 to 100 parts by mass per 1 part by mass of the compound (XI).

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

After the reaction is completed, for example, the reaction mixture may be mixed with water or methanol and then filtered, if necessary, to obtain compound (IV).

The compound (XII) can be produced by a known method such as the method described in j.med.chem.2012, 55, 3398-.

< coloring agent of the present invention >

The colorant of the present invention (hereinafter sometimes referred to as "colorant (a)") contains compound (I) as an active ingredient. The colorant (a) may be composed of only the compound (I), or may contain a dye and/or a pigment other than the compound (I). The colorant (a) preferably contains a pigment in addition to the compound (I). When the compound (I) is used alone, the content of the compound (I) in the colorant (A) is usually 1 to 100% by mass, preferably 3 to 100% by mass, and when the compound (I) and other dyes and/or pigments are used in combination, the content of the compound (I) in the colorant (A) is usually 3 to 70% by mass, preferably 3 to 60% by mass.

The colorant (a) is useful as a coloring agent contained in a colored curable resin composition used for a color filter of a device such as a liquid crystal display device.

Dyes other than compound (I) include: compounds classified under The color Index (color Index) (published by The Society of Dyers and colorists) as Solvent (Solvent), acid (acid), Basic (Basic), reactive (reactive), Direct (Direct), Disperse (Disperse), or reducing (Vat) and/or known dyes described in The handbook of dyeing (dyeing ノ - ト) (color dyes, Inc.). Specific examples of the chemical structure include azo dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, and phthalocyanine dyes. These dyes may be used alone or in combination of 2 or more.

More specifically, the following dyes of color index (c.i.) can be cited. C.i. solvent yellow 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

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

c.i. reactive yellow 2, 76, 116;

c.i. direct yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;

c.i. disperse yellow 51, 54, 76;

c.i. solvent orange 2, 7, 11, 15, 26, 41, 54, 56, 99;

c.i. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173;

c.i. reactive orange 16;

c.i. direct orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

c.i. solvent red 24, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;

c.i. acid red 73, 80, 91, 92, 97, 138, 151, 211, 274, 289;

c.i. acid violet 34, 102;

c.i. disperse violet 26, 27;

c.i. solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

c.i. solvent blue 14, 18, 35, 36, 45, 58, 59: 1. 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;

c.i. acid blue 25, 27, 40, 45, 78, 80, 112;

c.i. direct blue 40;

c.i. disperse blue 1, 14, 56, 60;

c.i. solvent green 1, 3, 5, 28, 29, 32, 33;

c.i. acid green 3, 5, 9, 25, 27, 28, 41;

c.i. alkaline green 1;

c.i. vat green 1, etc.

As The pigment, there can be mentioned known pigments such as pigments classified as pigments (pigments) in The color index (published by The Society of Dyers and Colourists), and they may be used alone or in combination of 2 or more.

Specifically, there may be mentioned yellow pigments such as c.i. pigment yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 194, 214;

orange pigments such as c.i. pigment orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;

red pigments such as c.i. pigment red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;

c.i. pigment blue 15, 15: 3. 15: 4. 15: 6. 60, etc. blue pigments;

c.i. pigment violet 1, 19, 23, 29, 32, 36, 38 and the like violet pigment;

green pigments such as c.i. pigment green 7, 36, 58, 59;

c.i. brown pigments such as pigment brown 23, 25; and

c.i. pigment black 1, 7 and the like.

Among the green pigment, the blue pigment and the yellow pigment, a phthalocyanine pigment is preferable, at least one selected from the group consisting of a copper halide phthalocyanine pigment and a zinc halide phthalocyanine pigment is more preferable, and at least one selected from the group consisting of c.i. pigment green 7, 36, 58 and 59 is particularly preferable. These pigments are suitable for use as green colorants, and by using colorants containing these pigments, the transmission spectrum can be easily optimized, and color filters having good light resistance and/or chemical resistance can be formed.

The pigment may also be treated as follows: rosin treatment, surface treatment using a pigment derivative or the like into which an acidic group or a basic group has been introduced, grafting treatment on the pigment surface with a polymer compound or the like, microparticulation treatment with a sulfuric acid microparticulation method or the like, washing treatment with an organic solvent and/or water or the like for removing impurities, removal treatment of ionic impurities with an ion exchange method or the like, and the like. The particle size of the pigment is preferably substantially uniform. By adding the pigment dispersant to the pigment and performing the dispersion treatment, a pigment dispersion liquid in a state of being uniformly dispersed in the pigment dispersant solution can be formed. The pigments may be dispersed individually or in combination.

Examples of the pigment dispersant include surfactants, and any of cationic, anionic, nonionic and amphoteric surfactants may be used. Specifically, the surfactant may be a polyester-based, polyamine-based, or acrylic surfactant. These pigment dispersants may be used alone or in combination of 2 or more. Examples of the pigment dispersant include those sold under the trade name KP (manufactured by shin-Etsu chemical Co., Ltd.), FLORENE (フ)ロ - レン (manufactured by Kyoeisha chemical Co., Ltd.), SOLSPERSE (ソルスパ - ス) (registered trademark) (manufactured by JIELIKANG corporation (ゼネカ Co.), EFKA (registered trademark) (manufactured by BASF corporation), AJISPER (ァジスパ) (manufactured by WEIYOUJINGZHIJI corporation (WEIKOKAI, KOKAI

ファィンテクノ (manufactured by Kagaku corporation)), Disperbyk (manufactured by BYK corporation (ビックケミ Co., Ltd.), and the like.

When a pigment dispersant is used, 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, per 100 parts by mass of the pigment. When the amount of the pigment dispersant used is within the above range, a pigment dispersion liquid in a more uniformly dispersed state tends to be obtained.

< colored curable resin composition of the present invention >

The colored curable resin composition of the present invention contains a colorant (a), a resin (hereinafter, sometimes referred to as "resin (B)"), a polymerizable compound (hereinafter, sometimes referred to as "polymerizable compound (C)"), a polymerization initiator (hereinafter, sometimes referred to as "polymerization initiator (D)") and a solvent (hereinafter, sometimes referred to as "solvent (E)"). In addition to these components, the colored curable resin composition of the present invention may contain a leveling agent. In addition to these components, the colored curable resin composition of the present invention may contain a polymerization initiation aid.

The content of the colorant (a) in the colored curable resin composition is usually 1 mass% or more and 70 mass% or less, preferably 1 mass% or more and 60 mass% or less, more preferably 5 mass% or more and 60 mass% or less, and particularly preferably 5 mass% or more and 50 mass% or less, based on the total amount of solids. When the content of the colorant (A) is within the above range, a desired spectral and/or color density can be more easily obtained. The "total amount of solids" in the present specification means the total amount of components excluding the solvent in the colored curable resin composition of the present invention. The total amount of solids and the contents of the respective components relative thereto can be measured by a known analytical method such as liquid chromatography or gas chromatography.

< resin (B) >

The resin (B) contained in the colored curable resin composition of the present invention is preferably an alkali-soluble resin, and more preferably an addition polymer having at least one structural unit derived from a group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. Examples of such resins include the following resins [ K1] to [ K6 ].

Resin [ K1 ]: a copolymer of at least one (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides and a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond.

Resin [ K2 ]: (a) and (b) and a monomer (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter, may be referred to as "(c)").

Resin [ K3 ]: (a) and (c) a copolymer.

Resin [ K4 ]: a resin obtained by reacting a copolymer of (a) and (c) with (b)

Resin [ K5 ]: a resin obtained by reacting a copolymer of (b) and (c) with (a)

Resin [ K6 ]: a resin obtained by reacting a copolymer of (b) and (c) with (a) and further with a carboxylic acid anhydride.

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

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

bicyclic unsaturated compounds having a carboxyl group such as methyl-5-norbornene-2, 3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-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] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;

unsaturated dicarboxylic acid anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3, 4, 5, 6-tetrahydrophthalic anhydride, 1, 2, 3, 6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5, 6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;

unsaturated mono [ (meth) acryloyloxyalkyl ] esters of 2-or more-membered polycarboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl ] ester and phthalic acid mono [2- (meth) acryloyloxyethyl ] ester;

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

Among them, acrylic acid, methacrylic acid and maleic anhydride are preferable from the viewpoint of copolymerization reactivity and solubility of the obtained resin in an aqueous alkali solution.

(b) The polymerizable compound has a cyclic ether structure having 2 to 4 carbon atoms (e.g., an oxirane ring, an oxetane ring, a tetrahydrofuran ring, etc.) and an ethylenically unsaturated bond. (b) Preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth) acryloyloxy group. In the present specification, "(meth) acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid, and "(meth) acryloyl group" and "(meth) acrylate" also have the same meaning.

(b) There may be mentioned a monomer (b1) having an oxirane group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b 1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b 2)"), and a monomer (b3) having a tetrahydrofuranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b 3)").

(b1) Examples thereof include a monomer (b1-1) containing an epoxidized structure of a linear or branched aliphatic unsaturated hydrocarbon (hereinafter sometimes referred to as "(b 1-1)") and a monomer (b1-2) containing an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter sometimes referred to as "(b 1-2)").

(b1-1) preferred is a monomer having a glycidyl group and an ethylenically unsaturated bond. Specific examples of (b1-1) include glycidyl (meth) acrylate, β -methylglycidyl (meth) acrylate, β -ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α -methyl-o-vinylbenzyl glycidyl ether, α -methyl-m-vinylbenzyl glycidyl ether, α -methyl-p-vinylbenzyl glycidyl ether, 2, 3-bis (glycidoxymethyl) styrene, 2, 4-bis (glycidoxymethyl) styrene, 2, 5-bis (glycidoxymethyl) styrene, 2, 6-bis (glycidoxymethyl) styrene, 2, 3, 4-tris (glycidoxymethyl) styrene, 2, 3, 5-tris (glycidoxymethyl) styrene, 2, 3, 6-tris (glycidoxymethyl) styrene, 3, 4, 5-tris (glycidoxymethyl) styrene and 2, 4, 6-tris (glycidoxymethyl) styrene.

Examples of (b1-2) include vinylcyclohexene monooxide, 1, 2-epoxy-4-vinylcyclohexane (for example, CELLOXIDE (セロキサィド) (registered trademark) 2000, manufactured by Daicel corporation ((LTD. ダィセル)), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER (サィクロマ one) A400, manufactured by Daicel corporation), (3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, CYCLOMER 100, manufactured by Daicel corporation)), a compound represented by formula (1), and a compound represented by formula (2).

