JP2021187913A - Phenothiazine-based compound and curable resin composition containing the same - Google Patents

Abstract

To provide a compound excellent in light resistance.SOLUTION: The compound is represented by formula (A-I) [where R7 and R8 each independently represent an optionally substituted C1-8 aliphatic hydrocarbon group or a hydrogen atom; R9 and R10 each independently represent an optionally substituted C1-30 hydrocarbon group, provided that a methylene group constituting the hydrocarbon group may be substituted with an oxygen atom, -NR- or -CO-; and Xt- represents a t-valent anion (excluding Cl-, Br- and I-)].SELECTED DRAWING: None

Description

The present invention relates to a compound useful as a colorant, a composition containing the compound, and the like.

Dyes are used as colorants for color filters included in liquid crystal displays, solid-state image sensors, and the like. As the dye, for example, Patent Document 1 describes BasicBlue24.

Japanese Unexamined Patent Publication No. 2012-207159

The light resistance of the Basic Blue 24 was not sufficiently satisfactory, and therefore the colored curable resin composition containing the Basic Blue 24 was also not sufficiently satisfactory in the light resistance.
An object of the present invention is to provide a compound having excellent light resistance, a composition containing the compound, and the like.

［式（Ａ−Ｉ）中、
Ｒ¹〜Ｒ⁶は、それぞれ独立して、置換基を有していてもよい炭素数１〜８の脂肪族炭化水素基、水素原子、ハロゲン原子、ニトロ基又はヒドロキシ基を表し、該脂肪族炭化水素基を構成するメチレン基は酸素原子又は−ＣＯ−に置き換わっていてもよい。
Ｒ⁷及びＲ⁸は、それぞれ独立して、置換基を有していてもよい炭素数１〜８の脂肪族炭化水素基、又は水素原子を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立して、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、該炭化水素基を構成するメチレン基は酸素原子、−ＮＲ−又は−ＣＯ−に置換されていてもよい。
Ｒは、置換基を有していてもよい炭素数１〜１０の炭化水素基を表す。
Ｒ⁷とＲ⁹とは、互いに結合して窒素原子とともに環を形成してもよく、Ｒ⁸とＲ¹⁰とは、互いに結合して窒素原子とともに環を形成してもよい。
ｐ及びｑは、それぞれ独立して、０〜５の整数を表す。
Ｘ^t-は、ｔ価のアニオン（ただし、Ｃｌ^-、Ｂｒ^-及びＩ^-を除く。）を表す。
ｔは、１〜３の整数を表す。］
［２］ 式（Ａ−Ｉ）におけるＸ^t-が、タングステン、モリブデン、ケイ素、及びリンからなる群から選ばれる少なくとも１つの元素と、酸素とを必須元素として含有するアニオンである［１］に記載の化合物。
［３］ 式（Ａ−Ｉ）におけるＸ^t-が含ホウ素アニオンである［１］に記載の化合物。
［４］ 式（Ａ−Ｉ）におけるＸ^t-が含アルミニウムアニオンである［１］に記載の化合物。
［５］ 式（Ａ−Ｉ）におけるＸ^t-が含フッ素アニオンである［１］に記載の化合物。
［６］ 式（Ａ−Ｉ）におけるＸ^t-とＨ⁺とから形成されるＸＨ_tのモル濃度に基づいて決定される酸解離定数ｐＫａ＝−ｌｏｇ₁₀（［Ｈ］^t・［Ｘ^t-］／［ＸＨ_t］）が−１５以上０以下である［１］〜［５］のいずれかに記載の化合物。
［７］ 式（Ａ−Ｉ）のｐ及びｑが１以上でありかつＲ⁹及びＲ¹⁰が、化合物（Ｘ）及び化合物（Ｙ）で測定されるハメット置換基定数が負となる基であるか、ｐ及びｑが０である［１］〜［６］のいずれかに記載の化合物。

［８］ Ｒ⁷及びＲ⁸が水素原子である［１］〜［７］のいずれかに記載の化合物。
［９］ ［１］〜［８］のいずれかに記載の化合物を含む着色分散液。
［１０］ ［１］〜［８］のいずれかに記載の化合物を含む着色硬化性樹脂組成物。
［１１］ ［１０］記載の着色硬化性樹脂組成物から形成される塗膜。
［１２］ ［１０］記載の着色硬化性樹脂組成物から形成されるカラーフィルタ。
［１３］ ［１２］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 (AI).

[In formula (AI),
R ^{1 to} R ⁶ each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms, which may have a substituent, a hydrogen atom, a halogen atom, a nitro group or a hydroxy group, and the aliphatic group thereof. The methylene group constituting the hydrocarbon group may be replaced with an oxygen atom or −CO−.
R ⁷ and R ⁸ each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom which may have a substituent.
R ⁹ and R ¹⁰ each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and the methylene group constituting the hydrocarbon group is an oxygen atom, -NR- or It may be replaced with −CO−.
R represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
R ⁷ and R ⁹ may be bonded to each other to form a ring with a nitrogen atom, and R ⁸ and R ¹⁰ may be bonded to each other to form a ring with a nitrogen atom.
p and q each independently represent an integer of 0 to 5.
X ^t-is, t-valent anion (provided, Cl ^-, Br ^- and I ^- excluding.) Represents the.
t represents an integer of 1 to 3. ]
^{[2] X t-} in the formula (AI) is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements [1]. The compound described.
[3] The compound according to [1], wherein ^{X t-} in the formula (AI) is a boron-containing anion.
[4] The compound according to [1], wherein ^{X t-} in the formula (AI) is an aluminum-containing anion.
[5] The compound according to [1], wherein ^{X t-} in the formula (AI) is a fluorine-containing anion.
_{[6] Acid dissociation constant pKa = -log 10} ([H] ^t · [X ^t- ] determined based on the molar concentration of _{XH t} formed from ^{X t-} and H ⁺ in the formula (AI). ] / [XH _t ]) is -15 or more and 0 or less, according to any one of [1] to [5].
[7] p and q of the formula (AI) are 1 or more, and R ⁹ and R ¹⁰ are groups having a negative Hammet substituent constant measured by the compound (X) and the compound (Y). Or the compound according to any one of [1] to [6], wherein p and q are 0.

[8] The compound according to any one of [1] to [7], wherein ^{R 7} and R ^{8 are hydrogen atoms.}
[9] A colored dispersion containing the compound according to any one of [1] to [8].
[10] A colored curable resin composition containing the compound according to any one of [1] to [8].
[11] A coating film formed from the colored curable resin composition according to [10].
[12] A color filter formed from the colored curable resin composition according to [10].
[13] A display device including the color filter according to [12].

The compound of the present invention and the composition containing the compound have excellent light resistance.

<Phenothiazine compound>
The compound of the present invention is a phenothiazine-based compound, and is specifically represented by the formula (AI) (hereinafter, may be referred to as “compound (AI)”). The compound (AI) has excellent light resistance, heat resistance, and solvent resistance, and the colored curable resin composition containing the compound (AI) also has good light resistance, heat resistance, and solvent resistance. become.

［式（Ａ−Ｉ）中、
Ｒ¹〜Ｒ⁶は、それぞれ独立して、置換基を有していてもよい炭素数１〜８の脂肪族炭化水素基、水素原子、ハロゲン原子、ニトロ基又はヒドロキシ基を表し、該脂肪族炭化水素基を構成するメチレン基は酸素原子又は−ＣＯ−に置き換わっていてもよい。
Ｒ⁷及びＲ⁸は、それぞれ独立して、置換基を有していてもよい炭素数１〜８の脂肪族炭化水素基、又は水素原子を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立して、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、該炭化水素基を構成するメチレン基は酸素原子、−ＮＲ−又は−ＣＯ−に置換されていてもよい。
Ｒは、置換基を有していてもよい炭素数１〜１０の炭化水素基を表す。
Ｒ⁷とＲ⁹とは、互いに結合して窒素原子とともに環を形成してもよく、Ｒ⁸とＲ¹⁰とは、互いに結合して窒素原子とともに環を形成してもよい。
ｐ及びｑは、それぞれ独立して、０〜５の整数を表す。
Ｘ^t-は、ｔ価のアニオン（ただし、Ｃｌ^-、Ｂｒ^-及びＩ^-を除く。）を表す。
ｔは、１〜３の整数を表す。］

[In formula (AI),
R ^{1 to} R ⁶ each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms, which may have a substituent, a hydrogen atom, a halogen atom, a nitro group or a hydroxy group, and the aliphatic group thereof. The methylene group constituting the hydrocarbon group may be replaced with an oxygen atom or −CO−.
R ⁷ and R ⁸ each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom which may have a substituent.
R ⁹ and R ¹⁰ each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and the methylene group constituting the hydrocarbon group is an oxygen atom, -NR- or It may be replaced with −CO−.
R represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
R ⁷ and R ⁹ may be bonded to each other to form a ring with a nitrogen atom, and R ⁸ and R ¹⁰ may be bonded to each other to form a ring with a nitrogen atom.
p and q each independently represent an integer of 0 to 5.
X ^t-is, t-valent anion (provided, Cl ^-, Br ^- and I ^- excluding.) Represents the.
t represents an integer of 1 to 3. ]

The aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{1 to} R ⁸ may be saturated or unsaturated, or may be a chain or an alicyclic.
Saturated or unsaturated chain hydrocarbon groups represented by R ^{1 to} R ⁸ include linear alkyl such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group. Group; isopropyl group, (1-ethyl) propyl group, isobutyl group, sec-butyl group, tert-butyl group, (1-ethyl) butyl group, (2-ethyl) butyl group, isopentyl group, neopentyl group, tert- Branched chain alkyl groups such as pentyl group, (2-methyl) pentyl group, isohexyl group, (5-methyl) hexyl group; vinyl group, 1-propenyl group, 2-propenyl group (allyl group), (1) -Methyl) ethenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, (1- (2-propenyl)) ethenyl group, (1,2-dimethyl) propenyl group, 2-pentenyl group, etc. Alkenyl group; etc. The ^{saturated or unsaturated chain hydrocarbon group represented by R 1 to} R ⁸ has preferably 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and further preferably 1 to 3 carbon atoms.

Examples of the saturated or unsaturated alicyclic hydrocarbon group represented by R ^{1 to} R ⁸ include a cycloalkyl group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; Cycloalkenyl groups such as a hexenyl group (eg, cyclohex-2-ene, cyclohex-3-ene), cycloheptenyl group, cyclooctenyl group; norbornyl group, bicyclo [2.2.2] octyl group and the like can be mentioned. The saturated or unsaturated alicyclic hydrocarbon group preferably has 3 to 8 carbon atoms, more preferably 5 to 7 carbon atoms.

The ^{substituent which the aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R 1 to} R ⁸ may have may be a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; a hydroxy group. An alkoxycarbonyl group having 2 to 10 carbon atoms such as a methoxycarbonyl group; a cyano group; an amino group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group and the like can be mentioned.

Examples of the group in which the methylene group constituting the aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{1 to} R ⁶ is replaced with an oxygen atom include a methoxy group, an ethoxy group and the like having 1 to 1 carbon atoms. The alkoxy group of 7 and the following are mentioned (* represents a bond).

Examples of the group in which the methylene group constituting the aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^{1 to} R ^{6 is replaced with −CO− include an acetyl group and the like having 2 to 8 carbon atoms.} Acyl groups; and include the following (* represents a bond).

Examples of the halogen atom represented by R ^{1 to} R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom or a chlorine atom is preferable.

As R ^{1 to} R ⁶ , a hydrogen atom or an aliphatic hydrocarbon group having 1 to 8 carbon atoms is preferable, and a hydrogen atom is more preferable.
As R ⁷ and R ⁸ , hydrogen atoms or aliphatic hydrocarbon groups having 1 to 8 carbon atoms are preferable, and hydrogen atoms and aliphatic hydrocarbon groups having 1 to 3 carbon atoms are more preferable.

Examples of the hydrocarbon group having 1 to 30 carbon atoms represented by R ⁹ and R ¹⁰ and the hydrocarbon group having 1 to 10 carbon atoms represented by R include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. .. Aliphatic hydrocarbon groups may be saturated or unsaturated, and may be chain or alicyclic.

