JP2015172178A - Dye and colored curable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dye which generates little foreign matter, is capable of forming a color filter having high quality and excellent heat resistance, is used for a colored curable resin composition, and is excellent in solubility in an organic solvent.SOLUTION: The dye has a group containing a silicon atom and has a squarylium skeleton. The dye is preferably a compound represented by formula (II). (Rand Rare each independently H, a halogen atom, a hydroxy group, or an optionally substituted 1-20C monovalent saturated hydrocarbon group; Rand Rare each independently H or a hydroxy group; and one of Rand Ris a group containing silicon and the other is H, an optionally substituted 1-20C monovalent saturated hydrocarbon group, or the like.)

Description

  The present invention relates to a dye and a colored curable resin composition.

For example, squarylium dyes are used in fields such as electrophotographic photoreceptors. As such a dye, for example, a compound represented by the formula (II-0) is known.
(Patent Document 1).

Japanese Patent Laid-Open No. 60-248652 (Example 1)

  The compound represented by the above formula (II-0) was not sufficiently soluble in an organic solvent.

［式（ｉｉａ）中、Ｒ^１４は、水素原子、ヒドロキシ基、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表す。複数のＲ^１４は、それぞれ同一であっても異なっていてもよい。
Ｌ^１は、炭素数１〜８のアルカンジイル基を表す。該アルカンジイル基に含まれる−ＣＨ_２−は、酸素原子で置き換わっていてもよい。
＊は、結合手を表す。］
［４］ケイ素原子を含む基が、−Ｓｉ（Ｒ^１４）_３で表される基である［１］〜［３］のいずれかに記載の染料。
［Ｒ^１４は水素原子、ヒドロキシ基、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表す。複数のＲ^１４は、それぞれ同一であっても異なっていてもよい。]
［５］ケイ素原子を含む基を有し、且つ、スクアリリウム骨格を有する染料が、式（ＩＩａ)で表される化合物である［１］〜［４］のいずれかに記載の染料。

［式（ＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^１１１及びＲ^１１２は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基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（該飽和炭化水素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）を表す。
Ｒ^３、Ｒ^４、Ｒ^１１３及びＲ^１１４は、それぞれ独立に、水素原子またはヒドロキシ基を表す。
Ｒ^５、Ｒ^６、Ｒ^１５及びＲ^１６は、それぞれ独立して、水素原子、ケイ素原子を含む基、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（該飽和炭素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）又は置換基を有していてもよいフェニル基を表す。ただし、Ｒ^５、Ｒ^６、Ｒ^１５及びＲ^１６の少なくとも１つは、ケイ素原子を含む基である。］
［６］ 式（ＩＩａ）中、ケイ素原子を含む基が、式（ｉｉａ）で表される基である［５］に記載の染料。

［式（ｉｉａ）中、Ｒ^１４は、水素原子、ヒドロキシ基、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表す。複数のＲ^１４は、それぞれ同一であっても異なっていてもよい。
Ｌ^１は、炭素数１〜８のアルカンジイル基を表す。該アルカンジイル基に含まれる−ＣＨ_２−は、酸素原子で置き換わっていてもよい。
＊は、結合手を表す。］
［７］式（ＩＩａ）で表される化合物が、式（ＩＩｂ）で表される化合物である［５］又は［６］に記載の染料。

［式（ＩＩｂ）中、Ｒ^１、Ｒ^２、Ｒ^１１１及びＲ^１１２は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基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（該飽和炭化水素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）を表す。
Ｒ^３、Ｒ^４、Ｒ^１１３及びＲ^１１４は、それぞれ独立に、水素原子またはヒドロキシ基を表す。
Ｒ^５、Ｒ^６、Ｒ^１５及びＲ^１６は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基（飽和炭素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）、式（ｉｉａ）で表される基または式（ｉ）で表される基であり、少なくとも１つは式（ｉｉａ）で表される基である。

（式（ｉ）中、Ｒ^１２は、水素原子、炭素数１〜２０の１価の飽和炭化水素基または炭素数２〜２０の１価の不飽和の炭化水素基を表し、ｍは１〜５の整数を表す。ｍが２以上のとき、複数のＲ^１２は、それぞれ同一であっても異なっていてもよい。＊は、窒素原子との結合の手を表す。）

［式（ｉｉａ）中、Ｒ^１４４は、水素原子、ヒドロキシ基、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表す。
Ｌ^１は、炭素数１〜８のアルカンジイル基を表す。該アルカンジイル基に含まれる−ＣＨ_２−は、酸素原子で置き換わっていてもよい。
＊は、窒素原子との結合手を表す。］
［８］式（ＩＩｂ）で表される化合物が、式（ＩＩ）で表される化合物である［７］に記載の染料。

［式（ＩＩ）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基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（該飽和炭化水素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）を表す。
Ｒ^３及びＲ^４は、それぞれ独立に、水素原子またはヒドロキシ基を表す。
Ｒ^５及びＲ^６のうちの、一方は式（ii）で表される基であり、他方は水素原子、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（飽和炭素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）または式（ｉ）で表される基である。

（式（ｉ）中、Ｒ^１２は、水素原子、炭素数１〜２０の１価の飽和炭化水素基または炭素数２〜２０の１価の不飽和の炭化水素基を表し、ｍは１〜５の整数を表す。ｍが２以上のとき、複数のＲ^１２は、それぞれ同一であっても異なっていてもよい。＊は、窒素原子との結合の手を表す。）

（式（ｉｉ）中、ｎは１〜８の整数を表し、Ｒ^１４は水素原子、ヒドロキシ基、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表し、＊は窒素原子との結合の手を表す。複数のＲ^１４は、それぞれ同一であっても異なっていてもよい。）]
［９］［１］〜［８］のいずれかに記載の染料を含む着色剤。
［１０］さらに黄色顔料を含む［９］に記載の着色剤。
［１１］黄色顔料が、Ｃ．Ｉ．ピグメントイエロー１３８、Ｃ．Ｉ．ピグメントイエロー１５０及びＣ．Ｉ．ピグメントイエロー１８５の群から少なくとも１つ選ばれる［１０］に記載の着色剤。
［１２］［１］〜［１１］のいずれかに記載の着色剤と、樹脂と、重合性化合物と、重合開始剤とを含む着色硬化性樹脂組成物。
［１３］［１２］に記載の着色硬化性樹脂組成物から形成される塗膜。
［１４］［１２］に記載の着色感光性樹脂組成物から形成されるカラーフィルタ。
［１５］［１４］に記載のカラーフィルタを含む表示装置。 The present invention includes the following inventions.
[1] A dye having a group containing a silicon atom and having a squarylium skeleton.
[2] The dye according to [1], wherein the group containing a silicon atom is a group containing a group represented by —Si (R ¹⁴ ) ₃ .
^{[R 14} represents a hydrogen atom, a hydroxy group, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms. The plurality of R ¹⁴ may be the same or different. ]
[3] The dye according to [1] or [2], wherein the group containing a silicon atom is a group represented by the formula (ia).

