JP2020125455A - Colored resin composition - Google Patents

Abstract

To provide a colored resin composition useful in forming a color filter excellent in chemical resistance.SOLUTION: The colored resin composition comprises a colorant and a resin, where the colorant comprises a compound represented by formula (I). [In the formula, one or more of R, R, R, R, Rand Rare groups having polar groups as substituents; n is an integer from 1 to 3; Ais a q-valent anion; q is an integer from 1 to 3; and p is a coefficient to keep the electric charge of the compound represented by formula (I) neutral.]SELECTED DRAWING: None

Description

The present invention relates to a colored resin composition.

Color filters used for display devices such as liquid crystal display devices, electroluminescence display devices and plasma displays, and solid-state imaging devices such as CCD and CMOS sensors are manufactured from a colored curable resin composition. As such a colored curable resin composition, a composition containing a compound represented by the formula (AX) as a colorant is known (Patent Document 1).

International Publication No. 2014/196464

In the composition containing the compound represented by the formula (AX) known in the related art, the color filter formed was not satisfactory in terms of chemical resistance.
Therefore, the present invention provides a colored resin composition useful for obtaining a color filter having excellent chemical resistance.

［式（Ｉ）中、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原
子、ヒドロキシ基、ニトロ基、シアノ基、ハロゲン原子、カルボキシ基、スルホ基、スルファモイル基、メタロセニル基、炭素数１〜３０の炭化水素基、又は前記炭化水素基中のメチレン基の１つ又は２つ以上が下記群Ｉから選ばれる２価の基で置き換えられた基を表し、ただし、２つ以上のメチレン基が下記群Ｉから選ばれる２価の基で置き換えられている場合、前記２価の基は隣り合わず、
前記炭化水素基に含まれる水素原子は、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、アミノ基、カルボキシ基、スルホ基、ホスホノ基、スルファモイル基、イソシアナト基、複素環で置換されていてもよく、
Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶は、それぞれ独立に、水素原子、炭素数１〜３０の炭化水素基、又は前記炭化水素基中のメチレン基の１つ又は２つ以上が下記群Ｉから選ばれる２価の基で置き換えられた基を表し、ただし、２つ以上のメチレン基が下記群Ｉから選ばれる２価の基で置き換えられている場合、前記２価の基は隣り合わず、
前記炭化水素基に含まれる水素原子は、複素環又は極性基で置換されていてもよく、
Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶のうちの１つ以上が、置換基として極性基を有する基であり、
ｎは、１〜３の整数を表し、
Ａ^q-は、ｑ価の陰イオンを表し、
ｑは１〜３の整数を表し、
ｐは式（Ｉ）で表される化合物の電荷を中性に保つ係数を表す。
群Ｉ：−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＯＣＳ−、−ＳＯ₂−、−ＳＯ₃−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＳＯ₂ＮＨ−、−ＮＨＳＯ₂−又は−Ｎ＝ＣＨ−］
[２] さらに、重合性化合物及び重合開始剤を含む[１]に記載の着色樹脂組成物。
[３] 着色剤が、さらに顔料（但し、式（Ｉ）で表される化合物を除く。）を含む[１]又は[２]に記載の着色樹脂組成物。
[４] [１]〜[３]のいずれか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。
なお本明細書において、各成分として例示する化合物は、特に断りのない限り、単独で又は複数種を組合せて使用することができる。 The present invention is as follows.
[1] A colored resin composition containing a colorant and a resin, and the colorant containing a compound represented by the formula (I).

[In the formula (I),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a hydroxy group, a nitro group, a cyano group, a halogen atom, One or more of a carboxy group, a sulfo group, a sulfamoyl group, a metallocenyl group, a hydrocarbon group having 1 to 30 carbon atoms, or a methylene group in the hydrocarbon group is a divalent group selected from the following group I. Represents a substituted group, provided that when two or more methylene groups are replaced by a divalent group selected from Group I below, the divalent groups are not adjacent to each other,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxy group, a sulfo group, a phosphono group, a sulfamoyl group, an isocyanato group, or a heterocycle. ,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently one or two of a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a methylene group in the hydrocarbon group. One or more represents a group substituted with a divalent group selected from the following group I, provided that two or more methylene groups are replaced with a divalent group selected from the following group I: Groups are not next to each other,
The hydrogen atom contained in the hydrocarbon group may be substituted with a heterocycle or a polar group,
At least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a group having a polar group as a substituent,
n represents an integer of 1 to 3,
A ^q- represents a q-valent anion,
q represents an integer of 1 to 3,
p represents a coefficient for keeping the charge of the compound represented by the formula (I) neutral.
Group I: -O -, - S - , - CO -, - COO -, - OCO -, - COS -, - OCS -, - SO 2 -, - SO 3 -, - NH -, - CONH -, - _{NHCO -, - SO 2 NH -} , - NHSO 2 - or -N = CH-]
[2] The colored resin composition according to [1], which further contains a polymerizable compound and a polymerization initiator.
[3] The colored resin composition according to [1] or [2], wherein the colorant further contains a pigment (excluding the compound represented by the formula (I)).
[4] A color filter formed from the colored resin composition according to any one of [1] to [3].
[5] A display device including the color filter according to [4].
In the present specification, the compounds exemplified as each component can be used alone or in combination of two or more kinds unless otherwise specified.

According to the colored resin composition of the present invention, a color filter having excellent chemical resistance can be obtained.

<Colored resin composition>
The colored resin composition of the present invention contains a colorant (hereinafter sometimes referred to as “colorant (A)”) and a resin (hereinafter sometimes referred to as “resin (B)”), and the colorant (A) includes a compound represented by the formula (I) (hereinafter sometimes referred to as “compound (I)”).
The colored resin composition of the present invention may further include a polymerizable compound (hereinafter sometimes referred to as “polymerizable compound (C)”) and a polymerization initiator (hereinafter sometimes referred to as “polymerization initiator (D)”). .) are preferably included.
The colored resin composition of the present invention may further contain a polymerization initiation aid (D1), a solvent (E), and a leveling agent (F).

<Colorant (A)>
The colored resin composition of the present invention contains the compound (I) as the colorant (A).

<Compound (I)>
Hereinafter, the present invention will be described in detail with reference to the formula (I). The compound (I) includes the resonance structure of the formula (I), and further includes formula (I) or each group in the resonance structure formula. A compound obtained by rotating around a bond axis of a carbon-carbon single bond or a carbon-nitrogen single bond is also included.

