JP6496350B2 - Colored composition, cured film, color filter, method of producing color filter, solid-state imaging device, image display device, polymer, xanthene dye - Google Patents

Description

  The present invention relates to a coloring composition and a cured film using the same. The present invention also relates to a color filter having a cured film, a method of manufacturing the color filter, a solid-state imaging device having the color filter, and an image display device. It also relates to polymers and xanthene dyes.

One of the methods for producing color filters used in liquid crystal display devices, solid-state imaging devices and the like is the pigment dispersion method. As this pigment dispersion method, colored photosensitivity in which a pigment is dispersed in various photosensitive compositions There is a method of manufacturing a color filter by a photolithographic method using a composition. That is, the curable composition is applied onto a substrate using a spin coater, a roll coater or the like, dried to form a coating film, and the coating film is pattern-exposed and developed to obtain colored pixels. A color filter is produced by repeating this operation for a desired hue.
The above method is stable against light and heat because it uses a pigment, and the positional accuracy is sufficiently secured because patterning is performed by the photolithographic method, and it is suitable as a method suitable for manufacturing a color filter for a color display, etc. It has been widely used.

  By the way, it is general to use a coloring composition containing a dye and a pigment for preparation of a color filter. For example, Patent Document 1 discloses a bis (perfluorosulfonyl) methane derivative. Patent Documents 2 to 5 disclose compositions containing a compound having a xanthene structure of a counter salt type as a colorant.

Unexamined-Japanese-Patent No. 6-503842 JP 2012-107192 A JP 2012-108469 A International Publication WO 2013/011687 Brochure International Publication WO2011 / 158748 Brochure

When the present inventors examined, when a color filter was formed using the compound of patent documents 2-5, it turned out that it exists in the tendency for heat resistance to be inferior.
An object of the present invention is to solve such problems, and it is an object of the present invention to provide a coloring composition capable of providing a color filter excellent in heat resistance. It is also an object to provide polymers and xanthene dyes.

一般式（Ａ１）中、Ｒ¹およびＲ²はそれぞれ独立して−ＳＯ₂−または−ＣＯ−を表す；
一般式（Ａ２）

一般式（Ａ２）中、Ｒ³は、−ＳＯ₂−または−ＣＯ−を表す；Ｒ⁴およびＲ⁵はそれぞれ独立して−ＳＯ₂−、−ＣＯ−または−ＣＮを表す。
＜２＞カチオン部位を有する色素構造が、キサンテン色素、シアニン色素、スクアリリウム色素およびジピロメテン色素から選ばれる色素構造を有する、＜１＞に記載の着色組成物。
＜３＞カチオン部位を有する色素構造がキサンテン構造である、＜１＞に記載の着色組成物。
＜４＞フッ素原子、フッ素原子を含む脂肪族炭化水素基、フッ素原子を含む芳香族炭化水素基、ニトロ基を含む芳香族炭化水素基およびシアノ基を含む芳香族炭化水素基のうち少なくともいずれか１つが、一般式（Ａ１）または一般式（Ａ２）で表される構造中のＲ¹〜Ｒ⁵の少なくとも１つと直接共有結合している構造を含む、＜１＞〜＜３＞のいずれかに記載の着色組成物。
＜５＞アニオン部位が、下記一般式（Ａ３−１）または一般式（Ａ３−２）で表される構造を含む、＜１＞〜＜４＞のいずれかに記載の着色組成物；
一般式（Ａ３−１）

一般式（Ａ３−１）中、Ｌ¹は、−ＳＯ₂−または−ＣＯ−を表す。Ｇは、炭素原子または窒素原子を表す；ｎ１は、Ｇが炭素原子の場合２を表し、Ｇが窒素原子の場合１を表す；Ｒ⁶は、フッ素原子を含むアルキル基、フッ素原子を含むアリール基、ニトロ基を含むアリール基またはシアノ基を含むアリール基を表す；ｎ１が２の場合、２つのＲ⁶はそれぞれ同一でも異なっていても良い；＊は、他の部位との結合部位を表す。
一般式（Ａ３−２）

一般式（Ａ３−２）中、Ｌ¹は、−ＳＯ₂−または−ＣＯ−を表す；Ｇは、炭素原子または窒素原子を表す；ｎ１は、Ｇが炭素原子の場合２を表し、Ｇが窒素原子の場合１を表す；Ｒ⁷は、フッ素原子を含むアルキレン基、フッ素原子を含むアリーレン基、ニトロ基を含むアリーレン基またはシアノ基を含むアリーレン基を表す；＊は、他の部位との結合部位を表す；ｎ１が２の場合、２つのＲ⁷はそれぞれ同一でも異なっていても良い。
＜６＞色素化合物が、カチオン部位を有する色素構造を分子内に２以上有する色素多量体である、＜１＞〜＜５＞のいずれかに記載の着色組成物。
＜７＞色素化合物が、一般式（Ａ４−１）および／または一般式（Ａ４−３）で表される繰り返し単位を有するポリマーである、＜６＞に記載の着色組成物；
一般式（Ａ４−１）

一般式（Ａ４−１）中、Ｒ¹⁰〜Ｒ¹⁴のうち１つが下記一般式（Ａ４−１−２）で表される繰り返し単位であり、Ｒ¹⁰〜Ｒ¹⁴の少なくとも１つが下記一般式（Ａ４−１−１）で表される基であり、その他のＲ¹⁰〜Ｒ¹⁴はそれぞれ独立して、水素原子、脂肪族炭化水素基または芳香族炭化水素基を表す；
一般式（Ａ４−１−１）

一般式（Ａ４−１−１）中、Ｌ¹は、単結合または２価の連結基を表す；Ｌ²は、−ＳＯ₂−または−ＣＯ−を表す；Ｇは、炭素原子または窒素原子を表す；ｎ１は、Ｇが炭素原子の場合２を表し、Ｇが窒素原子の場合１を表す；Ｒ⁶は、フッ素原子を含むアルキル基またはフッ素原子を含むアリール基を表す；ｎ１が２の場合、２つのＲ⁶はそれぞれ同一でも異なっていても良い；
一般式（Ａ４−１−２）

一般式（Ａ４−１−２）中、Ｌ¹¹は、単結合または２価の連結基を表す；Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す；
一般式（Ａ４−３）

一般式（Ａ４−３）中、Ｒ¹⁰〜Ｒ¹⁴のうち４つは、それぞれ独立して、水素原子、脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ¹⁰〜Ｒ¹⁴の１つは下記一般式（Ａ４−３−１）で表される繰り返し単位である；
一般式（Ａ４−３−１）

一般式（Ａ４−３−１）中、Ｌ¹は、単結合または２価の連結基を表す；Ｌ²は、−ＳＯ₂−または−ＣＯ−を表す；Ｌ³は、２価の連結基を表す；Ｇは、炭素原子または窒素原子を表す；ｎ２は、Ｇが炭素原子の場合１を表し、Ｇが窒素原子の場合０を表す；Ｒ^7AおよびＲ^7Bはそれぞれ独立してフッ素原子を含むアルキレン基またはフッ素原子を含むアリーレン基を表す；Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す。
＜８＞色素化合物が、一般式（Ａ４−３）で表される繰り返し単位を有するポリマーである、＜７＞に記載の着色組成物。
＜９＞色素化合物が、重合性基を有する、＜１＞〜＜８＞のいずれかに記載の着色組成物。
＜１０＞色素化合物が、アルカリ可溶性基を有する、＜１＞〜＜８＞のいずれかに記載の着色組成物。
＜１１＞さらに、光重合開始剤を含有する、＜１＞〜＜１０＞のいずれかに記載の着色組成物。
＜１２＞さらに、フタロシアニン骨格を有する顔料を含有する、＜１＞〜＜１１＞のいずれかに記載の着色組成物。
＜１３＞カラーフィルタの着色層形成に用いる、＜１＞〜＜１２＞のいずれかに記載の着色組成物。
＜１４＞＜１＞〜＜１２＞のいずれかに記載の着色組成物を硬化して得られた硬化膜。
＜１５＞＜１４＞に記載の硬化膜を有するカラーフィルタ。
＜１６＞＜１＞〜＜１３＞のいずれかに記載の着色組成物を用いて支持体上に着色組成物層を形成する工程と、着色組成物層をパターン状に露光する工程と、露光された着色組成物層の未露光部を現像する工程と、を含むカラーフィルタの製造方法。
＜１７＞＜１＞〜＜１３＞のいずれかに記載の着色組成物を支持体上に適用して着色組成物層を形成し、硬化して着色層を形成する工程、
着色層上にフォトレジスト層を形成する工程、
露光および現像することによりフォトレジスト層をパターニングしてレジストパターンを得る工程、および
レジストパターンをエッチングマスクとして着色層をドライエッチングする工程を含む、カラーフィルタの製造方法。
＜１８＞＜１５＞に記載のカラーフィルタ、または、＜１６＞もしくは＜１７＞に記載のカラーフィルタの製造方法により得られたカラーフィルタを有する固体撮像素子。
＜１９＞＜１５＞に記載のカラーフィルタ、または、＜１６＞もしくは＜１７＞に記載のカラーフィルタの製造方法により作製されたカラーフィルタを有する画像表示装置。
＜２０＞一般式（Ａ４−１）および／または一般式（Ａ４−３）で表される繰り返し単位を有するポリマー；
一般式（Ａ４−１）