[In formula (ia), R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The plurality of R ¹⁴ may be the same or different.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. —CH ₂ — contained in the alkanediyl group may be replaced with an oxygen atom.
* Represents a bond. ]
[4] The dye according to any one of [1] to [3], wherein the group containing a silicon atom is a group represented by —Si (R ¹⁴ ) ₃ .
^{[R 14} represents a hydrogen atom, a hydroxy group, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms. The plurality of R ¹⁴ may be the same or different. ]
[5] The dye according to any one of [1] to [4], wherein the dye having a group containing a silicon atom and having a squarylium skeleton is a compound represented by the formula (IIa).

[In Formula (II), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent group having 1 to 20 carbon atoms which may have a substituent. A saturated hydrocarbon group (an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated hydrocarbon group).
R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxy group.
R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a group containing a silicon atom, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent ( An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated carbon group) or a phenyl group which may have a substituent. However, at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is a group containing a silicon atom. ]
[6] The dye according to [5], wherein in the formula (IIa), the group containing a silicon atom is a group represented by the formula (ia).

[In formula (ia), R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The plurality of R ¹⁴ may be the same or different.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. —CH ₂ — contained in the alkanediyl group may be replaced with an oxygen atom.
* Represents a bond. ]
[7] The dye according to [5] or [6], wherein the compound represented by the formula (IIa) is a compound represented by the formula (IIb).

[In formula (IIb), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent group having 1 to 20 carbon atoms which may have a substituent. A saturated hydrocarbon group (an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated hydrocarbon group).
R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxy group.
R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (the carbon constituting the saturated carbon group). An oxygen atom or a sulfur atom may be inserted between atoms), a group represented by formula (ia) or a group represented by formula (i), at least one of which is represented by formula (ia) Group.

(In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, Represents an integer of 5. When m is 2 or more, the plurality of R ¹² may be the same or different from each other, and * represents a bond to a nitrogen atom.

[In the formula (ia), R ¹⁴⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. —CH ₂ — contained in the alkanediyl group may be replaced with an oxygen atom.
* Represents a bond with a nitrogen atom. ]
[8] The dye according to [7], wherein the compound represented by the formula (IIb) is a compound represented by the formula (II).

[In Formula (II), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent ( An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated hydrocarbon group).
R ³ and R ⁴ each independently represents a hydrogen atom or a hydroxy group.
One of R ⁵ and R ⁶ is a group represented by the formula (ii), and the other is a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. (An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated carbon group) or a group represented by formula (i).

(In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, Represents an integer of 5. When m is 2 or more, the plurality of R ¹² may be the same or different from each other, and * represents a bond to a nitrogen atom.

(In the formula (ii), n represents an integer of 1 to 8, R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * represents a nitrogen atom. And a plurality of R ¹⁴ may be the same or different.)]
[9] A colorant comprising the dye according to any one of [1] to [8].
[10] The colorant according to [9], further comprising a yellow pigment.
[11] The yellow pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150 and C.I. I. The colorant according to [10], wherein at least one selected from the group of CI Pigment Yellow 185.
[12] A colored curable resin composition comprising the colorant according to any one of [1] to [11], a resin, a polymerizable compound, and a polymerization initiator.
[13] A coating film formed from the colored curable resin composition according to [12].
[14] A color filter formed from the colored photosensitive resin composition according to [12].
[15] A display device including the color filter according to [14].

  The dye of the present invention is excellent in solubility in an organic solvent, and a color filter formed from a colored hardenable resin composition containing this dye is excellent in terms of heat resistance.

  The present invention is a dye having a group containing a silicon atom and having a squarylium skeleton. Examples of the dye having a group containing a silicon atom and having a squarylium skeleton include a dye having a squarylium skeleton having a siloxy group such as a trimethylsiloxy group, a triethylsiloxy group, a trimethoxysilyl group, and a triethoxysilyl group. .

In the dye having a group containing a silicon atom and having a squarylium skeleton, the group containing a silicon atom is preferably a group containing a group represented by —Si (R ¹⁴ ) _3. Is more preferably a group represented by —Si (R ¹⁴ ) ₃ . R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The plurality of R ¹⁴ may be the same or different.

Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ¹⁴ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

［式（ｉｉａ）中、Ｒ^１４４は、水素原子、ヒドロキシ基、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表す。
Ｌ^１は、炭素数１〜８のアルカンジイル基を表す。該アルカンジイル基に含まれる−ＣＨ_２−は、酸素原子で置き換わっていてもよい。
＊は、窒素原子との結合手を表す。］
Ｒ^１４４で表される炭素数１〜４のアルキル基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられる。
Ｒ^１４４で表される炭素数１〜４のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基が挙げられる。
Ｌ^１で表される炭素数１〜８のアルカンジイル基としては、メチレン基、エチレン基、プロパン−１，３−ジイル基、プロパン−１，２−ジイル基、ブタン−１，４−ジイル基、ブタン−１，３−ジイル基、ペンタン−１，５−ジイル基、ヘキサン−１，６−ジイル基、ヘプタン−１，７−ジイル基、オクタン−１，８−ジイル基等が挙げられる。Ｌ^１は、好ましくは、炭素数１〜４のアルカンジイル基である。

[In the formula (ia), R ¹⁴⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. —CH ₂ — contained in the alkanediyl group may be replaced with an oxygen atom.
* Represents a bond with a nitrogen atom. ]
Examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹⁴⁴ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ¹⁴⁴ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
Examples of the alkanediyl group having 1 to 8 carbon atoms represented by L ¹ include a methylene group, an ethylene group, a propane-1,3-diyl group, a propane-1,2-diyl group, and a butane-1,4-diyl group. , Butane-1,3-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group and the like. L ¹ is preferably an alkanediyl group having 1 to 4 carbon atoms.