[ CHEM 23 ]

(in the formula, R^aAnd R^bEach independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxyl group. X^aAnd X^bEach independently represents a single bond, or-R^c-、＊-R^c-O-、＊-R^c-S-or-R^c-NH-。R^cRepresents an alkylene group having 1 to 6 carbon atoms. A medicated pillowIndicates the bonding position to O. )

R^a、R^bExamples of the alkyl group having 1 to 4 carbon atoms include: methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl. R^a、R^bExamples 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, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group and a 4-hydroxybutyl group.

R^aAnd R^bIndependently of each other, a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 14 carbon atoms is preferable, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferable, a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group is more preferable, and a hydrogen atom or a methyl group is more preferable.

R^cThe alkylene group having 1 to 6 carbon atoms includes a linear or branched alkylene group, and specific examples thereof include a linear alkylene group of a methylene group, an ethylene group, a propane-1, 3-diyl group, a butane-1, 4-diyl group, a pentane-1, 5-diyl group, and a hexane-1, 6-diyl group; a branched alkylene group such as propane-1, 2-diyl.

X^aAnd X^bIndependently of one another, preferably a single bond, or^c-, or-R^c-O-, more preferably a single bond or-R^c-O-is particularly preferably a single bond, methylene, ethylene, or onium-CH₂-O-or O-CH₂CH₂-O-, more preferably a single bond or O-CH₂CH₂-O-. In the above formula, it represents a position bonded to O.

The compound represented by the formula (1) includes compounds represented by the formulae (1-1) to (1-15), and among them, compounds represented by the formulae (1-1), (1-3), (1-5), (1-7), (1-9) and (1-11) to (1-15) are preferable, and compounds represented by the formulae (1-1), (1-7), (1-9) and (1-15) are more preferable.

[ CHEM 24 ]

[ CHEM 25 ]

[ CHEM 26 ]

[ CHEM 27 ]

[ CHEM 28 ]

[ CHEM 29 ]

[ CHEM 30 ]

[ CHEM 31 ]

The compound represented by the formula (2) includes compounds represented by the formulae (2-1) to (2-15), among which compounds represented by the formulae (2-1), (2-3), (2-5), (2-7), (2-9) and (2-11) to (2-15) are preferable, and compounds represented by the formulae (2-1), (2-7), (2-9) and (2-15) are more preferable.

[ CHEM 32 ]

[ CHEM 33 ]

[ CHEM 34 ]

[ CHEM 35 ]

[ CHEM 36 ]

[ CHEM 37 ]

[ CHEM 38 ]

[ CHEM 39 ]

The compound represented by the formula (1) and the compound represented by the formula (2) may be used alone or in combination. When these compounds are used in combination, the ratio of the compound represented by the formula (1) to the compound represented by the formula (2) (the compound represented by the formula (1): the compound represented by the formula (2)) is preferably 5: 95 to 95: 5, more preferably 10: 90 to 90: 10, further preferably 20: 80 to 80: 20, further more preferably 30: 70 to 70: 30, and particularly preferably 40: 60 to 60: 40 on a molar basis.

(b2) Monomers having an oxetanyl group and a (meth) acryloyloxy group are more preferable. (b2) Mention may be made of 3-methyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyleneoxetane, 3-ethyl-3-methacryloyloxyethyloxetane and 3-ethyl-3-acryloyloxyethyleneoxetane.

(b3) Monomers having a tetrahydrofuranyl group and a (meth) acryloyloxy group are more preferable. (b3) Tetrahydrofurfuryl acrylate (e.g., VISCOAT (ビスコ - ト) V #150, manufactured by Osaka organic chemical industries, Ltd.), and tetrahydrofurfuryl methacrylate are exemplified.

From the viewpoint of higher reliability of the obtained color filter, such as heat resistance and chemical resistance, (b) is preferably (b1), and from the viewpoint of excellent storage stability of the colored curable resin composition, (b1) is preferably (b 1-2).

(c) Examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearate (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ] meth) acrylate^2，6]Decyl-8-yl ester (commonly known in the art as "(meth) acrylate dicyclopentyl ester". In addition, tricyclodecyl (meth) acrylate ".)^2，6]Decyl-8-yl ester (commonly known in the art as "dicyclopentenyl (meth) acrylate"), (meth) acrylic acid esters such as dicyclopentenyl (meth) acrylate, (meth) acrylic acid dicyclopentenyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, and benzyl (meth) acrylate;

hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;

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

bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2 '-hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5, 6-dihydroxybicyclo [2.2.1] hept-2-ene, 5, 6-bis (hydroxymethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-bis (2' -hydroxyethyl) bicyclo [2.2.1] hept-2-ene, 5, 6-dimethoxybicyclo [2.2.1] hept-2-ene, 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, bicyclic unsaturated compounds such as 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonybicyclo [2.2.1] hept-2-ene, 5-phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5, 6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene and 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene;

dicarbonylimide compounds such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate and N- (9-acridinyl) maleimide;

vinyl group-containing aromatic compounds such as styrene, α -methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as acrylonitrile and methacrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-containing amides such as acrylamide and methacrylamide; esters such as vinyl acetate; dienes such as 1, 3-butadiene, isoprene, and 2, 3-dimethyl-1, 3-butadiene; and the like.

Among them, vinyl group-containing aromatic compounds, dicarbonyl imide compounds, and bicyclic unsaturated compounds are preferable from the viewpoint of copolymerization reactivity and heat resistance. Particularly preferred are styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ] meth (acrylic acid)^2，6]Decyl-8-yl esters, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2.1]]Hept-2-ene.

In the resin [ K1], the ratio of the structural units derived from each resin [ K1] to the total structural units constituting the resin [ K1],

preference is given to

Structural unit derived from (a): 2 to 60 mol%

Structural units derived from (b): 40 to 98 mol percent,

more preferably

Structural unit derived from (a): 10 to 50 mol%

Structural units derived from (b): 50 to 90 mol%.

If the proportion of the structural unit of the resin [ K1] is within the above range, the colored curable resin composition tends to be excellent in storage stability, developability upon formation of a colored pattern, and solvent resistance of the resulting color filter.

The resin [ K1] can be produced, for example, by a method described in "Experimental protocols for Polymer Synthesis" (Experimental protocols for Polymer Synthesis) (published in 1972, 3 and 1 of 1972, 1 of the same chemical company, Inc., of the institute of Otsumadai), and by citations described in this document.

Specifically, the following methods are exemplified: the reaction vessel is charged with predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like, and the oxygen is replaced with nitrogen gas, for example, to keep the temperature by heating while stirring in a deoxygenated atmosphere. The polymerization initiator and the solvent used herein are not particularly limited, and those generally used in the art can be used. Examples of the polymerization initiator include azo compounds (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), and the like) and organic peroxides (e.g., benzoyl peroxide), and examples of the solvent include solvents that can dissolve the respective monomers, and solvents for the colored curable resin composition of the present invention described later.

The copolymer obtained may be used as it is as a solution after the reaction, may be used as a concentrated or diluted solution, or may be used as a solid (powder) obtained by a method such as reprecipitation. In particular, in the polymerization, by using the solvent contained in the colored curable resin composition of the present invention as a solvent, the solution after the reaction can be directly used for the preparation of the colored curable resin composition of the present invention, and therefore, the production process of the colored curable resin composition of the present invention can be simplified.

In the resin [ K21, the ratio of the structural units derived from each resin [ K21 ] is such that, with respect to the total structural units constituting the resin [ K2],

preference is given to

Structural unit derived from (a): 2 to 45 mol%

Structural units derived from (b): 2 to 95 mol%

Structural units derived from (c): 1 to 65 mol% of a surfactant,

more preferably

Structural unit derived from (a): 5 to 40 mol%

Structural units derived from (b): 5 to 80 mol%

Structural units derived from (c): 5 to 60 mol%.

When the proportion of the structural unit of the resin [ K2] is within the above range, the colored curable resin composition tends to be more excellent in storage stability, developability in forming a colored pattern, and solvent resistance, heat resistance, and mechanical strength of the resulting color filter.

The resin [ K2] can be produced, for example, by the same method as the method for producing the resin [ K1 ].

In the resin [ K3], the ratio of the structural units derived from each resin [ K3] to the total structural units constituting the resin [ K3],

preference is given to

Structural unit derived from (a): 2 to 60 mol%

Structural units derived from (c): 40 to 98 mol percent,

more preferably

Structural unit derived from (a): 10 to 50 mol%

Structural units derived from (c): 50 to 90 mol%.

The resin [ K3] can be produced, for example, by the same method as the method for producing the resin [ K1 ].

The resin [ K4] can be produced by obtaining a copolymer of (a) and (c) and adding a cyclic ether moiety having 2 to 4 carbon atoms of (b) to a carboxylic acid and/or a carboxylic acid anhydride contained in (a). Specifically, the production can be performed as follows. First, the copolymers (a) and (c) were produced in the same manner as described for the production of resin [ K1 ]. In this case, the ratio of the structural units derived from each of the sources is preferably the same as the ratio of the substances listed in the resin [ K3 ]. Then, a part of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer is reacted with (b) a cyclic ether compound having 2 to 4 carbon atoms. The copolymer of (a) and (c) is continuously produced by replacing nitrogen in the flask with air, and placing (b), a catalyst for the reaction of a carboxylic acid or a carboxylic anhydride with a cyclic ether compound (e.g., tris (dimethylaminomethyl) phenol) and a polymerization inhibitor (e.g., hydroquinone) in the flask, and reacting them at 60 to 130 ℃ for 1 to 10 hours to obtain a resin [ K4 ].

The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, based on 100 moles of (a). The colored curable resin composition containing a resin obtained by adjusting the amount of (b) to the above range tends to have a better balance among storage stability, developability in forming a pattern, and solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained pattern. From the viewpoint of high reactivity of the cyclic ether site and difficulty in leaving unreacted (b), the use of (b) in the resin [ K4] is preferably (b1), more preferably (b 1-1).

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

The method of adding each reagent, the reaction conditions such as reaction temperature and reaction time, and the like may be appropriately adjusted in consideration of the amount of heat generated by the production equipment or polymerization. In addition, similarly to the polymerization conditions, the method of addition and the reaction temperature may be appropriately adjusted in consideration of the production facilities, the amount of heat generation due to polymerization, and the like.

In the first step, a copolymer of (b) and (c) was obtained in the same manner as in the above-mentioned method for producing the resin [ K1] in the production of the resin [ K5 ]. The copolymer obtained may be used as it is as a solution after the reaction, or may be used as a concentrated or diluted solution, or may be obtained as a solid (powder) by a method such as reprecipitation. In the first stage, the proportions of the structural units derived from (b) and (c) are such that the structural units are present in the respective proportions relative to the total molar number of all the structural units constituting the copolymer of (b) and (c)

Preference is given to

Structural units derived from (b): 5 to 95 mol%

Structural units derived from (c): 5 to 95 mol% of a surfactant,

more preferably

Structural units derived from (b): 10 to 90 mol%

Structural units derived from (c): 10 to 90 mol%.