［式（Ｉ）中、
Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子、ヒドロキシ基、ニトロ基、シアノ基、ハロゲン原子、カルボキシ基、スルホ基、スルファモイル基、メタロセニル基、炭素数１〜３０の炭化水素基、又は前記炭化水素基中のメチレン基の１つ又は２つ以上が下記群Ｉから選ばれる２価の基で置き換えられた基を表し、ただし、２つ以上のメチレン基が下記群Ｉから選ばれる２価の基で置き換えられている場合、前記２価の基は隣り合わず、
前記炭化水素基に含まれる水素原子は、ハロゲン原子、ニトロ基、シアノ基、ヒドロキシ基、アミノ基、カルボキシ基、スルホ基、ホスホノ基、スルファモイル基、イソシアナト基、複素環で置換されていてもよく、
Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶は、それぞれ独立に、水素原子、炭素数１〜３０の炭化水素基、又は前記炭化水素基中のメチレン基の１つ又は２つ以上が下記群Ｉから選ばれる２価の基で置き換えられた基を表し、ただし、２つ以上のメチレン基が下記群Ｉから選ばれる２価の基で置き換えられている場合、前記２価の基は隣り合わず、
前記炭化水素基に含まれる水素原子は、複素環又は極性基で置換されていてもよく、
Ｒ¹¹、Ｒ¹²、Ｒ¹³、Ｒ¹⁴、Ｒ¹⁵及びＲ¹⁶のうちの１つ以上が、置換基として極性基を有する基であり、
ｎは、１〜３の整数を表し、
Ａ^q-は、ｑ価の陰イオンを表し、
ｑは１〜３の整数を表し、
ｐは式（Ｉ）で表される化合物の電荷を中性に保つ係数を表す。
群Ｉ：−Ｏ−、−Ｓ−、−ＣＯ−、−ＣＯＯ−、−ＯＣＯ−、−ＣＯＳ−、−ＯＣＳ−、−ＳＯ₂−、−ＳＯ₃−、−ＮＨ−、−ＣＯＮＨ−、−ＮＨＣＯ−、−ＳＯ₂ＮＨ−、−ＮＨＳＯ₂−又は−Ｎ＝ＣＨ−］

[In the formula (I),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a hydroxy group, a nitro group, a cyano group, a halogen atom, One or more of a carboxy group, a sulfo group, a sulfamoyl group, a metallocenyl group, a hydrocarbon group having 1 to 30 carbon atoms, or a methylene group in the hydrocarbon group is a divalent group selected from the following group I. Represents a substituted group, provided that when two or more methylene groups are replaced by a divalent group selected from Group I below, the divalent groups are not adjacent to each other,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxy group, a sulfo group, a phosphono group, a sulfamoyl group, an isocyanato group, or a heterocycle. ,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently one or two of a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a methylene group in the hydrocarbon group. One or more represents a group substituted with a divalent group selected from the following group I, provided that two or more methylene groups are replaced with a divalent group selected from the following group I: Groups are not next to each other,
The hydrogen atom contained in the hydrocarbon group may be substituted with a heterocycle or a polar group,
At least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a group having a polar group as a substituent,
n represents an integer of 1 to 3,
A ^q- represents a q-valent anion,
q represents an integer of 1 to 3,
p represents a coefficient for keeping the charge of the compound represented by the formula (I) neutral.
Group I: -O -, - S - , - CO -, - COO -, - OCO -, - COS -, - OCS -, - SO 2 -, - SO 3 -, - NH -, - CONH -, - _{NHCO -, - SO 2 NH -} , - NHSO 2 - or -N = CH-]

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ^{1 to} R ¹⁶ include an aliphatic hydrocarbon group having 1 to 30 carbon atoms and an aromatic hydrocarbon group having 6 to 30 carbon atoms.

The aliphatic hydrocarbon group having 1 to 30 carbon atoms may be saturated or unsaturated, and may be linear, branched or cyclic.

Examples of the linear or branched aliphatic hydrocarbon group having 1 to 30 carbon atoms include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, vinyl group, 1 -A straight-chain aliphatic hydrocarbon group such as a propenyl group and a 2-propenyl group (allyl group); a branched chain aliphatic hydrocarbon group such as an isopropyl group, an isobutyl group, an isopentyl group, a neopentyl group, and a 2-ethylhexyl group Is mentioned. The linear or branched aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 8 carbon atoms.
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. The cyclic aliphatic hydrocarbon group preferably has 3 to 18 carbon atoms, more preferably 3 to 15 carbon atoms, and still more preferably 4 to 15 carbon atoms.

Examples of the aromatic hydrocarbon group having 6 to 30 carbon atoms include phenyl group, naphthyl group, phenanthryl group and anthryl group. The carbon number of the aromatic hydrocarbon group is preferably 6 to 20, more preferably 6 to 18, and further preferably 6 to 15.

The hydrocarbon group having 1 to 30 carbon atoms may be a group obtained by combining two or more of the aliphatic hydrocarbon group and the aromatic hydrocarbon group mentioned above as long as the upper limit of the carbon number is 30 or less. .. Examples of such a group include a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di(2,2-dimethylpropyl)phenyl group, a benzyl group, a phenethyl group, and a 4-phenylbutyl group. The number of carbon atoms of the group in which two or more aliphatic hydrocarbon groups and aromatic hydrocarbon groups are combined is preferably 7 to 25, more preferably 8 to 20, and further preferably 8 to 15.

Examples of the group in which one of the methylene groups in the hydrocarbon group represented by R ^{1 to} R ¹⁶ is replaced with a divalent group selected from Group I below include the following.
Group I: -O -, - S - , - CO -, - COO -, - OCO -, - COS -, - OCS -, - SO 2 -, - SO 3 -, - NH -, - CONH -, - _{NHCO -, - SO 2 NH -} , - NHSO 2 - or -N = CH-

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with -O- include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with -S- include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with -CO- include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with -COO- include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with -OCO- include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with -COS- include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with -OCS- include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced by —SO ₂ — include, for example,
The following are mentioned (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced by —SO ₃ — include, for example,
The following are mentioned (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with -NH- include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with -CONH- include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with -NHCO- include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with —SO ₂ NH— include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced with —NHSO ₂ — include the following (* represents a bond).

Examples of the group in which one of the methylene groups in the hydrocarbon group is replaced by -N=CH- include the following (* represents a bond).

As a group in which two or more of the methylene groups in the hydrocarbon group represented by R ^{1 to} R ¹⁶ are replaced with a divalent group selected from Group I, the divalent groups must be adjacent to each other. The divalent group may be any of the above-mentioned group I, and a group in which one of the methylene groups in the hydrocarbon group is replaced with a divalent group selected from the group I is appropriately combined. Can be mentioned.

As a group in which one or more of the methylene groups in the hydrocarbon group represented by R ^{11 to} R ¹⁶ are replaced with a divalent group selected from Group I, it is preferable that a polar group is not formed. ..