［式（ＩＩ）中、Ｒ^１、Ｒ^２、Ｒ^１１１及びＲ^１１２は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基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（該飽和炭化水素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）を表す。
Ｒ^３、Ｒ^４、Ｒ^１１３及びＲ^１１４は、それぞれ独立に、水素原子またはヒドロキシ基を表す。
Ｒ^５、Ｒ^６、Ｒ^１５及びＲ^１６は、それぞれ独立して、水素原子、ケイ素原子を含む基、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（該飽和炭素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）又は置換基を有していてもよいフェニル基を表す。ただし、Ｒ^５、Ｒ^６、Ｒ^１５及びＲ^１６の少なくとも１つは、ケイ素原子を含む基である。］ The dye having a group containing a silicon atom and having a squarylium skeleton is preferably a compound represented by the formula (IIa) (hereinafter sometimes referred to as the compound (IIa)). More preferably, it is a compound represented by (IIb) (hereinafter, compound (IIb), more preferably a compound represented by formula (II) (hereinafter, compound (II). Compound (IIa), Compound (IIb) and compound (II) also include tautomers thereof.

[In Formula (II), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent group having 1 to 20 carbon atoms which may have a substituent. A saturated hydrocarbon group (an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated hydrocarbon group).
R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxy group.
R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a group containing a silicon atom, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent ( An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated carbon group) or a phenyl group which may have a substituent. However, at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is a group containing a silicon atom. ]

［式（ＩＩｂ）中、Ｒ^１、Ｒ^２、Ｒ^１１１及びＲ^１１２は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基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（該飽和炭化水素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）を表す。
Ｒ^３、Ｒ^４、Ｒ^１１３及びＲ^１１４は、それぞれ独立に、水素原子またはヒドロキシ基を表す。
Ｒ^５、Ｒ^６、Ｒ^１５及びＲ^１６は、それぞれ独立に、水素原子、置換基を有していてもよい炭素数１〜２０の１価の飽和炭化水素基（飽和炭素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）、式（ｉｉａ）で表される基または式（ｉ）で表される基であり、少なくとも１つは式（ｉｉａ）で表される基である。

（式（ｉ）中、Ｒ^１２は、水素原子、炭素数１〜２０の１価の飽和炭化水素基または炭素数２〜２０の１価の不飽和の炭化水素基を表し、ｍは１〜５の整数を表す。ｍが２以上のとき、複数のＲ^１２は、それぞれ同一であっても異なっていてもよい。＊は、窒素原子との結合の手を表す。）

［式（ｉｉａ）中、Ｒ^１４４は、水素原子、ヒドロキシ基、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表す。
Ｌ^１は、炭素数１〜８のアルカンジイル基を表す。該アルカンジイル基に含まれる−ＣＨ_２−は、酸素原子で置き換わっていてもよい。
＊は、結合手を表す。］

[In formula (IIb), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent group having 1 to 20 carbon atoms which may have a substituent. A saturated hydrocarbon group (an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated hydrocarbon group).
R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxy group.
R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (the carbon constituting the saturated carbon group). An oxygen atom or a sulfur atom may be inserted between atoms), a group represented by formula (ia) or a group represented by formula (i), at least one of which is represented by formula (ia) Group.

(In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, Represents an integer of 5. When m is 2 or more, the plurality of R ¹² may be the same or different from each other, and * represents a bond to a nitrogen atom.

[In the formula (ia), R ¹⁴⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. —CH ₂ — contained in the alkanediyl group may be replaced with an oxygen atom.
* Represents a bond. ]

式（ＩＩ）中、Ｒ^１及びＲ^２は、それぞれ独立に、水素原子、ハロゲン原子、ヒドロキシ基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（該飽和炭化水素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）を表す。
Ｒ^３及びＲ^４は、それぞれ独立に、水素原子またはヒドロキシ基を表す。
Ｒ^５とＲ^６のうちの、一方は式（ii）で表される基であり、他方は水素原子、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（飽和炭素基を構成する炭素原子間に、酸素原子または硫黄原子が挿入されていてもよい）または式（ｉ）で表される基である。

（式（ｉ）中、Ｒ^１２は、水素原子、炭素数１〜２０の１価の飽和炭化水素基または炭素数２〜２０の１価の不飽和の炭化水素基を表し、ｍは１〜５の整数を表す。ｍが２以上のとき、複数のＲ^１２は、それぞれ同一であっても異なっていてもよい。＊は、窒素原子との結合の手を表す。）

（式（ｉｉ）中、ｎは１〜８の整数を表し、Ｒ^１４は水素原子、ヒドロキシ基、炭素数１〜４のアルキル基または炭素数１〜４のアルコキシ基を表し、＊は窒素原子との結合の手を表す。複数のＲ^１４は、それぞれ同一であっても異なっていてもよい。）

In formula (II), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent ( An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated hydrocarbon group).
R ³ and R ⁴ each independently represents a hydrogen atom or a hydroxy group.
One of R ⁵ and R ⁶ is a group represented by the formula (ii), and the other is a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. (An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated carbon group) or a group represented by formula (i).

(In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, Represents an integer of 5. When m is 2 or more, the plurality of R ¹² may be the same or different from each other, and * represents a bond to a nitrogen atom.

(In the formula (ii), n represents an integer of 1 to 8, R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * represents a nitrogen atom. And a plurality of R ¹⁴ may be the same or different.)

