JP2020045436A - Compound - Google Patents

Abstract

To provide a pigment compound which becomes a raw material of a coloring resin composition forming a color filter used in a liquid crystal display device, an electroluminescence display device and a plasma display and a solid-state image sensor such as CCD and CMOS sensors, and is excellent in heat resistance.SOLUTION: A compound (A-16) can be prepared by mixing C.I. acid blue 90, manganese chloride tetrahydrate in ion exchange water, cooling the obtained reaction suspension, filtrating the reaction suspension, washing the filtrated solid with ion exchange water, and drying the solid under reduced pressure at 60°C.SELECTED DRAWING: None

Description

  The present invention relates to compounds.

A color filter used for a display device such as a liquid crystal display device, an electroluminescence display device, and a plasma display, and a solid-state imaging device such as a CCD or a CMOS sensor is manufactured from a colored resin composition. In such a colored resin composition, a pigment is used as a coloring agent. Although it is not known to be used in a resin composition, C.I. which is a compound represented by formula (i) as a pigment is used. I. Pigment Blue 24 is known (Non-Patent Document 1).

Color Index International (British Dyeing Society, American Association of Textile Chemistry and Dyeing Technology)

  However, C.I. I. Pigment Blue 24 has low heat resistance and is not suitable for a colored resin composition for forming a color filter. Thus, the present invention provides a compound having excellent heat resistance.

［式（ＩＡ）中、
Ｒ^A1〜Ｒ^A10は、それぞれ独立に、水素原子、ヒドロキシ基、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、式（ａ）で表される基、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、Ｒ^A1〜Ｒ^A10の少なくとも２つは、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、又は式（ａ）で表される基を表す。

（式（ａ）中、
Ｒ^A11は、水素原子、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
Ｌ^A1は、置換基を有していてもよい２価の芳香族炭化水素基を表す。
Ａａ^(-)は、−ＣＯ₂ ^-、又は−ＳＯ₃ ^-を表す。
但し、式中の＊は、結合手を意味する。）
Ｔ^A1は、置換基を有していてもよい炭素数６〜１０の芳香族炭化水素基を表す。ただし、該芳香族炭化水素基は−ＳＯ₃ ^-を置換基として有しない。
Ａｎは、式（ＩＡ）で表される化合物が有する−ＣＯ₂ ^-、−ＳＯ₃ ^-、及び−Ｏ^-の個数の和を表す。
Ａｍは、１以上の整数を表す。
ＡＸ^Ak(+)は、Ａｋ価の金属カチオンを表す。
Ａｋは、２以上の整数を表す。]

［式（ＩＢ）中、
Ｒ^B1〜Ｒ^B10は、それぞれ独立に、水素原子、ヒドロキシ基、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、式（ｂ）で表される基、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、Ｒ^B1〜Ｒ^B10の少なくとも２つは、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、又は式（ｂ）で表される基を表す。

（式（ｂ）中、
Ｒ^B11は、水素原子、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
Ｌ^B1は、置換基を有していてもよい２価の芳香族炭化水素基を表す。
Ｂｂ^(-)は、−ＣＯ₂ ^-、又は−ＳＯ₃ ^-を表す。
但し、式中の＊は、結合手を意味する。）
Ｂｎは、式（ＩＢ）で表される化合物が有する−ＣＯ₂ ^-、−ＳＯ₃ ^-、及び−Ｏ^-の個数の和を表す。
Ｔ^B1は、置換基を有していてもよい炭素数６〜１４の２価の芳香族炭化水素基を表す。ただし、該芳香族炭化水素基は−ＳＯ₃ ^-を置換基として有しない。
Ｌ^B0は、Ｂｍ価の連結基を表す。
Ｂｍは、２以上の整数を表す。
ＢＸ^Bk(+)は、Ｂｋ価の金属カチオンを表す。
Ｂｋは、１以上の整数を表す。]

［式（ＩＣ）中、
Ｒ^C1〜Ｒ^C4は、それぞれ独立に、水素原子、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
Ｒ^C5〜Ｒ^C12は、それぞれ独立に、水素原子、又は炭素数１〜８の炭化水素基を表す。
Ｔ^C1は、置換基を有していてもよい炭素数６〜１４の３価の芳香族炭化水素基を表す。
ＣＸ^Ck(+)は、Ｃｋ価の金属カチオンを表す。
Ｃｋは、１以上の整数を表す。]

［式（ＩＤ）中、
Ｒ^D1〜Ｒ^D10は、それぞれ独立に、水素原子、ヒドロキシ基、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、式（ｄ）で表される基、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、Ｒ^D1〜Ｒ^D10の少なくとも２つは、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、又は式（ｄ）で表される基を表す。

（式（ｄ）中、
Ｒ^D11は、水素原子、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
Ｌ^D1は、置換基を有していてもよい２価の芳香族炭化水素基を表す。
Ｄｄ^(-)は、−ＣＯ₂ ^-、又は−ＳＯ₃ ^-を表す。
但し、式中の＊は、結合手を意味する。）
Ｔ^D1は、置換基を有していてもよい炭素数６〜１０の２価の芳香族炭化水素基を表す。ただし、該芳香族炭化水素基は−ＳＯ₃ ^-を置換基として有しない。
Ｒ^D21は、水素原子、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
ＤＸ⁽⁺⁾は、１価の金属カチオンを表す。］
［２］ 着色剤及び樹脂を含み、着色剤が、［１］に記載の式（ＩＡ）で表される化合物、式（ＩＢ）で表される化合物、式（ＩＣ）で表される化合物、及び式（ＩＤ）で表される化合物からなる群から選ばれる少なくとも１つを含む着色樹脂組成物。
［３］ ［２］に記載の着色樹脂組成物と、重合性化合物と、重合開始剤とを含む着色樹脂組成物。
［４］ ［３］に記載の着色樹脂組成物から形成されるカラーフィルタ。
［５］ ［４］に記載のカラーフィルタを含む表示装置。 The present invention includes the following inventions.
[1] A compound represented by the formula (IA), the formula (IB), the formula (IC), or the formula (ID).

[In the formula (IA),
R ^{A1 to} R ^A10 each independently have a hydrogen atom, a hydroxy group, —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , a group represented by the formula (a), or a substituent. Represents a hydrocarbon group having a good carbon number of 1 to 20, and at least two of R ^{A1 to} R ^A10 represent —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (a). .

(In the formula (a),
^RA11 represents a hydrogen atom or a C1-C20 hydrocarbon group which may have a substituent.
L ^A1 represents a divalent aromatic hydrocarbon group which may have a substituent.
Aa ^(-) is, -CO ₂ ^-, or -SO ₃ ^- represents a.
However, * in the formula means a bond. )
T ^A1 represents an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. However, the aromatic hydrocarbon group does not have —SO ₃ ^— as a substituent.
An represents the sum of the numbers of —CO ₂ ⁻ , —SO ₃ ⁻ , and —O ⁻ that the compound represented by the formula (IA) has.
Am represents an integer of 1 or more.
AX ^{Ak (+)} represents an Ak-valent metal cation.
Ak represents an integer of 2 or more. ]

[In the formula (IB),
R ^B1 to R ^B10 are each independently a hydrogen atom, hydroxy _{^{group, -CO 2 -, -SO 3 -}} , -O -, have group represented by the formula (b), or a substituent Represents a hydrocarbon group having a good carbon number of 1 to 20, and at least two of R ^{B1 to} R ^B10 represent —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (b) .

(In the equation (b),
R ^B11 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
L ^B1 represents a divalent aromatic hydrocarbon group which may have a substituent.
Bb ^(-) is, -CO ₂ ^-, or -SO ₃ ^- represents a.
However, * in the formula means a bond. )
Bn is, -CO ₂ where the compound represented by formula (IB) has ^-, -SO ₃ ^-, and -O ^- represents the sum of the number of.
T ^B1 represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent. However, the aromatic hydrocarbon group does not have —SO ₃ ^— as a substituent.
L ^B0 represents a Bm-valent linking group.
Bm represents an integer of 2 or more.
BX ^{Bk (+)} represents a Bk-valent metal cation.
Bk represents an integer of 1 or more. ]

[In the formula (IC),
R ^{C1 to} R ^C4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
R ^{C5 to} R ^C12 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
T ^C1 represents an optionally substituted trivalent aromatic hydrocarbon group having 6 to 14 carbon atoms.
CX ^{Ck (+)} represents a Ck-valent metal cation.
Ck represents an integer of 1 or more. ]

[In the formula (ID),
R ^{D1 to} R ^D10 each independently have a hydrogen atom, a hydroxy group, —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , a group represented by the formula (d), or a substituent. Represents a hydrocarbon group having a good carbon number of 1 to 20, and at least two of R ^{D1 to} R ^D10 represent —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (d). .