Further, in the second stage, the carboxylic acid or carboxylic anhydride of (a) is reacted with the cyclic ether site derived from (b) which is contained in the copolymer of (b) and (c) under the same conditions as in the production process of the resin [ K4], thereby obtaining a resin [ K5 ].

In the second stage, the amount of (a) to be reacted with the copolymer of (b) and (c) is preferably 5 to 80 moles based on 100 moles of (b). From the viewpoint of high reactivity of the cyclic ether site and difficulty in leaving unreacted (b), the (b) used in the resin [ K5] is preferably (b1), and more preferably (b 1-1).

The resin [ K6] is a resin obtained by further reacting the resin [ K5] with a carboxylic anhydride, and specifically can be produced by reacting a hydroxyl group generated by the reaction of the cyclic ether site derived from (b) with the carboxylic acid or the carboxylic anhydride of (a) with a carboxylic anhydride.

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

Examples of the resin (B) include resins [ K1] such as a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, a 3, 4-epoxytricyclo [5.2.1.02, 6] decyl (meth) acrylate/(meth) acrylic acid copolymer; resins [ K2] such as glycidyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, 3, 4-epoxytricyclo [5.2.1.02, 6] decyl (meth) acrylate/(meth) acrylic acid/N-cyclohexylmaleimide copolymer, 3, 4-epoxytricyclo [52.1.02, 6] decyl (meth) acrylate/vinyltoluene copolymer, and 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer; resins such as benzyl (meth) acrylate/(meth) acrylic acid copolymers, styrene/(meth) acrylic acid copolymers, benzyl (meth) acrylate/(tricyclodecanyl (meth) acrylate/(meth) acrylic acid copolymers [ K3 ]; resins obtained by adding glycidyl (meth) acrylate to benzyl (meth) acrylate/(meth) acrylic acid copolymer, resins obtained by adding glycidyl (meth) acrylate to tricyclodecanyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, and resins obtained by adding glycidyl (meth) acrylate to tricyclodecanyl (meth) acrylate/(benzyl (meth) acrylic acid copolymer [ K4 ]; resins such as resins obtained by reacting (meth) acrylic acid with a tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate) copolymer and resins obtained by reacting (meth) acrylic acid with a tricyclodecyl (meth) acrylate/styrene/(glycidyl (meth) acrylate) copolymer [ K5 ]; resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecanyl (meth) acrylate/(glycidyl (meth) acrylate), and resins obtained by further reacting tetrahydrophthalic anhydride [ K6 ].

The resin (B) is preferably one selected from the group consisting of resin [ K1], resin [ K2] and resin [ K3], and more preferably one selected from the group consisting of resin [ K1] and resin [ K2 ]. These resins provide a colored curable resin composition having excellent developability. From the viewpoint of the adhesion between the colored pattern and the substrate, resin [ K1] is more preferable.

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

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

The acid value of the resin (B) is preferably 20 to 170mg-KOH/g, more preferably 30 to 170mg-KOH/g, particularly preferably 40 to 170mg-KOH/g, more preferably 150mg-KOH/g or less, and further preferably 135mg-KOH/g or less, in terms of solid content or solution acid value. The acid value is a measured value of the amount (mg) of potassium hydroxide required for neutralizing 1g of the resin (B), and can be obtained by, for example, titration with an aqueous solution of potassium hydroxide.

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 most preferably 17 to 55% by mass, based on the total amount of solid components. When the content of the resin (B) is within the above range, the formation of a colored pattern is facilitated, and the resolution and residual film ratio of the colored pattern tend to be improved.

< polymerizable Compound (C) >

The polymerizable compound (C) is a compound polymerizable by an active radical and/or an acid generated by a polymerization initiator, and examples thereof include polymerizable compounds having an ethylenically unsaturated bond, and preferably compounds having a (meth) acrylate structure. The polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds, and more preferably a polymerizable compound having 5 to 6 or more ethylenically unsaturated bonds.

Examples of the polymerizable compound having 1 ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-mentioned (a), (b) and (c). Examples of the polymerizable compound having 2 ethylenically unsaturated bonds include 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di (meth) acrylate. Polymerizable compounds having 3 or more ethylenically unsaturated bonds include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, pentaerythritol hexa (meth) acrylate, and the like, Caprolactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate.

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

The content of the polymerizable compound (C) in the colored curable resin composition of the present invention is usually 5 to 65% by mass, 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 solid components. The content ratio of the resin (B) to the polymerizable compound (C) (the resin (B): the polymerizable compound (C)) is usually 20: 80 to 80: 20, preferably 35: 65 to 80: 20 on the mass basis. When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming a 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/or heat to initiate polymerization, and a known polymerization initiator can be used.

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

The O-acyloxime compound is a compound having a structure represented by formula (d 1). The following symbol denotes a bonding position.

[ CHEM 40 ]

As the O-acyloxime compound, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -1-butanone-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -1-octanone-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentyl-1-propanone-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- { 2-methyl-4- (3, 3-dimethyl-2, 4-dioxocyclopentylmethoxy) benzoyl } -9H-carbazol-3-yl ] ethane-1-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-imine and N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentyl-1-propanon-2-imine. Commercially available products such as IRGACURE (イルガキュア) (registered trademark), OXE01, OXE02 (manufactured by BASF corporation, supra), and N-1919 (manufactured by ADEKA corporation) can be used. Particularly preferred is at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylthiophenyl) -1-butanone-2-imine, N-benzoyloxy-1- (4-phenylthiophenyl) -1-octanone-2-imine, and N-benzoyloxy-1- (4-phenylthiophenyl) -3-cyclopentyl 1-propanone-2-imine, and more preferred is N-benzoyloxy-1- (4-phenylthiophenyl) -1-octanone-2-imine.

The alkylphenone compound has a structure represented by the formula (d2) or a structure represented by the formula (d 3). In addition, the benzene ring in these structures may have a substituent.

[ CHEM 41 ]

Examples of the compound having the structure represented by formula (d2) include 2-methyl-2-morpholino-1- (4-methylthiophenyl) -1-propanone, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzyl-1-butanone, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholino) phenyl ] -1-butanone. Commercially available products such as IRGACURE369, 907, and 379 (manufactured by BASF) can be used.

Examples of the compound having the structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] -1-propanone, 1-hydroxycyclohexylphenylketone, oligomers of 2-hydroxy-2-methyl-1- [ 4-isopropenylphenyl ] -1-propanone, α -diethoxyacetophenone, and benzyldimethyl ketal.

From the viewpoint of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by the formula (d 2).

Examples of the triazine compounds include 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6-piperonyl-1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [ 4-methoxystyryl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (furan-2-yl) vinyl ] -1, 3, 5-triazine, 2, 4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) vinyl ] -1, 3, 5-triazine and 2, 4-bis (trichloromethyl) -6- [2- (3, 4-dimethoxyphenyl) vinyl ] -1, 3, 5-triazine.

As the acylphosphine oxide, 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide is exemplified.

Examples of the bisimidazole compound include compounds represented by the formula (d 4).

[ CHEM 42 ]

(in the formula, R⁵¹～R⁵⁶Represents 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 tolyl group, a xylyl group, an ethylphenyl group and a naphthyl group, with a phenyl group being preferred. Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom is preferable. 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 preferable.

Specific examples of the biimidazole compound include 2, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole, 2 ' -bis (2, 3-dichlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole (see, for example, Japanese patent application laid-open No. 6-75372, Japanese patent application laid-open No. 6-75373, etc.), 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetraphenylbiimidazole, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (alkoxyphenyl) biimidazole, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (dialkoxyphenyl) biimidazole, 2, 2 ' -bis (2-chlorophenyl) -4, 4 ', 5, 5 ' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, Japanese patent publication No. Sho 48-38403 and Japanese patent application laid-open No. Sho 62-174204), and imidazole compounds in which the phenyl group at the 4, 4 ', 5, 5 ' -position is substituted with an alkoxycarbonyl group (see, for example, Japanese patent application laid-open No. Hei 07-010913). Among them, compounds represented by the following formula and mixtures thereof are preferable.

[ CHEM 43 ]

Examples of the other polymerization initiator include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenylsulfide, 3 ', 4, 4 ' -tetrakis (t-butylperoxycarbonyl) benzophenone, and 2, 4, 6-trimethylbenzophenone; quinone compounds such as 9, 10-phenanthrenequinone, 2-ethylanthraquinone, camphorquinone, etc.; 10-butyl-2-chloroacridone, benzil, methyl phenylacetate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiation aid (particularly, an amine-based polymerization initiation aid) described later.

Examples of the polymerization initiator generating an acid include: onium salts such as 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate and diphenyliodonium hexafluoroantimonate, nitrobenzyltoluenesulfonate and benzoin toluenesulfonate.

The polymerization initiator (D) is preferably a polymerization initiator that generates active radicals, more preferably contains at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide, an O-acyloxime compound, and a bisimidazole compound, and further preferably contains an O-acyloxime compound.

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

< polymerization initiation aid >

The polymerization initiation aid is a compound used for promoting the polymerization of the polymerizable compound (C) whose polymerization is initiated by the polymerization initiator (D), or a sensitizer. When the colored curable resin composition of the present invention contains a polymerization initiator aid, it is usually used in combination with the polymerization initiator (D).

Examples of the polymerization initiator include amine-based polymerization initiators, alkoxy anthracene-based polymerization initiators, thioxanthone-based polymerization initiators, and carboxylic acid-based polymerization initiators.

Examples of the amine-based polymerization initiation aid include alkanolamines such as triethanolamine, methyldiethanolamine, triisopropanolamine; aminobenzoic acid esters such as methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate and 2-ethylhexyl 4-dimethylaminobenzoate; n, N-dimethyl-p-toluidine, 4 ' -bis (dimethylamino) benzophenone (known as michler's ketone), 4 ' -bis (diethylamino) benzophenone, and 4, 4 ' -bis (ethylmethylamino) benzophenone, and among them, alkylamino benzophenones such as 4, 4 ' -bis (diethylamino) benzophenone are preferable. Among them, alkylaminobenzophenones are preferred, and 4, 4' -bis (diethylamino) benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Baotu chemical industries, Ltd.) can be used.

Examples of the alkoxy anthracene-based polymerization initiator include 9, 10-dimethoxyanthracene, 2-ethyl-9, 10-dimethoxyanthracene, 9, 10-diethoxyanthracene, 2-ethyl-9, 10-diethoxyanthracene, 9, 10-dibutoxyanthracene, and 2-ethyl-9, 10-dibutoxyanthracene.