一般式（Ａ４−１）中、Ｒ¹⁰〜Ｒ¹⁴のうち１つが下記一般式（Ａ４−１−２）で表される繰り返し単位であり、Ｒ¹⁰〜Ｒ¹⁴の少なくとも１つが下記一般式（Ａ４−１−１）で表される基であり、その他のＲ¹⁰〜Ｒ¹⁴はそれぞれ独立して、水素原子、脂肪族炭化水素基または芳香族炭化水素基を表す；
一般式（Ａ４−１−１）

一般式（Ａ４−１−１）中、Ｌ¹は、単結合または２価の連結基を表す；Ｌ²は、−ＳＯ₂−または−ＣＯ−を表す；Ｇは、炭素原子または窒素原子を表す；ｎ１は、Ｇが炭素原子の場合２を表し、Ｇが窒素原子の場合１を表す。Ｒ⁶は、フッ素原子を含むアルキル基またはフッ素原子を含むアリール基を表す；ｎ１が２の場合、２つのＲ⁶はそれぞれ同一でも異なっていても良い；
一般式（Ａ４−１−２）

一般式（Ａ４−１−２）中、Ｌ¹¹は、単結合または２価の連結基を表す；Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す；
一般式（Ａ４−３）

一般式（Ａ４−３）中、Ｒ¹⁰〜Ｒ¹⁴のうち４つは、それぞれ独立して、水素原子、脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ¹⁰〜Ｒ¹⁴の１つは下記一般式（Ａ４−３−１）で表される繰り返し単位である；
一般式（Ａ４−３−１）

一般式（Ａ４−３−１）中、Ｌ¹は、単結合または２価の連結基を表す；Ｌ²は、−ＳＯ₂−または−ＣＯ−を表す；Ｌ³は、２価の連結基を表す；Ｇは、炭素原子または窒素原子を表す；ｎ２は、Ｇが炭素原子の場合１を表し、Ｇが窒素原子の場合０を表す；Ｒ^7AおよびＲ^7Bはそれぞれ独立してフッ素原子を含むアルキレン基またはフッ素原子を含むアリーレン基を表す；Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す。
＜２１＞一般式（Ａ５）で表されるキサンテン色素；
一般式（Ａ５）

一般式（Ａ５）中、Ｒ²⁰〜Ｒ²³はそれぞれ独立して、水素原子、脂肪族炭化水素基または芳香族炭化水素基を表す；Ａは下記一般式（ＡＮ−１）〜（ＡＮ−４）のいずれかで表されるアニオン部位を表す；

一般式（ＡＮ−１）中、＊はキサンテン構造との結合部位を表す；Ｒｆ₁は脂肪族炭化水素基、ハロゲン化された脂肪族炭化水素基、芳香族炭化水素基またはハロゲン化された芳香族炭化水素基を表す；
一般式（ＡＮ−２）中、＊はキサンテン構造との結合部位を表す；Ｒｆ₂はハロゲン化された脂肪族炭化水素基を表す；
一般式（ＡＮ−３）中、＊はキサンテン構造との結合部位を表す；Ｒｆ₃は脂肪族炭化水素基、ハロゲン化された脂肪族炭化水素基、芳香族炭化水素基またはハロゲン化された芳香族炭化水素基を表す；Ｂは置換基を表す；
一般式（ＡＮ−４）中、＊はキサンテン構造との結合部位を表す；Ｒｆ₄はハロゲン化された脂肪族炭化水素基を表す；Ｂは置換基を表す。 As a result of the present inventors' examination in detail, it turned out that heat resistance is inferior in the compounds described in the above-mentioned patent documents 2 to 5 because they are dye compounds having a low nucleophilic anion as a counter anion. That is, in a dye compound having a low nucleophilic anion as a counter anion, it was found that the counter anion undergoes salt exchange with another anion, which is the cause of poor heat resistance. Then, the present inventors have found that the above problem can be solved by adopting, as a dye compound, a compound having a predetermined low nucleophilic anion site and a cationic site in the same molecule.
Specifically, the above problem is solved by the following means <1>, preferably by <2> to <21>.
<1> A dye structure having a cation site, an anion site containing at least one of a structure represented by the following general formula (A1), a structure represented by the following general formula (A2), and a structure containing a boron atom And a dye compound in which an anionic site and a cationic site are linked via a covalent bond to be present in the same molecule,
A curable compound,
A colored composition comprising a solvent;
General formula (A1)

In general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-;
General formula (A2)

In formula (A2), R ³ is, -SO ₂ - or an -CO-; R ⁴ and R ⁵ each independently -SO ₂ -, - CO- or an -CN.
The coloring composition as described in <1> in which the pigment | dye structure which has a <2> cation site | part has a pigment | dye structure chosen from a xanthene pigment, a cyanine pigment, a squarylium pigment, and a dipyrromethene pigment.
The coloring composition as described in <1> whose pigment | dye structure which has a <3> cation site | part is a xanthene structure.
<4> at least one of a fluorine atom, an aliphatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a nitro group, and an aromatic hydrocarbon group containing a cyano group Any of <1> to <3>, including a structure in which one is directly covalently bonded to at least one of R ^{1 to} R ^{5 in} the structure represented by General Formula (A1) or General Formula (A2) The coloring composition as described in.
The coloring composition in any one of <1>-<4> in which a <5> anion site | part contains the structure represented by the following general formula (A3-1) or general formula (A3-2);
General formula (A3-1)

In general formula (A3-1), L ¹ represents -SO ₂ -or -CO-. G represents a carbon atom or a nitrogen atom; n1 represents 2 when G is a carbon atom and 1 when G is a nitrogen atom; R ⁶ represents an alkyl group containing a fluorine atom or an aryl containing a fluorine atom Group, an aryl group including a nitro group or an aryl group including a cyano group; when n1 is 2, two R ⁶ may be the same or different; * represents a binding site to another site .
General formula (A3-2)

In the general formula (A3-2), L ¹ represents -SO ₂ -or -CO-; G represents a carbon atom or a nitrogen atom; n 1 represents 2 when G is a carbon atom; In the case of a nitrogen atom, 1 represents; R ⁷ represents an alkylene group containing a fluorine atom, an arylene group containing a fluorine atom, an arylene group containing a nitro group or an arylene group containing a cyano group; And when n1 is 2, two R ^{7 s} may be the same or different.
The coloring composition in any one of <1>-<5> whose <6> pigment | dye compound is a pigment | dye multimer which has 2 or more of pigment | dye structures which have a cation part in a molecule | numerator.
The coloring composition as described in <6> whose <7> pigment compound is a polymer which has a repeating unit represented by general formula (A4-1) and / or general formula (A4-3);
General formula (A4-1)

In general formula (A4-1), one of R ^{10 to} R ¹⁴ is a repeating unit represented by the following general formula (A4-1-2), and at least one of R ^{10 to} R ¹⁴ is a general formula And R ^{10 to} R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group;
General formula (A4-1-1)

In formula (A4-1-1), L ¹ represents a single bond or a divalent linking group; L ² represents -SO ₂ -or -CO-; G represents a carbon atom or a nitrogen atom N1 represents 2 when G is a carbon atom and 1 when G is a nitrogen atom; R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom; when n1 is 2 , And two R ⁶ may be the same or different;
General formula (A4-1-2)

