CN106019840B

CN106019840B - Colored curable resin composition

Info

Publication number: CN106019840B
Application number: CN201610193018.7A
Authority: CN
Inventors: 中野骏
Original assignee: Dongwoo Fine Chem Co Ltd
Current assignee: Dongwoo Fine Chem Co Ltd
Priority date: 2015-03-30
Filing date: 2016-03-30
Publication date: 2021-01-29
Anticipated expiration: 2036-03-30
Also published as: CN106019840A; KR101970385B1; KR20160117271A

Abstract

The present invention aims to obtain a color filter having an excellent pattern shape. The colored curable resin composition of the present invention contains a colorant, a resin, a polymerizable compound, and a polymerization initiator, and is characterized in that the colorant contains a dye, the dye content is 90 parts by mass or more per 100 parts by mass of the colorant, and the polymerization initiator contains a compound represented by the following formula (d 1).

Description

Colored curable resin composition

Technical Field

The present invention relates to a colored curable resin composition.

Background

The colored curable resin composition is used for producing color filters used in display devices such as liquid crystal display devices, electroluminescent display devices, and plasma displays. Patent document 1 describes a photosensitive coloring composition containing a salt-forming compound composed of a triarylmethane-based basic dye and a counter compound, and an oxime ester-based photopolymerization initiator (patent document 1).

In addition, as a high-sensitivity photoinitiator in a photopolymerizable composition, an oxime ester derivative of a benzocarbazole compound has been proposed (patent document 2).

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open No. 2014-170098

Patent document 2: japanese Kokai publication No. 2014-500852

Disclosure of Invention

Problems to be solved by the invention

The above-mentioned photosensitive coloring composition known in the prior art cannot sufficiently satisfy the requirement of the shape of the color filter, which is the obtained colored pattern. Therefore, the present invention has an object to obtain a color filter having an excellent pattern shape.

Patent document 2 teaches the use of an oxime ester derivative of a benzocarbazole compound as a photoinitiator in a photopolymerizable composition, but does not teach any change in pattern shape when the composition contains a colorant.

Means for solving the problems

The present invention includes the following inventions.

[1] A colored curable resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant contains a dye in an amount of 90 parts by mass or more per 100 parts by mass of the colorant, and the polymerization initiator contains a compound represented by the following formula (d 1).

[ chemical formula 1]

[ in the formula (d1),

R^d1represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, an optionally substituted alkyl group having 1 to 15 carbon atoms or an optionally substituted aralkyl group having 7 to 33 carbon atoms, and a methylene group (-CH) contained in the alkyl group or the aralkyl group₂-) can be replaced by-O-, -CO-, -S-, -SO₂-or-N (R)^d5)-。

R^d2Represents an aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.

R^d3The heterocyclic group is an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted heterocyclic group having 3 to 36 carbon atoms.

R^d4Represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, and a methylene group (-CH) contained in the aliphatic hydrocarbon group₂-) may be replaced with-O-, -CO-or-S-, and the methine group (-CH <) contained in the above aliphatic hydrocarbon group may be replaced with-PO₃<, the hydrogen atom contained in the above aliphatic hydrocarbon group may be substituted with an OH group.

R^d5Represents an alkyl group having 1 to 10 carbon atoms, and a methylene group (-CH) contained in the alkyl group₂-) can be replaced by-O-or-CO-.]

[2] [1] the colored curable resin composition, wherein the colorant is free of a pigment.

[3] [1] the colored curable resin composition according to [1] or [2], wherein the dye comprises at least one dye selected from the group consisting of a xanthene dye, a triarylmethane dye, a compound represented by formula (Ab2), a coumarin dye, an anthraquinone dye, and a tetraazaporphyrin dye.

[ chemical formula 2]

[ in the formula (Ab2), R⁴¹～R⁴⁴Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, wherein in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-. R⁴¹And R⁴²May be combined and form a ring together with the nitrogen atom to which they are combined, R⁴³And R⁴⁴May be bonded to form a ring together with the nitrogen atom to which they are bonded.

R⁴⁷～R⁵⁴Each independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, wherein when the alkyl group has 2 to 8 carbon atoms, a methylene group constituting the alkyl group may be replaced by an oxygen atom or-CO-, R⁴⁸And R⁵²May combine with each other to form-NH-, -S-or-SO₂-. However, in the alkyl group, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and terminal methylene groups are not replaced by oxygen atoms or-CO-.

Ring T¹Represents an optionally substituted aromatic heterocycle having 3 to 10 carbon atoms.

[Y]^m-Represents an arbitrary m-valent anion.]

[4] The colored curable resin composition according to any one of [1] to [3], wherein the dye includes a xanthene dye and a compound represented by the formula (Ab 2).

[5] A color filter comprising the colored curable resin composition according to any one of [1] to [4 ].

[6] A liquid crystal display device comprising the color filter according to [5 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the colored curable resin composition of the present invention, a color filter having an excellent shape can be formed.

Drawings

Fig. 1 is a schematic view illustrating a cross-sectional shape of a colored pattern.

Detailed Description

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

In the present specification, the compounds exemplified as the respective components may be used alone or in combination of two or more unless otherwise specified.

< colorant (A) >)

The colored curable resin composition of the present invention contains a dye as the colorant (a).

Examples of The dye include compounds classified as substances having a color tone other than pigments in The color index (published by The Society of Dyers and Colourists), and known dyes described in dyeing notes (color dyeing Co., Ltd.). Further, depending on the chemical structure, azo dyes, cyanine dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium (スクアリリウム) dyes, acridine dyes, styryl dyes, quinoline dyes, nitro dyes, and the like can be cited. Among these, dyes dissolved in an organic solvent are preferable.

Specifically, c.i. solvent yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 162;

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

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, 222, 227, 230, 245, 247;

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

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. 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. acid red 73, 80, 91, 97, 138, 151, 211, 274;

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

c.i. acid violet 34, 120;

c.i. acid blue 25, 27, 40, 45, 78, 80, 112; and the like C.I. acid dye,

C.i. alkaline green 1; and the like C.I. basic dye,

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

c.i. reactive orange 16; c.I. reactive dyes,

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

c.i. direct blue 40; c.I. direct dye,

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

c.i. disperse violet 26, 27;

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

As the c.i. mordant dyes, c.i. mordant yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

c.i. mordant oranges 3,4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; c.I. mordant dyes,

C.i. vat dyes such as c.i. vat green 1, and the like.

Among them, the dye preferably contains at least one dye selected from the group consisting of a xanthene dye (Aa), a triarylmethane dye (Ab), a compound represented by the formula (Ab2), a coumarin dye (Ac), an anthraquinone dye (Ad), and a tetraazaporphyrin dye (Ae) (hereinafter sometimes referred to as "dye (a 1)"), more preferably contains at least one dye selected from the group consisting of a xanthene dye (Aa), a triarylmethane dye (Ab), and a compound represented by the formula (Ab2), further preferably contains a xanthene dye (Aa), and a triarylmethane dye (Ab) or a compound represented by the formula (Ab2), and particularly preferably contains a xanthene dye and a compound represented by the formula (Ab 2).

In the present specification, the dye means a dye soluble in a solvent.

The xanthene dye (Aa) is a dye containing a compound having a xanthene skeleton in the molecule. Examples of the xanthene dye (Aa) include c.i. acid red dyes such as c.i. acid red 51 (hereinafter, the description of c.i. acid red is omitted, and only the number is described), 52, 87, 92, 94, 289, and 388; c.i. acid violet dyes such as c.i. acid violet 9, 30, 102; c.i. basic red dyes such as c.i. basic red 1 (rhodamine 6G), 2, 3,4, 8, 10 (rhodamine B), and 11; c.i. basic violet dyes such as c.i. basic violet 10, 11, 25; c.i. solvent red dyes such as c.i. solvent red 218; c.i. mordant red 27 and other c.i. mordant red dyes; c.i. reactive red dyes such as c.i. reactive red 36 (rose bengal B); sulforhodamine G; the xanthene dye described in Japanese patent application laid-open No. 2010-32999; and xanthene dyes described in patent No. 4492760; and the like. As the xanthene dye (Aa), a dye dissolved in an organic solvent is preferable.

Among these, the xanthene dye (Aa) is preferably a dye containing a compound represented by the formula (1a) (hereinafter, may be referred to as "compound (1 a)"). The compound (1a) may be a tautomer thereof. When the compound (1a) is used, the content of the compound (1a) in the xanthene dye (Aa) is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more. In particular, as the xanthene dye (Aa), it is preferable to use only the compound (1 a).

[ chemical formula 3]

[ in the formula (1a), R¹～R⁴Independently represent a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms and optionally having a substituent, or an aromatic hydrocarbon group having 1 carbon atom and optionally having a substituent and having 6 to 10 carbon atoms, and a methylene group (-CH) contained in the saturated hydrocarbon group₂-) may be substituted by-O-, -CO-or-NR¹¹-substitution. R¹And R²May together form a ring containing nitrogen atoms, R³And R⁴May together form a ring containing a nitrogen atom.

R⁵represents-OH or-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃R⁸or-SO₂NR⁹R¹⁰。

R⁶And R⁷Independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

m represents an integer of 0 to 5. When m is 2 or more, plural R⁵May be the same or different.

a represents an integer of 0 or 1.

X represents a halogen atom.

Z⁺To represent⁺N(R¹¹)₄、Na⁺Or K⁺4 of R¹¹May be the same or different.

R⁸Represents a C1-20 saturated hydrocarbon group, wherein hydrogen atoms contained in the saturated hydrocarbon group may be substituted by halogen atoms.

R⁹And R¹⁰Independently represent a hydrogen atom or a C1-20 saturated hydrocarbon group which may have a substituent, and-CH contained in the saturated hydrocarbon group₂May be substituted by-O-, -CO-, -NH-or-NR⁸-substitution, R⁹And R¹⁰May be bonded to each other to form a heterocyclic ring having 3 to 10 membered rings containing a nitrogen atom.

R¹¹Represents a hydrogen atom, a C1-20 saturated hydrocarbon group or a C7-10 aralkyl group.]

In the formula (1a), -SO₃ ^-When present, the number thereof is 1.

As R¹～R⁴In the (C6-C10) aromatic hydrocarbon group having a valence of 1, for example, phenyl, tolyl, xylyl, mesityl, propylphenyl and butylphenyl can be mentioned.

As the substituent that the aromatic hydrocarbon group may have, a halogen atom, -R⁸、-OH、-OR⁸、-SO₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-CO₂H、-CO₂R⁸、-SR⁸、-SO₂R⁸、-SO₃R⁸or-SO₂NR⁹R¹⁰Preferably, these substituents replace the hydrogen atoms contained in the aromatic hydrocarbon groups. Among these, as the substituent, -SO is preferable₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-SO₃R⁸and-SO₂NR⁹R¹⁰More preferably-SO₃ ^-Z⁺and-SO₂NR⁹R¹⁰. as-SO in this case₃ ^-Z⁺preferably-SO₃ ^-+N(R¹¹)₄. In addition, as-SO₂NR⁹R¹⁰preferably-SO₂NHR⁹. If R is¹～R⁴As such groups, a color filter which generates little foreign matter and has excellent heat resistance can be formed from the colored curable resin composition of the present invention containing the compound (1 a).

As R¹～R⁴And R⁸～R¹¹In the (1) -valent saturated hydrocarbon group having 1 to 20 carbon atoms, examples thereof include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl and eicosyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl groups; and C3-20 cyclic alkyl groups such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and the like.

R¹～R⁴The hydrogen atom contained in the saturated hydrocarbon group in (1) may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. As a substitutable R¹～R⁴The saturated hydrocarbon group of (2) is an aromatic hydrocarbon group having 6 to 10 carbon atoms as the hydrogen atom, and R is¹～R⁴In (b), the same groups as those exemplified for the aromatic hydrocarbon group having 6 to 10 carbon atoms are exemplified.

R⁹And R¹⁰The hydrogen atom contained in the saturated hydrocarbon group in (1) may be substituted with, for example, a hydroxyl group or a halogen atom as a substituent.

As R¹And R²Together form a ring, and R³And R⁴Examples of the ring to be formed together include the following rings, and a ring containing no double bond is more preferable.

[ chemical formula 4]

as-OR⁸Examples thereof include methoxy groupAlkoxy groups such as an ethoxy group, a propoxy group, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group, an octoxy group, a 2-ethylhexoxy group, and an eicosoxy group.

as-CO₂R⁸Examples thereof include alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl and eicosyloxycarbonyl.

As a-SR⁸Examples thereof include alkylsulfanyl groups such as methylsulfanyl, ethylsulfanyl, butylsulfanyl, hexylsulfanyl, decylthioyl, and eicosylsulfanyl groups.

as-SO₂R⁸Examples thereof include alkylsulfonyl such as methylsulfonyl, ethylsulfonyl, butylsulfonyl, hexylsulfonyl, decylsulfonyl and eicosylsulfonyl.

as-SO₃R⁸Examples thereof include an alkoxysulfonyl group such as a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group and a eicosyloxysulfonyl group. as-SO₃R⁸R of (A) to (B)⁸The branched or chain alkyl group has preferably 3 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 2-ethylhexyl group. A color filter with less generation of foreign matters can be formed.

as-SO₂NR⁹R¹⁰For example, sulfamoyl groups;

n-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylsulfamoyl, 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-cyclopentylsulfamoyl, N-butylsulfamoyl, N-butyl, N-1 substituted sulfamoyl groups such as N-hexylsulfamoyl, N- (1, 3-dimethylbutyl) sulfamoyl, N- (3, 3-dimethylbutyl) sulfamoyl, N-heptylsulfamoyl, N- (1-methylhexyl) sulfamoyl, N- (1, 4-dimethylpentyl) sulfamoyl, N-octylsulfamoyl, N- (2-ethylhexyl) sulfamoyl, N- (1, 5-dimethylhexyl) sulfamoyl, and N- (1, 1, 2, 2-tetramethylbutyl) sulfamoyl;

n, N-2-substituted sulfamoyl groups such as N, N-dimethylsulfamoyl, N-ethylsulfamoyl, N-diethylsulfamoyl, N-propylmethylsulfamoyl, N-isopropylmethylsulfamoyl, N-tert-butylmethylsulfamoyl, N-butylethylsulfamoyl, N-bis (1-methylpropyl) sulfamoyl, and N, N-heptylmethylsulfamoyl.

In the above N-1 substituted sulfamoyl group, R is⁸The branched or chain alkyl group has preferably 3 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 2-ethylhexyl group. A color filter with less generation of foreign matters can be formed.

As R⁵preferably-CO₂H、-CO₂ ^-Z⁺、-CO₂R⁸、-SO₃ ^-、-SO₃ ^-Z⁺、-SO₃H or-SO₂NHR⁹More preferably-SO₃ ^-、-SO₃ ^-Z⁺、-SO₃H or-SO₂NHR⁹。

m is preferably 1 to 4, more preferably 1 or 2.

As R⁶And R⁷The alkyl group having 1 to 6 carbon atoms in (A) includes those having 1 to 6 carbon atoms in the above-mentioned alkyl groups. Wherein, as R⁶、R⁷Preferably a hydrogen atom.

As R¹¹Examples of the aralkyl group having 7 to 10 carbon atoms in the above group include benzyl, phenylethyl and phenylbutyl.

As R¹¹Preferably, the alkyl group is a C1-20 saturated hydrocarbon group or a benzyl group.

Z⁺Is composed of⁺N(R¹¹)₄、Na⁺Or K⁺Preferably, it is⁺N(R¹¹)₄。

As mentioned above⁺N(R¹¹)₄Preferably 4R¹¹Wherein at least 2 are C5-20 saturated hydrocarbon groups with valence of 1. In addition, 4R¹¹The total number of carbon atoms of (A) is preferably 20 to 80, more preferably 20 to 60. In the compound (1a)⁺N(R¹¹)₄If present, if R¹¹These groups enable the formation of a color filter with less foreign matters from the colored curable resin composition of the present invention containing the compound (1 a).

As R¹～R⁴In a combination of (1), preferably R¹And R³Is a hydrogen atom, R²And R⁴Is a combination of C6-10 aromatic hydrocarbon groups with 1 valence having substituent. As the substituent of the above aromatic hydrocarbon group, -SO is preferred₃ ^-、-SO₃H、-SO₃ ^-Z⁺、-SO₃R⁸or-SO₂NHR⁹More preferably-SO₃ ^-Z⁺or-SO₂NHR⁹. These substituents replace the hydrogen atoms contained in the aromatic hydrocarbon groups.