Examples of the halogen atom represented by R ^{1 to} R ¹⁰ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom is preferable.

Examples of the metallocenyl group represented by R ^{1 to} R ¹⁰ include a ferrocenyl group, a nickelocenyl group, a cobaltnyl group, a ferrocene alkyl group, and a ferrocene alkoxy group.

Examples of the halogen atom which may be substituted for the hydrogen atom contained in the hydrocarbon group represented by R ^{1 to} R ¹⁰ include the same halogen atom represented by R ^{1 to} R ¹⁰ .

The number of carbon atoms of the heterocycle in which the hydrogen atom contained in the hydrocarbon group represented by R ^{1 to} R ¹⁶ may be substituted is preferably 1 to 20. Examples of the heterocycle include a heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and specifically, azetidine, pyrrole, benzoxazole, thiazole, oxetane, furan, and the like. Examples include thietane and thiophene.

As R ^{1 to} R ¹⁰ , a hydrogen atom or a halogen atom is preferable, ^{1 to} 6 of R ^{1 to} R ¹⁰ are halogen atoms, and the others are more preferably hydrogen atoms, and R ^{1 to} R ¹⁰ are preferable. It is more preferable that 1 to 4 of them are halogen atoms and the others are hydrogen atoms, and it is even more preferable that 2 of R ^{1 to} R ¹⁰ are halogen atoms and the others are hydrogen atoms.

When two of R ^{1 to} R ¹⁰ are halogen atoms, the two halogen atoms are preferably any two of R ^{7 to} R ¹⁰ , and R ⁷ and R ⁹ are halogen atoms. Is more preferable.

The polar group optionally substituted with a hydrogen atom contained in the hydrocarbon group represented by R ^{11 to} R ¹⁶ refers to a functional group containing at least one hetero atom other than a carbon atom and a hydrogen atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, a phosphorus atom, a nitrogen atom and a halogen atom. Specific examples of the polar group include carbon numbers such as a hydroxy group, a carboxy group, an epoxy group, an amide group (N-methylamide group, N-isopropylamide group, N-cyclopropylamide group, N-phenylamide group, etc. 1 to 12 also includes N-substituted amide group), nitrile group, amino group, imide group, isocyanato group, thiol group, alkoxy group, sulfo group, phosphono group, nitro group, alkoxycarbonyl group, Examples thereof include an acyl group such as an acetyl group and a halogen atom, and an acid group such as a carboxy group, an amide group, a sulfo group and a phosphono group is preferable, a carboxy group or an amide group is more preferable, and a carboxy group is still more preferable.

Examples of the group having a polar group as a substituent in which a hydrogen atom contained in a hydrocarbon group is substituted with a polar group include, for example, the following formulas (po-1) to (po-6) in which the polar group is a carboxy group. And a group represented by the following formula (po-7) to formula (po-10) in which the polar group is an amide group. In the formula, * represents a bond.

At least one of R ¹¹ to R ¹⁶ are hydrogen atoms contained in the hydrocarbon group represented by R ¹¹ to R ¹⁶ is substituted with a polar group, a group having a polar group as a substituent. When at least one of R ^{11 to} R ¹⁶ is a group having a polar group as a substituent, a color filter having excellent chemical resistance can be formed.

As R ^{11 to} R ¹⁶ , a hydrocarbon group having 1 to 30 carbon atoms is preferable, a hydrocarbon group having 1 to 20 carbon atoms is more preferable, and a hydrocarbon group is further preferably an aliphatic hydrocarbon group, Even more preferably, the hydrogen group is a saturated straight-chain aliphatic hydrocarbon group. The saturated linear aliphatic hydrocarbon group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. When R ^{11 to} R ¹⁶ are groups having a polar group as a substituent, R ^{11 to} R ¹⁶ may be an aliphatic hydrocarbon group, or an aliphatic hydrocarbon group and an aromatic hydrocarbon group. A combination of two or more groups is preferable, and when R ^{11 to} R ¹⁶ are groups having no polar group as a substituent, R ^{11 to} R ¹⁶ are an aliphatic hydrocarbon group or an aromatic carbon group. It is preferably a hydrogen group.

Moreover, it is preferable that 1 to 4 of R ^{11 to} R ¹⁶ are groups having a polar group as a substituent, more preferably 2 to 4 are groups having a polar group as a substituent, and R ^{11 to} R ¹⁶ It is more preferable that two of them are groups having a polar group as a substituent.

As n, 1-2 are preferable and 1 is more preferable.

The q-valent anion represented by A ^q- is a 1-3-valent anion, and may be an inorganic anion or an organic anion.
Examples of the inorganic anion include hydroxide ion, halide ion (fluoride ion, chloride ion, bromide ion, iodide ion, etc.), nitrate ion, perchlorate ion, chlorate ion, sulfate ion, Thiocyanate ion, phosphate ion, phosphotungstate ion, phosphomolybdate ion, phosphotungsten molybdate ion, hexafluorophosphate ion, molybdate ion, tungstate ion, titanate ion, zirconate ion, borate ion, Tetrafluoroborate ion etc. are mentioned.
Examples of the organic anion include an acetate, a trifluoroacetate ion, a benzoate ion, a palmitate ion, a tartaric acid ion, an ethylenediaminetetraacetic acid iron ion, and other organic carboxylic acid anions; methanesulfonate ion, dodecylsulfonate ion. Ion, vinyl sulfonate ion, benzene sulfonate ion, trifluoromethane sulfonate ion, nonafluorobutane sulfonate ion, 3-(trihydroxysilyl)-1-propane sulfonate ion, toluene sulfonate ion, chlorobenzene sulfonate ion, Pentafluorobenzene sulfonate ion, 3-carboxyphenyl sulfonate ion, 3-nitrophenyl sulfonate ion, benzenedisulfonate ion, diphenylamine-4-sulfonate ion, 2-amino-4-methyl-5-chlorobenzenesulfonate ion, 2-amino-5-nitrobenzene sulfonate ion, phthalocyanine sulfonate ion, perfluoro-4-ethylcyclohexane sulfonate ion, naphthalene monosulfonate ion, naphthalene disulfonate ion, naphthalene trisulfonate ion, naphthylamine monosulfonate ion, Naphthylamine disulfonate ion, naphthylamine trisulfonate ion, 8-{[3-(trimethoxysilyl)propyl]amino}naphthalene-1-sulfonate ion, 8-{[3-(trimethoxysilyl)propyl]amino}naphthalene -1,5-disulfonate ion, isoquinoline-5-sulfonate ion, naphthol monosulfonate ion, naphthol disulfonate ion, naphthol trisulfonate ion, N,N-bis(2-hydroxyethyl)-2-aminoethane Organic sulfonate anions such as sulfonate ions; octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion, phenyl phosphate ion, nonylphenyl phosphate ion, 2,2′-methylenebis(4,6-di- Organic phosphate anions such as t-butylphenyl)phosphonate ion and 3-(trihydroxysilyl)propylmethylphosphonate ion; lauryl sulfate ion, laureth sulfate ion, polyoxyethylene alkylphenol sulfonate ion, lauryl sulfate ion and the like Organic sulfate anions; Tetraarylborate ions, butyltriphenylborate ions and other organic borate anions; Tricyanomethide ions, Tris(trifluoromethanes) Rufonyl)methide ion, tris(perfluoroethylsulfonyl)methide ion, and other methide ions; dicyanamide ion; trifluoromethanesulfonamide ion, benzenesulfonamide ion, and other sulfonamide ions; N,N-bis(fluorosulfonyl)imide ion, bis (Trifluoromethylsulfonyl)imide ion, bis(nonafluorobutanesulfonyl)imide ion, N,N-hexafluoro-1,3-disulfonylimide ion, 1,1,2,2,3,3-hexafluoropropane-1 , 3-disulfonimide ion and other sulfonimide ions; and the like.