(In the equation (d),
R ^D11 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
L ^D1 represents a divalent aromatic hydrocarbon group which may have a substituent.
Dd ^(-) is, -CO ₂ ^-, or -SO ₃ ^- represents a.
However, * in the formula means a bond. )
T ^D1 represents a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. However, the aromatic hydrocarbon group does not have —SO ₃ ^— as a substituent.
R ^D21 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
DX ⁽⁺⁾ represents a monovalent metal cation. ]
[2] A compound containing a colorant and a resin, wherein the colorant is a compound represented by the formula (IA), a compound represented by the formula (IB), a compound represented by the formula (IC) according to [1], And a colored resin composition containing at least one selected from the group consisting of compounds represented by formula (ID).
[3] A colored resin composition comprising the colored resin composition according to [2], a polymerizable compound, and a polymerization initiator.
[4] A color filter formed from the colored resin composition according to [3].
[5] A display device including the color filter according to [4].

  According to the present invention, a novel compound having excellent heat resistance is provided. Further, according to the compound of the present invention, a color filter having excellent heat resistance can be formed.

<Compound>
The compound according to the present invention includes a compound represented by the formula (IA) (hereinafter sometimes referred to as compound (IA)) and a compound represented by the formula (IB) (hereinafter sometimes referred to as compound (IB)). Or a compound represented by the formula (IC) (hereinafter sometimes referred to as compound (IC)) or a compound represented by the formula (ID) (hereinafter sometimes referred to as compound (ID)). Hereinafter, the present invention will be described in detail with reference to Formula (IA), Formula (IB), Formula (IC), or Formula (ID), and it is intended that Compound (IA), Compound (IB), Compound (IC), or Compound (IC) be used. (ID) includes a tautomer of the formula (IA), the formula (IB), the formula (IC), or the formula (ID), a formula (IA), a formula (IB), a formula (IC), or A compound obtained by rotating each group in the formula (ID) around the bond axis of a carbon-carbon single bond is also included.

<< Compound (IA) >>
A compound represented by the formula (IA):

［式（ＩＡ）中、
Ｒ^A1〜Ｒ^A10は、それぞれ独立に、水素原子、ヒドロキシ基、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、式（ａ）で表される基、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、Ｒ^A1〜Ｒ^A10の少なくとも２つは、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、又は式（ａ）で表される基を表す。

（式（ａ）中、
Ｒ^A11は、水素原子、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
Ｌ^A1は、置換基を有していてもよい２価の芳香族炭化水素基を表す。
Ａａ^(-)は、−ＣＯ₂ ^-、又は−ＳＯ₃ ^-を表す。
但し、式中の＊は、結合手を意味する。）
Ｔ^A1は、置換基を有していてもよい炭素数６〜１０の芳香族炭化水素基を表す。ただし、該芳香族炭化水素基は−ＳＯ₃ ^-を置換基として有しない。
Ａｎは、式（ＩＡ）で表される化合物が有する−ＣＯ₂ ^-、−ＳＯ₃ ^-、及び−Ｏ^-の個数の和を表す。
Ａｍは、１以上の整数を表す。
ＡＸ^Ak(+)は、Ａｋ価の金属カチオンを表す。
Ａｋは、２以上の整数を表す。]

[In the formula (IA),
R ^{A1 to} R ^A10 each independently have a hydrogen atom, a hydroxy group, —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , a group represented by the formula (a), or a substituent. Represents a hydrocarbon group having a good carbon number of 1 to 20, and at least two of R ^{A1 to} R ^A10 represent —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (a). .

(In the formula (a),
^RA11 represents a hydrogen atom or a C1-C20 hydrocarbon group which may have a substituent.
L ^A1 represents a divalent aromatic hydrocarbon group which may have a substituent.
Aa ^(-) is, -CO ₂ ^-, or -SO ₃ ^- represents a.
However, * in the formula means a bond. )
T ^A1 represents an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. However, the aromatic hydrocarbon group does not have —SO ₃ ^— as a substituent.
An represents the sum of the numbers of —CO ₂ ⁻ , —SO ₃ ⁻ , and —O ⁻ that the compound represented by the formula (IA) has.
Am represents an integer of 1 or more.
AX ^{Ak (+)} represents an Ak-valent metal cation.
Ak represents an integer of 2 or more. ]

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{A1 to} R ^A10 and R ^A11 include an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms. Is exemplified.

  The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be either saturated or unsaturated, and the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic. There may be.

Examples of the linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms 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 vinyl group, Linear aliphatic hydrocarbon groups such as 1-propenyl group and 2-propenyl group (allyl group); branched aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group And the like.
The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di (2,2-dimethylpropyl) phenyl group, and a naphthyl group.

Examples of the substituent which the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{A1 to} R ^A10 and R ^A11 may have include a halogen atom such as a fluorine atom, a chlorine atom and an iodine; a hydroxy group; Groups; sulfamoyl groups; nitro groups; alkoxy groups having 1 to 10 carbon atoms such as methoxy groups and ethoxy groups; and alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl groups and ethoxycarbonyl groups.

The divalent aromatic hydrocarbon group represented by L ^A1 is preferably a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and is preferably a monovalent aromatic hydrocarbon group represented by R ^{A1 to} R ^A10 and R ^A11 . Examples include a group having one of the hydrogen atoms contained in the hydrogen group as a bond.

Examples of the substituent which the divalent aromatic hydrocarbon group represented by L ^A1 may have include a hydrocarbon group having 1 to 20 carbon atoms represented by R ^{A1 to} R ^A10 and R ^A11. Are the same as the substituents which may be substituted.

When the compound (IA) has a plurality of groups represented by the formula (a) and a plurality of R ^A11 , L ^A1 , and Aa ⁽⁻⁾ are present in the compound (IA), they are the same. May also be different.

The aromatic hydrocarbon group having 6 to 10 carbon atoms represented by T ^A1, a phenyl group, a xylyl group, trimethylphenyl group, a naphthyl group, and the like.

Examples of the substituent which the aromatic hydrocarbon group having 6 to 10 carbon atoms represented by T ^A1 may have include a halogen atom such as a fluorine atom, a chlorine atom and an iodine; a hydroxy group; a carboxy group; a sulfamoyl group; -NR ^x R ^y (R ^x and R ^y are each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent); a nitro group; a methoxy group, an ethoxy group A C1-C10 alkoxy group such as a group; a C1-C10 alkoxycarbonyl group such as a methoxycarbonyl group or an ethoxycarbonyl group;

Specific examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^x and R ^y , and the substituent which the hydrocarbon group may have are the same as R ^{A1 to} R ^A10 and R ^A11 . is there.

Among the metal cations of Ak valence represented by AX ^{Ak (+)} , the metal whose Ak is 2 (that is, a divalent metal) includes, for example, alkaline earth metals such as magnesium, calcium, strontium and barium; zinc , Copper, nickel, manganese and the like, and a transition metal such as a typical metal such as aluminum; a transition metal such as cobalt and iron; .

As the compound (IA), those in which R ^{A1 to} R ^A10 , T ^A1 , An, Am, and AX ^{Ak (+)} are as follows are preferable.

Of R ^{A1 to} R ^A10, the number of groups represented by —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or formula (a) is preferably 2 to 6, and 2 to 4 is preferable. Is more preferable, and the number is more preferably two to three. That is, An is preferably from 2 to 6, more preferably from 2 to 4, and even more preferably from 2 to 3. When two or more groups represented by —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or formula (a) are included in R ^{A1 to} R ^A10 , one or more of R ^{A1 to} R ^A6 are used. There _{^{-CO 2 -, -SO 3 -,}} -O -, or a group represented by the formula (a), -CO ₂ one or more of R ^A7 to R ^A10 is ^-, -SO ₃ ^-, -O ^-, or it is preferably a group of formula (a).

When the compound (IA) has a substituent represented by the formula (a), at least two of R ^{A1 to} R ^A10 are preferably a group represented by the formula (a), and two to four are preferably More preferably, the group represented by the formula (a) does not have —CO ₂ ⁻ , —SO ₃ ⁻ , or —O ⁻ , and two are groups represented by the formula (a); _{^{2 -, -SO 3 -, -O}} - more preferably no. When the compound (IA) has a plurality of groups represented by the formula (a), the groups represented by the plurality of formulas (a) are preferably the same.