As R¹～R⁴In combination with (1), R is also preferred¹～R⁴Combinations of saturated hydrocarbon groups all having a valence of 1. In this case, the saturated hydrocarbon group is preferably a methyl group or an ethyl group.

In addition, as R¹～R⁴In combination with (1), R is also preferred¹And R³Is C1-10 saturated hydrocarbon group which may have substituent, R²And R⁴Is a combination of phenyl groups which may have a substituent.

In this case, R¹May be substituted with R²The substituent of the phenyl group of (A) forms a ring, R³May be substituted with R⁴The substituents of the phenyl group of (a) form a ring.

In addition, R¹And R³The number of carbon atoms of (A) is preferably 1 to 3 independently of each other. As R¹、R³The substituent of the hydrogen atom contained in the saturated hydrocarbon group (2) is preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms which may be substituted with an alkoxy group having 1 to 3 carbon atoms, or a halogen atom.

In addition, as R²And R⁴The substituent which the phenyl group may have is preferably an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group. R is to be²And R⁴The number of the phenyl-substituted substituent(s) is 0 to 5, preferably 0 to 2, more preferably 0 or 1.

As a substituent for the above R²And R⁴Examples of the alkyl group having 1 to 4 carbon atoms in the phenyl group include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, sec-butyl, tert-butyl and the like.

In addition, the above-mentioned R may be substituted²And R⁴Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in the phenyl group include methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, butylsulfanyl group, and isopropylsulfanyl group.

Further, the above-mentioned R may be substituted²And R⁴Examples of the alkylsulfonyl group having 1 to 4 carbon atoms in the phenyl group include methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, and isopropylsulfonyl group.

Examples of the compound (1a) include compounds represented by the formulae (1-1) to (1-43). In the formula, R⁴⁰The C1-valent saturated hydrocarbon group having 1 to 20 carbon atoms is preferably a C6-12 branched chain alkyl group, and more preferably a 2-ethylhexyl group.

[ chemical formula 5]

[ chemical formula 6]

[ chemical formula 7 ]

[ chemical formula 8 ]

[ chemical formula 9 ]

[ chemical formula 10 ]

[ chemical formula 11 ]

[ chemical formula 12 ]

Further, in formula (Ab2) described later, R⁴⁸And R⁵²Compounds which combine with each other to form-O-are also exemplified as xanthene dyes (Aa).

Of these, a sulfonamide of c.i. acid red 289, a quaternary ammonium salt of c.i. acid red 289, a sulfonamide of c.i. acid violet 102, or a quaternary ammonium salt of c.i. acid violet 102 is preferable. Examples of such compounds include compounds represented by the formulae (1-1) to (1-8), the formulae (1-11) and the formulae (1-12).

Further, compounds represented by any of formulae (1-24) to (1-33) are also preferable in terms of excellent solubility in organic solvents.

As the xanthene dye (Aa), commercially available xanthene dyes (for example, "Chugai amino Fast Pink R-H/C" manufactured by Zhongzhou chemical industry Co., Ltd., and "Rhodamin 6G" manufactured by Tiangang chemical industry Co., Ltd.) can be used. Alternatively, a commercially available xanthene dye may be used as a starting material and synthesized in Japanese patent application laid-open No. 2010-32999.

When the xanthene dye (Aa) is contained, the content thereof is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, particularly preferably 18 parts by mass or more, preferably 50 parts by mass or less, more preferably 40 parts by mass or less, further preferably 35 parts by mass or less, per 100 parts by mass of the dye (a 1).

The triarylmethane dye (Ab) is a dye comprising a compound having a structure in which 3 aromatic groups are bonded to one carbon atom. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the triarylmethane dye (Ab) include c.i. solvent blue 2, 4, 5, 43, and 124; c.i. basic violet 3, 14, 25; and triarylmethane dyes described in c.i. basic blue nos. 1,5, 7, 11 and 26 and patent No. 4492760. Dyes dissolved in organic solvents are preferred.

Of these, the triarylmethane dye (Ab) preferably contains a compound represented by the formula (Ab1) (hereinafter, may be referred to as "compound (Ab 1)").

[ chemical formula 13 ]

[ in the formula (Ab1), R^1A～R^8AEach independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or a saturated hydrocarbon group having 1 to 20 carbon atoms, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group constituting the saturated hydrocarbon group may be replaced by an oxygen atom or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-.

R^9A～R^12AEach independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted aralkyl group having 7 to 30 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may beWhen the carbon number of the saturated hydrocarbon group is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or-CO-. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-. R^9AAnd R^10AMay be combined and form a ring together with the nitrogen atom to which they are combined, R^11AAnd R^12AMay be bonded to form a ring together with the nitrogen atom to which they are bonded.

A represents an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms.

[G]^g-Represents an arbitrary g-valent anion. g represents 0 or an arbitrary natural number.]

In the formula (Ab1), when a plurality of cations represented by the following formula are contained in 1 molecule, they may have the same structure or different structures.

[ chemical formula 14 ]

[ in the formula, A and R^1A～R^12AAre respectively synonymous with the above.]

From R^1A～R^12AThe saturated hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, and preferably is a chain. R^1A～R^12AThe number of carbon atoms of the saturated hydrocarbon group (2) is more preferably 1 to 10, and still more preferably 1 to 8. Examples of the linear or branched saturated hydrocarbon group (alkyl group) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a nonyl group, and a decyl group. The number of carbon atoms of the chain-like saturated hydrocarbon group (alkyl group) is preferably 1 to 10, more preferably 1 to 8, and still more preferably 1 to 6.

From R^1A～R^12AThe cyclic saturated hydrocarbon group (alicyclic saturated hydrocarbon group) may be a monocyclic ring or a polycyclic ring. Examples of the cyclic saturated hydrocarbon group (alicyclic saturated hydrocarbon group) include cyclopropyl and cyclobutylAlkyl, cyclopentyl, cyclohexyl, adamantyl, and the like. The cyclic saturated hydrocarbon (alicyclic saturated hydrocarbon group) group preferably has 3 to 10 carbon atoms, more preferably 6 to 10 carbon atoms.

As a group consisting of R^1A～R^12ASpecific examples of the saturated hydrocarbon group include those represented by the following formulae. In the following formula, the bonding end is represented.

[ chemical formula 15 ]

From R^1A～R^12AWhen the carbon number of the saturated hydrocarbon group is 2 to 20, a methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or a-CO-, and preferably may be replaced by an oxygen atom. Further, an oxygen atom may be inserted between methylene groups constituting the saturated hydrocarbon group. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-. The carbon number of the saturated hydrocarbon group in which the methylene group may be replaced with an oxygen atom or-CO-is preferably 2 to 10, more preferably 2 to 8, and still more preferably 2 to 6. The saturated hydrocarbon group in which the methylene group may be replaced with an oxygen atom is preferably a linear or branched saturated hydrocarbon group (i.e., a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (i.e., a linear alkyl group). Examples of the group include groups represented by the following formulae. In the following formula, the bonding end is represented.

[ chemical formula 16 ]

When the methylene group is replaced with an oxygen atom or-CO-, the number of carbon atoms between the terminal and the oxygen atom or-CO-, or between the oxygen atom or-CO-and the oxygen atom or-CO-is preferably 1 to 4, more preferably 2 to 3.

As R^9A～R^12AWith or without substitution of saturated hydrocarbon groupsSubstituted amino groups, which may be exemplified by amino groups; n-methylamino, N-ethylamino, N-phenylamino, N-dimethylamino, N-diethylamino, etc. In addition, as R^9A～R^12AExamples of the halogen atom that the saturated hydrocarbon group of (2) may have include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In addition, from R^9A～R^12AThe number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 12. Examples of the aromatic hydrocarbon group include a phenyl group, a tolyl group, an ethylphenyl group, a propylphenyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group. Phenyl, naphthyl and the like are preferred. The aromatic hydrocarbon group may have 1 or 2 or more substituents, and examples of the substituents include halogen atoms such as a fluorine atom, a chlorine atom, an iodine atom, and a bromine atom; a C1-6 haloalkyl group such as chloromethyl group and trifluoromethyl group; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a sulfamoyl group; c1-6 alkylsulfonyl such as methylsulfonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; and the like.

Further, from R^9A～R^12AThe aralkyl group has 7 to 30 carbon atoms, preferably 7 to 20 carbon atoms, and more preferably 7 to 17 carbon atoms. As a group consisting of R^9A～R^12AThe aralkyl group represented by the formula (I) is exemplified as R^9A～R^12AAnd a group in which an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, and a propylene group is bonded to a group described as the aromatic hydrocarbon group in (1).

Wherein, as R^1A～R^8AThe alkyl group is preferably a hydrogen atom or a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group), more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

R^9A～R^12AFrom the viewpoint of ease of synthesis, the alkyl group is preferably a saturated hydrocarbon group (preferably an alkyl group) having 1 to 10 carbon atoms, an optionally substituted aromatic hydrocarbon group having 6 to 20 carbon atoms or an optionally substituted aralkyl group having 7 to 30 carbon atoms, and more preferably a saturated hydrocarbon group (preferably an alkyl group) having 1 to 8 carbon atoms, a phenyl group, a naphthyl group, an optionally substituted aralkyl groupA phenyl group having a methyl group, a naphthyl group having a methyl group; the aralkyl group may be unsubstituted or substituted with 1 or more, particularly 1, of a halogen atom, methoxy group, ethoxy group, sulfamoyl group, methylsulfonyl group, methoxycarbonyl group, and ethoxycarbonyl group, and each of them is preferably a linear alkyl group having 1 to 4 carbon atoms.

The aromatic hydrocarbon group represented by A includes aromatic hydrocarbon groups having 6 to 20 carbon atoms such as a phenyl group, a tolyl group, an ethylphenyl group, a xylyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

Examples of the substituent that may be contained in the aromatic hydrocarbon group represented by a include a halogen atom such as a fluorine atom, a chlorine atom, and an iodine atom; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a sulfamoyl group; c1-6 alkylsulfonyl such as methylsulfonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl; an amino group which may be substituted; a sulfo group; -SO₃ ^-；-SO₃J, and the like. Examples of the substituent which may substitute for the amino group include alkyl groups having 1 to 20 carbon atoms such as methyl group which may be substituted with an amino group or a halogen atom; can be substituted by C1-4 alkyl, hydroxy, SO₃ ^-Aryl groups such as phenyl groups substituted with a methyl sulfonyl group, a dialkylamino group, or an alkoxy group having 1 to 10 carbon atoms; and the like.

Among them, as a, an aromatic hydrocarbon group which may have a substituent is preferable.

Examples of J include inorganic cations and organic cations. Specifically, Z in the above-mentioned compound (1a) is exemplified⁺The same cation, a cation of the following formula, and the like.

[ chemical formula 17 ]

Specific examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulae. In the following formula, the bonding end is represented.

Specific examples of the aralkyl group which may have a substituent include a group in which a methylene group is bonded to a bonding end of each specific example of the aromatic hydrocarbon group described below.

[ chemical formula 18 ]

[ chemical formula 19 ]

In A, as the optionally substituted aromatic hydrocarbon group, a group represented by the following formula is exemplified. Denotes a bonding end.

[ chemical formula 20 ]

Among them, preferred are groups represented by the formula (A1-1) and the formula (A1-3).

[G]^g-Represents anions of g valency. g may be 0, and is usually 1 to 14, preferably 1 to 12, more preferably 1 to 10, still more preferably 1 to 6, and particularly preferably 1 to 4. As [ G ]]^g-Examples thereof include known anions, and F^-、Cl^-、Br^-The halide ion is preferably a boron-containing anion, an aluminum-containing anion, or a fluorine-containing anion in view of heat resistance.

Examples of the boron-containing anion and the aluminum-containing anion include anions represented by the following formula (y 4).

[ chemical formula 21 ]

[ in the formula (y4), W¹、W²Each independently represents a group having 2 substituents which are formed by liberating protons from a 1-valent proton-donating substituent. M3 representsBoron or aluminum.]

Examples of the group having 2 substituents which are capable of donating a proton from a 1-valent proton-donating substituent include groups which are capable of donating a proton from each of 2 proton-donating substituents from a compound having at least 2 proton-donating substituents (for example, a hydroxyl group, a carboxylic acid group, etc.) having 1-valent protons. As the compound, preferred are catechol which may have a substituent, 2, 3-dihydroxynaphthalene which may have a substituent, 2' -biphenol which may have a substituent, 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, salicylic acid which may have a substituent, benzyl acid which may have a substituent, or mandelic acid which may have a substituent.

In the above-exemplified compounds, examples of the substituent include a saturated hydrocarbon group (e.g., an alkyl group, a cycloalkyl group, etc.), a halogen atom, a haloalkyl group, a hydroxyl group, an amino group, a nitro group, an alkoxy group, etc.

Examples of the salicylic acid which may have a substituent include monoaminosalicylic acids such as salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-methoxysalicylic acid, 3-nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3, 5-di-tert-butylsalicylic acid, 3-aminosalicylic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, and 6-aminosalicylic acid; monohydroxysalicylic acids such as 3-hydroxysalicylic acid (2, 3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2, 4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2, 5-dihydroxybenzoic acid), and 6-hydroxysalicylic acid (2, 6-dihydroxybenzoic acid); dihydroxysalicylic acids such as 4, 5-dihydroxysalicylic acid and 4, 6-dihydroxysalicylic acid; monohalogenated salicylic acids such as 3-chlorosalicylic acid, 4-chlorosalicylic acid, 5-chlorosalicylic acid, 6-chlorosalicylic acid, 3-bromosalicylic acid, 4-bromosalicylic acid, 5-bromosalicylic acid, 6-bromosalicylic acid, etc.; dihalogenated salicylic acids such as 3, 5-dichlorosalicylic acid, 3, 5-dibromosalicylic acid, 3, 5-diiodosalicylic acid, etc.; trihalosalicylic acids such as 3,5, 6-trichlorosalicylic acid; and the like.

As the benzyl acid which may have a substituent(s), there may be mentioned

[ chemical formula 22 ]

Mandelic acid which may have a substituent(s) is exemplified by

[ chemical formula 23 ]

And the like.

Preferred anions among the anions represented by the formula (y4) include anions (BC-1) to (BC-24) having substituents shown in Table 1, anions (BC-25) to (BC-28) represented by the formulae (BC-25), (BC-26), (BC-27) and (BC-28), respectively.

[ chemical formula 24 ]

[ TABLE 1]

Anion(s)	R⁶¹	R⁶²	R⁶³	R⁶⁴
					Anion (BC-1)	H	H	H	H
Anion (BC-2)	OH	H	H	H
					Anion (BC-3)	H	OH	H	H
Anion (BC-4)	H	H	OH	H
					Anion (BC-5)	H	H	H	OH
Anion (BC-6)	Cl	H	H	H
					Anion (BC-7)	H	Cl	H	H
Anion (BC-8)	H	H	Cl	H
					Anion (BC-9)	H	H	H	Cl
Anion (BC-10)	Br	H	H	H
					Anion (BC-11)	H	Br	H	H
Anion (BC-12)	H	H	Br	H
					Anion (BC-13)	H	H	H	Br
Anion (BC-14)	NH₂	H	H	H
					Anion (BC-15)	H	NH₂	H	H
Anion (BC-16)	H	H	NH₂	H
					Anion (BC-17)	H	H	H	NH₂
Anion (BC-18)	H	tBu	H	tBu
					Anion (BC-19)	H	Cl	H	Cl
Anion (BC-20)	H	Br	H	Br
					Anion (BC-21)	H	I	H	I
Anion (BC-22)	H	OH	OH	H
					Anion (BC-23)	OH	H	OH	H
Anion (BC-24)	Cl	Cl	H	Cl

[ chemical formula 25 ]

As the anion represented by the formula (y4), anion (BC-1), anion (BC-2), anion (BC-3) and anion are preferable(BC-25), an anion (BC-26) and an anion (BC-27), more preferably an anion (BC-1), an anion (BC-2) and an anion (BC-25), and still more preferably an anion (BC-1) and an anion (BC-2). By using these anions as [ G ]]^g-The dye represented by the formula (Ab2) tends to have excellent solubility in an organic solvent.

Examples of the fluorine-containing anion include anions represented by the following formulae (y6), (y7), (y8), and (y 9).