As the q-valent anion represented by A ^q- , hexafluorophosphate ion, tungstate ion, monovalent organic carboxylic acid anion, monovalent or divalent organic sulfonic acid anion, monovalent Preferred are organic phosphate anions, monovalent organic borate anions, monovalent methide ions, dicyanamide ions, monovalent sulfonamide ions, and monovalent sulfonimide ions, and tungstate ion Monovalent organic carboxylic acid anion, monovalent or divalent organic sulfonic acid anion, monovalent organic phosphate anion, monovalent methide ions, dicyanamide ion, and monovalent sulfonimide Ions are more preferable, and tungstate ion, monovalent organic carboxylic acid anion, monovalent or divalent organic sulfonic acid anion, monovalent organic phosphate anion, monovalent methide ions, and Monovalent sulfonimide ions are more preferable, and tungstate ion, monovalent organic carboxylic acid anion, monovalent or divalent organic sulfonic acid anion, monovalent organic phosphate anion, and 1 Even more preferred are monovalent sulfonimide ions, more preferred are tungstate ions, monovalent organic carboxylic acid anions, monovalent or divalent organic sulfonic acid anions, and monovalent sulfonimide ions. Monovalent organic sulfonic acid anions and monovalent sulfonimide ions are even more preferable, and 3-carboxyphenyl sulfonic acid and bis(trifluoromethylsulfonyl)imide ion are particularly preferable.

Examples of the compound (I) include the compounds represented by the formulas (I-1) to (I-146) shown in Tables 1 to 4.
The compound (I) is preferably formula (I-25) to formula (I-48), formula (I-73), formula (I-74), formula (I-77) to formula (I-80), The compounds represented by formula (I-87), formula (I-88), formula (I-109) to formula (I-127).

In Tables 1 to 4, Et represents an ethyl group, Pr represents a propyl group, Ph represents a phenyl group, and po-2 to po-4, po-6, po-7, and po-9 are each represented by the above formula ( po-2) to a formula (po-4), a formula (po-6), a formula (po-7), and a formula (po-9) are represented by an-1 to an-21. Represent groups represented by the following formula (an-1) to formula (an-21), respectively.

The method for synthesizing the compound (I) is not particularly limited, but the compound (I) can also be synthesized with reference to the method described in WO 2014/196464.

The content of the compound (I) is preferably 0.05 to 100 parts by mass, more preferably 0.1 to 80 parts by mass, and 0.5 to 100 parts by mass of the resin (B). To 50 parts by mass is more preferable, and 0.5 to 30 parts by mass is even more preferable.

The content of the compound (I) is preferably 1% by mass or more and more preferably 5% by mass or more in the total amount of the colorant (A).

The colorant (A) may contain a colorant different from the compound (I) in addition to the compound (I), and the colorant different from the compound (I) is a dye (hereinafter, dye (A1)). Or a pigment (hereinafter, sometimes referred to as a pigment (A2)), and the colorant different from the compound (I) is one of the dye (A1) and the pigment (A2). Or both may be included.

The dye (A1) is not particularly limited as long as it does not include the compound (I), and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes and mordant dyes. Examples of the dye include compounds that are classified into those having a hue other than pigment by the Color Index (published by The Society of Dyers and Colourists), and known dyes described in Dyeing Note (Color Dye Co.). To be Further, according to the chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, anthraquinone dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin. Examples thereof include dyes, quinoline dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

The pigment (A2) is not particularly limited, and known pigments can be used, and examples thereof include pigments classified as pigments by the 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, 185, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and the like orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 202, 209, 215, 216, 224, 242, 254, 255, 264, 265, 269, Red pigments such as 291;
C. I. Pigment Blue 15, 15:3, 15:4, 15:6, 60 and other blue pigments;
C. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet color pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment Brown 23, 25 and other brown pigments;
C. I. Pigment Black 1, 7 and the like black pigments and the like.

Examples of the pigment (A2) include C.I. I. Pigment Yellow 185 and other yellow pigments; C.I. I. Pigment Red 177, 202, 264, 269, 291 and the like; C.I. I. Pigment Blue 15:6 and other blue pigments are preferred.

The pigment preferably has a uniform particle size, and by performing a dispersion treatment by adding a pigment dispersant, a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the above-mentioned pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, acrylic, and other surfactants.
When a pigment dispersant is used, its amount is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A2). When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniform dispersed state tends to be obtained.

The content of the colorant (A) is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, and further preferably 3 with respect to the total solid content of the colored resin composition. Is 45% by mass. Here, the “total amount of solids” in the present specification refers to the amount obtained by removing the content of the solvent from the total amount of the colored resin composition. The total amount of solid content and the content of each component relative thereto 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 at least one kind (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter, “(a) The resin having a structural unit derived from (4) may be more preferable. The resin (B) further has a structure derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”). A structural unit derived from a unit, a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter sometimes referred to as “(c)”). , And at least one structural unit selected from the group consisting of structural units having an ethylenically unsaturated bond in the side chain.

Specific examples of (a) include acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, succinic acid mono[2-(meth Acryloyloxyethyl] and the like, and preferably acrylic acid, methacrylic acid, 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 addition, in this specification, "(meth)acrylic acid" represents at least one selected from the group consisting of acrylic acid and methacrylic acid. The expressions such as “(meth)acryloyl” and “(meth)acrylate” have the same meaning.
Examples of (b) include glycidyl (meth)acrylate, vinylbenzyl glycidyl ether, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl (meth)acrylate, and 3-ethyl-3-. Examples thereof include (meth)acryloyloxymethyloxetane and tetrahydrofurfuryl (meth)acrylate, and preferably glycidyl (meth)acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl( (Meth)acrylate and 3-ethyl-3-(meth)acryloyloxymethyloxetane.

