JP2016011419A - Colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a colored curable resin composition which allows a colored pattern and a color filter excellent in solvent resistance to be provided.SOLUTION: The colored curable resin composition contains a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D). The colorant (A) contains a red pigment (A-1) and a dye (A-2). The dye (A-2) contains a xanthene dye and a coumarin dye. The red pigment (A-1) is preferably at least one pigment selected from the group consisting of Pigment Red 177, Pigment Red 242, and Pigment Red 254.

Description

  The present invention relates to a colored curable resin composition.

  The colored curable resin composition is used, for example, for producing a color filter such as a liquid crystal display device. As such a colored curable resin composition, a colored curable resin composition containing a red pigment such as Pigment Red 254, Pigment Red 242, and Pigment Red 177 and a xanthene dye as a colorant is known (patent). Reference 1).

JP 2010-211198 A

  In the above-mentioned colored curable resin composition known hitherto, the solvent resistance of the color filter obtained from the colored curable resin composition was not sufficiently satisfactory.

［式（１ａ）中、Ｒ¹〜Ｒ⁴は、互いに独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基又は置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表し、該記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^２は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^３及びＲ^４は、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、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸又は−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す。
Ｒ⁶及びＲ⁷は、互いに独立に、水素原子又は炭素数１〜６のアルキル基を表す。
ｍは、０〜５の整数を表す。ｍが２以上のとき、複数のＲ⁵は同一でも異なってもよい。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
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。
Ｒ⁹及びＲ¹⁰は、互いに独立に、水素原子又は置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^８−で置き換っていてもよく、Ｒ⁹及びＲ¹⁰は、そそれらが結合する窒素原子と一緒になって３〜１０員窒素含有複素環を形成していてもよい。
Ｒ¹¹は、互いに独立に、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。］
〔４〕 クマリン染料が式（Ａｄ２）で表される化合物である〔１〕〜〔３〕のいずれかに記載の着色硬化性樹脂組成物。

［式（Ａｄ２）中、Ｌ^Ｃは、炭素数１〜２０の２価の炭化水素基またはスルホニル基を表し、該炭化水素基に含まれる水素原子は、フッ素原子で置換されていてもよい。
Ｘ^Ｃは、酸素原子または硫黄原子を表す。
Ｒ^１Ｃ及びＲ^２Ｃ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炭素原子間に酸素原子が挿入されていてもよい。
Ｒ^７Ｃ〜Ｒ^１３Ｃは、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、カルバモイル基、スルファモイル基、−ＳＯ_３Ｍ^Ｃ、−ＣＯ_２Ｍ^Ｃ、ヒドロキシ基、ホルミル基、アミノ基、炭素数１〜２０の１価の炭化水素基を表し、該炭化水素基を構成する炭素原子間に、酸素原子、硫黄原子、−Ｎ（Ｒ^１４Ｃ）−、スルホニル基またはカルボニル基が挿入されていてもよく、該炭化水素基に含まれる水素原子は、ハロゲン原子、シアノ基、ニトロ基、カルバモイル基、スルファモイル基、−ＳＯ_３Ｍ^Ｃ、−ＣＯ_２Ｍ^Ｃ、ヒドロキシ基、ホルミル基またはアミノ基に置換されていてもよい。
Ｒ^１４Ｃは、水素原子または炭素数１〜２０の１価の炭化水素基を表し、Ｒ^１４Ｃが複数存在する場合、それらは同一であってもよいし、異なっていてもよい。
Ｍ^Ｃは、水素原子またはアルカリ金属原子を表す。］
〔５〕 キサンテン染料及びクマリン染料の含有比（キサンテン染料：クマリン染料）が、質量基準で６０：４０〜９９：１である〔１〕〜〔４〕のいずれかに記載の着色硬化性樹脂組成物。
〔６〕 〔１〕〜〔５〕のいずれかに記載の着色硬化性樹脂組成物を用いて形成されるカラーフィルタ。
〔７〕 〔６〕記載のカラーフィルタを含む液晶表示装置。 The present invention provides the following [1] to [7].
[1] In a colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D),
The colorant (A) includes a red pigment (A-1) and a dye (A-2),
The colored curable resin composition in which the dye (A-2) contains a xanthene dye and a coumarin dye.
[2] The colored curable resin composition according to [1], wherein the red pigment (A-1) is at least one pigment selected from the group consisting of Pigment Red 177, Pigment Red 242 and Pigment Red 254.
[3] The colored curable resin composition according to [1] or [2], wherein the xanthene dye is a compound represented by the formula (1a).

[In Formula (1a), R ^{1 to} R ⁴ each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —CO— or —NR ¹¹ —. May be. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing a nitrogen atom.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰
R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
m represents an integer of 0 to 5. When m is 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
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.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and is contained in the saturated aliphatic hydrocarbon group − CH ₂ — may be replaced by —O—, —CO—, —NH— or —NR ⁸ —, wherein R ⁹ and R ¹⁰ together with the nitrogen atom to which they are attached 3 A 10-membered nitrogen-containing heterocycle may be formed.
R ¹¹ 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. ]
[4] The colored curable resin composition according to any one of [1] to [3], wherein the coumarin dye is a compound represented by the formula (Ad2).

[In Formula (Ad2), L ^C represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group, and a hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom.
X ^C represents an oxygen atom or a sulfur atom.
R ^1C and R ^2C each independently represent a phenyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between carbon atoms constituting the alkyl group. May be.
R ^7C to R ^{@ 13 C} are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{^{group, -SO 3 M C, -CO 2}} M C, hydroxy group, formyl group, an amino group, Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, —N (R ^14C ) —, a sulfonyl group or a carbonyl group is inserted between the carbon atoms constituting the hydrocarbon group. at best, hydrogen atoms contained in the hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{^{group, -SO 3 M C, -CO 2}} M C, hydroxy group, formyl group or an amino group May be substituted.
R ^14C represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^14C are present, they may be the same or different.
M ^C represents a hydrogen atom or an alkali metal atom. ]
[5] The colored curable resin composition according to any one of [1] to [4], wherein the content ratio of the xanthene dye and the coumarin dye (xanthene dye: coumarin dye) is 60:40 to 99: 1 on a mass basis. object.
[6] A color filter formed using the colored curable resin composition according to any one of [1] to [5].
[7] A liquid crystal display device comprising the color filter according to [6].

  According to the colored curable resin composition of the present invention, it is possible to provide a colored pattern and a color filter excellent in solvent resistance.

The colored curable resin composition of the present invention includes a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D).
The colorant (A) includes a red pigment (A-1) and a dye (A-2), and the dye (A-2) includes a xanthene dye and a coumarin dye. The content ratio of xanthene dye and coumarin dye (xanthene dye: coumarin dye) is preferably 60:40 to 99: 1 on a mass basis.
The colored curable resin composition of the present invention preferably further contains at least one selected from the group consisting of a solvent (E) and a leveling agent (F).
The colored curable resin composition of the present invention may further contain a polymerization initiation assistant (D1).
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
The red pigment (A-1) is not particularly limited, and a known pigment can be used. Examples thereof include red pigments classified as pigments according to the color index (published by The Society of Dyers and Colorists).

Examples of red pigments include C.I. I. Pigment Red 9 (hereinafter, description of CI pigment is omitted and only the number is described. Others are also the same), 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 207, 209, 215, 216, 224, 242, 254, 255, 264, 265, 272, preferably C.I. I. Pigment red 149, 176, 177, 207, 242, 254, 255, 264, 272, and more preferably C.I. I. Pigment red 177, 242, and 254.
By including the pigment, it is easy to optimize the transmission spectrum of the red color filter, and the luminance of the color filter is improved.

Furthermore, the colored curable resin composition according to the present invention may include a pigment (A-3) other than the red pigment (A-1). Examples of the pigment (A-3) other than the red pigment (A-1) 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; I. And orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73.
These pigments may be appropriately selected according to a desired spectral spectrum of the color filter. These pigments may be used alone or in combination of two or more.

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 pigment preferably has a uniform particle size. By carrying out a dispersion treatment by containing a pigment dispersant, a pigment dispersion in which the pigment is uniformly dispersed in the solution can be obtained.

Examples of the pigment dispersant include cationic, anionic, nonionic, amphoteric, polyester, polyamine, and acrylic surfactants. These pigment dispersants may be used alone or in combination of two or more. As a pigment dispersant, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Florene (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (manufactured by Geneca Corporation), EFKA (registered trademark) (manufactured by BASF), Examples include Ajisper (manufactured by Ajinomoto Fine Techno Co., Ltd.), Disperbyk (registered trademark) (manufactured by Big Chemie).
When the pigment dispersant is used, the amount used is preferably 1% by mass or more and 100% by mass or less, more preferably 5% by mass or more and 50% by mass or less, based on the total amount of the pigment (A-1). . 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 red pigment (A-1) is preferably 1 to 99% by mass, more preferably 5 to 98% by mass, and still more preferably 10 to 95% with respect to the total amount of the colorant (A). % By mass.
When the pigment (A-3) is included, the content is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on the total amount of the colorant (A).

The dye (A-2) includes a xanthene dye and a coumarin dye.
A xanthene dye is a dye containing a compound having a xanthene skeleton in the molecule. Examples of xanthene dyes include C.I. I. Acid Red 51, 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A, xanthene dyes described in Japanese Patent No. 4492760, and the like.