[ chemical formula 26 ]

[ in the formula (y6), W³And W⁴Each independently represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W³And W⁴Together form a fluorinated alkylene group having 1 to 4 carbon atoms.]

[ chemical formula 27 ]

[ in the formula (y7), W⁵～W⁷Each independently represents a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms.]

[ chemical formula 28 ]

[ in the formula (Y8), Y¹Represents a fluorinated alkylene group having 1 to 4 carbon atoms.]

[ chemical formula 29 ]

[ in the formula (Y9), Y²Represents a fluorinated alkyl group having 1 to 4 carbon atoms.]

In the formulae (y6) and (y7), the fluorination is carried out with 1 to 4 carbon atomsAlkyl, preferably perfluoroalkyl. As the perfluoroalkyl group, there may be mentioned-CF₃、-CF₂CF₃、-CF₂CF₂CF₃、-CF(CF₃)₂、-CF₂CF₂CF₂CF₃、-CF₂CF(CF₃)₂、-C(CF₃)₃And the like.

In the formula (y6), the fluorinated alkylene group having 1 to 4 carbon atoms is preferably a perfluoroalkylene group, and examples thereof include-CF₂-、-CF₂CF₂-、-CF₂CF₂CF₂-、-C(CF₃)₂-、-CF₂CF₂CF₂CF₂-and the like.

In the formula (y8), the fluorinated alkylene group having 1 to 4 carbon atoms is preferably a perfluoroalkylene group. As the perfluoroalkylene group, there may be mentioned-CF₂-、-CF₂CF₂-、-CF₂CF₂CF₂-、-C(CF₃)₂-、-CF₂CF₂CF₂CF₂-and the like.

In the formula (y9), the fluorinated alkyl group having 1 to 4 carbon atoms is preferably a perfluoroalkyl group. As the perfluoroalkyl group, there may be mentioned-CF₃、-CF₂CF₃、-CF₂CF₂CF₃、-CF(CF₃)₂、-CF₂CF₂CF₂CF₃、-CF₂CF(CF₃)₂、-C(CF₃)₃And the like.

Examples of the anion represented by the formula (y6) (hereinafter, may be referred to as "anion (6)") include anions represented by the formulae (6-1) to (6-6) (hereinafter, may be referred to as "anion (6-1)" to "anion (6-6)").

[ chemical formula 30 ]

Examples of the anion represented by the formula (y7) (hereinafter, may be referred to as "anion (7)") include anion (7-1) represented by the following formula.

[ chemical formula 31 ]

Examples of the anion represented by the formula (y8) (hereinafter, may be referred to as "anion (8)") include anions represented by the formulae (8-1) to (8-4) (hereinafter, may be referred to as "anion (8-1)" to "anion (8-4)").

[ chemical formula 32 ]

Examples of the anion represented by the formula (y9) (hereinafter, may be referred to as "anion (9)") include anions represented by the formulae (9-1) to (9-4) (hereinafter, may be referred to as "anion (9-1)" to "anion (9-4)").

[ chemical formula 33 ]

The solubility of the dye represented by the formula (Ab2) in an organic solvent can be improved by containing an anion (i.e., a fluorine-containing anion) selected from at least 1 of the anion (6), the anion (7), the anion (8) and the anion (9), and the solubility of the dye in an organic solvent can be improved. Among these, anions (6) and (7) are preferable, anion (6-1), anion (6-2), and anion (7-1) are more preferable, and anion (6-2) is particularly preferable.

The alkali metal salt of the anion represented by the formula (6), the formula (7), the formula (8) or the formula (9) may be produced by a method described in International publication No. 2008/075672, Japanese patent application laid-open No. 2010-280586, or the like, using a commercially available product.

Examples of the compound represented by the formula (Ab1) include compounds represented by the following formula. Wherein J is the same as defined above.

[ chemical formula 34 ]

[ chemical formula 35 ]

[ chemical formula 36 ]

When the triarylmethane dye (Ab) is contained, the content thereof is preferably 1 part by mass or more, more preferably 50 parts by mass or more, further preferably 60 parts by mass or more, further preferably 65 parts by mass or more, preferably 99 parts by mass or less, more preferably 95 parts by mass or less, further preferably 90 parts by mass or less, further preferably 85 parts by mass or less, and particularly preferably 82 parts by mass or less, based on 100 parts by mass of the dye (a 1).

The compound represented by the formula (Ab2) (hereinafter sometimes referred to as compound (Ab 2)) also includes tautomers thereof.

[ chemical formula 37 ]

[ in the formula (Ab2), R⁴¹～R⁴⁴Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, wherein in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or-CO-. However, in the C2-20 saturated hydrocarbon group, adjacent methylene groups are not simultaneously placedThe terminal methylene group is not replaced by an oxygen atom or-CO-by replacing it with an oxygen atom. R⁴¹And R⁴²May be combined and form a ring together with the nitrogen atom to which they are combined, R⁴³And R⁴⁴May be bonded to form a ring together with the nitrogen atom to which they are bonded.

R⁴⁷～R⁵⁴Independently represents a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and when the alkyl group has 2 to 8 carbon atoms, the methylene group contained in the alkyl group may be replaced by an oxygen atom or-CO-, R⁴⁸And R⁵²May combine with each other to form-NH-, -S-or-SO₂-. However, in the alkyl group, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-.

[Y]^m-Represents an arbitrary m-valent anion.

m represents an arbitrary natural number. ]

When 1 molecule contains a plurality of cations represented by the following formula, they may have the same structure or different structures.

[ chemical formula 38 ]

[ in the formula, a ring T¹、R⁴¹～R⁴⁴And R⁴⁷～R⁵⁴Are respectively synonymous with the above.]

The above-mentioned ring T¹The aromatic heterocyclic ring of (a) may be a monocyclic ring or a fused ring. By a ring T¹The aromatic heterocycle has 3 to 10 carbon atoms, preferably 3 to 8 carbon atoms. The aromatic heterocycle is preferably a 5-to 10-membered ring, and more preferably a 5-to 9-membered ring. Examples of the monocyclic aromatic heterocycle include a 5-membered ring containing a nitrogen atom such as a pyrrole ring, an oxazole ring, a pyrazole ring, an imidazole ring, and a thiazole ring; 5-membered rings containing no nitrogen atom, such as furan ring, chromene ring, and thiophene ring(ii) a A 6-membered ring containing a nitrogen atom such as a pyridine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring; examples of the fused ring aromatic heterocyclic ring include nitrogen atom-containing fused rings such as indole ring, benzimidazole ring, benzothiazole ring and quinoline ring; a ring containing no nitrogen atom such as a benzofuran ring; and the like.

As a ring T¹The aromatic heterocyclic ring of (a) may have a substituent(s) such as a halogen atom, a cyano group, a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms) which may have a substituent(s), a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent(s), and preferably a saturated hydrocarbon group having 1 to 20 carbon atoms (preferably an alkyl group having 1 to 20 carbon atoms), a substituted or unsubstituted amino group, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent(s).

Wherein, as a ring T¹The aromatic heterocyclic ring of (3) is preferably an aromatic heterocyclic ring having a nitrogen atom, and more preferably an aromatic heterocyclic ring having a 5-membered ring having a nitrogen atom.

In addition, a ring T¹More preferably a ring represented by the formula (Ab2-x 1).

[ chemical formula 39 ]

[ in the formula (Ab2-x1),

ring T²Represents an aromatic heterocycle having 3 to 10 carbon atoms.

R⁴⁵And R⁴⁶Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, wherein in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or a halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be substituted with an oxygen atom or-CO-. However, in the C2-20 saturated hydrocarbon group, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by oxygenAtom or-CO-. R⁴⁵And R⁴⁶May be bonded to form a ring together with the nitrogen atom to which they are bonded.

R⁵⁵Represents a saturated hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms and having a substituent.

k1 represents 0 or 1.

Represents a bonding end with a carbocation. ]

Further, a ring T¹Particularly preferred is a ring represented by the formula (Ab2-y 1).

[ chemical formula 40 ]

[ in the formula (Ab2-y1),

R⁵⁶represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

X2 represents an oxygen atom, -NR⁵⁷-or a sulfur atom.

R⁵⁷Represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

R⁴⁵And R⁴⁶Are synonymous with the above.

Represents a bonding end with a carbocation. ]

In the above formula, ring T²The aromatic heterocyclic ring of (A) may be mentioned as a ring T¹The aromatic heterocyclic ring shown in (1) above is the same as the ring shown in (1).

In addition, a ring T¹Also preferred is a ring represented by the formula (Ab2-x2),

[ chemical formula 41 ]

[ in the formula (Ab2-x2),

ring T³Represents an aromatic heterocycle having 3 to 10 carbon atoms and having a nitrogen atom.

R⁵⁸Represents a C1-20 saturated hydrocarbon group or a carbon having a substituentA number of 6 to 20.

R⁵⁹Represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent.

k2 represents 0 or 1.

Represents a bonding end with a carbocation. ]

Ring T¹More preferably, it is a ring represented by the formula (Ab2-y 2).

[ chemical formula 42 ]

[ in the formula (Ab2-y2),

R⁶⁰represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

R⁵⁹Are synonymous with the above.

Represents a bonding end with a carbocation. ]

From R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰The saturated hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, still more preferably 1 to 6, and particularly preferably 1 to 4. As a group consisting of R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰The saturated hydrocarbon group having 1 to 20 carbon atoms represented by R¹Examples of the saturated hydrocarbon group are the same as those shown above. The number of carbon atoms in the chain-like saturated hydrocarbon group (alkyl group) is preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4. The carbon number of the cyclic saturated hydrocarbon group (alicyclic hydrocarbon group) is preferably 3 to 10, more preferably 6 to 10.

In addition, from R⁴¹～R⁴⁶When the carbon number of the saturated hydrocarbon group is 2 to 20, the methylene group contained in the saturated hydrocarbon group may be replaced by an oxygen atom or-CO-,preferably may be replaced by an oxygen atom. Further, an oxygen atom may be inserted between methylene groups constituting the saturated hydrocarbon group. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom or-CO-. In this case, the saturated hydrocarbon group is preferably a linear or branched saturated hydrocarbon group (i.e., a linear or branched alkyl group), and more preferably a linear saturated hydrocarbon group (i.e., a linear alkyl group). The carbon number of the saturated hydrocarbon group in which the methylene group is replaced with an oxygen atom or-CO-is preferably 2 to 10, more preferably 2 to 8. When the methylene group is replaced with an oxygen atom or-CO-, the number of carbon atoms between the terminal and the oxygen atom or-CO-, or between the oxygen atom or-CO-and the oxygen atom or-CO-is preferably 1 to 4, more preferably 2 to 3.

From R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰The saturated hydrocarbon group represented may be substituted with a substituted or unsubstituted amino group or a halogen atom. Examples of the substituted amino group include alkylamino groups such as dimethylamino group and diethylamino group. Examples of the halogen atom include fluorine, chlorine, bromine and iodine. When the halogen atom is a fluorine atom, the group R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶And R⁵⁸～R⁶⁰The saturated hydrocarbon group substituted with a halogen atom (fluorine atom) is preferably a perfluoroalkyl group such as a trifluoromethyl group, a pentafluoroethyl group, or a heptafluoropropyl group.

As a group consisting of R⁵⁹Examples of the substituent which the alkyl group may have include a halogen atom and a cyano group.

In addition, as represented by R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶、R⁵⁸～R⁶⁰The optionally substituted aromatic hydrocarbon group represented by R^9AThe aromatic hydrocarbon group which may be substituted is the same group. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 10. The aromatic hydrocarbon group is preferably a phenyl group, a tolyl group, a xylyl group, or a naphthyl group. In addition, the aromatic hydrocarbon group may have 1 or 2 or more substituents.

As a group consisting of R⁴¹～R⁴⁶、R⁵⁹The aralkyl group which may be substituted is represented by R^9AThe aralkyl group which may be substituted is the same group as the above-mentioned aralkyl group.

As a group consisting of R⁵⁷The alkyl group having 1 to 10 carbon atoms is represented by R^9AExamples of the branched or straight chain alkyl group include those having 1 to 10 carbon atoms.

From R⁴¹～R⁴⁶、R⁵⁵、R⁵⁶、R⁵⁸～R⁶⁰In the groups represented, as the substituents in the above aromatic hydrocarbon group and the above aralkyl group, there may be mentioned halogen atoms such as fluorine atom, chlorine atom, iodine and the like; alkoxy groups having 1 to 6 carbon atoms such as methoxy and ethoxy; a hydroxyl group; alkyl groups having 1 to 6 carbon atoms such as methyl group and ethyl group; a sulfamoyl group; c1-6 alkylsulfonyl such as methylsulfonyl; alkoxycarbonyl having 1 to 6 carbon atoms such as methoxycarbonyl and ethoxycarbonyl.

From R⁴⁷～R⁵⁴The alkyl group having 1 to 8 carbon atoms may be any of straight, branched and cyclic, preferably a chain, and includes R¹Examples of the alkyl group include straight chain, branched chain and cyclic alkyl groups having 1 to 8 carbon atoms.

In addition, as represented by R⁴⁷～R⁵⁴The group represented by R wherein the methylene group constituting the C2-C8 alkyl group is replaced with an oxygen atom or-CO- (preferably, a group replaced with an oxygen atom is preferred, however, in the alkyl group, adjacent methylene groups are not simultaneously replaced with an oxygen atom, and the terminal methylene group is not replaced with an oxygen atom or-CO-), is exemplified by⁴¹～R⁴⁶The methylene group constituting the alkyl group having 2 to 20 carbon atoms is replaced by an oxygen atom or a group having 8 or less carbon atoms.

Wherein, as R⁴¹～R⁴⁴、R⁵⁵、R⁵⁸、R⁵⁹Preferably a saturated hydrocarbon group (preferably an alkyl group) having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent.

In addition, as R⁴⁷～R⁵⁴Each independently preferably being a hydrogen atom, a halogen atom or a carbon numberThe alkyl group of 1 to 8 is particularly preferably a hydrogen atom, a methyl group, a fluorine atom or a chlorine atom.

Further, as R⁵⁶The alkyl group is preferably a saturated hydrocarbon group (preferably an alkyl group) having 1 to 10 carbon atoms or an aromatic hydrocarbon group which may have a substituent, and more preferably a saturated hydrocarbon group (preferably an alkyl group) having 1 to 8 carbon atoms, a halogen atom, a halogenated alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, or an aromatic hydrocarbon group which may be substituted with a methylsulfonyl group.

As R⁵⁷Preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

Examples of the cation moiety of formula (Ab2) include cations 1 to 12 represented by formula (Ab2-1) shown in Table 2 below. In the table, the bonding end is denoted by symbol.

[ chemical formula 43 ]

[ TABLE 2]

In table 2, Ph1 to Ph9 mean groups represented by the following formulae. Wherein, represents a bonding end.

[ chemical formula 44 ]

Further, as the cation moiety of the formula (Ab2), cations 13 to 16 represented by the formula (Ab2-II) and the like can be mentioned as shown in the following Table 3. In the table, the bonding end is denoted by symbol.

[ chemical formula 45 ]

[ TABLE 3]

R⁴¹

R⁴²

R⁴³

R⁴⁴

R⁵⁹

R⁶⁰

Cation 13

CH₂CH₃

CH₃

Ph1

Cation 14

CH₂CH₃

(CH₂)₅CH₃

Ph10

Cation 15

CH₂CH(CH₃)CH₃

CH₃

Ph1

Cation 16

CH₂CH₃

Ph1

CH₂CH₃

Ph1

(CH2)₅CH₃

Ph11

In table 3, Ph1, Ph10, and Ph11 mean groups represented by the following formulae. Wherein, represents a bonding end.

[ chemical formula 46 ]

Among them, the cation moiety of the formula (Ab2) is preferably cation 1 to cation 6, cation 11 or cation 12, and particularly preferably cation 1, cation 2 or cation 12.

As [ Y ]]^m-Examples of the above-mentioned known compounds includeExamples of the anion of (b) include anions represented by the formulae (y10) and (y 11).

[ chemical formula 47 ]

[ in the formula, R^B6Represents an organic group having a valence of 2. R^B7Represents a 3-valent aromatic hydrocarbon group. n represents a natural number.]

Examples of the anion represented by the formula (y10) include a methanedisulfonic acid anion, a propanedisulfonic acid anion, a toluenedisulfonic acid anion, a naphthalenedisulfonic acid anion, and an anion represented by the following formula.