Examples of (c) include 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, Examples thereof include N-cyclohexylmaleimide, N-benzylmaleimide, styrene and vinyltoluene, and preferably styrene, vinyltoluene, 2-hydroxyethyl(meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide and N-benzylmaleimide. , Tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-9-yl(meth)acrylate and the like are preferable.

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

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. ..
The dispersity [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, and more preferably 1.2 to 4.

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

The content of the resin (B) is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and further preferably 25 to 70, based on the total solid content of the colored resin composition. It is% 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 ethylenic unsaturated bond, and the like. Is a (meth)acrylic acid ester 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( Examples thereof include (meth)acrylate.

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

When the polymerizable compound (C) is contained, the content of the polymerizable compound (C) is preferably 5 to 60% by mass, more preferably 10 to 10% by mass based on the total amount of the solid content of the colored resin composition. It is 50% by mass, more preferably 15 to 40% by mass.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound capable of generating active radicals, acids and the like by the action of light or heat and initiating polymerization, and known polymerization initiators 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-hydroxycyclohexylphenylketone, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4,6-trimethylbenzoyl Examples thereof include diphenylphosphine oxide and 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole.

The polymerization initiator is preferably a polymerization initiator containing at least one selected from the group consisting of triazine compounds, acylphosphine oxide compounds, alkylphenone compounds, oxime compounds and biimidazole compounds, and more preferably a polymerization initiator containing oxime compounds. ..

When the polymerization initiator (D) is contained, the content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Parts, and 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 for promoting the polymerization of the polymerizable compound whose polymerization is initiated by the polymerization initiator. When the polymerization initiator auxiliary agent (D1) is contained, it is usually used in combination with the polymerization initiator (D).
As the polymerization initiation aid (D1), 4,4′-bis(dimethylamino)benzophenone (commonly called Michler's ketone), 4,4′-bis(diethylamino)benzophenone, 9,10-dimethoxyanthracene, 2,4-diethylthioxanthone , N-phenylglycine and the like.

When using these polymerization initiation aids (D1), the content thereof is preferably 0.1 to 30 parts by mass, and more preferably 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (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, ester solvent (solvent containing -COO- in the molecule and not containing -O-), ether solvent (solvent containing -O- in the molecule, not containing -COO-), ether ester solvent (intramolecular) 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-,- CO- and -COO--free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like.

As a solvent,
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 (within the molecule -COO- And a solvent not containing -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, not containing -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, and diethylene glycol monoethyl ether acetate (within 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 but not -COO-) ;
Alcohol solvents such as butanol, cyclohexanol, propylene glycol (solvents containing OH in the molecule and not containing -O-, -CO- and -COO-);
Amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone; and the like.
As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), ethyl lactate and ethyl 3-ethoxypropionate are more preferable.

When the solvent (E) is included, the content of the solvent (E) is preferably 60 to 95% by mass, more preferably 65 to 92% 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 5 to 40% by mass, more preferably 8 to 35% by mass. When the content of the solvent (E) is within the above range, the flatness at the time of application becomes good, and the display characteristics tend to become good because the color density is not insufficient when the color filter is formed. ..

<Leveling agent (F)>
Examples of the leveling agent (F) include a silicone-based surfactant, a fluorine-based surfactant, and a fluorine-containing silicone-based surfactant. These may have a polymerizable group in the side chain.

Examples of the silicone-based surfactant include a surfactant having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.); KP321, KP322, KP323, KP324. , KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.); TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452 and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) and the like. ..

Examples of the fluorine-based surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F543. R30, RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Examples thereof include S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daikin Fine Chemical Laboratories, Inc.).

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

When the leveling agent (F) is contained, 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. It is 0.1% by mass. The content of the pigment dispersant is not included in this content. 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 may optionally contain additives known in the art, such as a filler, a polymer compound, an adhesion promoter, an antioxidant, a light stabilizer and a chain transfer agent. ..

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

<Method of manufacturing color filter>
Examples of the 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 preferable.

When the colored resin composition contains a colorant and a resin, and the colorant contains the compound (I), a color filter having excellent chemical resistance can be produced. 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, etc.) and a solid-state image sensor.

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 parts representing the content or the amount used are based on mass unless otherwise specified.

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

[Synthesis example 2]
An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer to create a nitrogen atmosphere, 280 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 80° C. with stirring. Then, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2. A solution of 289 parts of a mixture of ^1.02,6 ] decan-9-yl acrylate (content ratio: 1:1) dissolved in 125 parts of propylene glycol monomethyl ether acetate was added dropwise over about 5 hours using a dropping pump. .. On the other hand, a solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile), a polymerization initiator, dissolved in 235 parts of propylene glycol monomethyl ether acetate was dropped into the flask over about 6 hours using another dropping pump. did. After the dropping was completed, the temperature was kept at the same temperature for 4 hours and then cooled to room temperature to obtain a copolymer (resin (B-2)) solution having a solid content of 35.1%. The produced copolymer had a weight average molecular weight Mw of 9,200, a dispersity of 2.08, and an acid value in terms of solid content of 77 mg-KOH/g. The resin (B-2) has the following structural unit.

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.
Device: 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: 0.001-0.01 mass%
Injection volume: 50 μL
Detector ；RI
Calibration standard; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured by Tosoh Corporation)
The polystyrene equivalent weight average molecular weight and number average molecular weight ratio (Mw/Mn) obtained above was taken as the dispersity.

[Synthesis Example 3]
4 parts of N,N-diethylamino-3-phenol, 0.5 parts of a compound represented by the following formula (B-1), and 7.4 parts of trifluorosulfonic acid were mixed and stirred at 100° C. for 3 hours. A reaction solution was obtained. After the reaction solution was cooled to room temperature, 50 parts of water was added to the reaction solution, extracted with chloroform and ethyl acetate, and each organic layer was washed with water. The organic layers washed with water were combined and the solvent was distilled off. 0.9 part of p-chloranil and 50 parts of acetonitrile were added to the residue, and the mixture was stirred at room temperature for 12 hours. After distilling off the solvent from the reaction solution, 50 parts of chloroform was added, and the precipitated solid was separated by filtration. After concentrating the filtrate, 50 parts of a 4% aqueous sodium hydroxide solution was added to the concentrated filtrate and the mixture was stirred at room temperature for 12 hours. The reaction solution was neutralized to pH 4 with 2N hydrochloric acid, and the precipitated solid was collected by filtration. The obtained solid was dispersed and washed with a mixed solution of ethyl acetate-hexane (3:1) for 3 hours, dried and then dissolved in 5 parts of concentrated hydrochloric acid to obtain a solution. The obtained solution was filtered with a filter, the filtrate was crystallized with 20% saline, and neutralized with a 25% aqueous sodium hydroxide solution until the pH reached 4. The precipitated solid was collected by filtration and dried in a vacuum oven at 60° C. to obtain 0.21 part (yield 24%) of the compound represented by the formula (AY).