As the group represented by the formula (a), L ^A1 is preferably a phenylenemethylene group, a methylphenylenemethylene group, or a dimethylphenylenemethylene group which may have a substituent, and L ^A1 represents a substituent. An unsubstituted phenylenemethylene group, a methylphenylenemethylene group, or a dimethylphenylenemethylene group, wherein R ^A11 is a hydrogen atom or an unsubstituted saturated hydrocarbon group having 1 to 2 carbon atoms, and Aa ^{(− )} is -SO ₃ ^- a is group is more preferable.

  Examples of the group represented by the formula (a) include groups represented by the following formulas (a-1) to (a-8).

（式中の＊は、結合手を意味する。）

(* In the formula means a bond.)

When the compound (IA) does not have a substituent represented by the formula (a), at least two of R ^{A1 to} R ^A10 are more preferably —CO ₂ ⁻ or —O ⁻ , and two to four of -CO ₂ ^-, or -O ^- more preferably, two are -CO ₂ ^- and more preferably a ^- and one is -O.

^Examples of —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , represented by R ^{A1 to} R ^A10 , and groups other than the group represented by Formula (a) include a hydrogen atom or a C 1-20 fatty acid. A group hydrocarbon group is preferable, and a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or a linear aliphatic group having 1 to 5 carbon atoms. A hydrocarbon group is more preferred, and a hydrogen atom or a methyl group is even more preferred.

Among R ^{A1 to} R ^A10, the number of hydrogen atoms is preferably 4 to 8, and more preferably 6 to 8.

T ^A1 is preferably a phenyl group which may have a substituent, a fluorine atom as a substituent, a chlorine atom, a halogen atom such as iodine, more preferably a phenyl group having -NR ^x R ^y, substituents still more preferably a phenyl group having a chlorine atom, or -NR ^x R ^y as.

As the -NR ^x R ^y, R ^x is a hydrogen atom, it is preferred that R ^y is a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent group, R ^y is a substituent More preferably, it is an aromatic hydrocarbon group having 6 to 10 carbon atoms which may have, and R ^y is an aromatic hydrocarbon having 6 to 10 carbon atoms having an alkoxy group having 1 to 5 carbon atoms as a substituent. More preferably, it is a group.

Examples of T ^A1 include groups represented by the following formulas (aa-1) to (aa-8).

（式中の＊は、結合手を意味する。）

(* In the formula means a bond.)

  Am is preferably 2 to 5, more preferably 2 to 3, and still more preferably 2.

The Ak valent metal cation represented by AX ^{Ak (+)} is preferably a cation of a metal having Ak of 2 to 3 (that is, a divalent to trivalent metal), and is preferably a metal of which Ak is 2 (that is, 2). More preferably, it is a cation of barium, zinc, or manganese, which is a (valent metal).

  Examples of the compound (IA) include compounds represented by Formulas (A-1) to (A-27) shown in Table 1.

  In Table 1, Me represents a methyl group, and a-6, aa-1, aa-2, and aa-6 are represented by the above formulas (a-6), (aa-1), (aa-2), It means a group represented by (aa-6).

<< Compound (IB) >>
A compound represented by the formula (IB):

［式（ＩＢ）中、
Ｒ^B1〜Ｒ^B10は、それぞれ独立に、水素原子、ヒドロキシ基、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、式（ｂ）で表される基、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、Ｒ^B1〜Ｒ^B10の少なくとも２つは、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、又は式（ｂ）で表される基を表す。

（式（ｂ）中、
Ｒ^B11は、水素原子、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
Ｌ^B1は、置換基を有していてもよい２価の芳香族炭化水素基を表す。
Ｂｂ^(-)は、−ＣＯ₂ ^-、又は−ＳＯ₃ ^-を表す。
但し、式中の＊は、結合手を意味する。）
Ｂｎは、式（ＩＢ）で表される化合物が有する−ＣＯ₂ ^-、−ＳＯ₃ ^-、及び−Ｏ^-の個数の和を表す。
Ｔ^B1は、置換基を有していてもよい炭素数６〜１４の２価の芳香族炭化水素基を表す。ただし、該芳香族炭化水素基は−ＳＯ₃ ^-を置換基として有しない。
Ｌ^B0は、Ｂｍ価の連結基を表す。
Ｂｍは、２以上の整数を表す。
ＢＸ^Bk(+)は、Ｂｋ価の金属カチオンを表す。
Ｂｋは、１以上の整数を表す。]

[In the formula (IB),
R ^B1 to R ^B10 are each independently a hydrogen atom, hydroxy _{^{group, -CO 2 -, -SO 3 -}} , -O -, have group represented by the formula (b), or a substituent Represents a hydrocarbon group having a good carbon number of 1 to 20, and at least two of R ^{B1 to} R ^B10 represent —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (b) .

(In the equation (b),
R ^B11 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
L ^B1 represents a divalent aromatic hydrocarbon group which may have a substituent.
Bb ^(-) is, -CO ₂ ^-, or -SO ₃ ^- represents a.
However, * in the formula means a bond. )
Bn is, -CO ₂ where the compound represented by formula (IB) has ^-, -SO ₃ ^-, and -O ^- represents the sum of the number of.
T ^B1 represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent. However, the aromatic hydrocarbon group does not have —SO ₃ ^— as a substituent.
L ^B0 represents a Bm-valent linking group.
Bm represents an integer of 2 or more.
BX ^{Bk (+)} represents a Bk-valent metal cation.
Bk represents an integer of 1 or more. ]

R ^B1 to R ^B10, and examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^B11, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms such as Is exemplified.

  The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be either saturated or unsaturated, and the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic. There may be.

Examples of the linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms 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 vinyl group and a vinyl group. Linear aliphatic hydrocarbon groups such as -propenyl group and 2-propenyl group (allyl group); branched aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; Is mentioned.
The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic, and may be an aliphatic hydrocarbon group containing two or more aliphatic hydrocarbon rings. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, an ethylcyclohexyl group, a group in which one hydrogen atom of dimethylnorbornane is a bond, and a group of diethylnorbornane. A group in which one hydrogen atom is a bond, a group in which one hydrogen atom in dimethyl adamantane is a bond, a group in which one hydrogen atom is a bond in diethyl adamantane, and one group of di (methylcyclohexyl) methane A group in which one hydrogen atom is a bond, a group in which one hydrogen atom of di (ethylcyclohexyl) methane is a bond, a group in which one hydrogen atom of di (dimethylcyclohexyl) methane is a bond, A group in which one hydrogen atom of (diethylcyclohexyl) methane is a bond, di (trimethyl) One hydrogen atom of chlorohexyl) methane is a bond, one hydrogen atom of di (triethylcyclohexyl) methane is a bond, and one hydrogen atom of di (methylcyclohexyl) dimethylmethane is a bond. And a group in which one hydrogen atom of di (ethylcyclohexyl) dimethylmethane is a bond.

  Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di (2,2-dimethylpropyl) phenyl group, and a naphthyl group.

The R ^B1 to R ^B10, and a hydrocarbon group substituents which may be possessed by 1 to 20 carbon atoms represented by R ^B11, a fluorine atom, a chlorine atom, a halogen atom and iodine; hydroxy; carboxy Groups; sulfamoyl groups; nitro groups; alkoxy groups having 1 to 10 carbon atoms such as methoxy groups and ethoxy groups; and alkoxycarbonyl groups having 1 to 10 carbon atoms such as methoxycarbonyl groups and ethoxycarbonyl groups.

Examples of the divalent aromatic hydrocarbon group represented by L ^B1, preferably a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms, R ^B1 ~R ^B10, and monovalent aromatic in R ^B11 carbide Examples include groups in which one of the hydrogen atoms contained in a hydrogen group (not including those having 11 to 20 carbon atoms) is a bond.

Examples of the substituent which the divalent aromatic hydrocarbon group represented by L ^B1 may have include a hydrocarbon group having 1 to 20 carbon atoms represented by R ^{B1 to} R ^B10 and R ^B11. Are the same as the substituents which may be substituted.

When compound (IB) has a plurality of groups represented by formula (b) and a plurality of R ^B11 , L ^B1 , and Bb ⁽⁻⁾ are present in compound (IB), they are the same and May also be different.

Examples of the divalent aromatic hydrocarbon group having 6 to 14 carbon atoms represented by T ^B1 include a monovalent aromatic hydrocarbon group represented by R ^{B1 to} R ^B10 and R ^B11 (however, a monovalent aromatic hydrocarbon group having 15 to 20 carbon atoms). ) Are included as a bond.

Specific examples of the divalent aromatic hydrocarbon group substituent which may be have 6-14 carbon atoms represented by T ^B1 is, R ^B1 ~R ^B10, and carbon atoms represented by R ^B11 1 And the same as the substituents which the hydrocarbon groups may have.