  As the xanthene dye, a dye containing a compound represented by the formula (1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. Compound (1a) may be a tautomer thereof. When using a compound (1a), content of the compound (1a) in a xanthene dye becomes like this. Preferably it is 50 mass% or more, More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye.

［式（１ａ）中、Ｒ¹〜Ｒ⁴は、互いに独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基又は置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表し、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^２は、一緒になって窒素原子を含む環を形成してもよく、Ｒ^３及びＲ^４は、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、−ＳＯ₃ ^-、−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、０〜５の整数を表す。ｍが２以上のとき、複数のＲ⁵は同一でも異なってもよい。
ａは、０又は１の整数を表す。
Ｘは、ハロゲン原子を表す。
Ｚ⁺は、⁺Ｎ（Ｒ¹¹）₄、Ｎａ⁺又はＫ⁺を表す。
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。
Ｒ⁹及びＲ¹⁰は、互いに独立に、水素原子又は置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基を表し、該飽和脂肪族炭化水素基に含まれる−ＣＨ_２−は、−Ｏ−、−ＣＯ−、−ＮＨ−又は−ＮＲ^８−で置き換っていてもよく、Ｒ⁹及びＲ¹⁰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３〜１０員窒素含有複素環を形成していてもよい。
Ｒ¹¹は、互いに独立に、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。］

[In Formula (1a), R ^{1 to} R ⁴ each independently have a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent. Represents a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is replaced by —O—, —CO— or —NR ¹¹ —. Also good. R ¹ and R ² may be combined to form a ring containing a nitrogen atom, and R ³ and R ⁴ may be combined to form a ring containing a nitrogen atom.
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰
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 5. When m is 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
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.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and is contained in the saturated aliphatic hydrocarbon group − CH ₂ — may be replaced by —O—, —CO—, —NH— or —NR ⁸ —, and R ⁹ and R ¹⁰ are bonded together and together with the nitrogen atom to which they are bonded. To form a 3- to 10-membered nitrogen-containing heterocycle.
R ¹¹ 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 represented by R ^{1 to} R ⁴ and R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group. Straight chain alkyl groups such as heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group, icosyl group; branched chain such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group An alkyl group; an alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.
The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{1 to} R ⁴ may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.
The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ⁹ and R ¹⁰ may be substituted with, for example, a hydroxy group or a halogen atom.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms represented by R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group.
The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 -, -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 them, as the _{^{substituent, -SO 3 -, -SO 3 H}} , -SO 3 - Z + and preferably _{^{-SO 2 NR 9 R 10, -SO}} 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ Is more preferable. In this case, —SO ₃ ^{− +} N (R ¹¹ ) ₄ is preferable as —SO ₃ ⁻ Z ⁺ . When R ^{1 to} R ⁴ are these groups, a color filter having less generation of foreign matters and excellent heat resistance can be formed from the red colored curable resin composition of the present invention containing the compound (1a).

Examples of the ring formed by R ¹ and R ² together with a nitrogen atom and the ring formed by R ³ and R ⁴ together with a nitrogen atom include the following.

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 —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 —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.
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 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-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2 substituted sulfamoyl groups such as a group.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ⁹ and R ¹⁰ may have a substituent. Examples of the substituent include a hydroxy group and a halogen atom.

R ⁹ and R ¹⁰ may be bonded together to form a 3 to 10-membered nitrogen-containing heterocycle (a heterocycle containing one or more nitrogen atoms in the ring) together with the nitrogen atom. Examples of the heterocyclic ring include the following.

R ^{5 _{is, -CO 2 H, -CO 2 -}} Z +, -CO 2 R 8, -SO 3 -, -SO 3 - Z +, -SO 3 H and _SO 2 NHR ⁹ are preferred, SO ₃ ^{-, _{-SO 3 - Z +, -SO 3}} H and _SO 2 NHR ⁹ is more preferable.
m is preferably an integer of 1 to 4, and more preferably 1 and 2.

The alkyl group having 1 to 6 carbon atoms represented by R ⁶ and R ^7, among the alkyl groups listed above, include those having 1 to 6 carbon atoms.

Examples of the aralkyl group having 7 to 10 carbon atoms in R ⁸ and 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. It is preferable that the total number of carbon atoms of the four R ¹¹ is 20 to 80, and more preferably from 20 to 60. When ⁺ N (R ¹¹ ) ₄ is present in the compound (1a), when R ¹¹ is any of these groups, the color of the present invention containing the compound (1a) is reduced from the colored red curable resin composition of the present invention. A filter can be formed.

Examples of compound (1a) include compounds represented by formula (1-1) to formula (1-63). In the formula, R ⁸⁶ and R ¹⁰⁰ represent a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, preferably a branched alkyl group having 6 to 12 carbon atoms, more preferably a 2-ethylhexyl group. It is.

Among these, C.I. I. Acid red 289 sulfonamidation product, C.I. I. Quaternary ammonium salt of Acid Red 289, C.I. I. Acid violet 102 sulfonamidate or C.I. I. The quaternary ammonium salt of Acid Violet 102 is preferred. Examples of such a compound include compounds represented by formula (1-1) to formula (1-8), formula (1-11), or formula (1-12).
In addition, a compound represented by any one of formulas (1-24) to (1-33) is also preferable in that it has excellent solubility in an organic solvent.

  As the xanthene dye, a commercially available xanthene dye (for example, “Chugai Aminol Fast Pink R—H / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industries, Ltd.) can be used. . Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material.

  The coumarin dye is a dye containing a compound having a coumarin skeleton in the molecule. Examples of the coumarin dye include C.I. I. Acid Yellow 227, 250, C.I. I. Disperse Yellow 82, 184, C.I. I. Solvent Orange 112, C.I. I. Examples include Solvent Yellow 160 and 172, and Coumarin dyes described in Japanese Patent No. 1299948.

  Among these, as the coumarin dye, a compound represented by the formula (Ad2) (hereinafter sometimes referred to as “compound (Ad2)”) is preferable, and tautomers and salts thereof are also included.

In formula (Ad2), L ^C represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group, and the hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom.
X ^C represents an oxygen atom or a sulfur atom.
R ^1C and R ^2C each independently represent a phenyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between carbon atoms constituting the alkyl group. May be.
R ^7C to R ^{@ 13 C} are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{^{group, -SO 3 M C, -CO 2}} M C, hydroxy group, formyl group, an amino group, Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, —N (R ^14C ) —, a sulfonyl group or a carbonyl group is inserted between the carbon atoms constituting the hydrocarbon group. at best, hydrogen atoms contained in the hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{^{group, -SO 3 M C, -CO 2}} M C, hydroxy group, formyl group or an amino group May be substituted.
R ^14C represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^14C are present, they may be the same or different.
M ^C represents a hydrogen atom or an alkali metal atom.

L ^C is preferably a ^C 1-5 divalent hydrocarbon group or sulfonyl group which may be substituted with a fluorine atom, more preferably a propane-2,2-diyl group or hexafluoropropane. -2,2-diyl group or sulfonyl group.
X ^C is preferably an oxygen atom.

The R ^1C and ^{R 2C} substituent which may be a phenyl group optionally having a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{^{group, -SO 3 M C, -CO 2}} M C, hydroxy group, Examples include a formyl group, an amino group, and a monovalent hydrocarbon group having 1 to 20 carbon atoms.

Examples of the compound (Ad2) include a compound represented by the following formula.

  The coumarin dye may be a dye consisting only of the compound (Ad2) or may contain other coumarin dyes. The coumarin dye preferably contains the compound (Ad2) in a proportion of 70 to 100% by mass.

The content of the dye (A-2) is preferably 1 to 99% by mass, more preferably 2 to 95% by mass, and still more preferably 5 to 90% with respect to the total amount of the colorant (A). % By mass.
In the dye (A-2), the content ratio of the xanthene dye and the coumarin dye is, on a mass basis, usually 60:40 to 99: 1, preferably 65:35 to 99: 1, more preferably 70:30 to 98: 2.
The content of the colorant (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 10 to 55% by mass with respect to the total amount of the solid content. 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)>
The resin (B) is not particularly limited, but is preferably an alkali-soluble resin, and an addition polymer having a structural unit derived from at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic anhydride. More preferred. Examples of such resins include the following resins [K1] to [K6].
Resin [K1] At least one (a) selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (hereinafter sometimes referred to as “(a)”), a cyclic ether structure having 2 to 4 carbon atoms, A copolymer with a monomer (b) having 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.

Specific examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
Maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyl Unsaturated dicarboxylic acids such as tetrahydrophthalic acid 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.

  Examples of (b1) include a monomer having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and a structure in which an alicyclic unsaturated hydrocarbon is epoxidized. Monomer.

  (B2) is 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 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.

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 said to be “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) ) Rishikuro (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, vinyl toluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene , Isoprene, 2,3-dimethyl-1,3-butadiene and the like.
Of these, styrene, vinyltoluene, 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.

  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., 1st edition, 1st edition, published on March 1, 1972) It can be produced with reference to the cited references described in the literature.

  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. For example, as polymerization initiators, 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.

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 Resin with glycidyl (meth) acrylate added to tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer, resin with glycidyl (meth) acrylate added, 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. Is mentioned.
Of these, 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.