[ chemical formula 48 ]

Examples of the anion represented by the formula (y11) include anions represented by the following formula. In the formula, n represents a natural number.

[ chemical formula 49 ]

From the viewpoint of heat resistance, preferred anions are boron-containing anions, aluminum-containing anions, and fluorine-containing anions.

Examples of the compound (Ab2) include compounds represented by the following formulae.

[ chemical formula 50 ]

[ chemical formula 51 ]

[ chemical formula 52 ]

[ chemical formula 53 ]

[ chemical formula 54 ]

[ chemical formula 55 ]

[ chemical formula 56 ]

When the compound represented by the formula (Ab2) is contained, the content thereof is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, further preferably 65 parts by mass or more, preferably 95 parts by mass or less, more preferably 90 parts by mass or less, further preferably 85 parts by mass or less, and particularly preferably 82 parts by mass or less, in 100 parts by mass of the dye (a 1).

Coumarin dyes (Ac) are dyes comprising compounds having a coumarin skeleton within the molecule. Examples of the coumarin dye (Ac) include c.i. acid yellow 227, 250; c.i. disperse yellow 82, 184; c.i. solvent orange 112; c.i. solvent yellow 160, 172; coumarin dyes described in patent No. 1299948; and the like. Dyes dissolved in organic solvents are preferred.

Among these, as the coumarin dye, for example, a compound represented by the formula (Ac1) (hereinafter, may be referred to as "compound (Ac 1)") is preferable.

[ chemical formula 57 ]

[ in the formula (Ac1), X^CRepresents an oxygen atom or a sulfur atom.

R^1CEach independently represents a saturated hydrocarbon group having 1 to 20 carbon atoms, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group constituting the saturated hydrocarbon group may be replaced with an oxygen atom. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom.

R^2C～R^13CEach independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl group, -SO₃M、-CO₂M, hydroxyl, formyl, amino, C1-20 alkyl with 1 valence, methylene constituting the alkyl can be replaced by oxygen atom, sulfur atom, -N (R)^14C) -, sulfonyl or carbonyl, the hydrogen atom contained in the hydrocarbon group being possibly replaced by a halogen atom, cyano, nitro, carbamoyl, sulfamoyl, -SO₃M、-CO₂M, hydroxyl, formyl or amino.

R^14CA hydrogen atom or a C1-20 hydrocarbon group, wherein a plurality of R are present^14CIn the case of (2), they may be the same or different.

M represents a hydrogen atom or an alkali metal atom.

L^CRepresents a C1-20 alkyl group or sulfonyl group having a valence of 2.]

R^1CThe saturated hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic, and is preferably linear. Specifically, R may be mentioned¹Examples of the saturated hydrocarbon group having 1 to 20 carbon atoms include the same groups as those described above.

In addition, from R^1CWhen the number of carbon atoms in the saturated hydrocarbon group is 2 to 20,the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom. Further, an oxygen atom may be inserted between methylene groups constituting the saturated hydrocarbon group. However, in the saturated hydrocarbon group having 2 to 20 carbon atoms, adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by an oxygen atom.

As R^2C～R^14CThe C1-20 hydrocarbon group includes C1-20 saturated hydrocarbon group, C1-20 unsaturated aliphatic hydrocarbon group, and C6-10 aromatic hydrocarbon group. The C1-20 saturated hydrocarbon group includes R¹The same groups as those exemplified for the 1-valent saturated hydrocarbon group having 1 to 20 carbon atoms in (A). Examples of the 1-valent unsaturated hydrocarbon group having 1 to 20 carbon atoms include linear alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, hexadecenyl, octadecenyl, and eicosenyl groups; cycloalkenyl groups such as cyclopentenyl, cyclohexenyl and cycloheptenyl; and the like. The C6-10 1-valent aromatic hydrocarbon group includes R¹In (b), the same groups as those exemplified for the aromatic hydrocarbon group having 6 to 10 carbon atoms are exemplified.

As L^CThe C1-20 2-valent hydrocarbon group includes C1-20 2-valent saturated hydrocarbon group, C1-20 2-valent unsaturated hydrocarbon group, and C6-10 2-valent aromatic hydrocarbon group, and R is^2CWherein 1 hydrogen atom contained in the C1-valent hydrocarbon group of 1 to 20 is a group at the bonding end.

Further, a plurality of R^1C～R^13CThe same groups as each other are preferred.

Wherein, as R^1CThe alkyl group is preferably a C1-20 chain alkyl group, and more preferably a C1-10 chain alkyl group.

As R^2C～R^6CThe hydrocarbon group is preferably a hydrogen atom or a C1-valent hydrocarbon group, more preferably a hydrogen atom or a C1-10 saturated hydrocarbon group, and still more preferably a hydrogen atom or a C1-5 chain alkyl group.

As R^7C～R^13CThe hydrogen atom or the 1-valent hydrocarbon group having 1 to 20 carbon atoms is preferable, and the hydrogen atom is particularly preferable.

As L^CPreferably a C1-20 saturated hydrocarbon group such as a sulfonyl group, a methylene group, a propylene group, etc. In addition, L^CThe 2-valent hydrocarbon group(s) is preferably a C1-10 hydrocarbon group, more preferably a C1-5 hydrocarbon group.

In addition, as X^CParticularly, an oxygen atom is preferable.

Examples of the compound (Ac1) include compounds represented by the following formula.

[ chemical formula 58 ]

[ chemical formula 59 ]

When the coumarin dye (Ac) is contained, the content thereof is preferably 1 part by mass or more, more preferably 50 parts by mass or more, further preferably 80 parts by mass or more, further preferably 100 parts by mass or less, and further preferably 99 parts by mass or less, based on 100 parts by mass of the dye (a 1).

As the anthraquinone dye (Ad), a known one can be used. Examples of the anthraquinone dye (Ad) include

C.i. solvent yellow 117 (hereinafter, the description of c.i. solvent yellow is omitted, and only the reference numeral is given), 163, 167, 189, and,

C.I. solvent orange 77, 86,

C.i. solvent red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,

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

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, 9,

C.I. solvent Green 3, 28, 29, 32, 33,

C.I. acid red 80,

C.I. acid Green 25, 27, 28, 41,

C.I. acid violet 34,

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

C.I. disperse yellow 51,

C.I. disperse Violet 26, 27,

C.I. disperse blues 1, 14, 56, 60,

C.I. direct blue 40,

C.I. mordant Red 3, 11,

C.i. mordant blue 8

And the like. The anthraquinone dye (Ad) is preferably a dye dissolved in an organic solvent, more preferably a blue, violet or red anthraquinone dye.

Among these, as the anthraquinone dye (Ad), a compound represented by the formula (1d) (hereinafter, sometimes referred to as "compound (1 d)") is preferable.

[ chemical formula 60 ]

[ in the formula (1d), R⁹¹And R⁹²Each independently represents a hydrogen atom, an optionally substituted aliphatic hydrocarbon group having 1 to 10 carbon atoms, an optionally substituted alicyclic hydrocarbon group having 3 to 10 carbon atoms, or a compound represented by the formula (1 d')

[ chemical formula 61 ]

(in the formula (1 d'), R⁹³Represents an alkyl group having 1 to 6 carbon atoms, a halogen atom or-SO₃H、-CO₂H、-CO₂R⁹⁴、-NHCOR⁹⁴、-SO₃R⁹⁴or-SO₂NR⁹⁴R⁹⁵。

R⁹⁴Represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxyl group or an amino group, or an alicyclic hydrocarbon group having 3 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxyl group or an amino group.

R⁹⁵Represents a hydrogen atom or a C1-10 saturated hydrocarbon group.

r represents an integer of 0 to 5. When R is 2 or more, a plurality of R⁹³May be the same or different.

X⁹¹Represents a single bond or an alkylene group having 1 to 6 carbon atoms. )

The groups shown. ]

Compound (1d) has-SO₃H and/or-CO₂In the case of H, they may form salts (e.g., Na salts, K salts).

R⁹¹And R⁹²、R⁹⁴And R⁹⁵Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group.

Examples of the substituent that these aliphatic hydrocarbon groups may have include a hydroxyl group, a halogen atom, and an amino group, and a hydroxyl group or a halogen atom is preferable.

As a group consisting of R⁹¹、R⁹²And R⁹⁴Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, tricyclodecyl, and the like.

Examples of the substituent which these alicyclic hydrocarbon groups may have include a hydroxyl group, a halogen atom, an amino group, and the like, and a hydroxyl group or a halogen atom is preferable.

As a group consisting of R⁹³Examples of the alkyl group having 1 to 6 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, and neopentyl.

as-CO₂R⁹⁴Examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, tert-butoxycarbonyl, hexyloxycarbonyl and eicosyloxycarbonylAlkylcarbonyl, and the like.

as-NHCOR⁹⁴Examples thereof include N-acetylamino, N-propionylamino, N-butyrylamino, N-isobutyrylamino and N-pivaloylamino.

as-SO₃R⁹⁴Examples thereof include methoxysulfonyl, ethoxysulfonyl, propoxysulfonyl, tert-butoxysulfonyl, hexyloxysulfonyl and eicosyloxysulfonyl.

as-SO₂NR⁹⁴R⁹⁵Examples thereof include N-methylsulfamoyl, N-ethylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-sec-butylsulfamoyl, N-tert-butylsulfamoyl, N-pentylsulfamoyl, 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-cyclopentylsulfamoyl, N-propylsulfamoyl, N-isopropylsulfamoyl, N-butylsulfamoyl, N-isobutylsulfamoyl, N-butylsulfamoyl, N-sec-butylsulfamoyl, N-2-dimethylpropyl-sulfamoyl, N- (1, N-1 substituted sulfamoyl groups such as N-cyclohexylsulfamoyl, N-hexylsulfamoyl, N- (1, 3-dimethylbutyl) sulfamoyl, N- (3, 3-dimethylbutyl) sulfamoyl, N-heptylsulfamoyl, N- (1-methylhexyl) sulfamoyl, N- (1, 4-dimethylpentyl) sulfamoyl, N-octylsulfamoyl, N- (2-ethylhexyl) sulfamoyl, N- (1, 5-dimethyl) hexylsulfamoyl, N- (1, 1, 2, 2-tetramethylbutyl) sulfamoyl, and N- (5-aminopentyl) sulfamoyl; n, N-2-substituted sulfamoyl groups such as N, N-dimethylsulfamoyl, N-ethylsulfamoyl, N-diethylsulfamoyl, N-propylmethylsulfamoyl, N-isopropylmethylsulfamoyl, N-tert-butylmethylsulfamoyl, N-butylethylsulfamoyl, N-bis (1-methylpropyl) sulfamoyl, and N, N-heptylmethylsulfamoyl.

X⁹¹In the above formula, the alkylene group having 1 to 6 carbon atoms includes methylene, ethylene, propane-1, 3-diyl, propane-1, 2-diyl, butane-1, 4-diyl, pentane-1, 5-diyl, hexane-1, 6-diyl, ethane-1, 1-diyl and butane-1, 3-diyl2-methylpropane-1, 3-diyl, 2-methylpropane-1, 2-diyl, pentane-1, 4-diyl, 2-methylbutane-1, 4-diyl, and the like.

As R⁹³Preferably an alkyl group having 1 to 5 carbon atoms which may have a hydroxyl group, -SO₃R⁹⁴、-SO₂NR⁹⁴R⁹⁵More preferably-SO₂NR⁹⁴R⁹⁵Further preferred is-SO₂NHR⁹⁴(in the formulae, R⁹⁴And R⁹⁵Same as defined above).

Examples of the compound (1d) include compounds represented by the formulae (3-1) to (3-11).

[ chemical formula 62 ]

As the anthraquinone dye (Ad), a compound represented by the formula (1d), preferably R⁹¹And R⁹²A hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a phenyl group which may have a halogen atom, and a group represented by the formula (1 d'), and more preferably compounds represented by the formulae (3-4) and (3-11). These anthraquinone dyes can form a coating film or pattern with high contrast, and can form a coating film or pattern with little generation of foreign matter and excellent light resistance.

When the anthraquinone dye (Ad) is contained, the content thereof is preferably 1 part by mass or more and 99 parts by mass or less in 100 parts by mass of the dye (a 1).

Porphyrazine dye (Ae) is a compound having a porphyrazine skeleton in a molecule. When the tetraazaporphyrin dye (Ae) is an acid dye or a basic dye, it may form a salt with any cation or anion.

Among these, as the porphyrazine dye (Ae), a dye containing a structure represented by formula (1e) (hereinafter, may be referred to as compound (1 e)).

[ chemical formula 63 ]

[ in the formula (1e), R⁷¹～R⁷⁸Each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyloxy group, or a substituted or unsubstituted amino group, and M4 represents a2 hydrogen atom, a2 1-valent metal atom, a 2-valent metal atom, a 3-valent substituted metal atom, or a metal oxide.

The aryl group in the formula (1e) is an aromatic hydrocarbon group having 6 to 30 carbon atoms such as a phenyl group and a naphthyl group; preferably, the aromatic hydrocarbon group is an aromatic hydrocarbon group having 3 to 20 carbon atoms such as furyl, thienyl, pyridyl and the like.

In the formula (1e), R⁷¹～R⁷⁸Preferably, each independently represents a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 24 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 4 to 30 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms, or a substituted amino group having 1 to 30 carbon atoms.

R⁷¹～R⁷⁸More preferably, each independently represents a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 16 carbon atoms, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 24 carbon atoms, or a substituted amino group having 1 to 16 carbon atoms.

R⁷¹～R⁷⁸More preferably, each independently represents a hydrogen atom, a fluorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 16 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 16 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 16 carbon atoms, or a substituted amino group having 1 to 12 carbon atoms.

Formula (1e)In the following, R is shown⁷¹～R⁷⁸Specific examples of (3) are as follows.

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

Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, a n-hexyl group, a 1-methylpentyl group, a 4-methyl-2-pentyl group, a 2-ethylbutyl group, a n-heptyl group, a 1-methylhexyl group, a n-octyl group, a 1-methylheptyl group, a 2-ethylhexyl group, a 2-propylpentyl group, a n-nonyl group, a2, 2-dimethylheptyl group, a2, 6-dimethyl-4-heptyl group, a 3,5, 5-trimethylhexyl group, a n-decyl group, a 1-ethyloctyl group, a n-undecyl group, a 1-methyldecyl group, a n-dodecyl group, a n, A straight-chain, branched or cyclic alkyl group containing only carbon atoms and hydrogen atoms, such as a n-hexadecyl group, a n-heptadecyl group, a 1-octylnonyl group, a n-octadecyl group, a 1-nonyldecyl group, a 1-decyldenlecyl group, a n-eicosyl group, a n-docosyl group, a n-tetracosyl group, a 1-adamantyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, or the like.

Examples of the substituent in the alkyl group include an alkoxy group having 1 to 16 carbon atoms, an alkoxyalkoxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, a halogen atom, a haloalkoxy group, and the like.