Examples of the thioxanthone-based polymerization initiator aid include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2, 4-diethylthioxanthone, 2, 4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Examples of the carboxylic acid-based polymerization initiator include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthyloxyacetic acid.

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

In the present invention, the compound having a mercapto group (-SH) in the molecule may contain a thiol compound.

Examples of the compound having 1 mercapto group in the molecule include 2-mercaptooxazole, 2-mercaptothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptonicotinic acid, 2-mercaptopyridine, 2-mercapto-3-pyridinol, 2-mercaptopyridine-N-oxide, 4-amino-6-hydroxy-2-mercaptopyrimidine, 4-amino-2-mercaptopyrimidine, 6-amino-5-nitroso-2-thiouracil, 4, 5-diamino-6-hydroxy-2-mercaptopyrimidine, 4, 6-diamino-2-mercaptopyrimidine, 2-mercaptopyridine, 2-amino-2-, 2, 4-diamino-6-mercaptopyrimidine, 4, 6-dihydroxy-2-mercaptopyrimidine, 4, 6-dimethyl-2-mercaptopyrimidine, 4-hydroxy-2-mercapto-6-methylpyrimidine, 4-hydroxy-2-mercapto-6-propylpyrimidine, 2-mercapto-4-methylpyrimidine, 2-mercaptopyrimidine, 2-thiouracil, 3, 4, 5, 6-tetrahydropyrimidine-2-thiol, 4, 5-diphenylimidazole-2-thiol, 2-mercaptoimidazole, 2-mercapto-1-methylimidazole, 4-amino-3-hydrazino-5-mercapto-1, 2, 4-triazole, 3-amino-5-mercapto-1, 2, 4-triazole, 2-methyl-4H-1, 2, 4-triazole-3-thiol, 4-methyl-4H-1, 2, 4-triazole-3-thiol, 3-mercapto-1H-1, 2, 4-triazole-3-thiol, 2-amino-5-mercapto-1, 3, 4-thiazole, 5-amino-1, 3, 4-thiazole-2-thiol, 2, 5-dimercapto-1, 3, 4-thiazole, (furan-2-yl) methanethiol, 2-mercapto-5-thiazolidinone, 2-mercaptothiazoline, and mixtures thereof, 2-mercapto-4 (3H) -quinazoline, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-mercapto-5-methylbenzimidazole, 2-mercapto-5-nitrobenzimidazole, 6-amino-2-mercaptobenzothiazole, 5-chloro-2-mercaptobenzothiazole, 6-ethoxy-2-mercaptobenzothiazole, 6-nitro-2-mercaptobenzothiazole, 2-mercaptonaphthylimidazole, 2-mercaptonaphthyloxazole, 3-mercapto-1, 2, 4-triazole, 4-amino-6-mercaptopyrazolo [2, 4-d ] pyridine, 2-amino-6-purine thiol, 1-phenyl-1H-tetrazole, 2-quinoline thiol, 2-mercapto-5-methylbenzimidazole, 2-mercapto-nitro-2-mercaptobenzothiazole, 2-mercaptonaphthylimidazole, 2-mercaptooxazole, 3-mercapto-1, 2, 4-triazole, 6-mercaptopurine, 4-mercapto-1H-pyrazolo [2, 4-d ] pyrimidine, and the like.

Examples of the compound having 2 or more mercapto groups in the molecule include hexanedithiol, decanedithiol, 1, 4-bis (methylthio) benzene, butanediol bis (3-mercaptopropionate), butanediol bis (3-mercaptoacetate), ethylene glycol bis (3-mercaptoacetate), trimethylolpropane tris (3-mercaptoacetate), butanediol bis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptoacetate), trimethylol tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate), and 1, 4-bis (3-mercaptobutoxy) butane.

The thiol compound is preferably a compound having 1 mercapto group in the molecule.

The content of the thiol compound is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the polymerization initiator (D). When the content of the thiol compound is within this range, the sensitivity tends to be high and the developability tends to be good.

< solvent (E) >

The solvent (E) is not limited, and solvents generally used in the art may be used alone or in combination of 2 or more. Specific examples thereof include ester solvents (solvents containing-COO-and not containing-O-in the molecule), ether solvents (solvents containing-O-and not containing-COO-in the molecule), ether ester solvents (solvents containing-COO-and not containing-O-in the molecule), ketone solvents (solvents containing-CO-and not containing-COO-in the molecule), alcohol solvents (solvents containing OH, and not containing-O-, -CO-, and-COO-, in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

The ester solvent includes methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ -butyrolactone.

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

Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol methyl acetate, propylene glycol ethyl acetate, Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate.

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

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

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

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

These solvents may be used in combination of 2 or more.

Among the above solvents, organic solvents having a boiling point of 120 ℃ or higher and 210 ℃ or lower under 1atm are preferable from the viewpoint of coatability and drying property. Of these, 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-4-methyl-2-pentanone, N-dimethylformamide, and N-methylpyrrolidone are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, butyl ether, dipropylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, 4-hydroxy-4-methyl-2-pentanone, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, butyl propionate, n, N-dimethylformamide and N-methylpyrrolidone.

The content of the solvent (E) is usually 70 to 95% by mass, preferably 75 to 92% by mass, and more preferably 75 to 90% by mass, based on the total amount of the colored curable resin composition. If the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and further, the color density is not insufficient at the time of forming a color filter, so that the display characteristics tend to be good.

< leveling agent >

Examples of the leveling agent include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These may have a polymerizable group in a side chain.

The silicone surfactant includes surfactants having a siloxane bond in the molecule. Specifically, Donglicone (ト - レシリコ - ン) DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (manufactured by Toyo Corning Co., Ltd. (Dong- レ - ダウコ - ニング), 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 (manufactured by Michigan Kagaku material Japan Co., Ltd. (モメンテイブ - パフォ - マンス - マテリアルズ - ジヤパン) can be mentioned).

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specific examples thereof include FLUORAD (フロ)

ド) (registered trademark) FC430, homo FC431 (manufactured by sumitomo 3M corporation, sumitomo スリ - エ (ltd)), MEGAFAC (メガフアック) (registered trademark) F142D, homo F171, homo F172, homo F173, homo F177, homo F183, homo F554, homo P30, homo RS-718-K (manufactured by DIC), EFTOP (エフトツプ) (registered trademark) EF301, homo EF303, homo EF351, homo EF352 (manufactured by mitsubishi マテリアル electronization corporation)), surfon (サ - フロン) (registered trademark) S381, homo S382, homo SC101, homo SC105 (manufactured by xu nitre corporation), and E5844 (manufactured by seiki kumi institute of chemical industry (ltd) ダイキンフアインケミカル).

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in a molecule. Specifically, MEGAFAC (registered trademark) R08, XERYK BL20, XERYK F475, XERYK F477, and XERYK F443 (available from DIC corporation) can be mentioned.

The content of the leveling agent is usually 0.0005 mass% or more and 0.6 mass% or less, preferably 0.001 mass% or more and 0.5 mass% or less, more preferably 0.001 mass% or more and 0.2 mass% or less, further preferably 0.002 mass% or more and 0.1 mass% or less, and particularly preferably 0.005 mass% or more and 0.07 mass% or less, based on the total amount of the colored curable resin composition. If the content of the leveling agent is within the above range, the flatness of the color filter can be improved.

< other Components >

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

< method for producing colored curable resin composition >

The colored curable resin composition of the present invention can be prepared by, for example, mixing the colorant (a), the resin (B), the polymerizable compound (C), the polymerization initiator (D), the solvent (E), and, if necessary, a leveling agent, a polymerization initiation aid, and other components. In addition to the colorant (A), a pigment and/or a dye may be further mixed. The pigment is preferably mixed with a part or all of the solvent (E) in advance, and dispersed by a ball mill or the like until the average particle diameter of the pigment becomes about 0.2 μm or less, and used in the form of a pigment dispersion liquid. In this case, a part or all of the pigment dispersant and the resin (B) may be mixed as necessary.

Preferably, the compound (I) is dissolved in a part or the whole of the solvent (E) in advance to prepare a solution. Further, the solution is preferably filtered through a sieve having a pore diameter of about 0.01 to 1 μm.

The colored curable resin composition after mixing is preferably filtered through a filter sieve having a pore diameter of about 0.01 to 10 μm.

< method for producing color Filter >

Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include photolithography, ink jet printing, and printing. Among them, photolithography is preferable. The photolithography method is a method in which a colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. In the photolithography method, a colored coating film which is a cured product of the colored composition layer can be formed without using a photomask and/or without developing during exposure. The colored pattern and the colored coating film formed in this way are the color filter of the present invention.

The film thickness of the color filter to be produced is not particularly limited, and may be suitably adjusted depending on the purpose and/or application, and is usually 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

As the substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass coated with a silica coating on the surface thereof; a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or a substrate having a thin film of aluminum, silver, or a silver/copper/palladium alloy formed on the substrate. On these substrates, other color filter layers, resin layers, transistors, circuits, and the like may be formed.

The formation of each color pixel by photolithography can be performed under a known or conventional apparatus and conditions. For example, the production can be performed as follows.

First, a colored curable resin composition is applied onto a substrate, and volatile components such as a solvent are removed by heat drying (prebaking) and/or drying under reduced pressure, and dried to obtain a smooth composition layer. Examples of the coating method include spin coating, slit spin coating, and the like. The temperature for heating and drying is preferably 30 to 120 ℃, more preferably 50 to 110 ℃. The heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes. When the drying is performed under reduced pressure, the drying is preferably performed under a pressure of 50 to 150Pa and at a temperature of 20 to 25 ℃. The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target filter.

Next, the colored composition layer is exposed through a photomask for forming a target colored pattern. The pattern on the photomask is not particularly limited, and a pattern suitable for the intended use may be used. The light source used for the exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, the wavelengths of light of less than 350nm may be cut by using a filter that cuts the wavelength region of less than 350nm, or the wavelengths of light may be selectively obtained by using a band-pass filter that obtains wavelength regions in the vicinity of 436nm, 408 nm, or 365 nm. Specific examples of the light source include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps. In order to uniformly irradiate parallel light rays to the entire exposure surface and accurately position the positions of the photomask and the substrate on which the colored composition layer is formed, an exposure apparatus such as a mask aligner and a stepper is preferably used. The exposed colored composition layer is brought into contact with a developer to develop the composition layer, thereby forming a colored pattern on the substrate. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed. The developer is preferably an aqueous solution of an alkaline compound such as potassium hydroxide, sodium bicarbonate, sodium carbonate, or tetramethylammonium hydroxide. The concentration of the basic compound is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass. The developer may not contain a surfactant. The developing method may be any of a paddle stirring method, a dipping method, and a spraying method. The substrate may be tilted at any angle during further development. Preferably, the post-development washing is carried out with water.