The saturated or unsaturated chain hydrocarbon group having 1 to 30 carbon atoms represented by R ⁹ and R ¹⁰ and the saturated or unsaturated chain hydrocarbon group having 1 to 10 carbon atoms represented by R are R. Examples thereof include groups similar to saturated or unsaturated alicyclic hydrocarbon groups having 1 to 8 carbon atoms represented by ^{1 to} R ^{8, and further, linear alkyl groups such as nonyl group and decyl group; (3-3).} Examples thereof include branched alkyl groups such as ethyl) heptyl groups. The ^{saturated or unsaturated chain hydrocarbon group represented by R 9} and R ¹⁰ has preferably 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 6 carbon atoms, and more. More preferably, it is 1 to 3. The saturated or unsaturated chain hydrocarbon group represented by R has preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 1 to 3 carbon atoms.

As ^{the saturated or unsaturated alicyclic hydrocarbon group having 1 to 30 carbon atoms represented by R 9} and R ¹⁰ , and the saturated or unsaturated alicyclic hydrocarbon group having 1 to 10 carbon atoms represented by R. , R ^{1 to} R ⁸ , a group similar to a saturated or unsaturated alicyclic hydrocarbon group having 1 to 8 carbon atoms, and further, an adamantyl group. The ^{saturated or unsaturated alicyclic hydrocarbon group represented by R 9} and R ¹⁰ has preferably 3 to 18 carbon atoms, more preferably 3 to 15 carbon atoms, and further preferably 4 to 15 carbon atoms. The saturated or unsaturated alicyclic hydrocarbon group represented by R has preferably 3 to 8 carbon atoms, more preferably 3 to 7 carbon atoms, and further preferably 5 to 7 carbon atoms.

Examples of the aromatic hydrocarbon group represented by R ⁹ , R ¹⁰ and R include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like, and an aromatic hydrocarbon group represented by ^{R 9} and R ^10. Further, a phenyl group, an anthryl group, a pyrenyl group and the like can also be mentioned. The ^{number of carbon atoms of the aromatic hydrocarbon group represented by R 9} and R ¹⁰ is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15. The number of carbon atoms of the aromatic hydrocarbon group represented by R is preferably 6 to 10, more preferably 6 to 8, and even more preferably 6 to 7.

The ^{hydrocarbon groups represented by R 9} and R ¹⁰ include the above-mentioned chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups as long as the upper limit of the number of carbon atoms is 30 or less. It may be a group in which one or more are combined. Such a group may be, for example, a group in which an aromatic hydrocarbon group is combined with at least one of a group selected from a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. In the hydrocarbon group by the combination, the chain hydrocarbon group may be combined as a divalent group (for example, an arcandyl group). Examples of the hydrocarbon group by combination include an aralkyl group such as a benzyl group, a phenethyl group and a 1-methyl-1-phenylethyl group; an arylalkenyl group such as a phenylethenyl group (phenylvinyl group); a phenylethynyl group and the like. Arylalkynyl group; o-tolyl group, m-tolyl group, p-tolyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 2,3-dimethylphenyl group, 2,4-dimethyl Phenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-tri Alkylaryl groups such as isopropylphenyl group and 4-butylphenyl group; 2,3-dihydro-4-indenyl group, 1,2,3,5,6,7-hexahydro-4-s-indacenyl group, 5,6 , 7,8-Tetrahydro-1-naphthyl group, 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl group or other alkandyl group bonded aryl group; biphenylyl Examples include an aryl group to which one or more aryl groups such as a group and a terphenylyl group are bonded; a cyclohexylmethylphenyl group, a benzylphenyl group, a (dimethyl (phenyl) methyl) phenyl group and the like. Further, the above-mentioned hydrocarbon group may be, for example, a hydrocarbon group formed by a combination of a chain hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include a 1-methylcyclopropyl group and a 1-methylcyclohexyl group. , 2-Methylcyclohexyl group, 1,2-dimethylcyclohexyl group, 1,3-dimethylcyclohexyl group, 2,4,6-trimethylcyclohexyl group, 2,2,6,6-tetramethylcyclohexyl group, 4-pentylcyclohexyl An alicyclic hydrocarbon group to which one or more alkyl groups such as a group and a 4-octylcyclohexyl group are bonded; cyclopropylmethyl group, cyclopropylethyl group, cyclobutylmethyl group, cyclobutylethyl group, cyclopentylmethyl group, cyclopentylethyl Examples thereof include an alkyl group to which one or more alicyclic hydrocarbon groups such as a group, a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, a cyclohexylethyl group and an adamantylmethyl group are bonded. The carbon number of a group in which two or more chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups are combined is preferably 4 to 30, and more preferably 6 to 20.

The hydrocarbon group represented by R is a combination of two or more of the above-mentioned chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups as long as the upper limit of the number of carbon atoms is 10 or less. It may be a group. Such a group may be, for example, a group in which an aromatic hydrocarbon group is combined with at least one of a group selected from a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. In the hydrocarbon group according to the combination, the chain hydrocarbon group may be combined as a divalent group (for example, an arcandyl group). Examples of the hydrocarbon group by combination include those having 10 or less carbon atoms from those exemplified as the hydrocarbon group by combination in ^{R 9} and R ^10.

The substituents that the hydrocarbon groups represented by ^{R 9} , R ¹⁰ and R may have include the substituents that the aliphatic hydrocarbon groups represented by ^{R 1 to} R ^{8 may have.} Similar groups can be mentioned.

As a group in which the methylene group constituting the hydrocarbon group having 1 to 30 carbon atoms represented by ^{R 9} and R ^{10 is replaced with an oxygen atom, the group represented by R 1 to} R ⁶ has 1 to 8 carbon atoms. Examples of the same group as the group in which the methylene group constituting the aliphatic hydrocarbon group of the above is replaced with an oxygen atom are mentioned, and the following are further mentioned (* represents a bond).

The group in which the methylene group constituting the hydrocarbon group having 1 to 30 carbon atoms represented by ^{R 9} and R ^{10 is replaced with −CO− is represented by R 1 to} R ⁶ and has 1 to 1 carbon atoms. Examples of the same group as the group in which the methylene group constituting the aliphatic hydrocarbon group of 8 is replaced with -CO- are mentioned, and the following are further mentioned (* represents a bond).

Examples of the group in which the methylene group constituting the hydrocarbon group having 1 to 30 carbon atoms represented by R ⁹ and R ^{10 is replaced with −NR— include the alkylamino group having 1 to 30 carbon atoms shown below.} , A dialkylamino group having 2 to 30 carbon atoms, an alkylarylamino group having 7 to 30 carbon atoms, and the like (* indicates a bond).

Examples of the ring in which R ⁷ and R ⁹ are bonded to each other to form with a nitrogen atom and the ring in which R ⁸ and R ¹⁰ are bonded to each other to form with a nitrogen atom are as follows (* indicates). Represents a bond).

R ⁹ and R ¹⁰ may be a group in which the Hammet substituent constant measured in the compound (X) and the compound (Y) is positive, a negative group, or a negative group. Is preferable.

As a group having a positive Hammet substituent constant, a saturated chain hydrocarbon group having 1 to 8 carbon atoms having a halogen atom as a substituent and a methylene group of a saturated chain hydrocarbon group having 1 to 8 carbon atoms are oxygen. A group substituted with an atom, a group in which the methylene group of a saturated chain hydrocarbon group having 1 to 8 carbon atoms is replaced with −CO—, and the like are preferable. As the saturated chain hydrocarbon group having 1 to 8 carbon atoms having a halogen atom as the substituent, for example, a perfluoroalkyl group such as a trifluoromethyl group is preferable. As the group in which the methylene group of the saturated chain hydrocarbon group having 1 to 8 carbon atoms is substituted with an oxygen atom, for example, an alkoxy group having 1 to 7 carbon atoms such as a methoxy group and an ethoxy group is preferable. As the group in which the methylene group of the saturated chain hydrocarbon group having 1 to 8 carbon atoms is replaced with −CO−, an acyl group having 1 to 8 carbon atoms such as an acetyl group is preferable.

Groups having a negative Hammet substituent constant include a saturated chain hydrocarbon group having 1 to 8 carbon atoms and a group in which the methylene group of a saturated chain hydrocarbon group having 1 to 8 carbon atoms is replaced with -NR-. Is preferable. As the saturated chain hydrocarbon group having 1 to 8 carbon atoms, for example, an alkyl group such as a methyl group or an ethyl group is preferable. As the group in which the methylene group of the saturated chain hydrocarbon group having 1 to 8 carbon atoms is replaced with −NR−, for example, an alkylamino group having 1 to 8 carbon atoms such as a methylamino group and a dimethylamino group is preferable. ..

p and q are preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1. When p and q are 1, R ⁹ and R ¹⁰ may be in the ortho position, the meta position, or the para position with respect to ^{−N (−R 7} ) or −N (−R ^8). The ortho-position or meta-position is preferable, and the ortho-position is more preferable.

R ⁹ , R ¹⁰ , p, q are preferably a combination in which the Hammet substituent constant is zero or negative, and specifically, when p and q are zero or p and q are 1 or more, R ⁹ And the Hammet substituent constant of ^{R 10 is preferably negative.}
Of the compound (AI), ^{the portion other than X t-} (hereinafter, may be referred to as a cation) is preferably represented by the formula (A-II).

［式（Ａ−ＩＩ）中、
Ｒ²¹〜Ｒ²⁶は、それぞれ独立して、炭素数１〜８の脂肪族炭化水素基、又は水素原子を表し、水素原子であることが好ましい。
Ｒ²⁷及びＲ²⁸は、それぞれ独立して、炭素数１〜８の脂肪族炭化水素基、又は水素原子を表し、水素原子であることが好ましい。
Ｒ²⁹及びＲ³⁰は、それぞれ独立して、置換基を有していてもよい炭素数１〜３０の炭化水素基を表し、該炭化水素基を構成するメチレン基は酸素原子、−ＮＲ^x−又は−ＣＯ−に置換されていてもよい。Ｒ^xは、置換基を有していてもよい炭素数１〜１０の炭化水素基を表し、前記Ｒと同様の基が挙げられる。
ｐａ及びｑａは、それぞれ独立して、０又は１である。］

[In formula (A-II),
R ^{21 to} R ²⁶ each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom, and are preferably hydrogen atoms.
R ²⁷ and R ²⁸ each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom, and are preferably hydrogen atoms.
R ²⁹ and R ³⁰ each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and the methylene group constituting the hydrocarbon group is an oxygen atom, −NR ^x −. Alternatively, it may be replaced with −CO−. R ^x represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, and examples thereof include the same groups as R.
pa and qa are independently 0 or 1, respectively. ]

As R ²⁹ and R ³⁰ , a group having a negative Hammet substituent constant when bonded to the meta position of benzoic acid, for example, a saturated chain hydrocarbon group having 1 to 8 carbon atoms such as a methyl group and an ethyl group, Alkylamino groups having 1 to 8 carbon atoms such as methyl group and dimethylamino group; groups having a positive Hammet substituent constant when bonded to the meta position of benzoic acid, for example, methoxy group, ethoxy group and the like. Preferred are 1 to 7 alkoxy groups, acyl groups having 2 to 10 carbon atoms such as acetyl groups, and alkyl halides having 1 to 8 carbon atoms such as trifluoromethyl groups and pentafluoroethyl groups. A group having a negative Hammet substituent constant when bound to the meta position of benzoic acid is more preferable.

When pa and qa are 1 and the Hammet substituent constants of ^{R 29} and R ^{30 are negative, then R 29} and R ³⁰ are relative to -N (-R ²⁷ ) and -N (-R ^28). , Ortho-position or meta-position is preferable, and ortho-position is more preferable.
When pa and qa are 1 and the Hammet substituent constants of ^{R 29} and R ^{30 are positive, then R 29} and R ³⁰ are relative to -N (-R ²⁷ ) and -N (-R ^28). , Ortho position or meta position is preferable, and meta position is more preferable.

From ^{the viewpoint of heat resistance, X t-} contains at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, an anion containing boron, a boron-containing anion, an aluminum-containing anion, and fluorine-containing. Anions are preferable, and anions containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, and fluorine-containing anions are more preferable, and groups consisting of tungsten, molybdenum, silicon and phosphorus. An anions containing at least one element selected from the above and oxygen as essential elements are even more preferable.

As the anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements, an anion containing tungsten is preferable, and an anion containing heteropolyacid or isopolyic acid is preferable, and phosphorus is preferable. Anions of tungsten acid, silicate tungsten acid and tungsten-based isopolyic acid are more preferable.