Specific examples of the alkyl group having a substituent include a methoxymethyl group, an ethoxymethyl group, an n-butoxymethyl group, an n-hexyloxymethyl group, (2-ethylbutoxy) methyl group, an n-octyloxymethyl group, an n-decyloxymethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a 2-n-propoxyethyl group, a 2-isopropoxyethyl group, a 2-n-butoxyethyl group, a 2-n-pentyloxyethyl group, a 2-n-hexyloxyethyl group, a 2- (2 '-ethylbutoxy) ethyl group, a 2-n-heptyloxyethyl group, a 2-n-octyloxyethyl group, a 2- (2' -ethylhexyloxy) ethyl group, a 2-n-decyloxyethyl group, a 2-n-dodecyloxyethyl group, a, 2-n-tetradecyloxyethyl, 2-cyclohexyloxyethyl, 2-methoxypropyl, 3-ethoxypropyl, 3-n-propoxypropyl, 3-isopropoxypropyl, 3- (n-butoxy) propyl, 3- (n-pentyloxy) propyl, 3- (n-hexyloxy) propyl, 3- (2 '-ethylbutoxy) propyl, 3- (n-octyloxy) propyl, 3- (2' -ethylhexyloxy) propyl, 3- (n-decyloxy) propyl, 3- (n-dodecyloxy) propyl, 3- (n-tetradecyloxy) propyl, 3-cyclohexyloxypropyl, 4-methoxybutyl, m-propyloxy, n-tetradecyloxy, n-propyloxy, n-cyclohexyloxy, 4-ethoxybutyl, 4-n-propoxybutyl, 4-isopropoxybutyl, 4-n-butoxybutyl, 4-n-hexyloxybutyl, 4-n-octyloxybutyl, 4-n-decyloxybutyl, 4-n-dodecyloxybutyl, 5-methoxypentyl, 5-ethoxypentyl, 5-n-propoxypentyl, 6-ethoxyhexyl, 6-isopropoxyhexyl, 6-n-butoxyhexyl, 6-n-hexyloxyhexyl, 6-n-decyloxyhexyl, 4-methoxycyclohexyl, 7-ethoxyheptyl, 7-isopropoxyheptyl, 8-methoxyoctyl, 10-methoxydecyl, 10-n-butoxydecyl, 4-isopropoxydecyl, 5-methoxypentyl, 5-ethoxypentyl, 6-ethoxyhexyl, 6-isopropoxyhexyl, 6-n-decyloxyhexyl, and so-called, Alkyl groups having an alkoxy group such as 12-ethoxydodecyl group, 12-isopropoxydodecyl group, and tetrahydrofurfuryl group;

(2-methoxyethoxy) methyl, (2-ethoxyethoxy) methyl, (2-n-butoxyethoxy) methyl, (2-n-hexyloxyethoxy) methyl, (3-methoxypropoxy) methyl, (3-ethoxypropoxy) methyl, (3-n-butoxypropoxy) methyl, (3-n-pentyloxypropoxy) methyl, (4-methoxybutoxy) methyl, (6-methoxyhexyloxy) methyl, (10-ethoxydecyloxy) methyl, 2- (2 '-methoxyethoxy) ethyl, 2- (2' -ethoxyethoxy) ethyl, 2- (2 '-n-butoxyethoxy) ethyl, 3- (2' -ethoxyethoxy) propyl, methyl, ethyl, propyl, An alkyl group having an alkoxyalkoxy group such as a 3- (2 '-methoxypropoxy) propyl group, a 3- (2' -isopropoxypropoxy) propyl group, a 3- (3 '-methoxypropoxy) propyl group, or a 3- (3' -ethoxypropoxy) propyl group;

an alkyl group having an aralkyloxy group such as benzyloxymethyl, 2-benzyloxyethyl, 2-phenethyloxyethyl, 2- (4 '-methylbenzyloxy) ethyl, 2- (2' -methylbenzyloxy) ethyl, 2- (4 '-fluorobenzyloxy) ethyl, 2- (4' -chlorobenzyloxy) ethyl, 3-benzyloxypropyl, 3- (4 '-methoxybenzyloxy) propyl, 4-benzyloxybutyl, 2- (benzyloxymethoxy) ethyl, and 2- (4' -methylbenzyloxymethoxy) ethyl;

phenoxymethyl, 4-methylphenoxymethyl, 3-methylphenoxymethyl, 2-methylphenoxymethyl, 4-methoxyphenoxymethyl, 4-fluorophenoxymethyl, 4-chlorophenoxymethyl, 2-phenoxyethyl, 2- (4 '-methylphenoxy) ethyl, 2- (4' -ethylphenoxy) ethyl, 2- (4 '-methoxyphenoxy) ethyl, 2- (4' -chlorophenoxy) ethyl, 2- (4 '-bromophenoxy) ethyl, 2- (1' -naphthoxy) ethyl, 2- (2 '-naphthoxy) ethyl, 3-phenoxypropyl, 3- (2' -naphthoxy) propyl, 4-phenoxybutyl, p-tolyl, An aryloxy-containing alkyl group such as a 4- (2 ' -ethylphenoxy) butyl group, a 5- (4 ' -tert-butylphenoxy) pentyl group, a 6- (2 ' -chlorophenoxy) hexyl group, an 8-phenoxyoctyl group, a 10-phenoxydecyl group, a 10- (3 ' -chlorophenoxy) decyl group, a 2- (2 ' -phenoxyethoxy) ethyl group, a 3- (2 ' -phenoxyethoxy) propyl group, or a 4- (2 ' -phenoxyethoxy) butyl group;

alkyl groups having an alkylthio group such as n-butylthiomethyl, n-hexylthiomethyl, 2-methylthioethyl, 2-ethylthioethyl, 2-n-butylthioethyl, 2-n-hexylthioethyl, 2-n-octylthioethyl, 2-n-decylthioethyl, 3-methylthiopropyl, 3-ethylthiopropyl, 3-n-butylthiopropyl, 4-ethylthiobutyl, 4-n-propylthiobutyl, 4-n-butylthiobutyl, 5-ethylthiopentyl, 6-methylthiohexyl, 6-ethylthiohexyl, 6-n-butylthiohexyl, 8-methylthiooctyl, etc.;

fluoromethyl, 3-fluoropropyl, 6-fluorohexyl, 8-fluorooctyl, trifluoromethyl, 1-dihydro-perfluoroethyl, 1-dihydro-perfluoro-n-propyl, 1, 3-trihydro-perfluoro-n-propyl, 2-hydro-perfluoro-2-propyl, 1-dihydro-perfluoro-n-butyl, 1-dihydro-perfluoro-n-pentyl, 1-dihydro-perfluoro-n-hexyl, 6-fluorohexyl, 4-fluorocyclohexyl, 1-dihydro-perfluoro-n-octyl, 1-dihydro-perfluoro-n-decyl, 1-dihydro-perfluoro-n-dodecyl, 1-dihydro-perfluoro-n-dodecyl, An alkyl group having a halogen atom such as 1, 1-dihydro-perfluoro-n-tetradecyl group, 1-dihydro-perfluoro-n-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, 2, 2-bis (trifluoromethyl) propyl group, dichloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chlorooctyl group, and 2, 2, 2-trichloroethyl group;

fluoromethoxymethyl, 3-fluoro-n-propoxymethyl, 6-fluoro-n-hexyloxymethyl, trifluoromethoxy-methyl, 1-dihydro-perfluoroethoxymethyl, 1-dihydro-perfluoro-n-propoxymethyl, 2-hydro-perfluoro-2-propoxymethyl, 1-dihydro-perfluoro-n-butoxymethyl, 1-dihydro-perfluoro-n-pentyloxymethyl, 1-dihydro-perfluoro-n-hexyloxymethyl, 1-dihydro-perfluoro-n-octyloxymethyl, 1-dihydro-perfluoro-n-decyloxymethyl, 1-dihydro-perfluoro-n-tetradecyloxymethyl, n-hexyloxymethyl, 2, 2-bis (trifluoromethyl) propoxymethyl, 3-chloro-n-propoxymethyl, 2- (8-fluoro-n-octyloxy) ethyl, 2- (1, 1-dihydro-perfluoroethoxy) ethyl, 2- (1, 1, 3-trihydro-perfluoro-n-propoxy) ethyl, 2- (1, 1-dihydro-perfluoro-n-pentyloxy) ethyl, 2- (6-fluoro-n-hexyloxy) ethyl, 2- (1, 1-dihydro-perfluoro-n-octyloxy) ethyl, 3- (4-fluorocyclohexyloxy) propyl, 3- (1, 1-dihydro-perfluoroethoxy) propyl, 3- (1, alkyl groups having a halogenated alkoxy group such as 1-dihydro-perfluoro-n-dodecyloxy) propyl group, 4- (perfluoro-n-hexyloxy) butyl group, 4- (1, 1-dihydro-perfluoroethoxy) butyl group, 6- (2-chloroethoxy) hexyl group, and 6- (1, 1-dihydro-perfluoroethoxy) hexyl group;

phenoxymethyl, 4-methylphenoxymethyl, 3-methylphenoxymethyl, 2-methylphenoxymethyl, 4-ethylphenoxymethyl, 4-n-propylphenoxymethyl, 4-n-butylphenoxymethyl, 4-tert-butylphenoxymethyl, 4-n-hexylphenoxymethyl, 4-n-octylphenoxymethyl, 4-n-decylphenoxymethyl, 4-methoxyphenoxymethyl, 4-ethoxyphenoxymethyl, 4-butoxyphenoxymethyl, 4-n-pentyloxyphenoxymethyl, 4-fluorophenoxymethyl, 3-fluorophenoxymethyl, 2-fluorophenoxymethyl, 3, 4-difluorophenoxymethyl, 4-chlorophenoxymethyl, 2-chlorophenoxymethyl group, 4-phenylphenoxymethyl group, 1-naphthyloxymethyl group, 2-furyloxymethyl group, 1-phenoxyethyl group, 2- (4 '-methylphenoxy) ethyl group, 2- (4' -ethylphenoxy) ethyl group, 2- (4 '-n-hexylphenoxy) ethyl group, 2- (4' -methoxyphenoxy) ethyl group, 2- (4 '-n-butoxyphenoxy) ethyl group, 2- (4' -fluorophenoxy) ethyl group, 2- (4 '-chlorophenoxy) ethyl group, 2- (4' -bromophenoxy) ethyl group, 2- (1 '-naphthoxy) ethyl group, 2- (2' -naphthoxy) ethyl group, 2-phenoxyethyl, An aryloxy-containing alkyl group such as a 2-phenoxypropyl group, a 3- (4 '-methylphenoxy) propyl group, a 3- (2' -naphthyloxy) propyl group, a 4-phenoxybutyl group, a 4- (2 '-ethylphenoxy) butyl group, a 4-phenoxypentyl group, a 5- (4' -tert-butylphenoxy) pentyl group, a 6-phenoxyhexyl group, a 6- (2 '-chlorophenoxy) hexyl group, an 8-phenoxyoctyl group, a 10-phenoxydecyl group, or a 10- (3' -methylphenoxy) decyl group.

As the unsubstituted alkoxy group, there may be mentioned alkoxy groups derived from the specific examples of the above-mentioned alkyl groups. Examples of the substituent in the substituted alkoxy group include the same substituents as those in the alkyl group.

Examples of the unsubstituted aryl group include a phenyl group, a 1-naphthyl group, a 2-anthryl group, a 1-phenanthryl group, a 2-phenanthryl group, a 3-phenanthryl group, a 1-pyrenyl group, a 2-perylenyl group, a 3-perylenyl group, a 2-anthryl group, a 3-anthryl group, a 7-anthryl group and an 8-anthryl group.

In the substituted aryl group, examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, an aryl group, a halogen atom, and the like.

Specific examples of the substituent aryl group include aryl groups having an alkyl group such as 1-methyl-2-pyrenyl, 2-methylphenyl, 4-ethylphenyl, 4-tert-butylphenyl, 4- (4' -tert-butylcyclohexyl) phenyl, 3-cyclohexylphenyl, 2-cyclohexylphenyl, 4-ethyl-1-naphthyl, 6-n-butyl-2-naphthyl, and 2, 4-dimethylphenyl;

aryl groups having an alkoxy group and an aryloxy group such as a 4-methoxyphenyl group, a 3-ethoxyphenyl group, a 2-ethoxyphenyl group, a 4-n-propoxyphenyl group, a 3-n-propoxyphenyl group, a 4-isopropoxyphenyl group, a 3-isopropoxyphenyl group, a 2-sec-butoxyphenyl group, a 4-n-pentyloxyphenyl group, a 4-isopentoxyphenyl group, a 2-methyl-5-methoxyphenyl group, and a 2-phenoxyphenyl group;

aryl groups having an aryl group such as a 4-phenylphenyl group, a 3-phenylphenyl group, a2, 6-diphenylphenyl group, a 4- (2' -naphthyl) phenyl group, a 2-phenyl-1-naphthyl group, a 1-phenyl-2-naphthyl group, and a 7-phenyl-1-pyrenyl group;

an aryl group having a halogen atom such as a 4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2-methyl-3-chlorophenyl group, 2-methoxy-4-fluorophenyl group, or 2-fluoro-4-methoxyphenyl group;

further, there may be mentioned 2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3, 5-bis (trifluoromethyl) phenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl group, 4-ethylthiophenyl group, 4-cyanophenyl group, 3-cyanophenyl group and the like.

As the unsubstituted aryloxy group, there may be mentioned aryloxy groups derived from specific examples of the above-mentioned aryl groups. Examples of the substituent in the substituted aryloxy group include the same substituents as those in the above-mentioned aryl group.

Examples of the substituted or unsubstituted aralkyloxy group include an unsubstituted or alkyl-having aralkyloxy group such as a benzyloxy group, an α -methylbenzyloxy group, a phenethyloxy group, an α -methylbenzyloxy group, an α, α -dimethylbenzyloxy group, a 4-methylbenzyloxy group, or a 4-isopropylbenzyloxy group;

aralkyloxy having aryl or aralkyl such as 4-benzylbenzyloxy, 4-phenethylbenzyloxy and 4-phenylbenzyloxy; aralkyloxy group having a substituted oxy group such as 4-methoxybenzyloxy group, 4-n-tetradecyloxybenzyloxy group, 4-n-pentadecyloxybenzyloxy group, 3, 4-dimethoxybenzyloxy group, 4-methoxymethylbenzyloxy group, 4-vinyloxymethylbenzyloxy group, 4-benzyloxybenzyloxy group, 4-phenethyloxybenzyloxy group and the like;

an aralkyloxy group having a hydroxyl group such as a 4-hydroxybenzyloxy group or a 4-hydroxy-3-methoxybenzyloxy group; aralkyloxy group having a halogen atom such as 4-fluorobenzyloxy group, 3-chlorobenzyloxy group, 3, 4-dichlorobenzyloxy group and the like;

2-furfuryloxy, diphenylmethoxy, 1-naphthylmethoxy, 2-naphthylmethoxy and the like.

Specific examples of the amino group having a substituent include amino groups having an alkyl group such as an N-methylamino group, an N-ethylamino group, an N-N-butylamino group, an N-cyclohexylamino group, an N-N-octylamino group, and an N-N-decylamino group;

an amino group having an aralkyl group or an aryl group such as an N-benzylamino group, an N-phenylamino group, an N- (3-methylphenyl) amino group, an N- (4-N-butylphenyl) amino group, an N- (4-methoxyphenyl) amino group, an N- (3-fluorophenyl) amino group, an N- (4-chlorophenyl) amino group, an N- (1-naphthyl) amino group, or an N- (2-naphthyl) amino group;

an amino group having 2 alkyl groups or an aralkyl group as a substituent, such as an N, N-dimethylamino group, an N, N-diethylamino group, an N, N-di-N-butylamino group, an N, N-di-N-hexylamino group, an N, N-di-N-octylamino group, an N, N-di-N-decylamino group, an N, N-di-N-dodecylamino group, an N-methyl-N-ethylamino group, an N-ethyl-N-butylamino group, an N-methyl-N-phenylamino group, an N-ethyl-N-phenylamino group, an N-butyl-N-phenylamino group, or the like;

n, N-diphenylamino, N-bis (3-methylphenyl) amino, N-bis (4-ethylphenyl) amino, N-bis (4-tert-butylphenyl) amino, N-bis (4-N-hexylphenyl) amino, N-bis (4-methoxyphenyl) amino, N-bis (4-ethoxyphenyl) amino, N-bis (4-N-butoxyphenyl) amino, N-bis (4-N-hexyloxyphenyl) amino, N-bis (1-naphthyl) amino, N-bis (2-naphthyl) amino, N-phenyl-N- (3-methylphenyl) amino, N-, N-phenyl-N- (4-methylphenyl) amino, N-phenyl-N- (4-octylphenyl) amino, N-phenyl-N- (4-methoxyphenyl) amino, N-phenyl-N- (4-ethoxyphenyl) amino, N-phenyl-N- (4-N-hexyloxyphenyl) amino, and amino groups having 2 aryl groups as substituents such as N-phenyl-N- (4-fluorophenyl) amino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl-N- (3-phenylphenyl) amino group, and N-phenyl-N- (4-phenylphenyl) amino group.

In formula (1e), M represents 2 hydrogen atoms, 2 metal atoms having a valence of 1, 2 metal atoms, 3 substituted metal atoms, or oxidized metal atoms, more preferably 2 hydrogen atoms, 2 metal atoms, or oxidized metal atoms, and still more preferably 2 metal atoms or oxidized metal atoms.

Examples of the 1-valent metal atom represented by M include Na, K, and Li.

Examples of the 2-valent metal atom represented by M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, and Sn.

Examples of the 3-valent substituted metal atom represented by M include Al-Cl, Ga-Br, Ga-I, In-Cl and Al-C₆H₅、In-C₆H₅、Mn(OH)、Mn[OSi(CH₃)₃]Fe-Cl, etc.

