JP2015038201A - Colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition excellent in heat resistance.SOLUTION: The colored curable resin composition contains: a colorant (A) which contains a salt (A1) comprising a dye represented by formula (A-VI) and a counter ion, and at least one dye (A2) selected from an anthraquinone dye and a tetraazaporphyrin dye; a resin (B); a polymerizable compound (C); a polymerization initiator (D); and a solvent (E). [Rto Rare each independently H, a halogen atom, a nitro group, an alkyl group, or the like; Rto Rare each independently H, an aryl group, or a C1-20 alkyl group which may be substituted with an amino group or a halogen atom; and A is an aromatic group or a heteroaromatic group which may have a substituent.]

Description

  The present invention relates to a colored curable resin composition.

As a colored curable resin composition for forming a color filter included in a liquid crystal display device or the like, a solid-state imaging device or the like, Patent Document 1 discloses a compound represented by the formula (A-III-1), a binder resin, and a solvent. , A colored curable resin composition containing a polymerization initiator and a curing agent is described.

WO2012 / 053211

  Conventionally known colored curable resin compositions containing the above-mentioned compounds have not been sufficiently satisfactory in terms of heat resistance.

［式（Ａ−ＶＩ）中、Ｒ^１Ａ〜Ｒ^８Ａは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、スルホニル基、ヒドロキシル基、あるいは炭素数１〜２０のアルキル基を表し、該アルキル基を構成するメチレン基間に酸素原子が挿入されていてもよい。
Ｒ^９Ａ〜Ｒ^１２Ａは、それぞれ独立して、水素原子、置換されていてもよいアリール基又は炭素数１〜２０のアルキル基を表し、該アルキル基を構成するメチレン基間に酸素原子が挿入されていてもよく、該アルキル基に含まれる水素原子はハロゲン原子又は置換されていてもよいアミノ基に置き換わっていてもよい。あるいは置換されていてもよいアリール基を表す。Ｒ^９ＡとＲ^１０Ａとが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ^１１AとＲ^１２Aとが結合してそれらが結合する窒素原子とともに環を形成してもよい。
Ａは、置換基を有していてもよい芳香族基またはヘテロ芳香族基を表す。］
［２］式（Ａ−ＶＩ）で表される染料と対イオンとからなる塩（Ａ１）を含む着色剤（Ａ）と、樹脂（Ｂ）と、光重合性化合物（Ｃ）と、光重合開始剤（Ｄ）と溶剤（Ｅ）と、無色の金属錯体（Ｆ）とを含む着色硬化性樹脂組成物。

［式（Ａ−ＶＩ）中、Ｒ^１Ａ〜Ｒ^８Ａは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、スルホニル基、ヒドロキシル基、あるいは炭素数１〜２０のアルキル基を表し、該アルキル基を構成するメチレン基間に酸素原子が挿入されていてもよい。
Ｒ^９Ａ〜Ｒ^１２Ａは、それぞれ独立して、水素原子、置換されていてもよいアリール基又は炭素数１〜２０のアルキル基を表し、該アルキル基を構成するメチレン基間に酸素原子が挿入されていてもよく、該アルキル基に含まれる水素原子は、ハロゲン原子又は置換されていてもよいアミノ基に置き換わっていてもよい。Ｒ^９AとＲ^１０Aとが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ^１１AとＲ^１２Aとが結合してそれらが結合する窒素原子とともに環を形成してもよい。
Ａは、置換基を有していてもよい芳香族基またはヘテロ芳香族基を表す。］
［３］さらに無色の金属錯体（Ｆ）を含む［１］に記載の着色硬化性樹脂組成物。
［４］式（Ａ−ＶＩ）で表される染料と対イオンとからなる塩が、式（Ａ−ＶＩ）で表される染料と、フッ素原子を有していてもよいアニオンとからなる塩である［１］〜［3］のいずれかに記載の着色硬化性樹脂組成物。
［５］式（Ａ−ＶＩ）で表される染料と対イオンとからなる塩が、式(Ａ-Ｉ)で表される塩である［１］〜［4］のいずれかに記載の着色硬化性樹脂組成物。

［式（Ａ−Ｉ）中、Ｘは、酸素原子、−ＮＨ−または硫黄原子を示す。Ｙは、任意のｍ価のアニオンを表す。Ｒ^４１〜Ｒ^４６は、それぞれ独立して、水素原子、置換されていてもよいアリール基又は炭素数１〜２０のアルキル基を表し、該アルキル基を構成するメチレン基間に酸素原子が挿入されていてもよく、該アルキル基に含まれる水素原子は、ハロゲン原子又は置換されていてもよいアミノ基に置き換わっていてもよい。Ｒ^４１とＲ^４２とが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ^４３とＲ^４４とが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ^４５とＲ^４６とが結合してそれらが結合する窒素原子とともに環を形成してもよい。Ｒ^４７〜Ｒ^５４は、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、スルホニル基、ヒドロキシル基、あるいは炭素数１〜８のアルキル基を表し、該アルキル基を構成するメチレン基間に酸素原子が挿入されていてもよい。Ｒ^５５は、水素原子、炭素数１〜２０のアルキル基、あるいは置換されていてもよいアリール基を表す。
なお、１分子中に複数の

が含まれる場合、それらは同じ構造であっても異なる構造であってもよい。ｍは任意の自然数を表す。］
［６］さらに、青色顔料を含む［１］〜［５］のいずれかに記載の着色硬化性樹脂組成物。
［７］さらに酸化防止剤（Ｈ）を含む［１］〜［６］のいずれかに記載の着色硬化性樹脂組成物。
［８］［１］〜［７］のいずれかに記載の着色硬化性樹脂組成物から形成される塗膜。
［９］［１］〜［７］のいずれかに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。
［１０］［９］に記載のカラーフィルタを含む表示装置。 The present invention provides the following [1] to [10].
[1] Coloring including a salt (A1) composed of a dye represented by formula (A-VI) and a counter ion, and at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye A colored curable resin composition comprising an agent (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E).

[In formula (A-VI), R ^{1A to} R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms, An oxygen atom may be inserted between the methylene groups constituting the group.
R ^{9A to} R ^12A each independently represents a hydrogen atom, an optionally substituted aryl group or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between the methylene groups constituting the alkyl group. The hydrogen atom contained in the alkyl group may be replaced with a halogen atom or an optionally substituted amino group. Or the aryl group which may be substituted is represented. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic group or a heteroaromatic group which may have a substituent. ]
[2] Colorant (A) containing salt (A1) composed of dye represented by formula (A-VI) and counter ion, resin (B), photopolymerizable compound (C), and photopolymerization A colored curable resin composition comprising an initiator (D), a solvent (E), and a colorless metal complex (F).

[In formula (A-VI), R ^{1A to} R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms, An oxygen atom may be inserted between the methylene groups constituting the group.
R ^{9A to} R ^12A each independently represents a hydrogen atom, an optionally substituted aryl group or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between the methylene groups constituting the alkyl group. The hydrogen atom contained in the alkyl group may be replaced with a halogen atom or an optionally substituted amino group. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic group or a heteroaromatic group which may have a substituent. ]
[3] The colored curable resin composition according to [1], further comprising a colorless metal complex (F).
[4] A salt comprising a dye represented by the formula (A-VI) and a counter ion comprising a dye represented by the formula (A-VI) and an anion which may have a fluorine atom. The colored curable resin composition according to any one of [1] to [3].
[5] The coloring according to any one of [1] to [4], wherein the salt composed of the dye represented by the formula (A-VI) and a counter ion is a salt represented by the formula (AI). Curable resin composition.

[In the formula (AI), X represents an oxygen atom, -NH- or a sulfur atom. Y represents an arbitrary m-valent anion. R ^{41 to} R ⁴⁶ each independently represents a hydrogen atom, an optionally substituted aryl group or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between the methylene groups constituting the alkyl group. The hydrogen atom contained in the alkyl group may be replaced with a halogen atom or an optionally substituted amino group. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded, R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded. R ^{47 to} R ⁵⁴ each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom between methylene groups constituting the alkyl group. An atom may be inserted. ^R55 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted.
In addition, a plurality of molecules per molecule

May be the same or different structures. m represents an arbitrary natural number. ]
[6] The colored curable resin composition according to any one of [1] to [5], further including a blue pigment.
[7] The colored curable resin composition according to any one of [1] to [6], further comprising an antioxidant (H).
[8] A coating film formed from the colored curable resin composition according to any one of [1] to [7].
[9] A color filter formed from the colored curable resin composition according to any one of [1] to [7].
[10] A display device including the color filter according to [9].

  According to the colored curable resin composition of the present invention, a color filter having good heat resistance can be obtained.

  The colorant (A) contained in the colored curable resin of the present invention may be a salt (A1) composed of a dye represented by the formula (A-VI) and a counter ion (hereinafter referred to as a dye (A1)). )including. The dye (A1) includes a tautomer thereof.

［式（Ａ−ＶＩ）中、Ｒ^１Ａ〜Ｒ^８Ａは、それぞれ独立して、水素原子、ハロゲン原子、ニトロ基、スルホニル基、ヒドロキシル基、あるいは炭素数１〜２０のアルキル基を表し、該アルキル基を構成するメチレン基間に酸素原子が挿入されていてもよい。
Ｒ^９Ａ〜Ｒ^１２Ａは、それぞれ独立して、水素原子、置換されていてもよいアリール基又は炭素数１〜２０のアルキル基を表し、該アルキル基を構成するメチレン基間に酸素原子が挿入されていてもよく、該アルキル基に含まれる水素原子は、ハロゲン原子又は置換されていてもよいアミノ基で置き換わっていてもよい。Ｒ^９ＡとＲ^１０Ａとが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ^１１AとＲ^１２Aとが結合してそれらが結合する窒素原子とともに環を形成してもよい。
Ａは、置換基を有していてもよい芳香族基または置換基を有していてもよいヘテロ芳香族基を表す。］ <Dye (A1)>

[In formula (A-VI), R ^{1A to} R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms, An oxygen atom may be inserted between the methylene groups constituting the group.
R ^{9A to} R ^12A each independently represents a hydrogen atom, an optionally substituted aryl group or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between the methylene groups constituting the alkyl group. The hydrogen atom contained in the alkyl group may be replaced with a halogen atom or an optionally substituted amino group. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic group which may have a substituent or a heteroaromatic group which may have a substituent. ]

The alkyl group having 1 to 20 carbon atoms represented by R ^{1A to} R ^12A may be linear, branched or cyclic, and examples thereof include groups represented by the following formulae. . In the following formula, * represents a bond with a carbon atom or a nitrogen atom.

Examples of the group having 1 to 20 carbon atoms represented by R ^{1A to} R ^12A and having an oxygen atom inserted between methylene groups constituting the alkyl group include groups represented by the following formulae: Can be mentioned. In the following formula, * represents a bond with a carbon atom or a nitrogen atom. Among them, an alkyl group having 1 to 10 carbon atoms, preferably a group in which an oxygen atom is inserted between methylene groups constituting the alkyl group, is an alkyl group having 1 to 6 carbon atoms, A group in which an oxygen atom is inserted between methylene groups constituting the group is more preferable.

The amino group which may be substituted is an amino group having one alkyl group having 1 to 4 carbon atoms such as methylamino group or ethylamino group; carbon number such as dimethylamino group, diethylamino group or ethylmethylamino group An amino group having two alkyl groups of 1 to 4;
Examples of the optionally substituted amino group represented by R ^{9A to} R ^12A or the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

In the ^optionally substituted aryl group represented by R ^{9A to} R ^12A , examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and iodine; a carbon number of 1 to 1 such as a chloromethyl group and a trifluoromethyl group A haloalkyl group having 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group.
Specific examples of the aryl group which may be substituted include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

^A ring formed by combining R ^4A and R ^5A together with the nitrogen atom to which they are bonded, a ring formed by combining R ^9A and R ^10A together with the nitrogen atom to which they are bonded, and R ^11A and R ^12A bonded together Examples of the ring formed together with the nitrogen atom to which they are bonded include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.

R ^{1A to} R ^8A are each independently preferably a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms from the viewpoint of ease of synthesis, and each independently represents a hydrogen atom, methyl A group, a fluorine atom or a chlorine atom is more preferred.

R ^{9A to} R ^12A are each independently preferably an alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group from the viewpoint of ease of synthesis, and each independently represents a halogen atom, It is more preferably an aryl group which may be substituted with a haloalkyl group, a methoxy group, an ethoxy group, a hydroxy group, a sulfo group or a methylsulfonyl group, or an alkyl group having 1 to 8 carbon atoms. More preferably, it is an alkyl group of 1 to 8 or an aryl group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

  Examples of the aromatic group that may have a substituent represented by A include groups represented by the following formulae. * Represents a bond with a carbon atom.

  Especially, group represented by Formula (A1-2) and Formula (A1-7) is preferable.

The heteroaromatic group represented by A means an aromatic group having at least one hetero atom as a ring component. Examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom.
A is preferably a heteroaromatic group having at least one nitrogen atom as a ring component.
Examples of the heteroaromatic group which may have a substituent represented by A include groups represented by the following formulae. * Represents a bond with a carbon atom.

  Especially, group represented by a formula (A1-12) and a formula (A1-13) is preferable.

The counter ion constituting the dye (A1) may be a cation or an anion.
Examples of the anion that forms a salt with the dye represented by the formula (A-VI) include known anions. From the viewpoint of heat resistance, a boron-containing anion, an aluminum-containing anion, a fluorine-containing anion, and tungsten, molybdenum, An anion containing at least one element selected from the group consisting of silicon and phosphorus and oxygen as essential elements is preferable.

［式（４）中、Ｗ^１及びＷ^２は、それぞれ独立に、１価のプロトン供与性置換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。］
１価のプロトン供与性置換基からプロトンを放出してなる置換基２つを有する基としては１価のプロトン供与性置換基（例えばヒドロキシ基、カルボキシ基等）を少なくとも２つ有する化合物から２つのプロトン供与性置換基それぞれからプロトンが放出されてなる基が挙げられ、当該化合物は、置換基を有していてもよいカテコール、置換基を有していてもよい２，３−ジヒドロキシナフタレン、置換基を有していてもよい２，２’−ビフェノール、置換基を有していてもよい３−ヒドロキシ−２−ナフトエ酸、置換基を有していてもよい２−ヒドロキシ−１−ナフトエ酸、置換基を有していてもよい１−ヒドロキシ−２−ナフトエ酸、置換基を有していてもよいビナフトール、置換基を有していてもよいサリチル酸、置換基を有していてもよいベンジル酸又は置換基を有していてもよいマンデル酸であることが好ましい。
置換基としては、フッ素原子、塩素原子、臭素原子等のハロゲン原子；メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ｎ−ペンチル基、シクロペンチル基、ｎ−ヘキシル基、シクロヘキシル基等のハロゲン原子を有していてもよい炭素数１〜６のアルキル基；メトキシ基、エトキシ基等の炭素数１〜６のアルコキシ基；ニトロ基；ヒドロキシ基；アミノ基が挙げられる。 Examples of the boron-containing anion and the aluminum-containing anion include anions represented by the following formula (4).

[In Formula (4), W ¹ and W ² each independently represent a group having two substituents formed by releasing a proton from a monovalent proton-donating substituent. M represents a boron atom or an aluminum atom. ]
As the group having two substituents formed by releasing protons from a monovalent proton-donating substituent, two groups from compounds having at least two monovalent proton-donating substituents (for example, a hydroxy group, a carboxy group, etc.) are used. Examples include groups in which protons are released from each proton-donating substituent, and the compound includes catechol which may have a substituent, 2,3-dihydroxynaphthalene which may have a substituent, substituted 2,2′-biphenol optionally having a group, 3-hydroxy-2-naphthoic acid optionally having a substituent, 2-hydroxy-1-naphthoic acid optionally having a substituent 1-hydroxy-2-naphthoic acid which may have a substituent, binaphthol which may have a substituent, salicylic acid which may have a substituent, It is preferably a good benzylic acid or mandelic acid which may have a substituent.
Examples of the substituent include halogen atoms such as fluorine atom, chlorine atom, bromine atom; methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, An alkyl group having 1 to 6 carbon atoms which may have a halogen atom such as a cyclopentyl group, an n-hexyl group or a cyclohexyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; a nitro group; Group; an amino group is mentioned.

  Examples of the salicylic acid which may have a substituent include salicylic acid, 3-methylsalicylic acid, 3-tert-butylsalicylic acid, 3-aminosalicylic acid, 3-chlorosalicylic acid, 4-bromosalicylic acid, 3-methoxysalicylic acid and 3-nitros. Salicylic acid, 4-trifluoromethylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-dibromosalicylic acid, 3,5-dichlorosalicylic acid, 3,5,6-trichlorosalicylic acid, 3-hydroxysalicylic acid (2, 3-dihydroxybenzoic acid), 4-hydroxysalicylic acid (2,4-dihydroxybenzoic acid), 5-hydroxysalicylic acid (2,5-dihydroxybenzoic acid), 6-hydroxysalicylic acid (2,6-dihydroxybenzoic acid), etc. Can be mentioned.

Examples of benzylic acid that may have a substituent include those described below.

Examples of the mandelic acid that may have a substituent include those described below.

（式中、Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４は、それぞれ独立して、水素原子、ヒドロキシル基、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。）
Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４で表されるハロゲン原子としては、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。
Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４で表される炭素数１〜４のアルキル基としては、メチル基、エチル基、ｎ−プロピル基、イソプロピル基、ｎ−ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基が挙げられる。
Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４で表される炭素数１〜４のハロアルキル基としては、トリフルオロメチル基、トリクロロメチル基、トリブロモメチル基、テトラフルオロエチル基、テトラクロロエチル基、テトラブロモエチル基等が挙げられる。
Ｒ^６１、Ｒ^６２、Ｒ^６３及びＲ^６４で表される炭素数１〜４のアルコキシ基としては、メトキシ基、エトキシ基、ｎ−プロポキシ基、イソプロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基が挙げられる。 As an anion represented by Formula (4), the anion represented by a following formula is mentioned.