The Bm-valent linking group represented by L ^B0, a divalent 5 divalent hydrocarbon group having 1 to 20 carbon atoms, -CH ₂ contained in the hydrocarbon group - part oxygen atoms Or a group in which a part of> CH— contained in the hydrocarbon group may be optionally replaced by a nitrogen atom; A part of —CH ₂ — contained in the hydrocarbon group is replaced with an oxygen atom or a sulfur atom, or a part of> CH— contained in the hydrocarbon group is nitrogen. It is more preferable that one or more of the oxygen atom, the sulfur atom, and the nitrogen atom that is replaced by an atom is a group having all the bonds of a linking group. The Bm-valent linking group is a group in which (Bm-1) hydrogen atoms contained in the monovalent hydrocarbon group in R ^{B1 to} R ^B10 and R ^B11 are a bond. A group in which a part of —CH ₂ — contained therein may be replaced by an oxygen atom or a sulfur atom, and a part of> CH— contained in the hydrocarbon group may be replaced by a nitrogen atom is exemplified.

Among the metal cations having a valence of Bk represented by BX ^{Bk (+)} , examples of the metal having Bk of 1 (that is, a monovalent metal) include alkali metals such as lithium, sodium, potassium, and cesium; Examples of the metal having a Bk of 2 (ie, a divalent metal) include alkaline earth metals such as magnesium, calcium, strontium, and barium; transition metals such as zinc, copper, nickel, and manganese; Examples of the metal 3 (that is, a trivalent metal) include a typical metal such as aluminum; and a transition metal such as cobalt and iron.

As the compound ^{(IB), R B1 ~R B10} , Bn, T B1, L B0, Bm, and BX ^{Bk (+)} is what is as follows preferred.

Among R ^{B1 to} R ^B10, the number of groups represented by —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or formula (b) is preferably 2 to 6, and 2 to 4 is preferable. Is more preferable, and it is more preferable that there are two. That is, Bn is preferably 2 to 6, more preferably 2 to 4, and still more preferably 2. _{^{R B1 ~R B10, -CO 2 -}} , -SO 3 -, -O -, or group of two or more of the formula (b), one or more of R ^B1 to R ^B6 is - CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (b), wherein one or more of R ^{B7 to} R ^B10 is —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , Alternatively, it is preferably a group represented by the formula (b).

When the compound (IB) has a substituent represented by the formula (b), at least two of R ^{B1 to} R ^B10 are preferably a group represented by the formula (b), and two to four are preferably a group represented by the formula ^{_{(b), -CO 2 -,}} -SO 3 -, -O - is more preferable to have no, or a group represented by 2 Exemplary ethynylphenylbiadamantane derivatives (b), -CO _{^{2 -, -SO 3 -, -O}} - more preferably no. When the compound (IB) has a plurality of groups represented by the formula (b), the groups represented by the plurality of formulas (b) are preferably the same.

As the group represented by the formula (b), L ^B1 is preferably a phenylenemethylene group, methylphenylenemethylene group, or dimethylphenylenemethylene group which may have a substituent, and L ^B1 represents a substituent. An unsubstituted phenylenemethylene group, a methylphenylenemethylene group, or a dimethylphenylenemethylene group, wherein R ^B11 is a hydrogen atom or an unsubstituted saturated hydrocarbon group having 1 to 2 carbon atoms, and Bb ^{(− )} is -SO ₃ ^- a is group is more preferable.

  Examples of the group represented by the formula (b) include groups represented by the following formulas (b-1) to (b-8).

（式中の＊は、結合手を意味する。）

(* In the formula means a bond.)

-CO ₂ represented by _{^{R B1 ~R B10 -, -SO 3}} -, -O -, and as the group other than the group represented by the formula (b), each independently, a hydrogen atom, or a carbon 1 To 20 aliphatic hydrocarbon groups are preferable, and a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or a linear chain having 1 to 5 carbon atoms is preferable. Is more preferably an aliphatic hydrocarbon group, and even more preferably a hydrogen atom or a methyl group.

Among R ^{B1 to} R ^B10, the number of hydrogen atoms is preferably 4 to 8, and more preferably 6 to 8.

T ^B1 is an optionally substituted phenylene group, or preferably a naphthylene group, a phenylene group having no substituent, or a naphthylene group is more preferable.

L ^B0 is preferably a divalent hydrocarbon group having 1 to 20 carbon atoms, more preferably a divalent saturated cyclic aliphatic hydrocarbon group having 1 to 20 carbon atoms, and the saturated cyclic aliphatic group is carbon atoms contained in the hydrocarbon group are more groups that are replaced by a nitrogen atom preferably, the carbon atom to replace the nitrogen atom, it is even more preferred is a carbon atom linked to the T ^B1.

Examples of ^LB0 include a linking group represented by the following formulas (LB-1) to (LB-8).

（式中の＊は、結合手を意味する。）

(* In the formula means a bond.)

  Bm is preferably 2 to 5, more preferably 2 to 3, and most preferably 2.

The Bk-valent metal cation represented by BX ^{Bk (+)} is preferably a cation of a metal having a Bk of 1 to 3 (that is, a monovalent to trivalent metal), and a metal having a Bk of 2 (that is, 2 More preferably, it is a cation of barium, zinc, or manganese, which is a (valent metal).

  Examples of the compound (IB) include compounds represented by Formulas (B-1) to (B-48) shown in Table 2.

  In Table 2, Me represents a methyl group, phe represents a phenylene group, naph represents a naphthylene group, and b-6, b-7, LB-3, and LB-4 represent the above formulas (b-6) and (b-6), respectively. -7), (LB-3) and (LB-4).

<< Compound (IC) >>
A compound represented by the formula (IC).

［式（ＩＣ）中、
Ｒ^C1〜Ｒ^C4は、それぞれ独立に、水素原子、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
Ｒ^C5〜Ｒ^C12は、それぞれ独立に、水素原子、又は炭素数１〜８の炭化水素基を表す。
Ｔ^C1は、置換基を有していてもよい炭素数６〜１４の３価の芳香族炭化水素基を表す。
ＣＸ^Ck(+)は、Ｃｋ価の金属カチオンを表す。
Ｃｋは、１以上の整数を表す。]

[In the formula (IC),
R ^{C1 to} R ^C4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
R ^{C5 to} R ^C12 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
T ^C1 represents an optionally substituted trivalent aromatic hydrocarbon group having 6 to 14 carbon atoms.
CX ^{Ck (+)} represents a Ck-valent metal cation.
Ck represents an integer of 1 or more. ]

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{C1 to} R ^C4 include an aliphatic hydrocarbon group having 1 to 20 carbon atoms and an aromatic hydrocarbon group having 6 to 20 carbon atoms. .

  The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be either saturated or unsaturated, and the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic. There may be.

Examples of the linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms 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 vinyl group and a vinyl group. Linear aliphatic hydrocarbon groups such as -propenyl group and 2-propenyl group (allyl group); branched aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; Is mentioned.
The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di (2,2-dimethylpropyl) phenyl group, and a naphthyl group.

Examples of the substituent which the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{C1 to} R ^C4 may have include a halogen atom such as a fluorine atom, a chlorine atom and an iodine; a hydroxy group; a carboxy group; a sulfamoyl group A nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group;

Specific examples of the hydrocarbon group having 1 to 8 carbon atoms represented by R ^{C5 to} R ^C12 and the substituent which the hydrocarbon group may have are those other than those not including those having 9 to 20 carbon atoms. Is the same as R ^{C1 to} R ^C4 .

Examples of the trivalent aromatic hydrocarbon group having 6 to 14 carbon atoms represented by T ^C1 include the monovalent aromatic hydrocarbon groups represented by R ^{C1 to} R ^C4 (however, those having 15 to 20 carbon atoms are not included. )) Is a group in which two of the hydrogen atoms contained in the above are bonded.

Specific examples of the substituent which may be possessed by the trivalent aromatic hydrocarbon group having 6 to 14 carbon atoms represented by T ^C1 include carbon atoms having 1 to 20 carbon atoms represented by R ^{C1 to} R ^C4. It is the same as the substituent which the hydrogen group may have.

Among Ck-valent metal cations represented by CX ^{Ck (+)} , examples of the metal having Ck of 1 (that is, a monovalent metal) include alkali metals such as lithium, sodium, potassium, and cesium; Examples of the metal having Ck of 2 (ie, a divalent metal) include alkaline earth metals such as magnesium, calcium, strontium, and barium; transition metals such as zinc, copper, nickel, and manganese; Examples of the metal 3 (that is, a trivalent metal) include a typical metal such as aluminum; and a transition metal such as cobalt and iron.