In the general formula (A4-1-2), L ¹¹ represents a single bond or a divalent linking group; R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group;
General formula (A4-3)

In general formula (A4-3), four of R ^{10 to} R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and one of R ^{10 to} R ¹⁴ Is a repeating unit represented by the following general formula (A4-3-1);
General formula (A4-3-1)

In the general formula (A4-3-1), L ¹ represents a single bond or a divalent linking group; L ² represents -SO ₂ -or -CO-; L ³ represents a divalent linking group G represents a carbon atom or a nitrogen atom; n2 represents 1 when G is a carbon atom; 0 when G is a nitrogen atom; R ^7A and R ^7B each independently represent a fluorine atom R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.
The coloring composition as described in <7> which is a polymer which has a repeating unit represented by <8> pigment | dye compound represented by General formula (A4-3).
The coloring composition in any one of <1>-<8> in which a <9> pigment | dye compound has a polymeric group.
The coloring composition in any one of <1>-<8> in which a <10> pigment compound has an alkali-soluble group.
<11> Furthermore, the coloring composition in any one of <1>-<10> which contains a photoinitiator.
<12> The colored composition according to any one of <1> to <11>, further comprising a pigment having a phthalocyanine skeleton.
The coloring composition in any one of <1>-<12> used for colored layer formation of a <13> color filter.
The cured film obtained by hardening | curing the coloring composition in any one of <14><1>-<12>.
The color filter which has a cured film as described in <15><14>.
The process of forming a coloring composition layer on a support body using the coloring composition in any one of <16><1>-<13>, the process of exposing the coloring composition layer to pattern shape, exposure And developing the unexposed area of the colored composition layer.
A step of applying a colored composition according to any one of <17><1> to <13> onto a support to form a colored composition layer, and curing to form a colored layer,
Forming a photoresist layer on the colored layer,
A method for producing a color filter, comprising the steps of: patterning a photoresist layer by exposure and development to obtain a resist pattern; and dry etching the colored layer using the resist pattern as an etching mask.
The solid-state image sensor which has a color filter obtained by the manufacturing method of the color filter as described in <18><15>, or the color filter as described in <16> or <17>.
The image display apparatus which has a color filter produced by the manufacturing method of the color filter as described in <19><15>, or the color filter as described in <16> or <17>.
<20> A polymer having a repeating unit represented by Formula (A4-1) and / or Formula (A4-3);
General formula (A4-1)

In general formula (A4-1), one of R ^{10 to} R ¹⁴ is a repeating unit represented by the following general formula (A4-1-2), and at least one of R ^{10 to} R ¹⁴ is a general formula And R ^{10 to} R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group;
General formula (A4-1-1)

In formula (A4-1-1), L ¹ represents a single bond or a divalent linking group; L ² represents -SO ₂ -or -CO-; G represents a carbon atom or a nitrogen atom N1 represents 2 when G is a carbon atom, and 1 when G is a nitrogen atom. R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom; when n 1 is 2, two R ^{6 s} may be the same or different;
General formula (A4-1-2)

In the general formula (A4-1-2), L ¹¹ represents a single bond or a divalent linking group; R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group;
General formula (A4-3)

In general formula (A4-3), four of R ^{10 to} R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and one of R ^{10 to} R ¹⁴ Is a repeating unit represented by the following general formula (A4-3-1);
General formula (A4-3-1)

In the general formula (A4-3-1), L ¹ represents a single bond or a divalent linking group; L ² represents -SO ₂ -or -CO-; L ³ represents a divalent linking group G represents a carbon atom or a nitrogen atom; n2 represents 1 when G is a carbon atom; 0 when G is a nitrogen atom; R ^7A and R ^7B each independently represent a fluorine atom R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.
The xanthene dye represented by <21> general formula (A5);
General formula (A5)

In the general formula (A5), R ²⁰ ~R ²³ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or aromatic hydrocarbon group; A is the following general formula (AN-1) ~ (AN -4 Represents an anion site represented by any of

In the general formula (AN-1), * represents a bonding site to a xanthene structure; R f ₁ represents an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogenated aromatic Represent a group hydrocarbon group;
In the general formula (AN-2), * represents a binding site to a xanthene structure; R f ₂ represents a halogenated aliphatic hydrocarbon group;
In the general formula (AN-3), * represents a binding site to a xanthene structure; R f ₃ represents an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogenated aromatic Group hydrocarbon group; B represents a substituent;
In general formula (AN-4), * represents a bonding site to a xanthene structure; Rf ₄ represents a halogenated aliphatic hydrocarbon group; B represents a substituent.

  ADVANTAGE OF THE INVENTION According to this invention, it became possible to provide the coloring composition excellent in heat resistance.

Is a diagram showing ¹ H-NMR spectrum of a xanthene dye compounds (P-1). It is a figure which shows the < ¹ > H-NMR spectrum of a xanthene pigment compound (P-25). It is a figure which shows the < ¹ > H-NMR spectrum of a xanthene pigment compound (P-29).

Hereinafter, the contents of the present invention will be described in detail. In the specification of the present application, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value. Moreover, the organic EL element in this invention means the thing of an organic electroluminescent element.
In the present specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the coloring composition.
In the notation of groups (atomic groups) in the present specification, the notations not describing substitution and non-substitution include those having no substituent and those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
Further, "radiation" in the present specification means, for example, a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams and the like. In the present invention, light means actinic rays or radiation. Unless otherwise specified, the "exposure" in the present specification is not only exposure by far ultraviolet rays represented by a mercury lamp or excimer laser, X-rays, EUV light, etc., but also drawing by particle beams such as electron beams or ion beams Also included in the exposure.
Further, in the present specification, “(meth) acrylate” represents both or either of acrylate and methacrylate, “(meth) acrylic” represents both or either of acrylic and methacryl, “( ) Acryloyl "represents both or either of acryloyl and methacryloyl.
In the present specification, "monomer" and "monomer" are synonymous. A monomer as used herein is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less. In the present specification, the polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group involved in the polymerization reaction.
In the present specification, Me in the chemical formula represents a methyl group, Et represents an ethyl group, Pr represents a propyl group, Bu represents a butyl group, and Ph represents a phenyl group.
In the present specification, the term "process" is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process .

The coloring composition of the present invention (hereinafter sometimes referred to simply as "the composition of the present invention") has (A) a structure represented by the following general formula (A1), a structure represented by the following general formula (A2) And a dye compound having a cation site and an anion site containing at least one of a structure containing a boron atom, and a cation site, wherein the anion site and the cation site are linked via a covalent bond to be present in the same molecule.
(B) a curable compound,
(C) containing a solvent.
By employing such a configuration, a colored composition having excellent heat resistance can be provided. Moreover, the solubility with respect to a solvent can also be improved. Furthermore, the color transferability when forming a colored pattern can be improved, and the spectral change before and after development can be suppressed.
When the anion site and the cation site are bound via a covalent bond, the anion site may be directly covalently linked to the dye structure having a cation site, or the anion site and the cation site are linked via a linking group All bonds in the linking group may be covalent bonds.

（一般式（Ａ１）中、Ｒ¹およびＲ²はそれぞれ独立して−ＳＯ₂−または−ＣＯ−を表す。）
一般式（Ａ２）

（一般式（Ａ２）中、Ｒ³は、ＳＯ₂−または−ＣＯ−を表す。Ｒ⁴およびＲ⁵はそれぞれ独立して−ＳＯ₂−、−ＣＯ−または−ＣＮを表す。） <(A) Dye Compound>
The (A) dye compound used in the present invention has an anion moiety containing at least one of a structure represented by the following general formula (A1), a structure represented by the following general formula (A2) and a structure containing a boron atom And a dye structure having a cationic site, and the anionic site and the cationic site are linked via a covalent bond to be present in the same molecule. The dye compound (A) preferably contains an anionic site containing a structure represented by the following general formula (A1) and / or (A2).
The dye compound in the present invention is a so-called betaine structure, but may contain an anion structure having a counter cation or a cation structure having a counter anion in the molecule without departing from the spirit of the present invention .
General formula (A1)

(In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—.)
General formula (A2)

(In general formula (A2), R ³ represents SO ₂ -or -CO-. R ⁴ and R ⁵ each independently represent -SO _2- , -CO- or -CN.)