(In the formula, R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom, a hydroxyl group, an amino group, a nitro group, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or 1 to 1 carbon atoms. 4 represents a haloalkyl group or an alkoxy group having 1 to 4 carbon atoms.)
Examples of the halogen atom represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ 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 is mentioned.
Examples of the haloalkyl group having 1 to 4 carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ include trifluoromethyl group, trichloromethyl group, tribromomethyl group, tetrafluoroethyl group, tetrachloroethyl group, tetra A bromoethyl group etc. are mentioned.
Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a sec-butoxy group. , Tert-butoxy group.

  For example, the following anions (BC-1) to anions (BC-28) may be mentioned. M represents a boron atom or an aluminum atom. TBu in Table 1 represents a tert-butyl group.

  Especially, as an anion represented by Formula (4), an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), an anion (BC-27) is preferable, an anion (BC-1), an anion (BC-2), and an anion (BC-25) are more preferable, and an anion (BC-1) and an anion (BC-2) are more preferable. When these anions are used, the salt formed by the dye and the anion represented by the formula (A-IV) of the present invention tends to be excellent in solubility in an organic solvent.

［式（６）中、Ｗ^３及びＷ^４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、Ｗ^３とＷ^４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。］

［式（７）中、Ｗ^５、Ｘ^６及びＷ^７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。］

［式（８）中、Ｙ^１は炭素数１〜４のフッ化アルカンジイル基を表す。］

［式（９）中、Ｙ^２は炭素数１〜４のフッ化アルキル基を表す。］ Examples of the fluorine-containing anion include groups represented by the following formulas (6), (7), (8), and (9).

[In Formula (6), 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 form 1 to 1 carbon atoms. 4 fluorinated alkanediyl groups are formed. ]

Wherein ^(7), the W 5, ^{X 6} and ^{W 7} each independently represent a fluorine atom or a fluorinated alkyl group having 1 to 4 carbon atoms. ]

Wherein (8), ^{Y 1} represents a fluorinated alkanediyl group having 1 to 4 carbon atoms. ]

Wherein (9), ^{Y 2} represents a fluorinated alkyl group having 1 to 4 carbon atoms. ]

In the formulas (6) and (7), the fluorinated alkyl group having 1 to 4 carbon atoms represented by W ^{3 to} W ⁷ is preferably a perfluoroalkyl group, 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 and the like.

In the formula (6), the fluorinated alkanediyl group having 2 to 4 carbon atoms formed by combining W ³ and W ⁴ is preferably a perfluoroalkanediyl group, for example, —CF ₂ CF ₂ —, —CF _{2 CF 2 CF 2 -, -} CF 2 CF 2 CF 2 CF 2 - , and the like.

The fluorinated alkanediyl group having 1 to 4 carbon atoms represented by ^{Y 1} in formula (8), perfluoro alkanediyl group is preferred, 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.

The fluorinated alkyl group having 1 to 4 carbon atoms represented by ^{Y 2} in formula (9), a perfluoroalkyl group is _{preferred, -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.

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

Examples of the anion represented by the formula (7) (hereinafter sometimes referred to as “anion (7)”) include the following anion (7-1).

Examples of the anion represented by the formula (8) (hereinafter sometimes referred to as “anion (8)”) include the following anions (8-1) to (8-4).

Examples of the anion represented by the formula (9) (hereinafter sometimes referred to as “anion (9)”) include the following anions (9-1) to (9-4).

  Containing at least one anion selected from the group consisting of anion (6), anion (7), anion (8) and anion (9) (hereinafter sometimes referred to as “anions (6) to (9)”) Thereby, the solubility to the organic solvent of the salt formed with the dye represented by Formula (A-VI) and an anion can be improved. Among these, anion (6-1), anion (6-2) and anion (7-1) are preferable, and anion (6-2) is particularly preferable.

  Examples of the anion that forms a salt with the dye represented by the formula (A-VI) include an anion containing at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, and oxygen as essential elements. An anion of heteropolyacid or isopolyacid containing tungsten as an essential element is preferable, and anions of phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacid are more preferable.

Examples of the anion of heteropolyacid or isopolyacid containing tungsten as an essential element include Keggin-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⁻ , Keggin type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ⁴⁻ , β- [SiW ₁₂ O ₄₀ ] ⁴⁻ , γ- [ SiW ₁₂ O ₄₀ ] ⁴⁻ , and other examples include [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] ^{-, [W 10 O 32]}} 4-, WO 4 2- , and the like.

  Among the anions other than the anion of heteropolyacid or isopolyacid containing tungsten as an essential element, an anion composed of at least one element selected from the group consisting of silicon and phosphorus and oxygen is preferable.

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, because of the ease of synthesis and post-treatment, heteropolyacid anions such as Keggin-type phosphotungstate ion, Dawson-type phosphotungstate ion, and Keggin-type silicate-tungstate ion, and isopolyacid anions such as [W ₁₀ O ₃₂ ] ^4- preferable.

  Specific examples of the dye represented by the formula (A-VI) include compounds represented by the following formula.

Among the ions represented by the formula (A-VI), a compound represented by the following formula is preferable.

Examples of the counter ion that forms a salt with the dye represented by the formula (A-VI) include a counter ion represented by the following formula.

Specific examples of the salt formed from the ion represented by the formula (A-VI) and the counter ion include salts represented by the following formula.

［式（Ａ−Ｉ）中、Ｘは、酸素原子、−ＮＨ−または硫黄原子を示す。Ｙは、任意のｍ価のアニオンを表す。Ｒ^４１〜Ｒ^４６は、それぞれ独立して、水素原子、置換されていてもよいアリール基、又は炭素数１〜２０のアルキル基を表し、該アルキル基を構成するメチレン基間に酸素原子が挿入されていてもよく、該アルキル基に含まれる水素原子は、ハロゲン原子又は置換されていてもよいアミノ基で置き換わっていてもよい。Ｒ^４１とＲ^４２とが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ^４３とＲ^４４とが結合してそれらが結合する窒素原子とともに環を形成してもよく、Ｒ^４５とＲ^４６とが結合してそれらが結合する窒素原子とともに環を形成してもよい。Ｒ^４７〜Ｒ^５４は、それぞれ独立して、水素原子、−ＮＨ−ハロゲン原子、ニトロ基、スルホニル基、ヒドロキシル基、あるいは炭素数１〜８のアルキル基を表し、該アルキル基を構成するメチレン基間に酸素原子が挿入されていてもよい。Ｒ^５５は、水素原子、炭素数１〜２０のアルキル基、あるいは置換されていてもよいアリール基を表す。
なお、１分子中に複数の

が含まれる場合、それらは同じ構造であっても異なる構造であってもよい。ｍは任意の自然数を表す。］ The dye (A1) is preferably a compound represented by the formula (AI) (hereinafter sometimes referred to as the compound (AI)). The compound represented by the formula (AI) includes tautomers thereof.

[In the formula (AI), X represents an oxygen atom, -NH- or a sulfur atom. Y represents an arbitrary m-valent anion. R ^{41 to} R ⁴⁶ each independently represents a hydrogen atom, an optionally substituted aryl group, or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between methylene groups constituting the alkyl group. The hydrogen atom contained in the alkyl group may be replaced with a halogen atom or an optionally substituted amino group. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded, R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded. R ^{47 to} R ⁵⁴ each independently represent a hydrogen atom, —NH-halogen atom, nitro group, sulfonyl group, hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and a methylene group constituting the alkyl group An oxygen atom may be inserted between them. ^R55 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted.
In addition, a plurality of molecules per molecule

May be the same or different structures. m represents an arbitrary natural number. ]

  In the formula (AI), X represents an oxygen atom, —NH— or a sulfur atom, preferably a sulfur atom.

The alkyl group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ may be linear, branched or cyclic, and examples thereof include groups represented by the following formulae. . In the following formula, * represents a bond with a nitrogen atom. Especially, a C1-C8 alkyl group is preferable, a C1-C6 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

The amino group which may be substituted is an amino group having one alkyl group having 1 to 4 carbon atoms such as methylamino group or ethylamino group; carbon number such as dimethylamino group, diethylamino group or ethylmethylamino group. An amino group having two alkyl groups of 1 to 4;
Examples of the optionally substituted amino group represented by R ^{41 to} R ⁴⁶ or the alkyl group having 1 to 20 carbon atoms substituted with a halogen atom include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

Examples of the group having 1 to 20 carbon atoms represented by R ^{41 to} R ⁴⁶ and having an oxygen atom inserted between methylene groups constituting the alkyl group include groups represented by the following formulae: Can be mentioned. In the following formula, * represents a bond with a nitrogen atom. Among them, an alkyl group having 1 to 10 carbon atoms, preferably a group in which an oxygen atom is inserted between methylene groups constituting the alkyl group, is an alkyl group having 1 to 6 carbon atoms, A group in which an oxygen atom is inserted between methylene groups constituting the group is more preferable.

In the optionally substituted aryl group represented by R ^{41 to} R ⁴⁶ , examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and iodine; a carbon number of 1 to 1 such as a chloromethyl group and a trifluoromethyl group A haloalkyl group having 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; a hydroxy group; a sulfamoyl group; an alkylsulfonyl group having 1 to 6 carbon atoms such as a methylsulfonyl group.
Specific examples of the aryl group which may be substituted include groups represented by the following formulae. In the following formula, * represents a bond with a nitrogen atom.

A ring formed by combining R ⁴¹ and R ⁴² together with the nitrogen atom to which they are bonded, a ring formed by combining R ⁴³ and R ⁴⁴ together with the nitrogen atom to which they are bonded, and R ⁴⁵ and R ⁴⁶ are combined. Examples of the ring formed together with the nitrogen atom to which they are bonded include a pyrrolidine ring, a morpholine ring, a piperidine ring, and a piperazine ring.

R ^{41 to} R ⁴⁶ are preferably each independently an alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group, from the viewpoint of ease of synthesis, and each independently having 1 carbon atom. It is more preferably an alkyl group of ˜8 or an aryl group represented by the following formula. In the following formula, * represents a bond with a nitrogen atom.

Examples of the group in which an oxygen atom may be inserted between the alkyl group having 1 to 8 carbon atoms represented by R ^{47 to} R ⁵⁴ and the methylene group constituting the alkyl group include groups represented by the following formulae: It is done. In the following formula, * represents a bond with a carbon atom.

R ^{47 to} R ⁵⁴ are preferably each independently a hydrogen atom, a halogen atom, or an alkyl group having 1 to 8 carbon atoms from the viewpoint of ease of synthesis, and each independently represents a hydrogen atom, methyl A group, a fluorine atom or a chlorine atom is more preferred.

The alkyl group having 1 to 20 carbon atoms represented by R ⁵⁵ may be linear, branched or cyclic, and examples thereof include groups represented by the following formulae.

In the aryl group which may be substituted represented by R ^55, examples of the substituent, a fluorine atom, a chlorine atom, a halogen atom such as iodine; chloromethyl group, a haloalkyl having 1 to 6 carbon atoms such as a trifluoromethyl group Groups: alkoxy groups having 1 to 6 carbon atoms such as methoxy group and ethoxy group; hydroxy groups; sulfamoyl groups; alkylsulfonyl groups having 1 to 6 carbon atoms such as methylsulfonyl groups. Specific examples of the aryl group which may be substituted include groups represented by the following formulae. In the following formula, * represents a bond with a carbon atom.

R ⁵⁵ is preferably an alkyl group having 1 to 20 carbon atoms or an optionally substituted aryl group, and more preferably an alkyl group having 1 to 8 carbon atoms or the following formula, from the viewpoint of ease of synthesis. And more preferably an aryl group represented by the following formula. In the following formula, * represents a bond with a carbon atom.

Examples of the cation moiety of formula (AI) include cation 1 to cation 12 represented by formula (AI-1) shown in Table 2 below.

  Among them, as the cation moiety of the formula (AI), cation 1 to cation 6, cation 11 and cation 12 are preferable, cation 1 and cation 12 are more preferable, and cation 1 is more preferable.

  Examples of Y include the aforementioned known anions. From the viewpoint of heat resistance, preferred anions are selected from the group consisting of boron-containing anions, aluminum-containing anions, fluorine-containing anions, and tungsten, molybdenum, silicon and phosphorus. An anion containing at least one element and oxygen as essential elements.

Examples of the boron-containing anion and the aluminum-containing anion include the anion represented by the formula (4).
Especially, as an anion represented by Formula (4), an anion (BC-1), an anion (BC-2), an anion (BC-3), an anion (BC-25), an anion (BC-26), an anion (BC-27) is preferable, an anion (BC-1), an anion (BC-2), and an anion (BC-25) are more preferable, and an anion (BC-1) and an anion (BC-2) are more preferable. When these anions are used, the compound (AI) of the present invention tends to be excellent in solubility in an organic solvent.

Examples of the fluorine-containing anion include groups represented by the formulas (6), (7), (8), and (9).
Containing at least one anion selected from the group consisting of anion (6), anion (7), anion (8) and anion (9) (hereinafter sometimes referred to as “anions (6) to (9)”) Thus, the solubility of the salt of the dye represented by the formula (AI) in an organic solvent can be improved. Among these, anion (6-1), anion (6-2) and anion (7-1) are preferable, and anion (6-2) is particularly preferable.

  An anion containing as an essential element at least one element selected from the group consisting of tungsten, molybdenum, silicon, and phosphorus, which is represented as Y, and a heteropolyacid or isopolyacid containing tungsten as an essential element Anions, particularly phosphotungstic acid, silicotungstic acid and tungsten-based isopolyacids are preferred.

As anions of heteropolyacid or isopolyacid containing tungsten as an essential element, Keggin-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- , Keggin-type silicotungstate ion α- [SiW ₁₂ O ₄₀ ] ^4- , β- [SiW ₁₂ O ₄₀ ] ^4- , γ- [SiW ₁₂ O ₄₀ ] ⁴⁻ , [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-,}} [ ^{_{10 O 32] 4-, WO 4}} 2- , and the like.

  Among the anions other than the anion of heteropolyacid or isopolyacid containing tungsten as an essential element, an anion composed of at least one element selected from the group consisting of silicon and phosphorus and oxygen is preferable.

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, because of the ease of synthesis and post-treatment, heteropolyacid anions such as Keggin-type phosphotungstate ion, Dawson-type phosphotungstate ion, and Keggin-type silicate-tungstate ion, and isopolyacid anions such as [W ₁₀ O ₃₂ ] ^4- preferable.

Compound (AI) includes any one of the cations 1 to 11, anions (BC-1) to (BC-28), anions (6-1) to (6-6), anions (7-1), anions (8-1) to (8-4), and combinations with any one anion among anions (9-1) to (9-4), among the cations 1 to 11 Combination of any three cations and anion α- [PW ₁₂ O ₄₀ ] ³⁻ , Combination of any six cations of the cations 1 to 11 and anion α- [P ₂ W ₁₈ O ₆₂ ] ⁶⁻ A combination of any four cations of the cations 1 to 11 and the anion α- [SiW ₁₂ O ₄₀ ] ⁴⁻ or [W ₁₀ O ₃₂ ] ⁴⁻ is exemplified.

Compound (AI) comprises a compound represented by formula (A-II) (hereinafter sometimes referred to as compound (A-II)) and an alkali metal salt of an anion [Y] ^m- in a solvent. It can manufacture by mixing with. Examples of the alkali metal include lithium, sodium and potassium.

Mixing with the compound (A-II) and the alkali metal salt of the anion [Y] ^m- may be performed by dissolving both in a solvent or not.
Solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, ethyl acetate, toluene, methanol, ethanol, isopropanol, acetone, tetrahydrofuran, dioxane, water and chloroform. Is mentioned.
Among these, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, methanol, ethanol, isopropanol and water are preferable. When these solvents are used, the solubility of the alkali metal salt of the compound (A-II) and the anion [Y] ^m- tends to be high.
When the solvent is water, an acid such as acetic acid or hydrochloric acid may be added.

The mixing temperature of the compound (A-II) and the anion [Y] ^m- alkali metal salt is preferably 0 ° C to 150 ° C, more preferably 10 ° C to 120 ° C, and further preferably 20 ° C to 100 ° C. . The mixing time is preferably 1 hour to 72 hours, more preferably 2 hours to 24 hours, and further preferably 3 hours to 12 hours.

When a solvent compatible with water is used, the solution is mixed and further stirred for 1 to 3 hours as necessary, and then the precipitate is obtained by filtration to obtain the compound (AI). Can be obtained. If necessary, the obtained compound (AI) may be washed with ion-exchanged water.
When a solvent that is not compatible with water is used, the reaction mixture and ion-exchanged water are mixed, and further stirred for 1 to 3 hours as necessary. Thereafter, the organic layer is obtained by liquid separation, whereby the compound ( A solution containing AI) can be obtained. If necessary, the solution may be washed with ion exchange water. The compound (AI) can be obtained by removing the solvent from the solution containing the compound (AI).

Compound (A-II) can be produced, for example, by reacting a compound represented by formula (BI) with a compound represented by formula (CI). Such a reaction may be performed in the presence of an organic solvent or may be performed without a solvent.

［式（Ｂ−Ｉ）及び式（Ｃ−Ｉ）中、Ｒ^４１〜Ｒ^５５は、それぞれ前記と同じ意味を表す。］

[In formula (BI) and formula (CI), R ^{41 to} R ⁵⁵ each have the same meaning as described above. ]

Compound (A-II) can be produced by reacting a compound represented by formula (B-II) with a compound represented by formula (C-II). Such a reaction may be performed in the presence of an organic solvent or may be performed without a solvent.