Examples of the tungsten-containing heteropolyacid or isopolyacid anion include kegin-type phosphotungstate ion α- [PW ₁₂ O ₄₀ ] ^3- , Dawson-type phosphotungstate ion α- [P ₂ W ₁₈ O ₆₂ ] ^6- , β- [P ₂ W ₁₈ O ₆₂ ] ^6- , Kegin-type heteropolytungate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ^{4 -} , As yet other examples, [P ₂ W ₁₇ O ₆₁ ] ^10- , [P ₂ W ₁₅ O ₅₆ ] ^12- , [H ₂ P ₂ W ₁₂ O ₄₈ ] ^12- , [NaP ₅ W ₃₀ O ₁₁₀ ] ^14- , α- [SiW ₉ O ₃₄ ] ^10- , γ- [SiW ₁₀ O ₃₆ ] ^8- , α- [SiW ₁₁ O ₃₉ ] ^8- , β- [SiW ₁₁ O ₃₉ ] ^8- , [W _6] O ₁₉ ] ^2- , [W ₁₀ O ₃₂ ] ^4- , WO ₄ ^2-, etc. can be mentioned.

Examples of the anion composed of oxygen and at least one element selected from the group consisting of silicon and phosphorus include SiO ₃ ^2- and PO ₄ ^3- .

In particular, due to the ease of synthesis and post-treatment, heteropolyacid anions such as kegin-type phosphotungstate ion, Dawson-type phosphotungstate ion, and kegin-type keitungstate ion, and isopolyacid anions such as _{[W 10} O ₃₂ ] ^{4-are used.} preferable.

Examples of the boron-containing anion represented by X ^t- and the aluminum-containing anion include an anion represented by the following formula (1).

［式（１）中、Ｗ¹及びＷ²は、それぞれ独立に、１価のプロトン供与性置換基を少なくとも２つ有し、該基からプロトンを放出してなる置換基２つを有する基を表す。Ｍは、ホウ素原子又はアルミニウム原子を表す。］

[In the formula (1), W ¹ and W ² each independently have at least two monovalent proton-donating substituents, and each group has two substituents obtained by releasing a proton from the group. show. M represents a boron atom or an aluminum atom. ]

Examples of the monovalent proton-donating substituent in a group formed by releasing two protons from a compound having two monovalent proton-donating substituents include a hydroxy group and a carboxy group. The compound having two monovalent proton donating substituents includes a catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, and a substituent. It may have 2,2'-biphenol, 3-hydroxy-2-naphthoic acid which may have a substituent, 2-hydroxy-1-naphthoic acid which may have a substituent, and has a substituent. 1-Hydroxy-2-naphthoic acid which may be present, binaftor which may have a substituent, salicylic acid which may have a substituent, benzylic acid which may have a substituent or a substituent. It is preferably mandelic acid which may be possessed.
Examples of the substituent include a halogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; a nitro group; a hydroxy group; an amino group.

Examples of salicylic acid that may have the above-mentioned substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, 4-bromosalicylic acid, and 3-methoxysalicylic acid. , 3-Nitrosalicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5,6-trichlorosalicylic acid, 3-hydroxy Salicylic acid (2,3-dihydroxysalicylic acid), 4-hydroxysalicylic acid (2,4-dihydroxysaltic acid), 5-hydroxysalicylic acid (2,5-dihydroxysalicylic acid), 6-hydroxysalicylic acid (2,6-dihydroxysaltic acid) Acid) and the like.

が挙げられる。 Examples of the benzylic acid which may have the above-mentioned substituent include, for example.

Can be mentioned.

等が挙げられる。 As the mandelic acid which may have the above-mentioned substituent, for example,

And so on.

Examples of the anion represented by the formula (1) include an anions represented by the following formula.

［式中、Ｒ⁶¹、Ｒ⁶²、Ｒ⁶³及びＲ⁶⁴は、それぞれ独立して、水素原子、ヒドロキシ基、アミノ基、ニトロ基、ハロゲン原子、炭素数１〜４のアルキル基、炭素数１〜４のハロアルキル基又は炭素数１〜４のアルコキシ基を表す。Ｍは、ホウ素原子又はアルミニウム原子を表す。］

[In the formula, R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently have a hydrogen atom, a hydroxy group, an amino group, a nitro group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, and 1 to 1 carbon atoms. Represents a haloalkyl group of 4 or an alkoxy group having 1 to 4 carbon atoms. M represents a boron atom or an aluminum atom. ]

For example, anions (BC-1) to anions (BC-24) shown in Table 1 can be mentioned. TBu in Table 1 represents a tert-butyl group.

Examples of the anion represented by the formula (1) include anions (BC-25) to (BC-28).

（式中、Ｍは、ホウ素原子又はアルミニウム原子を表す。）

(In the formula, M represents a boron atom or an aluminum atom.)

Among them, the anions represented by the formula (1) include anions (BC-1), anions (BC-2), anions (BC-3), anions (BC-25), anions (BC-26), and anions. (BC-27) is preferable, anion (BC-1) and anion (BC-25) are more preferable, and anion (BC-1) is more preferable. With these anions, the compound (AI) of the present invention tends to have excellent solubility in an organic solvent.

Examples of the fluorine-containing anion include anions represented by the formula (2), the formula (3), the formula (4), or the formula (5), and the anion represented by the formula (2) is preferable.

［式（２）中、Ｗ³及びＷ⁴はそれぞれ独立に、フッ素原子又は炭素数１〜４のフッ化アルキル基を表すか、又は、Ｗ³とＷ⁴とが結合して炭素数１〜４のフッ化アルカンジイル基を形成する。］
Ｗ³及びＷ⁴は炭素数１〜４のフッ化アルキル基が好ましく、トリフルオロメチル基又はペンタフルオロエチル基が好ましい。

[In the formula (2), W ³ and W ⁴ each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms, or W ³ and W ⁴ are bonded to each other and have 1 to 1 carbon atoms. Form the fluorinated alkanediyl group of 4. ]
W ³ and W ⁴ are preferably an alkyl fluoride group having 1 to 4 carbon atoms, and preferably a trifluoromethyl group or a pentafluoroethyl group.

［式（３）中、Ｗ⁵、Ｗ⁶及びＷ⁷はそれぞれ独立に、フッ素原子又は炭素数１〜４のフッ化アルキル基を表す。］

[In formula (3), W ⁵ , W ⁶ and W ⁷ each independently represent a fluorine atom or an alkyl fluoride group having 1 to 4 carbon atoms. ]

［式（４）中、Ｙ¹は炭素数１〜４のフッ化アルカンジイル基を表す。］

[In formula (4), Y ¹ represents an alkanediyl fluoride group having 1 to 4 carbon atoms. ]

［式（５）中、Ｙ²は炭素数１〜４のフッ化アルキル基を表す。］

[In formula (5), Y ² represents an alkyl fluoride group having 1 to 4 carbon atoms. ]

^{As the fluoroalkyl group having 1 to 4 carbon atoms represented by W 3 to} W ⁷ in the formulas (2) and (3), a perfluoroalkyl group is preferable, and for example, −CF ₃ , −CF ₂ CF ₃ , − CF ₂ CF ₂ CF ₃ , -CF (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) ₂ , -C (CF ₃ ) _3, etc. can be mentioned.

As the fluorinated alkanediyl group having 2 to 4 carbon atoms formed by bonding ^{W 3} and W ⁴ in the formula (2), _{a perfluoroalkanediyl group is preferable, and for example, −CF 2} CF ₂ −, _{−CF 2} CF ₂ CF ₂ −, − CF ₂ CF ₂ CF ₂ CF ₂ − and the like can be mentioned.

As the fluorinated alkanediyl group having 1 to 4 carbon atoms represented by ^{Y 1} in the formula (4), _{a perfluoroalkanediyl group is preferable, and for example, −CF 2} −, − CF ₂ CF ₂ −, −CF ₂ CF. ₂ CF ₂ −, −C (CF ₃ ) ₂ −, −CF ₂ CF ₂ CF ₂ CF ₂ − and the like can be mentioned.

As the fluoroalkyl group having 1 to 4 carbon atoms represented by ^{Y 2} in the formula (5), _{a perfluoroalkyl group is preferable, −CF 3} , −CF ₂ CF ₃ , −CF ₂ CF ₂ CF ₃ , −CF. (CF ₃ ) ₂ , -CF ₂ CF ₂ CF ₂ CF ₃ , -CF ₂ CF (CF ₃ ) ₂ , -C (CF ₃ ) _{3, and the} like can be mentioned.

Examples of the anion represented by the formula (2) (hereinafter, may be referred to as “anion (2)”) include the following anions (2-1) to (2-6).

Examples of the anion represented by the formula (3) (hereinafter, may be referred to as “anion (3)”) include the following anion (3-1).

Examples of the anion represented by the formula (4) (hereinafter, may be referred to as “anion (4)”) include the following anions (4-1) to (4-4).

Examples of the anion represented by the formula (5) (hereinafter, may be referred to as “anion (5)”) include the following anions (5-1) to (5-4).

Containing at least one anion (hereinafter sometimes referred to as "anion (2) to (5)") selected from the group consisting of anion (2), anion (3), anion (4) and anion (5). Therefore, the solubility of the compound (AI) of the present invention in an organic solvent can be improved. Among them, the anion (2) is preferable, and the anion (2-1) and the anion (2-2) are more preferable.

The X ^t- is preferably derived from a strong acid. The total acid dissociation constant pKa = -log ₁₀ ([H] ^t · [X ^t- ] / [XH _t ]) _{determined based on the molar concentration of XH t} formed from ^{X t-} and H ^{+ is} For example, it is 0 or less, preferably −0.5 or less, more preferably -10.0 or less, and -15.0 or more. Further, the total acid dissociation constant of _{XH t (pKa = -log 10} ([H] ^t · [X ^t- ] / [XH _t ])) or the acid dissociation constant at the first ionization step (pKa = -log _10). ^{X t- in} which ([H] / [(XH _t-1 ) ^-1 ] / [XH _t ]) is smaller than _{H 2} SO ₄ is preferable. Further, X ^t- derived from a strong acid is other than an organic acid. An acid is preferable, and an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon and phosphorus and oxygen as essential elements is more preferable.

Examples of the compound (AI) include the compounds specified in Table 2 in the formula (A-III).

The compound (AI) is a compound represented by the formula (MI) (hereinafter, may be referred to as “compound (MI)”) and the formula (M-IIA) and the formula (M-IIB). A compound represented by the formula (XI) by reacting with a represented compound (hereinafter, may be referred to as “compound (M-II)”) (hereinafter, may be referred to as “compound (XI)”). ), And the compound ( ^XI ) and Xt-t (Z ⁺ ) are reacted to produce the compound (XI).

（式中、Ｒ¹〜Ｒ¹⁰、ｐ、ｑ、Ｘ^t-、ｔは前記と同じ。Ｚ⁺は、リチウムイオン、ナトリウムイオン、カリウムイオンなどのアルカリ金属イオン、又はプロトンを表す）

(In the formula, R ^{1 to} R ¹⁰ , p, q, X ^t- , t are the same as above. Z ⁺ represents an alkali metal ion such as lithium ion, sodium ion, potassium ion, or proton)

<Coloring dispersion><Coloring curable resin composition>
The compound (AI) is useful as a colorant (A). The colorant (A) constitutes a color dispersion liquid together with the solvent (E) and the like. The colorant (A) constitutes a color-curable resin composition together with the resin (B), the polymerizable compound (C), the polymerization initiator (D) and the like. The color curable resin composition may contain a solvent (E). The color curable resin composition is useful for forming a coating film, the obtained coating film is used as a color filter, and the color filter is used for a display device.

<Colorant (A)>
The colorant (A) may be composed of only the compound (AI), or may further contain a colorant other than the compound (AI). The compound (AI) is, for example, 10% by mass or more, preferably 30% by mass or more, and more preferably 80% by mass or more in 100% by mass of the colorant (A).

Examples of the colorant other than the compound (AI) include a compound represented by the formula (BI) (hereinafter, may be referred to as “compound (BI)”).