As the compound (IC), those in which R ^{C1 to} R ^C12 , T ^C1 and CX ^{Ck (+)} are as follows are preferable.

R ^{C1 to} R ^C4 are each independently preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and preferably a saturated linear aliphatic hydrocarbon group having 1 to 8 carbon atoms. More preferably, it is a saturated linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, even more preferably, a methyl group or an ethyl group.

In R ^{C1 to} R ^C4 , R ^C1 and R ^C3 , and R ^C2 and R ^C4 are preferably the same group, and more preferably, R ^{C1 to} R ^C4 are all the same group.

R ^{C5 to} R ^C12 are each independently preferably a hydrogen atom or a saturated linear aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrogen atom.

T ^C1 is preferably a trivalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent, and a trivalent aromatic hydrocarbon group having 6 to 10 carbon atoms which has no substituent; Alternatively, a trivalent aromatic hydrocarbon group having 6 to 10 carbon atoms and having a hydroxy group as a substituent is more preferable.

Examples of the group in which two —SO ₃ ^— are bonded to T ^C1 include groups represented by the following formulas (cc-1) to (cc-22).

（式中の＊は、結合手を意味する。）

(* In the formula means a bond.)

The Ck-valent metal cation represented by CX ^{Ck (+)} is preferably a cation of a metal having Ck of 1 to 3 (that is, a monovalent to trivalent metal), and a metal having a Ck of 2 (that is, 2C). More preferably, it is a cation of barium, zinc, or manganese, which is a (valent metal).

  Examples of the compound (IC) include compounds represented by Formulas (C-1) to (C-18) shown in Table 3.

  In Table 3, Me represents a methyl group, Et represents an ethyl group, and cc-3, cc-8, and cc-20 are represented by the above formulas (cc-3), (cc-8), and (cc-20), respectively. Means a group represented by

<< Compound (ID) >>
A compound represented by the formula (ID).

［式（ＩＤ）中、
Ｒ^D1〜Ｒ^D10は、それぞれ独立に、水素原子、ヒドロキシ基、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、式（ｄ）で表される基、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表し、Ｒ^D1〜Ｒ^D10の少なくとも２つは、−ＣＯ₂ ^-、−ＳＯ₃ ^-、−Ｏ^-、又は式（ｄ）で表される基を表す。

（式（ｄ）中、
Ｒ^D11は、水素原子、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
Ｌ^D1は、置換基を有していてもよい２価の芳香族炭化水素基を表す。
Ｄｄ^(-)は、−ＣＯ₂ ^-、又は−ＳＯ₃ ^-を表す。
但し、式中の＊は、結合手を意味する。）
Ｔ^D1は、置換基を有していてもよい炭素数６〜１０の２価の芳香族炭化水素基を表す。ただし、該芳香族炭化水素基は−ＳＯ₃ ^-を置換基として有しない。
Ｒ^D21は、水素原子、又は置換基を有していてもよい炭素数１〜２０の炭化水素基を表す。
ＤＸ⁽⁺⁾は、１価の金属カチオンを表す。］

[In the formula (ID),
R ^{D1 to} R ^D10 each independently have a hydrogen atom, a hydroxy group, —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , a group represented by the formula (d), or a substituent. Represents a hydrocarbon group having a good carbon number of 1 to 20, and at least two of R ^{D1 to} R ^D10 represent —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (d). .

(In the equation (d),
R ^D11 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
L ^D1 represents a divalent aromatic hydrocarbon group which may have a substituent.
Dd ^(-) is, -CO ₂ ^-, or -SO ₃ ^- represents a.
However, * in the formula means a bond. )
T ^D1 represents a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. However, the aromatic hydrocarbon group does not have —SO ₃ ^— as a substituent.
R ^D21 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
DX ⁽⁺⁾ represents a monovalent metal cation. ]

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{D1 to} R ^D10 , R ^D11 , and R ^D21 include an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples thereof include a hydrogen group.

  The aliphatic hydrocarbon group having 1 to 20 carbon atoms may be either saturated or unsaturated, and the aliphatic hydrocarbon group having 1 to 20 carbon atoms may be linear, branched or cyclic. There may be.

Examples of the linear or branched aliphatic hydrocarbon group having 1 to 20 carbon atoms 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 vinyl group and a vinyl group. Linear aliphatic hydrocarbon groups such as -propenyl group and 2-propenyl group (allyl group); branched aliphatic hydrocarbon groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group and 2-ethylhexyl group; Is mentioned.
The cyclic aliphatic hydrocarbon group may be monocyclic or polycyclic. Examples of the cyclic aliphatic hydrocarbon group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

  Examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di (2,2-dimethylpropyl) phenyl group, and a naphthyl group.

As the substituent which the hydrocarbon group having 1 to 20 carbon atoms represented by R ^{D1 to} R ^D10 , R ^D11 and R ^D21 may have, a halogen atom such as a fluorine atom, a chlorine atom and an iodine; A carboxy group; a sulfamoyl group; a nitro group; an alkoxy group having 1 to 10 carbon atoms such as a methoxy group and an ethoxy group; an alkoxycarbonyl group having 1 to 10 carbon atoms such as a methoxycarbonyl group and an ethoxycarbonyl group; .

As the divalent aromatic hydrocarbon group represented by L ^D1 , a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms is preferable, and the monovalent aromatic hydrocarbon group in R ^{D1 to} R ^D10 , R ^D11 and R ^D21 is preferred. Examples thereof include groups in which one of the hydrogen atoms contained in the aromatic hydrocarbon group is a bond.

Examples of the substituent which the divalent aromatic hydrocarbon group represented by L ^D1 may have include hydrocarbons having 1 to 20 carbon atoms represented by R ^{D1 to} R ^D10 , R ^D11 , and R ^D21. It is the same as the substituent which the group may have.

When the compound (ID) has a plurality of groups represented by the formula (d) and a plurality of R ^D11 , L ^D1 , and Dd ⁽⁻⁾ are present in the compound (ID), they are the same and May also be different.

Examples of the divalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by T ^D1 include a monovalent aromatic hydrocarbon group represented by R ^{D1 to} R ^D10 , R ^D11 , and R ^D21 (provided that the number of carbon atoms is 11). To 20) are included as a bond.

Examples of the divalent aromatic hydrocarbon group substituents which may be possessed by the 6 to 10 carbon atoms represented by ^{T D1, R D1 ~R D10,} R D11, and the number of carbon atoms represented by R ^D21 It is the same as the substituent which the hydrocarbon group of 1 to 20 may have.

Examples of the metal of the monovalent metal cation represented by DX ⁽⁺⁾ include alkali metals such as lithium, sodium, potassium, and cesium.

As the compound (ID), those in which R ^{D1 to} R ^D10 , T ^D1 , R ^D21 and DX ⁽⁺⁾ are as follows are preferable.

Among R ^{D1 to} R ^D10, the number of groups represented by —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or formula (d) is preferably 2 to 6, and 2 to 4 is preferable. Is more preferable, and it is more preferable that there are two. When two or more groups represented by —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or formula (d) among R ^{D1 to} R ^D10 , one or more of R ^{D1 to} R ^D6 are —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (d), and one or more of R ^{D7 to} R ^D10 is —CO ₂ ⁻ , —SO ₃ ⁻ , or —O ^−. Or a group represented by the formula (d).

When the compound (ID) has a substituent represented by the formula (d), at least two of R ^{D1 to} R ^D10 are preferably a group represented by the formula (d), and two to four are preferably a group represented by the formula ^{_{(d), -CO 2 -,}} -SO 3 -, -O - is more preferable to have no, or a group represented by 2 Exemplary ethynylphenylbiadamantane derivatives (d), -CO _{^{2 -, -SO 3 -, -O}} - more preferably no. When the compound (ID) has a plurality of groups represented by the formula (d), the groups represented by the plurality of formulas (d) are preferably the same.

As the group represented by the formula (d), L ^D1 is preferably a benzyl group, a methylbenzyl group, or a dimethylbenzyl group which may have a substituent, and L ^D1 has no substituent. benzyl group, a methylbenzyl group, or dimethyl phenylene group, a saturated hydrocarbon group having 1 to 2 carbon atoms which R ^D11 has no hydrogen atom, or a substituent, Dd ^(-) is -SO ₃ ^- Is more preferred.

  Examples of the group represented by the formula (d) include groups represented by the following formulas (d-1) to (d-8).

（式中の＊は、結合手を意味する。）

(* In the formula means a bond.)