In general formula (A1), R ¹ and R ² each independently represent —SO ₂ — or —CO—, and it is preferable that at least one of R ¹ and R ² represents —SO ₂ —, R ¹ and It is more preferred that both of R ² represent -SO _2- .
In general formula (A2), R ³ represents -SO ₂ -or -CO-, and R ⁴ and R ⁵ each independently represent -SO _2- , -CO- or -CN. Preferably representing the at least two R ³ to R ⁵ is -SO ₂ - - at least one of R ³ to R ⁵ is -SO ₂ more preferably represents. In particular, all of R ^{3 to} R ⁵ represent -SO _2- , or R ³ and R ⁵ represent -SO _2- and R ⁴ represents -CO-, or R ⁴ and R ⁵ represent- It is preferred that it represents SO _2- , and R ³ represents -CO-.

The (A) dye compound used in the present invention includes a fluorine atom, an aliphatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a nitro group and an aroma containing a cyano group. It is preferable that at least one of the group hydrocarbon groups be directly covalently bonded to at least one of R ^{1 to} R ^{5 in} the structure represented by Formula (A1) or Formula (A2).
Although this mechanism is presumed, by adopting the configuration as described above, since the anion site can be shielded by a more steric or hydrophobic effect, electrostatic interaction between molecules can be further suppressed. As a result, it is estimated that the solvent solubility can be further improved.
The aliphatic hydrocarbon group containing a fluorine atom is preferably an alkyl group containing a fluorine atom or an alkylene group containing a fluorine atom. 1-6 are preferable, as for carbon number of the aliphatic hydrocarbon group containing a fluorine atom, 1-4 are more preferable, and 1-3 are more preferable. Moreover, although the aliphatic hydrocarbon group containing a fluorine atom may be linear, branched or cyclic, linear is more preferable.
The aromatic hydrocarbon group containing a fluorine atom is preferably an aryl group containing a fluorine atom or an arylene group containing a fluorine atom. 6-18 are preferable, as for carbon number of the aromatic hydrocarbon group containing a fluorine atom, 6-12 are more preferable, and 6 is more preferable.
It is preferable that the fluorine atom content rate is 50% or more, and, as for the aromatic hydrocarbon group containing a fluorine atom, it is more preferable that it is a perfluoro group. The fluorine atom content is represented by the following.
Fluorine atom content rate = [(fluorine atom weight) × (number of fluorine atoms) / (molecular weight of aliphatic hydrocarbon group containing fluorine atom or aromatic hydrocarbon group containing fluorine atom)] × 100
The aromatic hydrocarbon group containing a nitro group is preferably an aryl group containing a nitro group or an arylene group containing a nitro group. 6-18 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-12 are more preferable, and 6 is more preferable.
The aromatic hydrocarbon group containing a cyano group is preferably an aryl group containing a cyano group or an arylene group containing a nitro group. 6-18 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-12 are more preferable, and 6 is more preferable.

（一般式（Ａ３−１）中、Ｌ¹は、−ＳＯ₂−または−ＣＯ−を表す。Ｇは、炭素原子または窒素原子を表す。ｎ１は、Ｇが炭素原子の場合２を表し、Ｇが窒素原子の場合１を表す。Ｒ⁶は、フッ素原子を含むアルキル基、フッ素原子を含むアリール基、ニトロ基を含むアリール基またはシアノ基を含むアリール基を表す。ｎ１が２の場合、２つのＲ⁶はそれぞれ同一でも異なっていても良い。＊は、他の部位との結合部位を表す。）
一般式（Ａ３−２）

（一般式（Ａ３−２）中、Ｌ¹は、−ＳＯ₂−または−ＣＯ−を表す。Ｇは、炭素原子または窒素原子を表す。ｎ１は、Ｇが炭素原子の場合２を表し、Ｇが窒素原子の場合１を表す。Ｒ⁷は、フッ素原子を含むアルキレン基、フッ素原子を含むアリーレン基、ニトロ基を含むアリーレン基またはシアノ基を含むアリーレン基を表す。＊は、他の部位との結合部位を表す。ｎ１が２の場合、２つのＲ⁷はそれぞれ同一でも異なっていても良い。） The (A) dye compound used in the present invention preferably includes the structure in which the above-mentioned anion site is represented by the following general formula (A3-1) or general formula (A3-2).
General formula (A3-1)

(In the general formula (A3-1), L ¹ represents -SO ₂ -or -CO-. G represents a carbon atom or a nitrogen atom. N 1 represents 2 when G is a carbon atom, G represents When is a nitrogen atom, it represents 1. R ⁶ represents an alkyl group containing a fluorine atom, an aryl group containing a fluorine atom, an aryl group containing a nitro group or an aryl group containing a cyano group. And each R ⁶ may be the same or different. * Represents a binding site to another site.)
General formula (A3-2)

(In the general formula (A3-2), L ¹ represents -SO ₂ -or -CO-. G represents a carbon atom or a nitrogen atom. N 1 represents 2 when G is a carbon atom, G represents When is a nitrogen atom, it represents 1. R ⁷ represents an alkylene group containing a fluorine atom, an arylene group containing a fluorine atom, an arylene group containing a nitro group, or an arylene group containing a cyano group. And when n1 is 2, two R ^{7 s} may be the same or different.)

In formula (A3-1), R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and has the same meaning as the alkyl group containing a fluorine atom or the aryl group containing a fluorine atom described above; Methyl is preferred.
In general formula (A3-1), * represents a binding site to another site. Here, another site | part represents site | parts other than the structure represented with general formula (A3-1) in (A) pigment compound. The bond between * in the general formula (A3-1) and the other site is a covalent bond.

In general formula (A3-2), R ⁷ represents an alkylene group containing a fluorine atom, an arylene group containing a fluorine atom, an arylene group containing a nitro group or an arylene group containing a cyano group, and an alkylene containing the above-mentioned fluorine atom Group, an arylene group containing a fluorine atom, an arylene group containing a nitro group or an arylene group containing a cyano group, and an alkylene group containing a fluorine atom or an arylene group containing a fluorine atom is preferable, and a perfluorocarbon having 1 to 3 carbon atoms An alkylene group or a C6-C12 perfluoroarylene group is more preferable.
In General Formula (A3-2), * represents a binding site to another site, and has the same meaning as * in General Formula (A3-1).

<Pigment structure>
The dye structure having a cation site in the dye compound (A), that is, the partial structure derived from the dye (hereinafter, also referred to as a "dye structure") is not particularly limited as long as it has a cation in the molecule. Various things, including known dye structures, can be applied. Specifically, dipyrromethene dyes, carbonium dyes (diphenylmethane dyes, xanthene dyes, acridine dyes, etc.), polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), subphthalocyanine Dyes and dye structures derived from dyes selected from those metal complex dyes can be mentioned.

  Among these dye structures, from the viewpoint of color characteristics, a dye structure derived from a dye selected from dipyrromethene dyes, caribonium dyes, and polymethine dyes is preferable, and a dye selected from xanthene dyes, cyanine dyes, squarylium dyes and dipyrromethene dyes The pigment structure derived from is preferred, and the pigment structure derived from xanthene pigment is particularly preferred.

<< xanthene dye >>
The dye structure derived from the xanthene dye is preferably represented by, for example, the following general formula (J).