Examples of the halogen atom represented by R ¹ or R ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ , R ² , R ⁵ , R ⁶ , R ¹¹¹ , R ¹¹² , R ¹¹⁵ , R ¹¹⁶ and R ¹² include methyl group, ethyl group, propyl group A linear alkyl group having 1 to 20 carbon atoms such as a group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group, hexadecyl group and icosyl group; isopropyl group, isobutyl group , Sec-butyl group, tert-butyl group, isopentyl group, neopentyl group and 2-ethylhexyl group, etc., branched alkyl groups having 3 to 20 carbon atoms; cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclo C3-C20 alicyclic saturated hydrocarbon groups, such as an octyl group and a tricyclodecyl group, are mentioned.

Examples of the substituent of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ¹ , R ² , R ⁵ , R ⁶ , R ¹¹¹ , R ¹¹² , R ¹¹⁵ and R ¹¹⁶ include a halogen atom, a hydroxy group, Examples thereof include alkylamino groups having 1 to 8 carbon atoms.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
Examples of the alkylamino group having 1 to 8 carbon atoms include methylamino group, ethylamino group, n-propylamino group, n-butylamino group, n-pentylamino group, dimethylamino group, diethylamino group, and dipropylamino group. And an ethylmethylamino group.
As a C1-C20 monovalent saturated hydrocarbon group which has these substituents, group represented by a following formula is mentioned, for example.

Monovalent substituent having saturated hydrocarbon groups of R ^{5, R 6,} carbon atoms for ^{R 115} and ^{R 116} 1 to 20 may be a group containing a silicon atom.

^{R 1, R 2, R 5} , R 6, R 111, R 112, between carbon atoms constituting a monovalent saturated carbon group having 1 to 20 carbon atoms in ^{R 115} and ^{R 116} to an oxygen atom or a sulfur atom Examples of the inserted group include a group represented by the following formula.

R ¹ , R ² , R ¹¹¹ and R ¹¹² are each independently preferably a hydrogen atom, a hydroxy group and an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a hydroxy group and a methyl group, More preferred is a hydrogen atom.

At least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ represents a group containing a silicon atom;
At least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is preferably a group represented by the formula (ia),
It is preferable that at least one of R ⁵ and R ⁶ is a group represented by the formula (ia), and at least one of R ¹⁵ and R ¹⁶ is a group represented by the formula (ia).
In the case of compound (II), at least one of R ⁵ and R ⁶ represents a group containing a silicon atom,
One of R ⁵ and R ⁶ is a group represented by the formula (ia), and the other is a hydrogen atom or a monovalent saturated hydrocarbon having 1 to 20 carbon atoms which may have a substituent. It is preferably a group represented by a group (an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated carbon group) or a formula (i),
One of R ⁵ and R ⁶ is a group represented by the formula (ii), and the other is a hydrogen atom or a monovalent saturated hydrocarbon having 1 to 20 carbon atoms which may have a substituent. A group represented by a group (an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated carbon group) or a group represented by formula (i) is more preferable.

Examples of the substituent that the phenyl group represented by R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ may have include a group containing a silicon atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, carbon Examples thereof include monovalent unsaturated hydrocarbon groups of 2 to 20.
Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples thereof include alkyl groups such as n-hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group and n-dodecyl group.
Examples of the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms include 2 to 20 carbon atoms such as a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group. Of the alkenyl group.

In the formula (i), the monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms represented by R ¹² includes a vinyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, Examples thereof include alkenyl groups having 2 to 20 carbon atoms such as nonenyl group and decenyl group.
Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms represented by R ¹² include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group. Alkyl groups such as n-pentyl group, n-hexyl group, n-heptyl group, 2-ethylhexyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. Can be mentioned.

R ¹² is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and more preferably a hydrogen atom, a methyl group or an ethyl group.

Examples of the group represented by the formula (i) include the following groups. * Represents a bond with a nitrogen atom.

  In the formula (IIa), the group containing a silicon atom is preferably a group represented by the formula (iii), and more preferably a group represented by the formula (ii).

In formula (ii), examples of the alkyl group having 1 to 4 carbon atoms represented by R ¹⁴ include a methyl group, an ethyl group, a propyl group, and a butyl group.
Examples of the alkoxy group having 1 to 4 carbon atoms represented by R ¹⁴ include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.
R ¹⁴ is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, more preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, or a propoxy group. And more preferably a hydrogen atom, a methyl group, an ethyl group, a methoxy group or an ethoxy group.
The three R ¹⁴ are preferably the same.
n is preferably an integer of 1 to 6, and more preferably an integer of 1 to 4.

  As group represented by a formula (iia), the group shown below is mentioned, for example. * Represents a bond with a nitrogen atom or a carbon atom. Of these, a group represented by the formula (ii-1) to a group represented by the formula (ii-6) is preferable.

In the groups represented by R ⁵ and R ⁶ , a hydrogen atom and a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (between the carbon atoms constituting the saturated carbon group, oxygen An atom or a sulfur atom may be inserted), one group selected from the group consisting of the group represented by formula (i) and the group represented by formula (ii) is preferably a hydrogen atom, a carbon number 1 to 20 saturated hydrocarbon groups, a group represented by formula (i) and a group represented by formula (ii), more preferably a hydrogen atom.

で表される基としては、次のような基が挙げられる（Ｒ^５及びＲ^６は、それぞれ前記と同じ意味を表し、＊は炭素原子との結合手を表す）。 The following formula representing a combination of R ⁵ and R ⁶

The following groups are exemplified as the group represented by (R ⁵ and R ⁶ each have the same meaning as described above, and * represents a bond to a carbon atom).

Examples of the dye having a group containing a silicon atom and having a squarylium skeleton include compounds represented by the formula (AII-1) to (AII- 75 ).

  From the viewpoint of raw material availability, the compound represented by formula (AII-4) to the compound represented by formula (AII-6), the compound represented by formula (AII-31) to formula (AII-33) The compounds represented are more preferred.

（式（ＩV-1）中、Ｒ^１〜Ｒ^６は、それぞれ上記と同じ意味を表す。） Compound (II) is, for example, a method described in JP-A No. 2002-363434, a compound represented by formula (IV-1) and squaric acid (3,4-dihydroxy-3-cyclobutene-1,2dione) Can be made to react.