-CO ₂ represented by _{^{R D1 ~R D10 -, -SO 3}} -, -O -, and as the group other than the group represented by the formula (d), a hydrogen atom, or an aliphatic having 1 to 20 carbon atoms A group hydrocarbon group is preferable, and a hydrogen atom or a linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms is more preferable, and a hydrogen atom or a linear aliphatic group having 1 to 5 carbon atoms. A hydrocarbon group is more preferred, and a hydrogen atom or a methyl group is even more preferred.

Among R ^{D1 to} R ^D10, the number of hydrogen atoms is preferably 4 to 8, and more preferably 6 to 8.

T ^D1 is preferably a phenylene group which may have a substituent, and more preferably a phenylene group having no substituent.

R ^D21 is preferably a phenylene group which may have a substituent, and more preferably a phenylene group having an alkoxy group having 1 to 5 carbon atoms as a substituent.

Examples of R ^D21 include groups represented by the following formulas (dd-1) to (dd-8).

（式中の＊は、結合手を意味する。）

(* In the formula means a bond.)

The monovalent metal cation represented by DX ⁽⁺⁾ is preferably an alkali metal cation, and more preferably a cesium cation.

  Examples of the compound (ID) include compounds represented by Formulas (D-1) to (D-8) shown in Table 4.

  In Table 4, Me represents a methyl group, phe represents a phenylene group, and d-6, d-7, dd-1, and dd-4 represent the above formulas (d-6), (d-7), and (d-7), respectively. dd-1) and (dd-4).

Compound (IA), compound (IB), compound (IC), and compound (ID) can be produced according to a known method. For example, it is produced by reacting a known dye with an acetate, carbonate, phosphate, sulfate, silicate, cyanide, or halide (preferably chloride) of an r-valent metal ion ^{Mr +.} be able to. In addition, as for the method for producing the connecting portion of compound (IB), WO 2018/003708 may be referred to as appropriate.

<Colored resin composition>
The colored resin composition of the present invention comprises a colorant (hereinafter, sometimes referred to as “colorant (A)”) and a resin (hereinafter, sometimes referred to as “resin (B)”). Contains at least one selected from the group consisting of compound (IA), compound (IB), compound (IC), and compound (ID).
The colored resin composition of the present invention further comprises a polymerizable compound (hereinafter sometimes referred to as “polymerizable compound (C)”) and a polymerization initiator (hereinafter sometimes referred to as “polymerization initiator (D)”). It is preferred to include.
The colored resin composition of the present invention further comprises a polymerization initiation aid (hereinafter sometimes referred to as “polymerization initiation aid (D1)”), a solvent (hereinafter sometimes referred to as “solvent (E)”), and a leveling agent. (Hereinafter, may be referred to as “leveling agent (F)”).
In the present specification, compounds exemplified as each component can be used alone or in combination of two or more, unless otherwise specified.

<Colorant (A)>
The colored resin composition of the present invention contains, as the colorant (A), at least one selected from the group consisting of compound (IA), compound (IB), compound (IC), and compound (ID). The content of compound (IA), compound (IB), compound (IC), and / or compound (ID) is preferably 0.1 to 150 parts by mass with respect to 100 parts by mass of resin (B). , 0.5 to 100 parts by mass, more preferably 1 to 80 parts by mass.
The content of the compound (IA), the compound (IB), the compound (IC), and / or the compound (ID) is preferably 50% by mass or more, and more preferably 80% by mass or more based on the total amount of the colorant (A). Is more preferable, and it is further preferable that it is 90 mass% or more.

  The colored resin composition of the present invention includes, as a colorant (A), a dye (A1) and a pigment (A2) in addition to the compound (IA), the compound (IB), the compound (IC), and / or the compound (ID). ) May be included.

  The dye (A1) is not particularly limited, and a known dye can be used. Examples thereof include a solvent dye, an acid dye, a direct dye, and a mordant dye. Examples of the dye include compounds classified into those having a hue other than pigment by a color index (published by The Society of Dyers and Colorists), and known dyes described in a dyeing notebook (Syokusensha). Can be According to the chemical structure, an azo dye, a cyanine dye, a triphenylmethane dye (excluding the compound (IA), the compound (IB), the compound (IC), and the compound (ID)), a xanthene dye, and a phthalocyanine dye And anthraquinone dyes, naphthoquinone dyes, quinone imine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

The pigment (A2) is not particularly limited, and a known pigment can be used. Examples of the pigment include pigments classified into pigments according to a color index (published by The Society of Dyers and Colorists).
Examples of the pigment include C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. Red pigments such as CI Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265;
C. I. Blue pigments such as CI Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60; I. Violet color pigments such as CI Pigment Violet 1, 19, 23, 29, 32, 36, 38;
C. I. Green pigments such as Pigment Green 7, 36, 58;
C. I. Brown pigments such as Pigment Brown 23 and 25;
C. I. And black pigments such as CI Pigment Black 1 and 7.

The content of the coloring agent (A) is preferably from 0.1 to 70% by mass, more preferably from 0.5 to 60% by mass, based on the total amount of solid components of the colored resin composition. Preferably it is 1 to 50% by mass.
Here, the “total amount of solid content” in the present specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored resin composition or the colored curable resin composition. The total amount of the solid content and the content of each component with respect to the solid content 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 at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter referred to as “(a)”). Is more preferable. The resin (B) further includes a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”); A structural unit derived from a monomer (c) copolymerizable with (a) (but different from (a) and (b)) (hereinafter sometimes referred to as “(c)”), and It is preferable to have at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the chain.

  As (a), specifically, for example, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic mono [2- (meta) ) Acryloyloxyethyl] and the like, and preferred are acrylic acid, methacrylic acid and maleic anhydride.

(B) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and a (meth) acryloyloxy group. .
In this specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.
(B) includes, for example, glycidyl (meth) acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl (meth) acrylate, 3-ethyl-3- (Meth) acryloyloxymethyloxetane, tetrahydrofurfuryl (meth) acrylate and the like are preferable, and glycidyl (meth) acrylate and 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decyl ( (Meth) acrylate and 3-ethyl-3- (meth) acryloyloxymethyloxetane.

As (c), for example, methyl (meth) acrylate, butyl (meth) acrylate cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8 -Yl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-9-yl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, styrene, vinyltoluene and the like are mentioned, and styrene, vinyltoluene, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, tricyclo [ 5.2.1.0 ^2,6] de Down-8-yl (meth) acrylate, tricyclo [5.2.1.0 ^{2, 6]} decane-9-yl (meth) acrylate are preferable.

  The resin having a structural unit having an ethylenically unsaturated bond in a side chain is obtained by adding (b) to a copolymer of (a) and (c) or by copolymerizing (b) with (c). To (a). The resin may be a resin obtained by adding (a) to a copolymer of (b) and (c) and further reacting with a carboxylic anhydride.

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

  The acid value of the resin (B) is preferably from 20 to 170 mg-KOH / g, more preferably from 30 to 150 mg-KOH / g, and still more preferably from 40 to 135 mg-KOH / g, in terms of solid content. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be determined, for example, by titration using an aqueous solution of potassium hydroxide. .

  The content of the resin (B) is preferably from 5 to 65% by mass, more preferably from 15 to 60% by mass, and still more preferably from 20 to 50% by mass, based on the total solid content of the colored resin composition. 55% by mass.

<Polymerizable compound (C)>
The polymerizable compound (C) is a compound that can be polymerized by an active radical and / or an acid generated from the polymerization initiator (D), and examples thereof include a compound having a polymerizable ethylenically unsaturated bond and the like. Is a (meth) acrylate compound.

  Among them, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such a polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate and the like.

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

  When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably from 5 to 65% by mass, more preferably from 15 to 60% by mass, based on the total amount of solids. And more preferably 20 to 55% by mass.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating an active radical, an acid or the like by the action of light or heat and initiating polymerization, and a known polymerization initiator can be used. Examples of the polymerization initiator that generates an active radical include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl). ) Octane-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine, N-acetyloxy-1- (4-phenyl Sulfanylphenyl) -3-cyclohexylpropan-1-one-2-imine, 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4- Morpholinophenyl) -2-benzylbutan-1-one, 1-hydroxycyclohexylphenyl Tone, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (2-chlorophenyl) -4, 4 ', 5,5'-tetraphenylbiimidazole and the like.

  When the polymerization initiator (D) is contained, the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Parts, more preferably 1 to 20 parts by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity of the color filter is improved.

<Polymerization initiation aid (D1)>
The polymerization initiation aid (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound whose polymerization has been initiated by the polymerization initiator. When the polymerization initiator (D1) is contained, it is usually used in combination with the polymerization initiator (D).
Examples of the polymerization initiator (D1) include 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 9,10-dimethoxyanthracene, and 2,4-diethylthioxanthone. , N-phenylglycine and the like.