（一般式（Ｊ）中、Ｒ⁸¹、Ｒ⁸²、Ｒ⁸³およびＲ⁸⁴は、各々独立に、水素原子または１価の置換基を表し、Ｒ⁸⁵は、各々独立に１価の置換基を表し、ｍは、０〜５の整数を表す。）

(In the general formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ⁸⁵ each independently represents a monovalent substituent. , M represents an integer of 0 to 5))

R ⁸¹ and R ⁸² in the general formula (J), R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are each independently bonded to each other to be 5-membered, 6-membered or 7-membered saturated It may form a ring or a 5-, 6- or 7-membered unsaturated ring. When the 5-, 6- or 7-membered ring to be formed is a further substitutable group, it may be substituted by the substituents described for R ^{81 to} R ⁸⁵ , and two or more substituents When substituted, the substituents may be the same or different.
R ⁸¹ and R ⁸² in the above general formula (J), R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more are each independently bonded to each other and have no substituent, 5-membered, When forming a 6- and 7-membered saturated ring or a 5-, 6- and 7-membered unsaturated ring, the 5-, 6- and 7-membered saturated ring or 5-membered, 6-membered and 7-membered -Membered unsaturated ring includes, for example, pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine A ring, a pyrazine ring and a pyridazine ring can be mentioned, and preferably a benzene ring and a pyridine ring can be mentioned.
Examples of the substituent that can be taken by R ^{81 to} R ⁸⁴ and R ⁸⁵ in General Formula (J) include Substituent Group A described later.
In the dye structure, the cation is delocalized, so it is present on a nitrogen atom or a carbon atom of a xanthene ring, for example as shown below.

  The compound having a xanthene skeleton represented by the general formula (J) can be synthesized by a method described in the literature. Specifically, the method described in Tetrahedron Letters, 2003, vol. 44, No. 23, 4355-4360, Tetrahedron, 2005, vol. 61, No. 12, 3097-3106, etc. Can be applied.

  Although the example of the pigment | dye structure of a xanthene compound is shown below, this invention is not limited to this.

  The dye compound (A) used in the coloring composition of the present invention may be a dye monomer having one dye structure having the above-mentioned cation site in the molecule (hereinafter also referred to as a monomer type xanthene compound) It may be a dye multimer having two or more dye structures each having the above-mentioned cation site in the molecule (hereinafter, also referred to as a polymer xanthene compound). In particular, the (A) dye compound is preferably a dye multimer.

<Monomer type xanthene compound>
The monomer type xanthene compound used in the present invention preferably contains a polymerizable group.
Such a configuration tends to improve the heat resistance. Only one type of polymerizable group may be contained, or two or more types may be contained.
As the polymerizable group, a radical, an acid, a known polymerizable group crosslinkable by heat can be used. For example, a group containing an ethylenically unsaturated bond, a cyclic ether group (epoxy group, oxetane group), a methylol group And the like, and in particular, a group containing an ethylenically unsaturated bond is preferable, and a (meth) acryloyl group is more preferable.

  1-4 are preferable and, as for the number of the polymeric groups in 1 molecule of a monomer type xanthene compound, 1-2 are more preferable.

The monomeric xanthene compound may have an acid group. As an acid group, a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group are illustrated.
In addition, the monomer-type xanthene compound may have alkali solubility. Examples of the alkali soluble group include phenolic hydroxyl group and carboxylic acid. As a method for introducing an alkali-soluble group into the monomer-type xanthene compound, a method in which an alkali-soluble group is previously introduced into the monomer-type xanthene compound can be mentioned.
1-4 are preferable and, as for the number of the acid groups in 1 molecule of a monomer type xanthene compound, 1-2 are more preferable.
Other functional groups that may be possessed by the monomer type xanthene compound include lactones, acid anhydrides, amides, -COCH ₂ CO-, development accelerating groups such as cyano groups, long chain and cyclic alkyl groups, aralkyl groups, The hydrophilicity adjusting group such as an aryl group, a polyalkylene oxide group, a hydroxyl group, a maleimide group, an amino group and the like can be mentioned and can be introduced appropriately.

  The acid value of the monomer type xanthene compound used in the present invention is preferably 5 to 200 mg KOH / g, and more preferably 10 to 180 mg KOH / g.

一般式（Ａ５）中、Ｒ²⁰〜Ｒ²³はそれぞれ独立して、水素原子、脂肪族炭化水素基または芳香族炭化水素基を表す；Ａは下記一般式（ＡＮ−１）〜（ＡＮ−４）のいずれかで表されるアニオン部位を表す；

一般式（ＡＮ−１）中、＊はキサンテン構造との結合部位を表す；Ｒｆ₁は脂肪族炭化水素基、ハロゲン化された脂肪族炭化水素基、芳香族炭化水素基またはハロゲン化された芳香族炭化水素基を表す；
一般式（ＡＮ−２）中、＊はキサンテン構造との結合部位を表す；Ｒｆ₂はハロゲン化された脂肪族炭化水素基を表す；
一般式（ＡＮ−３）中、＊はキサンテン構造との結合部位を表す；Ｒｆ₃は脂肪族炭化水素基、ハロゲン化された脂肪族炭化水素基、芳香族炭化水素基またはハロゲン化された芳香族炭化水素基を表す；Ｂは置換基を表す；
一般式（ＡＮ−４）中、＊はキサンテン構造との結合部位を表す；Ｒｆ₄はハロゲン化された脂肪族炭化水素基を表す；Ｂは置換基を表す。 The monomer type xanthene compound (xanthene dye) is preferably a compound represented by General Formula (A5).
General formula (A5)

In the general formula (A5), R ²⁰ ~R ²³ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or aromatic hydrocarbon group; A is the following general formula (AN-1) ~ (AN -4 Represents an anion site represented by any of

In the general formula (AN-1), * represents a bonding site to a xanthene structure; R f ₁ represents an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogenated aromatic Represent a group hydrocarbon group;
In the general formula (AN-2), * represents a binding site to a xanthene structure; R f ₂ represents a halogenated aliphatic hydrocarbon group;
In the general formula (AN-3), * represents a binding site to a xanthene structure; R f ₃ represents an aliphatic hydrocarbon group, a halogenated aliphatic hydrocarbon group, an aromatic hydrocarbon group or a halogenated aromatic Group hydrocarbon group; B represents a substituent;
In general formula (AN-4), * represents a bonding site to a xanthene structure; Rf ₄ represents a halogenated aliphatic hydrocarbon group; B represents a substituent.

In formula (A5), R ²⁰ preferably represents a hydrogen atom or an aliphatic hydrocarbon group, more preferably a hydrogen atom. 1-6 are preferable and, as for carbon number of an aliphatic hydrocarbon group, 1-3 are more preferable. The aliphatic hydrocarbon group is preferably an alkyl group. The aliphatic hydrocarbon group may have a substituent. As a substituent, the substituent group A mentioned later is mentioned.
In formula (A5), R ²¹ preferably represents an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and more preferably an aromatic hydrocarbon group. 1-6 are preferable and, as for carbon number of an aliphatic hydrocarbon group, 1-3 are more preferable. The aliphatic hydrocarbon group is preferably an alkyl group. The aromatic hydrocarbon group may be monocyclic or polycyclic, but is preferably monocyclic. The carbon number of the aromatic hydrocarbon group is preferably 6 to 15 carbon atoms, and more preferably 6 to 12 carbon atoms. The aromatic hydrocarbon group is preferably an aryl group. The carbon number of the aromatic hydrocarbon group is preferably 6 to 12 carbon atoms, and more preferably 6 to 9 carbon atoms. The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent. As a substituent, the substituent group A mentioned later is mentioned.
In formula (A5), R ²² has the same meaning as R ²⁰ in formula (A5), and the preferred range is also the same.
In formula (A5), R ²³ has the same meaning as R ²¹ in formula (A5), and the preferred range is also the same.
When Rf ₁ represents an aliphatic hydrocarbon group in General Formula (AN-1), the carbon number of the aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 or 2. . The aliphatic hydrocarbon group is preferably a methyl group.
When Rf ₁ represents a halogenated aliphatic hydrocarbon group in general formula (AN-1), the carbon number of the aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and 1 or 2 is more preferred. The halogenated aliphatic hydrocarbon group is preferably a fluorine atom-substituted alkyl group, more preferably a perfluoroalkyl group.
In the general formula (AN-1), when R f ₁ represents an aromatic hydrocarbon group, it may be monocyclic or polycyclic, but is preferably monocyclic. The carbon number of the aromatic hydrocarbon group is preferably 6 to 12 carbon atoms, and more preferably 6 to 9 carbon atoms. The aromatic hydrocarbon group is preferably a phenyl group.
In the general formula (AN-1), when R f ₁ represents a halogenated aromatic hydrocarbon group, it may be monocyclic or polycyclic, but is preferably monocyclic. The carbon number of the aromatic hydrocarbon group is preferably 6 to 12 carbon atoms, and more preferably 6 to 9 carbon atoms. The halogenated aromatic hydrocarbon group is preferably an aryl group substituted with a fluorine atom, and more preferably a perfluoroaryl group.