［式（Ｂ−ＩＩ）及び式（Ｃ−ＩＩ）中、Ｒ^４１〜Ｒ^５５は、それぞれ上記と同じ意味を表す。］

[In formula (B-II) and formula (C-II), R ^{41 to} R ⁵⁵ each represent the same meaning as described above. ]

The amount of the compound represented by the formula (CI) to be used is preferably 0.5 mol or more and 8 mol or less, more preferably 1 mol per 1 mol of the compound represented by the formula (BI). It is 1 mol or more and 3 mol or less.
The amount of the compound represented by the formula (C-II) to be used is preferably 0.5 mol or more and 8 mol or less, more preferably 1 mol per 1 mol of the compound represented by the formula (B-II). It is 1 mol or more and 3 mol or less.

  The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 80 ° C to 130 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

  Any reaction is preferably carried out in an organic solvent from the viewpoint of yield. Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene, and chloroform; alcohol solvents such as methanol, ethanol, isopropanol, and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl Ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone; and the like. The amount of the organic solvent to be used is preferably 1 part by mass or more and 20 parts by mass or less, more preferably 2 parts by mass with respect to 1 part by mass of the compound represented by the formula (BI) or (B-II). The amount is 10 parts by mass or less.

  The above reaction is preferably carried out in the presence of a condensing agent from the viewpoint of yield. Examples of the condensing agent include phosphoric acid, polyphosphoric acid, phosphorus oxychloride, sulfuric acid, thionyl chloride and the like.

  The amount of the condensing agent to be used is preferably 0.1 parts by mass or more and 20 parts by mass or less, more preferably 0 with respect to 1 part by mass of the compound represented by the formula (BI) or (B-II). .2 parts by mass or more and 5 parts by mass or less.

  The method for obtaining the target compound (A-II) from the reaction mixture is not particularly limited, and various known methods can be employed. For example, the reaction mixture can be mixed with alcohol (for example, methanol etc.), and the precipitated crystals can be collected by filtration. The reaction mixture is preferably added to the alcohol. The temperature at which the reaction mixture is added is preferably −100 ° C. or higher and 50 ° C. or lower, more preferably −80 ° C. or higher and 0 ° C. or lower. Thereafter, it is preferable to stir at the same temperature for about 0.5 to 2 hours. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

  Examples of the method for producing compound (BI) or (B-II) include various known methods, for example, the methods described in West German Patent Application P3928243.0.

  As a method for producing the compound (CI) or (C-II), various known methods are employed, for example, the method described in Patent Document 1.

  As the alkali metal salt of the anion represented by the formula (4), commercially available ones may be used. For example, Patent No. 4097704, Patent No. 4341251 and Journal of The Electrochemical Society, Vol. 148, Phase 1, 2001. Can be produced by the method described in 1. above.

  As the alkali metal salt of the anion represented by the compounds (6), (7), (8), and (9), commercially available ones may be used, for example, described in WO2008 / 077562 and JP2010-280586. It can manufacture by the method made.

  An alkali metal salt of an anion containing at least one element selected from the group consisting of tungsten, silicon, and phosphorus and oxygen as essential elements can be produced by a publicly known and commonly used method. Also good. Examples of such compounds include corresponding heteropoly acid salts, isopoly acid salts, silicates, and phosphates. As these various salts, monovalent metal salts such as sodium, lithium, and potassium are preferable because they are excellent in water solubility and can be easily synthesized and worked up.

The colored curable resin composition of the present invention includes at least one selected from the group consisting of a salt (A1) composed of a dye represented by the formula (A-VI) and a counter ion, an anthraquinone dye and a tetraazaporphyrin dye. Colored curable resin composition 1 containing a colorant (A) containing two dyes (A2), a resin (B), a polymerizable compound (C), a polymerization initiator (D) and a solvent (E) ,
A colorant (A) containing a salt (A1) composed of a dye represented by the formula (A-VI) and a counter ion, a resin (B), a photopolymerizable compound (C), a photopolymerization initiator ( There is a colored curable resin composition 2 containing D), a solvent (E), and a colorless metal complex (F).

  The colorant (A) contained in the colored curable resin composition 1 of the present invention is at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye (hereinafter referred to as a dye (A2)). Yes.)

As the anthraquinone dye, a known substance may be used. As an anthraquinone dye, for example,
C. I. Solvent Yellow 117 (hereinafter, CI Solvent Yellow is omitted, and only the number is described), 163, 167, 189,
C. I. Solvent orange 77, 86,
C. I. Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247,
C. I. Solvent violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60,
C. I. Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59: 1, 63, 68, 69, 78, 79, 83, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139,
C. I. Solvent Green 3, 28, 29, 32, 33,
C. I. Acid Red 80,
C. I. Acid Green 25, 27, 28, 41,
C. I. Acid Violet 34,
C. I. Acid Blue 25, 27, 40, 45, 78, 80, 112
C. I. Disperse Yellow 51,
C. I. Disperse violet 26, 27,
C. I. Disperse Blue 1, 14, 56, 60,
C. I. Direct Blue 40,
C. I. Modern Red 3, 11,
C. I. Modern Blue 8
Etc. The anthraquinone dye is preferably soluble in an organic solvent, and more preferably a blue, violet or red anthraquinone dye.

  As the anthraquinone dye, a compound represented by the formula (1b) (hereinafter sometimes referred to as “compound (1b)”) is preferable.

［式（１ｂ）中、Ｒ^９１及びＲ^９２は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜１０の脂肪族炭化水素基、置換基を有していてもよい炭素数３〜１０の脂環式炭化水素基又は式（１ｂ’）

式（１ｂ’）中、Ｒ^９３は、炭素数１〜６のアルキル基、ハロゲン原子、−ＳＯ_３Ｈ、−ＣＯ_２Ｈ、−ＣＯ_２Ｒ^９４、−ＮＨＣＯＲ^９４、−ＳＯ_３Ｒ^９４又は−ＳＯ_２ＮＲ^９４Ｒ^９５を表す。
Ｒ^９４は、ハロゲン原子、ヒドロキシ基又はアミノ基で置換されていてもよい炭素数１〜１０の飽和炭化水素基、またはハロゲン原子、ヒドロキシ基又はアミノ基で置換されていてもよい炭素数３〜１０の脂環式炭化水素基を表す。
Ｒ^９５は、水素原子又は炭素数１〜１０の飽和炭化水素基を表す。
ｒは、０〜５の整数を表す。ｒが２以上の場合、複数のＲ^９３は同一でも異なってもよい。
Ｘ^９１は、単結合又は炭素数１〜６のアルカンジイル基を表す。）
で表される基を表す。］
化合物（１ｂ）が、−ＳＯ_３Ｈ及び／又は−ＣＯ_２Ｈを有する場合、これらは塩（例えば、Ｎａ塩やＫ塩）を形成していてもよい。

[In Formula (1b), R ⁹¹ and R ⁹² may each independently have a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, or a substituent. Good C3-10 alicyclic hydrocarbon group or formula (1b ′)

In formula (1b ′), R ⁹³ represents an alkyl group having 1 to 6 carbon atoms, a halogen atom, —SO ₃ H, —CO ₂ H, —CO ₂ R ⁹⁴ , —NHCOR ⁹⁴ , —SO ₃ R ⁹⁴ or — It represents an SO ₂ NR ⁹⁴ R ^95.
R ⁹⁴ is a saturated hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a halogen atom, a hydroxy group or an amino group, or 3 to 3 carbon atoms which may be substituted with a halogen atom, a hydroxy group or an amino group. 10 alicyclic hydrocarbon groups are represented.
R ⁹⁵ represents a hydrogen atom or a saturated hydrocarbon group having 1 to 10 carbon atoms.
r represents an integer of 0 to 5. When r is 2 or more, the plurality of R ⁹³ may be the same or different.
X ⁹¹ represents a single bond or an alkanediyl group having 1 to 6 carbon atoms. )
Represents a group represented by ]
When the compound (1b) has —SO ₃ H and / or —CO ₂ H, these may form a salt (for example, Na salt or K salt).

Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms represented by R ⁹¹ and R ⁹² include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, Examples thereof include alkyl groups having 1 to 10 carbon atoms such as decyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group, neopentyl group, and 2-ethylhexyl group.
Examples of the substituent that these aliphatic hydrocarbon groups may have include a hydroxy group and a halogen atom.

Examples of the alicyclic hydrocarbon group having 3 to 10 carbon atoms represented by R ⁹¹ , R ⁹² and R ⁹⁴ include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group. Examples thereof include cycloalkyl groups having 3 to 10 carbon atoms.
Examples of the substituent that these alicyclic hydrocarbon groups may have include a hydroxy group and a halogen atom.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁹³ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, sec-butyl group, and tert-butyl group. , Isopentyl group, neopentyl group and the like.

Examples of the saturated hydrocarbon group having 1 to 10 carbon atoms represented by R ⁹⁴ and R ⁹⁵ include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. C1-C10 alkyl groups, such as group, are mentioned.

Examples of —CO ₂ R ⁹⁴ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of —NHCOR ⁹⁴ include an N-acetylamino group, an N-propanoylamino group, an N-butyrylamino group, an N-isobutyrylamino group, and an N-pivaloylamino group.

Examples of —SO ₃ R ⁹⁴ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

The -SO ₂ NR ⁹⁴ R ^95, N- methylsulfamoyl group, N- ethylsulfamoyl group, N- propyl sulfamoyl group, N- isopropyl sulfamoyl group, N- butylsulfamoyl group, N-isobutylsulfamoyl group, N-sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl 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-cyclopentylsulfa Yl group, N-cyclohexylsulfamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfa Moyl group, N- (1-methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1, N-1-substituted sulfamoyl groups such as 5-dimethyl) hexylsulfamoyl group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group, N- (5-aminopentyl) sulfamoyl group; N, N -Dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N- Propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1- And N, N-2 substituted sulfamoyl groups such as (methylpropyl) sulfamoyl group and N, N-heptylmethylsulfamoyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms representing X ⁹¹ include methylene group, ethylene group, propane-1,3-diyl group, propane-1,2-diyl group, butane-1,4-diyl group, and pentane. -1,5-diyl group, hexane-1,6-diyl group, ethane-1,1-diyl group, butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methyl A propane-1,2-diyl group, a pentane-1,4-diyl group, a 2-methylbutane-1,4-diyl group, and the like can be given.

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

  As an anthraquinone dye, the compound represented by Formula (3-4) and the compound represented by Formula (3-11) are more preferable. When these anthraquinone dyes are used, a high-contrast coating film or pattern can be formed, and there is little generation of foreign matter, and a coating film or pattern with excellent light resistance can be formed.

  The tetraazaporphyrin dye is a compound having a tetraazaporphyrin skeleton in the molecule. Further, when the tetraazaporphyrin dye is an acid dye or a basic dye, it may form a salt with any cation or anion.

Among these, as the tetraazaporphyrin dye, a dye containing a compound represented by the formula (1c) (hereinafter sometimes referred to as a compound (1c)) is preferable.

[In the formula (1c), R ^{71 to} R ⁷⁸ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted group. An aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyloxy group, or a substituted or unsubstituted amino group, M represents two hydrogen atoms, two monovalent metal atoms, 2 A valent metal atom, a trivalent substituted metal atom, or a metal oxide atom is represented. ]