Examples of the metal oxide atom represented by M include VO, MnO, TiO and the like.

In the formula (1e), M is more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO and TiO, still more preferably Cu, Ni, Pd and VO, and particularly preferably Cu, Pd and VO.

Specific examples of the compound (1e) include compounds represented by the formulae (2-1) to (2-38).

[ chemical formula 64 ]

[ chemical formula 65 ]

[ chemical formula 66 ]

[ chemical formula 67 ]

[ chemical formula 68 ]

As the porphyrazine dye (Ae), a compound represented by the formula (2-29) is preferable.

When the porphyrazine dye (Ae) is contained, the content thereof is preferably 1 part by mass or more and 99 parts by mass or less based on 100 parts by mass of the dye (a 1).

In the dye, the content of the dye (a1) is preferably 70% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and further preferably 85% by mass or more and 100% by mass or less, based on the total amount of the dye.

The content of the dye in the colorant (a) is 90 parts by mass or more, preferably 93 parts by mass or more, more preferably 95 parts by mass or more, still more preferably 99 parts by mass or more, and particularly preferably 100 parts by mass, that is, no pigment is contained, per 100 parts by mass of the colorant.

The colorant (a) may further contain a pigment (a 2). As The pigment (a2), known pigments can be used without particular limitation, and examples thereof include pigments classified as pigments in The color index (published by The Society of Dyers a and Colourists), and these may be used alone or in combination of 2 or more.

The content of the colorant (a) is preferably 1 mass% or more and 60 mass% or less, more preferably 3 mass% or more and 55 mass% or less, and further preferably 5 mass% or more and 50 mass% or less, with respect to the total amount of solid components. When the content of the colorant (A) is within the above range, the color density in the production of a color filter is sufficient, and a resin or a polymerizable compound can be contained in a necessary amount in the composition, so that a colored pattern having sufficient mechanical strength can be formed. Here, the "total amount of solid components" in the present specification means an amount in which the content of the solvent is removed from the total amount of the colored curable resin composition. The total amount of the solid components and the contents of the components relative to the total amount can be measured by a known analytical means such as liquid chromatography or gas chromatography.

< resin (B) >

The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and is preferably a polymer having at least 1 kind of structural unit selected from unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides. The monomer (a) is preferably used in the resin (B) by copolymerizing at least one of a monomer (B) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond and a monomer (c) copolymerizable with the monomer (a).

The reaction sequence is not limited, and the monomer (a) and at least one of the monomers (b) and (c) may be copolymerized at once. When all of the monomers (a) to (c) are used, the monomer (c) may be reacted after the monomers (a) and (b) are copolymerized, or the monomer (b) may be reacted after the monomers (a) and (c) are copolymerized. Further, the monomer (a), the copolymer of the monomer (b) and the monomer (c), and the carboxylic anhydride may be reacted.

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

carboxyl group-containing bicyclic unsaturated compounds 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-carboxymethylbicyclo [2.2.1] hept-2-ene and 5-carboxyethylbicyclo [2.2.1] hept-2-ene;

carboxylic acid anhydrides such as anhydrides of the above unsaturated dicarboxylic acids excluding fumaric acid and mesaconic acid; and the like.

Examples thereof include 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;

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

Among these, acrylic acid, methacrylic acid, maleic anhydride and the like 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 (for example, at least 1 selected from an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) Preferred are monomers having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group.

Examples of (b) include a monomer (b1) (hereinafter sometimes referred to as "(b 1)") having an oxiranyl group and an ethylenically unsaturated bond, a monomer (b2) (hereinafter sometimes referred to as "(b 2)") having an oxetanyl group and an ethylenically unsaturated bond, and a monomer (b3) (hereinafter sometimes referred to as "(b 3)") having a tetrahydrofuranyl group and an ethylenically unsaturated bond.

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

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

Examples of (b1-2) include vinylcyclohexene monoxide, 1, 2-epoxy-4-vinylcyclohexane (for example, セロキサイド (registered trademark) 2000, (manufactured by strain) ダイセル), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, サイクロマー (registered trademark) a400, (manufactured by strain) ダイセル), 3, 4-epoxycyclohexylmethyl (meth) acrylate (for example, サイクロマー (registered trademark) M100, (manufactured by strain) ダイセル), a compound represented by the formula (BI), a compound represented by the formula (BII), and the like.

[ chemical formula 69 ]

[ formula (BI) and formula (BII) wherein R^b1And R^b2Each 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^b1And X^b2Represents a single bond, or-R^b3-、＊-R^b3-O-、＊-R^b3-S-or-R^b3-NH-。

R^b3Represents an alkylene group having 1 to 6 carbon atoms.

Denotes a bonding end with O. ]

As R^b1、R^b2Examples of the C1-4 alkyl group include methyl and ethyl.

As R^b1、R^b2Examples of the alkyl group in which the hydrogen atom of (3) is substituted with a hydroxyl group include a hydroxymethyl group and a hydroxyethyl group.

As R^b1And R^b2The alkyl group is preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyalkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and further preferably a hydrogen atom or a methyl group.

As R^b3The alkylene group of (b) may be a straight chain or branched chain alkylene group, and specifically, a methylene group or an ethylene group may be mentioned.

As X^b1And X^b2Preferably a single bond, perylene-R^b3-, or-R^b3-O-, more preferably a single bond, or^b3Further preferably, it is a single bond or perylene-CH₂-O-and-CH₂CH₂-O-is particularly preferably a single bond, or-CH₂CH₂-O- (. sup. -.

Examples of the compound represented by formula (BI) include compounds represented by any one of formulae (BI-1) to (BI-15). Among them, preferred are compounds represented by formula (BI-1), formula (BI-3), formula (BI-5), formula (BI-7), formula (BI-9) or formula (BI-11) to formula (BI-15), and more preferred are compounds represented by formula (BI-1), formula (BI-7), formula (BI-9) or formula (BI-15).

[ chemical formula 70 ]

[ chemical formula 71 ]

Examples of the compound represented by the formula (BII) include compounds represented by any one of the formulae (BII-1) to (BII-15). Among them, preferred are compounds represented by formula (BII-1), formula (BII-3), formula (BII-5), formula (BII-7), formula (BII-9) or formulae (BII-11) to (BII-15), and more preferred are compounds represented by formula (BII-1), formula (BII-7), formula (BII-9) or formula (BII-15).

[ chemical formula 72 ]

[ chemical formula 73 ]

The compound represented by the formula (BI) and the compound represented by the formula (BII) may be used each independently, or 2 or more may be used in combination. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, their content ratio [ the compound represented by formula (BI): the compound represented by formula (BII) ] is preferably 5: 95-95: 5, more preferably 20: 80-80: 20.

as the above (b2), monomers having an oxetanyl group and a (meth) acryloyloxy group are more preferable. Examples of (b2) include 3-methyl-3- (meth) acryloyloxymethyloxetane, 3-ethyl-3- (meth) acryloyloxymethyloxetane, 3-methyl-3- (meth) acryloyloxyethyloxyoxetane, and 3-ethyl-3- (meth) acryloyloxyethyloxyoxetane.

Examples of (c) 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, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, and tricyclo [5.2.1.0 (meth) acrylate^2,6]Decan-8-yl ester (in this technical field, as a common name, dicyclopentyl "(meth) acrylate". moreover, tricyclodecanyl (meth) acrylate ". The) and tricyclo (meth) acrylate [5.2.1.0 ]^2,6]Decan-9-yl ester, tricyclo [5.2.1.0 ] meth (acrylic acid)^2,6]Decen-8-yl ester (commonly known in the art as "dicyclopentenyl (meth) acrylate"), tricyclo (meth) acrylate [5.2.1.0 ]^2,6](meth) acrylates such as decen-9-yl ester, dicyclopentanyloxyethyl (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, Bicyclo-2-enes such as 5, 6-dimethoxybicyclo [2.2.1] hept-2-ene, 5, 6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2.2.1] hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-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, 5, 6-bis (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene An agent;

dicarbonylimide derivatives 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, vinyltoluene and p-methoxystyrene; vinyl group-containing nitriles such as (meth) acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-containing amides such as (meth) acrylamide; esters such as vinyl acetate; dienes such as 1, 3-butadiene, isoprene, and 2, 3-dimethyl-1, 3-butadiene; and the like.

Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance.

The polymerization initiator, the solvent, and the like are not particularly limited, and those generally used in the art can be used. For example, the polymerization initiator may be an azo compound (e.g., 2 '-azobisisobutyronitrile, 2' -azobis (2, 4-dimethylvaleronitrile), or the like), an organic peroxide (e.g., benzoyl peroxide), or a solvent in which each monomer is dissolved, and the solvent (E) described below as the solvent (E) of the colored curable resin composition of the present invention may be used.

The obtained copolymer 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 used as a product taken out as a solid (powder) 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.

Further, a reaction catalyst of a carboxylic acid or a carboxylic anhydride with a cyclic ether (for example, tris (dimethylaminomethyl) phenol) and the like, a polymerization inhibitor (for example, hydroquinone and the like) and the like may be used as necessary.

Examples of the carboxylic 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 mol based on 1 mol of the amount of (a).

Specific examples of the resin (B) include a 3, 4-epoxycyclohexylmethyl (meth) acrylate/(meth) acrylic acid copolymer, and an acrylic acid 3, 4-epoxytricyclo [5.2.1.0 ]^2.6]Resins [ K1] such as decyl ester/(meth) acrylic acid copolymers](ii) a Glycidyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer, glycidyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, 3, 4-epoxy tricyclo (meth) acrylate [5.2.1.0 ]^2.6]Resins such as decyl ester/(meth) acrylic acid/N-cyclohexylmaleimide copolymer and 3-methyl-3- (meth) acryloyloxymethyloxetane/(meth) acrylic acid/styrene copolymer [ K2](ii) a Benzyl (meth) acrylate/(meth) acrylic acid copolymer,Resins such as styrene/(meth) acrylic acid copolymers [ K3](ii) a Resins obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate/(meth) acrylic acid copolymer, resins obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate/styrene/(meth) acrylic acid copolymer, and resins obtained by adding glycidyl (meth) acrylate to a tricyclodecyl (meth) acrylate/(benzyl (meth) acrylate/(meth) acrylic acid copolymer [ K4 ]](ii) a Resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate/(glycidyl (meth) acrylate), and resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecyl (meth) acrylate/styrene/(glycidyl (meth) acrylate) [ K5 ]](ii) a Resins such as resins obtained by reacting a copolymer of (meth) acrylic acid and tricyclodecanyl (meth) acrylate/(glycidyl (meth) acrylate), and further reacting the resulting resin with tetrahydrophthalic anhydride [ K6 ]]And the like.

Among them, the resin [ K1] and the resin [ K2] are preferable as the resin (B).

The weight average molecular weight of the resin (B) in terms of polystyrene is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and still more preferably 5,000 to 30,000. When the molecular weight is within the above range, the color filter tends to have high hardness, a high residual film ratio, good solubility of an unexposed portion in a developer, and high resolution of a colored pattern.

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 solid acid value of the resin (B) is preferably 50 to 170mg-KOH/g, more preferably 60 to 150mg-KOH/g, and still more preferably 70 to 135 mg-KOH/g. The solid acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1g of the resin (B), and can be determined by titration with an aqueous solution of potassium hydroxide, for example.

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and still more preferably 17 to 55% by mass, based on the total amount of solid components. If the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and the 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 the polymerization initiator (D), and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and preferably (meth) acrylate compounds.

Among them, the polymerizable compound (C) is preferably a polymerizable compound having 3 or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include compounds having 1 ethylenically unsaturated bond such as nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the compounds exemplified as (a), (b), and (c);

compounds having 2 ethylenically unsaturated bonds such as 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;

compounds having 3 ethylenically unsaturated bonds such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isocyanurate, and the like;

compounds having 4 ethylenically unsaturated bonds such as pentaerythritol tetra (meth) acrylate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, and caprolactone-modified pentaerythritol tetra (meth) acrylate;

compounds having 5 ethylenically unsaturated bonds such as dipentaerythritol penta (meth) acrylate;

compounds having 6 ethylenically unsaturated bonds such as dipentaerythritol hexa (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, and caprolactone-modified dipentaerythritol hexa (meth) acrylate;

compounds having 7 or more ethylenically unsaturated bonds such as tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, and tetrapentaerythritol deca (meth) acrylate; and the like.

Among them, 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 ethylenically unsaturated bonds. Dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are particularly preferred.

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

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

In addition, the content ratio of the resin (B) to the polymerizable compound (C) [ resin (B): the polymerizable compound (C) ] is preferably 20: 80-80: 20, more preferably 35: 65-80: 20.

< polymerization initiator (D) >)

The polymerization initiator (D) is a compound which generates active radicals by the action of light or heat and can initiate polymerization. The colored curable resin composition of the present invention contains a compound represented by the following formula (d1) (hereinafter, may be referred to as "compound (d 1)") as a polymerization initiator.

[ chemical formula 74 ]

[ in the formula (d1),

R^d1represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms and optionally havingA heterocyclic group having 3 to 36 carbon atoms as a substituent, an alkyl group having 1 to 15 carbon atoms which may have a substituent, or an aralkyl group having 7 to 33 carbon atoms which may have a substituent, wherein the alkyl group or the aralkyl group contains a methylene group (-CH)₂-) can be replaced by-O-, -CO-, -S-, -SO₂-or-N (R)^d5)-。

From R^d1The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, with a phenyl group and a naphthyl group being more preferable, and a phenyl group being particularly preferable.

In addition, from R^d1The aromatic hydrocarbon group represented may have 1 or 2 or more substituents. The substituent is preferably substituted at the α -position or the γ -position of the aromatic hydrocarbon group, and more preferably at the γ -position. Examples of the substituent include alkyl groups having 1 to 15 carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, and the like; halogen atoms such as fluorine atom, chlorine atom, iodine atom, and bromine atom; and the like.

The carbon number of the alkyl group as the substituent is preferably 1 to 10, more preferably 1 to 7.The alkyl group as the substituent may be any of a straight chain, a branched chain, and a cyclic group, and may be a combination of a chain group and a cyclic group. Methylene group (-CH) contained in alkyl group as the substituent₂-) may be replaced with-O-or-S-. The hydrogen atom contained in the alkyl group may be substituted with a halogen atom such as a fluorine atom, chlorine atom, iodine atom, or bromine atom, and is preferably substituted with a fluorine atom.

As a group consisting of R^d1Examples of the alkyl group as a substituent of the aromatic hydrocarbon group include groups represented by the following formulae. Wherein represents a bonding terminal.

[ chemical formula 75 ]

[ chemical formula 76 ]

As a group consisting of R^d1The aromatic hydrocarbon group which may have a substituent(s) is represented by the following formula. Wherein, represents a bonding end.

[ chemical formula 77 ]

[ chemical formula 78 ]

As a group consisting of R^d1The aromatic hydrocarbon group which may have a substituent(s) is preferably a group represented by the following formula.

[ chemical formula 79 ]

[ in the formula, R^d6Represents an alkyl group having 1 to 10 carbon atoms which may be substituted with a halogen atom, R^d6The hydrogen atom contained in (1) may be substituted with a halogen atom. m2 represents an integer of 1 to 5.]

As a group consisting of R^d6The alkyl group represented by R may be mentioned^d1Examples of the substituent of the aromatic hydrocarbon group include the same alkyl groups. From R^d6The number of carbon atoms of the alkyl group is preferably 2 to 7, more preferably 2 to 5. In addition, R^d6The alkyl group (b) may be linear, branched or cyclic, and is preferably linear.

As substitutable R^d6Examples of the halogen atom as a hydrogen atom in (b) include a fluorine atom, a chlorine atom, an iodine atom and a bromine atom, and a fluorine atom is particularly preferable. In addition, R is preferred^d6In (b), 2 or more and 10 or less of the hydrogen atoms contained in (a) are substituted with halogen atoms, preferably 3 or more and 6 or less are substituted with halogen atoms. R^d6The substitution position of the O-group is preferably an ortho-position or a para-position, and particularly preferably a para-position.

M2 is preferably 1 to 2, and particularly preferably 1.

From R^d1The number of carbon atoms of the heterocyclic group is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.

In addition, R^d1The heterocyclic group of (a) may have 1 or 2 or more substituents. As the substituent, there may be mentioned^d1The aromatic hydrocarbon group in (2) may have the same substituent as the exemplified group.