0.77 parts of the compound represented by the formula (AY), 0.5 part of bis(trifluoromethanesulfonyl)lithium, and 12.3 parts of N,N-dimethylsulfoxide are mixed and stirred at 50° C. for 3 hours. Then, a reaction solution was obtained. The resulting reaction solution was added dropwise to 40 parts of 20% saline, and the precipitated solid was collected by filtration. The solid was dissolved in chloroform, the organic layer was washed with water, sodium sulfate was added and dried, the solvent was distilled off, and the residue was dried in a vacuum oven at 60° C. to give the compound represented by the formula (A-2) at 0. 73 parts (yield 76%) was obtained. The mass spectrometry result of the obtained compound was m/z=654 [M] ⁺ . In the mass spectrometry, LC was measured using Agilent model 1200 and MASS was measured using Agilent model LC/MSD6130 (the same applies to the following mass spectrometry).

[Synthesis Example 4]
3 parts of the compound represented by the formula (A-2), 5 parts of ethyl 4-aminobenzoate, 6 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, 4-dimethylaminopyridine 0.5. Parts, 0.4 parts of (+)-10-camphorsulfonic acid, and 156 parts of dimethyl sulfoxide were mixed and stirred at room temperature for 3 hours. The reaction product was crystallized in saturated saline, and the precipitated solid was collected by filtration and washed with 100 parts of water three times. It was dried in a vacuum oven at 60° C. to obtain 1.6 parts (yield 34%) of the compound represented by the formula (A-6). The mass analysis result of the obtained compound was m/z=892 [M] ⁺ .

[Synthesis example 5]
2.0 parts (yield 42%) of the compound represented by the formula (A-7) was obtained in the same manner as in Synthesis Example 4 except that ethyl 4-aminobenzoate was changed to aniline. The mass spectrometry result of the obtained compound was m/z=804 [M] ⁺ .

[Synthesis example 6]
0.6 part of 3-hydroxydiphenylamine, 0.6 part of the compound represented by the above formula (B-1), and 8.8 parts of trifluoromethanesulfonic acid were mixed and stirred at 100° C. for 4 hours to obtain a reaction liquid. Obtained. After cooling the reaction solution to room temperature, 50 parts of water was added to the reaction solution, extracted with chloroform and ethyl acetate, and each organic layer was washed with water. The organic layers washed with water were combined and the solvent was distilled off. 0.6 part of p-chloranil and 11 parts of acetonitrile were added to the residue, and the mixture was stirred at room temperature for 10 hours. After distilling off the solvent from the reaction solution, 30 parts of chloroform was added, and the precipitated solid was separated by filtration. After concentrating the filtrate, 20 parts of a 4% aqueous sodium hydroxide solution was added to the concentrated filtrate, and the mixture was stirred at room temperature for 12 hours. The reaction solution was neutralized to pH 4 with 2N hydrochloric acid, and the precipitated solid was collected by filtration. The obtained solid was dispersed and washed in a mixed solution of ethyl acetate-hexane (3:1) for 5 hours, dried and then dissolved in 5 parts of concentrated hydrochloric acid to obtain a solution. The obtained solution was filtered with a filter, the filtrate was crystallized with 20% saline, and neutralized with a 25% aqueous sodium hydroxide solution until the pH reached 4. The precipitated solid was collected by filtration, mixed with 7.6 parts of ethyl iodide, 4.1 parts of potassium carbonate, and 5 parts of N-methyl-2-pyrrolidone, and stirred at 75°C for 17 hours. After cooling the reaction solution to room temperature, 70 parts of 2N hydrochloric acid was added to the reaction solution, extracted with chloroform, the organic layer was washed with water, and the solvent was distilled off. It was dried in a vacuum oven at 60° C. to obtain 0.2 part (yield 15%) of the compound represented by the formula (B-2). The mass spectrometry result of the obtained compound was m/z=750 [M] ⁺ .
Subsequently, 0.2 part of the compound represented by the formula (B-2), 0.1 part of bis(trifluoromethanesulfonyl)lithium, and 2.7 parts of N,N-dimethylsulfoxide are mixed, and the mixture is mixed at 50° C. for 5 minutes. After stirring for a time, a reaction solution was obtained. The resulting reaction solution was added dropwise to 40 parts of 20% saline, and the precipitated solid was collected by filtration. The solid was dissolved in chloroform, the organic layer was washed with water, sodium sulfate was added and dried, the solvent was distilled off, and the residue was dried in a vacuum oven at 60° C. to give the compound represented by the formula (A-8) at 0. Two parts (yield 90%) were obtained.

[Synthesis example 7]
3,5-Dichloroaniline 15.0 parts, ethyl 4-bromobutyrate 19.9 parts, N,N-diisopropylethylamine 35.9 parts, and N,N-dimethylformamide 52.5 parts were mixed, and at 120°C. The mixture was heated and stirred for 2 hours. Subsequently, 28.9 parts of ethyl iodide was added to the reaction solution, and the mixture was heated and stirred at 70° C. for 24 hours. After cooling to room temperature, the reaction product was extracted with ethyl acetate, and then the extracted reaction product was washed with water. The solvent was distilled off from the organic layer, and the residue was purified by silica gel column chromatography (developing solvent:ethyl acetate:hexane=1:5). Furthermore, 28.4 parts of phosphoryl chloride and 52.5 parts of N,N-dimethylformamide were mixed with the compound obtained at 0° C., and the mixture was heated with stirring at 60° C. for 6 hours. The reaction product was crystallized in a 4% aqueous sodium hydroxide solution, and the precipitated solid was collected by filtration and washed with 100 parts of methanol. It was dried in a vacuum oven at 60° C. to obtain 5.0 parts (yield 16%) of the compound represented by the formula (B-3). The mass spectrometry result of the obtained compound was m/z=333 [M+H] ⁺ .

The compound represented by the formula (B-1) was replaced by the compound represented by the formula (B-3), and 3-hydroxydiphenylamine was replaced by N,N-diethylaminophenol. 1.3 parts (yield 31%) of the compound represented by (B-4) was obtained. The mass spectrometry result of the obtained compound was m/z=596 [M] ⁺ .