In formula (1c), R ^{71 to} R ⁷⁸ are preferably each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 24 carbon atoms, or 1 to 24 carbon atoms. Substituted or unsubstituted alkoxy group, substituted or unsubstituted aryl group having 4 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 4 to 30 carbon atoms, substituted or unsubstituted aralkyl having 5 to 30 carbon atoms An oxy group and a substituted amino group having 1 to 30 carbon atoms.
R ^{71 to} R ⁷⁸ are more preferably each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 16 carbon atoms, or a C 1 to 16 carbon atom. A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group having 6 to 24 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 24 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 24 carbon atoms Group, a substituted amino group having 1 to 16 carbon atoms.
R ^{71 to} R ⁷⁸ are more preferably each independently a hydrogen atom, a fluorine atom, a bromine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted group having 1 to 10 carbon atoms. Substituted alkoxy group, substituted or unsubstituted aryl group having 6 to 16 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 16 carbon atoms, substituted or unsubstituted aralkyloxy group having 7 to 16 carbon atoms, carbon It is a substituted amino group of formula 1-12.
Specific examples of R ^{71 to} R ⁷⁸ in formula (1c) are shown below.
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the unsubstituted alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl Group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2, 6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, 1-ethyloctyl group, n-undecyl group 1-methyldecyl group, n-dodecyl group, n-tridecyl group, 1-hexylheptyl group, n-tetradecyl group, n-pentadecyl group, 1-heptyloctyl group, n-hexadecyl group, n-heptadecyl group, 1-octyl Carbon atoms such as nonyl group, n-octadecyl group, 1-nonyldecyl group, 1-decylundecyl group, n-eicosyl group, n-docosyl group, n-tetracosyl group, 1-adamantyl group, cyclopentyl group, cyclohexyl group, norbornyl group And a linear, branched or cyclic alkyl group consisting of only hydrogen atoms.
In the substituted alkyl group, examples of the substituent include an alkyloxy group having 1 to 16 carbon atoms, an alkyloxyalkyloxy group, an aralkyloxy group, an aryloxy group, an alkylthio group, a halogen atom, a halogenoalkyloxy group, and an aryloxy group. Is mentioned.
Specific examples of the alkyl group having a substituent include a methoxymethyl group, an ethoxymethyl group, an n-butoxymethyl group, an n-hexyloxymethyl group, a (2-ethylbutyloxy) methyl group, an n-octyloxymethyl group, n-decyloxymethyl group, 2-methoxyethyl group, 2-ethoxyethyl group, 2-n-propoxyethyl group, 2-isopropoxyethyl group, 2-n-butoxyethyl group, 2-n-pentyloxyethyl group 2-n-hexyloxyethyl group, 2- (2′-ethylbutyloxy) ethyl group, 2-n-heptyloxyethyl group, 2-n-octyloxyethyl group, 2- (2′-ethylhexyloxy) Ethyl group, 2-n-decyloxyethyl group, 2-n-dodecyloxyethyl group, 2-n-tetradecyloxyethyl group, 2-cyclohexane Siloxyethyl group, 2-methoxypropyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 3-n-propoxypropyl group, 3-isopropoxypropyl group, 3- (n-butoxy) propyl group, 3- (N-pentyloxy) propyl group, 3- (n-hexyloxy) propyl group, 3- (2′-ethylbutoxy) propyl group, 3- (n-octyloxy) propyl group, 3- (2′-ethylhexyl) Oxy) propyl group, 3- (n-decyloxy) propyl group, 3- (n-dodecyloxy) propyl group, 3- (n-tetradecyloxy) propyl group, 3-cyclohexyloxypropyl group, 4-methoxybutyl group 4-ethoxybutyl group, 4-n-propoxybutyl group, 4-isopropoxybutyl group, 4-n-butoxybutyl group, 4-n- Xyloxybutyl group, 4-n-octyloxybutyl group, 4-n-decyloxybutyl group, 4-n-dodecyloxybutyl group, 5-methoxypentyl group, 5-ethoxypentyl group, 5-n-propoxypentyl Group, 6-ethoxyhexyl group, 6-isopropoxyhexyl group, 6-n-butoxyhexyl group, 6-n-hexyloxyhexyl group, 6-n-decyloxyhexyl group, 4-methoxycyclohexyl group, 7-ethoxy Heptyl group, 7-isopropoxyheptyl group, 8-methoxyoctyl group, 10-methoxydecyl group, 10-n-butoxydecyl group, 12-ethoxydodecyl group, 12-isopropoxydecyl group, tetrahydrofurfuryl group, etc. An alkyl group having an alkyloxy group;
(2-methoxyethoxy) methyl group, (2-ethoxyethoxy) methyl group, (2-n-butyloxyethoxy) methyl group, (2-n-hexyloxyethoxy) methyl group, (3-methoxypropyloxy) methyl Group, (3-ethoxypropyloxy) methyl group, (3-n-butyloxypropyloxy) methyl group, (3-n-pentyloxypropyloxy) methyl group, (4-methoxybutyloxy) methyl group, (6 -Methoxyhexyloxy) methyl group, (10-ethoxydecyloxy) methyl group, 2- (2'-methoxyethoxy) ethyl group, 2- (2'-ethoxyethoxy) ethyl group, 2- (2'-n- Butoxyethoxy) ethyl group, 3- (2′-ethoxyethoxy) propyl group, 3- (2′-methoxypropyloxy) propyl group, 3- (2′-isopropyl) An alkyl group having an alkyloxyalkyloxy group, such as a ruoxypropyloxy) propyl group, a 3- (3′-methoxypropyloxy) propyl group, a 3- (3′-ethoxypropyloxy) propyl group; Methyl group, 2-benzyloxyethyl group, 2-phenethyloxyethyl group, 2- (4′-methylbenzyloxy) ethyl group, 2- (2′-methylbenzyloxy) ethyl group, 2- (4′-fluoro) Benzyloxy) ethyl group, 2- (4′-chlorobenzyloxy) ethyl group, 3-benzyloxypropyl group, 3- (4′-methoxybenzyloxy) propyl group, 4-benzyloxybutyl group, 2- (benzyl) Aralkyloxy groups such as oxymethoxy) ethyl group and 2- (4′-methylbenzyloxymethoxy) ethyl group Having an alkyl group;
Phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-methoxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 4-chlorophenyloxymethyl group Group, 2-chlorophenyloxymethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-methoxyphenyl) Oxy) ethyl group, 2- (4′-chlorophenyloxy) ethyl group, 2- (4′-bromophenyloxy) ethyl group, 2- (1′-naphthyloxy) ethyl group, 2- (2′-naphthyloxy) ) Ethyl group, 3-phenyloxypropyl group, 3- (2′-naphthyloxy) propyl group, 4-phenyloxy Til group, 4- (2'-ethylphenyloxy) butyl group, 5- (4'-tert-butylphenyloxy) pentyl group, 6- (2'-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3′-chlorophenyloxy) decyl group, 2- (2′-phenyloxyethoxy) ethyl group, 3- (2′-phenyloxyethoxy) propyl group, 4- (2 ′ -An alkyl group having an aryloxy group, such as a phenyloxyethoxy) butyl group;
n-butylthiomethyl group, n-hexylthiomethyl group, 2-methylthioethyl group, 2-ethylthioethyl group, 2-n-butylthioethyl group, 2-n-hexylthioethyl group, 2-n-octyl Thioethyl group, 2-n-decylthioethyl group, 3-methylthiopropyl group, 3-ethylthiopropyl group, 3-n-butylthiopropyl group, 4-ethylthiobutyl group, 4-n-propylthiobutyl group Alkylthio groups such as 4-n-butylthiobutyl group, 5-ethylthiopentyl group, 6-methylthiohexyl group, 6-ethylthiohexyl group, 6-n-butylthiohexyl group, 8-methylthiooctyl group, etc. Having an alkyl group;
Fluoromethyl group, 3-fluoropropyl group, 6-fluorohexyl group, 8-fluorooctyl group, trifluoromethyl group, 1,1-dihydro-perfluoroethyl group, 1,1-dihydro-perfluoro-n-propyl 1,1,3-trihydro-perfluoro-n-propyl group, 2-hydro-perfluoro-2-propyl group, 1,1-dihydro-perfluoro-n-butyl group, 1,1-dihydro- Perfluoro-n-pentyl group, 1,1-dihydro-perfluoro-n-hexyl group, 6-fluorohexyl group, 4-fluorocyclohexyl group, 1,1-dihydro-perfluoro-n-octyl group, 1, 1-dihydro-perfluoro-n-decyl group, 1,1-dihydro-perfluoro-n-dodecyl group, 1,1-dihydro-perfluoro-n- Tradecyl group, 1,1-dihydro-perfluoro-n-hexadecyl group, perfluoroethyl group, perfluoro-n-propyl group, perfluoro-n-pentyl group, perfluoro-n-hexyl group, 2,2- Bis (trifluoromethyl) propyl group, dichloromethyl group, 2-chloroethyl group, 3-chloropropyl group, 4-chlorocyclohexyl group, 7-chloroheptyl group, 8-chlorooctyl group, 2,2,2-trichloroethyl An alkyl group having a halogen atom such as a group;
Fluoromethyloxymethyl group, 3-fluoro-n-propyloxymethyl group, 6-fluoro-n-hexyloxymethyl group, trifluoromethyloxymethyl group, 1,1-dihydro-perfluoroethyloxymethyl group, 1, 1-dihydro-perfluoro-n-propyloxymethyl group, 2-hydro-perfluoro-2-propyloxymethyl group, 1,1-dihydro-perfluoro-n-butyloxymethyl group, 1,1-dihydro- Perfluoro-n-pentyloxymethyl group, 1,1-dihydro-perfluoro-n-hexyloxymethyl group, 1,1-dihydro-perfluoro-n-octyloxymethyl group, 1,1-dihydro-perfluoro -N-decyloxymethyl group, 1,1-dihydro-perfluoro-n-tetradecyloxymethyl Group, 2,2-bis (trifluoromethyl) propyloxymethyl group, 3-chloro-n-propyloxymethyl group, 2- (8-fluoro-n-octyloxy) ethyl group, 2- (1,1- Dihydro-perfluoroethyloxy) ethyl group, 2- (1,1,3-trihydro-perfluoro-n-propyloxy) ethyl group, 2- (1,1-dihydro-perfluoro-n-pentyloxy) ethyl Group, 2- (6-fluoro-n-hexyloxy) ethyl group, 2- (1,1-dihydro-perfluoro-n-octyloxy) ethyl group, 3- (4-fluorocyclohexyloxy) propyl group, 3 -(1,1-dihydro-perfluoroethyloxy) propyl group, 3- (1,1-dihydro-perfluoro-n-dodecyloxy) propyl group, 4- (perful (Ro-n-hexyloxy) butyl group, 4- (1,1-dihydro-perfluoroethyloxy) butyl group, 6- (2-chloroethyloxy) hexyl group, 6- (1,1-dihydro-perfluoro) An alkyl group having a halogenoalkyloxy group, such as an ethyloxy) hexyl group;
Phenyloxymethyl group, 4-methylphenyloxymethyl group, 3-methylphenyloxymethyl group, 2-methylphenyloxymethyl group, 4-ethylphenyloxymethyl group, 4-n-propylphenyloxymethyl group, 4-n -Butylphenyloxymethyl group, 4-tert-butylphenyloxymethyl group, 4-n-hexylphenyloxymethyl group, 4-n-octylphenyloxymethyl group, 4-n-decylphenyloxymethyl group, 4-methoxy Phenyloxymethyl group, 4-ethoxyphenyloxymethyl group, 4-butoxyphenyloxymethyl group, 4-n-pentyloxyphenyloxymethyl group, 4-fluorophenyloxymethyl group, 3-fluorophenyloxymethyl group, 2- Fluorophenyloxymethyl group, 3, -Difluorophenyloxymethyl group, 4-chlorophenyloxymethyl group, 2-chlorophenyloxymethyl group, 4-phenylphenyloxymethyl group, 1-naphthyloxymethyl group, 2-naphthyloxymethyl group, 2-furyloxymethyl group, 1-phenyloxyethyl group, 2-phenyloxyethyl group, 2- (4′-methylphenyloxy) ethyl group, 2- (4′-ethylphenyloxy) ethyl group, 2- (4′-n-hexylphenyl) Oxy) ethyl group, 2- (4′-methoxyphenyloxy) ethyl group, 2- (4′-n-butoxyphenyloxy) ethyl group, 2- (4′-fluorophenyloxy) ethyl group, 2- (4 '-Chlorophenyloxy) ethyl group, 2- (4'-bromophenyloxy) ethyl group, 2- (1'-naphthyloxy) Group, 2- (2′-naphthyloxy) ethyl group, 2-phenyloxypropyl group, 3-phenyloxypropyl group, 3- (4′-methylphenyloxy) propyl group, 3- (2′-naphthyloxy) ) Propyl group, 4-phenyloxybutyl group, 4- (2'-ethylphenyloxy) butyl group, 4-phenyloxypentyl group, 5-phenyloxypentyl group, 5- (4'-tert-butylphenyloxy) Pentyl group, 6-phenyloxyhexyl group, 6- (2′-chlorophenyloxy) hexyl group, 8-phenyloxyoctyl group, 10-phenyloxydecyl group, 10- (3′-methylphenyloxy) decyl group, etc. And an alkyl group having an aryloxy group.
The substituted or unsubstituted alkoxy group is an alkoxy group which may have a substituent similar to the alkyl group listed above, and an alkoxy group derived from the alkyl group shown as a specific example of the alkyl group is Can be mentioned.
Examples of the unsubstituted aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, 2-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 1-pyrenyl group, 2- Examples include a pyrenyl group, a 2-perylenyl group, a 3-perylenyl group, a 2-fluoranthenyl group, a 3-fluoranthenyl group, a 7-fluoranthenyl group, and an 8-fluoranthenyl group.
In the substituted aryl group, examples of the substituent include an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an aryloxy group, an aryl group, and a halogen atom.
Specific examples of the aryl group having a substituent include 1-methyl-2-pyrenyl group, 2-methylphenyl group, 4-ethylphenyl group, 4- (4′-tert-butylcyclohexyl) phenyl group, and 3-cyclohexyl. An aryl group having an alkyl group such as a phenyl group, 2-cyclohexylphenyl group, 4-ethyl-1-naphthyl group, 6-n-butyl-2-naphthyl group, 2,4-dimethylphenyl group;
4-methoxyphenyl group, 3-ethoxyphenyl group, 2-ethoxyphenyl group, 4-n-propoxyphenyl group, 3-n-propoxyphenyl group, 4-isopropoxyphenyl group, 3-isopropoxyphenyl group, 2- Alkoxy groups such as isopropoxyphenyl group, 2-sec-butoxyphenyl group, 4-n-pentyloxyphenyl group, 4-isopentyloxyphenyl group, 2-methyl-5-methoxyphenyl group, 2-phenyloxyphenyl group And an aryl group having an aryloxy group;
For example, 4-phenylphenyl group, 3-phenylphenyl group, 2-phenylphenyl group, 2,6-diphenylphenyl group, 4- (2′-naphthyl) phenyl group, 2-phenyl-1-naphthyl group, 1- An aryl group having an aryl group such as a phenyl-2-naphthyl group and a 7-phenyl-1-pyrenyl group;
4-fluorophenyl group, 3-fluorophenyl group, 2-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, 2-chloro-5-methylphenyl group, 2-chloro-6-methylphenyl group, 2 An aryl group having a halogen atom such as a methyl-3-chlorophenyl group, a 2-methoxy-4-fluorophenyl group, or a 2-fluoro-4-methoxyphenyl group;
2-trifluoromethylphenyl group, 3-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 3,5-bistrifluoromethylphenyl group, 4-perfluoroethylphenyl group, 4-methylthiophenyl group, 4- Examples thereof include an ethylthiophenyl group, a 4-cyanophenyl group, and a 3-cyanophenyl group.
The substituted or unsubstituted aryloxy group is an aryloxy group which may have a substituent similar to the substituted aryl group listed above, and is shown as a specific example of the substituted aryl group listed above. Examples thereof include a substituted or unsubstituted aryloxy group derived from a substituent.
As the substituted or unsubstituted aralkyloxy group, benzyloxy group, α-methylbenzyloxy group, phenethyloxy group, α-methylphenethyloxy group, α, α-dimethylbenzyloxy group, α, α-dimethylphenethyloxy group An aralkyloxy group having an unsubstituted or alkyl group, such as 4-methylphenethyloxy group, 4-methylbenzyloxy group, 4-isopropylbenzyloxy group;
An aralkyloxy group having an aryl group or an aralkyl group such as 4-benzylbenzyloxy group, 4-phenethylbenzyloxy group, 4-phenylbenzyloxy group; 4-methoxybenzyloxy group, 4-n-tetradecyloxybenzyl Oxy group, 4-n-heptadecyloxybenzyloxy group, 3,4-dimethoxybenzyloxy group, 4-methoxymethylbenzyloxy group, 4-vinyloxymethylbenzyloxy group, 4-benzyloxybenzyloxy group, 4- An aralkyloxy group having a substituted oxy group such as a phenethyloxybenzyloxy group;
Aralkyloxy groups having a hydroxyl group such as 4-hydroxybenzyloxy group, 4-hydroxy-3-methoxybenzyloxy group; 4-fluorobenzyloxy group, 3-chlorobenzyloxy group, 3,4-dichlorobenzyloxy group, etc. An aralkyloxy group having a halogen atom;
Examples include 2-furfuryloxy group, diphenylmethyloxy group, 1-naphthylmethyloxy group, 2-naphthylmethyloxy group and the like.
Specific examples of the amino group having a substituent include N-methylamino group, N-ethylamino group, Nn-butylamino group, N-cyclohexylamino group, Nn-octylamino group, and Nn-. An amino group having an alkyl group such as a decylamino group;
For example, N-benzylamino group, N-phenylamino group, N- (3-methylphenyl) amino group, N- (4-methylphenyl) amino group, N- (4-n-butylphenyl) amino group, N -(4-methoxyphenyl) amino group, N- (3-fluorophenyl) amino group, N- (4-chlorophenyl) amino group, N- (1-naphthyl) amino group, N- (2-naphthyl) amino group An amino group having an aralkyl group or an aryl group, such as
For example, N, N-dimethylamino group, N, N-diethylamino group, N, N-di-n-butylamino group, N, N-di-n-hexylamino group, N, N-di-n-octyl Amino group, N, N-di-n-decylamino group, N, N-di-n-dodecylamino group, N-methyl-N-ethylamino group, N-ethyl-Nn-butylamino group, N- Alkyl groups or aralkyl groups such as methyl-N-phenylamino group, N-ethyl-N-phenylamino group, Nn-butyl-N-phenylamino group;
For example, N, N-diphenylamino group, N, N-di (3-methylphenyl) amino group, N, N-di (4-methylphenyl) amino group, N, N-di (4-ethylphenyl) amino Group, N, N-di (4-tert-butylphenyl) amino group, N, N-di (4-n-hexylphenyl) amino group, N, N-di (4-methoxyphenyl) amino group, N, N-di (4-ethoxyphenyl) amino group, N, N-di (4-n-butoxyphenyl) amino group, N, N-di (4-n-hexyloxyphenyl) amino group, N, N-di (1-naphthyl) amino group, N, N-di (2-naphthyl) amino group, N-phenyl-N- (3-methylphenyl) amino group, N-phenyl-N- (4-methylphenyl) amino group N-phenyl-N- (4-octylphenyl) Mino group, N-phenyl-N- (4-methoxyphenyl) amino group, N-phenyl-N- (4-ethoxyphenyl) amino group, N-phenyl-N- (4-n-hexyloxyphenyl) amino group N-phenyl-N- (4-fluorophenyl) amino group, N-phenyl-N- (1-naphthyl) amino group, N-phenyl-N- (2-naphthyl) amino group, N-phenyl-N— An amino group disubstituted by an aryl group such as (3-phenylphenyl) amino group and N-phenyl-N- (4-phenylphenyl group) can be used.
In the formula (1c), M represents two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, a trivalent substituted metal atom, or a metal oxide atom, more preferably two A hydrogen atom, a divalent metal atom, or a metal oxide atom, and more preferably a divalent metal atom or a metal oxide atom.
Examples of the monovalent metal atom represented by M include alkali metal atoms such as Na, K, and Li.
Examples of the divalent metal atom represented by M include Cu, Zn, Fe, Co, Ni, Ru, Rh, Pd, Pt, Mn, Mg, Ti, Be, Ca, Ba, Cd, Hg, Pb, and Sn. And so on.
Examples of the trivalent substituted metal atom represented by M include, for example, Al—Cl, Ga—Br, Ga—I, In—Cl, Al—C ₆ H ₅ , In—C ₆ H ₅ , Mn (OH). , Mn [OSi (CH ₃ ) ₃ ], Fe—Cl, and the like.
Examples of the metal oxide atom represented by M include VO, MnO, and TiO.
In the formula (1c), M is preferably a divalent metal atom and a metal oxide atom, more preferably Cu, Zn, Fe, Co, Ni, Pd, Mn, Mg, VO and TiO, and Cu, Ni, Pd and VO are preferable, and Cu, Pd and VO are particularly preferable.

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

As the tetraazaporphyrin dye, a compound represented by the formula (2-29) is preferable.
A composition containing this tetraazaporphyrin dye can form a high-contrast coating film or pattern, and generates less foreign matter.

  The content of the dye (A1) is preferably 0.5% by mass or more and 80% by mass or less, and more preferably 40% by mass or more and 80% by mass or less, with respect to the total amount of the colorant (A).

  The content of the dye (A2) is preferably 1 to 100 parts by mass, and more preferably 10 to 100 parts by mass, with respect to 100 parts by mass of the dye (A1).

[式（１０）中、Ｒ^8１〜Ｒ^8４は、それぞれ独立に、水素原子、炭素数1〜4のアルキル基および水酸基を表す] <Colorless metal complex (F)>
The colored curable resin composition 2 of the present invention contains a colorless metal complex (F). Moreover, the colored curable resin composition 1 of this invention may contain the colorless metal complex (F).
Examples of the colorless metal complex (F) include a zinc complex represented by the formula (10).

[In Formula (10), R ^{81 to} R ⁸⁴ each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a hydroxyl group]

Examples of the alkyl group having 1 to 4 carbon atoms in R ^{81 to} R ⁸⁴ in the formula (10) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Groups. Specific examples of the zinc complex represented by the formula (10) include those shown in Table 3. Below, in the table ^- t _C 4 _{H 9} represents a tert- butyl group. Of these, (10) -18 is preferred from the viewpoint of improving heat resistance.

  The content of the colorless metal complex is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.1% by mass or more and 30% by mass or less, and 0.5% by mass with respect to the colorant (A). More preferably, it is 15 mass% or less.

The colored curable resin composition 1 of the present invention is at least 1 selected from the group consisting of a salt (A1) composed of a dye represented by formula (A-VI) and a counter ion, an anthraquinone dye and a tetraazaporphyrin dye. A colorant (A) containing two dyes (A2), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) are included. In addition, the colored curable resin composition 2 includes a colorant (A) containing a salt (A1) composed of a dye represented by formula (A-VI) and a counter ion, a resin (B), and photopolymerizability. A compound (C), a photoinitiator (D), a solvent (E), and a colorless metal complex (F) are included.
These colored curable resin compositions preferably further contain a polymerization initiation assistant (D1), a leveling agent (F), or an antioxidant (H), and more preferably contain an antioxidant (H). .
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
In addition to the dye (A1) and the dye (A2), the colorant (A) contained in the colored curable resin composition 1 of the present invention is further used for toning, that is, for adjusting spectral characteristics. Or dyes (P) or mixtures thereof.
The colorant (A) contained in the colored curable resin composition 2 of the present invention contains, in addition to the dye (A1), a dye other than the dye (A1), a pigment (P), or a mixture thereof. May be.

  Examples of the dye include oil-soluble dyes, acid dyes, basic dyes, direct dyes, mordant dyes, amine salts of acid dyes, sulfonamide derivatives of acid dyes, and the like, for example, Color Index (The Society of Dyers and Compounds classified as dyes by Colourists) and known dyes described in dyeing notes (color dyeing company). Also, according to chemical structure, azo dye, cyanine dye, triphenylmethane dye, xanthene dye, phthalocyanine dye, naphthoquinone dye, quinoneimine dye, methine dye, azomethine dye, squarylium dye, acridine dye, styryl dye, coumarin dye, quinoline And dyes and nitro dyes. Of these, organic solvent-soluble dyes are preferably used.