  Examples of the O-acyloxime compound include N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane- 1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-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 (registered trademark) OXE01, OXE02 (above, manufactured by BASF), N-1919 (manufactured by ADEKA) may be used. Among them, N-benzoyloxy-1- (4-phenylsulfanylphenyl) butan-1-one-2-imine, N-benzoyloxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine and At least one selected from the group consisting of N-benzoyloxy-1- (4-phenylsulfanylphenyl) -3-cyclopentylpropan-1-one-2-imine is preferred, and N-benzoyloxy-1- (4-phenyl) Sulfanylphenyl) octane-1-one-2-imine is more preferred.

  Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfanylphenyl) propan-1-one, 2-dimethylamino-1- (4-morpholinophenyl) -2-benzylbutane- 1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one, 2-hydroxy-2-methyl-1 -Phenylpropan-1-one, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl- 1- (4-Isopropenylphenyl) propan-1-one oligomer, α, α-diethoxyacetophenone, benzyldimethyl And luketal. Commercial products such as Irgacure (registered trademark) 369, 907, 379 (above, manufactured by BASF) may be used.

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-methoxy Naphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxystyryl) ) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) 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) -Methylphenyl 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 amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 4- 2-ethylhexyl dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4,4′-bis ( Ethylmethylamino) benzophenone and the like, and 4,4′-bis (diethylamino) benzophenone is preferred. 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, and 9,10-dibutoxy. Anthracene, 2-ethyl-9,10-dibutoxyanthracene, etc. are mentioned.

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

  Carboxylic acid compounds 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.

  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 and the like are more preferable.

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)>
The colored curable resin composition of the present invention may contain a 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 a surfactant having a fluorocarbon chain in the molecule. Specifically, Florard (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M), MegaFac (registered trademark) F142D, F171, F172, F173, F177, F183, F183, F554, R30, RS-718-K (manufactured by D1C), EFtop (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 a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, F443 (manufactured by D1C Co., Ltd.) and the like can be mentioned.

  The content of the leveling agent (F) is preferably from 0.001% by mass to 0.2% by mass, and preferably from 0.002% by mass to 0.1%, based on the total amount of the colored curable resin composition. It is at most mass%, more preferably at least 0.005 mass% and at most 0.07 mass%. When the content of the leveling agent (F) is within the above range, the flatness of the color filter can be improved.

<Other ingredients>
The colored curable resin composition of the present invention includes additives known in the art, such as fillers, other polymer compounds, adhesion promoters, antioxidants, light stabilizers, chain transfer agents, etc., if necessary. May be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention includes, for example, a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), and a solvent (E) used as necessary. It can be prepared by mixing the leveling agent (F), the polymerization initiation assistant (D1) and other components.
When the pigment is included, it is preferable to mix it in advance with a part or all of the pigment and the solvent (E) and disperse using a bead mill or the like until the average particle size of the pigment is about 0.2 μm or less.
Under the present circumstances, you may mix | blend a pigment dispersant and some or all of 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 dye (A-2) 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. Specific examples include mercury lamps, light emitting diodes, metal halide lamps, halogen lamps, and the like.
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.

  According to the present invention, it is possible to provide a colored curable resin composition capable of producing a color filter with particularly high brightness. The color filter is suitably used for display devices (for example, liquid crystal display devices, organic EL devices, electronic paper, etc.) and solid-state image sensors.

  Next, the present invention will be described more specifically with reference to examples. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

  In the following synthesis examples, the structure of the compound was identified by NMR (JMM-ECA-500; manufactured by JEOL Ltd.).

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 / m1n
Test liquid solid content concentration: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: R1
Reference material for calibration; TSK STANDARD POLYSTYRENE
F-40, F-4, F-288, A-2500, A-500
(Manufactured 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 1
10.1 part of bis (3-amino-4-hydroxyphenyl) hexafluoropropane and 51 parts of methanol are mixed, and 12.6 parts of ethyl 3-ethoxy-3-iminopyropionate hydrochloride is added at 5 ° C. or lower with stirring. It was. The reaction mixture was then stirred at 10 ° C. or lower for only 5 hours, at room temperature for 24 hours, and at 60 ° C. for 24 hours. After cooling the reaction mixture to room temperature, 300 parts of water and 270 parts of ethyl acetate were added, and the ethyl acetate layer was separated. To the aqueous layer was added 135 parts of ethyl acetate, and the ethyl acetate layer was separated. To the aqueous layer was added 135 parts of ethyl acetate, and the ethyl acetate layer was separated. The ethyl acetate layers were combined, washed three times with 300 parts of water, dried over magnesium sulfate, and filtered. The filtrate was evaporated to give a residue. This residue was purified by column chromatography to obtain 14.5 parts of a compound represented by the formula (pt1).

<Identification of Compound Represented by Formula (pt1)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 559.1
Exact Mass: 558.1

Under a nitrogen atmosphere, 75 parts of dimethyl sulfoxide and 8.45 parts of potassium hydroxide were mixed and stirred at room temperature for 0.5 hour. To this mixture, 25 parts of 3-methoxydiphenylamine was added and stirred at room temperature for 0.5 hour. To this mixture, 21.5 parts of iodoethane was added and stirred at room temperature for 2 hours. To the obtained mixture, 4.23 parts of potassium hydroxide was added and stirred at room temperature for 1 hour, and then 10.8 parts of iodoethane was added and stirred at room temperature for 12 hours. To the obtained mixture, 4.23 parts of potassium hydroxide was added and stirred at room temperature for 1 hour, and then 10.8 parts of iodoethane was added and stirred at room temperature for 2 hours. To the obtained mixture, 4.23 parts of potassium hydroxide was added and stirred at room temperature for 1 hour, and then 10.8 parts of iodoethane was added and stirred at room temperature for 13 hours. To the obtained mixture, 158 parts of water and 135 parts of ethyl acetate were added, and the ethyl acetate layer was separated. 90 parts of ethyl acetate was added to the aqueous layer, and the ethyl acetate layer was separated. The ethyl acetate layers were combined and washed 3 times with 100 parts of water. The ethyl acetate solution was dried over magnesium sulfate and filtered. The solvent of this filtrate was distilled off to obtain 28.4 parts of a compound represented by the formula (pt3-1).

<Identification of Compound Represented by Formula (pt3-1)>
(Mass Spectrometry) ionization mode = ESI +: m / z = [M + H] + 228.1
Exact Mass: 227.1

Under a nitrogen atmosphere, 28.4 parts of the compound represented by the formula (pt3-1) and 302 parts of methylene chloride were mixed. While maintaining this mixture at 4 to 10 ° C., 44.8 parts of boron tribromide was added, followed by stirring at room temperature for 12 hours. The obtained mixture was added to a mixture of 341 parts of water and 302 parts of methylene chloride while keeping the temperature of the mixture of 341 parts of water and 302 parts of methylene chloride at 4 to 19 ° C. The mixture was stirred at room temperature for 2 hours, and the methylene chloride layer was separated. This methylene chloride solution was washed four times with 227 parts of 10 wt% brine, dried over magnesium sulfate, and filtered. The solvent of this filtrate was distilled off to obtain 23.3 parts of a compound represented by the formula (pt4-1).

<Identification of compound represented by formula (pt4-1)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 214.1
Exact Mass: 213.1

Under a nitrogen atmosphere, 25.1 parts of phosphoryl chloride was added to 47.7 parts of N, N-dimethylformamide while maintaining the temperature at 6-15 ° C. A mixture of 23.3 parts of the compound represented by the formula (pt4-1) and 31.4 parts of N, N-dimethylformamide was added to the mixture while maintaining the temperature of the mixture at 6 to 25 ° C. The mixture was stirred at 40 ° C. for 2 hours and then cooled to room temperature. The obtained mixture was added to a mixture of 109 parts of a 48 wt% aqueous sodium hydroxide solution and 410 parts of water while maintaining the temperature at 14-19 ° C. and stirred for 1 hour. To the obtained mixture, 67.2 parts of 35 wt% hydrochloric acid was added while maintaining the temperature at 12 to 17 ° C. To the resulting mixture, 210 parts of ethyl acetate and celite were added and filtered. The obtained filtrate was washed twice with 233 parts of 10 wt% brine, dried over magnesium sulfate, and filtered. The solvent of the obtained filtrate was distilled off to obtain a residue. This residue was purified by column chromatography to obtain 23.9 parts of a compound represented by the formula (pt5-1).

<Identification of Compound Represented by Formula (pt5-1)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 242.1
Exact Mass: 241.1

Under a nitrogen atmosphere, 10.9 parts of the compound represented by the formula (pt5-1), 12.0 parts of the compound represented by the formula (pt1), 0.915 parts of piperidine, and 83.8 parts of toluene were mixed.
The mixture was stirred at 100 ° C. for 19 hours. The solvent of this mixed solution was distilled off to obtain a residue.
This residue was purified by column chromatography to obtain 10.6 parts of a compound represented by the formula (Ad2-12).

<Identification of Compound Represented by Formula (Ad2-12)>
¹ H-NMR (CDCl ₃ , 270 MHz) δ 1.31 (6H), 3.84 (4H), 6.58-6.61 (4H), 7.16-7.24 (4H), 7.31 -7.39 (6H), 7.46-7.52 (4H), 7.55 (2H), 7.99 (2H), 8.63 (2H)

Synthesis example 2
2,2.4 parts of 2,4-dimethylaniline, 35.4 parts of triethylamine and 132 parts of N, N-dimethylformamide were mixed and stirred at 50 ° C. While maintaining the temperature of this mixture at 50 to 60 ° C, 56.8 parts of iodoethane was added, and then the mixture was stirred at 60 ° C for 65 hours. The mixture was allowed to cool to room temperature, 1000 parts of water and 433 parts of toluene were added, and the toluene layer was separated. The toluene layer was washed three times with 1000 parts of a saturated aqueous sodium chloride solution, and then the solvent was distilled off with a rotary evaporator. The obtained residue was purified by column chromatography to obtain 18.8 parts of a compound represented by the formula (pt2-2).