Subsequently, a compound represented by the formula (A-9) in the same manner as in Synthesis Example 6 except that the compound represented by the formula (B-2) is changed to the compound represented by the formula (B-4). 0.4 part (yield 64%) was obtained.

[Synthesis Example 8]
0.3 parts of the compound represented by the formula (A-10) (yield 45%) was obtained in the same manner as in Synthesis Example 7 except that bis(trifluoromethanesulfonyl)lithium was changed to monosodium 3-sulfobenzoate. Obtained.

[Synthesis Example 9]
0.88 parts of the compound represented by the formula (A-11) (yield 91%) in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to lithium bis(fluorosulfonyl)imide. Obtained.

[Synthesis Example 10]
0.77 parts (yield 71%) of the compound represented by formula (A-12) was obtained in the same manner as in Synthesis Example 3 except that lithium trifluoromethanesulfonate was used instead of bis(trifluoromethanesulfonyl)lithium. ..

[Synthesis Example 11]
0.5 part of the compound represented by the formula (A-13) (yield 72%) was obtained in the same manner as in Synthesis Example 3 except that lithium bis(trifluoromethanesulfonyl)lithium was changed to lithium nonafluoro-1-butanesulfonate. )Obtained.

[Synthesis Example 12]
0.93 parts (yield 83%) of a compound represented by the formula (A-14) was obtained in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to sodium tetraphenylborate. ..

[Synthesis Example 13]
0.78 parts (yield 93%) of a xanthene compound represented by the formula (A-15) was obtained in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to sodium dicyanamide.

[Synthesis Example 14]
0.58 parts (yield 63%) of a compound represented by the formula (A-16) was obtained in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to lithium hexafluorophosphate. ..

[Synthesis Example 15]
0.74 parts (yield 75%) of a compound represented by the formula (A-17) was obtained in the same manner as in Synthesis Example 3 except that sodium bis(trifluoromethanesulfonyl)lithium was changed to sodium 3-nitrobenzenesulfonate. It was

[Synthesis Example 16]
0.65 parts of the compound represented by the formula (A-18) (yield 63%) in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to sodium isoquinoline-5-sulfonate. Obtained.

[Synthesis Example 17]
0.74 parts (yield 75%) of the compound represented by the formula (A-19) was obtained in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to trifluoromethanesulfonamide.

[Synthesis Example 18]
A compound represented by the formula (A-20) in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to N,N-bis(2-hydroxyethyl)-2-aminoethanesulfonic acid. 0.87 part (yield 87%) was obtained.

[Synthesis Example 19]
0.65 parts of the compound represented by the formula (A-21) was obtained in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to ethylenediaminetetraacetic acid monosodium iron(III) hydrate. Yield 60%) was obtained.

[Synthesis Example 20]
0.65 parts (yield 74%) of the compound represented by the formula (A-22) was obtained in the same manner as in Synthesis Example 3 except that sodium bis(trifluoromethanesulfonyl)lithium was changed to vinyl sulfonate.

[Synthesis Example 21]
0.47% of the compound represented by the formula (A-23) was prepared in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to 3-(trihydroxysilyl)propylmethylphosphonate monosodium salt solution. Part (yield 46%) was obtained.

[Synthesis Example 22]
0.32% of the xanthene compound represented by the formula (A-24) was obtained in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to 3-(trihydroxysilyl)propane-1-sulfonic acid. Parts (yield 36%) were obtained.

[Synthesis Example 23]
After mixing 0.2 part of 1,8-naphtho sultone, 0.2 part of 3-aminopropyltriethoxysilane and 8.5 part of dimethylsulfoxide and stirring at room temperature for 3 hours, the compound represented by the formula (B-5) was used. A compound was obtained. Then, 0.78 parts of the compound represented by the formula (A-25) was prepared in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to the compound represented by the formula (B-5). (Yield 93%) was obtained.

[Synthesis Example 24]
0.5 part of the compound represented by the formula (A-26) (yield 44 %)Obtained.

[Synthesis Example 25]
0.5 parts (yield 72%) of a compound represented by the formula (A-27) was obtained in the same manner as in Synthesis Example 3 except that bis(trifluoromethanesulfonyl)lithium was changed to phosphotungstic acid hydrate. It was

[Synthesis example 26]
Lithium bis(trifluoromethanesulfonyl)lithium was changed to 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonimide lithium in the same manner as in Synthesis Example 3 except that the formula (A-28) 0.69 parts (yield 63%) of a xanthene compound represented by

[Synthesis Example 27]
0.63 parts of the compound represented by the formula (A-29) (yield 58%) was obtained in the same manner as in Synthesis Example 3 except that potassium tris(trifluoromethanesulfonyl)methanide was used instead of bis(trifluoromethanesulfonyl)lithium. )Obtained.

[Preparation of dispersion 1]
C. I. Pigment Red 291 (pigment) 10.0 parts, dispersing agent (BYK BYKLPN-6919; propylene glycol monomethyl ether acetate 60% solution) 3.3 parts, resin (B-2) (solid content conversion) 4 0.0 parts and 12.7 parts of propylene glycol monomethyl ether were mixed, 41.3 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and a paint conditioner (manufactured by LAU) was used. And shaken for 1 hour. Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 1.

[Preparation of dispersion 2]
C. I. Pigment Red 177 (pigment) 10.0 parts, dispersant (BYK, BYKLPN-6919; propylene glycol monomethyl ether acetate 60% solution) 4.3 parts, resin (B-2) (solid content conversion) 4 0.0 parts and 59.2 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 2.

[Preparation of dispersion 3]
C. I. Pigment Red 202 (pigment) 10.0 parts, dispersant (BYK BYKLPN-6919; propylene glycol monomethyl ether acetate 60% solution) 7.5 parts, resin (B-2) (solid content conversion) 3 0.5 parts, propylene glycol monomethyl ether 8.5 parts, and propylene glycol monomethyl ether acetate 202 parts were mixed, 0.4 μm zirconia beads 600 parts were added, and the mixture was shaken for 1 hour using a paint conditioner (manufactured by LAU). .. Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 3.

[Preparation of dispersion 4]
C. I. Pigment Red 264 (pigment) 10.0 parts, dispersant (BYK, BYKLPN-6919; propylene glycol monomethyl ether acetate 60% solution) 7.6 parts, and resin (B-2) (solid content conversion) 3 6 parts, 6.7 parts of propylene glycol monomethyl ether, and 55.4 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and a paint conditioner (manufactured by LAU) was used for 1 hour. Shaken. Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 4.