The resulting colored pattern is preferably further subjected to post-baking. The post-drying temperature is preferably 150-250 ℃, and more preferably 160-235 ℃. The post-baking time is preferably 1 to 120 minutes, and more preferably 10 to 60 minutes.

After the color filter layer is formed, for example, a black matrix (ブテツクマトリクス), spacers (スパ - サ), a protective layer, a contact hole forming layer, and the like may be provided in addition to the pixels and/or pixel electrodes.

The color filter formed from the colored curable resin composition of the present invention is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) and a solid-state imaging device.

[ examples ] A method for producing a compound

The present invention will be described in more detail with reference to examples. In the examples, "%" and "parts" are% by mass and parts by mass unless otherwise specified.

In the following synthesis examples, the structure of the compound was confirmed by NMR (JMM-ECA-500, manufactured by Nippon electronics Co., Ltd.) or a MASS spectrometer (LC: model 1200 manufactured by Agilent, MASS; LC/MSD6130 manufactured by Agilent).

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

The device comprises the following steps: HLC-8120GPC (manufactured by DONGO JIAO ソ A, DONG)

A chromatographic column: TSK-GELG2000HXL

Column temperature: 40 deg.C

Solvent: tetrahydrofuran (THF)

Flow rate: 1.0 mL/min

Analysis of solid component concentration of sample: 0.001 to 0.01% by mass

Sample introduction amount: 50 μ L

A detector: RI (Ri)

Calibration standard substance: PSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corp.)

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

Example 1

4.98 parts of 2, 2-bis (3-amino-4-hydroxyphenyl) sulfone and 28.1 parts of methanol were mixed. To the resulting mixture was slowly added 8.18 parts of ethyl 3-ethoxy-3-iminopropionate hydrochloride at 10 ℃ or lower with stirring. The resulting mixture was stirred at 10 ℃ or lower for 7 hours, at room temperature for 24 hours, and at 60 ℃ for 24 hours. The resulting reaction mixture was cooled to room temperature, and then filtered to obtain precipitated crystals. The obtained crystals were washed with methanol and dried under reduced pressure at 60 ℃ to obtain 6.77 parts of a compound represented by the formula (pt 1).

[ CHEM 44 ]

< identification of Compound represented by formula (pt1) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺473

Exact Mass：472

2, 4-dimethylaniline (15.2 parts) and triethylamine (12.7 parts) were mixed together with 47.3 parts of N, N-dimethylformamide, and the mixture was stirred at 50 ℃. While maintaining the temperature of the mixture at 50 to 60 ℃, 24.9 parts of 8-bromo-1-octene was added, followed by stirring at 60 ℃ for 65 hours. After the mixture was allowed to cool to room temperature, 500 parts of water and 300 parts of toluene were added to separate a toluene layer. The toluene layer was washed 3 times with 500 parts of a saturated aqueous sodium chloride solution, and then the solvent was distilled off by a rotary evaporator. The obtained residue was purified by column chromatography to give 4.33 parts of a compound represented by the formula (pt 2-1).

[ CHEM 45 ]

< identification of Compound represented by the formula (pt2-1) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺232

Exact Mass：231

10.9 parts of the compound represented by the mixed formula (pt2-1), 8.81 parts of 3-bromoanisole, 0.318 part of palladium (II) acetate, 7.94 parts of potassium tert-butoxide, 0.806 parts of 2, 8, 9-triisopropyl-2, 5, 8, 9-tetraaza-1-phosphabicyclo [3.3.3] undecane (1.0M toluene solution) and 123 parts of toluene were stirred under nitrogen atmosphere at 100 ℃ for 6 hours. The resulting mixture was allowed to cool to room temperature, and then added to 250 parts of water. After the resulting mixture was filtered, the toluene layer was separated. The toluene layer was washed with a saturated aqueous sodium bicarbonate solution, dried over magnesium sulfate, and filtered. The filtrate was distilled off by a rotary evaporator, and the obtained residue was purified by column chromatography to obtain 1.26 parts of a compound represented by the formula (pt 3-1).

[ CHEM 46 ]

< identification of Compound represented by the formula (pt3-1) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺338

Exact Mass：337

Under nitrogen atmosphere, 1.26 parts of the compound represented by the mixed formula (pt3-1) and 15.0 parts of dichloromethane were mixed. The mixed solution is maintained at 15 to 23 ℃, and boron tribromide (1.0M dichloromethane solution) is added in an amount equal to the molar amount of the compound represented by the formula (pt 3-1). Then, the mixture was stirred at room temperature for 8 hours. The resulting mixture was added to 25.0 parts of ice water, and the methylene chloride layer was separated. The dichloromethane layer was washed with 25.0 parts of water, dried over magnesium sulfate, and filtered. The solvent was distilled off from the resulting liquid by a rotary evaporator. The obtained residue was purified by column chromatography to give 0.983 parts of a compound represented by the formula (pt 4-1).

[ CHEM 47 ]

< identification of Compound represented by the formula (pt4-1) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺324

Exact Mass：323

4.10 parts of a compound represented by a mixed formula (pt4-1) and 9.44 parts of N, N-dimethylformamide. The mixture was cooled to below 10 ℃ with a bath of ice water. While the mixture was stirred, 3.83 parts of phosphorus oxychloride was added dropwise over 35 minutes. The ice-water bath was removed and the mixture was warmed to room temperature. Then, the mixture was stirred at 65 to 70 ℃ for 1 hour. After the mixture was allowed to cool to room temperature, a mixture of 69.4 parts of toluene and 40.0 parts of water was added. While the mixture was stirred, 7.60 parts of a 48% aqueous sodium hydroxide solution was added. The mixture was allowed to stand to remove the toluene solution layer. The toluene solution was washed with 38.0 parts of water. The toluene solution was washed with 51.6 parts of a saturated aqueous sodium chloride solution. The toluene solution was dried over magnesium sulfate 0.600 parts and then filtered. To the filtrate was added 2.50 parts of activated clay, followed by filtration. The solvent was removed from the filtrate by distillation using a rotary evaporator. This residue was purified by column chromatography to give 1.52 parts of a compound represented by the formula (pt 5-1).

[ CHEM 48 ]

< identification of Compound represented by the formula (pt5-1) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺352

Exact Mass：351

To a reaction equipped with a Dean-Stark trap, 1.50 parts of the compound represented by formula (pt5-1), 1.00 parts of the compound represented by formula (pt1), 0.0400 parts of piperidine and 10.4 parts of toluene were added. The mixture is stirred at 100-110 ℃ for 7 hours. The mixture was allowed to cool to room temperature. To the mixture was added 9.50 parts of methanol, and the mixture was stirred for 30 minutes. The precipitate was obtained by filtration. The precipitate was washed with a mixture of 2.60 parts of toluene and 4.75 parts of methanol. Subsequently, the precipitate was washed with 7.13 parts of methanol. The precipitate was dried. To the precipitate was added 8.97 parts of N, N-dimethylformamide. To the resulting solution, 28.5 parts of water was added dropwise. To the mixture was added 2.85 parts of sodium chloride. The precipitate was obtained by filtration. The precipitate was washed with 9.00 parts of water. Subsequently, the precipitate was washed with 7.13 parts of methanol. The precipitate was dried to give 1.81 parts of a compound represented by the formula (I-34).

[ CHEM 49 ]

< identification of the Compound represented by the formula (I-34) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺1047

Exact Mass：1046

Example 2

Compounds represented by the formulae (pt2-2), (pt3-2) and (pt4-2) were obtained in the same manner as in example 1, except that allyl bromide was used instead of 8-bromo-1-octane in example 1.

[ CHEM 50 ]

< identification of respective Compounds >

A compound represented by the formula (pt2-2)

(Mass Spectrometry) ionization mode-FSI +: m/z ═ M + H]⁺162

Exact Mass：161

A compound represented by the formula (pt3-2)

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺268

Exact Mass：267

A compound represented by the formula (pt4-2)

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺254

Exact Mass：253

35.4 parts of a compound represented by a mixed formula (pt4-2) and 85.9 parts of N, N-dimethylformamide. The mixture was cooled to below 10 ℃ with a bath of ice water. While the mixture was stirred, 42.9 parts of phosphorus oxychloride was added dropwise over 1 hour. The ice-water bath was removed and the mixture was warmed to room temperature. Then, the mixture was stirred at 60 ℃ for 1 hour. After the mixture was cooled to room temperature, it was added to a mixture of 500 parts of water and 243 parts of toluene. To the mixture was added 84.0 parts of a 48% aqueous sodium hydroxide solution. The mixture was allowed to stand to obtain a toluene solution layer. The toluene solution was washed with 500 parts of water 2 times, with 552 parts of saturated aqueous sodium bicarbonate solution 1 time, and with 680 parts of saturated aqueous sodium chloride solution 1 time. The toluene solution was dried over magnesium sulfate 7.00 parts, and then filtered. 70.0 parts of activated clay was added to the filtrate, followed by filtration. The solvent of the filtrate was distilled off by a rotary evaporator to obtain 34.9 parts of a compound represented by the formula (pt 5-2).

[ CHEM 51 ]

< identification of the Compound represented by the formula (pt5-2) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺282

Exact Mass：281

To a reaction flask equipped with a Dean-Stark trap, 34.4 parts of the compound represented by formula (pt5-2), 27.8 parts of the compound represented by formula (pt1), 1.00 parts of piperidine and 97.0 parts of toluene were added. The mixture is stirred at 100-110 ℃ for 24 hours. After the mixture was allowed to cool to room temperature, the solvent was distilled off using a rotary evaporator. To the resulting residue, 88.7 parts of methanol was added, and the mixture was stirred overnight. The precipitate was obtained by filtration. The precipitate was dried. The precipitate was purified by column chromatography to give 22.2 parts of a compound represented by the formula (I-6).

[ CHEM 52 ]

< identification of Compound represented by formula (I-6) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺907

Exact Mass：906

Example 3

To 138 parts of resorcinol, 64.5 parts of 2-ethylhexylamine was added, and the mixture was stirred at 150 to 155 ℃ for 18 hours while removing water produced. After cooling, 250 parts of toluene was added to the reaction mixture, and the mixture was washed with 500 parts of warm water 3 times. To the toluene solution, 20.0 parts of anhydrous magnesium sulfate was added, and the mixture was stirred and then filtered. The solvent of the filtrate was distilled off to obtain 113 parts of a residue containing the compound represented by the formula (pt4-3-1) as a main component.