Specifically, C.I. I. Solvent Yellow 4, 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C. I. Solvent Red 45, 49, 125, 130, 218;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56;
C. I. Solvent Blue 4, 5, 37, 67, 70, 90;
C. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dyes,
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, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 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, 17, 19, 30, 102;
C. I. Acid Blue 1, 7, 9, 15, 18, 22, 29, 42, 59, 60, 62, 70, 72, 74, 82, 83, 86, 87, 90, 92, 93, 100, 102, 103, 104, 113, 117, 120, 126, 130, 131, 142, 147, 151, 154, 158, 161, 166, 167, 168, 170, 171, 184, 187, 192, 199, 210, 229, 234, 236, 242, 243, 256, 259, 267, 285, 296, 315, 335;
C. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. I. Acid dyes,

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, 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, 6, 8, 15, 22, 25, 41, 57, 71, 76, 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, 2 5,246,247,248,249,250,251,252,256,257,259,260,268,274,275,293;
C. I. Direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. I. Direct dyes,
C. I. C. such as Disperse Yellow 54, 76 I. Disperse dyes,
C. I. Basic Red 1, 10;
C. I. Basic Blue 1, 3, 5, 7, 9, 19, 24, 25, 26, 28, 29, 40, 41, 54, 58, 59, 64, 65, 66, 67, 68;
C. I. C. such as Basic Green 1; I. Basic dyes,
C. I. Reactive Yellow 2, 76, 116;
C. I. Reactive Orange 16;
C. I. Reactive Red 36; I. Reactive dyes,
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Red 1, 2, 4, 9, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 30, 32, 33, 36, 37, 38, 39, 41, 43 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95;
C. I. Modern 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. Modern violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58;
C. I. Modern Blue 1, 2, 3, 7, 9, 12, 13, 15, 16, 19, 20, 21, 22, 26, 30, 31, 39, 40, 41, 43, 44, 49, 53, 61 74, 77, 83, 84;
C. I. Modern Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Modern dyes,
C. I. C. of Bat Green 1 etc. I. Vat dye,
Etc.
Of these, blue dyes, violet dyes and red dyes are preferred.
These dyes may be used alone or in combination of two or more.

  In addition, xanthene dyes are preferred for classification by chemical structure.

［式（１）中、Ｒ¹及びＲ^２は、それぞれ独立に、置換基を有していてもよいフェニル基を表す。
Ｒ^３及びＲ^４は、互いに独立に、炭素数１〜１０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子はハロゲン原子で置換されていてもよく、該飽和炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−又は−ＮＲ^１１−で置き換わっていてもよい。
Ｒ¹及びＲ^３は互いに結合して、それらが結合する窒素原子と一緒になって窒素原子を含む環を形成してもよく、Ｒ^２及びＲ^４は互いに結合して、それらが結合する窒素原子と一緒になって窒素原子を含む環を形成してもよい。
Ｒ⁵は、−ＯＨ、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、それぞれ独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜４の整数を表す。ｍが２以上の整数である場合、複数のＲ⁵は同一であっても異なってもよい。
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
Ｒ⁹及びＲ¹⁰は、それぞれ独立に、水素原子又は炭素数１〜２０の１価の飽和炭化水素基を表し、Ｒ⁹及びＲ¹⁰は、互いに結合して窒素原子と一緒に３〜１０員含窒素複素環を形成していてもよい。
Ｒ¹¹は、それぞれ独立に、水素原子、炭素数１〜２０の１価の飽和炭化水素基又は炭素数７〜１０のアラルキル基を表す。］ A known substance can be used as the xanthene dye. For example, a compound represented by the formula (1) is preferable.

[In Formula (1), R < ¹ > and R < ² > represents the phenyl group which may have a substituent each independently.
R ³ and R ⁴ each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom, and the saturated —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —CO— or —NR ¹¹ —.
R ¹ and R ³ may be bonded together to form a ring containing a nitrogen atom together with the nitrogen atom to which they are bonded, and R ² and R ⁴ are bonded to each other to form a nitrogen to which they are bonded. A ring containing a nitrogen atom may be formed together with the atom.
R ⁵ _{is, -OH, -SO 3 H, -SO} 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ NR ⁹ R ¹⁰ Represents.
R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 4. When m is an integer of 2 or more, the plurality of R ⁵ may be the same or different.
R ⁸ 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.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
R ⁹ and R ¹⁰ each independently represents a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and R ⁹ and R ¹⁰ are bonded to each other to form 3 to 10 members together with a nitrogen atom. A nitrogen-containing heterocycle may be formed.
R ¹¹ each independently 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. ]

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms representing R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, and heptyl. Straight chain alkyl group having 1 to 20 carbon atoms such as octyl group, nonyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group; isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, isopentyl group A branched alkyl group having 3 to 20 carbon atoms such as a group, neopentyl group and 2-ethylhexyl group; 3 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and tricyclodecyl group ˜20 alicyclic saturated hydrocarbon groups.

Examples of —CO ₂ R ⁸ include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a tert-butoxycarbonyl group, a hexyloxycarbonyl group, and an icosyloxycarbonyl group.

Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl 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-cyclopentylsulfamoyl group, N-hexylsulfamoyl N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1-methylhexyl) sulfamoyl group, N- (1 , 4-Dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group, N- (1,1,2, , 2-tetramethylbutyl) sulfamoyl group and the like N-1 substituted sulfamoyl group; N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N , N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfamoyl group, N, N-tert-butylmethylsulfa N, N-2 substituted sulfamoyl groups such as yl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl group, etc. Can be mentioned.

R ⁹ and R ¹⁰ may be bonded to each other to form a 3- to 10-membered nitrogen-containing heterocycle together with the nitrogen atom. Examples of the heterocyclic ring include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms representing R ³ and R ⁴ include those having 1 to 10 carbon atoms. The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms representing R ³ and R ⁴ may be substituted with a halogen atom, and —CH ₂ — contained in the saturated hydrocarbon group is -O -, - CO- or ^{-NR 11} - may be replaced by.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
Examples of the saturated hydrocarbon group substituted with a halogen atom include a fluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a perfluoroethyl group, and a chlorobutyl group.

Examples of the alkyl group having 1 to 6 carbon atoms representing R ⁶ and R ⁷ include, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, sec-butyl group, tert. -A butyl group, an isopentyl group, a neopentyl group, etc. are mentioned.

Examples of the aralkyl group having 7 to 10 carbon atoms representing R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

Z ⁺ is ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ¹¹ ) ₄ .
As the ⁺ N (R ¹¹ ) ₄ , at least two of the four R ¹¹ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable.

The phenyl group representing R ¹ and R ² may have a substituent. Examples of the substituent include a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 R 8, -SR 8, -SO 2 R ⁸ , —SO ₃ R ⁸ and —SO ₂ NR ⁹ R ¹⁰ may be mentioned. Among these substituents, —R ⁸ is preferable, and a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable. -SO ₃ in this case ^- Z ^{+ _{The, -SO 3 - + N (R}} 11) 4 are preferred.

Examples of —OR ⁸ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group.
Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.

As R ³ and R ⁴ , an unsubstituted monovalent saturated hydrocarbon group having 1 to 10 carbon atoms is preferable, a monovalent saturated hydrocarbon group having 1 to 4 carbon atoms is more preferable, and a methyl group and an ethyl group are preferable. Further preferred.

R ¹ and R ³ may be bonded together to form a ring containing a nitrogen atom together with the nitrogen atom to which they are bonded, and R ² and R ⁴ are bonded to each other to form a nitrogen to which they are bonded. A ring containing a nitrogen atom may be formed together with the atom. Examples of the ring containing a nitrogen atom include the following.

The _{^{R 5, -SO 3 H, -SO}} 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ are preferred.
R ⁶ and R ⁷ are preferably a hydrogen atom, a methyl group and an ethyl group, and more preferably a hydrogen atom.
m is preferably an integer of 0 to 2, and more preferably 0 or 1.

［式（１）中、Ｒ²¹、Ｒ²²、Ｒ²³及びＲ²⁴は、それぞれ独立に、炭素数１〜４のアルキル基を表す。
ｐ及びｑは、それぞれ独立に、０〜５の整数を表す。ｐが２以上である場合、複数のＲ²³は同一でも異なってもよく、ｑが２以上である場合、複数のＲ²⁴は同一でも異なってもよい。］ As the compound (1), a compound represented by the formula (2) is preferable.

Wherein ^{(1), R 21, R} 22, R 23 and R ²⁴ each independently represents an alkyl group having 1 to 4 carbon atoms.
p and q represent the integer of 0-5 each independently. When p is 2 or more, the plurality of R ²³ may be the same or different, and when q is 2 or more, the plurality of R ²⁴ may be the same or different. ]

Examples of the alkyl group having 1 to 4 carbon atoms representing R ²¹ , R ²² , R ²³ and R ²⁴ 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. Groups and the like.
R ²¹ and R ²² are preferably, independently of each other, a methyl group and an ethyl group. R ²³ and R ²⁴ are preferably methyl groups.
m and n are preferably integers of 0 to 2, and are preferably 0 or 1.

［式（３）中、Ｒ³¹及びＲ³²は、それぞれ独立に、炭素数１〜４のアルキル基を表す。
Ｒ³³及びＲ³⁴は、それぞれ独立に、水素原子又は炭素数１〜４のアルキル基を表す。］ Ｒ³¹、Ｒ³²、Ｒ³³及びＲ³⁴を表す炭素数１〜４のアルキル基としては、前記と同じものが挙げられる。Ｒ³¹及びＲ³²は、それぞれ独立に、メチル基又はエチル基であることが好ましい。Ｒ³³及びＲ³⁴は、それぞれ独立に、水素原子又はメチル基であることが好ましい。 As the compound (1), a compound represented by the formula (3) is preferable.

[In formula (3), R ³¹ and R ³² each independently represents an alkyl group having 1 to 4 carbon atoms.
R ³³ and R ³⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. As the alkyl group having 1 to 4 carbon atoms that represent R ^31, R ^32, R ³³ and R ^34, same as those described above. R ³¹ and R ³² are preferably each independently a methyl group or an ethyl group. R ³³ and R ³⁴ are preferably each independently a hydrogen atom or a methyl group.

  Examples of compound (1) include compounds represented by formula (1-1) to formula (1-7), respectively. Especially, the compound represented by Formula (1-1) is preferable at the point which is excellent in the solubility to an organic solvent.

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

  The pigment (P) is preferably a blue pigment, more preferably a phthalocyanine pigment and a dioxazine pigment, and still more preferably C.I. I. At least one selected from the group consisting of CI Pigment Blue 15: 6 and CI Pigment Violet 23. By including the pigment, it is easy to optimize the transmission spectrum, and the heat resistance, light resistance and chemical resistance of the color filter are improved.

If necessary, the pigment can be atomized by rosin treatment, surface treatment using a pigment derivative having an acidic group or basic group introduced, graft treatment on the pigment surface with a polymer compound, sulfuric acid atomization method, etc. A treatment, a cleaning treatment with an organic solvent or water for removing impurities, a removal treatment with an ion exchange method of ionic impurities, or the like may be performed. The pigments preferably have a uniform particle size.
The pigment can be made into a pigment dispersion in a state of being uniformly dispersed in the pigment dispersant solution by carrying out a dispersion treatment by containing a pigment dispersant. The pigments may be subjected to a dispersion treatment alone, or a plurality of types may be mixed and dispersed.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic pigment dispersants. These pigment dispersants may be used alone or in combination of two or more. As a pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Co., Ltd.), EFKA (manufactured by BASF), Ajispur (Ajinomoto Fine) (Techno Co., Ltd.), Disperbyk (Bic Chemie) and the like.
When the pigment dispersant is used, the amount used is preferably 100 parts by mass or less, more preferably 5 parts by mass or more and 50 parts by mass or less, with respect to 100 parts by mass of the pigment. When the amount of the pigment dispersant used is in the above range, there is a tendency that a pigment dispersion in a uniform dispersion state is obtained.

  The content of the colorant (A) is preferably 5% by mass or more and 70% by mass or less, more preferably 5% by mass or more and 60% by mass or less, and further preferably 5% by mass with respect to the total amount of the solid content. % To 50% by mass. When the content of the colorant (A) is within the above range, a desired spectrum and color density can be obtained.

  In this specification, the “total amount of solids” refers to the total amount of components obtained by removing the solvent (E) from the colored curable resin composition of the present invention. The total amount of solids and the content of each component relative thereto can be measured by known analytical means such as liquid chromatography or gas chromatography, for example.

<Resin (B)>
Although it does not specifically limit as resin (B), It is preferable that it is alkali-soluble resin (B). The alkali-soluble resin (B) (hereinafter sometimes referred to as “resin (B)”) is derived from at least one monomer (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride. A copolymer containing structural units.
Examples of such a resin (B) include the following resins [K1] to [K6].
Resin [K1] at least one monomer (a) selected from the group consisting of unsaturated carboxylic acid and unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), and having 2 to 4 carbon atoms A copolymer of a monomer (b) having a cyclic ether structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b)”);
Resin [K2] (a) and (b), monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter referred to as “(c)”) In some cases)
Resin [K3] Copolymer of (a) and (c);
Resin [K4] A resin obtained by reacting (b) with a copolymer of (a) and (c);
Resin [K5] A resin obtained by reacting (a) with a copolymer of (b) and (c);
Resin [K6] A resin obtained by reacting (a) with a copolymer of (b) and (c) and further reacting with a carboxylic acid anhydride.

As (a), specifically, 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 and 1,4-cyclohexene dicarboxylic 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, 5-carboxy-6-ethylbicyclo [2.2.1] hept-2-ene;
Maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic 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 polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] 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 copolymerization reactivity and the solubility of the resulting resin in an alkaline aqueous solution.

(B) is, for example, a polymerizable compound having a C2-C4 cyclic ether structure (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring and a tetrahydrofuran ring) and an ethylenically unsaturated bond. Say.
(B) is preferably a monomer having a C2-C4 cyclic ether and a (meth) acryloyloxy group.
In the present specification, “(meth) acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth) acryloyl” and “(meth) acrylate” have the same meaning.

  Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(b1)”), and a single monomer having an oxetanyl group and an ethylenically unsaturated bond. Monomer (b2) (hereinafter sometimes referred to as “(b2)”), monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (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)”) And a monomer (b1-2) having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized (hereinafter sometimes referred to as “(b1-2)”).

  As (b1-1), glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p -Vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis (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- Examples include tris (glycidyloxymethyl) styrene.

  Examples of (b1-2) include vinylcyclohexene monooxide, 1,2-epoxy-4-vinylcyclohexane (for example, Celoxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth) acrylate (for example, Cyclomer M100; manufactured by Daicel Corporation), a compound represented by Formula (II), and Formula (III) The compound etc. which are represented by these are mentioned.

[In Formula (II) and Formula (III), 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. May be.
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, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with hydroxy include hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxyethyl group, 1-hydroxypropyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 1-hydroxy Examples include a -1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^a and R ^b are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group and a 2-hydroxyethyl group, more preferably a hydrogen atom and a methyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, and a pentane-1,5. -A diyl group, a hexane-1, 6-diyl group, etc. are mentioned.
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—, more preferably a single bond, * —CH _2. CH ₂ —O— (* represents a bond with O).

  Examples of the compound represented by the formula (II) include compounds represented by any one 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) A compound represented by formula (II-1), formula (II-7), formula (II-9) or formula (II-15) is more preferred.

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

  The compound represented by the formula (II) and the compound represented by the formula (III) may be used alone or in combination with the compound represented by the formula (II) and the compound represented by the formula (III). May be. When these are used in combination, the content ratio of the compound represented by the formula (II) and the compound represented by the formula (III) is preferably 5:95 to 95: 5, more preferably 10:90 to 5 on a molar basis. 90:10, more preferably 20:80 to 80:20.

  (B2) is more preferably a monomer having an oxetanyl group and a (meth) acryloyloxy group. (B2) includes 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 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.

  (B3) is more preferably a monomer having a tetrahydrofuryl group and a (meth) acryloyloxy group. Specific examples of (b3) include tetrahydrofurfuryl acrylate (for example, Biscoat V # 150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, and the like.

  (B) is preferably (b1) in that the color filter obtained can have higher reliability such as heat resistance and chemical resistance. Furthermore, (b1-2) is more preferable in that the storage stability of the colored curable resin composition is excellent.

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 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) There is a bird) Black (in the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) [5.2.1.0 ^2,6] decene-8-yl (meth) acrylate, dicyclopenta Nyloxyethyl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, allyl (meth) acrylate, propargyl (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, benzyl (meth) acrylate, etc. (Meth) acrylic acid esters of
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 itaconate;
Bicyclo [2.2.1] hept-2-ene, 5-methylbicyclo [2.2.1] hept-2-ene, 5-ethylbicyclo [2.2.1] hept-2-ene, 5- Hydroxybicyclo [2.2.1] hept-2-ene, 5-hydroxymethylbicyclo [2.2.1] hept-2-ene, 5- (2′-hydroxyethyl) bicyclo [2.2.1] Hept-2-ene, 5-methoxybicyclo [2.2.1] hept-2-ene, 5-ethoxybicyclo [2.2.1] hept-2-ene, 5,6-dihydroxybicyclo [2.2 .1] Hept-2-ene, 5,6-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 (cyclohexyloxycarbonyl) bicyclo [2.2.1] hept-2-ene, etc. Bicyclounsaturated compounds;
N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, 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.
Among these, styrene, vinyltoluene, benzyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate, N from the viewpoint of copolymerization reactivity and heat resistance. -Phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene are preferred.

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

  The resin [K1] is, for example, a method described in the document “Experimental Method for Polymer Synthesis” (Takayuki Otsu, published by Kagaku Dojin Co., Ltd., First Edition, First Edition, issued March 1, 1972) and the document Can be produced with reference to the cited references described in 1.

  Specifically, a predetermined amount of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, for example, by substituting oxygen with nitrogen to create a deoxygenated atmosphere, with stirring, The method of heating and heat retention is mentioned. In addition, the polymerization initiator, the solvent, and the like used here are not particularly limited, and those usually used in the field can be used. Examples of the polymerization initiator include azo compounds (2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). As the solvent, any solvent that dissolves each monomer may be used. Examples of the solvent (E) for the colored curable resin composition of the present invention include a solvent described later.