<Identification of Compound Represented by Formula (pt2-2)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 150.1
Exact Mass: 149.1

Under a nitrogen atmosphere, 29.8 parts of the compound represented by the formula (pt2-2), 37.4 parts of 3-bromoanisole, 1.35 parts of palladium (II) acetate, 33.7 parts of potassium tert-butoxide, 2 , 8,9-Triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo [3.3.3] undecane (1M toluene solution) 3.42 parts and toluene 520 parts were mixed and mixed at 100 ° C. For 6 hours. The mixture was allowed to cool to room temperature and then added to 1000 parts of water. After filtering this liquid mixture, the toluene layer was fractionated. The toluene solution was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, and then filtered. The solvent of this filtrate was distilled off using a rotary evaporator, and the resulting residue was purified by column chromatography to obtain 41.9 parts of a compound represented by the formula (pt3-2).

<Identification of compound represented by formula (pt3-2)>
(Mass Spectrometry) ionization mode = ESI +: m / z = [M + H] + 256.2
Exact Mass: 255.2

The synthesis was performed in the same manner as in Synthesis Example 1 except that the compound represented by the formula (pt3-1) was replaced with the compound represented by the formula (pt3-2) in Synthesis Example 1, and the formula (pt4-2) The compound represented by Formula (pt5-2) and Formula (Ad2-14) was obtained.

<Identification of each compound>
Compound (mass spectrometry) ionization mode represented by formula (pt4-2) = ESI +: m / z = [M + H] ⁺ 242.2
Exact Mass: 241.2
Compound (mass spectrometry) ionization mode represented by formula (pt5-2) = ESI +: m / z = [M + H] ⁺ 270.2
Exact Mass: 269.1
Compound represented by formula (Ad2-14)
¹ H-NMR (CDCl ₃ , 270 MHz) δ 1.30 (6H), 2.09 (6H), 2.39 (6H), 3.59 (2H), 3.86 (2H), 6.42 ( 4H), 7.00 (2H), 7.12 (2H), 7.18 (2H), 7.30-7.37 (4H), 7.54 (2H), 7.98 (2H), 8 .62 (2H)

４−（ジブチルアミノ）サリチルアルデヒド（２．４９ｇ，１０ｍｍｏｌ）、シアノ酢酸エチル（１．１３ｇ，１０ｍｍｏｌ）および２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン（１．８３ｇ，５ｍｍｏｌ）をｎ−ペンタノール（２２ｇ，２５０ｍｍｏｌ）に溶解し、安息香酸（０．４１ｇ，３．４ｍｍｏｌ）を加え窒素気流下１３５℃で７時間撹拌した。反応終了後、ｎ−ペンタノールを減圧留去し、残渣をトルエンに溶解して水で洗浄した。トルエン層を硫酸ナトリウムで乾燥後濃縮し、シリカゲルカラムクロマトグラフィー（ヘキサン／酢酸エチル）で精製して、式（４−４４）で表される化合物（１．３９ｇ，１．５ｍｍｏｌ）を３０％の収率で得た。 ^１Ｈ−ＮＭＲにて式(Ａｄ２−１１)で表される化合物の構造を確認した。 Synthesis example 3

4- (dibutylamino) salicylaldehyde (2.49 g, 10 mmol), ethyl cyanoacetate (1.13 g, 10 mmol) and 2,2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane (1.83 g, 5 mmol) was dissolved in n-pentanol (22 g, 250 mmol), benzoic acid (0.41 g, 3.4 mmol) was added, and the mixture was stirred at 135 ° C. for 7 hours under a nitrogen stream. After completion of the reaction, n-pentanol was distilled off under reduced pressure, and the residue was dissolved in toluene and washed with water. The toluene layer was dried over sodium sulfate, concentrated, and purified by silica gel column chromatography (hexane / ethyl acetate) to give 30% of the compound (1.39 g, 1.5 mmol) represented by the formula (4-44). Obtained in yield. The structure of the compound represented by the formula (Ad2-11) was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (Ad2-11)>
¹ H-NMR (400 MHz, CDCl ₃ ): 0.99 (12H, t), 1.36 to 1.42 (8H, m), 1.59-1.67 (8H, m), 3.37 ( 8H, t), 6.51 (2H, d), 6.63 (2H, dd), 7.32 (2H, d), 7.41 (2H, d), 7.54 (2H, d), 7.9 (2H, s), 8.61 (2H, s)

Synthesis example 4
4.98 parts of bis (3-amino-4-hydroxyphenyl) sulfone and 28.1 parts of methanol are mixed, and gradually 8.18 parts of ethyl 3-ethoxy-3-iminopyropionate hydrochloride is added at 10 ° C. or lower with stirring. Added to. The reaction mixture was then stirred at 10 ° C. or lower for only 7 hours, at room temperature for 24 hours, and at 60 ° C. for 24 hours. The reaction mixture was cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. This residue was washed with methanol and dried under reduced pressure at 60 ° C. to obtain 6.77 parts of a compound represented by the formula (pt2).

<Identification of Compound Represented by Formula (pt2)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 473.1
Exact Mass: 472.1

2,4-dimethylaniline 42.4 parts (0.35 mol), triethylamine 35.4 parts (0.35 mol) and N, N-dimethylformamide 132 parts were mixed and stirred at 50 ° C. While maintaining the temperature of this mixture at 50 to 60 ° C., 70.2 parts (0.364 mol) of 1-bromo-2-ethylhexane was added, and then the mixture was stirred at 60 ° C. for 65 hours. The mixture was allowed to cool to room temperature, 1000 parts of water and 433 parts of toluene were added, and the toluene layer was separated.
The toluene layer was washed three times with 1000 parts of a saturated aqueous sodium chloride solution, and then the solvent was distilled off with a rotary evaporator. The obtained residue was purified by column chromatography to obtain 50.6 parts of a compound represented by the formula (pt2-1).

<Identification of compound represented by formula (pt2-1)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 234.2
Exact Mass: 233.2

Under a nitrogen atmosphere, 46.7 parts (0.2 mol) of the compound represented by the formula (pt2-1), 37.4 parts (0.2 mol) of 3-bromoanisole, palladium (II) acetate 1.35 Parts (0.006 mol), potassium tert-butoxide 33.7 parts (0.3 mol), 2,8,9-triisopropyl-2,5,8,9-tetraaza-1-phosphabicyclo [3. 3.3] 3.42 parts (0.01 mol) of undecane (1.0 M toluene solution) and 520 parts of toluene were mixed and stirred at 100 ° C. for 6 hours. The mixture was allowed to cool to room temperature and then added to 1000 parts of water.
After filtering this liquid mixture, the toluene layer was fractionated. The toluene solution was washed with a saturated aqueous sodium hydrogen carbonate solution, dried over magnesium sulfate, and then filtered. The filtrate was distilled off using a rotary evaporator, and the resulting residue was purified by column chromatography to obtain 30.9 parts of a compound represented by the formula (pt3-3).

<Identification of Compound Represented by Formula (pt3-3)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 340.3
Exact Mass: 339.3

Under a nitrogen atmosphere, 17.0 parts (0.05 mol) of the compound represented by the formula (pt3-3) and 199 parts of dichloromethane were mixed. While maintaining this mixed liquid at 15 to 23 ° C., boron tribromide (1.0 M dichloromethane solution) is mixed with boron tribromide and the compound represented by the formula (pt3-3) in the same number of moles ( 0.05 mole) was added. Thereafter, the mixture was stirred at room temperature for 8 hours.
This mixture was added to 250 parts of ice water, and the dichloromethane layer was separated. The dichloromethane layer was washed with 250 parts of water, dried over magnesium sulfate, and filtered. The obtained filtrate was evaporated using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 13.9 parts of a compound represented by the formula (pt4-3).

<Identification of Compound Represented by Formula (pt4-3)>
(Mass Spectrometry) ionization mode = ESI +: m / z = [M + H] + 326.3
Exact Mass: 325.2

13.9 parts (0.0427 mol) of the compound represented by the formula (pt4-3) and 26.4 parts of N, N-dimethylformamide were mixed. While maintaining the mixture at 23-55 ° C., 13.1 parts (0.0854 mol) of phosphoryl chloride was added. The mixture was then stirred at 60 ° C. for 6 hours. The mixture was allowed to cool to room temperature, added to 150 parts of ice water, and neutralized with a 48% aqueous sodium hydroxide solution. To this mixture, 300 parts of ethyl acetate was added and filtered, and the ethyl acetate layer was separated from the obtained filtrate. This ethyl acetate solution was washed with 300 parts of water, dried over magnesium sulfate, and filtered. The obtained filtrate was evaporated using a rotary evaporator. The obtained residue was purified by column chromatography to obtain 11.6 parts of a compound represented by the formula (pt5-3).