[ CHEM 53 ]

< identification of the Compound represented by the formula (pt4-3-1) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺222

Exact Mass：221

10.1 parts of the compound represented by the mixed formula (pt4-3-1) and 5.22 parts of water were stirred at 80 ℃. Then, 7.60 parts of 3-iodo-1-propene (manufactured by Tokyo chemical Co., Ltd.) was added thereto, and the mixture was stirred at 80 ℃ for 3 hours, followed by addition of 1.83 parts of a 48% aqueous solution of sodium hydroxide. The mixture was stirred for 24 hours while being refluxed. After cooling, the reaction mixture was adjusted to pH 5 using 10% aqueous sodium hydroxide solution, and 200 parts of toluene was added, stirred, and the toluene layer was extracted. The toluene extract was washed with 600 parts of water for 2 times, and 30.0 parts of anhydrous magnesium sulfate was added thereto, followed by stirring and filtration. The solvent was removed from the filtrate by distillation to obtain a residue. This residue was purified by column chromatography to give 1.33 parts of a residue containing the compound represented by the formula (pt4-3-2) as a main component.

[ CHEM 54 ]

< identification of the Compound represented by the formula (pt4-3-2) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺262

Exact Mass：261

The same procedures as in example 1 were carried out except that the compound represented by the formula (pt4-3-2) was used in place of the compound represented by the formula (pt4-1) in example 1 to give compounds represented by the formulae (pt5-3) and (I-2).

[ CHEM 55 ]

< identification of respective Compounds >

A compound represented by the formula (pt5-3)

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺290

Exact Mass：289

A compound represented by the formula (I-2)

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺923

Exact Mass：922

Example 4

218.0 parts of 3-aminophenol, 352.8 parts of sodium hydrogencarbonate and 1510 parts of N, N-dimethylformamide were mixed. While stirring the resulting mixture, 532.4 parts of allyl bromide were added dropwise over 5 hours at 50 ℃ to 55 ℃. The resulting mixture was stirred at 50-55 ℃ for 20 hours. After cooling, 6000 parts of water and 3468 parts of toluene were added to the mixture, and the mixture was stirred. The mixture was allowed to stand to obtain a toluene solution layer. The obtained toluene solution was washed with 6618 parts of saturated aqueous sodium bicarbonate solution for 2 times, and 100 parts of anhydrous magnesium sulfate was added thereto, followed by stirring and filtration. To the obtained filtrate, 500 parts of activated clay was added, followed by stirring and filtration. The solvent in the resulting solution was distilled off to obtain 362.1 parts of a mixture containing the compound represented by the formula (pt 4-4).

[ CHEM 56 ]

< identification of the Compound represented by the formula (pt4-4) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺190

Exact Mass：189

353.3 parts of the compound containing the obtained compound represented by the formula (pt4-4) and 1068 parts of N, N-dimethylformamide were mixed and cooled to 10 ℃ or lower. 533.6 parts of phosphorus oxychloride was added dropwise over 3 hours while stirring the resulting mixture at 2 to 9 ℃. The resulting mixture was adjusted to room temperature and then stirred at 60 ℃ for 16 hours. The resulting mixture was allowed to cool and added to a mixture of ice 5046 parts and toluene 3017 parts. While the resulting mixture was stirred, 1505 parts of a 48% aqueous sodium hydroxide solution was added thereto, and the mixture was allowed to stand to obtain a toluene solution layer. The resulting toluene solution was washed 2 times with a saturated aqueous sodium bicarbonate solution 5758, and 87 parts of anhydrous magnesium sulfate was added thereto, stirred, and filtered. 435 parts of activated clay was added to the obtained solution, followed by stirring and filtration to obtain a solution (1) and a residue. To the resulting residue, 3017 parts of toluene was added, followed by filtration to obtain a solution (2). The solution (1) and the solution (2) were combined, and the solvent was distilled off to obtain a residue. To the residue, 413 parts of methanol was added, and the solvent was distilled off to obtain 279.0 parts of a mixture containing the compound represented by the formula (pt 5-4).

[ CHEM 57 ]

< identification of the Compound represented by the formula (pt5-4) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺218

Exact Mass：217

133.4 parts of the compound represented by the formula (pt1), 134.6 parts of a mixture containing the compound represented by the formula (pt5-4), 5.52 parts of piperidine and 1014 parts of toluene were added to a reaction equipped with a Dean-Stark trap and mixed. The resulting mixture was stirred at 102-104 ℃ for 9 hours. The mixture was stirred at 100 ℃ for 12 hours. The resulting mixture was allowed to cool, and then filtered to obtain a residue. The resulting residue was washed with 451 parts of toluene, then 412 parts of methanol, and dried at 120 ℃. The obtained residue was added to 1888 parts of N, N-dimethylformamide, and heated to 110 ℃ to obtain a solution. The resulting solution was stirred at 10 ℃ or lower for 1 hour to obtain a mixture. The resulting mixture was filtered, and the residue was washed with 472 parts of N, N-dimethylformamide, followed by 396 parts of methanol. The residue was dried at 120 ℃. 1529 parts of N, N-dimethylformamide was added to the obtained residue, and the mixture was heated to 110 ℃ to obtain a solution. The resulting solution was allowed to cool to room temperature and then filtered to obtain a residue. The resulting residue was washed with 472 parts of N, N-dimethylformamide, followed by washing with 396 parts of methanol and drying at 120 ℃ to obtain 143.6 parts of a compound represented by the formula (I-1).

[ CHEM 58 ]

< identification of Compound represented by formula (I-1) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺779

Exact Mass：778

Example 5

18.0 parts of 3-aminophenol, 38.2 parts of sodium hydrogencarbonate and 113 parts of N, N-dimethylformamide were mixed. While stirring the resulting mixture at 70 ℃ to 75 ℃, 49.8 parts of 4-bromo-1-butene was added over 1 hour. The resulting mixture was stirred at 70-75 ℃ for 24 hours. The resulting mixture was stirred at 90 ℃ for 20 hours. After the resulting mixture was allowed to cool, 495 parts of water and 82.4 parts of toluene were added thereto, and the mixture was stirred and allowed to stand to obtain a toluene solution layer. The toluene solution thus obtained was washed 2 times with 546 parts of a saturated aqueous sodium bicarbonate solution, and 8.25 parts of anhydrous magnesium sulfate was added thereto, followed by stirring and filtration. To the obtained liquid was added 41.2 parts of activated clay, followed by stirring and filtration. The solvent was distilled off from the filtrate by a rotary evaporator to obtain 32.3 parts of a mixture containing the compound represented by the formula (pt 4-5).

[ CHEMICAL 59 ]

< identification of the Compound represented by the formula (pt4-5) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺218

Exact Mass：217

32.2 parts of a mixture containing the obtained compound represented by the formula (pt4-5) and 95.3 parts of N, N-dimethylformamide were mixed. While stirring the resulting mixture at-5 ℃ to 4 ℃, 49.7 parts of phosphorus oxychloride was added over 1 hour. The resulting mixture was adjusted to room temperature and then stirred at 60 ℃ for 18 hours. The resulting mixture was allowed to cool, and then added to a mixture of 402 parts of ice and 351 parts of toluene. While stirring the resulting mixture, a 48% aqueous sodium hydroxide solution was slowly added to neutralize the mixture, and after standing, a toluene aqueous layer was obtained. The resulting toluene solution was washed with 447 parts of saturated aqueous sodium bicarbonate solution for 2 times, and 6.75 parts of anhydrous magnesium sulfate was added thereto, followed by stirring and filtration. To the obtained liquid was added 33.8 parts of activated clay, followed by stirring for 30 minutes and filtration to obtain a filtrate (3) and a residue. To the obtained residue was added 117 parts of toluene, followed by filtration to obtain a filtrate (4). The filtrate (3) and the filtrate (4) were combined, and the solvent was distilled off. To the resulting residue was added 238 parts of methanol. The solvent in the resulting solution was distilled off to obtain 26.6 parts of a mixture containing the compound represented by the formula (pt 5-5).

[ CHEM 60 ]

< identification of the Compound represented by the formula (pt5-5) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺246

Exact Mass：245

22.3 parts of the compound represented by the formula (pt1), 26.0 parts of a mixture containing the compound represented by the formula (pt5-5), 0.920 parts of piperidine and 169 parts of toluene were added to a reaction flask equipped with a Dean-Stark trap and mixed. The resulting mixture was stirred at 105 ℃ to 110 ℃ for 1.5 hours. To the resulting mixture was added 130 parts of toluene, and the mixture was stirred at 100 ℃ for 21 hours. The resulting mixture was allowed to cool and then filtered. The resulting residue was washed with 151 parts of toluene and 138 parts of methanol in this order. The resulting residue was dried at 120 ℃.

The obtained residue was added to 217 parts of N, N-dimethylformamide, and stirred at 100 ℃ to obtain a solution. The resulting solution was allowed to cool to room temperature and then filtered. The resulting residue was washed with 94.4 parts of N, N-dimethylformamide, followed by washing with 79.2 parts of methanol and drying at 120 ℃. The resulting residue was purified by column chromatography to give 25.0 parts of a compound represented by the formula (I-8).

[ CHEM 61 ]

< identification of the Compound represented by the formula (I-8) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺835

Exact Mass：834

Synthesis example 1

An appropriate amount of nitrogen was introduced into a 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was replaced with nitrogen, and 371 parts of propylene glycol monomethyl ether acetate was added thereto and heated to 85 ℃ with stirring. Then, use 454 parts of acrylic acid and 3, 4-epoxy tricyclo [5.2.1.0 ] acrylic acid are dropwise added in the reaction solution for hours^2，6]A mixed solution of 225 parts of a mixture of decane-8 and/or 9-yl ester, 81 parts of vinyl toluene (an isomer mixture), and 80 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution of 30 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, dissolved in 160 parts of propylene glycol monomethyl ether acetate, was added dropwise over 5 hours. After the completion of the dropwise addition of the initiator solution, the temperature was maintained at the same temperature for 4 hours, and then the mixture was cooled to room temperature to obtain a B-type copolymer (resin B1) solution having a viscosity (23 ℃) of 246 mPas, a solid content of 37.5% and a solution acid value of 43 mg-KOH/g. The weight average molecular weight Mw of the obtained resin B1 was 10600, and the molecular weight distribution was 2.01.