  In addition, the obtained copolymer may use the solution after reaction as it is, a concentrated or diluted solution may be used, and it took out as solid (powder) by methods, such as reprecipitation. Things may be used. In particular, by using the solvent contained in the colored curable resin composition of the present invention as a solvent during the polymerization, the solution after the reaction is used as it is for the preparation of the colored 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 of the structural units in the resin [K2]
Structural unit derived from (a); 2-45 mol%
Structural unit derived from (b); 2 to 95 mol%
Structural unit derived from (c); 1 to 65 mol%
It is preferable that
Structural unit derived from (a); 5 to 40 mol%
Structural unit derived from (b); 5 to 80 mol%
Structural unit derived from (c); 5 to 60 mol%
It is more preferable that
When the ratio of the structural unit of the resin [K2] is in the above range, the storage stability of the colored curable resin composition, the developability when forming a colored pattern, and the solvent resistance of the resulting color filter, There is a tendency to be excellent in heat resistance and mechanical strength.

  Resin [K2] can be produced, for example, in the same manner as the method described as the production method of resin [K1].

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

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

Next, the C2-C4 cyclic ether which (b) has is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer.
Subsequent to the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b) a reaction catalyst of carboxylic acid or carboxylic anhydride and cyclic ether (for example, tris ( Dimethylaminomethyl) phenol, etc.) and a polymerization inhibitor (eg, hydroquinone, etc.) are placed in a flask and reacted, for example, at 60-130 ° C. for 1-10 hours to produce resin [K4]. it can.
The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By making it within this range, the storage stability of the colored curable resin composition, the developability when forming the pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the resulting pattern are improved. Tend. Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (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, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment and the amount of heat generated by polymerization. In addition, like the polymerization conditions, the charging method and the reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by polymerization, and the like.

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

Further, under the same conditions as in the method for producing the resin [K4], the cyclic ether derived from (b) of the copolymer of (b) and (c) is added to the carboxylic acid or carboxylic acid anhydride of (a). Resin [K5] can be obtained by reacting the product.
As for the usage-amount of (a) made to react with the said copolymer, 5-80 mol is preferable with respect to 100 mol of (b). Since the reactivity of the cyclic ether is high and unreacted (b) hardly remains, (b1) is preferable as (b) used for the resin [K5], and (b1-1) is more preferable.

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

Specific examples of the resin (B) include 3,4-epoxycyclohexylmethyl (meth) acrylate / (meth) acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6. ] Resin such as decyl (meth) 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 ] decyl (meth) acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3 , 4-epoxytricyclo [5.2.1.0 ^2.6] decyl (meth) acrylate / (meth) acrylic acid / vinyl toluene copolymer, 3- menu Resin such as ru-3- (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer [K2]; benzyl (meth) acrylate / (meth) acrylic acid copolymer, styrene / (meth) Acrylic acid copolymer, resin such as benzyl (meth) acrylate / tricyclodecyl (meth) acrylate / (meth) acrylic acid copolymer [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer A resin in which glycidyl (meth) acrylate is added to a resin, a resin in which glycidyl (meth) acrylate is added to a tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, tricyclodecyl (meth) acrylate / Benzyl (meth) acrylate / (meth) acrylic acid copolymer with glycidyl (meth) acrylate Resin [K4] such as a resin to which a relate is added; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid, tricyclodecyl (meth) acrylate / Resin such as a resin obtained by reacting a copolymer of styrene / glycidyl (meth) acrylate with (meth) acrylic acid [K5]; a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate (meth) Examples thereof include a resin [K6] such as a resin obtained by reacting acrylic acid with a resin further reacted with tetrahydrophthalic anhydride.

The resin (B) is preferably a kind selected from the group consisting of a resin [K1], a resin [K2] and a resin [K3], and more preferably from a group consisting of a resin [K2] and a resin [K3]. It is the kind chosen. When these resins are used, the colored curable resin composition is excellent in developability.
Resin [K2] is more preferable from the viewpoint of adhesion between the coloring pattern and the substrate.

The polystyrene equivalent weight average molecular weight of the resin (B) is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and further preferably 5,000 to 30,000. . When the molecular weight is in the above range, the coating film hardness is improved, the residual film ratio is high, the solubility of the unexposed area in the developer is good, and the resolution of the colored pattern tends to be improved.
The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (B) is preferably 1.1 to 6, 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, and still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the resin (B), and can be determined by titration with an aqueous potassium hydroxide solution, for example.

  Content of resin (B) becomes like this. Preferably it is 7-65 mass% with respect to the total amount of solid content, More preferably, it is 13-60 mass%, More preferably, it is 17-55 mass%. When the content of the resin (B) is in the above range, a colored pattern can be formed, and the resolution and remaining 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 a compound having a polymerizable ethylenically unsaturated bond. Is a (meth) acrylic acid ester compound.

  Examples of the polymerizable compound having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. And 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 (Meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.

  Especially, it is preferable that a polymeric compound (C) is a polymeric compound which has 3 or more of ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( (Meth) acrylate, tripentaerythritol octa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, tetrapentaerythritol nona (meth) acrylate, tris (2- (meth) acryloyloxyethyl) ) Isocyanurate, ethylene glycol modified pentaerythritol tetra (meth) acrylate, ethylene glycol modified dipentaerythritol Hexa (meth) acrylate, propylene glycol modified pentaerythritol tetra (meth) acrylate, propylene glycol modified dipentaerythritol hexa (meth) acrylate, caprolactone modified pentaerythritol tetra (meth) acrylate, caprolactone modified dipentaerythritol hexa (meth) acrylate, etc. 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 from 150 to 2,900, more preferably from 250 to 1,500.

The content of the polymerizable compound (C) is preferably 7 to 65% by mass, more preferably 13 to 60% by mass, and further preferably 17 to 55% by mass with respect to the total amount of the solid content. is there.
Further, the content ratio of the resin (B) and 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 remaining film ratio at the time of forming the colored pattern and the chemical resistance of the color filter tend to be improved.

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

前記Ｏ−アシルオキシム化合物としては、例えば、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−｛２−メチル−４−（３，３−ジメチル−２，４−ジオキサシクロペンタニルメチルオキシ）ベンゾイル｝−９Ｈ−カルバゾール−３−イル］エタン−１−イミン、Ｎ−アセトキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−イミン、Ｎ−ベンゾイルオキシ−１−［９−エチル−６−（２−メチルベンゾイル）−９Ｈ−カルバゾール−３−イル］−３−シクロペンチルプロパン−１−オン−２−イミン等が挙げられる。イルガキュアＯＸＥ０１、ＯＸＥ０２（以上、ＢＡＳＦ社製）、Ｎ−１９１９（ＡＤＥＫＡ社製）等の市販品を用いてもよい。中でも、Ｏ−アシルオキシム化合物は、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）ブタン−１−オン−２−イミン、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミン及びＮ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）−３−シクロペンチルプロパン−１−オン−２−イミンからなる群から選ばれる少なくとも１種が好ましく、Ｎ−ベンゾイルオキシ−１−（４−フェニルスルファニルフェニル）オクタン−１−オン−２−イミンがより好ましい。これらのＯ−アシルオキシム化合物であると、高明度なカラーフィルタが得られる傾向にある。 The O-acyl oxime compound is a compound having a partial structure represented by the formula (d1). Hereinafter, * represents a bond.

Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine and N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane. -1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1- [9-ethyl-6- (2-Methylbenzoyl) -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- [9-ethyl-6- {2-methyl-4- (3,3-dimethyl-2, 4-Dioxacyclopentanylmethyloxy) benzoyl} -9H-carbazol-3-yl] ethane-1-imine, N-acetoxy-1- 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -3-cyclopentylpropane-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) ) -9H-carbazol-3-yl] -3-cyclopentylpropan-1-one-2-imine and the like. Commercial products such as Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (ADEKA) may be used. Among these, O-acyloxime compounds include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, 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-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy -1- (4-Phenylsulfanylphenyl) octane-1-one-2-imine is more preferred. When these O-acyloxime compounds are used, a color filter with high brightness tends to be obtained.

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, 2-dimethylamino-1- (4 -Morpholinophenyl) -2-benzylbutan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one Etc. Commercial products such as Irgacure 369, 907, 379 (above, 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, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomer of 2-hydroxy-2-methyl-1- (4-isopropenylphenyl) propan-1-one, α, α-diethoxy Examples include acetophenone and benzyl dimethyl ketal.
In terms of sensitivity, the alkylphenone compound is preferably a compound having a partial structure represented by the formula (d2).

［式（ｄ５）中、Ｒ^１３〜Ｒ^１８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。］ The biimidazole compound is, for example, a compound represented by the formula (d5).

[In 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. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned, for example, Preferably it is a chlorine atom. As a C1-C4 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, a butoxy group etc. are mentioned, for example, Preferably it is a methoxy group.

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 and JP-A-6-75373), 2,2′-bis (2-chlorophenyl) -4, 4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (alkoxyphenyl) biimidazole, 2,2′-bis ( 2-chlorophenyl) -4,4 ′, 5,5′-tetra (dialkoxyphenyl) biimidazole, 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetra (trialkoxy) Phenyl) biimidazo (See, for example, JP-B-48-38403, JP-A-62-174204, etc.), Imidazole compounds in which the phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group ( For example, see JP-A-7-10913. Among these, compounds represented by the following formula and mixtures thereof are preferable.

  Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- Methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-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- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino- 2-methylpheny ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

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

Furthermore, as the polymerization initiator (D), benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether; benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl- Benzophenone compounds such as 4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone; 9,10-phenanthrenequinone, Examples include quinone compounds such as 2-ethylanthraquinone and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.
These are preferably used in combination with a polymerization initiation assistant (D1) (particularly amines) described later.

  The polymerization initiator (D) is preferably a polymerization initiator containing at least one selected from the group consisting of alkylphenone compounds, triazine compounds, acylphosphine oxide compounds, O-acyloxime compounds and biimidazole compounds, 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 per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass.

<Polymerization initiation aid (D1)>
The polymerization initiation assistant (D1) is a compound or a sensitizer used for accelerating the polymerization of the polymerizable compound that has been polymerized by the polymerization initiator. When the polymerization initiation assistant (D1) is included, 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, 4 2-dimethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (Ethylmethylamino) benzophenone and the like can be mentioned, among which 4,4′-bis (diethylamino) benzophenone is preferable. Commercial products such as EAB-F (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, 9,10-di. Examples include butoxyanthracene and 2-ethyl-9,10-dibutoxyanthracene.

  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, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like can be mentioned.

  When using these polymerization initiation assistants (D1), 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). Preferably it is 1-20 mass parts. When the amount of the polymerization initiation assistant (D1) is within this range, a colored pattern can be formed with higher sensitivity and the productivity of the color filter tends to be improved.

<Solvent (E)>
A solvent (E) is not specifically limited, The solvent normally used in the said field | area can be used. For example, an ester solvent (a solvent containing —COO— in the molecule and not containing —O—), an ether solvent (a solvent containing —O— in the molecule and not containing —COO—), an ether ester solvent (intramolecular) Solvent containing -COO- and -O-), ketone solvent (solvent containing -CO- in the molecule and not containing -COO-), alcohol solvent (containing OH in the molecule, -O-,- A solvent not containing CO- and -COO-), an aromatic hydrocarbon solvent, an amide solvent, dimethyl sulfoxide and the like.

  As ester solvents, methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, 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.

  Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether , Propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethyl Glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

  Examples of ether ester solvents 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 ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate and the like.

  Examples of 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. Etc.

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- Methoxy-1-butanol, 4-hydroxy-4-methyl-2-pentanone, N, N-dimethylformamide, N-methylpyrrolidone and the like are preferable, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethylene glycol monobutyl ether, di Propylene glycol methyl ether acetate, ethyl lactate, 3-methoxy Chill acetate, 3-methoxy-1-butanol, ethyl 3-ethoxypropionate, N- methylpyrrolidone is more preferred.

The content of the solvent (E) is preferably 70 to 95% by mass and more preferably 75 to 92% by mass with respect to 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 when the color filter is formed, the color density does not become insufficient and the display characteristics tend to be good.

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

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

  Examples of the silicone-based surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by DIC Corporation), and the like can be given.

  When the leveling agent (F) is contained, the content thereof is preferably 0.001% by mass or more and 0.2% by mass or less, more preferably 0.002%, based on the total amount of the colored curable resin composition. It is 0.005 mass% or more and 0.07 mass% or less more preferably. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Antioxidant (H)>
From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use an antioxidant alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an antioxidant generally used industrially, and a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, and the like can be used.

  Examples of the phenol-based antioxidant include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation). Irganox 1076 (Irganox 1076: octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corporation), Irganox 1330 (Irganox 1330: 3, 3 ′, 3 ′ ', 5,5', 5 ''-hexa-t-butyl-a, a ', a' '-(mesitylene-2,4,6-triyl) tri-p-cresol, manufactured by BASF Corp.) Irganox 3114: 1,3,5-tris (3,5-di-tert-butyl- -Hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF), Irganox 3790 (Irganox 3790: 1,3,5-Tris ( (4-t-butyl-3-hydroxy-2,6-xylyl) methyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, manufactured by BASF Corporation) Irganox 1035 (Irganox 1035: thiodiethylenebis [3- (3,5-di-teRt-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Irganox 1135 (Irganox 1135: benzenepropanoic acid, 3,5-bis (1,1-dimethylethyl) -4-hydroxy, C7-C9 side chain alkyl ester, BASF Corporation ), Irganox 1520L (Irganox 1520L: 4,6-bis (octylthiomethyl) -o-cresol, manufactured by BASF), Irganox 3125 (Irganox 3125, manufactured by BASF), Irganox 565 ( Irganox 565: 2,4-bis (n-octylthio) -6- (4-hydroxy 3 ′, 5′-di-t-butylanilino) -1,3,5-triazine, manufactured by BASF Corp.), ADK STAB AO -80 (Adekastab AO-80: 3,9-bis (2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4 , 8,10-tetraoxaspiro (5,5) undecane, manufactured by ADEKA), Sumilizer BHT (Sumil zer BHT (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cyanox 1790, ( And Vitamin E (manufactured by Eisai Co., Ltd.).

  Examples of the phosphorus antioxidant include Irgafos 168 (Irgafos 168: Tris (2,4-di-t-butylphenyl) phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: Tris [2- [[2,4,8,10-tetra-t-butyldibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, manufactured by BASF Corp.) Irgafos 38 (Irgafos 38: bis (2,4-bis (1,1-dimethylethyl) -6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF Corp.), Adekastab 329K (produced by ADEKA Corp.), ADK STAB PEP36 (manufactured by ADEKA), ADK STAB PEP-8 (manufactured by ADEKA), Sandstab P-E Q (manufactured by Clariant), Weston 618 (Weston 618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (manufactured by Ultranox 626, manufactured by GE), and Sumitizer GP: 6- [ 3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propoxy] -2,4,8,10-tetra-tert-butyldibenz [d, f] [1.3.2] dioxaphosphine Pin) (manufactured by Sumitomo Chemical Co., Ltd.).

  Examples of the sulfur-based antioxidant include dialkylthiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl or distearyl, and β-alkyl mercaptopropion of polyols such as tetrakis [methylene (3-dodecylthio) propionate] methane. Examples include acid ester compounds.

<Other ingredients>
The colored curable resin composition of the present invention may contain additives known in the art, such as fillers, other polymer compounds, adhesion promoters, light stabilizers, chain transfer agents, and the like, if necessary. .

<Method for producing colored curable resin composition>
The colored curable resin composition 1 of the present invention includes, for example, a dye (A1) and a dye (A2) as a colorant (AA), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and It can be prepared by mixing the solvent (E), the leveling agent (F), the polymerization initiation assistant (D1), the antioxidant (H), and other components used as necessary.
The colored curable resin composition 2 of the present invention includes, for example, a dye (A1), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a colorless metal complex (F) as the colorant (A). ), The solvent (E), and a leveling agent (F), a polymerization initiation assistant (D1), an antioxidant (H), and other components used as necessary.
The pigment in the case of containing the pigment (P) is preferably mixed with a part or all of the solvent (E) in advance and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. . Under the present circumstances, you may mix | blend a part or all of the said pigment dispersant and resin (B) as needed. The desired colored curable resin composition can be prepared by mixing the remaining components in the pigment dispersion thus obtained so as to have a predetermined concentration.
It is preferable to prepare a solution by dissolving the colorant (A) dye in part or all of the solvent (E) in advance. The solution is preferably filtered with a filter having a pore size of about 0.01 to 1 μm.
The colored curable resin composition after mixing is preferably filtered with a filter having a pore size of about 0.01 to 10 μm.

<Color filter manufacturing method>
Examples of the method for producing a colored pattern from the colored curable resin composition of the present invention include a photolithographic method, an inkjet method, and a printing method. Of these, the photolithographic method is preferable. The photolithographic method is a method in which the colored curable resin composition is applied to a substrate, dried to form a colored composition layer, and the colored composition layer is exposed through a photomask and developed. In the photolithography method, a colored coating film that is a cured product of the colored composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film thus formed are the color filter of the present invention.
The film thickness of the color filter to be produced is not particularly limited, and can be adjusted as appropriate according to the purpose and application. ~ 6 μm.

  As the substrate, quartz glass, borosilicate glass, alumina silicate glass, glass plate such as soda lime glass coated with silica on the surface, resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, on the substrate In addition, aluminum, silver, or a silver / copper / palladium alloy thin film is used. On these substrates, another color filter layer, a resin layer, a transistor, a circuit, and the like may be formed.