[In the formula (BI ^{), R b1 to R b4} are independently of each other, a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have, and the methylene group (−CH ₂₋ ) contained in the saturated hydrocarbon group is −O−, −CO− or. It may be replaced by −N (R ^{b11) −.} R ^b1 and R ^b2 may be combined to form a ring containing a nitrogen atom, and R ^b3 and R ^b4 may be combined to form a ring containing a nitrogen atom.
R ^{b5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R b8, -SO 3 R b8 or -SO ₂ Represents N (R ^b9 ) (R ^b10 ).
R ^b6 and R ^b7 represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms independently of each other.
m represents an integer from 0 to 5. When m is 2 or more, a plurality of R ^b5s may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ^b11 ) ₄ , Na ⁺ or K ⁺ , and the four R ^b11s may be the same or different.
R ^b8 represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom.
R ^b9 and R ^b10 represent monovalent saturated hydrocarbon groups having 1 to 20 carbon atoms which may have hydrogen atoms or substituents independently of each other, and are contained in the saturated aliphatic hydrocarbon group-. CH ₂ − may be replaced by −O −, −CO−, −NH− or −N (R ^b8 ) −, and R ^b9 and R ^b10 are bonded to each other and contain nitrogen atoms 3 to 10 It may form a heterocyclic ring of members.
R ^b11 represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms. ]
In the formula (1a), when −SO ₃ ⁻ is present, the number is preferably 1.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{b1 to} R ^b4 include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group and a butylphenyl group.

The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R b8, -OH, -OR b8} , -SO 3 -, -SO 3 H, -SO 3 - Z +, - CO ₂ H, −CO ₂ R ^b8 , −SR ^b8 , −SO ₂ R ^b8 , −SO ₃ R ^b8 or −SO ₂ N (R ^b9 ) (R ^b10 ), these substituents are aromatic hydrocarbons. It is preferable to replace the hydrogen atom contained in the hydrogen group. Among them, as the _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - Z +, -SO 3 R b8 and ^{_{-SO 2 N (R b9) (}} R b10) are preferred, -SO ₃ ^—— Z ⁺ and −SO ₂ N (R ^b9 ) (R ^b10 ) are more preferred. In this case, as −SO ₃ ⁻ Z ⁺ , −SO ₃ ^{− +} N (R ^b11 ) ₄ is preferable. Further, as −SO ₂ N (R ^b9 ) (R ^b10 ), −SO ₂ NHR ^b9 is preferable. When R ^{b1 to} R ^b4 are these groups, a color filter containing less foreign matter and excellent heat resistance can be formed from the colored curable resin composition containing the compound (BI).

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{b1 to} R ^b4 and R ^{b8 to} R ^b11 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group and a heptyl group. , Octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group and other linear alkyl groups; isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group and other branched chain alkyl groups; Examples thereof include a cyclic alkyl group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group and a tricyclodecyl group.
The ^{hydrogen atom contained in the saturated hydrocarbon group in R b1 to} R ^b4 may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom as a substituent. R ^b1 As the saturated hydrocarbon substituted optionally aromatic carbon atoms which may 6-10 hydrocarbon group in which a hydrogen atom of the group to R ^b4, aromatic hydrocarbons having 6 to 10 carbon atoms in the R ^b1 to R ^b4 Examples thereof include groups similar to the groups exemplified as the groups.
The ^{hydrogen atom contained in the saturated hydrocarbon group in R b9} and R ^b10 may be substituted with, for example, a hydroxy group or a halogen atom as a substituent.

Examples of the ring formed by R ^b1 and R ^b2 together and the ring formed by R ^b3 and R ^b4 together include the following, and those containing no double bond are more preferable. ..

The −OR ^b8 includes, for example, an alkyloxy group such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a 2-ethylhexyloxy group and an icosyloxy group. Can be mentioned.

Examples of the −CO ₂ R ^b8 include an alkyloxycarbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group and an icosyloxycarbonyl group.

Examples of the −SR ^b8 include an alkylsulfanyl group such as a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group and an icosylsulfanyl group.

Examples of the −SO ₂ R ^b8 include an alkylsulfonyl group such as a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group and an icosylsulfonyl group.
Examples of the −SO ₃ R ^b8 include alkyloxysulfonyl groups such as methoxysulfonyl group, ethoxysulfonyl group, propoxysulfonyl group, tert-butoxysulfonyl group, hexyloxysulfonyl group and icosyloxysulfonyl group. The R ^b8 of -SO ₃ R ^b8, preferably branched chain alkyl group having 3 to 20 carbon atoms, more preferably a branched chain alkyl group having 6 to 12 carbon atoms, 2-ethylhexyl group is more preferred. It is possible to form a color filter that generates less foreign matter.

-SO ₂ N (R ^b9 ) (R ^b10 ) includes, for example, sulfamoyl group; N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl. Group, N-butyl sulfamoyl group, N-isobutyl sulfamoyl group, N-sec-butyl sulfamoyl group, N-tert-butyl sulfamoyl group, N-pentyl sulfamoyl group, N- (1) -Ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1) -Methylbutyl) sulfamoyl group, N- (2-methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentyl sulfamoyl group, N-hexyl sulfamoyl group, N- (1,3-dimethyl) Butyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptyl sulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octyl sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethylhexyl) sulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, etc. N-1 substituted sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl Examples thereof include N, N-2 substituted sulfamoyl groups such as groups.
In the above N-1-substituted sulfamoyl group, as R ^b8 , a branched chain alkyl group having 3 to 20 carbon atoms is preferable, a branched chain alkyl group having 6 to 12 carbon atoms is more preferable, and a 2-ethylhexyl group is further preferable. .. It is possible to form a color filter that generates less foreign matter.

The _{^{R b5, -CO 2 H, -CO}} 2 - Z +, -CO 2 R b8, -SO 3 -, -SO 3 - Z +, -SO 3 H or -SO ₂ NHR ^b9 are preferred, -SO ^{_{3 -, -SO 3 - Z +}} , -SO 3 H or -SO ₂ NHR ^b9 is more preferable.

Examples of the alkyl group having 1 to 6 carbon atoms in R ^b6 and R ^b7 include those having 1 to 6 carbon atoms among the alkyl groups listed above. Of these, hydrogen atoms are preferable as ^{R b6} and R ^b7.

^Examples of the aralkyl group having 7 to 10 carbon atoms in R b11 include a benzyl group, a phenylethyl group, a phenylbutyl group and the like.
As R ^b11 , a saturated hydrocarbon group or a benzyl group having 1 to 20 carbon atoms is preferable.

Z ⁺ is ⁺ N (R ^b11 ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ^b11 ) ₄ .
As the ⁺ N (R ^b11 ) ₄ , ^{it is preferable that at least two of the four R b11s} are monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total carbon number of the four R ^b11s is preferably 20 to 80, more preferably 20 to 60. ^{When +} N (R ^b11 ) ₄ is present in the compound (1a), ^{if R b11} is these groups, the color filter containing the compound (1a) and having less foreign matter can be obtained from the colored curable resin composition of the present invention. Can be formed.
m is preferably 1 to 4, more preferably 1 or 2.

As ^{the combination of R b1 to} R ^b4, a combination in which R ^b1 and R ^b3 are hydrogen atoms and R ^b2 and R ^b4 are aromatic hydrocarbon groups having a monovalent substituent having 6 to 10 carbon atoms is preferable. .. The substituent of the aromatic hydrocarbon _{^{group, -SO 3 -, -SO 3 H}} , -SO 3 - Z +, -SO 3 R b8 or -SO ₂ NHR ^b9 are preferred, -SO ₃ ^- Z ⁺ or -SO ₂ NHR ^b9 is more preferred. These substituents shall replace the hydrogen atom contained in the aromatic hydrocarbon group.

As the combination of ^{R b1 to} R ^{b4, a combination in which all of R b1 to} R ^b4 are monovalent saturated hydrocarbon groups is also preferable. In this case, the saturated hydrocarbon group is preferably a methyl group or an ethyl group.

Further, as a combination of ^{R b1 to} R ^{b4 , R b1} and R ^b3 are saturated hydrocarbon groups having 1 to 10 carbon atoms which may have a substituent, and R ^b2 and R ^b4 have a substituent. A combination of phenyl groups may also be preferred.
In this case, R ^b1 may form a ring with a substituent substituting the phenyl group of ^{R b2 , and R b3} may form a ring with the substituent substituting the phenyl group of R ^b4.
Further, ^{the carbon numbers of R b1} and R ^b3 are preferably 1 to 3 independently of each other. As ^{the substituent of the hydrogen atom contained in the saturated hydrocarbon group of R b1} and R ^b3 , an aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted with an alkoxy group having 1 to 3 carbon atoms, or a halogen. Atoms are preferred.
The ^{substituents that the phenyl group of R b2} and R ^b4 may have include an alkyl group having 1 to 4 carbon atoms, an alkylsulfanyl group having 1 to 4 carbon atoms or an alkylsulfonyl group having 1 to 4 carbon atoms. Is preferable, an alkyl group having 1 to 4 carbon atoms is more preferable, and a methyl group is even more preferable. The number of substituents substituting the phenyl group of R ^b2 and R ^b4 is 0 to 5, preferably 0 to 2, and more preferably 0 or 1.
^Examples of the alkyl group having 1 to 4 carbon atoms that may replace the phenyl group of R ^b2 and R b4 include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert. -Butyl group and the like can be mentioned.
Further, ^{as the alkylsulfanyl group having 1 to 4 carbon atoms which may replace the phenyl group of R b2} and R ^b4, a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, an isopropylsulfanyl group and the like can be used. Can be mentioned.
Further, ^{examples of the alkylsulfonyl group having 1 to 4 carbon atoms which may replace the phenyl group of R b2} and R b4 include a methyl sulfonyl group, an ethyl sulfonyl group, a propyl sulfonyl group, a butyl sulfonyl group and an isopropyl sulfonyl group. Can be mentioned.

Examples of the compound (BI) include compounds represented by the formulas (1-1) to (1-43). In the formula, R ⁴⁰ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched chain alkyl group having 6 to 12 carbon atoms, and more preferably a 2-ethylhexyl group.

Examples of the compound (BI) further include a compound having a structure in which an aromatic heterocycle having 3 to 9 carbon atoms is bonded to the 9-position carbon of the xanthene ring. The aromatic heterocycle may have a substituent.
Examples of the compound (BI) include compounds represented by the formulas (1-1) to (1-8), C.I. I. C.I., a quaternary ammonium salt of Acid Red 289 (eg, a compound represented by the formula (1-11) or the formula (1-12)). I. Sulfonamides of Acid Violet 102 and C.I. I. The quaternary ammonium salt of acid violet 102 is preferable, the compounds represented by the formulas (1-1) to (1-8), and the compounds represented by the formulas (1-11) and (1-12). Is preferable.
Further, compounds represented by the formulas (1-24) to (1-33) are also preferable because they are excellent in solubility in an organic solvent.

As the compound (BI), a commercially available xanthene dye (for example, "Chugai Aminol Fast Pink RH / C" manufactured by Chugai Pharmaceutical Co., Ltd., "Rhodamin 6G" manufactured by Taoka Chemical Industry Co., Ltd.) should be used. Can be done. Further, it is also possible to synthesize using a commercially available xanthene dye as a starting material with reference to Japanese Patent Application Laid-Open No. 2010-32999.

The content of the compound (BI) is, for example, 0 parts by mass or more, preferably 3 parts by mass or more, more preferably 5 parts by mass or more, and for example, 50 parts by mass in 100 parts by mass of the colorant (A). Hereinafter, it is preferably 30 parts by mass or less, more preferably 20 parts by mass or less.
The compound (BI) is, for example, 0 parts by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, and for example, 100 parts by mass with respect to 100 parts by mass of the compound (AI). It is not less than parts by mass, preferably 90 parts by mass or less, and more preferably 70 parts by mass or less.

The colorant (A) may contain a colorant other than the compound (AI) and the compound (BI), and the colorant other than the compound (AI) and the compound (BI) may be contained. May be a dye (hereinafter, may be referred to as “dye (A)”) or a pigment (hereinafter, may be referred to as “pigment (A)”).

The dye (A) is not particularly limited, and known dyes can be used, and examples thereof include solvent dyes, acid dyes, direct dyes, and mordant dyes. Examples of dyes include compounds classified by the Color Index (The Society of Dyers and Colorists) as having a hue other than pigments, and known dyes described in dyeing notes (color dyeing company). Be done. Also, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, phthalocyanine dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridin dyes, styryl dyes, coumarin dyes, quinoline. Examples include dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferred.