In the general formula (AN-2), Rf ₂ represents a halogenated aliphatic hydrocarbon group, which is the same as Rf ₁ in the general formula (AN-1) represents a halogenated aliphatic hydrocarbon group The preferable range is also the same.
When Rf ₃ represents an aliphatic hydrocarbon group in general formula (AN-3), the carbon number of the aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 or 2. .
When Rf ₃ represents a halogenated aliphatic hydrocarbon group in General Formula (AN-3), the carbon number of the aliphatic hydrocarbon group is preferably 1 to 6, and more preferably 1 to 3. The halogenated aliphatic hydrocarbon group is preferably a fluorine atom-substituted alkylene group, more preferably a perfluoroalkylene group.
In the general formula (AN-3), when Rf ₃ represents an aromatic hydrocarbon group, it may be monocyclic or polycyclic, but is preferably monocyclic. The carbon number of the aromatic hydrocarbon group is preferably 6 to 12 carbon atoms, and more preferably 6 to 9 carbon atoms.
In the general formula (AN-3), when Rf ₃ represents a halogenated aromatic hydrocarbon group, it may be monocyclic or polycyclic, but is preferably monocyclic. The carbon number of the aromatic hydrocarbon group is preferably 6 to 12 carbon atoms, and more preferably 6 to 9 carbon atoms. The halogenated aromatic hydrocarbon group is preferably an arylene group substituted with a fluorine atom, and more preferably a perfluoroarylene group.
In general formula (AN-3), B represents a substituent, and preferably contains a crosslinkable group. The crosslinkable group is a polymerizable group (eg, (meth) acryloyloxy group, vinyl group etc.), leaving group (eg, fluorine group, chlorine group, bromine group, iodine group, tosyl group etc.), hydroxyl group, thiol At least one of a group, an amino group and a carboxyl group is preferred. In particular, B in the general formula (AN-3) is preferably a group consisting of a combination of a crosslinkable group and a linking group. Specifically, a crosslinkable group, an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, -O-, -S-, -CO-, -SO-, -SO ₂ -,- A group consisting of a combination of at least one type of linking group selected from NR- is preferred. R in -NR- is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
In General Formula (AN-4), Rf ₄ represents a halogenated aliphatic hydrocarbon group, and is the same as Rf _{3 in} General Formula (AN-3) represents a halogenated aliphatic hydrocarbon group. The preferable range is also the same.
In general formula (AN-4), B is synonymous with B in general formula (AN-3), and its preferable range is also the same.

（一般式（Ａ）中、Ｘ¹は重合によって形成される連結基を表し、Ｌ¹は単結合または２価の連結基を表す。ＤｙｅＩは色素構造を表す。）
以下、一般式（Ａ）について詳細に説明する。 <Polymer-type xanthene compound>
It is preferable that the polymer type xanthene compound used for this invention contains the structural unit represented by the following general formula (A). The structural unit represented by formula (A) may be of one type or of two or more types. Moreover, these combinations may be sufficient. Furthermore, as described later, other constituent units may be included.
General formula (A)

(In the general formula (A), X ¹ represents a linking group formed by polymerization, L ¹ represents a single bond or a divalent linking group. Dye I represents a dye structure.)
Hereinafter, the general formula (A) will be described in detail.

In formula (A), X ¹ represents a linking group formed by polymerization. That is, it refers to a portion that forms a repeating unit corresponding to the main chain formed by the polymerization reaction. In addition, the site | part represented by two * becomes a repeating unit. The X ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer, but particularly the linking groups represented by the following (XX-1) to (X-24) are preferable, (XX -1) and (XX-2), (meth) acrylic linking chains, (XX-10) to (XX-17), styrenic linking chains, and (XX-24) Is more preferably selected from vinyl-based linking chains, (meth) acrylic linking chains represented by (XX-1) and (XX-2), and styrenic linking chains represented by (XX-11) Is more preferred.
In (XX-1) to (X-24), it represents linking to L ¹ at a site indicated by *. Me represents a methyl group. Moreover, R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

In Formula (A), L ¹ represents a single bond or a divalent linking group. When L ¹ represents a divalent linking group, examples of the divalent linking group include substituted or unsubstituted alkylene groups having 1 to 30 carbon atoms (eg, methylene, ethylene, trimethylene, propylene, butylene) And the like), a substituted or unsubstituted arylene group having 6 to 30 carbon atoms (eg, a phenylene group, a naphthalene group, etc.), a substituted or unsubstituted heterocyclic linking group, -CH = CH-, -O-, -S- , -C (= O)-, -CO _2- , -NR-, -CONR-, -O ₂ C-, -SO-, -SO ₂ -and a linking group formed by linking two or more of these Represents Here, each R independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
In the general formula (A), DyeI represents a dye structure derived from the dye compound described above.

The dye multimer having a constitutional unit represented by the general formula (A) is prepared by addition polymerization of a monomer having a dye residue (1), (2) an isocyanate group, an acid anhydride group or an epoxy group It can be synthesized by a method of reacting a polymer having a highly reactive functional group with a dye having a functional group (hydroxyl group, primary or secondary amino group, carboxyl group, etc.) capable of reacting with the highly reactive group.
Although known addition polymerization (radical polymerization, anionic polymerization, cationic polymerization) can be applied to the addition polymerization, among them, synthesis by radical polymerization is particularly preferable because the reaction conditions can be relaxed and the dye structure is not decomposed. Known reaction conditions can be applied to radical polymerization.
Among them, the dye multimer having the structural unit represented by the general formula (A) in the present invention is obtained by radical polymerization using a dye monomer having an ethylenically unsaturated bond from the viewpoint of heat resistance. It is preferably a radical polymer.

（一般式（Ａ４−１）中、Ｒ¹⁰〜Ｒ¹⁴のうち１つが下記一般式（Ａ４−１−２）で表される繰り返し単位であり、Ｒ¹⁰〜Ｒ¹⁴の少なくとも１つが下記一般式（Ａ４−１−１）で表される基であり、その他のＲ¹⁰〜Ｒ¹⁴はそれぞれ独立して、水素原子、脂肪族炭化水素基または芳香族炭化水素基を表す。）
一般式（Ａ４−１−１）

（一般式（Ａ４−１−１）中、Ｌ¹は、単結合または２価の連結基を表す。Ｌ²は、−ＳＯ₂−または−ＣＯ−を表す。Ｇは、炭素原子または窒素原子を表す。ｎ１は、Ｇが炭素原子の場合２を表し、Ｇが窒素原子の場合１を表す。Ｒ⁶は、フッ素原子を含むアルキル基またはフッ素原子を含むアリール基を表す。ｎ１が２の場合、２つのＲ⁶はそれぞれ同一でも異なっていても良い。）
一般式（Ａ４−１−２）

（一般式（Ａ４−１−２）中、Ｌ¹¹は、単結合または２価の連結基を表す。Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す。） The polymer xanthene compound is preferably a polymer having a repeating unit represented by General Formula (A4-1) and / or General Formula (A4-3), and a repetition represented by General Formula (A4-3) It is more preferable that it is a polymer having a unit.
General formula (A4-1)

(In general formula (A4-1), one of R ^{10 to} R ¹⁴ is a repeating unit represented by the following general formula (A4-1-2), and at least one of R ^{10 to} R ¹⁴ is a general formula And R ^{10 to} R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group.
General formula (A4-1-1)

(In the general formula (A4-1-1), L ¹ represents a single bond or a divalent linking group. L ² represents -SO ₂ -or -CO-. G represents a carbon atom or a nitrogen atom. N 1 represents 2 when G is a carbon atom, and 1 when G is a nitrogen atom R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom n 1 is 2. In the case, two R ⁶ may be the same or different.)
General formula (A4-1-2)

(In the general formula (A4-1-2), L ¹¹ represents a single bond or a divalent linking group. R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.)