<Identification of compound represented by formula (pt5-3)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 354.2
Exact Mass: 353.2

Under a nitrogen atmosphere, 9.65 parts (0.0273 mol) of the compound represented by the formula (pt5-3), 6.14 parts (0.013 mol) of the compound represented by the formula (pt2), and 0.81 of piperidine. 553 parts (0.0065 mol) and 51.1 parts of toluene were mixed. The mixture was stirred at 100 ° C. for 19 hours. This mixture was added to 231 parts of methanol. The generated precipitate was obtained by removing the supernatant. To this precipitate, 231 parts of methanol was added and stirred, and then the mixed solution was subjected to suction filtration. The obtained residue was washed with 20 parts of methanol and obtained as a residue of suction filtration. This residue was purified by column chromatography to obtain 9.1 parts of a compound represented by the formula (Ad2-2).

<Identification of Compound Represented by Formula (Ad2-2)>
¹ H-NMR (CDCl ₃ , 270 MHz) δ 0.82-0.92 (12H, m), 1.26-1.52 (16H, br m), 1.77 (2H, br s), 2. 05 (6H, s), 2.38 (6H, s), 3.32-3.42 (2H, m), 3.71-3.78 (2H, m), 6.42-6.45 ( 4H, m), 7.02 (2H, d), 7.11 (2H, d), 7.15 (2H, s), 7.33 (2H, d), 7.66 (2H, d), 7.96 (2H, dd), 8.39 (2H, d), 8.62 (2H, s)

Synthesis example 5
Except that 1-bromo-2-ethylhexane is replaced with 1-bromooctane, in the same manner as in Synthesis Example 1, formula (pt2-3), formula (pt3-3), formula (pt4-4), formula (pt5 -4) and a compound represented by the formula (Ad2-4) were obtained.

<Identification of compounds represented by formula (pt2-3), formula (pt3-3), formula (pt4-4) and formula (pt5-4)>

<Identification of compound represented by formula (Ad2-4)>
¹ H-NMR (CDCl ₃ , 270 MHz) δ 0.88 (6H, t), 1.28-1.32 (20 H, m), 1.72 (4H, br s), 2.07 (6H, s ), 2.38 (6H, s), 3.44 (2H, br m), 3.77 (2H, br m), 6.39 (4H, br s), 6.99 (2H, d), 7.12 (2H, d), 7.17 (2H, s), 7.34 (2H, d), 7.66 (2H, d), 7.96 (2H, dd), 8.39 (2H) , D), 8.62 (2H, s)

Synthesis Example 6
275 parts of resorcinol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 101 parts of n-hexylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred for 20 hours while removing water produced at 150 to 155 ° C. After allowing to cool, the reaction mixture was dissolved in 433 parts of toluene, and this toluene solution was washed three times with 1000 parts of warm water at 40 ° C. 50 parts of anhydrous magnesium sulfate was added to this toluene solution and stirred, followed by filtration. The solvent of the filtrate was distilled off to obtain a crude product. This crude product was dissolved in 234 parts of toluene and stirred at 0 ° C. or lower, and the crystallized product was collected by filtration. This crystallized product was dried under reduced pressure at 50 ° C. to obtain 95.7 parts of a compound represented by the formula (pt3).

<Identification of compound represented by formula (pt3)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 194.2
Exact Mass: 193.2

95.3 parts of the compound represented by the formula (pt3) and 48 parts of water were mixed and stirred at 80 ° C. Subsequently, while adding 107 parts of 1-bromo-2-ethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.), the mixture was stirred at 80 ° C. for 3 hours, and then 22.4 parts of a 48% aqueous sodium hydroxide solution was added. The mixture was stirred at 110 ° C. for 18 hours. After allowing to cool, the pH of the reaction mixture was adjusted to 5 using 10% aqueous sodium hydroxide solution, 130 parts of toluene was added and stirred, and the toluene layer was extracted. The toluene extract was washed twice with 500 parts of warm water, 25.0 parts of anhydrous magnesium sulfate was added, and the mixture was stirred and filtered. The solvent of the filtrate was distilled off to obtain 154 parts of a residue containing the compound represented by the formula (pt4) as a main component.

<Identification of compound represented by formula (pt4)>
(Mass Spectrometry) ionization mode = ESI +: m / z = [M + H] + 306.3
Exact Mass: 305.3

154 parts of the residue containing the compound represented by (pt4) as a main component and 597 parts of N, N-dimethylformamide were mixed and stirred at -6 ° C to 3 ° C. To this, 258 parts of phosphoryl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added while maintaining the liquid temperature at −6 ° C. to 3 ° C. The mixture was stirred at room temperature for 1 hour and then stirred at 60 ° C. for 4 hours. After allowing to cool, the reaction mixture was added to 1500 parts of ice and neutralized with a 48% aqueous sodium hydroxide solution. To this, 867 parts of toluene was added, and the toluene layer was extracted. This toluene extract was washed twice with 1200 parts of a 15% aqueous sodium chloride solution. 60 parts of anhydrous magnesium sulfate was added to this toluene extract and stirred, followed by filtration. The filtrate was evaporated to give a residue. This residue was purified by column chromatography to obtain 94.4 parts of a compound represented by the formula (pt5).

<Identification of compound represented by formula (pt5)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 334.3
Exact Mass: 333.3

10.6 parts of bis (3-amino-4-hydroxyphenyl) sulfone (manufactured by Tokyo Chemical Industry Co., Ltd.), 25.3 parts of a compound represented by the formula (pt5), benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) ) 3.2 parts, 184 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.59 parts of ethyl cyanoacetate (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 120 ° C. for 3 hours. In this reaction solution, 25.4 parts of the compound represented by the formula (pt5), 3.21 parts of benzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd.), 90 parts of 1-pentanol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 8.59 parts of ethyl cyanoacetate (Tokyo Chemical Industry Co., Ltd.) was mixed and stirred at 120 ° C. for 12 hours. The reaction solution was cooled to room temperature, added to 1800 parts of methanol, and the precipitated crystals were obtained as a residue of suction filtration. The residue was purified by column chromatography to obtain 20.6 parts of a compound represented by the formula (Ad2-10). ^The structure was confirmed by ¹ H-NMR.

<Identification of Compound Represented by Formula (Ad2-10)>
¹ H-NMR (500 MHz, DMSO-d ₆ ): 0.85 (6H, t), 0.87 (6H, t), 0.87 (6H, t), 1.20 to 1.40 (28H) , 1.56 (4H, tt), 1.75 (2H, ttt), 3.34 (4H, d), 3.43 (4H, t), 6.55 (2H, d), 6.79 ( 2H, dd), 7.64 (2H, d), 7.91 (2H, d), 8.01 (2H, dd), 8.36 (2H, d), 8.73 (2H, s)

式（ｐｐ’’１−１）で表される４−ジエチルアミノサリチルアルデヒド１．９３ｇ（１０ｍｍｏｌ）と、式（ｐｐ’’５−１）で表されるマロン酸ジエチル３．２ｇ（２０ｍｍｏｌ）と、ピペリジン１ｍＬとを、５０ｍＬの無水エタノールに溶解した。次いで、還流条件下で６時間撹拌しながら反応を行った。反応終了後、エタノールを減圧留去して、反応混合物に濃塩酸１０ｍＬと氷酢酸１０ｍＬとを加え、さらに６時間撹拌した。反応混合物を室温まで冷却した後、２００ｍＬの氷水中に入れてさらに冷却し、次いで、反応混合物に３０質量％水酸化ナトリウム水溶液を滴下することにより、反応混合物のｐＨを約５に調整した。反応混合物を３０分間撹拌した後、生じた沈殿物をろ過し、水で洗浄して乾燥した。こうして得られた沈殿物をトルエンで再結晶することにより、式（ｐｐ’’２−１）で表される７−ジエチルアミノクマリンを得た。収量は１．７４ｇ（８ｍｍｏｌ）、収率は８０％であった。 Synthesis example 7
<Synthesis of 7-diethylaminocoumarin>

4-diethylamino salicylaldehyde 1.93 g (10 mmol) represented by the formula (pp ″ 1-1), 3.2 g (20 mmol) diethyl malonate represented by the formula (pp ″ 5-1), 1 mL of piperidine was dissolved in 50 mL of absolute ethanol. The reaction was then carried out with stirring for 6 hours under reflux conditions. After completion of the reaction, ethanol was distilled off under reduced pressure, 10 mL of concentrated hydrochloric acid and 10 mL of glacial acetic acid were added to the reaction mixture, and the mixture was further stirred for 6 hours. After the reaction mixture was cooled to room temperature, it was further cooled by placing it in 200 mL of ice water, and then the pH of the reaction mixture was adjusted to about 5 by dropwise addition of 30% by mass aqueous sodium hydroxide solution to the reaction mixture. After the reaction mixture was stirred for 30 minutes, the resulting precipitate was filtered, washed with water and dried. The precipitate thus obtained was recrystallized from toluene to obtain 7-diethylaminocoumarin represented by the formula (pp ″ 2-1). The yield was 1.74 g (8 mmol), and the yield was 80%.