Specifically, C.I. I. Solvent Yellow 4 (Hereinafter, the description of CI Solvent Yellow is omitted and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99. 117, 162, 163, 167, 189;
C. I. Solvent Red 45, 49, 111, 125, 130, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56, 77, 86 ,;
C. I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;
C. I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 45, 58, 59, 59: 1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139;
C. I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and the like. I. Solvent dye,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176,182,183,195,198,206,211,215,216,217,227,228,249,252,257,258,260,261,266,268,270, 274,277,280,281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
C. I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;
C. I. Acid Blue 1,3,5,7,9,11,13,15,17,18,22,23,24,25,26,27,29,34,38,40,41,42,43,45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90: 1, 91, 92, 93, 93: 1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324: 1, 335, 340;
C. I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50: 1, 58, 63, 65, 80, C.I. of 104, 105, 106, 109 and the like. I. Acid dye,
C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241 and 243, 246, 250;
C. I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
C. I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;
C. I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293;
C. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. Direct dye,
C. I. Disperse Yellow 51, 54, 76;
C. I. Disperse Violet 26, 27;
C. I. Disperse Blue 1, 14, 56, 60, etc. I. Disperse dye,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89;
C. I. Basic Violet 2;
C. I. Basic Red 9;
C. I. Basic Green 1; etc. C.I. I. Basic dye,
C. I. Reactive Yellow 2,76,116;
C. I. Reactive orange 16;
C. I. Reactive Red 36; etc. I. Reactive dye C. I. Modant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modant tread 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38 , 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95;
C. I. Modant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;
C. I. Modant Violet 1, 1: 1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28 , 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58;
C. I. Modant Blue 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39,40,41,43 , 44, 48, 49, 53, 61, 74, 77, 83, 84;
C. I. Modant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53, etc. I. Mordant dye,
C. I. C. of Bat Green 1 etc. I. Vat dyes and the like can be mentioned.
These dyes may be appropriately selected according to the spectral spectrum of the desired color filter.

As the pigment (A), a known pigment can be used without particular limitation, and examples thereof include pigments classified as pigments in 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, 194, 214;
C. I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;
C. I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265 and other red pigments;
C. I. Pigment Blue 15, 15: 3, 15: 4, 15: 6, 60 and other blue pigments; C.I. I. Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other violet pigments;
C. I. Pigment Green 7, 36, 58 and other green pigments;
C. I. Pigment brown 23, 25 and other brown pigments;
C. I. Examples thereof include black pigments such as Pigment Black 1 and 7.

The pigment (A) may be treated with a rosin, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the pigment surface with a polymer compound or the like, a sulfuric acid atomization method, etc., if necessary. It may be subjected to atomization treatment by the above, cleaning treatment with an organic solvent, water or the like for removing impurities, removal treatment of ionic impurities by an ion exchange method or the like.
The pigment (A) preferably has a uniform particle size. By carrying out the dispersion treatment by containing a pigment dispersant, it is possible to obtain a pigment dispersion liquid in which the pigment is uniformly dispersed in the solution.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. Pigment dispersants include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Zeneca Co., Ltd.), EFKA (manufactured by CIBA), and Ajinomoto Fine. Examples include (manufactured by Techno Co., Ltd.) and Disperbyk (manufactured by Big Chemie).
When a pigment dispersant is used, the amount used is, for example, 1 part by mass or more and 100 parts by mass or less, preferably 5 parts by mass or more and 50 parts by mass or less, based on 100 parts by mass of the total amount of the pigment (A). .. When the amount of the pigment dispersant used is in the above range, a pigment dispersion liquid in a uniformly dispersed state tends to be obtained.

The total amount of the dye (A) and the pigment (A) is, for example, 0 parts by mass or more, preferably 5 parts by mass or more, and for example, 90 parts by mass or less, preferably 50 parts by mass in 100 parts by mass of the colorant (A). It may be 20 parts by mass or less, 20 parts by mass or less, or 10 parts by mass or less.

As the colorant other than the compound (AI) and the compound (BI), the pigment (A) is preferable, and the blue pigment is more preferable. The blue pigment is, for example, 0 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, for example, 90 parts by mass or less, and 70 parts by mass in 100 parts by mass of the colorant (A). It may be as follows.
The blue pigment is, for example, 0 parts by mass or more, preferably 100 parts by mass or more, and 300 parts by mass or more, for example, 1000 parts by mass or less, preferably 700 parts by mass with respect to 100 parts by mass of the compound (AI). By mass or less, more preferably 500 parts by mass or less. Further, it may be 200 parts by mass or less, 100 parts by mass or less, or 10 parts by mass or less.

<Resin (B)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]; a structural unit derived from at least one (a) selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides (hereinafter, may be referred to as “(a)”), and 2 carbon atoms. A copolymer having a cyclic ether structure of ~ 4 and a structural unit derived from a monomer (b) having an ethylenically unsaturated bond (hereinafter, may be referred to as “(b)”);
Resin [K2]; Structural unit derived from (a), structural unit derived from (b), and monomer (c) copolymerizable with (a) (however, (a) and (b) are Different.) Copolymer having a structural unit derived from (hereinafter sometimes referred to as “(c)”);
Resin [K3]; a copolymer having a structural unit derived from (a) and a structural unit derived from (c);
Resin [K4]; A copolymer having a structural unit derived from (a) with (b) added and a structural unit derived from (c);
Resin [K5]; A copolymer having a structural unit obtained by adding (a) to a structural unit derived from (b) and a structural unit derived from (c);
Resin [K6]; A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to the structural unit derived from (b) and further adding a carboxylic acid anhydride.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid, 1,4-cyclohexendicarboxylic acid;
Methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo [2.2.1] hept-2-ene, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene, 5-carboxy-5-methylbicyclo [2.2.1] hept-2-ene, 5-carboxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-carboxy-6-methylbicyclo Bicyclounsaturated compounds containing a carboxy group such as [2.2.1] hept-2-ene and 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic acid anhydride, 4-vinylphthalic acid anhydride, 3,4,5,6-tetrahydrophthalic acid anhydride, 1,2,3,6- Unsaturated dicarboxylic acid anhydrides such as tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride;
Unsaturated mono [(meth) acryloyloxyalkyl] esters of divalent or higher valent carboxylic acids such as monosuccinic acid mono [2- (meth) acryloyloxyethyl] and mono [2- (meth) acryloyloxyethyl] phthalates. Kind;
Examples thereof include unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α- (hydroxymethyl) acrylic acid.
Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferable from the viewpoint of copolymerizability and solubility of the obtained resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxylan ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say. In (b), a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth) acryloyloxy group is preferable.
In addition, 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.

Examples of (b) include a monomer (b1) having an oxylanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single having an oxetanyl group and an ethylenically unsaturated bond. A metric (b2) (hereinafter sometimes referred to as "(b2)"), a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (b3) (hereinafter sometimes referred to as "(b3)"), etc. Can be mentioned.

As (b1), for example, a monomer (b1-1) having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized (hereinafter referred to as “(b1-1)”). There is), a monomer (b1-2) having an epoxidized structure of an alicyclic unsaturated hydrocarbon (hereinafter, may be referred to as “(b1-2)”).

Examples of (b1-1) include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p. -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (glycidyloxymethyl) styrene , 2,4-bis (glycidyloxymethyl) styrene, 2,5-bis (glycidyloxymethyl) styrene, 2,6-bis (glycidyloxymethyl) styrene, 2,3,4-tris (glycidyloxymethyl) styrene , 2,3,5-tris (glycidyloxymethyl) styrene, 2,3,6-tris (glycidyloxymethyl) styrene, 3,4,5-tris (glycidyloxymethyl) styrene, 2,4,6-tris (Glysidyloxymethyl) styrene and the like can be mentioned.

Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, seroxide 2000; manufactured by Daicel Co., Ltd.), and 3,4-epoxycyclohexylmethyl (meth) acrylate (for example,). Cyclomer A400; manufactured by Dycel Co., Ltd.), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Dycel Co., Ltd.), a compound represented by the formula (I) and a compound represented by the formula (II). Examples thereof include compounds represented by.

[In the formulas (I) and (II), R ^a and R ^b represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group is substituted with a hydroxy group. You may.
X ^a and X ^b is a single ^{bond, * - R c -, *} - R c -O -, * - represents the R ^c -S- or * -R ^c -NH-.
R ^c represents an alkanediyl group having 1 to 6 carbon atoms.
* Represents a bond with O. ]

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group and the like.
The alkyl groups in which the hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group and 1-hydroxy. Examples thereof include -1-methylethyl group, 2-hydroxy-1-methylethyl group, 1-hydroxybutyl group, 2-hydroxybutyl group, 3-hydroxybutyl group and 4-hydroxybutyl group.
Examples of R ^a and R ^b include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, and more preferably a hydrogen atom and a methyl group.

The alkanediyl group includes a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-. Examples include 1,6-diyl group.
Examples of X ^a and X ^b are preferably a single bond, a methylene group, an ethylene group, * -CH _2- O- and * -CH ₂ CH _2- O-, and more preferably a single bond, * -CH ₂ CH _2- O-can be mentioned (* represents a bond with O).

Examples of the compound represented by the formula (I) include compounds represented by any of the formulas (I-1) to (I-15). Among them, formula (I-1), formula (I-3), formula (I-5), formula (I-7), formula (I-9) or formula (I-11) to formula (I-15). The compound represented by the formula (I-1) is preferable, and the compound represented by the formula (I-1), the formula (I-7), the formula (I-9) or the formula (I-15) is more preferable.

Examples of the compound represented by the formula (II) include compounds represented by any of the formulas (II-1) to (II-15). Among them, formula (II-1), formula (II-3), formula (II-5), formula (II-7), formula (II-9) or formula (II-11) to formula (II-15). The compound represented by the formula (II-1), the formula (II-7), the formula (II-9) or the compound represented by the formula (II-15) is more preferable.

The compound represented by the formula (I) and the compound represented by the formula (II) may be used alone or in combination of two or more. When the compound represented by the formula (I) and the compound represented by the formula (II) are used in combination, the content ratio thereof [the compound represented by the formula (I): the compound represented by the formula (II)] is On a molar basis, it is preferably 5:95 to 95: 5, more preferably 20:80 to 80:20.

As (b2), a monomer having an oxetanyl group and a (meth) acryloyloxy group is more preferable. Examples of (b2) include 3-methyl-3-methacrylloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, and 3-ethyl-3-acryloyloxymethyloxetane. , 3-Methyl-3-methacryloyloxyethyl oxetane, 3-methyl-3-acryloyloxyethyl oxetane, 3-ethyl-3-methacryloyloxyethyl oxetane, 3-ethyl-3-acryloyloxyethyl oxetane and the like.

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

As (b), (b1) is preferable in that the reliability of the obtained color filter such as heat resistance and chemical resistance can be further improved. Further, (b1-2) is more preferable in that the color-curable resin composition has excellent storage stability.

Examples of (c) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] Decane-8-yl (meth) acrylate (In the art, it is commonly referred to as "dicyclopentanyl (meth) acrylate", and in the case of "tricyclodecyl (meth) acrylate". ), Tricyclo [5.2.1.0 ^2,6 ] decene-8-yl (meth) acrylate (in the art, it is commonly referred to as "dicyclopentenyl (meth) acrylate". ), Dicyclopentanyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (Meta) acrylic acid esters such as (meth) acrylate;
Hydroxy group-containing (meth) acrylic acid esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate;
Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconic acid;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2'-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2] .1] Hept-2-ene, 5,6-di (hydroxymethyl) bicyclo [2.2.1] Hept-2-ene, 5,6-di (2'-hydroxyethyl) bicyclo [2.2. 1] Hept-2-ene, 5,6-dimethoxybicyclo [2.2.1] hept-2-ene, 5,6-diethoxybicyclo [2.2.1] hept-2-ene, 5-hydroxy -5-Methylbicyclo [2.2.1] hept-2-ene, 5-hydroxy-5-ethylbicyclo [2.2.1] hept-2-ene, 5-hydroxymethyl-5-methylbicyclo [2] .2.1] Hept-2-ene, 5-tert-butoxycarbonylbicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylbicyclo [2.2.1] hept-2-ene, 5-Phenoxycarbonylbicyclo [2.2.1] hept-2-ene, 5,6-bis (tert-butoxycarbonyl) bicyclo [2.2.1] hept-2-ene, 5,6-bis (cyclohexyl) Bicyclounsaturated compounds such as oxycarbonyl) bicyclo [2.2.1] hept-2-ene;
N-Phenylmaleimide, N-Cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide caproate, N-succinimidyl-3 -Dicarbonylimide derivatives such as maleimide propionate, N- (9-acridinyl) maleimide;
Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, vinyltoluene, 2-hydroxyethyl (meth) acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo [2.2. 1] Hept-2-ene and the like are preferable.