（一般式（Ａ４−３）中、Ｒ¹⁰〜Ｒ¹⁴のうち４つは、それぞれ独立して、水素原子、脂肪族炭化水素基または芳香族炭化水素基を表し、Ｒ¹⁰〜Ｒ¹⁴の１つは下記一般式（Ａ４−３−１）で表される繰り返し単位である。）
一般式（Ａ４−３−１）

（一般式（Ａ４−３−１）中、Ｌ¹は、単結合または２価の連結基を表す。Ｌ²は、−ＳＯ₂−または−ＣＯ−を表す。Ｌ³は、２価の連結基を表す。Ｇは、炭素原子または窒素原子を表す。ｎ２は、Ｇが炭素原子の場合１を表し、Ｇが窒素原子の場合０を表す。Ｒ^7AおよびＲ^7Bはそれぞれ独立してフッ素原子を含むアルキレン基またはフッ素原子を含むアリーレン基を表す。Ｒ^Xは、水素原子、メチル基、ヒドロキシメチル基またはアルコキシメチル基を表す。） General formula (A4-3)

(In the general formula (A4-3), four out of R ^{10 to} R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and one of R ^{10 to} R ¹⁴ One is a repeating unit represented by the following general formula (A4-3-1).
General formula (A4-3-1)

(In the general formula (A4-3-1), L ¹ represents a single bond or a divalent linking group. L ² represents -SO ₂ -or -CO-. L ³ represents a divalent linkage. G represents a carbon atom or a nitrogen atom, n2 represents 1 when G is a carbon atom, and 0 when G is a nitrogen atom, R ^7A and R ^7B each independently represent a fluorine atom And an arylene group containing a fluorine atom, and R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group.

When R ^{10 to} R ¹⁴ in the general formula (A4-1) represent an aliphatic hydrocarbon group, an alkyl group is preferable. The carbon number of the aliphatic hydrocarbon group is preferably 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms, and still more preferably a methyl group or an ethyl group.
When R ^{10 to} R ¹⁴ in the general formula (A4-1) represent an aromatic hydrocarbon group, an aryl group is preferable. The aromatic hydrocarbon group may be monocyclic or polycyclic, but is preferably monocyclic. The carbon number of the aromatic hydrocarbon group is preferably 6 to 12 carbon atoms, and more preferably 6 to 9 carbon atoms.
The aliphatic hydrocarbon group and the aromatic hydrocarbon group may have a substituent. As a substituent, the substituent group A mentioned later is mentioned.

In general formula (A4-1-1), L ¹ represents a single bond or a divalent linking group, and is preferably a single bond. As a bivalent coupling group, the group etc. which consist of a C1-C6 alkylene group, a C6-C12 arylene group, -O-, -S-, or these combination etc. are mentioned.
In general formula (A4-1-1), R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and R ⁶ in the general formula (A3-1) described above is an alkyl containing a fluorine atom It is synonymous with the case where it represents the group or the aryl group containing a fluorine atom, and its preferable range is also the same.

In general formula (A4-1-2), L ¹¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 18 carbon atoms, -O -, - CO -, - S -, - SO 2 -, - NR A R B - or The group etc. which consist of these combinations are mentioned. The C1-C6 alkylene group may be linear, branched or cyclic. The C 6-18 arylene group may be monocyclic or polycyclic. In -NR ^A R ^B- , R ^A and R ^B each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^A and R ^B are bonded to each other to form a ring It is also good.
In general formula (A4-1-2), R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group, preferably a hydrogen atom or a methyl group. When R ^X represents an alkoxymethyl group, the number of carbon atoms of the alkoxymethyl group is preferably 1 to 3.

In General Formula (A4-3), four of R ^{10 to} R ¹⁴ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and R ^{10 to} R ¹⁴ Is a repeating unit represented by formula (A4-3-1). In particular, R ¹⁴ is preferably a group represented by general formula (A4-3-1). The aliphatic hydrocarbon group and aromatic hydrocarbon group, the general formula (A4-1) in the same meaning as R ¹⁰ to R ^14, and preferred ranges are also the same.
In general formula (A4-3-1), L ¹ represents a single bond or a divalent linking group, and is preferably a single bond. Examples of the divalent linking group has the same meaning as L ¹ in the general formula (A4-1-1).
In general formula (A4-3-1), L ³ represents a divalent linking group. The divalent linking group is the same as the case where L ¹¹ in General Formula (A4-1-2) represents a divalent linking group, and is an arylene group having 6 to 18 carbon atoms (preferably a phenylene group),- ^A group consisting of O-, -CO-, -S-, -NR ^A R ^B -or a combination thereof is preferable, and a group consisting of a combination of a phenylene group, -O- and -CO- is more preferable. -NR ^A R ^B -is synonymous with -NR ^A R ^B- described for L ¹¹ in General Formula (A4-1-2).
In general formula (A4-3-1), R ^7A and R ^7B each independently represent a fluorine atom-containing alkylene group or a fluorine atom-containing arylene group, and R ⁷ in the general formula (A3-2) described above It is synonymous with the case where represents the alkylene group containing a fluorine atom, or arylene containing a fluorine atom, and its preferable range is also the same.
In the general formula (A4-3-1), R ^X represents a hydrogen atom, a methyl group, a hydroxymethyl group or an alkoxymethyl group, and has the same meaning as R ^X in the general formula (A4-1-2), and preferred The range is also the same.

一般式（Ａ４−１ａ）中、Ｒ¹⁰〜Ｒ¹⁴のうち１つが上記一般式（Ａ４−１−２）で表される繰り返し単位であり、Ｒ¹⁰〜Ｒ¹⁴の少なくとも１つが上記一般式（Ａ４−１−１）で表される基であり、その他のＲ¹⁰〜Ｒ¹³はそれぞれ独立して、水素原子、脂肪族炭化水素基または芳香族炭化水素基を表す。その他のＲ¹⁴、およびＲ¹⁵〜Ｒ²⁰は、それぞれ独立して、水素原子、ハロゲン原子、脂肪族炭化水素基または芳香族炭化水素基を表す。ｎは０〜５の整数を表す。Ｒ¹⁰とＲ¹⁵、Ｒ¹¹とＲ¹⁶、Ｒ¹²とＲ¹⁸、Ｒ¹³とＲ¹⁹、複数のＲ¹⁴がそれぞれ結合して、環を形成していても良い。
一般式（Ａ４−１ａ）中、Ｒ¹⁰〜Ｒ²⁰が脂肪族炭化水素基または芳香族炭化水素基を表す場合、上記一般式（Ａ４−１）中のＲ¹⁰〜Ｒ¹⁴が脂肪族炭化水素基または芳香族炭化水素基を表す場合と同義であり、好ましい範囲も同様である。 The polymer xanthene compound is a polymer having at least one of the repeating units represented by the above general formula (A4-1), the above general formula (A4-3) and the following general formula (A4-1a) It is also good.
General formula (A4-1a)

In general formula (A4-1a), one of R ^{10 to} R ¹⁴ is a repeating unit represented by the above general formula (A4-1-2), and at least one of R ^{10 to} R ¹⁴ is a group represented by the general formula (A4-1a) And R ^{10 to} R ¹³ each independently represent a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Other R < ¹⁴ > and R < ¹⁵ > -R < ²⁰ > respectively independently represent a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. n represents an integer of 0 to 5; R ¹⁰ and R ¹⁵ , R ¹¹ and R ¹⁶ , R ¹² and R ¹⁸ , R ¹³ and R ¹⁹ , and a plurality of R ¹⁴ may be combined to form a ring.
When R ^{10 to} R ²⁰ in the general formula (A4-1a) represent an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R ^{10 to} R ¹⁴ in the general formula (A4-1) are aliphatic hydrocarbons It is synonymous with the case where a group or an aromatic hydrocarbon group is represented, and its preferable range is also the same.

The polymer xanthene compound may have another repeating unit other than the repeating unit represented by the above general formula (A4-3). As another repeating unit, a repeating unit containing at least one of a polymerizable group, an acid group and an alkali-soluble group is exemplified.
It is preferable that the polymer type xanthene compound used for this invention contains the repeating unit which has a polymeric group. When the polymer type xanthene compound used in the present invention contains a repeating unit having a polymerizable group, the amount thereof is, for example, preferably 1 to 60 moles, more preferably 10 to 50 moles, per 100 moles of all the repeating units. .
The acid value of the repeating unit having an acid group is preferably 5 mg KOH / g to 200 mg KOH / g, more preferably 10 mg KOH / g to 180 mg KOH / g, and preferably 20 mg KOH / g to 170 mg KOH / g. More preferable. The acid value can be calculated, for example, from the average content of acid groups in the polymeric xanthene compound.
When the polymer type xanthene compound contains a repeating unit having a polymerizable group, the amount thereof is, for example, preferably 1 to 90 mol, and more preferably 5 to 80 mol with respect to 100 mol of all the repeating units.
When the polymer xanthene compound contains a repeating unit represented by general formula (A4-3) and a repeating unit having an acid group, the ratio of the repeating unit containing a repeating unit having an acid group is represented by the general formula (A4) For example, 5-90 mol is preferable with respect to 100 mol of repeating units represented by -3), and 10-80 mol is more preferable.