(In formula (IV-1), R ^{1 to} R ⁶ each have the same meaning as described above.)

  The amount of squaric acid used is preferably 0.5 mol or more and 0.8 mol or less, more preferably 0.55 mol or more and 0.6 mol or less with respect to 1 mol of the compound represented by the formula (IV-I). It is below the mole.

  The reaction temperature is preferably 30 ° C to 180 ° C, more preferably 80 ° C to 140 ° C. The reaction time is preferably 1 hour to 12 hours, and more preferably 3 hours to 8 hours.

  The reaction is preferably performed in an organic solvent from the viewpoint of yield. Organic solvents include hydrocarbon solvents such as toluene and xylene; halogenated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and chloroform; alcohol solvents such as methanol, ethanol, isopropanol and butanol; nitro hydrocarbon solvents such as nitrobenzene; methyl isobutyl Examples include ketone solvents such as ketones; amide solvents such as 1-methyl-2-pyrrolidone; and the like. Of these, a mixed solvent of butanol and toluene is preferable. The amount of the organic solvent to be used is preferably 30 parts by mass or more and 200 parts by mass or less, more preferably 50 parts by mass or more and 150 parts by mass or less with respect to 1 part by mass of the compound represented by the formula (IV-I). is there.

  The method for obtaining the target compound (II) from the reaction mixture is not particularly limited, and various known techniques can be employed. For example, after cooling, a method of filtering the precipitated crystals can be mentioned. The crystals collected by filtration are preferably washed with water and then dried. Moreover, you may refine | purify further by well-known methods, such as recrystallization, as needed.

The colored curable resin composition of the present invention includes a colorant (A) having a group containing a silicon atom and a dye having a squarylium skeleton, a resin (B), a polymerizable compound (C), And a polymerization initiator (D). Furthermore, a solvent (E) may be included.
In this specification, unless otherwise indicated, the compound illustrated as each component can be used individually or in combination of multiple types.

<Colorant (A)>
In addition to the compound of the present invention, the colorant (A) further contains another dye (A2), pigment (P), or a mixture thereof for toning, that is, to adjust spectral characteristics. Also good.
Examples of the dye (A2) include oil-soluble dyes, acid dyes, amine salts of acid dyes, and sulfonamides of acid dyes. For example, dyes are classified by color index (published by The Society of Dyers and Colorists). And known dyes described in Dyeing Notes (Color Dyeing). In addition, according to the chemical structure, coumarin dyes, metal-containing azo dyes, pyridone azo dyes, barbiturazo dyes, quinophthalone dyes, methine dyes, cyanine dyes, anthraquinone dyes, triphenylmethane dyes, xanthene dyes, phthalocyanine dyes, etc. It is done. These dyes may be used alone or in combination of two or more.

Specifically, C.I. I. Solvent Yellow 4 (hereinafter, description of CI Solvent Yellow is omitted, and only the number is described), 14, 15, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99 162;
C. I. Solvent Orange 2, 7, 11, 15, 26, 56; I. Solvent dyes,
C. I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251;
C. I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173; I. Acid dyes,

C. I. Direct Yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 136, 138, 141;
C. I. Direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; I. Direct dyes,
C. I. Modern yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
C. I. Modern Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; etc. . I. Examples include modern dyes.

  The dye (A2) is preferably a yellow dye such as a coumarin dye, a metal-containing azo dye, a pyridone azo dye, a barbiturazo dye, a quinophthalone dye, a methine dye, or a cyanine dye.

  Content of the dye of this invention is 3-99.9 mass% normally with respect to the total amount of a coloring agent, Preferably it is 4-50 mass%, More preferably, it is 5-30 mass%. When the content of the dye of the present invention is within the above range, the lightness of the color filter is high, which is preferable.

The pigment (P) is not particularly limited, and a known pigment can be used. Examples thereof include pigments classified as pigments according to a color index (published by The Society of Dyers and Colorists).
For example, C.I. I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, Yellow pigments such as 147, 148, 150, 153, 154, 166, 173, 194, 214;
C. I. Orange pigments such as CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73;
C. I. And green pigments such as CI Pigment Green 7, 36, and 58.

Examples of the pigment (P) 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. Green pigments such as C.I. Pigment Green 7, 36 and 58 are preferred; I. Pigment yellow 138, 150, 185 and C.I. I. Pigment Green 36 and 58 are more preferable, and C.I. I. Pigment yellow 150, 185 and C.I. I. Pigment Green 58 is more preferable. By including the pigment, the transmission spectrum can be easily optimized, and the light resistance and chemical resistance of the color filter are improved.

  The content of the colorant (A) is preferably 5 to 60% by mass, more preferably 8 to 55% by mass, and further preferably 10 to 50% by mass with respect to the total amount of the solid content. When the content of the colorant (A) is within the above range, the color density when it is used as a color filter is sufficient, and the resin (B) and the polymerizable compound (C) are contained in a necessary amount in the composition. Therefore, a pattern with sufficient mechanical strength can be formed. Here, the “total amount of solid content” in this specification refers to an amount obtained by removing the content of the solvent from the total amount of the colored curable resin composition. 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. Examples of the resin (B) include the following resins [K1] to [K6].
Resin [K1]; at least one selected from the group consisting of an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride (Ba) (hereinafter sometimes referred to as “(Ba)”), and a cyclic ether having 2 to 4 carbon atoms A copolymer of a monomer (Bb) having a structure and an ethylenically unsaturated bond (hereinafter sometimes referred to as “(Bb)”);
Resin [K2]; (Ba), (Bb), and monomer (Bc) copolymerizable with (Ba) (however, different from (Ba) and (Bb)) (hereinafter referred to as “(Bc)”) In some cases)
Resin [K3]; Copolymer of (Ba) and (Bc);
Resin [K4]; a resin obtained by reacting (Bb) with a copolymer of (Ba) and (Bc);
Resin [K5]; a resin obtained by reacting (Ba) with a copolymer of (Bb) and (Bc);
Resin [K6]: a resin obtained by reacting a copolymer of (Bb) and (Bc) with (Ba) and further reacting with a carboxylic acid anhydride.

Specific examples of (Ba) 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.