塩化ホスホリル２ｍＬを入れた反応容器に、０℃、窒素雰囲気下で脱水ジメチルホルムアミド２ｍＬを徐々に滴下した後、室温まで昇温して３０分間撹拌した。次いで、式（ｐｐ’’２−１）で表される７−ジエチルアミノクマリン１．５ｇ（６．９１ｍｍｏｌ）を脱水ジメチルホルムアミド１０ｍＬに溶解して反応容器に入れ、５０℃で１２時間撹拌した。反応混合物を、２００ｍＬの氷水中に入れ、２０質量％水酸化ナトリウム水溶液を加えた。生じた沈殿物をろ過し、水で洗浄して乾燥した。こうして得られた沈殿物をエタノールで再結晶することにより、式（ｐｐ’’３−１）で表される７−ジエチルアミノクマリン−３−アルデヒドを得た。収量は１．２ｇ（４．８９ｍｍｏｌ）、収率は７０％であった。 <Synthesis of 7-diethylaminocoumarin-3-aldehyde>

To a reaction vessel containing 2 mL of phosphoryl chloride, 2 mL of dehydrated dimethylformamide was gradually added dropwise at 0 ° C. in a nitrogen atmosphere, and then the mixture was warmed to room temperature and stirred for 30 minutes. Next, 1.5 g (6.91 mmol) of 7-diethylaminocoumarin represented by the formula (pp ″ 2-1) was dissolved in 10 mL of dehydrated dimethylformamide and placed in a reaction vessel, followed by stirring at 50 ° C. for 12 hours. The reaction mixture was placed in 200 mL of ice water and 20% by weight aqueous sodium hydroxide solution was added. The resulting precipitate was filtered, washed with water and dried. The precipitate thus obtained was recrystallized from ethanol to obtain 7-diethylaminocoumarin-3-aldehyde represented by the formula (pp ″ 3-1). The yield was 1.2 g (4.89 mmol), and the yield was 70%.

式（ｐｐ’’３−１）で表される７−ジエチルアミノクマリン−３−アルデヒド２ｇ（８．１５ｍｍｏｌ）と、式（ｐｐ’’４−１）で表される２，２−ビス（３−アミノ−４−ヒドロキシフェニル）ヘキサフルオロプロパン１．４９ｇ（４．０８ｍｍｏｌ）と、酢酸ナトリウム１２．６ｇ（１６３ｍｍｏｌ）とを、氷酢酸４０ｍＬに溶解して、９０℃で１０時間撹拌した。次いで、反応混合物を２００ｍＬの水中に入れた。生じた沈殿物をろ過してジクロロメタンに溶解し、水とともに分液漏斗に入れて洗浄した。分液漏斗から回収したジクロロメタン層を硫酸ナトリウムで乾燥した後、シリカゲルカラムクロマトグラフィーで精製することにより、化合物（Ａｄ２−１６）を得た。収量は１．６７ｇ（２．０４ｍｍｏｌ）、収率は５０％であった。 <Synthesis of Compound (Ad2-16)>

2 g (8.15 mmol) of 7-diethylaminocoumarin-3-aldehyde represented by the formula (pp ″ 3-1) and 2,2-bis (3- 1.49 g (4.08 mmol) of amino-4-hydroxyphenyl) hexafluoropropane and 12.6 g (163 mmol) of sodium acetate were dissolved in 40 mL of glacial acetic acid and stirred at 90 ° C. for 10 hours. The reaction mixture was then placed in 200 mL of water. The resulting precipitate was filtered, dissolved in dichloromethane, and washed with water in a separatory funnel. The dichloromethane layer collected from the separatory funnel was dried over sodium sulfate and purified by silica gel column chromatography to obtain the compound (Ad2-16). The yield was 1.67 g (2.04 mmol), and the yield was 50%.

Synthesis example 8
4.98 parts of bis (3-amino-4-hydroxyphenyl) sulfone and 28.1 parts of methanol are mixed, and gradually 8.18 parts of ethyl 3-ethoxy-3-iminopyropionate hydrochloride is added at 10 ° C. or lower with stirring. Added to. The reaction mixture was then stirred at 10 ° C. or lower for 7 hours, at room temperature for 24 hours, and at 60 ° C. for 24 hours. The reaction mixture was cooled to room temperature, and the precipitated crystals were obtained as a residue of suction filtration. This residue was washed with methanol and dried under reduced pressure at 60 ° C. to obtain 6.77 parts of a compound represented by the formula (pt2).

<Identification of Compound Represented by Formula (pt2)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 473.1
Exact Mass: 472.1

Under a nitrogen atmosphere, 24 parts of m-anisidine, 99.7 parts of 4-iodo-m-xylene, 117 parts of potassium carbonate, 27.3 parts of copper powder, 4.64 parts of 18-crown-6, o-dichlorobenzene 511 The parts were mixed and stirred at 175 ° C. for 19 hours. Thereafter, 35.1 parts of potassium carbonate, 8.19 parts of copper powder, 1.39 parts of 18-crown-6, and 22.0 parts of o-dichlorobenzene were added and stirred at 175 ° C. for 17 hours. The mixture was allowed to cool to room temperature and filtered.
450 parts of ethyl acetate was added to the filtrate and washed 3 times with 450 parts of 2N hydrochloric acid and 3 times with 470 parts of 18 wt% sodium chloride aqueous solution. The resulting ethyl acetate solution was dried over magnesium sulfate and filtered. The solvent of the filtrate was distilled off with a rotary evaporator, and then the obtained residue was purified by column chromatography to obtain 64.1 parts of a compound represented by the formula (pt6).

<Identification of compound represented by formula (pt6)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 332.2
Exact Mass: 331.2

31.7 parts of the compound represented by the formula (pt6) and 190 parts of dehydrated dichloromethane were mixed at 0 ° C. under a nitrogen atmosphere. Subsequently, 199 parts of a 17 wt% boron tribromide dichloromethane solution was added and stirred for 1 hour. Then, it stirred at room temperature for 12 hours. After this mixture was added to 1100 parts of ice water, 740 parts of chloroform was added, and the chloroform layer was extracted. The obtained chloroform solution was washed twice with 470 parts of an 18 wt% aqueous sodium chloride solution, dried over magnesium sulfate, and filtered. After the solvent of the filtrate was distilled off with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 30 parts of a compound represented by the formula (pt7).

<Identification of Compound Represented by Formula (pt7)>
(Mass Spectrometry) Ionization mode = ESI +: m / z = [M + H] ⁺ 318.2
Exact Mass: 317.2

7.46 parts of the compound represented by the formula (pt7) and 14.4 parts of N, N-dimethylformamide were mixed under a nitrogen atmosphere at 5 to 10 ° C. While maintaining the temperature of this mixture at 5 to 10 ° C., 7.21 parts of phosphoryl chloride was added. Thereafter, the mixture was stirred at 10 ° C. or lower for 1 hour, at room temperature for 1 hour, and at 80 ° C. for 1 hour. The reaction mixture was allowed to cool to room temperature, 100 parts of ice water was added, and the mixture was neutralized with a 48% aqueous sodium hydroxide solution. To this mixture was added 180 parts of ethyl acetate, followed by celite and stirring. The mixture was filtered and the ethyl acetate layer was extracted. The ethyl acetate layer was dried over magnesium sulfate and filtered. After the solvent of this filtrate was distilled off with a rotary evaporator, the obtained residue was purified by column chromatography to obtain 6.26 parts of a compound represented by the formula (pt8).

<Identification of compound represented by formula (pt8)>
(Mass spectrometry) ionization mode = ESI +: m / z = [M + H] ⁺ 346.2
Exact Mass: 345.2

6.01 parts of the compound represented by the formula (pt8), 4.04 parts of the compound represented by the formula (pt2), 0.357 parts of piperidine and 33.4 parts of toluene were mixed and stirred at 105 ° C. for 6 hours. did. The mixture was allowed to cool to room temperature and then added to 153 parts of methanol. The precipitate was obtained as a residue of suction filtration. The obtained residue was purified by column chromatography to obtain 7.76 parts of a compound represented by the formula (Ad2-13).

<Identification of Compound Represented by Formula (Ad2-13)>
¹ H-NMR (CDCl ₃ , 270 MHz) δ 2.13 (12H), 2.34 (12H), 6.38 (2H), 6.52 (2H), 6.92-7.02 (8H), 7.10 (4H), 7.37 (2H), 7.67 (2H), 7.98 (2H), 8.40 (2H), 8.64 (2H)

Synthesis Example 9
50 parts of the compound represented by the formula (X-1) and 350 parts of isopropyl alcohol (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed at room temperature, and 18.1 parts of diethylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) are mixed into the mixture. Was added dropwise at a temperature not exceeding 20 ° C. and stirred at 20 ° C. for 3 hours. The reaction solution was added to 2100 parts of 10% hydrochloric acid. The obtained precipitate was obtained as a residue of suction filtration, washed with 373 parts of ion exchange water and then dried to obtain 23.6 parts of a compound represented by the formula (X-3). The yield was 43%.

（質量分析）イオン化モード＝ＥＳＩ^＋： ｍ／ｚ＝ [Ｍ＋H]^＋ ４４２．１
Ｅｘａｃｔ Ｍａｓｓ： ４４１．１ Identification of compound represented by formula (X-3)

(Mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 442.1
Exact Mass: 441.1

5.0 parts of the compound represented by the formula (X-3) and 35 parts of N-methylpyrrolidone (manufactured by Wako Pure Chemical Industries, Ltd.) are mixed at room temperature, and dipropylamine (Tokyo Chemical Industry Co., Ltd.) is mixed into the mixture. 3.4 parts) was added dropwise at a temperature not exceeding 20 ° C., heated to 80 ° C. and stirred for 3 hours. After cooling the reaction solution to room temperature, 3.4 parts of concentrated hydrochloric acid was added, and the resulting mixture was added to 315 parts of saturated brine. The obtained precipitate was obtained as a residue of suction filtration, washed with 630 parts of ion-exchanged water and dried to obtain 3.9 parts of a compound represented by the formula (1-51). The yield was 69%.