Formation of each color pixel by the photolithographic method can be performed by a known or commonly used apparatus and conditions. For example, it can be produced as follows.
First, a colored curable resin composition is applied on a substrate, dried by heating (pre-baking) and / or drying under reduced pressure to remove volatile components such as a solvent, and a smooth colored composition layer is obtained.
Examples of the coating method include spin coating, slit coating, and slit and spin coating.
30-120 degreeC is preferable and the temperature in the case of performing heat drying has more preferable 50-110 degreeC. In addition, the heating time is preferably 10 seconds to 60 minutes, and more preferably 30 seconds to 30 minutes.
When performing vacuum drying, it is preferable to carry out in the temperature range of 20-25 degreeC under the pressure of 50-150 Pa.
The film thickness of the coloring composition layer is not particularly limited, and may be appropriately selected according to the film thickness of the target color filter.

Next, the coloring composition layer is exposed through a photomask for forming a target coloring pattern. The pattern on the photomask is not particularly limited, and a pattern according to the intended use is used.
The light source used for exposure is preferably a light source that generates light having a wavelength of 250 to 450 nm. For example, light less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, 408 nm, and 365 nm can be selectively extracted using a bandpass filter that extracts these wavelength ranges. Or you may. Specifically, examples of the light source include a mercury lamp, a light emitting diode, a metal halide lamp, and a halogen lamp.
Use an exposure device such as a mask aligner or a stepper because the entire exposure surface can be illuminated with parallel rays uniformly, or the photomask can be accurately aligned with the substrate on which the colored composition layer is formed. Is preferred.

A colored pattern is formed on the substrate by developing the exposed colored composition layer in contact with a developer. By the development, the unexposed portion of the colored composition layer is dissolved in the developer and removed.
As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, 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 paddle method, dipping method, 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.

  Furthermore, it is preferable to post-bake the obtained colored pattern. The post-bake temperature is preferably 150 to 250 ° C, more preferably 160 to 235 ° C. The post-bake time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes.

  By using the colored curable resin composition of the present invention, a color filter having particularly high brightness can be produced. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these Examples. In the examples, “%” and “part” representing the content or amount used are based on mass unless otherwise specified.
In the following, the structure of the compound was confirmed by mass spectrometry (LC; Agilent 1200 type, MASS; Agilent LC / MSD type).

Synthesis example 1
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 36.3 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with ice, 45.7 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 35.3 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 52.0 parts of a compound represented by the formula (BI-1). Yield 50%

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 9.3 parts of the compound represented by the formula (BI-1), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10. After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 19.8 parts of a compound represented by the formula (A-II-1). Yield 100%

Identification of compound represented by formula (A-II-1) (mass spectrometry) ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺
Exact Mass: 636.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-1), 4.5 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 100.0 parts of N, N-dimethylformamide were added, followed by stirring at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.3 parts of a compound represented by the formula (AI-1). Yield 82%

0.35 g of the compound represented by the formula (A-I-1) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λmax = 628 nm.

Synthesis example 2
An appropriate amount of nitrogen was passed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to make a nitrogen atmosphere, 100 parts of propylene glycol monomethyl ether acetate was added, and the mixture was heated to 85 ° C. with stirring. Next, 19 parts of methacrylic acid, 3,4-epoxytricyclo [5.2.1.0 ^2,6 ] decan-8-yl acrylate and 3,4-epoxytricyclo [5.2. 1.0 ^2,6 ] decan-9-yl acrylate mixture (content ratio is 50:50 in molar ratio) (trade name “E-DCPA”, manufactured by Daicel Corporation) 171 parts propylene glycol monomethyl ether acetate 40 parts The solution dissolved in was dropped over about 5 hours using a dropping pump. On the other hand, a solution prepared by dissolving 26 parts of a polymerization initiator 2,2′-azobis (2,4-dimethylvaleronitrile) in 120 parts of propylene glycol monomethyl ether acetate was placed in a flask over about 5 hours using another dropping pump. It was dripped. After dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-1) solution having a solid content of 43.5%. The obtained resin (B-1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mg-KOH / g.

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

Synthesis example 3
250.4 parts of propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, a dropping funnel, a condenser, a thermometer, and a gas introduction tube, stirred while purging with nitrogen, and heated to 120 ° C. Next, 37.4 parts of methacrylic acid, 61.3 parts of benzyl methacrylate, 18.5 parts of glycidyl methacrylate, and 19.2 parts of monomethacrylate having a tricyclodecane skeleton (FA-513M manufactured by Hitachi Chemical Co., Ltd.) 6.13 parts of t-butyl hydroperoxide (Nippon Yushi Co., Ltd. perbutyl O) was added to the monomer mixture consisting of This was dropped into the flask from the dropping funnel over 2 hours, and further stirred at 120 ° C. for 2 hours for aging. Next, the inside of the flask was replaced with air, and 0.96 parts of trisdimethylaminomethylphenol (DMP-30) and hydroquinone 0. 145 parts were charged into the aged product and the reaction was continued at 120 ° C. for 6 hours to obtain a copolymer (resin (B-2) solution having a solid content of 38.4% by mass and an acid value of 122 mg-KOH / g. The obtained resin (B-2) had a weight average molecular weight Mw of 10700 and a molecular weight distribution of 2.18, and the weight average molecular weight and the molecular weight distribution were the same as those of the resin (B-1). It was measured by.

Synthesis example 4
50 parts of methanol was added to 2.00 parts of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) and dissolved. Furthermore, 15.41 parts of 2,6-dihydroxybenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) and 3.09 parts of boric acid (manufactured by Wako Pure Chemical Industries, Ltd.) were added and stirred at 65 ° C. for 8.5 hours. did.
The mixture was cooled to room temperature, and the precipitate was collected by suction filtration and washed with 237 parts of ion-exchanged water to obtain 10.90 parts of a compound represented by the formula (BC-1-Na).

Synthesis example 5
The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-1), 5.3 parts of the compound represented by the formula (BC-1-Na), and N, After adding 100.0 parts of N-dimethylformamide, the mixture was stirred at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 12.0 parts of a compound represented by the formula (AI-3). Yield 83%

0.35 g of the compound represented by the formula (AI-3) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.6 (arbitrary unit) at λmax = 628 nm.

Synthesis Example 6
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 32.2 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of 2-fluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and 40.5 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 31.3 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 49.9 parts of a compound represented by the formula (BI-7). Yield 51%

Synthesis example 7
The following reaction was performed in a nitrogen atmosphere. 9. In a flask equipped with a condenser and a stirrer, 9.9 parts of the compound represented by the formula (BI-7), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 17.2 parts of a compound represented by the formula (A-II-7). Yield 85%

Identification of compound represented by formula (A-II-7) (mass spectrometry) ionization mode = ESI +: m / z = 619.3 [M-Cl] ⁺
Exact Mass: 654.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-7), 5.7 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.9 parts of a compound represented by the formula (AI-7). Yield 86%

0.35 g of the compound represented by the formula (AI-7) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 3.1 (arbitrary unit) at λmax = 630 nm.

Synthesis Example 8
The following reaction was performed in a nitrogen atmosphere. After charging 23.3 parts of potassium thiocyanate and 160.0 parts of acetone in a flask equipped with a condenser and a stirrer, the mixture was stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-bromobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and 29.3 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 22.6 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 41.6 parts of a compound represented by the formula (BI-8). Yield 45%

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 12.9 parts of a compound represented by the formula (BI-8), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10. After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 17.6 parts of a compound represented by the formula (A-II-8). Yield 80%

Identification of compound represented by formula (A-II-8) (mass spectrometry) ionization mode = ESI +: m / z = 679.3 [M-Cl] ⁺
Exact Mass: 714.2

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-8), 5.2 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 12.9 parts of a compound represented by the formula (AI-8). Yield 96%

0.35 g of the compound represented by the formula (AI-7) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.6 (arbitrary unit) at λmax = 632 nm.

Synthesis Example 9
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 33.0 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-methylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with ice, 41.6 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 32.1 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 40.5 parts of a compound represented by the formula (BI-9). Yield 41%

The following reaction was performed in a nitrogen atmosphere. 9. In a flask equipped with a condenser and a stirrer, 9.7 parts of the compound represented by the formula (BI-9), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried under reduced pressure at 60 ° C. to obtain 15.1 parts of a compound represented by the formula (A-II-9). Yield 75%

Identification of compound represented by formula (A-II-9) (mass spectrometry) ionization mode = ESI +: m / z = 615.4 [M-Cl] ⁺
Exact Mass: 650.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-8), 5.7 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 13.2 parts of a compound represented by the formula (AI-8). Yield 96%

0.35 g of the compound represented by the formula (AI-9) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.7 (arbitrary unit) at λmax = 627 nm.

Synthesis Example 10
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirring device was charged with 24.5 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of 2-trifluoromethylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and 30.8 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 23.8 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 31.1 parts of a compound represented by the formula (BI-10). Yield 36%

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 11.4 parts of the compound represented by the formula (BI-10), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10. After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 15.2 parts of a compound represented by the formula (A-II-10). Yield 70%

Identification of compound represented by formula (A-II-10) (mass spectrometry) ionization mode = ESI +: m / z = 669.3 [M-Cl] ⁺
Exact Mass: 704.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-10), 4.1 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Further, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.4 parts of a compound represented by the formula (AI-10). Yield 85%

0.35 g of the compound represented by the formula (AI-10) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 1.9 (arbitrary unit) at λmax = 631 nm.

Synthesis Example 11
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 33.0 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Next, 50.0 parts of 2-methylbenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and 39.7 parts of dibutylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 32.1 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 70.0 parts of a compound represented by the formula (BI-11). Yield 72%

The following reaction was performed in a nitrogen atmosphere. 9. In a flask equipped with a condenser and a stirrer, 9.6 parts of the compound represented by the formula (BI-11), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 19.7 parts of a compound represented by the formula (A-II-11). Yield 98%

Identification of compound represented by formula (A-II-11) (mass spectrometry) ionization mode = ESI +: m / z = 609.4 [M-Cl] ⁺
Exact Mass: 644.4

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-11), 4.4 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.7 parts of a compound represented by the formula (AI-11). Yield 85%

0.35 g of the compound represented by formula (AI-11) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 3.0 (arbitrary unit) at λmax = 613 nm.

Synthesis Example 12
The following reaction was performed in a nitrogen atmosphere. After putting 29.2 parts of potassium thiocyanate and 160.0 parts of acetone into a flask equipped with a condenser and a stirrer, the mixture was stirred at room temperature for 30 minutes. Then, 50.0 parts of 2-chlorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after ice-cooling the reaction mixture, 43.8 parts of bis (2-ethoxyethyl) amine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 28.4 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 45.0 parts of a compound represented by the formula (BI-12). Yield 44%

The following reaction was performed in a nitrogen atmosphere. 10. In a flask equipped with a condenser and a stirrer, 10.6 parts of the compound represented by the formula (BI-12), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 21.3 parts of a compound represented by the formula (A-II-12). Yield 99%

Identification of compound represented by formula (A-II-12) (mass spectrometry) ionization mode = ESI +: m / z = 661.3 [M-Cl] ⁺
Exact Mass: 696.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-12), 4.1 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.4 parts of a compound represented by the formula (AI-12). Yield 85%

0.35 g of the compound represented by the formula (AI-12) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.5 (arbitrary unit) at λmax = 625 nm.

Synthesis example 13
The following reaction was performed in a nitrogen atmosphere. To a flask equipped with a condenser and a stirrer was charged 5.0 parts of 2-bromo-4 ′-(methylsulfonyl) acetophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50.0 parts of a 50% aqueous isopropanol solution. The mixture was stirred at room temperature for 30 minutes. Subsequently, 2.6 parts of potassium thiocyanate was added over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 3 hours. Next, 50.0 parts of tap water was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After the precipitated yellow solid was filtered off, the resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 1.0 part of a compound represented by the formula (B-II-13). Yield 22%

The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer, 5.0 parts of the compound represented by the formula (B-II-13) and 50.0 parts of ethanol were added, followed by stirring at room temperature for 30 minutes. Next, 2.5 parts of piperidine (Tokyo Kasei Co., Ltd.) and 1.2 parts of glacial acetic acid were added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred for 2 hours with heating under reflux. After allowing the reaction solution to cool to room temperature, 70.0 parts of tap water was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After the precipitated yellow solid was filtered off, the resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 3.8 parts of a compound represented by the formula (BI-13). Yield 61%

The following reaction was performed in a nitrogen atmosphere. 10. In a flask equipped with a condenser and a stirrer, 10.2 parts of the compound represented by the formula (BI-13), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 6.8 parts of a compound represented by the formula (A-II-13). Yield 33%

Identification of compound represented by formula (A-II-13) (mass spectrometry) ionization mode = ESI +: m / z = 629.3 [M-Cl] ⁺
Exact Mass: 664.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-13), 4.7 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.4 parts of a compound represented by the formula (AI-13). Yield 80%

0.35 g of the compound represented by the formula (AI-13) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.5 (arbitrary unit) at λmax = 636 nm.

Synthesis example 14
The following reaction was performed in a nitrogen atmosphere. To a flask equipped with a condenser and a stirrer, 5.0 parts of 4-chlorophenacyl bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 50.0 parts of a 50% aqueous isopropanol solution were added, followed by stirring at room temperature for 30 minutes. did. Next, 3.1 parts of potassium thiocyanate was added over 10 minutes. After completion of dropping, the mixture was further stirred at room temperature for 3 hours. Next, 50.0 parts of tap water was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After the precipitated yellow solid was filtered off, the resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 4.0 parts of a compound represented by the formula (B-II-14). Yield 89%

The following reaction was performed in a nitrogen atmosphere. Into a flask equipped with a condenser and a stirrer was charged 5.0 parts of the compound represented by the formula (B-II-14) and 50.0 parts of ethanol, and the mixture was stirred at room temperature for 30 minutes. Next, 3.0 parts of piperidine (manufactured by Tokyo Chemical Industry Co., Ltd.) and 1.4 parts of glacial acetic acid were added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred for 2 hours with heating under reflux. After allowing the reaction solution to cool to room temperature, 70.0 parts of tap water was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. After the precipitated yellow solid was filtered off, the resulting yellow solid was purified by column chromatography. The purified yellow solid was dried at 60 ° C. under reduced pressure to obtain 3.7 parts of a compound represented by the formula (BI-14). Yield 57%

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 8.8 parts of the compound represented by the formula (BI-14), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) 10. After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 5.3 parts of a compound represented by the formula (A-II-14). Yield 26%

Identification of compound represented by formula (A-II-14) (mass spectrometry) ionization mode = ESI +: m / z = 585.3 [M-Cl] ⁺
Exact Mass: 620.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-14), 8.0 parts of potassium tris (trifluoromethanesulfonyl) methide (manufactured by Central Glass Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 13.6 parts of a compound represented by the formula (AI-14). Yield 85%

0.35 g of the compound represented by the formula (AI-14) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.7 (arbitrary unit) at λmax = 623 nm.

Synthesis example 15
The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer was charged with 33.0 parts of potassium thiocyanate and 160.0 parts of acetone, and then stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of benzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Next, the reaction mixture was ice-cooled, and 41.6 parts of N-isopropylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 32.1 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 44.8 parts of a compound represented by the formula (BI-15). Yield 47%

The following reaction was performed in a nitrogen atmosphere. 9. In a flask equipped with a condenser and a stirrer, 9.3 parts of the compound represented by the formula (BI-15), 4,4′-bis (diethylamino) benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) After adding 0 parts and 20.0 parts of toluene, 14.8 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 20.5 parts of a compound represented by the formula (A-II-15). Yield 100%

Identification of compound represented by formula (A-II-15) (mass spectrometry) ionization mode = ESI +: m / z = 601.3 [M-Cl] ⁺
Exact Mass: 636.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-15), 5.9 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.7 parts of a compound represented by the formula (AI-15). Yield 85%

0.35 g of the compound represented by the formula (AI-15) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.8 (arbitrary unit) at λmax = 626 nm.

Synthesis example 16
A solution of 4,4′-dichlorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) (10 g, 90 mmol) in N, N-dimethylformamide (100 ml) was cooled in an ice bath, and sodium hydride (60%, 4.3 g, 90 mmol) was added, and after stirring for a while, Compound 2 (6.5 g, 30 mmol) was added little by little. After stirring at room temperature for 5 hours, water was added, dichloromethane extraction was performed, and the residue was purified by silica gel column chromatography to obtain a compound represented by the formula (BP2) (3.1 g, yield 24%).

The following reaction was performed in a nitrogen atmosphere. 7.6 parts of the compound represented by the formula (BI-7), 10.0 parts of the compound represented by the formula (BP2) and 20.0 parts of toluene were charged into a flask equipped with a condenser and a stirrer. Then, 11.4 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 17.8 parts of a compound represented by the formula (A-II-16). Yield 100%

Identification of compound represented by formula (A-II-16) (mass spectrometry) ionization mode = ESI +: m / z = 715.3 [M-Cl] ⁺
Exact Mass: 750.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-16), 5.0 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.9 parts of a compound represented by the formula (AI-16). Yield 90%

0.35 g of the compound represented by the formula (AI-16) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.9 (arbitrary unit) at λmax = 622 nm.

Synthesis example 17
The following reaction was performed in a nitrogen atmosphere. After putting 28.9 parts of potassium thiocyanate and 160.0 parts of acetone in a flask equipped with a condenser and a stirrer, the mixture was stirred at room temperature for 30 minutes. Subsequently, 50.0 parts of 2,6-difluorobenzoic acid chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise over 10 minutes. After completion of the dropwise addition, the mixture was further stirred at room temperature for 2 hours. Subsequently, after cooling the reaction mixture with ice, 36.4 parts of N-ethyl-o-toluidine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Next, after cooling the reaction mixture with ice, 34.2 parts of a 30% aqueous sodium hydroxide solution was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 30 minutes. Then, 28.1 parts of chloroacetic acid was added dropwise at room temperature. After completion of the dropwise addition, the mixture was stirred for 7 hours under heating and reflux. Next, after allowing the reaction mixture to cool to room temperature, the reaction solution was poured into 120.0 parts of tap water, 200 parts of toluene was added, and the mixture was stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 200 parts of 1N hydrochloric acid, then with 200 parts of tap water, and finally with 200 parts of saturated saline. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a pale yellow liquid. The resulting pale yellow liquid was purified by column chromatography. The purified pale yellow liquid was dried at 60 ° C. under reduced pressure to obtain 25.2 parts of a compound represented by the formula (BI-17). Yield 27%

The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer is charged with 8.1 parts of the compound represented by the formula (BI-17), 10.0 parts of the compound represented by the formula (BP2) and 20.0 parts of toluene. Then, 11.4 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. The resulting blue-violet solid was purified by column chromatography. The purified blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 18.3 parts of a compound represented by the formula (A-II-17). Yield 100%

Identification of compound represented by formula (A-II-17) (mass spectrometry) ionization mode = ESI +: m / z = 733.3 [M-Cl] ⁺
Exact Mass: 768.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-17), 4.9 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 30.0 parts of N, N-dimethylformamide were added, followed by stirring at 40 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 500.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 11.5 parts of a compound represented by the formula (AI-17). Yield 87%

0.35 g of the compound represented by the formula (AI-17) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.6 (arbitrary unit) at λmax = 626 nm.