(Bb) 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. (Bb) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms 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 (Bb) include a monomer having an oxiranyl group and an ethylenically unsaturated bond, a monomer having an oxetanyl group and an ethylenically unsaturated bond, and a tetrahydrofuryl group and an ethylenically unsaturated bond. And monomers.

  (Bb) is preferably a monomer having an oxiranyl group and an ethylenically unsaturated bond from the viewpoint that the color filter to be obtained can have higher reliability such as heat resistance and chemical resistance. .

Examples of (Bc) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, and 2-ethylhexyl (meth). Acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl (meth) acrylate (in this technical field, it is called “dicyclopentanyl (meth) acrylate” as a common name. In the case of “tricyclodecyl (meth) acrylate”) ) (In the art, it is said that "dicyclopentenyl (meth) acrylate" as trivial name.) Cyclo [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.
Among these, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo [2.2.1] hept-2-ene and the like are preferable from the viewpoint of copolymerization reactivity and heat resistance. preferable.

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 acrylate / (meth) acrylic acid copolymer [K1]; glycidyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic acid copolymer, glycidyl (meth) acrylate / styrene / (meta ) Acrylic acid copolymer, 3,4-epoxytricyclo [5.2.1.0 ^2.6 ] decyl acrylate / (meth) acrylic acid / N-cyclohexylmaleimide copolymer, 3-methyl-3- ( Resin [K2] such as (meth) acryloyloxymethyloxetane / (meth) acrylic acid / styrene copolymer; benzyl (meth) acrylate / Glycidyl (meth) acrylate was added to resin [K3]; benzyl (meth) acrylate / (meth) acrylic acid copolymer such as (meth) acrylic acid copolymer and styrene / (meth) acrylic acid copolymer Resin, tricyclodecyl (meth) acrylate / styrene / (meth) acrylic acid copolymer added with glycidyl (meth) acrylate, tricyclodecyl (meth) acrylate / benzyl (meth) acrylate / (meth) acrylic Resins such as resins obtained by adding glycidyl (meth) acrylate to an acid copolymer [K4]; resins obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid , Tricyclodecyl (meth) acrylate / styrene / glycidyl (meth) acrylate Resin [K5] such as a resin obtained by reacting a copolymer with (meth) acrylic acid; a resin obtained by reacting a copolymer of tricyclodecyl (meth) acrylate / glycidyl (meth) acrylate with (meth) acrylic acid Furthermore, resin [K6] such as a resin obtained by reacting tetrahydrophthalic anhydride may be used.
Especially, as resin (B), resin [K1] and resin [K2] are preferable.

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

  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.

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 within the above range, the hardness of the color filter is improved, the residual film ratio is high, the solubility of the unexposed portion in the 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 within the above range, a colored pattern can be formed, and the resolution of the colored pattern and the remaining film rate 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.

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 150 to 2,900, more preferably 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. 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 that generates an active radical include an O-acyloxime compound, an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, and a biimidazole compound.

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

  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, benzyldi And methyl ketal. Commercial products such as Irgacure (registered trademark) 369, 907, 379 (above, manufactured by BASF) may be used.

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

  Examples of the acylphosphine oxide compound include 2,4,6-trimethylbenzoyldiphenylphosphine oxide. Commercial products such as Irgacure (registered trademark) 819 (manufactured by BASF) may be used.

  Examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 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 (trial Xylphenyl) biimidazole (for example, see JP-B-48-38403, JP-A-62-174204, etc.), a phenyl group at the 4,4 ′, 5,5′-position is substituted with a carboalkoxy group. Imidazole compounds (see, for example, JP-A-7-10913).

  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.

  Examples of the polymerization initiator that generates an acid include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxy Onium salts such as phenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, and nitrobenzyl tosylate And benzoin tosylate.

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

The content of the polymerization initiator (D) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts per 100 parts by mass of the total amount of the resin (B) and the polymerizable compound (C). Part by mass. When the content of the polymerization initiator (D) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so the productivity of the color filter is 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 and γ-butyrolactone.

  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, and the like phenetol and methyl anisole.

  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 and diethylene glycol monobutyl ether acetate.

  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, and glycerin.

  Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene and mesitylene.

  Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide and N-methylpyrrolidone.

  Among the above solvents, an organic solvent having a boiling point of 120 ° C. or more and 210 ° C. or less at 1 atm is preferable from the viewpoints of coating properties and drying properties. Solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone And N, N-dimethylformamide is preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, N, N-dimethylformamide, N-methylpyrrolidone, and ethyl 3-ethoxypropionate are more preferred.

  Content of a solvent (E) becomes like this. Preferably it is 70-95 mass% with respect to the total amount of the colored curable resin composition of this invention, More preferably, it is 75-92 mass%. In other words, the total amount of 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 within 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. .

<Other ingredients>
The colored curable resin composition of the present invention, if necessary, a polymerization initiation aid, leveling agent, filler, other polymer compound, adhesion promoter, antioxidant, light stabilizer, chain transfer agent, etc. Additives known in the art may be included.

<Method for producing colored curable resin composition>
The colored curable resin composition of the present invention is used, for example, as a colorant (A), a resin (B), a polymerizable compound (C), a polymerization initiator (D), a solvent (E), and as necessary. It can be prepared by mixing a leveling agent, a polymerization initiation assistant and other components.
The pigment (P) is preferably mixed in advance with part or all of the solvent (E) and dispersed using a bead mill or the like until the average particle diameter of the pigment is about 0.2 μm or less. Under the present circumstances, you may mix | blend a 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.
The dye may be previously dissolved in part or all of the solvent (E) to prepare a solution. The solution is preferably filtered through 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 0.1 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.

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

Example 1 Synthesis of Compound Represented by Formula (AII-32) 10.9 parts of 3-aminophenol (manufactured by Tokyo Chemical Industry Co., Ltd.) and 19 parts of triethoxysilane (manufactured by Tokyo Chemical Industry Co., Ltd.) And 5 parts of acetic acid were refluxed in 200 parts of tetrahydrofuran for 8 hours. After completion of the reaction, tetrahydrofuran was distilled off to obtain 29.8 parts of a compound represented by the following formula (AII-32-1).