Identification of compound represented by formula (1-51) (mass spectrometry) ionization mode = ESI ⁺ : m / z = [M + H] ⁺ 507.7
Exact Mass: 506.7

Synthesis Example 10
An appropriate amount of nitrogen was allowed to flow into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to form a nitrogen atmosphere. 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 completion of dropping of the polymerization initiator, the temperature was maintained at the same temperature for about 3 hours, and then cooled to room temperature to obtain a copolymer (resin B1) solution having a solid content of 43.5%. The obtained resin B1 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.

(Preparation of colored curable resin composition)
Example 1
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 36.7 parts, Acrylic pigment dispersant 15.9 parts, Resin (B): Resin B1 (solid content conversion) 13.7 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 265 A pigment dispersion in which 5 parts were mixed and the pigment was sufficiently dispersed using a bead mill;
Colorant (A): Compound represented by formula (1-51) 8.8 parts; Colorant (A): Compound represented by formula (Ad2-16) 2.4 parts; Resin (B): Resin B1 (solid content conversion) 36.3 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 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) 17 parts; Solvent (E): Propylene glycol monomethyl ether acetate 311.6 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 247.3 parts; and leveling agent (F): polyether-modified Corn oil; was obtained (Toray Silicone SH8400 manufactured by Toray Dow Corning Co.) colored curable resin composition by mixing 0.1 parts.

Example 2
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 37.8 parts, Acrylic pigment dispersant 16.4 parts, Resin (B): Resin B1 (solid content conversion) 14.1 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 272 A pigment dispersion in which 9 parts were mixed and the pigment was sufficiently dispersed using a bead mill;
Colorant (A): Compound represented by Formula (1-51) 8.9 parts; Colorant (A): Compound represented by Formula (Ad2-12) 2.5 parts; Resin (B): Resin B1 (solid content conversion) 35.9 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 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) 17 parts; Solvent (E): Propylene glycol monomethyl ether acetate 309.3 parts; Solvent (E): 4-hydroxy-4-methyl-2-pentanone 249.5 parts; and Leveling agent (F): Polyether-modified paper Corn oil; was obtained (Toray Silicone SH8400 manufactured by Toray Dow Corning Co.) colored curable resin composition by mixing 0.1 parts.

Example 3
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 37.5 parts, Acrylic pigment dispersant 16.3 parts, Resin (B): Resin B1 (solid content conversion) 14 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 271 parts A pigment dispersion obtained by mixing and thoroughly dispersing the pigment using a bead mill;
Colorant (A): Compound represented by formula (1-51) 8.9 parts; Colorant (A): Compound represented by formula (Ad2-14) 2.4 parts; Resin (B): Resin B1 (solid content conversion) 36 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts; Polymerization initiator (D): N-benzoyl Oxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 17 parts; Solvent (E): Propylene glycol Monomethyl ether acetate 310 parts; Solvent (E): 4-hydroxy-4-methyl-2-pentanone 249 parts; and Leveling agent (F): Polyether-modified silicone oil Was obtained; (manufactured by Dow Corning Toray Co., Toray Silicone SH8400) colored curable resin composition by mixing 0.1 parts.

Example 4
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 37.5 parts, Acrylic pigment dispersant 16.3 parts, Resin (B): Resin B1 (solid content conversion) 14 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 271 parts A pigment dispersion obtained by mixing and thoroughly dispersing the pigment using a bead mill;
Colorant (A): 8.9 parts of compound represented by formula (1-51); Colorant (A): Compound represented by formula (Ad2-11) 2.4 parts; Resin (B): Resin B1 (solid content conversion) 36 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts; Polymerization initiator (D): N-benzoyl Oxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 17 parts; Solvent (E): Propylene glycol Monomethyl ether acetate 310 parts; Solvent (E): 4-hydroxy-4-methyl-2-pentanone 249 parts; and Leveling agent (F): Polyether-modified silicone oil Was obtained; (manufactured by Dow Corning Toray Co., Toray Silicone SH8400) colored curable resin composition by mixing 0.1 parts.

Example 5
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 38.7 parts, Acrylic pigment dispersant 16.8 parts, Resin (B): Resin B1 (solid content conversion) 14.4 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 279 A pigment dispersion in which 4 parts were mixed and the pigment was sufficiently dispersed using a bead mill;
Colorant (A): Compound represented by formula (1-51) 8.9 parts; Colorant (A): Compound represented by formula (Ad2-10) 2.5 parts; Resin (B): Resin B1 (solid content conversion) 35.6 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 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) 17 parts; Solvent (E): Propylene glycol monomethyl ether acetate 307 parts; Solvent (E): 4-hydroxy-4-methyl-2-pentanone 251.3 parts; and Leveling agent (F): Polyether-modified silicone Oil; was obtained (Toray Silicone SH8400 manufactured by Toray Dow Corning Co.) colored curable resin composition by mixing 0.1 parts.

Example 6
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 39.2 parts, Acrylic pigment dispersant 17 parts, Resin (B): Resin B1 (solid content conversion) 14.6 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 283.5 A pigment dispersion in which the components are mixed and the pigment is sufficiently dispersed using a bead mill;
Colorant (A): Compound represented by formula (1-51) 8.9 parts; Colorant (A): Compound represented by formula (Ad2-13) 2.5 parts; Resin (B): Resin B1 (solid content conversion) 35.4 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 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) 17 parts; Solvent (E): Propylene glycol monomethyl ether acetate 305.6 parts; Solvent (E): 4-hydroxy-4-methyl-2-pentanone 252.4 parts; and Leveling agent (F): Polyether modified paper Corn oil; was obtained (Toray Silicone SH8400 manufactured by Toray Dow Corning Co.) colored curable resin composition by mixing 0.1 parts.

Example 7
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 38.1 parts, Acrylic pigment dispersant 16.5 parts, Resin (B): Resin B1 (solid content conversion) 14.2 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 275 A pigment dispersion in which 3 parts were mixed and the pigment was sufficiently dispersed using a bead mill;
Colorant (A): Compound represented by formula (1-51) 8.9 parts; Colorant (A): Compound represented by formula (Ad2-2) 2.5 parts; Resin (B): Resin B1 (solid content conversion) 35.8 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 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) 17 parts; Solvent (E): Propylene glycol monomethyl ether acetate 308.3 parts; Solvent (E): 4-hydroxy-4-methyl-2-pentanone 250.1 parts; and Leveling agent (F): Polyether-modified silica N'oiru; was obtained (Toray Silicone SH8400 manufactured by Toray Dow Corning Co.) colored curable resin composition by mixing 0.1 parts.

Example 8
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 38.4 parts, Acrylic pigment dispersant 16.6 parts, Resin (B): Resin B1 (solid content conversion) 14.3 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 277 A pigment dispersion in which 4 parts were mixed and the pigment was sufficiently dispersed using a bead mill;
Colorant (A): Compound represented by formula (1-51) 8.9 parts; Colorant (A): Compound represented by formula (Ad2-4) 2.5 parts; Resin (B): Resin B1 (solid content conversion) 35.7 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 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) 17 parts; Solvent (E): Propylene glycol monomethyl ether acetate 307.6 parts; Solvent (E): 4-hydroxy-4-methyl-2-pentanone 250.7 parts; and Leveling agent (F): Polyether-modified silica N'oiru; was obtained (Toray Silicone SH8400 manufactured by Toray Dow Corning Co.) colored curable resin composition by mixing 0.1 parts.

Example 9
Colorant (A): C.I. 1. Pigment red 254 (pigment) 14.8 parts, acrylic pigment dispersant 6.4 parts, resin (B): resin B1 (solid content conversion) 5.5 parts, and solvent (E): propylene glycol monomethyl ether acetate 107 A pigment dispersion in which 0.0 part was mixed and the pigment was sufficiently dispersed using a bead mill;
Colorant (A): 11.6 parts of compound represented by formula (1-51); Colorant (A): 7 parts of compound represented by formula (Ad2-16); Resin (B): Resin B1 ( 44.5 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts; Polymerization initiator (D): N-benzoyl Oxy-1- (4-phenylsulfanylphenyl) octane-1-one-2-imine (Irgacure (registered trademark) OXE-01; manufactured by BASF; O-acyloxime compound) 17 parts; Solvent (E): Propylene glycol Monomethyl ether acetate 404.5 parts; solvent (E): 4-hydroxy-4-methyl-2-pentanone 203.4 parts; and leveling agent (F): polyether-modified silica N'oiru; was obtained (Toray Silicone SH8400 manufactured by Toray Dow Corning Co.) colored curable resin composition by mixing 0.1 parts.