Synthesis example 2

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, a proper amount of nitrogen was introduced to obtain a nitrogen atmosphere, and 100 parts of propylene glycol monomethyl ether acetate was added and heated to 85 ℃ with stirring. Then, 19 parts of methacrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylic acid were added dropwise to the flask over about 5 hours by means of a dropping pump^2，6]Decan-8-yl ester and acrylic acid 3, 4-epoxytricyclo [5.2.1.0^2，6]171 parts of a mixture of decane-9-yl esters (containing 50: 50 parts by molar ratio) was dissolved in 40 parts of propylene glycol monomethyl ether acetate. On the other hand, a solution of 26 parts of 2, 2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator dissolved in 120 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over about 5 hours using another dropping funnel. After the completion of the dropwise addition of the polymerization initiator, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a copolymer (resin B2) solution having a solid content of 43.5%. The weight-average molecular weight Mw of the obtained resin B2 was 8000, the molecular weight distribution was 1.98, and the acid value in terms of solid matter was 53 mgKOH/g.

[ CHEM 62 ]

[ preparation of colored curable resin composition ]

Example 6

The following compounds were mixed to obtain a colored curable resin composition:

[ CHEM 63 ]

Polymerization initiator (D): a mixture of compounds represented by the following formula (CHEMCURE-TCDM;

cambridge (ケンブリッジ corporation); bisimidazole compound) 5.86 parts;

[ CHEM 64 ]

[ CHEM 65 ]

Example 7

A colored curable resin composition was obtained in the same manner as in example 6, except that the compound represented by the formula (I-34) was used in place of the compound represented by the formula (I-6) in example 6.

Comparative example 1

[ CHEM 66 ]

manufactured by Cambridge corporation; bisimidazole compound) 5.86 parts;

[ CHEM 67 ]

[ CHEM 68 ]

[ film thickness measurement ]

The film thickness was measured using DEKTAK3 (manufactured by NIPPON VACUUM TECHNOLOGY CO., LTD.).

Comparative example 2

[ preparation of colored coating film and evaluation of immersion in NMP ]

The colored curable resin composition obtained in comparative example 1 was applied onto a 2-inch square glass substrate (Fagle (イ - グル) XG; manufactured by Corning Inc. (コ - ニング)) by spin coating, and then prebaked at 100 ℃ for 3 minutes to form a colored composition layer. Cooling downThen, the resultant was exposed to an exposure apparatus (TME-150 RSK; manufactured by Topukang K.K.; トプコン K.) at 150mJ/cm in an atmospheric air atmosphere²Exposure with an exposure amount of (365nm basis). Subsequently, post-baking was performed at 230 ℃ for 30 minutes to obtain a colored coating film. The film thickness of the colored coating film was measured. The colored coating film was immersed in NMP at 23 ℃ for 5 minutes. The color difference (. DELTA.Eab.) before and after the colored coating film was immersed in NMP was measured using a color measuring machine (OSP-SP-200; manufactured by OLYMPUS corporation). The larger the color difference (. DELTA.Eab.) is, the larger the amount of the colorant eluted from the colored coating film into NMP becomes.

Example 8

A colored coating film was obtained in the same manner as in comparative example 2 except that the colored curable resin composition obtained in example 6 was used in place of the colored curable resin composition obtained in comparative example 1 in comparative example 2, and was similarly immersed in NMP to measure the color difference (Δ Eab @) before and after the immersion. The results are shown in Table 17.

Example 9

A colored coating film was obtained in the same manner as in comparative example 2 except that the colored curable resin composition obtained in example 7 was used in place of the colored curable resin composition obtained in comparative example 1 in comparative example 2, and was similarly immersed in NMP to measure the color difference (Δ Eab @) before and after the immersion. The results are shown in Table 17.

[ TABLE 17 ]

	Chromatic aberration (Delta Eab)
		Example 8	0.4
Example 9	0.4
		Comparative example 2	15.8

The results shown in Table 17 show that the compound of the present invention eluted from the colored coating film to NMP in a small amount.

Example 10

Mixing

Fully dispersing the pigment by using a ball mill to obtain pigment dispersion liquid,

examples 11 to 18

A colored curable resin composition was obtained in the same manner as in example 10, except that the pigment shown in table 18 was used instead of c.i. pigment green 7 in example 10, and the compound shown in table 18 was used instead of the compound shown in formula (I-6).

[ TABLE 18 ]

	Material	Compound (I)
			Example 11	C.i. pigment green 36	A compound represented by the formula (I-6)
Example 12	C.i. pigment green 58	A compound represented by the formula (I-6)
			Example 13	C.i. pigment green 7	A compound represented by the formula (I-34)
Example 14	C.i. pigment green 36	A compound represented by the formula (I-34)
			Example 15	C.i. pigment green 58	A compound represented by the formula (I-34)
Example 16	C.i. pigment green 7	A compound represented by the formula (I-2)
			Example 17	C.i. pigment green 36	A compound represented by the formula (I-2)
Example 18	C.IPigment green 58	A compound represented by the formula (1-2)

Example 19

[ preparation of colored Pattern ]

The colored curable resin composition obtained in example 10 was applied onto a 2-inch square glass substrate (Eagle XG; manufactured by Corning corporation) by a spin coating method, and then prebaked at 100 ℃ for 3 minutes to form a colored composition layer. After cooling, the gap between the substrate on which the colored composition layer was formed and a photomask made of quartz glass was set to 200 μm, and the resultant was exposed to an exposure apparatus (TME-150 RSK; manufactured by Topykang Co., Ltd.) at a pressure of 80mJ/cm in an atmospheric environment²Exposure was performed with the exposure amount (365nm standard). Further, the photomask used was a mask formed with a 100 μm line and space pattern. The exposed colored composition layer was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ℃ for 70 seconds, developed, and washed with water. The colored coating film was subjected to postbaking at 230 ℃ for 30 minutes to obtain a colored pattern.

Examples 20 to 27

A colored pattern was obtained by performing the same operations as in example 19, except that the colored curable resin composition shown in table 19 was used instead of the colored curable resin composition obtained in example 10 in example 19.

[ TABLE 19 ]

Example 28

10.0 parts of 2, 2-bis (3-amino-4-hydroxyphenyl) propane and 51.0 parts of methanol were mixed, and 18.2 parts of ethyl 3-ethoxy-3-iminopropionate hydrochloride was added thereto at 5 ℃ or lower with stirring. Then, the reaction mixture was stirred at 10 ℃ or lower for 13 hours, at room temperature for 24 hours, and at 60 ℃ for 24 hours. The reaction mixture was cooled to room temperature. The solvent was distilled off from the reaction mixture using a rotary evaporator. The resulting residue was purified by column chromatography to give 6.46 parts of a compound represented by the formula (pt 1-b).

[ CHEM 69 ]

< identification of Compound represented by the formula (pt1-b) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺451

Exact Mass：450

43.0 parts of the compound represented by the formula (pt5-1), 26.5 parts of the compound represented by the formula (pt1-b), 1.00 parts of piperidine and 97.0 parts of toluene were added to a reaction flask equipped with a Dean-Stark trap. The mixture is stirred at 100-110 ℃ for 24 hours. After the mixture was allowed to cool to room temperature, the solvent was distilled off using a rotary evaporator. The resulting residue was purified by column chromatography to give 3.29 parts of a compound represented by the formula (I-90).

[ CHEM 70 ]

< identification of the Compound represented by the formula (I-90) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺1026

Exact Mass：1025

Example 29

The same procedures as in example 28 were carried out except that the compound represented by the formula (pt5-2) was used instead of the compound represented by the formula (pt5-1) in example 28 to give a compound represented by the formula (I-62).

[ CHEM 71 ]

< identification of the Compound represented by the formula (I-62) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺885

Exact Mass：884

Example 30

The same procedures as in example 28 were carried out except that the compound represented by the formula (pt5-3) was used instead of the compound represented by the formula (pt5-1) in example 28 to give a compound represented by the formula (I-58).

[ CHEM 72 ]

< identification of the Compound represented by formula (I-58) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺901

Exact Mass：900

Example 31

The same procedures as in example 28 were carried out except that the compound represented by the formula (pt5-4) was used instead of the compound represented by the formula (pt5-1) in example 28 to give a compound represented by the formula (I-57).

[ CHEM 73 ]

< identification of the Compound represented by the formula (I-57) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺757

Exact Mass：756

Example 32

The same procedures as in example 28 were carried out except that the compound represented by the formula (pt5-5) was used instead of the compound represented by the formula (pt5-1) in example 28 to give a compound represented by the formula (I-64).

[ CHEM 74 ]

< identification of the Compound represented by formula (I-64) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺813

Exact Mass：812

Example 33

5.02 parts of 9, 9-bis (3-amino-4-hydroxyphenyl) fluorene and 30.0 parts of methanol were mixed, and 6.10 parts of ethyl 3-ethoxy-3-iminopropionate hydrochloride was added thereto at 5 ℃ or lower with stirring. Then, the reaction mixture was stirred at 10 ℃ or lower for only 14 hours, at room temperature for only 24 hours, and at 60 ℃ for only 24 hours. The reaction mixture was cooled to room temperature. The solvent was distilled off from the reaction mixture using a rotary evaporator. The resulting residue was purified by column chromatography to give 2.33 parts of a compound represented by the formula (pt 1-c).

[ CHEM 75 ]

< identification of Compound represented by formula (pt1-c) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺573

Exact Mass：572

The same procedures as in example 28 were carried out except that the compound represented by the formula (pt1-c) was used instead of the compound represented by the formula (pt1-b) in example 28 to give a compound represented by the formula (I-146).

[ CHEM 76 ]

< identification of the Compound represented by the formula (I-146) >

(Mass Spectrometry)Ionization mode is ESI +: m/z ═ M + H]⁺1148

Exact Mass：1147

Example 34

A compound represented by the formula (I-118) was obtained by the same procedures as in example 28, except that the compound represented by the formula (pt1-b) in example 28 was replaced with a compound represented by the formula (pt1-c), and the compound represented by the formula (pt5-2) was replaced with a compound represented by the formula (pt5-1) in example 28.

[ CHEM 77 ]

< identification of the Compound represented by formula (I-118) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺1007

Exact Mass：1006

Example 35

A compound represented by the formula (I-114) was obtained by the same procedures as in example 28, except that the compound represented by the formula (pt1-b) in example 28 was replaced with a compound represented by the formula (pt1-c), and the compound represented by the formula (pt5-3) was replaced with a compound represented by the formula (pt5-1) in example 28.

[ CHEM 78 ]

< identification of the Compound represented by formula (I-114) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺1024

Exact Mass：1022

Example 36

A compound represented by the formula (I-113) was obtained by carrying out the same procedures as in example 28, except that the compound represented by the formula (pt1-b) in example 28 was replaced with a compound represented by the formula (pt1-c) and the compound represented by the formula (pt5-4) was replaced with a compound represented by the formula (pt5-1) in example 28.

[ CHEM 79 ]

< identification of Compound represented by formula (I-113) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺879

Exact Mass：878

Example 37

A compound represented by the formula (I-120) was obtained by performing the same procedures as in example 28, except that the compound represented by the formula (pt1-b) in example 28 was replaced with a compound represented by the formula (pt1-c), and the compound represented by the formula (pt5-5) was replaced with a compound represented by the formula (pt5-1) in example 28.