[Preparation of dispersion 5]
C. I. Pigment Red 269 (pigment) 10.0 parts, dispersant (BYK Co. BYKLPN-6919; propylene glycol monomethyl ether acetate 60% solution) 5.0 parts, resin (B-2) (solid content conversion) 3 0.0 part, 5.5 parts of propylene glycol monomethyl ether, and 47.7 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and a paint conditioner (manufactured by LAU) was used for 1 hour. Shaken. Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 5.

[Preparation of Dispersion 6]
C. I. Pigment Yellow 185 (pigment) 10.0 parts, dispersant (BYK Co. BYKLPN-6919; propylene glycol monomethyl ether acetate 60% solution) 10.8 parts, resin (B-2) (solid content conversion) 3 0.5 parts, propylene glycol monomethyl ether 4.2 parts, and propylene glycol monomethyl ether acetate 96.5 parts are mixed, 0.4 μm zirconia beads 600 parts are added, and a paint conditioner (manufactured by LAU) is used for 1 hour. Shaken. Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 6.

[Preparation of dispersion 7]
C. I. Pigment Blue 15:6 (pigment) 10.0 parts, dispersant (BYK, BYKLPN-6919; propylene glycol monomethyl ether acetate 60% solution) 5.8 parts, resin (B-2) (solid content conversion). Was mixed with 4.0 parts of ethyl lactate and 96.5 parts of propylene glycol monomethyl ether acetate, 600 parts of 0.4 μm zirconia beads were added, and a paint conditioner (manufactured by LAU) was used for 1 hour. Shaken. Then, the zirconia beads were removed by filtration to obtain a dispersion liquid 7.

<Examples 1 to 36, Comparative Examples 1 and 2>
[Preparation of colored resin composition]
The components shown in Tables 5 to 7 were mixed to obtain each colored resin composition.

Color material 1: compound represented by formula (A-1)

Color material 2: compound represented by formula (A-2)

Color material 3: compound represented by formula (A-3)

Color material 4: compound represented by formula (A-4)

Color material 5: compound represented by formula (AX)

Color material 6: Compound represented by formula (A-6) Color material 7: Compound represented by formula (A-7) Color material 8: Compound represented by formula (A-8) Material 9: Compound represented by Formula (A-9)/Coloring Material 10: Compound represented by Formula (A-10)/Coloring Material 11: Compound represented by Formula (A-11)/Coloring Material 12 : Compound represented by Formula (A-12)/Coloring material 13: Compound represented by Formula (A-13)/Coloring material 14: Compound represented by Formula (A-14)/Coloring material 15: Formula Compound represented by (A-15)/Coloring material 16: Compound represented by Formula (A-16)/Coloring material 17: Compound represented by Formula (A-17)/Coloring material 18: Formula (A -18) compound/coloring material 19: compound represented by formula (A-19)/coloring material 20: compound represented by formula (A-20)/coloring material 21: formula (A-21) ) Compound/colorant 22: compound represented by formula (A-22)/colorant 23: compound represented by formula (A-23)/colorant 24: represented by formula (A-24) Compound/Coloring Material 25: Compound Represented by Formula (A-25)/Coloring Material 26: Compound Represented by Formula (A-26)/Coloring Material 27: Represented by Formula (A-27) Compound/coloring material 28: compound represented by formula (A-28)/coloring material 29: compound represented by formula (A-29)

-Resin (B): Resin (B-1) (solid content conversion)
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.)
-Polymerization initiator (D): TR-PBG327 (registered trademark) (Changzhou Power Electronics Co., Ltd.; oxime compound)
-Solvent (E): Solvent (E-1): Ethyl lactate
Solvent (E-2): diacetone alcohol
Solvent (E-3): Propylene glycol monomethyl ether acetate/leveling agent (F): Polyether-modified silicone oil (solid content conversion) (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.)

[Preparation of color filter (colored coating film)]
The colored resin composition was applied on a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Incorporated) by a spin coating method, and then prebaked at 100° C. for 3 minutes to form a colored resin composition layer. After cooling, light exposure was performed using an exposure device (TME-150RSK; manufactured by Topcon Corp.) in the air atmosphere at an exposure amount of 60 mJ/cm ² (365 nm standard). Then, post baking was performed at 230° C. for 20 minutes in an oven to obtain a color filter.

[Chemical resistance test]
The obtained color filter was immersed in N-methylpyrrolidone adjusted to 40° C. for 10 minutes. About the color filter before and after the immersion, the spectrum was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corp.), and the xy chromaticity coordinates in the XYZ color system of CIE were measured using the characteristic function of the C light source. (X, y) and the stimulation value Y were calculated. The color difference ΔE*ab was calculated from the measured values by the method described in JIS Z 8730:2009 (7. Calculation method of color difference), and the results are shown in Tables 8 to 9. The smaller ΔE*ab means that the color change is smaller.

Claims (5)

A colored resin composition comprising a colorant and a resin, wherein the colorant comprises a compound represented by the formula (I).

[In the formula (I),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, a hydroxy group, a nitro group, a cyano group, a halogen atom, One or more of a carboxy group, a sulfo group, a sulfamoyl group, a metallocenyl group, a hydrocarbon group having 1 to 30 carbon atoms, or a methylene group in the hydrocarbon group is a divalent group selected from the following group I. Represents a substituted group, provided that when two or more methylene groups are replaced by a divalent group selected from Group I below, the divalent groups are not adjacent to each other,
The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom, a nitro group, a cyano group, a hydroxy group, an amino group, a carboxy group, a sulfo group, a phosphono group, a sulfamoyl group, an isocyanato group, or a heterocycle. ,
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently one or two of a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a methylene group in the hydrocarbon group. One or more represents a group substituted with a divalent group selected from the following group I, provided that two or more methylene groups are replaced with a divalent group selected from the following group I: Groups are not next to each other,
The hydrogen atom contained in the hydrocarbon group may be substituted with a heterocycle or a polar group,
At least one of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ is a group having a polar group as a substituent,
n represents an integer of 1 to 3,
A ^q- represents a q-valent anion,
q represents an integer of 1 to 3,
p represents a coefficient for keeping the charge of the compound represented by the formula (I) neutral.
Group I: -O -, - S - , - CO -, - COO -, - OCO -, - COS -, - OCS -, - SO 2 -, - SO 3 -, - NH -, - CONH -, - _{NHCO -, - SO 2 NH -} , - NHSO 2 - or -N = CH-] The colored resin composition according to claim 1, further comprising a polymerizable compound and a polymerization initiator. The colored resin composition according to claim 1, wherein the coloring agent further contains a pigment (however, the compound represented by the formula (I) is excluded). A color filter formed from the colored resin composition according to claim 1. A display device including the color filter according to claim 4.