  When using these polymerization initiation assistants (D1), the content thereof is preferably 0.1 to 30 parts by mass, based on 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Preferably it is 1 to 20 parts by mass. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity, and the productivity of the color filter tends to be improved.

<Solvent (E)>
The solvent (E) is not particularly limited, and a solvent usually used in the art can be used. For example, an ester solvent (a solvent containing -COO- in the molecule but not containing -O-), an ether solvent (a solvent containing -O- in the molecule but not containing -COO-), and an ether ester solvent (a solvent containing -COO- in the molecule) , A solvent containing -COO- and -O-), a ketone solvent (a solvent containing -CO- in the molecule and not containing -COO-), an alcohol solvent (containing OH in the molecule, -O-,- Solvents that do not contain CO— and —COO—), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

As the solvent (E),
Ester solvents such as ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, n-butyl acetate, ethyl butyrate, butyl butyrate, ethyl pyruvate, methyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone (in the molecule, -COO- And a solvent containing no -O-);
Ether solvents such as ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, 3-methoxy-1-butanol, diethylene glycol dimethyl ether, and diethylene glycol methyl ethyl ether (solvent containing -O- in the molecule and containing no -COO-) );
Ether ester solvents such as methyl 3-methoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate (in the molecule, -COO- And a solvent containing -O-);
Ketone solvents such as 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), heptanone, 4-methyl-2-pentanone and cyclohexanone (solvents containing -CO- in the molecule and not containing -COO-) ;
Alcohol solvents such as butanol, cyclohexanol, and propylene glycol (solvents containing OH in the molecule and containing no -O-, -CO- and -COO-);
Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone;
Examples of the solvent (E) include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N-methylpyrrolidone, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate and ethyl 3-ethoxypropionate. More preferred.

  When the solvent (E) is contained, the content of the solvent (E) is preferably from 60 to 97% by mass, more preferably from 65 to 95% by mass, based on the total amount of the colored resin composition of the present invention. . In other words, the total solid content of the colored resin composition is preferably 3 to 40% by mass, more preferably 5 to 35% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of coating is good, and the display characteristics tend to be good because the color density is not insufficient when a color filter is formed. .

<Leveling agent (F)>
Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a silicone-based surfactant having a fluorine atom. These may have a polymerizable group in the side chain.
Examples of the silicone-based surfactant include a surfactant having a siloxane bond in a molecule. Specifically, Toray silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324 , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan GK). .

  Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in a molecule. Specifically, Florad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554 R30, RS-718-K (manufactured by DIC Corporation), EFTOP (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals, Inc.), Surflon (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Laboratory Co., Ltd.).

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

  When it contains a leveling agent (F), the content of the leveling agent (F) is preferably 0.001 to 0.2% by mass, more preferably 0.002 to 0.2% by mass, based on the total amount of the colored resin composition. 0.1% by mass. The content does not include the content of the pigment dispersant. When 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 resin composition of the present invention optionally contains 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. May be.

<Method for producing colored resin composition>
The colored resin composition of the present invention comprises a colorant (A) and a resin (B), and a polymerizable compound (C), a polymerization initiator (D), a polymerization initiation assistant (D1), and a solvent used as needed. It can be prepared by mixing (E), a leveling agent (F) and other components.

<Production method of color filter>
Examples of a method for producing a colored pattern from the colored resin composition of the present invention include a photolithographic method, an inkjet method, a printing method, and the like. Among them, the photolithographic method is preferred.

  When the colored resin composition contains the compound (IA), the compound (IB), the compound (IC), and / or the compound (ID) having excellent heat resistance, a color filter having excellent heat resistance can be produced. it can. The color filter is useful as a color filter used in a display device (for example, a liquid crystal display device, an organic EL device, electronic paper, or the like) and a solid-state imaging device.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples, "%" and "part" representing the content or the use amount are on a mass basis unless otherwise specified.

  In the following Examples, the structures of the compounds were confirmed by mass spectrometry (LC; model 1200 manufactured by Agilent, MASS; model LC / MSD manufactured by Agilent).

[Example 1]
The following reactions were performed under a nitrogen atmosphere. C. was added to a flask equipped with a condenser and a stirring device. I. 2.5 parts of Acid Blue 90 (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.2 parts of manganese chloride tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 15 parts of ion-exchanged water are added, and the mixture is heated to 50 ° C. And stirred for 2 hours. The resulting reaction suspension was allowed to cool, then filtered, and the collected solid was washed with 2.5 parts of ion-exchanged water, dried at 60 ° C. under reduced pressure, and then subjected to compound represented by the formula (A-16). 2.3 parts were obtained.

Identification of the compound represented by the formula (A-16): mass spectrometry, ionization mode ESI + m / z: 832.8
Exact Mass [(M-Mn) / 2 + 2H] ⁺ : 832.3

[Example 2]
The following reactions were performed under a nitrogen atmosphere. C. was added to a flask equipped with a condenser and a stirring device. I. 2.5 parts of Acid Blue 83 (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.0 part of cesium chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 20 parts of ion-exchanged water are added, and the mixture is stirred at 50 ° C. for 2 hours. did. The resulting reaction suspension was allowed to cool, then filtered, and the collected solid was washed with 10 parts of ion-exchanged water, dried at 60 ° C. under reduced pressure, and dried under reduced pressure. One part was obtained.

Identification of compound represented by formula (D-2) Mass spectrometry, ionization mode ESI + m / z: 804.5
Exact Mass [M-Cs + 2H] ⁺ : 804.3

[Example 3]
The following reactions were performed under a nitrogen atmosphere. C. was added to a flask equipped with a condenser and a stirring device. I. 2.5 parts of Acid Blue 90 (manufactured by Tokyo Chemical Industry Co., Ltd.), 0.8 parts of zinc chloride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 20 parts of ion-exchanged water are added, and the mixture is stirred at 50 ° C. for 2 hours. did. The resulting reaction suspension was allowed to cool, then filtered, and the collected solid was washed with 2.5 parts of ion-exchanged water, dried at 60 ° C. under reduced pressure, and then subjected to compound represented by the formula (A-18). 1.9 parts were obtained.

Identification of the compound represented by the formula (A-18): mass spectrometry, ionization mode ESI + m / z: 832.8
Exact Mass [(M-Zn) / 2 + 2H] ⁺ : 832.3

[Example 4]
The following reactions were performed under a nitrogen atmosphere. C. was added to a flask equipped with a condenser and a stirring device. I. 2.5 parts of Acid Green 9 (manufactured by Tokyo Chemical Industry Co., Ltd.), 1.9 parts of barium chloride dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 30 parts of ion-exchanged water are added, and the mixture is heated to 50 ° C. And stirred for 2 hours. The resulting reaction suspension was allowed to cool, then filtered, and the collected solid was washed with 2.5 parts of ion-exchanged water, dried at 60 ° C. under reduced pressure, and dried under reduced pressure to give the compound represented by the formula (A-2). 1.3 parts were obtained.

Identification of the compound represented by the formula (A-2) Mass spectrometry, ionization mode ESI + m / z: 703.5
Exact Mass [(M-Ba) / 2 + 2H] ⁺ : 703.2

[Example 5]
The following reactions were performed under a nitrogen atmosphere. C. was added to a flask equipped with a condenser and a stirring device. I. 2.5 parts of Modant Blue 1 (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.4 parts of barium chloride dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 30 parts of ion-exchanged water were added, and the mixture was added at 50 ° C. For 2 hours. The obtained reaction suspension was allowed to cool, filtered, and the solid collected by filtration was washed with 2.5 parts of ion-exchanged water, dried at 60 ° C. under reduced pressure, and dried under reduced pressure to give the compound represented by the formula (A-23). 2.9 parts were obtained.

Identification of the compound represented by the formula (A-23): mass spectrometry, ionization mode ESI + m / z: 459.5
Exact Mass [M-Ba + 3H] ⁺ : 459.0

[Example 6]
The following reactions were performed under a nitrogen atmosphere. C. was added to a flask equipped with a condenser and a stirring device. I. 2.5 parts of Acid Blue 1 (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.2 parts of barium chloride dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 30 parts of ion-exchanged water are added, and the mixture is heated to 50 ° C. And stirred for 2 hours. The resulting reaction suspension was allowed to cool, then filtered, and the collected solid was washed with 2.5 parts of ion-exchanged water, dried at 60 ° C. under reduced pressure, and then subjected to compound represented by the formula (C-11). 1.7 parts were obtained.