In the resin [K1], the ratio of the structural units derived from each is the ratio of all the structural units constituting the resin [K1].
Structural unit derived from (a); 2-60 mol%
Structural unit derived from (b); 40-98 mol%
Is preferable
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (b); 50-90 mol%
Is more preferable.
When the ratio of the structural units of the resin [K1] is within the above range, the color-curable resin composition is excellent in storage stability, developability when forming a color pattern, and solvent resistance of the obtained color filter. Tend.

The resin [K1] is, for example, the method described in the document "Experimental Method for Polymer Synthesis" (written by Takayuki Otsu, Kagaku-Dojin Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the relevant document. It can be manufactured with reference to the cited documents described in.

Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent and the like are placed in a reaction vessel, and for example, oxygen is replaced with nitrogen to create a deoxidized atmosphere, and the mixture is stirred. Examples thereof include a method of heating and keeping warm. The polymerization initiator, solvent and the like used here are not particularly limited, and those usually used in the art can be used. For example, as the polymerization initiator, an azo compound (2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), etc.) or an organic peroxide (benzoyl peroxide, etc.) As the solvent, any solvent may be used as long as it dissolves each monomer, and examples of the solvent (E) of the colored curable resin composition of the present invention include a solvent described later.

As the obtained copolymer, the solution after the reaction may be used as it is, a concentrated or diluted solution may be used, or the copolymer is taken out as a solid (powder) by a method such as reprecipitation. You may use the one. In particular, by using the solvent contained in the color curable resin composition of the present invention as a solvent during this polymerization, the solution after the reaction can be used as it is for the preparation of the color curable resin composition of the present invention. Therefore, the manufacturing process of the colored curable resin composition of the present invention can be simplified.

In the resin [K2], the ratio of the structural units derived from each is the ratio of all the structural units constituting the resin [K2].
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2-95 mol%
Structural unit derived from (c); 1-65 mol%
Is preferable
Structural unit derived from (a); 5-40 mol%
Structural unit derived from (b); 5-80 mol%
Structural unit derived from (c); 5-60 mol%
Is more preferable.
When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the color-curable resin composition, the developability when forming a color pattern, and the solvent resistance of the obtained color filter, It tends to have excellent heat resistance and mechanical strength.

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

In the resin [K3], the ratio of the structural units derived from each is the ratio of all the structural units constituting the resin [K3].
Structural unit derived from (a); 2-60 mol%
Structural unit derived from (c); 40-98 mol%
Is preferable
Structural unit derived from (a); 10-50 mol%
Structural unit derived from (c); 50-90 mol%
Is more preferable.
The resin [K3] can be produced, for example, in the same manner as the method described as the method for producing the resin [K1].

The resin [K4] is obtained by obtaining a copolymer of (a) and (c), and a carboxylic acid and / or a carboxylic acid anhydride having (a) a cyclic ether having 2 to 4 carbon atoms of (b). It can be manufactured by adding it to.
First, the copolymer of (a) and (c) is produced in the same manner as the method described as the method for producing the resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that mentioned in the resin [K3].

Next, the cyclic ether having 2 to 4 carbon atoms of (b) is reacted with a part of the carboxylic acid and / or the carboxylic acid anhydride derived from (a) in the copolymer.
Following the production of the copolymer of (a) and (c), the atmosphere in the flask was replaced with air from nitrogen, and (b) a reaction catalyst of the carboxylic acid or carboxylic acid anhydride and the cyclic ether (for example, Tris (for example, Tris). The resin [K4] can be produced by putting a dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (for example, hydroquinone, etc.) in a flask and reacting at 60 to 130 ° C. for 1 to 10 hours, for example. can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, based on 100 mol of (a). Within this range, the storage stability of the colored curable resin composition, the developability when forming a pattern, and the balance between the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained pattern are improved. Tend. Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K4], and (b1-1) is more preferable.
The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total amount of (a), (b) and (c).
The reaction conditions such as the charging method, the reaction temperature and the time can be appropriately adjusted in consideration of the production equipment, the calorific value due to the polymerization and the like. As with the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value due to the polymerization, and the like.

As the first step, the resin [K5] obtains a copolymer of (b) and (c) in the same manner as in the above-mentioned method for producing the resin [K1]. In the same manner as above, the obtained copolymer may be a solution after the reaction as it is, a concentrated or diluted solution may be used, or a solid (powder) may be used by a method such as reprecipitation. You may use the one taken out as.
The ratio of the structural units derived from (b) and (c) is, respectively, with respect to the total number of moles of all the structural units constituting the copolymer.
Structural unit derived from (b); 5 to 95 mol%
Structural unit derived from (c); 5 to 95 mol%
Is preferable
Structural unit derived from (b); 10-90 mol%
Structural unit derived from (c); 10-90 mol%
Is more preferable.

Further, under the same conditions as the method for producing the resin [K4], the carboxylic acid or carboxylic acid anhydride of (a) is added to the cyclic ether derived from (b) of the copolymer of (b) and (c). The resin [K5] can be obtained by reacting an object.
The amount of (a) used to react with the copolymer is preferably 5 to 80 mol with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and the unreacted (b) is unlikely to remain, (b1) is preferable as the (b) used for the resin [K5], and (b1-1) is more preferable.

The resin [K6] is a resin obtained by further reacting the resin [K5] with a carboxylic acid anhydride. The carboxylic acid anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic acid anhydride.
Examples of the carboxylic acid anhydride include maleic anhydride, citraconic acid anhydride, itaconic acid anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1 , 2,3,6-Tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo [2.2.1] hept-2-ene anhydride and the like. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mol with respect to 1 mol of the amount used in (a).

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer and 3,4-epoxytricyclo [5.2.1.02.6]. Resin such as decyl acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meth) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decylacrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- (meth) ) Acrylic loyloxymethyloxetane / (meth) acrylic acid / resin such as styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) acrylic acid copolymer, etc. Resin [K3]; tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, which is a resin obtained by adding glycidyl (meth) acrylate to a benzyl (meth) acrylate / (meth) acrylic acid copolymer. Resin with glycidyl (meth) acrylate added to, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / resin with glycidyl (meth) acrylate added to (meth) acrylic acid copolymer [K4 ]; A resin obtained by reacting a (meth) acrylic acid with a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate, a copolymer of tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate. Resin such as a resin reacted with (meth) acrylic acid [K5]; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid and further tetrahydrophthal. Examples thereof include a resin [K6] such as a resin obtained by reacting an acid anhydride.
Among them, as the resin (B), the resin [K1] and the resin [K2] are preferable, and the resin [K2] is particularly preferable.

The polystyrene-equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and even more preferably 5,000 to 30,000. .. When the molecular weight is within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the developing solution is good, and the resolution of the coloring pattern tends to be improved.
The molecular weight distribution dispersion degree [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) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, still more preferably 70 to 135 mg-KOH / g in terms of solid content. be. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (B), and can be obtained by titration using, for example, an aqueous potassium hydroxide solution. ..

The content of the resin (B) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass in the total solid content of 100% by mass. When the content of the resin (B) is within the above range, a colored pattern can be formed, and the resolution and residual film ratio of the colored pattern tend to be improved.

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

Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Etc., as well as the above-mentioned (a), (b) and (c).

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

Above all, the polymerizable compound (C) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylol propantri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (dipentaerythritol hexa (). Meta) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl ) Isocyanurate, ethylene glycol-modified pentaerythritol tetra (meth) acrylate, ethylene glycol-modified dipentaerythritol hexa (meth) acrylate, propylene glycol-modified pentaerythritol tetra (meth) acrylate, propylene glycol-modified dipentaerythritol hexa (meth) acrylate, Examples thereof include caprolactone-modified pentaerythritol tetra (meth) acrylate and caprolactone-modified dipentaerythritol hexa (meth) acrylate, and among them, dipentaerythritol penta (meth) acrylate and dipentaerythritol hexa (meth) acrylate are preferable.

The weight average molecular weight of the polymerizable compound (C) is preferably 150 or more and 2,900 or less, and more preferably 250 or more and 1,500 or less.
The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of solid content. be.
The content ratio of the resin (B) to the polymerizable compound (C) [resin (B): polymerizable compound (C)] is based on mass, preferably 20:80 to 80:20, more preferably. Is 35: 65-80: 20.
When the content of the polymerizable compound (C) is within the above range, the residual film ratio at the time of forming the coloring pattern and the chemical resistance of the color filter tend to be improved.

<Polymerization initiator (D)>
The polymerization initiator (D) is not particularly limited as long as it is a compound that can initiate polymerization by generating active radicals, acids and the like by the action of light or heat, and a known polymerization initiator can be used.
Examples of the polymerization initiator (D) include an O-acyloxime compound, an alkylphenone compound, a biimidazole compound, a triazine compound, an acylphosphine oxide compound and the like.

The O-acyloxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxym compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6-] (2-Methylbenzoyl) -9H-carbazole-3-yl] Etan-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2,, 3-dimethyl-2,) 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazole-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole) -3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -3-cyclopentylpropane- 1-on-2-imine and the like can be mentioned. Commercially available products such as Irgacure OXE01, OXE02 (all manufactured by BASF) and N-1919 (manufactured by ADEKA) may be used. Among them, the O-acyloxym compounds are N-benzoyloxy-1- (4-phenylsulfanylphenyl) butane-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1. At least one selected from the group consisting of −on-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine is preferable, and N-benzoyloxy is preferable. -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred.

The alkylphenone compound is, for example, a compound having a partial structure represented by the formula (d2) or a partial structure represented by the formula (d3). In these partial structures, the benzene ring may have a substituent.

Examples of the compound having a partial structure represented by the formula (d2) include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one and 2-dimethylamino-1- (4). -Morholinophenyl) -2-benzylbutane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butane-1-one And so on. Commercially available products such as Irgacure 369, 907, 379 (all manufactured by BASF) may be used.
Examples of the compound having a partial structure represented by the formula (d3) include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-hydroxy-2-methyl-1- [4- (2). -Hydroxyethoxy) phenyl] Propane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one oligomer, α, α-diethoxy Examples thereof include acetophenone and benzyldimethylketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

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

［式（ｄ５）中、Ｒ¹³〜Ｒ¹⁸は、置換基を有していてもよい炭素数６〜１０のアリール基を表す。］

[In the formula (d5), R ^{13 to} R ¹⁸ represent an aryl group having 6 to 10 carbon atoms which may have a substituent. ]

Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group and a naphthyl group, and a phenyl group is preferable.
Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a chlorine atom is preferable. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group and the like, and a methoxy group is preferable.

Examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole and 2,2'-bis (2,3-dichlorophenyl) -4. , 4', 5,5'-tetraphenylbiimidazole (see, for example, JP-A-6-75372, JP-A-6-75373, etc.), 2,2'-bis (2-chlorophenyl) -4, 4', 5,5'-Tetraphenyl biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole, 2,2'-bis (2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole 2-Chlorophenyl) -4,4', 5,5'-tetra (dialkoxyphenyl) biimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (trialkoxy) Phenyl) Biimidazole (see, for example, Japanese Patent Application Laid-Open No. 48-38403, Japanese Patent Application Laid-Open No. 62-174204, etc.), the phenyl group at the 4,4', 5,5'-position is substituted with a carboalkoxy group. Examples thereof include imidazole compounds (see, for example, Japanese Patent Laid-Open No. 7-10913). Of these, compounds represented by the following formulas and mixtures thereof are preferable.

Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6- (4-). Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxy) Styryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4 -Bis (trichloromethyl) -6- [2- (fran-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-) 2-Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. Can be mentioned.

Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

Further, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; benzophenone, o-methyl benzoyl benzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4'-methyldiphenylsulfide, 3,3', 4,4'-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthlenquinone, Kinon compounds such as 2-ethylanthraquinone and camphorquinone; examples thereof include 10-butyl-2-chloroacrydone, benzyl, methyl phenylglycioxylate, titanosen compounds and the like.
These are preferably used in combination with the polymerization initiation aid (D1) (particularly amines) described later.

The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound and a biimidazole compound, and more preferably. Is a polymerization initiator containing an O-acyloxime compound.

The content of the polymerization initiator (D) is preferably 0.1 to 40 parts by mass, more preferably 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). It is a mass part.

<Polymerization initiation aid (D1)>
The color curable resin composition may contain a polymerization initiation aid (D1). The polymerization initiator (D1) is a compound or a sensitizer used to promote the polymerization of the polymerizable compound 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 initiation aid (D1) include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and 4 -2-Ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4'-bis (diethylamino) benzophenone, 4,4'-bis Examples thereof include (ethylmethylamino) benzophenone, and among them, 4,4'-bis (diethylamino) benzophenone is preferable. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may be used.

Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and 9,10-di. Examples thereof include butoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene and the like.

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

Examples of the carboxylic acid compound include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, and dichlorophenylsulfanylacetic acid. Examples thereof include N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

When these polymerization initiation aids (D1) are used, the content thereof 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). It is preferably 1 to 20 parts by mass. When the amount of the polymerization initiation aid (D1) is within this range, a coloring 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 and not containing -COO-), ether ester solvent (solvent in the molecule). Solvent containing -COO- and -O-), Ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (solvent containing OH in the molecule, -O-,- CO- and -COO-free solvents), aromatic hydrocarbon solvents, amide solvents, dimethylsulfoxide and the like.

Ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate. , Methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, γ-butyrolactone and the like.

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

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

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone. And so on.

Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, glycerin and the like.
Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, mesitylene and the like.
Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and the like.

These solvents may be used alone or in combination of two or more.
Among them, propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 3-methoxybutyl acetate, 3- Preference is given to methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like, such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether and di. More preferred are propylene glycol methyl ether acetate, ethyl lactate, 3-methoxybutyl acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate and N-methylpyrrolidone.

The content of the solvent (E) is preferably 70 to 95% by mass, more preferably 75 to 92% by mass, based on the total amount of the colored curable resin composition. In other words, the solid content of the colored curable resin composition is preferably 5 to 30% by mass, more preferably 8 to 25% by mass. When the content of the solvent (E) is in the above range, the flatness at the time of coating is good, and the color density is not insufficient when the color filter is formed, so that the display characteristics tend to be good.
The content of the solvent (E) is preferably 1 to 99% by mass, more preferably 10 to 90% by mass, based on the total amount of the colored dispersion.

<Surfactant (F)>
The color curable resin composition may contain a surfactant (F). The surfactant (F) can be used as a leveling agent, and examples thereof 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 the molecule. Specifically, Torre 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, TSF4460 (manufactured by Momentive Performance Materials Japan GK) 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 Co., Ltd.), Megafuck (registered trademark) F142D, F171, F172, F173, F177, F183, F554, and F554. R30, RS-718-K (manufactured by DIC Co., Ltd.), Ftop (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronics 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 Laboratory Co., Ltd.).

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 MegaFvck (registered trademark) R08, BL20, F475, F477 and F443 (manufactured by DIC Corporation).

When the surfactant (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.% by mass, based on the total amount of the colored curable resin composition. It is 002% by mass or more and 0.1% by mass or less, more preferably 0.005% by mass or more and 0.07% by mass or less. 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 curable resin composition of the present invention is an additive known in the art such as a filler, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents and the like, if necessary. May include.

<Manufacturing method of color filter and liquid crystal display device>
Examples of the method for forming the coating film and the color filter by the colored curable resin composition of the present invention include a photolithography method, an inkjet method, a printing method and the like. Of these, the photolithography method is preferable. The photolithography method is a method in which the colored curable resin composition is applied to a substrate and dried to form a composition layer, and the composition layer is exposed and developed through a photomask. In the photolithography method, a colored coating film which is a cured product of the composition layer can be formed by not using a photomask at the time of exposure and / or not developing the photomask.

The film thickness of the color filter (cured film) is preferably 20 μm or less, more preferably 6 μm or less, still more preferably 3 μm or less, preferably 0.1 μm or more, more preferably 0.2 μm or more, still more preferably 0. It is 3 μm or more.

The substrate includes a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is silica-coated, a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate, silicon, or on the substrate. Aluminum, silver, silver / copper / palladium alloy thin films, etc. are formed on the glass. Another color filter layer, resin layer, transistor, circuit and the like may be formed on these substrates. Further, a substrate obtained by subjecting the silicon substrate to HMDS treatment may be used.

The formation of each color pixel by the photolithography method can be performed by a known or conventional device or condition. For example, it can be produced as follows. First, a colored curable resin composition is applied onto a substrate and dried by heat drying (pre-baking) and / or vacuum drying to remove volatile components such as a solvent to obtain a smooth composition layer. Examples of the coating method include a spin coating method, a slit coating method, a slit and spin coating method, and the like. The temperature for heat drying is preferably 30 to 120 ° C, more preferably 50 to 110 ° C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When drying under reduced pressure, it is preferable to carry out drying under a pressure of 50 to 150 Pa in a temperature range of 20 to 25 ° C. The film thickness of the composition layer is not particularly limited, and may be appropriately selected depending on the film thickness of the target color filter.

The composition layer is then exposed via a photomask to form the desired coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used. As the light source used for exposure, a light source that generates light having a wavelength of 250 to 450 nm is preferable. For example, light less than 350 nm is cut by using a filter that cuts this wavelength range, and light near 436 nm, 408 nm, and 365 nm is selectively extracted by using a bandpass filter that extracts these wavelength ranges. You may do it. Specific examples thereof include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps and the like. Since it is possible to uniformly irradiate the entire exposed surface with parallel rays and accurately align the photomask with the substrate, it is possible to use a reduced projection exposure device such as a mask aligner and a stepper or a proximity exposure device. preferable.

A colored pattern is formed on the substrate by bringing the exposed composition layer into contact with a developing solution for development. By development, the unexposed portion of the composition layer is dissolved in the developer and removed. As the developing solution, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. Further, the developer may contain a surfactant. The developing method may be any of a paddle method, a dipping method, a spray method and the like. Further, the substrate may be tilted at an arbitrary angle during development.
After development, it is preferable to wash with water.

Further, it is preferable to post-bake the obtained coloring pattern. The post-bake temperature is preferably 80 to 250 ° C, more preferably 100 to 245 ° C. The post-baking time is preferably 1 to 120 minutes, more preferably 2 to 30 minutes.

The colored pattern and the colored coating film thus obtained are useful as a color filter, and the color filter can be used for a display device (for example, a liquid crystal display device, an organic EL device, etc.), an electronic paper, a solid-state image pickup element, or the like. It is useful as a color filter used.

According to the color-curable resin composition of the present invention, it is possible to produce a color filter having a particularly excellent pattern shape. 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. In the examples,% and parts representing the content or the amount used are based on mass unless otherwise specified.
In the following synthetic examples, the structure of the compound was identified by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

[Synthesis Example 1]
To a flask equipped with a stirrer, 1 part of phenothiazine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 33 parts of methylene chloride were added and mixed at room temperature. Under stirring, a solution prepared by dissolving 4 parts of iodine (manufactured by Kanto Chemical Co., Inc.) in 100 parts of methylene chloride was slowly added, and the mixture was stirred at room temperature for 5 hours. After completion of the reaction, the precipitated solid was separated by filtration, washed with methylene chloride three times, and then dried under reduced pressure at 60 ° C. overnight to obtain 3.2 parts of the compound represented by the formula (MI-1). ..

Identification of the compound represented by the formula (MI-1) (mass spectrometry) Ionization mode = ESI ⁺ : m / z = 198.0 [MI ₄ ] ⁺
Exact Mass: 705.7

[Synthesis Example 2]
To a flask equipped with a stirrer, 1 part of the compound represented by the formula (MI-1) and 30 parts of methanol were added and mixed at room temperature. Under stirring, a solution prepared by dissolving 0.9 part of aniline (manufactured by Tokyo Chemical Industry Co., Ltd.) in 15 parts of methanol was slowly added, and the mixture was stirred overnight at room temperature. After completion of the reaction, the solvent was distilled off and 70 parts of diethyl ether was added. The precipitated solid was separated by filtration, washed twice with diethyl ether, and then dried under reduced pressure at 60 ° C. overnight to obtain 0.37 part of the compound represented by the formula (XI-1) (yield 52). %).

Identification of the compound represented by the formula (XI-1) (mass spectrometry) Ionization mode = ESI ⁺ : m / z = 380.1 [M-I] ⁺
Exact Mass: 507.0

[Synthesis Example 3]
To a flask equipped with a cooling tube and a stirrer, 0.8 part of the compound represented by the formula (XI-1) and 16 parts of methanol were added and mixed at 50 ° C. Under stirring, a solution prepared by dissolving 4.6 parts of phosphotungstic acid / n-hydrate (manufactured by Sigma-Aldrich Co., Ltd.) in 18 parts of methanol was slowly added, and the mixture was stirred at 50 ° C. for 9 hours. The obtained reaction solution was cooled to room temperature, the precipitated crystals were separated by filtration, washed twice with methanol, dried under reduced pressure at 60 ° C. overnight, and compound 0 represented by the formula (AI-1). .7 parts were obtained (yield 54%).

[Synthesis Example 4]
The formula was the same as in Synthesis Example 2 except that N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of aniline (manufactured by Tokyo Chemical Industry Co., Ltd.) in Synthesis Example 2. 2.1 parts of the compound represented by (XI-2) were obtained (yield 22%).

Identification of the compound represented by the formula (XI-2) (mass spectrometry) Ionization mode = ESI ⁺ : m / z = 408.2 [M-I] ⁺
Exact Mass: 535.1

[Synthesis Example 5]
In the same manner as in the synthesis example 3, except that the compound represented by the formula (XI-2) was used instead of the compound represented by the formula (XI-1) in the synthesis example 3. 0.9 part of the compound represented by the formula (AI-2) was obtained (yield 67%).

[Synthesis Example 6]
In the above synthesis example 2, the formula (in the same manner as in the above synthesis example 2) is that o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) is used instead of aniline (manufactured by Tokyo Chemical Industry Co., Ltd.). 5.1 parts of the compound represented by XI-3) was obtained (yield 46%).

Identification of the compound represented by the formula (XI-3) (mass spectrometry) Ionization mode = ESI ⁺ : m / z = 408.2 [M-I] ⁺
Exact Mass: 535.1

[Synthesis Example 7]
In the same manner as in the synthesis example 3, except that the compound represented by the formula (XI-3) was used instead of the compound represented by the formula (XI-1) in the synthesis example 3. 1.9 parts of the compound represented by the formula (AI-3) was obtained (yield 92%).

[Synthesis Example 8]
In Synthetic Example 2, 3-aminobenzotrifluoride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of aniline (manufactured by Tokyo Chemical Industry Co., Ltd.) in the same manner as in Synthetic Example 2. , 1.2 parts of the compound represented by the formula (XI-4) were obtained. (Yield 53%)

Identification of the compound represented by the formula (XI-4) (mass spectrometry) Ionization mode = ESI ⁺ : m / z = 516.1 [MI] ⁺
Exact Mass: 643.0

[Synthesis Example 9]
In the same manner as in the synthesis example 3, except that the compound represented by the formula (XI-4) was used instead of the compound represented by the formula (XI-1) in the synthesis example 3. 0.9 part of the compound represented by the formula (AI-4) was obtained. (Yield 71%)

[Synthesis Example 10]
To a flask equipped with a cooling tube and a stirrer, 0.8 part of the compound represented by the formula (XI-3) and 12 parts of N-methylpyrrolidone were added and mixed at 50 ° C. Under stirring, a solution prepared by dissolving 0.5 part of bistrifluoromethylsulfonamide (manufactured by Tokyo Chemical Industry Co., Ltd.) in 2.7 parts of N-methylpyrrolidone was slowly added, and the mixture was stirred at 50 ° C. for 9 hours. .. The obtained reaction solution was cooled to room temperature and then added to 50 parts of a 5 wt% sodium chloride aqueous solution to prepare a suspension. The precipitated crystals were separated by filtration, washed twice with ion-exchanged water, and dried under reduced pressure at 60 ° C. overnight to obtain 0.8 parts of the compound represented by the formula (AI-5). (Yield 80%)

[Synthesis Example 11]
In the same manner as in the synthesis example 10, except that the compound represented by the formula (XI-4) was used instead of the compound represented by the formula (XI-3) in the synthesis example 10. 0.4 part of the compound represented by the formula (AI-6) was obtained. (Yield 60%)

[Synthesis Example 12]
A compound represented by the formula (I-132) (hereinafter, may be referred to as “dye (BI-1)”) was synthesized by the method described in JP-A-2013-64096.