Synthesis Example 18
The following reaction was performed in a nitrogen atmosphere. After charging 15.3 parts of N-methylaniline (manufactured by Tokyo Chemical Industry Co., Ltd.) and 60 parts of N, N-dimethylformamide into a flask equipped with a condenser and a stirrer, the mixed solution was ice-cooled. Under ice cooling, 5.7 parts of 60% sodium hydride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little over 30 minutes, and the mixture was stirred for 1 hour while warming to room temperature. 10.4 parts of 4,4′-difluorobenzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the reaction solution little by little and stirred at room temperature for 24 hours. The reaction solution was added little by little to 200 parts of ice water, and then allowed to stand at room temperature for 15 hours. When water was removed by decantation, a viscous solid was obtained as a residue. After adding 60 parts of methanol to this viscous solid, the mixture was stirred at room temperature for 15 hours. The precipitated solid was filtered off and purified by column chromatography. The purified pale yellow solid was dried at 60 ° C. under reduced pressure to obtain 9.8 parts of the compound represented by the formula (BP3). Yield 53%

The following reaction was performed in a nitrogen atmosphere. A flask equipped with a condenser and a stirrer is charged with 8.2 parts of the compound represented by the formula (BI-7), 10.0 parts of the compound represented by the formula (BP3) and 20.0 parts of toluene. Then, 12.2 parts of phosphorus oxychloride was added and stirred at 95-100 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and diluted with 170.0 parts isopropanol. Next, the diluted reaction solution was poured into 300.0 parts of saturated brine, and then 100 parts of toluene was added and stirred for 30 minutes. Next, the stirring was stopped and the mixture was allowed to stand for 30 minutes. After the aqueous layer was discarded by a liquid separation operation, the organic layer was washed with 300 parts of saturated brine. An appropriate amount of bowsho was added to the organic layer and stirred for 30 minutes, followed by filtration to obtain a dried organic layer. The obtained organic layer was evaporated using an evaporator to obtain a blue-violet solid. Further, the blue-violet solid was dried at 60 ° C. under reduced pressure to obtain 18.4 parts of a compound represented by the formula (A-II-18). Yield 100%

Identification of compound represented by formula (A-II-18) (mass spectrometry) ionization mode = ESI +: m / z = 687.3 [M-Cl] ⁺
Exact Mass: 722.3

The following reaction was performed in a nitrogen atmosphere. In a flask equipped with a condenser and a stirrer, 10.0 parts of the compound represented by the formula (A-II-18), 5.9 parts of bis (trifluoromethanesulfonyl) imide lithium (manufactured by Tokyo Chemical Industry Co., Ltd.) And 100.0 parts of N, N-dimethylformamide were added, followed by stirring at 50 to 60 ° C. for 3 hours. The reaction mixture was then cooled to room temperature and then added dropwise to 2000.0 parts of tap water with stirring for 1 hour to obtain a dark blue suspension. The resulting suspension was filtered to give a blue-green solid. Furthermore, the blue-green solid was dried at 60 ° C. under reduced pressure to obtain 13.2 parts of a compound represented by the formula (AI-18). Yield 86%

0.35 g of the compound represented by the formula (AI-18) was dissolved in chloroform to a volume of 250 cm ³ , 2 cm ^{3 of} which was diluted with chloroform to a volume of 100 cm ³ (concentration: 0.028 g / L), an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). This compound showed an absorbance of 2.8 (arbitrary unit) at the maximum absorption wavelength λmax = 620 nm.

Synthesis Example 19
The following reaction was performed in a nitrogen atmosphere. To a flask equipped with a condenser and a stirrer, 8.0 parts of a compound represented by the formula (A-II-18) and 396.0 parts of methanol were added, and stirred at room temperature for 30 minutes to prepare a blue solution. did. Next, 396.0 parts of tap water was added to the blue solution, and then stirred at room temperature for 30 minutes to obtain a reaction solution.
Into a beaker, 53 parts of tap water is added. Further, 11.8 parts of Keggin phosphotungstic acid (manufactured by Aldrich) and 53 parts of methanol are introduced into the tap water and mixed at room temperature in an air atmosphere to phosphotungstic acid. A solution was prepared.
The obtained phosphotungstic acid solution was dropped into the previously prepared reaction solution over 1 hour. The mixture was further stirred at room temperature for 30 minutes and then filtered to obtain a blue solid. The obtained blue solid was put into 200.0 parts of methanol and dispersed for 1 hour, followed by filtration twice. The operation of filtering the blue solid obtained by this operation in 200.0 parts of tap water and dispersing for 1 hour was repeated twice. The blue solid obtained by this operation was dried at 60 ° C. under reduced pressure to obtain 17.1 parts of a compound represented by the formula (AI-19). Yield 94%

(Preparation of colored curable resin composition)
Example 1
Colorant (A): 13 parts of a dye represented by the formula (A-I-1);
Colorant (A): 13 parts of a dye represented by formula (3-11);
Alkali-soluble resin (B): 53 parts of resin (B-2) (solid content conversion);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;
And leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts;
Were mixed to obtain a colored curable resin composition.

Comparative Example 1
Colorant (A): 26 parts of a dye represented by the formula (A-III-1);
Alkali-soluble resin (B): 53 parts of resin (B-1) (in terms of solid content);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;
In addition, 0.15 part of leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) was mixed to obtain a colored curable resin composition.

[Production of color filters]
The colored curable resin composition was applied on a 2-inch square glass substrate (# 1737; manufactured by Corning) by spin coating, and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), exposure was performed at an exposure amount of 150 mJ / cm ² (based on 365 nm) in an air atmosphere. A photomask was not used. The colored composition layer after exposure was post-baked in an oven at 180 ° C. for 20 minutes to produce a color filter (film thickness: 2.8 μm).

[Heat resistance evaluation]
The coating film of the colored photosensitive resin composition was heated at 230 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). As a result of performing the above heat resistance evaluation about the coating film obtained in Example 1, color difference ((DELTA) Eab *) was 5.1. Moreover, as a result of carrying out heat resistance evaluation similarly about the comparative example 1, color difference ((DELTA) Eab *) was 12.1 and it turned out that this-application compound is excellent in heat resistance.

Example 2
Colorant (A): 20 parts of a dye represented by the formula (A-I-1);
Colorant (A): 6 parts of a dye represented by formula (3-11);
Alkali-soluble resin (B): 53 parts of resin (B-2) (solid content conversion);
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 16 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4 parts;
Solvent (E): 120 parts of propylene glycol monomethyl ether acetate;
Solvent (E): 480 parts of 4-hydroxy-4-methyl-2-pentanone;
And leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.15 parts;
Were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared and heat resistance was evaluated in the same manner as in Example 1. As a result, the color difference (ΔEab *) of the colored composition coating film was 4.8.

Example 3
Colorant (A): 20 parts of a dye represented by the formula (A-I-1);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
In addition, 6.1 parts of zinc complex: (10) -18 were mixed to obtain a colored curable resin composition.
As a result of preparing a coating film of the colored composition in the same manner as in Example 1 and evaluating the heat resistance, the color difference (ΔEab *) of the coating film of the colored composition was 2.4.
Example 4
Colorant (A): 20 parts of a dye represented by the formula (AI-7);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 39.1 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 26.1 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.5 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Further, 1.6 parts of zinc complex: 10- (18) was mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared and heat resistance was evaluated in the same manner as in Example 1. As a result, the color difference (ΔEab *) of the colored composition coating film was 2.1.

Example 5
Colorant (A): 20 parts of a dye represented by the formula (AI-7);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 38.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 25.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.4 parts;
Solvent (E-1): 200 parts of diacetone alcohol; Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
In addition, zinc complex: 10- (18) 3.2 parts were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared in the same manner as in Example 1, and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the colored composition coating film was 2.1.

Example 6
Colorant (A): 20 parts of a dye represented by the formula (AI-7);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
In addition, 6.1 parts of zinc complex: 10- (18) were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared and heat resistance was evaluated in the same manner as in Example 1. As a result, the color difference (ΔEab *) of the colored composition coating film was 2.7.

Example 7
Colorant (A): 20 parts of a dye represented by the formula (AI-7);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
In addition, 6.1 parts of zinc complex: 10- (18) were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared and heat resistance was evaluated in the same manner as in Example 1. As a result, the color difference (ΔEab *) of the colored composition coating film was 7.2.

Example 8
Colorant (A): 18.4 parts of dye represented by formula (A-I-1);
Colorant (A): 2 parts of a dye represented by formula (2-29);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.1 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 36.1 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 7.2 parts;
Solvent (E): 579 parts of propylene glycol monomethyl ether acetate;
And leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.9 part;
Were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared and heat resistance was evaluated in the same manner as in Example 1. As a result, the color difference (ΔEab *) of the colored composition coating film was 10.1.

Example 9
Colorant (A): 14.4 parts of a dye represented by the formula (AI-7);
Colorant (A): Dye represented by formula (3-11) 3.6 parts;
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 41.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 27.5 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E-1): 283 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E-2): 283 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.1 part;
In addition, zinc complex: 10- (18) 3.4 parts were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared in the same manner as in Example 1, and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the colored composition coating film was 10.0.

Example 10
Colorant (A): 14.4 parts of a dye represented by the formula (AI-7);
Colorant (A): Dye represented by formula (3-11) 3.6 parts;
Alkali-soluble resin (B): Resin (B-2) (in terms of solid content) 43.1 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 28.7 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 7.2 parts;
Solvent (E-1): 283 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E-2): 283 parts of propylene glycol monomethyl ether acetate;
And leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.1 part;
Were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared and heat resistance was evaluated in the same manner as in Example 1. As a result, the color difference (ΔEab *) of the colored composition coating film was 9.6.

Example 11
Colorant (A): 12.4 parts of a dye represented by the formula (AI-3);
Colorant (A): Dye represented by formula (3-11) 3.2 parts;
Alkali-soluble resin (B): Resin (B-2) (in terms of solid content) 41.0 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 22.5 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E-1): 288 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E-2): 288 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.1 part;
Also, 2.2 parts of zinc complex: 10- (18) were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared in the same manner as in Example 1 and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the colored composition coating film was 11.1.

Example 12
(A) Colorant: C.I. I. Pigment Blue 15: 6 (pigment) 4.48 parts Acrylic pigment dispersant 1.76 parts Propylene glycol monomethyl ether acetate 29.8 parts are mixed, and the pigment is sufficiently dispersed using a bead mill.
Colorant (A): 10.5 parts of a dye represented by the formula (AI-7);
Colorant (A): 3 parts of a dye represented by formula (3-11);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 26.7 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 17.8 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 4.5 parts;
Solvent (E): 600 parts of propylene glycol monomethyl ether acetate;
And leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.11 part;
In addition, a colored curable resin composition was obtained by mixing 3.0 parts of zinc complex: 10- (18).
A colored composition coating film was prepared in the same manner as in Example 1, and the heat resistance was evaluated. As a result, the color difference (ΔEab *) of the colored composition coating film was 0.5.

Example 13
Colorant (A): 20 parts of a dye represented by the formula (AI-8);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

Example 14
Colorant (A): 20 parts of a dye represented by the formula (AI-9);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

Example 15
Colorant (A): 20 parts of a dye represented by the formula (AI-10);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

Example 16
Colorant (A): 20 parts of a dye represented by the formula (A-I-11);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

Example 17
Colorant (A): 20 parts of a dye represented by the formula (AI-12);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

Example 18
Colorant (A): 20 parts of a dye represented by the formula (AI-13);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

Example 19
Colorant (A): 20 parts of a dye represented by the formula (AI-14);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

Example 20
Colorant (A): 20 parts of a dye represented by the formula (AI-15);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

Example 21
Colorant (A): 20 parts of a dye represented by the formula (AI-16);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

Example 22
Colorant (A): 20 parts of a dye represented by the formula (AI-17);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 200 parts of diacetone alcohol;
Solvent (E-2): 200 parts of propylene glycol monomethyl ether acetate;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

Example 23
Colorant (A): 16 parts of a compound represented by the formula (AI-18);
Colorant (A): 4 parts of a compound represented by formula (3-11);
Alkali-soluble resin (B): Resin (B-1) (solid content conversion) 34.3 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 34.3 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.9 parts;
Solvent (E-1): 365 parts of propylene glycol monomethyl ether acetate;
Solvent (E-2): 250 parts of 4-hydroxy-4-methyl-2-pentanone;
Solvent (E-3): 23 parts of propylene glycol monomethyl ether;
Solvent (E-4): 4 parts of ethyl lactate;
Solvent (E-5): 16 parts methyl 3-methoxypropionate;
And leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.06 parts;
Leveling agent (F): Fluorosurfactant (Megafac F554; manufactured by DIC Corporation) 0.08 parts;
Were mixed to obtain a colored curable resin composition.
A colored composition coating film was prepared and heat resistance was evaluated in the same manner as in Example 1. As a result, the color difference (ΔEab *) of the colored composition coating film was 1.6.

Example 24
Colorant (A): 20 parts of a compound represented by the formula (AI-19);
Alkali-soluble resin (B): Resin (B-2) (solid content conversion) 36.9 parts;
Polymerizable compound (C): dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 24.6 parts;
Polymerization initiator (D): N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 6.1 parts;
Solvent (E-1): 186 parts of diacetone alcohol;
Solvent (E-2): 214 parts of N-methylpyrrolidone;
Leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.2 part;
Also, 6.1 parts of zinc complex: (10) -18 are mixed to obtain a colored curable resin composition.

  When the colored curable resin composition containing the compound of the present invention is used, a color filter having excellent heat resistance can be provided. The color filter is useful as a color filter used in display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

Claims (10)

A colorant (A1) comprising a salt (A1) comprising a dye represented by formula (A-VI) and a counter ion, and at least one dye (A2) selected from the group consisting of an anthraquinone dye and a tetraazaporphyrin dye ), A resin (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a solvent (E).

[In formula (A-VI), R ^{1A to} R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms, An oxygen atom may be inserted between the methylene groups constituting the group.
R ^{9A to} R ^12A each independently represent a hydrogen atom, an optionally substituted aryl group, or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between the methylene groups constituting the alkyl group. The hydrogen atom contained in the alkyl group may be replaced with a halogen atom or an optionally substituted amino group. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic group which may have a substituent or a heteroaromatic group which may have a substituent. ] A colorant (A) containing a salt (A1) composed of a dye represented by the formula (A-VI) and a counter ion, a resin (B), a photopolymerizable compound (C), a photopolymerization initiator ( A colored curable resin composition comprising D), a solvent (E), and a colorless metal complex (F).

[In formula (A-VI), R ^{1A to} R ^8A each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms, An oxygen atom may be inserted between the methylene groups constituting the group.
R ^{9A to} R ^12A each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom may be inserted between the methylene groups constituting the alkyl group. The hydrogen atom contained may be replaced by a halogen atom or an optionally substituted amino group. R ^9A and R ^10A may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ^11A and R ^12A may be bonded to form a ring with the nitrogen atom to which they are bonded.
A represents an aromatic group which may have a substituent or a heteroaromatic group which may have a substituent. ]   Furthermore, the colored curable resin composition of Claim 1 containing a colorless metal complex (F).   The salt comprising the dye represented by the formula (A-VI) and a counter ion is a salt comprising the dye represented by the formula (A-VI) and an anion optionally having a fluorine atom. The colored curable resin composition according to any one of claims 1 to 3. The colored curable resin according to any one of claims 1 to 4, wherein the salt composed of a dye represented by the formula (A-VI) and a counter ion is a salt represented by the formula (AI). Composition.

[In the formula (AI), X represents an oxygen atom, -NH- or a sulfur atom. Y represents an arbitrary m-valent anion.
R ^{41 to} R ⁴⁶ each independently represents a hydrogen atom, an optionally substituted aryl group or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between the methylene groups constituting the alkyl group. The hydrogen atom contained in the alkyl group may be replaced with a halogen atom or an optionally substituted amino group. R ⁴¹ and R ⁴² may be bonded to form a ring with the nitrogen atom to which they are bonded, or R ⁴³ and R ⁴⁴ may be bonded to form a ring with the nitrogen atom to which they are bonded, R ⁴⁵ and R ⁴⁶ may be bonded to form a ring together with the nitrogen atom to which they are bonded.
R ^{47 to} R ⁵⁴ each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfonyl group, a hydroxyl group, or an alkyl group having 1 to 8 carbon atoms, and an oxygen atom between methylene groups constituting the alkyl group. An atom may be inserted. ^R55 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group which may be substituted.
In addition, a plurality of molecules per molecule

May be the same or different structures. m represents an arbitrary natural number. ]   Furthermore, the colored curable resin composition in any one of Claims 1-5 containing a blue pigment.   Furthermore, the colored curable resin composition in any one of Claims 1-6 containing antioxidant (H).   The coating film formed from the colored curable resin composition in any one of Claims 1-7.   The color filter formed from the colored curable resin composition in any one of Claims 1-7.   A display device comprising the color filter according to claim 9.