[ CHEM 80 ]

< identification of the Compound represented by formula (I-120) >

(Mass Spectrometry) ionization mode-ESI +: m/z ═ M + H]⁺935

Exact Mass：934

Example 38

A compound represented by the formula (pt1-d) was obtained in the same manner as in example 28 except that bis (3-amino-4-hydroxyphenyl) methane was used in place of 2, 2-bis (3-amino-4-hydroxyphenyl) propane in example 28.

[ CHEMICAL 81 ]

A compound represented by the formula (I-202) was obtained by the same procedures as in example 28, except that the compound represented by the formula (pt1-d) was used in place of the compound represented by the formula (pt 1-b).

[ CHEM 82 ]

Example 39

A compound represented by the formula (I-174) was obtained by performing the same procedures as in example 28, except that the compound represented by the formula (pt1-b) in example 28 was replaced with a compound represented by the formula (pt1-d) and the compound represented by the formula (pt5-2) was replaced with the compound represented by the formula (pt5-1) in example 28.

[ CHEM 83 ]

Example 40

The same procedures as in example 28 were carried out except that the compound represented by the formula (pt1-d) was used instead of the compound represented by the formula (pt1-b) in example 28, and the compound represented by the formula (pt5-3) was used instead of the compound represented by the formula (pt5-1) in example 28, to give a compound represented by the formula (I-170).

[ CHEM 84 ]

EXAMPLE 41

A compound represented by the formula (I-169) was obtained by the same procedures as in example 28, except that the compound represented by the formula (pt1-b) in example 28 was replaced with a compound represented by the formula (pt1-d), and the compound represented by the formula (pt5-4) was replaced with a compound represented by the formula (pt5-1) in example 28.

[ CHEM 85 ]

Example 42

A compound represented by the formula (I-176) was obtained by performing the same procedures as in example 28, except that the compound represented by the formula (pt1-b) in example 28 was replaced with a compound represented by the formula (pt1-d) and the compound represented by the formula (pt5-5) was replaced with the compound represented by the formula (pt5-1) in example 28.

[ CHEM 86 ]

[ preparation of colored curable resin composition ]

Examples 43 to 49

A colored curable resin composition was obtained in the same manner as in example 6, except that the compound represented by the formula (I-6) in example 6 was replaced with the compound represented by Table 20.

[ TABLE 20 ]

	Compound (I)
		Example 43	A compound represented by the formula (I-2)
Example 44	A compound represented by the formula (I-90)
		Example 45	A compound represented by the formula (I-62)
Example 46	A compound represented by the formula (I-58)
		Example 47	A compound represented by the formula (I-146)
Example 48	A compound represented by the formula (I-118)
		Example 49	A compound represented by the formula (I-114)

Examples 50 to 55

A colored curable resin composition was obtained in the same manner as in comparative example 1, except that the compound shown in table 21 was used instead of coumarin 6 in comparative example 1.

[ TABLE 21 ]

	Compound (I)
		Example 50	A compound represented by the formula (I-1)
Example 51	A compound represented by the formula (I-8)
		Example 52	A compound represented by the formula (I-57)
Example 53	Represented by the formula (I-64)Compound (I)
		Example 54	A compound represented by the formula (I-113)
Example 55	A compound represented by the formula (I-120)

[ preparation of colored coating film and evaluation of immersion in NMP ]

Examples 56 to 68

A colored coating film was obtained in the same manner as in comparative example 2 except that the colored curable resin composition shown in table 22 was used instead of the colored curable resin composition obtained in comparative example 1 in comparative example 2, and was similarly immersed in NMP to measure the color difference (Δ Eab). The results are shown in Table 22.

[ TABLE 22 ]

	Colored curable resin composition	Chromatic aberration (Delta Eab)
			Example 56	Colored curable resin composition obtained in example 43	3.4
Example 57	Colored curable resin composition obtained in example 44Article (A)	3.7
			Example 58	Colored curable resin composition obtained in example 45	4.0
Example 59	Colored curable resin composition obtained in example 46	4.4
			Example 60	Colored curable resin composition obtained in example 47	6.1
Example 61	Colored curable resin composition obtained in example 48	6.8
			Example 62	Colored curable resin composition obtained in example 49	7.6
Example 63	Colored curable resin composition obtained in example 50	1.6
			Example 64	Colored curable resin composition obtained in example 51	2.3
Example 65	Colored curable resin composition obtained in example 52	4.7
			Example 66	Colored curable resin composition obtained in example 53	3.9
Example 67	Colored curable resin composition obtained in example 54	4.9
			Example 68	Colored curable resin composition obtained in example 55	5.5

[ preparation of colored curable resin composition ]

Examples 69 to 87

A colored curable resin composition was obtained in the same manner as in example 10, except that the pigment shown in table 23 was used instead of c.i. pigment green 7 in example 10, and the compound shown in table 23 was used instead of the compound shown in formula (I-6).

[ TABLE 23 ]

	Pigment for pigment	Compound (I)
			Example 69	C.i. pigment green 59	A compound represented by the formula (I-6)
Example 70	C.i. pigment green 59	A compound represented by the formula (I-34)
			Example 71	C.i. pigment green 59	A compound represented by the formula (I-2)
Example 72	C.i. pigment green 7	A compound represented by the formula (I-1)
			Example 73	C.i. pigment green 36	A compound represented by the formula (I-1)
Example 74	C.i. pigment green 58	A compound represented by the formula (I-1)
			Example 75	C.i. pigment green 59	A compound represented by the formula (I-1)
Example 76	C.i. pigment green 7	A compound represented by the formula (I-8)
			Example 77	C.i. pigment green 36	A compound represented by the formula (I-8)
Example 78	C.i. pigment green 58	A compound represented by the formula (I-8)
			Example 79	C.i. pigment green 59	A compound represented by the formula (I-8)
Example 80	C.i. pigment green 7	A compound represented by the formula (I-90)
			Example 81	C.i. pigment green 36	A compound represented by the formula (I-90)
Example 82	C.i. pigment green 58	A compound represented by the formula (I-90)
			Example 83	C.i. pigment green 59	A compound represented by the formula (I-90)
Example 84	C.i. pigment green 7	A compound represented by the formula (I-146)
			Example 85	C.i. pigment green 36	A compound represented by the formula (I-146)
Example 86	C.i. pigment green 58	A compound represented by the formula (I-146)
			Example 87	C.i. pigment green 59	A compound represented by the formula (I-146)

[ preparation of colored Pattern ]

Examples 88 to 106

A colored pattern was obtained by performing the same operations as in example 19, except that the colored curable resin composition shown in table 24 was used instead of the colored curable resin composition obtained in example 10 in example 19.

[ TABLE 24 ]

	Colored curable resin composition
		Example 88	Colored curable resin composition obtained in example 69
Example 89	Colored curable resin composition obtained in example 70
		Example 90	Colored curable resin composition obtained in example 71
Example 91	Colored curable resin composition obtained in example 72
		Example 92	Colored curable resin composition obtained in example 73
Example 93	Colored curable resin composition obtained in example 74
		Example 94	Colored curable resin composition obtained in example 75
Example 95	Colored curable resin composition obtained in example 76
		Example 96	Colored curable resin composition obtained in example 77
Example 97	Colored curable resin composition obtained in example 78
		Example 98	Colored curable resin composition obtained in example 79
Example 99	Colored curable resin composition obtained in example 80
		Example 100	Colored curable resin composition obtained in example 81
Example 101	Colored curable resin composition obtained in example 82
		Example 102	Colored curable resin composition obtained in example 83
Example 103	Colored curable resin composition obtained in example 84
		Example 104	Colored curable resin composition obtained in example 85
Example 105	Colored curable resin composition obtained in example 86
		Example 106	Example 87 the resulting colored curable resin composition

It is found that the compound of the present invention is useful as a colored curable resin composition material capable of forming a color filter with a small amount of elution of a colorant from a colored coating film to NMP.

Industrial applicability

The invention can provide a colored curable resin composition for forming a color filter with less colorant elution amount from a colored coating film to NMP. Therefore, a color filter formed from the colored curable resin composition is suitably used in a display device such as a liquid crystal display device.

Claims

1. A compound represented by the formula (I),

[ CHEM 1]

Wherein L represents a C1-20 alkyl group having a valence of 2 or a sulfonyl group;

x represents an oxygen atom or a sulfur atom;

R¹represents an optionally substituted alkenyl group having 2 to 20 carbon atoms or an optionally substituted cycloalkenyl group having 3 to 20 carbon atoms, -CH constituting the alkenyl group or cycloalkenyl group₂Can be substituted by an oxygen atom, -N (R)¹⁰) -or carbonyl substitution;

R²represents a hydrogen atom or a 1-valent hydrocarbon group having 1 to 20 carbon atoms;

R³～R⁹each independently represents a hydrogen atom, a C1-20 hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, or-SO₃M、-CO₂M, hydroxy, formyl or amino;

R²～R⁹in the aforementioned hydrocarbon group represented by the formula, -CH₂May be substituted by oxygen, sulfur, -N (R)¹¹) -, sulfonyl or carbonyl, the hydrogen atom being optionally substituted by halogen, cyano, nitro, carbamoyl, sulfamoyl, -SO₃M、-CO₂M, hydroxy, formyl or amino;

R¹⁰and R¹¹Each independently represents a hydrogen atom or a 1-valent hydrocarbon group having 1 to 20 carbon atoms, and a plurality of R are present¹⁰And R¹¹When they are the same or different from each other;

m represents a hydrogen atom or an alkali metal atom.

2. A compound of claim 1, R¹The alkenyl group may have a substituent(s) and has 2 to 16 carbon atoms, or the cycloalkenyl group may have a substituent(s) and has 3 to 16 carbon atoms.

3. A compound according to claim 1 or 2, R¹The alkenyl group may have a substituent(s) and has 2 to 10 carbon atoms or the cycloalkenyl group may have a substituent(s) and has 3 to 10 carbon atoms.

4. A compound according to claim 1 or 2, R²The aryl group is an alkenyl group having 2 to 10 carbon atoms, an alkyl group having 3 to 10 carbon atoms, a cycloalkenyl group having 3 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.

5. A colorant comprising the compound according to any one of claims 1 to 4.

6. The colorant of claim 5, further comprising a pigment.

7. A colored curable resin composition comprising the colorant according to claim 5 or 6, a resin, a polymerizable compound, a polymerization initiator, and a solvent.

8. A color filter formed from the colored curable resin composition according to claim 7.

9. A liquid crystal display device comprising the color filter of claim 8.