[Synthesis Example 13]
An appropriate amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the nitrogen atmosphere, 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 ] decane-8-ylacrylate and 3,4-epoxytricyclo [5.2.2.10 ^{2, 6} ] A mixed solution of 25 parts of a mixture of decane-9-ylacrylate (content ratio is 1: 1 in molar ratio), 137 parts of N-cyclohexylmaleimide, 50 parts of 2-hydroxyethylmethacrylate, and 338 parts of propylene glycol monomethyl ether acetate. It was dropped over 5 hours. On the other hand, a solution prepared by dissolving 5 parts of 2,2-azobisisobutyronitrile in 88 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After completion of the dropping, the solution was held at 85 ° C. for 4 hours, cooled to room temperature, and measured with a B-type viscometer (23 ° C.) to have a viscosity of 23 mPas and a solid content of 25.6% in a copolymer (resin B-1) solution. Got The weight average molecular weight Mw of the produced copolymer was 8.0 × 10 ³ , the dispersity was 2.1, and the acid value in terms of solid content was 109 mg-KOH / g. Resin B-1 has the following structural units.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the resin were measured by using the GPC method under the following conditions.
Equipment; K2479 (manufactured by Shimadzu Corporation)
Column; SHIMADZU Shima-pack GPC-80M
Column temperature; 40 ° C
Solvent; Tetrahydrofuran (THF)
Test solution concentration; 25 mg / mL (solvent; THF)
Flow rate; 1.0 mL / min
Detector; RI
Calibration standard material; TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the polystyrene-equivalent weight average molecular weight and the number average molecular weight obtained above was defined as the degree of dispersion (Mw / Mn).

Example 1
<Preparation of Color Curable Resin Composition>
(A) Colorant: Dye (AI-1) 5.7 parts (B) Resin: Resin (B-1) (solid content equivalent) 50 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad) (Registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered) Trademark) OXE 01; manufactured by BASF) 9 parts (F) Surface initiator: polyether-modified silicone oil (Torre Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.04 part (E) Solvent: propylene glycol monomethyl ether 465 parts of acetate (E-1) (E) Solvent: 568 parts of N-methylpyrrolidone (E-2) were mixed to obtain a colored curable resin composition.

Examples 2 to 6 and Comparative Example 1
<Preparation of Color Curable Resin Composition>
In Example 1, a compound represented by the formulas (AI-2) to (AI-6) or Basic Blue 24 was used instead of the compound represented by the formula (AI-1). As shown in Table 3, the colored curable resin compositions of Examples 2 to 6 and Comparative Example 1 were obtained in the same manner as in Example 1 except for the above.

<Preparation of colored coating film>
A colored curable resin composition was applied onto a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Inc.) by a spin coating method, and then prebaked at 100 ° C. for 3 minutes to obtain a colored composition layer. After allowing to cool, the distance between the substrate on which the colored composition layer was formed and the quartz glass photomask was set to 100 μm, and an exposure machine (TME-150RSK; manufactured by Topcon Co., Ltd.) was used to create an air atmosphere of 60 mJ / cm. Light was irradiated with an exposure amount of ^{2 (based on 365 nm).} Then, it was post-baked in an oven at 230 ° C. for 20 minutes to obtain a colored coating film.

<Heat resistance evaluation>
The obtained colored coating film was heated in an oven at 230 ° C. for 2 hours.
^{The chromaticity after pre-baking and heating was measured, and the color difference ΔE *} ab was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method), and the results are shown in Table 3. rice field. ΔE ^* ab means that the smaller the color, the smaller the color change. Further, if the heat resistance of the colored coating film is good, it can be said that the coloring pattern produced from the same colored resin composition also has good heat resistance.

<Light resistance evaluation>
An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd .; which cuts light of 380 nm or less) is placed on the obtained colored coating film, and a light resistance tester (Suntest CPS +: manufactured by Toyo Seiki Co., Ltd.) is placed on the upper surface thereof. ), The xenon lamp light was irradiated for 48 hours.
^{The chromaticity after pre-baking and irradiation was measured, and the color difference ΔE *} ab was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method), and the results are shown in Table 3. rice field. ΔE ^* ab means that the smaller the color, the smaller the color change. Further, if the light resistance of the colored coating film is good, it can be said that the coloring pattern produced from the same colored resin composition also has good light resistance.

<Solvent resistance evaluation>
The obtained colored coating film was immersed in N-methylpyrrolidone at 23 ° C. for 40 minutes and then thoroughly washed with water.
^{The chromaticity after prebake and N-methylpyrrolidone immersion was measured, and the color difference ΔE *} ab was calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method), and the results were obtained. It is shown in Table 3. ΔE ^* ab means that the smaller the color, the smaller the color change. Further, if the solvent resistance of the colored coating film is good, it can be said that the colored pattern produced from the same colored resin composition also has good solvent resistance.

<Manufacturing of dispersion of blue pigment>
C. I. Pigment Blue 15: 6 19.2 parts, Dispersant (BYKLPN-6919 manufactured by BYK; 60% solution of propylene glycol monomethyl ether acetate) 6.7 parts, Acrylic resin 7.7 parts (solid content equivalent), Ethyl lactate 14 .7 parts and 141.7 parts of propylene glycol monomethyl ether acetate were mixed, 600 parts of 0.4 μm zirconia beads were added, and the obtained 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 of a blue pigment.

Example 7
<Preparation of Color Curable Resin Composition>
(A) Colorant: Dye (AI-1) 8.0 parts (A) Colorant: Blue pigment dispersion 317 parts (B) Resin: Resin (B-1) (solid content equivalent) 37 parts ( C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 9 parts (F) Solvent-modified silicone oil (Tore Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.13 parts (E) Solvent: 121 parts of propylene glycol monomethyl ether acetate (E-1) (E) Solvent: 794 parts of N-methylpyrrolidone (E-2) were mixed to obtain a colored curable resin composition. ..

Examples 8 to 10
<Preparation of Color Curable Resin Composition>
The above-mentioned Example 7 except that the compound represented by the formula (AI-2)-(AI-4) was used instead of the compound represented by the formula (AI-1). As shown in Table 4, the colored curable resin compositions of Examples 8 to 10 were obtained in the same manner as in Example 7.

Example 11
<Preparation of Color Curable Resin Composition>
(A) Colorant: Dye (AI-5) 3.0 parts (A) Colorant: Blue pigment dispersion 263 parts (B) Resin: Resin (B-1) (solid content equivalent) 39 parts ( C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization initiator: N-benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 9 parts (F) Solvent-modified silicone oil (Tore Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.12 parts (E) Solvent: 756 parts of propylene glycol monomethyl ether acetate (E-1) (E) Solvent: 293 parts of N-methylpyrrolidone (E-2) were mixed to obtain a colored curable resin composition. ..

Example 12 and Comparative Example 2
<Preparation of Color Curable Resin Composition>
In Example 11, the compound represented by the formula (AI-6) or Basic Blue 24 is used in place of the compound represented by the formula (AI-5), except that the compound represented by the formula (AI-5) is used. Similarly, as shown in Table 4, the colored curable resin compositions of Example 12 and Comparative Example 2 were obtained.

Example 13
<Preparation of Color Curable Resin Composition>
(A) Colorant: Dye (A-I-1) 7.9 parts (A) Colorant: Dye (B-I-1) 4.0 parts (A) Colorant: Blue pigment dispersion 274 parts (A) B) Resin: Resin (B-1) (solid content equivalent) 39 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization Initiator: N-Benzoyloxy-1- (4-phenylsulfanylphenyl) Octane-1-on-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 9 parts (F) Surface active agent: Poly Ether-modified silicone oil (Torre Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.13 parts (E) Solvent: Propropylene glycol monomethyl ether acetate (E-1) 260 parts (E) Solvent: N-methylpyrrolidone (E) -2) 784 parts (E) Solvent: 4-Hydroxy-4-methyl-2-pentanone (E-3) 12 parts were mixed to obtain a colored curable resin composition.

Comparative Example 3
<Preparation of Color Curable Resin Composition>
(A) Colorant: Basic Blue 24 2.9 parts (A) Colorant: Dye (B-I-1) 3.5 parts (A) Colorant: Pigment dispersion (A-3) 226 parts (B) Resin: Resin (B-1) (solid content equivalent) 41 parts (C) Polymerizable compound: Dipentaerythritol hexaacrylate (Kayarad (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts (D) Polymerization started Agent: N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE 01; manufactured by BASF) 9 parts (F) Surface active agent: Polyether modification Silicone oil (Torre Silicone SH8400: manufactured by Toray Dow Corning Co., Ltd.) 0.12 parts (E) Solvent: propylene glycol monomethyl ether acetate (E-1) 698 parts (E) Solvent: N-methylpyrrolidone (E-2) 290 parts (E) Solvent: 4-Hydroxy-4-methyl-2-pentanone (E-3) 11 parts were mixed to obtain a colored curable resin composition.

<Film thickness measurement>
The film thickness of the obtained coloring pattern was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

<Saturation evaluation>
For the colored coating film obtained after prebaking, the spectroscopy was measured using a colorimeter (OSP-SP-200; manufactured by Olympus Corporation), and the characteristic function of the C light source was used to measure xy in the XYZ color system of CIE. The chromaticity coordinates (x, y) and the stimulus value Y were measured.

According to the colored curable resin composition of the example, it was confirmed that the obtained color filter exhibited excellent heat resistance and light resistance.

Claims (13)

A compound represented by the formula (AI).

[In formula (AI),
R ^{1 to} R ⁶ each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms, which may have a substituent, a hydrogen atom, a halogen atom, a nitro group or a hydroxy group, and the aliphatic group thereof. The methylene group constituting the hydrocarbon group may be replaced with an oxygen atom or −CO−.
R ⁷ and R ⁸ each independently represent an aliphatic hydrocarbon group having 1 to 8 carbon atoms or a hydrogen atom which may have a substituent.
R ⁹ and R ¹⁰ each independently represent a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent, and the methylene group constituting the hydrocarbon group is an oxygen atom, -NR- or. It may be replaced with −CO−.
R represents a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent.
R ⁷ and R ⁹ may be bonded to each other to form a ring with a nitrogen atom, and R ⁸ and R ¹⁰ may be bonded to each other to form a ring with a nitrogen atom.
p and q each independently represent an integer of 0 to 5.
X ^t-is, t-valent anion (provided, Cl ^-, Br ^- and I ^- excluding.) Represents the.
t represents an integer of 1 to 3. ] ^{The compound according to claim 1, wherein X t-} in the formula (AI) is an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus and oxygen as essential elements. .. The compound according to claim 1, wherein ^{X t-} in the formula (AI) is a boron-containing anion. The compound according to claim 1, wherein ^{X t-} in the formula (AI) is an aluminum-containing anion. The compound according to claim 1, wherein ^{X t-} in the formula (AI) is a fluorine-containing anion. Formula (A-I) in the X ^t-and H ⁺ is determined based on the molar concentration of XH _t formed from the acid dissociation constant _{pKa = -log 10 ([H]} t · [X t-] / [ The compound according to any one of claims 1 to 5, wherein XH _{t]) is -15 or more and 0 or less.} Whether p and q of the formula (AI) are 1 or more and R ⁹ and R ¹⁰ are groups in which the Hammet substituent constant measured in the compound (X) and the compound (Y) is negative, or p. And the compound according to any one of claims 1 to 6, wherein q is 0.

The compound according to any one of claims 1 to 7, wherein R ⁷ and R ^{8 are hydrogen atoms.} A colored dispersion containing the compound according to any one of claims 1 to 8. A colored curable resin composition containing the compound according to any one of claims 1 to 8. A coating film formed from the colored curable resin composition according to claim 10. A color filter formed from the colored curable resin composition according to claim 10. A display device including the color filter according to claim 12.