From R^d1The number of carbon atoms in the alkyl group is preferably 1 to 12. As a group consisting of R^d1Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl. These alkyl groups may be linear, branched or cyclicThe functional group may be a combination of a chain group and a cyclic group. In addition, R^d1In the alkyl group of (1), methylene (-CH)₂-) can be replaced by-O-, -CO-, -S-, -SO₂-or-NR^d5The hydrogen atom may be substituted by an OH group or an SH group.

R^d5Represents an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be linear (linear or branched), or cyclic, and may be any of linear, branched, and cyclic, or a combination of a linear group and a cyclic group. In addition, R^d5In the alkyl group of (1), methylene (-CH)₂-) can be replaced by-O-, -CO-.

As a group consisting of R^d1The alkyl group which may have a substituent(s) may be specifically represented by the following formula. Denotes a bonding end.

[ chemical formula 80 ]

Further, from R^d1The aralkyl group which may have a substituent(s) represented is preferably R^d1An aromatic hydrocarbon group represented by the formula and the group consisting of the above R^d1The alkyl-derived alkylene group is a group formed by combining the above-mentioned alkylene groups. The aralkyl group preferably has 7 to 33 carbon atoms, more preferably 7 to 18 carbon atoms, and still more preferably 7 to 12 carbon atoms. The aralkyl group may have 1 or 2 or more substituents, and as the substituents, the above-mentioned R may be mentioned^d1An aromatic hydrocarbon group shown, and R^d1The substituents which the alkyl group may have are exemplified by the same groups. As the introduction of R^d1An aromatic hydrocarbon group represented by the formula and the group consisting of the above R^d1Specifically, the group formed by combining 2-valent groups derived from the alkyl groups is represented by the following formula. Wherein represents a bonding terminal.

[ chemical formula 81 ]

Wherein, as R^d1The aromatic hydrocarbon group which may have a substituent or the alkyl group which may have a substituent is preferable, and the aromatic hydrocarbon group which may have a substituent is more preferable.

From R^d2The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group.

From R^d2The number of carbon atoms of the heterocyclic group is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.

From R^d2The number of carbon atoms in the alkyl group is preferably 1 to 7, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. The alkyl group may be linear, branched, or cyclic, or may be a combination of a linear group and a cyclic group.

Wherein, as R^d2The alkyl group is preferably a chain alkyl group, more preferably a chain alkyl group having 1 to 5 carbon atoms, still more preferably a chain alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

From R^d3The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, and a phenyl group and a naphthyl group are more preferable.

In addition, from R^d3The aromatic hydrocarbon group represented may have 1 or 2 or more substituents. The substituent is preferably substituted at the α -position or γ -position of the aromatic hydrocarbon group. The substituent is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms, and specifically includes an alkyl group having 1 to 15 carbon atoms such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and the like; vinyl group,Alkenyl groups having 1 to 15 carbon atoms such as propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, decenyl, and the like; and the like.

The carbon number of the aliphatic hydrocarbon group as the substituent is more preferably 1 to 7. The aliphatic hydrocarbon group as the substituent may be any of a straight chain, a branched chain, and a cyclic group, or may be a combination of a chain group and a cyclic group. In the aliphatic hydrocarbon group as the substituent, a methylene group (-CH)₂-) can be replaced by-O-, -CO-or-S-, and the methine (-CH <) can be replaced by-N <.

As a group consisting of R^d3Examples of the aliphatic hydrocarbon group as a substituent of the aromatic hydrocarbon group include groups represented by the following formulae. Wherein represents a bonding terminal.

[ chemical formula 82 ]

As a group consisting of R^d3Examples of the aromatic hydrocarbon group which may have a substituent include groups represented by the following formulae. Wherein represents a bonding terminal.

[ chemical formula 83 ]

From R^d3The number of carbon atoms of the heterocyclic group is preferably 3 to 20, more preferably 3 to 10, and still more preferably 3 to 5. Examples of the heterocyclic group include a pyrrolyl group, a furyl group, a thienyl group, an indolyl group, a benzofuryl group, and a carbazolyl group.

In addition, from R^d3The heterocyclic group represented by (A) may have 1 or 2 or more substituents, and the substituents are exemplified by R^d1The aromatic hydrocarbon group may have the same group as the substituent exemplified above.

Wherein, as R^d3Preferably an aromatic hydrocarbon group having a substituent asThe substituent is preferably a chain alkyl group having 1 to 7 carbon atoms (more preferably 1 to 3 carbon atoms), and the number of the substituent is preferably 2 or more and 5 or less.

From R^d4The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 15, more preferably 6 to 12, and still more preferably 6 to 10. Examples of the aromatic hydrocarbon group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, and a terphenyl group, with a phenyl group and a naphthyl group being more preferable, and a phenyl group being particularly preferable.

In addition, from R^d4The aromatic hydrocarbon group represented may have 1 or 2 or more substituents. As the substituent, there may be mentioned^d1The aromatic hydrocarbon group in (2) may have the same substituent.

From R^d4The aliphatic hydrocarbon group preferably has 1 to 13 carbon atoms, more preferably 2 to 10 carbon atoms, and further preferably 4 to 9 carbon atoms. As R^d4Examples of the aliphatic hydrocarbon group of (1) include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group; alkenyl groups such as vinyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, and pentadecenyl; and the like. These aliphatic hydrocarbon groups may be linear (straight chain or branched chain), cyclic, or a combination of linear and cyclic groups. In addition, from R^d4Among the aliphatic hydrocarbon groups represented by (A), methylene (-CH)₂-) can be replaced by-O-, -CO-or-S-, and the methine (-CH <) can be replaced by-PO₃<. The hydrogen atom contained in the aliphatic hydrocarbon group may be substituted with an OH group.

As a group consisting of R^d4Examples of the aliphatic hydrocarbon group which may have a substituent include groups represented by the following formulae. Wherein represents a bonding terminal.

[ chemical formula 84 ]

As R^d4The aliphatic hydrocarbon group is preferably a chain aliphatic hydrocarbon group which may have a substituent, more preferably a chain alkyl group which may have no substituent, and still more preferably a branched chain alkyl group which may have no substituent.

As the compound (d1), compounds (d1-1) to (d1-67) represented by the formula (d1) are listed in the following tables 4 to 10. In the table, bonding terminals are shown.

[ chemical formula 85 ]

[ TABLE 4]

[ TABLE 5]

[ TABLE 6]

[ TABLE 7 ]

[ TABLE 8 ]

[ TABLE 9 ]

[ TABLE 10 ]

Among these compounds, compounds (d1-3) to (d1-6), (d1-18) to (d1-52), (d1-55), (d1-56), (d1-60) and (d1-61) are preferable, compounds (d1-3) to (d1-6) and (d1-18) to (d1-41) are more preferable, compounds (d1-24) and (d1-36) to (d1-40) are even more preferable, and compound (d1-24) is particularly preferable.

The content of the compound (D1) is preferably 2 parts by mass or more and 100 parts by mass or less, more preferably 30 parts by mass or more, further preferably 40 parts by mass or more, particularly preferably 50 parts by mass or more, preferably 90 parts by mass or less, more preferably 70 parts by mass or less, further preferably 60 parts by mass or less, in 100 parts by mass of the polymerization initiator (D).

The compound (d1) can be produced by the production method described in japanese patent application laid-open No. 2014-500852.

The polymerization initiator (D) may further contain a polymerization initiator other than the compound (D1). These are not particularly limited, and a known polymerization initiator can be used.

Examples of the polymerization initiator generating active radicals include O-acyloxime compounds, biimidazole compounds, alkylphenone compounds, triazine compounds, and acylphosphine oxide compounds other than the above-mentioned compound (d 1). Among them, the polymerization initiator (D) preferably contains a biimidazole compound or an alkylphenone compound in addition to the compound (D1), and more preferably contains a biimidazole compound.

Examples of the O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine, and 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, N-benzoyloxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -3-cyclopentylpropane-1-one-2-imine, and the like. Commercially available products such as イルガキュア (registered trademark), OXE01, OXE02 (manufactured by BASF Co., Ltd.), N-1919 (manufactured by ADEKA Co., Ltd.) and the like can be used. Among them, the O-acyloxime compound is preferably at least 1 selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine and N-acetoxy-1- [4- {4- (2-hydroxyethoxy) phenyl } sulfanylphenyl ] -propane-1-one-2-imine, and more preferably from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine -at least 1 of keto-2-imine and N-acetoxy-1- [4- {4- (2-hydroxyethoxy) phenyl } sulfanylphenyl ] -propane-1-keto-2-imine. In the case of these O-acyloxime compounds, color filters having high brightness tend to be obtained.

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 unexamined patent publication nos. 6-75372 and 6-75373), 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, 4 ', 5, 5' -tetrakis (trialkoxyphenyl) biimidazole (see, for example, Japanese patent publication No. 48-38403 and Japanese patent application laid-open No. 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. 7-10913).

Among them, the compound represented by the formula (d4) is preferable.

[ chemical formula 86 ]

[ in the formula (d4), R^d13～R^d16Each independently represents a hydrogen atom or an alkoxy group (preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group). R^d17And R^d18Each independently represents a hydrogen atom or a halogen atom (preferably a chlorine atom).]

As the compound represented by the above formula (d4), specifically, compounds represented by the following formula are exemplified, and a mixture of these is preferred.

[ chemical formula 87 ]

The alkylphenyl ketone compound is a compound having a partial structure represented by the formula (d5) or a partial structure represented by the formula (d 6). In these partial structures, the benzene ring may have a substituent.

[ chemical formula 88 ]

Examples of the compound having a partial structure represented by the formula (d5) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutan-1-one, and 2- (dimethylamino) -2- [ (4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl ] butan-1-one. Commercially available products such as イルガキュア 369, 907 and 379 (manufactured by BASF) can be used.

Examples of the compound having a partial structure represented by the formula (d6) include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl ] propan-1-one, 1-hydroxycyclohexylphenyl ketone, oligomers of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α -diethoxyacetophenone, benzildimethylketal, and the like.

In terms of sensitivity, as the alkylphenyl ketone compound, a compound having a partial structure represented by the formula (d5) is preferable.

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

Examples of the acylphosphine oxide compound include 2, 4, 6-trimethylbenzoyldiphenylphosphine oxide and the like. Commercially available products such as イルガキュア (registered trademark) 819 (manufactured by BASF) can be used.

Further, examples of the polymerization initiator (D) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4 ' -methyldiphenyl sulfide, 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 phenylglyoxylate, titanocene compounds, and the like. These are preferably used in combination with a polymerization initiation aid (D1) (particularly an amine) described later.

Among them, in the case of using 2 or more kinds of polymerization initiators, a combination of the compound (d1) and the biimidazole compound, a combination of the compound (d1) and the biimidazole compound and a thiol compound described later, a combination of the compound (d1) and an alkylphenone compound, or the like is preferable.

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, and still more preferably 2 to 15 parts by mass, based on 100 parts by mass of the total of the resin (B) and the polymerizable compound (C). If the content of the polymerization initiator (D) is within the above range, the sensitivity tends to be high and the exposure time tends to be short, so that the productivity of the color filter tends to be improved.

< polymerization initiation assistant (D1) >)

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

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

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

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

When the thioxanthone compound is contained, the content thereof is preferably 50 parts by mass or more and 100 parts by mass or less, and more preferably 70 parts by mass or more and 99 parts by mass or less, based on 100 parts by mass of the polymerization initiation aid.

Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylsulfanyl acetic acid, N-naphthylglycine, naphthyloxyacetic acid, and the like.

As the polymerization initiation assistant (D1), a thioxanthone compound is preferable.

When the polymerization initiator aid (D1) is used, the content thereof 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).

When the polymerization initiator aid (D1) is used, the content thereof is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, and still more preferably 15 to 250 parts by mass, based on 100 parts by mass of the total amount of the polymerization initiators (D). If the amount of the polymerization initiating assistant (D1) is within this range, a colored pattern can be further formed with high sensitivity, and the productivity of the color filter tends to be improved.

< thiol Compound (T) >

The colored curable resin composition of the present invention preferably further comprises a thiol compound (T).

The thiol compound is a compound having a sulfanyl group (-SH) in a molecule.

Examples of the compound having 1 sulfanyl group in the molecule include 2-sulfanyl oxazole, 2-sulfanyl thiazole, 2-sulfanyl benzimidazole, 2-sulfanyl benzothiazole, 2-sulfanyl benzoxazole, 2-sulfanyl nicotinic acid, 2-sulfanyl pyridine-3-thiol, 2-sulfanyl pyridine-N-oxide, 4-amino-6-hydroxy-2-sulfanyl pyrimidine, 4-amino-2-sulfanyl pyrimidine, 6-amino-5-nitroso-2-thiouracil, 4, 5-diamino-6-hydroxy-2-sulfanyl pyrimidine, 2-sulfanyl thiazole, 2-sulfanyl benzimidazole, 2-thiol, 2-, 4, 6-diamino-2-sulfanylpyrimidine, 2, 4-diamino-6-sulfanylpyrimidine, 4, 6-dihydroxy-2-sulfanylpyrimidine, 4, 6-dimethyl-2-sulfanylpyrimidine, 4-hydroxy-2-sulfanyl-6-methylpyrimidine, 4-hydroxy-2-sulfanyl-6-propylpyrimidine, 2-sulfanyl-4-methylpyrimidine, 2-sulfanylpyrimidine, 2-thiouracil, 3,4, 5, 6-tetrahydropyrimidine-2-thiol, 4, 5-diphenylimidazole-2-thiol, 2-sulfanylimidazole, 2-sulfanyl-1-methylimidazole, 4-amino-3-hydrazino-5-sulfanyl-1, 2, 4-triazole, 3-amino-5-sulfanyl-1, 2, 4-triazole, 2-methyl-4H-1, 2, 4-triazole-3-thiol, 4-methyl-4H-1, 2, 4-triazole-3-thiol, 3-sulfanyl 1H-1, 2, 4-triazole-3-thiol, 2-amino-5-sulfanyl-1, 3, 4-thiadiazole, 5-amino-1, 3, 4-thiadiazole-2-thiol, 2, 5-disulfanyl-1, 3, 4-thiadiazole, (furan-2-yl) methanethiol, 2-sulfanyl-5-thiazolidone, thiazolidinone, and the like, 2-sulfanylthiazoline, 2-sulfanyl-4 (3H) -quinazolinone, 1-phenyl-1H-tetrazole-5-thiol, 2-quinolinethiol, 2-sulfanyl-5-methylbenzimidazole, 2-sulfanyl-5-nitrobenzimidazole, 6-amino-2-sulfanylbenzothiazole, 5-chloro-2-sulfanylbenzothiazole, 6-ethoxy-2-sulfanylbenzothiazole, 6-nitro-2-sulfanylbenzothiazole, 2-sulfanylnaphthoimidazole, 2-sulfanylnaphthoxazole, 3-sulfanyl-1, 2, 4-triazole, 4-amino-6-sulfanylpyrazolo [2, 4-d ] pyridine, 2-amino-6-purine thiol, 6-sulfanylpurine, 4-sulfanyl-1H-pyrazolo [2, 4-d ] pyrimidine, and the like.

Examples of the compound having 2 or more sulfanyl groups in the molecule include hexanedithiol, decanedithiol, 1, 4-bis (methylsulfanyl) benzene, butanediolbis (3-sulfanyl propionate), butanediolbis (3-sulfanyl acetate), ethanediolbis (3-sulfanyl acetate), trimethylolpropane tris (3-sulfanyl acetate), butanediolbis (3-sulfanyl propionate), trimethylolpropane tris (3-sulfanylpropionate), trimethylolpropane tris (3-sulfanylacetate), pentaerythritol tetrakis (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanylacetate), trihydroxyethyltris (3-sulfanylpropionate), pentaerythritol tetrakis (3-sulfanylbutyrate), 1, 4-bis (3-sulfanylbutoxy) butane, and the like.

The thiol compound is preferably a compound having 1 sulfanyl group in the molecule, and particularly preferably 2-sulfanylbenzothiazole.

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

< solvent (E) >

The colored curable resin composition of the present invention preferably further contains a solvent (E).

The solvent (E) is not particularly limited, and a solvent generally used in this field can be used. Examples thereof include ester solvents (solvents containing-COO-or not-O-in the molecule), ether solvents (solvents containing-O-or not-COO-in the molecule), ether ester solvents (solvents containing-COO-or not-O-in the molecule), ketone solvents (solvents containing-CO-or not-COO-in the molecule), alcohol solvents (solvents containing OH, not-O-, -CO-or-COO-in the molecule), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-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 methylanisole.