Identification of the compound represented by the formula (C-11): mass spectrometry, ionization mode ESI + m / z: 545.5
Exact Mass [(M-Ba) / 2 + 2H] ⁺ : 545.2

[Example 7]
The following reactions were performed under a nitrogen atmosphere. C. was added to a flask equipped with a condenser and a stirring device. I. 2.5 parts of Acid Green 50 (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.1 parts of barium chloride dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 30 parts of ion-exchanged water are added, and the mixture is heated to 50 ° C. And stirred for 2 hours. The resulting reaction suspension was allowed to cool, then filtered, and the collected solid was washed with 2.5 parts of ion-exchanged water, dried at 60 ° C. under reduced pressure, and dried under reduced pressure to give a compound represented by the formula (C-8). 2.2 parts were obtained.

Identification of the compound represented by the formula (C-8): mass spectrometry, ionization mode ESI + m / z: 555.5
Exact Mass [(M-Ba) / 2 + 2H] ⁺ : 555.1

Example 8
The following reactions were performed under a nitrogen atmosphere. 2.5 parts of Acid Green A (manufactured by Tokyo Chemical Industry Co., Ltd.), 2.2 parts of barium chloride dihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), a flask equipped with a condenser and a stirrer, ion 30 parts of exchanged water was added, and the mixture was stirred at 50 ° C. for 2 hours. The resulting reaction suspension was allowed to cool, then filtered, and the collected solid was washed with 2.5 parts of ion-exchanged water, dried at 60 ° C. under reduced pressure, and dried under reduced pressure to give a compound represented by the formula (C-14). 0.9 parts were obtained.

Identification of the compound represented by the formula (C-14): mass spectrometry, ionization mode ESI + m / z: 573.5
Exact Mass [(M-Ba) / 2 + 2H] ⁺ : 573.2

<Heat resistance evaluation>
Using a thermogravimetric / differential calorimeter (TG / DTA6200; manufactured by Seiko Instruments Inc.), about 3000 μg of each compound was heated at a rate of 5 ° C./min from 45 ° C. and raised to 550 ° C. For each compound, the temperature T (° C.) at which a 5% weight loss from the initial weight was observed after 170 ° C. was measured. Table 5 shows the results.
As a comparative example, C.I. I. Pigment Blue 24 was used.

[Resin Synthesis Example 1]
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer, and the atmosphere was replaced with a nitrogen atmosphere. 141 parts of ethyl lactate and 178 parts of propylene glycol monomethyl ether acetate were added, and heated to 85 ° C. with stirring. Subsequently, 38 parts of acrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decane-8-yl acrylate and 3,4-epoxytricyclo [5.2.1.0 ^{2, 6} ] A mixed solution of 25 parts of a mixture of decane-9-yl acrylate (content is 1: 1), 137 parts of cyclohexylmaleimide, 50 parts of 2-hydroxyethyl methacrylate, and 338 parts of propylene glycol monomethyl ether acetate is dropped over 5 hours. did. On the other hand, a mixed solution in which 5 parts of 2,2-azobisisobutyronitrile was dissolved in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropwise addition, the mixture was maintained at the same temperature for 4 hours, and then cooled to room temperature to obtain a copolymer (resin (BX)) solution having a solid content of 25.6%. The weight average molecular weight Mw of the produced copolymer was 8000, the degree of dispersion was 2.1, and the acid value in terms of solid content was 111 mg-KOH / g. Resin (BX) has the following structural units.

The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by the GPC method under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature; 40 ° C
Solvent; THF
Flow rate: 1.0 mL / min
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Tosoh Corporation)
The ratio of the polystyrene-equivalent weight average molecular weight and number average molecular weight (Mw / Mn) obtained above was defined as the degree of dispersion.

<Preparation of colored resin composition>
Colorant (A): 0.5 part of compound (A-16) (in terms of solid content)
Resin (B): Resin (BX) 2.1 parts (in terms of solid content)
Polymerizable compound (C): 2.1 parts (solid content conversion) of dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octan-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyl oxime compound) 0.3 parts Solvent (E): propylene glycol monomethyl ether acetate 16.1 parts
Ethyl lactate 1.2 parts
N-methylpyrrolidone 24.5 parts Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.) 0.005 parts (solid content conversion)
Was mixed to obtain a colored resin composition. Compound (A-16) was dissolved in 24.5 parts of N-methylpyrrolidone and then mixed.

<Preparation of color filter (colored coating film)>
A colored curable resin composition is applied on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by spin coating so that the film thickness after post-baking is 2 μm, and then prebaked at 100 ° C. for 3 minutes. did. After cooling, post-baking is performed in an oven at 230 ° C. for 20 minutes to obtain a color filter. The color filter has high heat resistance.

Claims (5)

A compound represented by the formula (IA), (IB), (IC), or (ID).

[In the formula (IA),
R ^{A1 to} R ^A10 each independently have a hydrogen atom, a hydroxy group, —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , a group represented by the formula (a), or a substituent. Represents a hydrocarbon group having a good carbon number of 1 to 20, and at least two of R ^{A1 to} R ^A10 represent —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (a). .

(In the formula (a),
^RA11 represents a hydrogen atom or a C1-C20 hydrocarbon group which may have a substituent.
L ^A1 represents a divalent aromatic hydrocarbon group which may have a substituent.
Aa ^(-) is, -CO ₂ ^-, or -SO ₃ ^- represents a.
However, * in the formula means a bond. )
T ^A1 represents an optionally substituted aromatic hydrocarbon group having 6 to 10 carbon atoms. However, the aromatic hydrocarbon group does not have —SO ₃ ^— as a substituent.
An represents the sum of the numbers of —CO ₂ ⁻ , —SO ₃ ⁻ , and —O ⁻ that the compound represented by the formula (IA) has.
Am represents an integer of 1 or more.
AX ^{Ak (+)} represents an Ak-valent metal cation.
Ak represents an integer of 2 or more. ]

[In the formula (IB),
R ^B1 to R ^B10 are each independently a hydrogen atom, hydroxy _{^{group, -CO 2 -, -SO 3 -}} , -O -, have group represented by the formula (b), or a substituent Represents a hydrocarbon group having a good carbon number of 1 to 20, and at least two of R ^{B1 to} R ^B10 represent —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (b) .

(In the equation (b),
R ^B11 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
L ^B1 represents a divalent aromatic hydrocarbon group which may have a substituent.
Bb ^(-) is, -CO ₂ ^-, or -SO ₃ ^- represents a.
However, * in the formula means a bond. )
Bn is, -CO ₂ where the compound represented by formula (IB) has ^-, -SO ₃ ^-, and -O ^- represents the sum of the number of.
T ^B1 represents a divalent aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent. However, the aromatic hydrocarbon group does not have —SO ₃ ^— as a substituent.
L ^B0 represents a Bm-valent linking group.
Bm represents an integer of 2 or more.
BX ^{Bk (+)} represents a Bk-valent metal cation.
Bk represents an integer of 1 or more. ]

[In the formula (IC),
R ^{C1 to} R ^C4 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
R ^{C5 to} R ^C12 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
T ^C1 represents an optionally substituted trivalent aromatic hydrocarbon group having 6 to 14 carbon atoms.
CX ^{Ck (+)} represents a Ck-valent metal cation.
Ck represents an integer of 1 or more. ]

[In the formula (ID),
R ^{D1 to} R ^D10 each independently have a hydrogen atom, a hydroxy group, —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , a group represented by the formula (d), or a substituent. Represents a hydrocarbon group having a good carbon number of 1 to 20, and at least two of R ^{D1 to} R ^D10 represent —CO ₂ ⁻ , —SO ₃ ⁻ , —O ⁻ , or a group represented by the formula (d). .

(In the equation (d),
R ^D11 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
L ^D1 represents a divalent aromatic hydrocarbon group which may have a substituent.
Dd ^(-) is, -CO ₂ ^-, or -SO ₃ ^- represents a.
However, * in the formula means a bond. )
T ^D1 represents a divalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. However, the aromatic hydrocarbon group does not have —SO ₃ ^— as a substituent.
R ^D21 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
DX ⁽⁺⁾ represents a monovalent metal cation. ]   A colorant comprising: a compound represented by the formula (IA), a compound represented by the formula (IB), a compound represented by the formula (IC), and a compound represented by the formula (IC) according to claim 1. A colored resin composition containing at least one selected from the group consisting of compounds represented by ID).   A colored resin composition comprising the colored resin composition according to claim 2, a polymerizable compound, and a polymerization initiator.   A color filter formed from the colored resin composition according to claim 3.   A display device comprising the color filter according to claim 4.