Example 10
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 40.5 parts, Acrylic pigment dispersant 17.6 parts, Resin (B): Resin B1 (solid content conversion) 15.1 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 292 A pigment dispersion in which 6 parts were mixed and the pigment was sufficiently dispersed using a bead mill;
Colorant (A): Compound represented by formula (1-51) 9.1 parts; Colorant (A): Compound represented by formula (Ad2-16) 0.5 parts; Resin (B): Resin B1 (solid content conversion) 34.9 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 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) 17 parts; Solvent (E): Propylene glycol monomethyl ether acetate 305.0 parts; Solvent (E): 4-hydroxy-4-methyl-2-pentanone 243.8 parts; and Leveling agent (F): Polyether modified paper Corn oil; was obtained (Toray Silicone SH8400 manufactured by Toray Dow Corning Co.) colored curable resin composition by mixing 0.1 parts.

Comparative Example 1
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 17.8 parts, Acrylic pigment dispersant 7.7 parts, Resin (B): Resin B1 (solid content) 6.7 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 128 A pigment dispersion in which 9 parts were mixed and the pigment was sufficiently dispersed using a bead mill;
Colorant (A): C.I. 1. Pigment Yellow 138 (pigment) 7.4 parts, acrylic pigment dispersant 3.1 parts, resin (B): resin B1 (solid content conversion) 3.1 parts, and solvent (E): propylene glycol monomethyl ether acetate 47 A pigment dispersion in which 7 parts were mixed and the pigment was sufficiently dispersed using a bead mill;
Colorant (A): Compound represented by formula (1-51) 11.9 parts; Resin (B): Resin B1 (solid content conversion) 40.2 parts; Polymerizable compound (C): Dipentaerythritol hexa Acrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 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) 17 parts; Solvent (E): 349.9 parts of propylene glycol monomethyl ether acetate; Solvent (E): 4-hydroxy-4-methyl -2-pentanone 225.6 parts; and leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; Toray Dowco Manufactured by ring Ltd.) to obtain a colored curable resin composition by mixing 0.1 parts.

Comparative Example 2
Colorant (A): C.I. 1. Pigment Red 254 (pigment) 53.1 parts, Acrylic pigment dispersant 23 parts, Resin (B): Resin B1 (solid content conversion) 19.8 parts, and Solvent (E): Propylene glycol monomethyl ether acetate 383.5 A pigment dispersion in which the components are mixed and the pigment is sufficiently dispersed using a bead mill;
Colorant (A): 9 parts of compound represented by formula (1-51); Resin (B): Resin B1 (solid content conversion) 30.2 parts; Polymerizable compound (C): Dipentaerythritol hexaacrylate ( KAYARAD (registered trademark) DPHA; Nippon Kayaku Co., Ltd. 50 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) 17 parts; solvent (E): 261.2 parts of propylene glycol monomethyl ether acetate; solvent (E): 4-hydroxy-4-methyl-2 -Pentanone 276.3 parts; and leveling agent (F): polyether-modified silicone oil (Tore Silicone SH8400; Toray Dow Corning) Ltd.)) were mixed with 0.1 parts to obtain a colored resin composition.

[Preparation of colored pattern]
The colored curable resin composition was applied by spin coating on a 2-inch square glass substrate (Eagle XG; manufactured by Corning), and then pre-baked at 100 ° C. for 3 minutes to form a colored composition layer. After cooling, the distance between the substrate on which the colored composition layer is formed and the photomask made of quartz glass is set to 200 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), 60 mJ / cm ^{2 in} an air atmosphere. The exposure amount (standard on 365 nm) was used. A photomask having a 100 μm line and space pattern was used. The colored composition layer after exposure is developed by being immersed in an aqueous solution containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ° C. for 70 seconds, washed with water, A colored pattern was obtained by post-baking at 25 ° C. for 25 minutes.

[Film thickness measurement]
About the obtained coloring pattern, the film thickness was measured using the film thickness measuring apparatus (DEKTAK3; Nippon Vacuum Technology Co., Ltd. product). The results are shown in Table 2.

[Chromaticity evaluation]
About the obtained coloring pattern, spectroscopy was measured using the colorimeter (OSP-SP-200; Olympus Co., Ltd.), and the xy chromaticity coordinate in the XYZ color system of CIE was used using the characteristic function of C light source. (X, y) and tristimulus value Y were measured. The larger the value of Y, the higher the brightness. The results are shown in Table 2.

[Heat resistance evaluation]
The coating film of the colored photosensitive resin composition was heated at 230 ° C. for 2 hours, and the color difference (ΔEab *) before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The smaller the ΔEab value, the better the heat resistance. The results are shown in Table 2.

(Light resistance evaluation)
An ultraviolet cut filter (COLORED OPTICAL GLASS L38; manufactured by Hoya Co., Ltd .; cuts light of 380 nm or less) is disposed on the obtained colored coating film, and is placed on a light resistance tester (Suntest CPS +: manufactured by Toyo Seiki Co., Ltd.). Then, xenon lamp light was irradiated for 48 hours.
The xy chromaticity coordinates (x, y) and Y are measured before and after the irradiation, and the color difference ΔEab * is calculated from the measured values by the method described in JIS Z 8730: 2009 (7. Color difference calculation method). Are shown in Table 2. ΔEab * means that the smaller the color change is, the smaller the color change is. Moreover, if the light resistance of a colored coating film is favorable, it can be said that the light resistance of the coloring pattern produced from the same colored curable resin composition is also favorable. The results are shown in Table 2.

(Solvent resistance evaluation)
The chromaticity of the obtained colored curable composition film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). Subsequently, the obtained colored curable composition film was immersed in a large excess amount of N-methyl-2-pyrrolidone kept constant at 23 ° C. for 30 minutes, and the chromaticity of the colored curable composition film after the immersion Was measured in the same manner.
As a color difference evaluation standard, if ΔEab * is 2 or less, almost no change in hue is observed, showing good characteristics as a color filter, and if ΔEab * exceeds 2 and less than 5, slight hue change is recognized. However, if the color filter has a practically no problem level and ΔEab * is 5 or more, a clear hue change can be confirmed, which is a problematic level for the color filter. The results are shown in Table 2.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the colored curable resin composition which can manufacture the color filter excellent in solvent resistance, The color filter excellent in the solvent resistance manufactured from this colored curable resin composition is It can be suitably used for display devices such as liquid crystal display devices, organic EL devices, and electronic paper, and solid-state imaging devices.

Claims (7)

In a colored curable resin composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a polymerization initiator (D),
The colorant (A) includes a red pigment (A-1) and a dye (A-2),
The colored curable resin composition in which the dye (A-2) contains a xanthene dye and a coumarin dye.   The colored curable resin composition according to claim 1, wherein the red pigment (A-1) is at least one pigment selected from the group consisting of Pigment Red 177, Pigment Red 242 and Pigment Red 254. The colored curable resin composition according to claim 1 or 2, wherein the xanthene dye is a compound represented by the formula (1a).

[In Formula (1a), R ^{1 to} R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or a substituent having 6 to 10 carbon atoms. Represents a monovalent aromatic hydrocarbon group, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom, and the aromatic hydrocarbon The hydrogen atom contained in the group may be substituted with an alkoxy group having 1 to 3 carbon atoms, and —CH ₂ — contained in the saturated hydrocarbon group is —O—, —CO— or —NR ¹¹ —. It may be replaced with. R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom together with the nitrogen atom to which they are bonded, and R ³ 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 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰
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 5. When m is 2 or more, the plurality of R ⁵ may be the same or different.
a represents an integer of 0 or 1.
X represents a halogen atom.
Z ⁺ represents ⁺ N (R ¹¹ ) ₄ , Na ⁺ or K ⁺ .
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.
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and is contained in the saturated aliphatic hydrocarbon group − CH ₂ — may be replaced by —O—, —CO—, —NH— or —NR ⁸ —, and R ⁹ and R ¹⁰ are bonded to each other together with the nitrogen atom to which they are bonded. And may form a 3 to 10-membered nitrogen-containing heterocycle.
R ¹¹ 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. ] The colored curable resin composition according to any one of claims 1 to 3, wherein the coumarin dye is a compound represented by the formula (Ad2).

[In Formula (Ad2), L ^C represents a divalent hydrocarbon group having 1 to 20 carbon atoms or a sulfonyl group, and a hydrogen atom contained in the hydrocarbon group may be substituted with a fluorine atom.
X ^C represents an oxygen atom or a sulfur atom.
R ^1C and R ^2C each independently represent a phenyl group which may have a substituent or an alkyl group having 1 to 20 carbon atoms, and an oxygen atom is inserted between carbon atoms constituting the alkyl group. May be.
R ^7C to R ^{@ 13 C} are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{^{group, -SO 3 M C, -CO 2}} M C, hydroxy group, formyl group, an amino group, Represents a monovalent hydrocarbon group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom, —N (R ^14C ) —, a sulfonyl group or a carbonyl group is inserted between the carbon atoms constituting the hydrocarbon group. at best, hydrogen atoms contained in the hydrocarbon group, a halogen atom, a cyano group, a nitro group, a carbamoyl group, a sulfamoyl _{^{group, -SO 3 M C, -CO 2}} M C, hydroxy group, formyl group or an amino group May be substituted.
R ^14C represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 20 carbon atoms, and when a plurality of R ^14C are present, they may be the same or different.
M ^C represents a hydrogen atom or an alkali metal atom. ]   The colored curable resin composition according to any one of claims 1 to 4, wherein a content ratio of the xanthene dye and the coumarin dye (xanthene dye: coumarin dye) is 60:40 to 99: 1 on a mass basis.   The color filter formed using the colored curable resin composition in any one of Claims 1-5.   A liquid crystal display device comprising the color filter according to claim 6.