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, methyl ethoxyacetate, ethyl ethoxypropionate, ethyl 2-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxybutyl acetate, 3-methyl-3-, Propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and the like.

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

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

As the aromatic hydrocarbon solvent, benzene, toluene, xylene, 1,3, 5-trimethylbenzene, and the like are exemplified.

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

Among the above solvents, organic solvents having a boiling point of 120 ℃ to 180 ℃ under 1atm are preferable from the viewpoint of coatability and drying property. As the solvent, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone, and N, N-dimethylformamide are preferable, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, diacetone alcohol, and ethyl 3-ethoxypropionate are more preferable.

The content of the solvent (E) is preferably 35 to 95% by mass, and more preferably 40 to 92% by mass, based on the total amount of the colored curable resin composition of the present invention. In other words, the total amount of solid components in the colored curable resin composition is preferably 5 to 65% by mass, and more preferably 8 to 60% by mass. If the content of the solvent (E) is within the above range, the flatness at the time of coating becomes good, and the color density does not become insufficient at the time of forming a color filter, so that the display characteristics tend to become good.

< leveling agent (F) >

The colored curable resin composition of the present invention may contain a leveling agent (F).

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

Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, トーレシリコーン DC3PA, SH7PA, SH 11PA, SH21PA, SH28PA, SH29PA, SH30PA and SH8400 (trade name: manufactured by Tooli-Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340 and KP341 (manufactured by shin-Etsu chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by モメンティブ, パフォーマンス, マテリアルズ and ジャパン) can be mentioned.

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, フロラード (registered trademark) FC430, cochleate FC431 (manufactured by sumitomo スリーエム strain), メガファック (registered trademark) F142D, cochleate F171, cochleate F172, cochleate F173, cochleate F177, cochleate F183, cochleate F554, cochleate R30, cochleate RS-718-K (DIC strain), エフトップ (registered trademark) EF301, cochleate EF303, cochleate EF351, cochleate EF352 (manufactured by mitsubishi マテリアル electro-chemical strain), サーフロン (registered trademark) S381, cochleate S382, cochleate SC101, cochleate SC105 (manufactured by asahi nitre strain) and E5844 (manufactured by research of cochleate ダイキンファインケミカル) can be mentioned.

Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, メガファック (registered trademark) R08, homo BL20, homo F475, homo F477, and homo F443 (manufactured by DIC corporation) are mentioned.

The content of the leveling agent (F) is preferably 0.001 mass% or more and 0.2 mass% or less, more preferably 0.002 mass% or more and 0.1 mass% or less, and further preferably 0.01 mass% or more and 0.05 mass% or less, based on the total amount of the colored curable resin composition. The content does not include the content of the pigment dispersant. If the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

< other ingredients >

The colored curable resin composition of the present invention may contain, if necessary, 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.

Examples of the adhesion promoters include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxymethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane and the like.

< method for producing colored curable resin composition >

The colored curable resin composition of the present invention can be prepared by mixing, for example, the colorant (a), the resin (B), the polymerizable compound (C), the polymerization initiator (D), and if necessary, the solvent (E), the leveling agent (F), the polymerization initiation aid (D1), and other components.

For the dye, a solution may be prepared by dissolving in advance in a part or the whole of the solvent (E), respectively. The solution is preferably filtered through a filter having a pore size of about 0.01 to 1 μm.

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

< method for manufacturing color filter and liquid crystal display device >

Examples of the method for forming a color filter from the colored curable resin composition of the present invention include a photolithography method and a method using an ink jet device. The photolithography method is a method in which, for example, a colored curable resin composition of the present invention is applied to a substrate, volatile components such as a solvent are removed, and the composition is dried to form a colored composition layer, and the colored composition layer is exposed to light through a photomask and developed. After development, a colored pattern can be formed by heating as necessary. In the method for forming a colored pattern, 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 thus obtained can be used as a color filter.

As the substrate, a resin plate, silicon, a product in which a thin film of aluminum, silver/copper/palladium alloy, or the like is formed on the substrate, or the like can be used. Additional color filter layers, resin layers, transistors, circuits, and the like may be formed on these substrates.

The film thickness of the color filter to be produced is not particularly limited, and can be suitably adjusted according to the intended use, and is, for example, 0.1 to 30 μm, preferably 1 to 20 μm, and more preferably 1 to 6 μm.

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

First, a colored curable resin composition is applied onto a substrate, and is dried by heating (prebaking) and/or drying under reduced pressure to remove volatile components such as a solvent and dry the composition, thereby obtaining a smooth colored composition layer.

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

Next, the coloring composition layer is exposed to light through a photomask for forming a coloring pattern of an object.

Since the entire exposure surface can be uniformly irradiated with parallel light rays to perform accurate alignment between the photomask and the substrate on which the colored composition layer is formed, an exposure apparatus such as a mask aligner or a stepper is preferably used.

The exposed colored composition layer is brought into contact with a developer to develop the colored composition layer, thereby forming a colored pattern on the substrate. By the development, the unexposed portions of the colored composition layer are 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 developing method may be any of an immersion (パドル) method, a dipping method, a spraying method, and the like. Further, the substrate can be tilted at an arbitrary angle during development.

After development, washing with water is preferred.

Further, the obtained colored pattern is preferably post-baked.

According to the colored curable resin composition of the present invention, a color filter having a particularly excellent shape can be produced. The color filter can be used as a color filter for display devices (e.g., liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state imaging elements.

[ examples ]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the following examples, and it goes without saying that the present invention can be carried out by appropriately changing the examples within a range that can be adapted to the gist described later, and these examples are included in the technical scope of the present invention. In the following, unless otherwise specified, "part" means "part by mass" and "%" means "% by mass".

In the following synthesis examples, compounds were identified by MASS analysis (LC; Agilent 1200 type, MASS; Agilent LC/MSD type) or elemental analysis (VARIO-EL; エレメンタール (manufactured by LTD)).

[ Synthesis example 1]

In a flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was introduced at a flow rate of 0.02L/min to form a nitrogen atmosphere, 200 parts by mass of 3-methoxy-1-butanol and 105 parts by mass of 3-methoxybutyl acetate were charged, and the mixture was heated to 70 ℃ with stirring. Then, 60 parts by mass of methacrylic acid and 3, 4-epoxytricyclo [5.2.1.0 ] acrylate were added^2,6]Decyl ester (a mixture of the compound represented by the formula (I-1) and the compound represented by the formula (II-1) in a molar ratio of 50: 50.) 240 parts by mass was dissolved in 140 parts by mass of 3-methoxybutyl acetate to prepare a solution, and the solution was dropped into a flask kept at 70 ℃ for 4 hours using a dropping funnel. On the other hand, a solution in which 30 parts by mass of 2, 2' -azobis (2, 4-dimethylvaleronitrile), a polymerization initiator, was dissolved in 225 parts by mass of 3-methoxybutyl acetate was added dropwise to the flask over 4 hours using an additional dropping funnel. After completion of dropping of the polymerization initiator solution, the solution was held at 70 ℃ for 4 hours and then cooled to room temperature to obtain a resin B' 1 solution having a solid content of 32.6% by mass and an acid value of 110mg-KOH/g (in terms of solid content). The weight average molecular weight Mw of the obtained resin B' 1 was 13,400, and the molecular weight distribution was 2.50.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin obtained in synthesis example 1 were measured by GPC under the following conditions.

A device; k2479 ((manufactured by Kabushizu Shimadzu corporation))

A column; shimadzu Shim GPC-80M

Column temperature; 40 deg.C

A solvent; THF (tetrahydrofuran)

A flow rate; 1.0mL/min

A detector; RI (Ri)

A calibration standard substance; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Co., Ltd.)

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

Examples 1 to 3 and comparative examples 1 to 4

The respective components were mixed so as to have the compositions shown in table 11, to obtain colored curable resin compositions.

[ TABLE 11 ]

In table 11, the components are as follows.

Colorant (A-1): a compound represented by the formula (1)

[ chemical formula 89 ]

Colorant (a-2): a compound represented by the formula (2)

[ chemical formula 90 ]

Colorant (a-3): basic blue 7 (manufactured by Tokyo chemical industry Co., Ltd.)

[ chemical formula 91 ]

Colorant (a-4): a compound represented by the formula (Ac1-1)

[ chemical formula 92 ]

Resin (B): resin B' 1 obtained in Synthesis example 1

Polymerizable compound (C): (trade name: A-TMM-3LM-N, manufactured by Newzhongcun chemical industry Co., Ltd.)

Polymerization initiator (D-1): a compound represented by the formula (d1-40)

[ chemical formula 93 ]

Polymerization initiator (D-2): 1, 2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime) ] (trade name イルガキュア OXE01, manufactured by BASF)

Polymerization initiator (D-3): n-acetoxy-1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] ethane-1-imine (trade name イルガキュア OXE02, BASF corporation)

Polymerization initiation assistant (D-4): 2, 4-diethylthioxanthone (KAYACURE (registered trademark) DETX-2 manufactured by Nippon Kagaku K.K.)

Polymerization initiator (D-5): 2, 2 ', 4-tris (2-chlorophenyl) -5- (3, 4-dimethoxyphenyl) -4, 5-diphenyl-1, 1' -biimidazole (trade name: TCDM, manufactured by CHEMBIDGE INTERNATIONAL CORPORATION)

Thiol compound (T-1): 2-mercaptobenzothiazole (trade name サンセラー M, manufactured by shin-Etsu chemical Co., Ltd.)

Leveling agent (F): polyether modified silicone oil

(トーレシリコーン SH8400 manufactured by Tooli-Dow Corning Co., Ltd.)

Additive (G): 3-methacryloxypropyltrimethoxysilane

(KBM-503 manufactured by shin-Etsu chemical Co., Ltd.)

Solvent (E): propylene glycol monomethyl ether acetate

The compound represented by the above formula (d1-40) was prepared according to the method described in Japanese patent application laid-open No. 2014-500852.

[ formation of coating film ]

A2-inch square glass substrate (イーグル XG; manufactured by Dow Corning Co., Ltd.) was washed with a neutral detergent, water and alcohol in this order and then dried. The colored curable resin composition obtained above was spin-coated on the glass substrate so that the film thickness after post-baking became 3.0 μm, and then pre-baked in a clean oven at 90 ℃ for 3 minutes. Then, the resultant was heated at 230 ℃ for 20 minutes to obtain a coating film.

[ preparation of Pattern ]

A colored curable resin composition was applied onto a 2-inch square glass substrate (イーグル 2000; manufactured by Dow Corning Co., Ltd.) by spin coating so that the film thickness after postbaking became 2.0. mu.m, and then prebaked at 100 ℃ for 3 minutes to form a composition layer. After cooling, the distance between the substrate on which the composition layer was formed and the quartz glass photomask was set to 80 μm, and the substrate was exposed to an exposure apparatus (TME-150 RSK; manufactured by トプコン Co., Ltd.) at 40mJ/cm in an air atmosphere²Light irradiation was performed at the exposure amount (365nm basis). As the photomask, a photomask having a line and space pattern of 50 μm was used. The composition layer after the light irradiation was immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ℃ for 60 seconds to develop, and after washing with water, the composition layer was baked in an oven at 230 ℃ for 20 minutes to obtain a pattern. The obtained pattern was measured for film thickness using a film thickness measuring apparatus (DEKTAK 3; manufactured by Japan vacuum technology Co., Ltd.), and the film thickness was confirmed to be 2.0. mu.m.

The shapes of the colored patterns obtained in examples 1 to 3 and comparative examples 1 to 4 were observed with a scanning electron microscope (S-4000, manufactured by Hitachi ハイテクノロジーズ, Ltd.). In fig. 1, the shape indicated by (p1) (so-called "right cone shape") is indicated by o, and the shape indicated by (p2) is indicated by x. When the inorganic film has the shape represented by (p1), the inorganic film tends to be less likely to crack or peel when laminated on the colored pattern, and this is preferable. The results are shown in Table 12.

[ TABLE 12 ]

Industrial applicability of the invention

According to the present invention, a colored curable resin composition capable of forming a good colored pattern can be provided.

The pattern and coating film obtained from the colored curable resin composition of the present invention can be used as a transparent film, pattern, photo spacer, overcoat layer, insulating film, liquid crystal alignment control protrusion, microlens, coating layer, etc. constituting a part of a color filter substrate and/or an array substrate, and can be preferably used for a color filter substrate, an array substrate, etc. provided with these coating films or patterns as a part of their constituent members, and further a display device, such as a liquid crystal display device, an organic EL device, electronic paper, etc., provided with these color filter substrate and/or array substrate.

Claims

1. A colored curable resin composition containing a colorant, a resin, a polymerizable compound, and a polymerization initiator, wherein the colorant contains a dye in an amount of 90 parts by mass or more per 100 parts by mass of the colorant, and the polymerization initiator contains a compound represented by the following formula (d1) and a bisimidazole compound,

[ chemical formula 1]

In the formula (d1), R^d1Represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms, an optionally substituted alkyl group having 1 to 15 carbon atoms, or an optionally substituted aralkyl group having 7 to 33 carbon atoms, and a methylene group (-CH) contained in the alkyl group or the aralkyl group₂-) can be replaced by-O-, -CO-, -S-, -SO₂-or-N (R)^d5)-，

R^d2An aromatic hydrocarbon group having 6 to 18 carbon atoms, a heterocyclic group having 3 to 36 carbon atoms, or an alkyl group having 1 to 10 carbon atoms,

R^d3represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, an optionally substituted heterocyclic group having 3 to 36 carbon atoms,

R^d4represents an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms or an optionally substituted aliphatic hydrocarbon group having 1 to 15 carbon atoms, and a methylene group (-CH) contained in the aliphatic hydrocarbon group₂-) may be replaced with-O-, -CO-or-S-, and the methine group (-CH <) contained in the above aliphatic hydrocarbon group may be replaced with-PO-₃<, the hydrogen atoms contained in the above aliphatic hydrocarbon groups may be substituted with OH groups,

R^d5represents an alkyl group having 1 to 10 carbon atoms, and a methylene group (-CH) contained in the alkyl group₂-) can be replaced by-O-or-CO-.

2. The colored curable resin composition according to claim 1, wherein the colorant is free of a pigment.

3. The colored curable resin composition according to claim 1 or 2, wherein the dye comprises at least one dye selected from the group consisting of a xanthene dye, a triarylmethane dye, a compound represented by formula (Ab2), a coumarin dye, an anthraquinone dye, and a tetraazaporphyrin dye,

[ chemical formula 2]

In the formula (Ab2), R⁴¹～R⁴⁴Each independently represents a hydrogen atom, a saturated hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 30 carbon atoms which may have a substituent, wherein in the saturated hydrocarbon group having 1 to 20 carbon atoms, the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a substituted or unsubstituted amino group or halogen atom, and when the saturated hydrocarbon group has 2 to 20 carbon atoms, the methylene group contained in the saturated hydrocarbon group may be replaced with an oxygen atom or-CO-, but adjacent methylene groups in the saturated hydrocarbon group having 2 to 20 carbon atoms are not simultaneously replaced with an oxygen atom, the terminal methylene group is not replaced with an oxygen atom or-CO-, and R is⁴¹And R⁴²May be combined and form a ring together with the nitrogen atom to which they are combined, R⁴³And R⁴⁴May be combined and form a ring together with the nitrogen atom to which they are combined,

R⁴⁷～R⁵⁴each independently represents a hydrogen atomHalogen atom, nitro group, hydroxyl group, or C1-8 alkyl group, wherein when the carbon number of the alkyl group is 2-8, the methylene group constituting the alkyl group may be replaced by oxygen atom or-CO-, R⁴⁸And R⁵²May combine with each other to form-NH-, -S-or-SO₂In the alkyl group, however, the adjacent methylene groups are not simultaneously replaced by oxygen atoms, and the terminal methylene group is not replaced by oxygen atoms or-CO-,

ring T¹Represents an optionally substituted aromatic heterocycle having 3 to 10 carbon atoms,

[Y]^m-represents an arbitrary anion of valency m,

m represents an arbitrary natural number.

4. The colored curable resin composition according to claim 3, wherein the dye comprises a xanthene dye and a compound represented by the formula (Ab 2).

5. A color filter formed from the colored curable resin composition according to any one of claims 1 to 4.

6. A liquid crystal display device comprising the color filter according to claim 5.