2.9 parts of the compound represented by the formula (AII-32-1) obtained, 0.6 part of 3,4-dihydroxy-3-cyclobutene-1,2-dione (manufactured by Tokyo Chemical Industry Co., Ltd.), 1 part -90 parts of butanol and 60 parts of toluene were mixed. The resulting mixture was stirred at 125 ° C. for 3 hours while removing water produced using a Dean-Stark tube. After completion of the reaction, the solvent was distilled off, 15 parts of acetic acid was added, 18% brine was added dropwise, and the precipitated solid was collected by filtration. The solid collected by filtration was washed with hexane. The obtained solid was dried under reduced pressure to obtain 3.4 parts of a compound represented by the formula (AII-32).

Identification of compound represented by formula (AII-32) (mass spectrometry) ionization mode = ESI +: m / z = 680.4 [M + 1] ⁺
Exact Mass: 679.3

Example 2 Synthesis of Compound Represented by Formula (AII-5) Synthesis was performed in the same manner as in Example 1 except that aniline was used instead of 3-aminophenol. The compound represented by 5) was obtained.

Identification of compound represented by formula (AII-5) (mass spectrometry) ionization mode = ESI +: m / z = 650.0 [M + 1] ⁺
Exact Mass: 648.9

Example 3 Synthesis of Compound Represented by Formula (AII-31) Example 3 was synthesized in the same manner as in Example 1 except that trimethoxysilane was used instead of triethoxysilane. The compound represented by 31) was obtained.

Identification of compound represented by formula (AII-31) (mass spectrometry) ionization mode = ESI +: m / z = 597.8 [M + 1] ⁺
Exact Mass: 596.8

A compound represented by formula (AII-32), a compound represented by formula (AII-5), and 0.35 part of a compound represented by formula (AII-31) were each dissolved in chloroform to give a volume of 250 cm ^3. Then, 2 cm ³ was diluted with ion-exchanged water to a volume of 100 cm ³ (concentration: 0.028 g / L), and an absorption spectrum was measured using a spectrophotometer (quartz cell, optical path length: 1 cm). The maximum absorption wavelengths: λmax of these compounds were 688 nm, 680 nm, and 687 nm, respectively.

<Measurement of solubility>
Propylene glycol monomethyl ether (hereinafter abbreviated as PGME), ethyl lactate (hereinafter abbreviated as EL), propylene glycol monomethyl ether acetate of the compounds obtained in Examples 1 to 3 and the compound represented by formula (II-0) The solubility in (hereinafter abbreviated as PGMEA) was determined as follows.
In a 50 mL sample tube, the compound and the solvent were mixed in the following ratio, and then the sample tube was sealed and vibrated with an ultrasonic vibrator at 30 ° C. for 3 minutes. Then, after standing at room temperature for 30 minutes, suction filtration was performed, and the residue was visually observed. When the insoluble matter could not be confirmed, it was judged that the solubility was good, and it was judged as “Good”, and when the insoluble matter could be confirmed, it was judged that the solubility was poor, and it was judged as “poor”. The results are shown in Table 1.
5% compound 0.05g, solvent 1g
3% 0.03 g of compound, 1 g of solvent
1% compound 0.01g, solvent 1g

(Synthesis of resin)
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 dropping of the polymerization initiator was completed, the temperature was maintained at the same temperature for about 3 hours and then cooled to room temperature to obtain a copolymer (resin (B-1) solution having a solid content of 43.5%. The obtained resin (B-1 had a weight average molecular weight of 8,000, a molecular weight distribution of 1.98, and an acid value in terms of solid content of 53 mg-KOH / g.

(Preparation of colored curable resin composition)

Example 7
Colorant (A): 2 parts of a dye represented by the formula (AII-32);
Colorant (A): Pigment (P): C.I. I. Pigment Yellow 138 25.8 parts Resin (B): Resin B1 50 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts Polymerization initiator ( D): N-1919 (manufactured by ADEKA; O-acyloxime compound) 10 parts Solvent (E): E-1: Propylene glycol monomethyl ether acetate 870 parts Solvent (E): E-2: 290 parts of N-methylpyrrolidone Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.1 part was mixed to obtain a colored curable resin composition.

Example 8
Colorant (A): 2 parts of a dye represented by the formula (AII-5);
Colorant (A): Pigment (P): C.I. I. Pigment Yellow 150 34.1 parts Resin (B): Resin B1 50 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts Polymerization initiator ( D): N-1919 (manufactured by ADEKA; O-acyloxime compound) 10 parts Solvent (E): E-1: Propylene glycol monomethyl ether acetate 870 parts Solvent (E): E-2: 290 parts of N-methylpyrrolidone Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.1 part was mixed to obtain a colored curable resin composition.

Example 9
Colorant (A): 2 parts of a dye represented by the formula (AII-31);
Colorant (A): Pigment (P): C.I. I. Pigment Yellow 185 10.3 parts Resin (B): Resin B1 50 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts Polymerization initiator ( D): N-1919 (manufactured by ADEKA; O-acyloxime compound) 10 parts Solvent (E): E-1: Propylene glycol monomethyl ether acetate 870 parts Solvent (E): E-2: 290 parts of N-methylpyrrolidone Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.1 part was mixed to obtain a colored curable resin composition.

Comparative Example 2
Colorant (A): 1 part of a dye represented by the formula (II-0);
Colorant (A): Pigment (P): C.I. I. Pigment Yellow 185 10.3 parts Resin (B): Resin B1 50 parts Polymerizable compound (C): Dipentaerythritol hexaacrylate (KAYARAD (registered trademark) DPHA; manufactured by Nippon Kayaku Co., Ltd.) 50 parts Polymerization initiator ( D): N-1919 (manufactured by ADEKA; O-acyloxime compound) 10 parts Solvent (E): E-1: 70 parts of propylene glycol monomethyl ether acetate Solvent (E): E-2: 800 parts of N-methylpyrrolidone Leveling agent (F): polyether-modified silicone oil (Toray Silicone SH8400; manufactured by Toray Dow Corning Co., Ltd.) 0.1 part was mixed to obtain a colored curable resin composition.

[Formation of pattern]
A colored photosensitive 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 obtain a composition layer. After cooling, the distance between the glass substrate on which the composition layer is formed and the photomask made of quartz glass is set to 100 μm, and using an exposure machine (TME-150RSK; manufactured by Topcon Corporation), 150 mJ / cm ^{2 in} an air atmosphere. Is irradiated with light at an exposure amount (365 nm reference). A photomask having a 100 μm line and space pattern is used. After the light irradiation, the coating film was immersed and developed at 23 ° C. for 80 seconds in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide, washed with water, and then 200 ° C. in an oven. And post-baked for 20 minutes to obtain a pattern.

[Heat resistance evaluation]
The coating film of the colored photosensitive resin composition was heated at 200 ° C. for 20 minutes, and the color difference (ΔEab *) before and after heating of the coating film was measured using a colorimeter (OSP-SP-200; manufactured by OLYMPUS). The coating films obtained in Examples 7, 8, and 9 were subjected to the above heat resistance evaluation. As a result, the color difference (ΔEab *) was 12.6, 10.2, and 11.1. Moreover, as a result of carrying out heat resistance evaluation similarly about the comparative example 2, color difference ((DELTA) Eab *) is 20.5 and it turned out that this-application compound is excellent in heat resistance.

  The dye of the present invention is excellent in solubility in an organic solvent. Therefore, if the colored curable resin composition containing the colorant containing the dye of the present invention is used, it is possible to produce a high-quality color filter with less generation of foreign matters, and excellent in heat resistance. Can be provided.

Claims (15)

  A dye having a group containing a silicon atom and having a squarylium skeleton. The dye according to claim 1, wherein the group containing a silicon atom is a group containing a group represented by —Si (R ¹⁴ ) ₃ .
^{[R 14} represents a hydrogen atom, a hydroxy group, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms. The plurality of R ¹⁴ may be the same or different. ] The dye according to claim 1 or 2, wherein the group containing a silicon atom is a group represented by the formula (ia).

[In formula (ia), R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The plurality of R ¹⁴ may be the same or different.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. —CH ₂ — contained in the alkanediyl group may be replaced with an oxygen atom.
* Represents a bond. ] The dye according to any one of claims 1 to ₃ , wherein the group containing a silicon atom is a group represented by -Si (R ¹⁴ ) ₃ .
^{[R 14} represents a hydrogen atom, a hydroxy group, an alkyl group or an alkoxy group having 1 to 4 carbon atoms having 1 to 4 carbon atoms. The plurality of R ¹⁴ may be the same or different. ] The dye according to any one of claims 1 to 4, wherein the dye having a group containing a silicon atom and having a squarylium skeleton is a compound represented by the formula (IIa).

[In Formula (II), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent group having 1 to 20 carbon atoms which may have a substituent. A saturated hydrocarbon group (an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated hydrocarbon group).
R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxy group.
R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a group containing a silicon atom, or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent ( An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated carbon group) or a phenyl group which may have a substituent. However, at least one of R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ is a group containing a silicon atom. ] The dye according to claim 5, wherein the group containing a silicon atom in the formula (IIa) is a group represented by the formula (iii).

[In formula (ia), R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. The plurality of R ¹⁴ may be the same or different.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. —CH ₂ — contained in the alkanediyl group may be replaced with an oxygen atom.
* Represents a bond. ] The dye according to claim 5 or 6, wherein the compound represented by the formula (IIa) is a compound represented by the formula (IIb).

[In formula (IIb), R ¹ , R ² , R ¹¹¹ and R ¹¹² each independently represents a hydrogen atom, a halogen atom, a hydroxy group or a monovalent group having 1 to 20 carbon atoms which may have a substituent. A saturated hydrocarbon group (an oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated hydrocarbon group).
R ³ , R ⁴ , R ¹¹³ and R ¹¹⁴ each independently represent a hydrogen atom or a hydroxy group.
R ⁵ , R ⁶ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (the carbon constituting the saturated carbon group). An oxygen atom or a sulfur atom may be inserted between atoms), a group represented by formula (ia) or a group represented by formula (i), at least one of which is represented by formula (ia) Group.

(In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, Represents an integer of 5. When m is 2 or more, the plurality of R ¹² may be the same or different from each other, and * represents a bond to a nitrogen atom.

[In the formula (ia), R ¹⁴⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
L ¹ represents an alkanediyl group having 1 to 8 carbon atoms. —CH ₂ — contained in the alkanediyl group may be replaced with an oxygen atom.
* Represents a bond with a nitrogen atom. ] The dye according to claim 7, wherein the compound represented by the formula (IIb) is a compound represented by the formula (II).

[In Formula (II), R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a hydroxy group or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent ( An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated hydrocarbon group).
R ³ and R ⁴ each independently represents a hydrogen atom or a hydroxy group.
One of R ⁵ and R ⁶ is a group represented by the formula (ii), and the other is a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms which may have a substituent. (An oxygen atom or a sulfur atom may be inserted between carbon atoms constituting the saturated carbon group) or a group represented by formula (i).

(In formula (i), R ¹² represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent unsaturated hydrocarbon group having 2 to 20 carbon atoms, Represents an integer of 5. When m is 2 or more, the plurality of R ¹² may be the same or different from each other, and * represents a bond to a nitrogen atom.

(In the formula (ii), n represents an integer of 1 to 8, R ¹⁴ represents a hydrogen atom, a hydroxy group, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and * represents a nitrogen atom. And a plurality of R ¹⁴ may be the same or different.)]   The coloring agent containing the dye in any one of Claims 1-8.   Furthermore, the coloring agent of Claim 9 containing a yellow pigment.   The yellow pigment is C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 150 and C.I. I. The colorant according to claim 10, wherein at least one is selected from the group of CI Pigment Yellow 185.   A colored curable resin composition comprising the colorant according to any one of claims 9 to 11, a resin, a polymerizable compound, and a polymerization initiator.   The coating film formed from the colored curable resin composition of Claim 12.   A color filter formed from the colored photosensitive resin composition according to claim 12.   A display device comprising the color filter according to claim 14.