  Hereinafter, although the specific example of the repeating unit which the polymer type xanthene compound may have is shown, this invention is not limited to this.

The weight average molecular weight of the polymer xanthene compound is preferably 2,000 to 40,000, more preferably 3,000 to 35,000, and particularly preferably 4,000 to 30,000. .
In the present specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values by GPC measurement. In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh Corp.), and TSKgel Super AWM-H (manufactured by Tosoh Corp.), 6 as a column. 0 mm ID x 15.0 cm can be determined by using a 10 mmol / L lithium bromide NMP (N-methyl pyrrolidinone) solution as eluent.
Moreover, it is preferable that ratio [(Mw) / (Mn)] of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is 1.0-3.0, and is 1.6-2.5. It is more preferable to be present, and it is particularly preferable to be 1.6 to 2.0.
The glass transition temperature (Tg) of the polymer-type xanthene compound used in the present invention is preferably 50 ° C. or more, and more preferably 100 ° C. or more. The 5% weight loss temperature by thermogravimetric analysis (TGA measurement) is preferably 120 ° C. or more, more preferably 150 ° C. or more, and still more preferably 200 ° C. or more.

The light absorption coefficient per unit weight of the (A) dye compound used in the present invention (hereinafter referred to as ε ′; ε ′ = ε / average molecular weight, unit: L / g · cm) is preferably 30 or more, It is more preferably 60 or more, and still more preferably 100 or more. Within this range, in the case of producing a color filter by applying the coloring composition of the present invention, a color filter having good color reproducibility can be produced.
The maximum absorption wavelength of the (A) dye compound used in the present invention is preferably 400 to 650 nm, and more preferably 450 to 600 nm.

In the coloring composition of the present invention, the dye compound (A) used in the present invention may be used alone or in combination of two or more. When using 2 or more types, it is preferable that the total amount corresponds to content mentioned later.
5-60 mass% of the total solid of a composition is preferable, and, as for the compounding quantity of (A) pigment compound in the coloring composition of this invention, 10-40 mass% is more preferable.
In addition, the content of the (A) dye compound in the coloring composition of the present invention is preferably set in consideration of the content ratio with the pigment. The mass ratio of the (A) dye compound to the pigment is preferably 10 to 50%, more preferably 15 to 45%, and still more preferably 20 to 40%.

  In the dye compound (A) used in the present invention, a hydrogen atom in the dye structure may be substituted by a substituent selected from the following Substituent Group A without departing from the spirit of the present invention.

Substituent group A:
As a substituent, a halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group , Silyloxy, heterocyclic oxy, acyloxy, carbamoyloxy, amino (including alkylamino and anilino), acylamino, aminocarbonylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfa Moylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfinyl group, alkyl or aryl sulfonyl group Groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclic azo groups, imido groups, phosphino groups, phosphinyl groups, phosphinyl oxy groups, phosphinyl amino groups, silyl groups etc. Be Described in detail below.

  A halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), linear or branched alkyl group (linear or branched substituted or unsubstituted alkyl group, preferably alkyl group having 1 to 30 carbon atoms For example, methyl, ethyl, n-propyl, isopropyl, tert-butyl, n-octyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl), a cycloalkyl group (preferably having a carbon number of 3 to 30) or An unsubstituted cycloalkyl group such as cyclohexyl and cyclopentyl can be mentioned, and a polycycloalkyl group such as a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, for example, bicyclo 1,2,2] Heptan-2-yl, bicyclo [2,2,2] octane-3 Yl) or group of polycyclic structures such as tricycloalkyl groups. Preferably monocyclic cycloalkyl group, a bicycloalkyl group, a monocyclic cycloalkyl group is particularly preferred.)

  A linear or branched alkenyl group (a linear or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having a carbon number of 2 to 30, for example, vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl Group (preferably, a substituted or unsubstituted cycloalkenyl group having a carbon number of 3 to 30, and examples thereof include 2-cyclopenten-1-yl and 2-cyclohexen-1-yl; a polycycloalkenyl group such as bicyclo) An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having a carbon number of 5 to 30), for example, bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Octo-2-en-4-yl) or a tricycloalkenyl group, particularly preferably a monocyclic cycloalkenyl group) Le group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, e.g., ethynyl, propargyl, trimethylsilylethynyl group),

  An aryl group (preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, for example, phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic group (preferably 5 to 5) 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or fused heterocyclic group, more preferably, the ring constituting atoms are selected from carbon atoms, nitrogen atoms and sulfur atoms And a heterocyclic group having at least one hetero atom of any of nitrogen atom, oxygen atom and sulfur atom, more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. For example, 2-furyl, 2-thienyl, 2-pyridyl, 4-pyridyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydride Hexyl group, a nitro group, a carboxyl group,

  An alkoxy group (preferably, a substituted or unsubstituted alkoxy group having a carbon number of 1 to 30, for example, methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), an aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having a carbon number of 6 to 30, and examples thereof include phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy group (preferably, a silyloxy group having 3 to 20 carbon atoms, for example, trimethylsilyloxy, tert-butyldimethylsilyloxy), heterocyclic oxy group (preferably, 2 to 2 carbon atoms 30 substituted or unsubstituted heterocyclic oxy groups Heterocyclic portion is preferably described in the heterocyclic portion described above heterocyclic group, e.g., 1-phenyl-5-oxy, 2-tetrahydropyranyloxy),

  An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably, a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, N-n-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having a carbon number of 2 to 30) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), aryloxycarbonyloxy group (preferably having a carbon number of 7 to 30) A substituted aryloxycarbonyloxy group, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, p-n-hexadecyloxyphenoxycarbonyloxy),

  Amino group (preferably, amino group, substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, heterocyclic amino group having 0 to 30 carbon atoms For example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, N-1,3,5-triazin-2-ylamino), an acylamino group (preferably a formylamino group, carbon number) 1-30 substituted or unsubstituted alkylcarbonylamino group, substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, and examples thereof include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, and the like. 4,5-Tri-n-octyloxyphenylcarbonylamino), amino A carbinylamino group (preferably, a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), An alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),

  An aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably, a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino A sulfonylamino), an alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms, for example, methyl Sulfonyla Bruno, butyl sulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenyl sulfonylamino, p- methylphenyl sulfonylamino), a mercapto group,

  An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, for example, methylthio, ethylthio, n-hexadecylthio), an arylthio group (preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms) For example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic part is the above-mentioned heterocyclic group The heterocyclic moiety described in is preferred, for example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms), for example , N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfa Yl, N, N- dimethylsulfamoyl, N- acetyl sulfamoyl, N- benzoylsulfamoyl, N- (N'-phenylcarbamoyl) sulfamoyl), a sulfo group,

  An alkyl or arylsulfinyl group (preferably, a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a 6 to 30 substituted or unsubstituted arylsulfinyl group, for example, methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably, a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a 6 to 30 substituted or unsubstituted arylsulfonyl group, for example, methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), an acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbo D A group such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, p-n-octyloxyphenylcarbonyl), an aryloxycarbonyl group (preferably, a substituted or unsubstituted aryloxy group having preferably 7 to 30 carbon atoms). A carbonyl group, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, p-tert-butylphenoxycarbonyl),

  An alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably, a carbon number 1 to 30 substituted or unsubstituted carbamoyl, such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero A cyclic azo group (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the hetero ring portion is a hetero ring described in the aforementioned heterocyclic group) Ring is preferred), for example, phenyl Zo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), an imide group (preferably a substituted or unsubstituted imide group having 2 to 30 carbon atoms, for example, N-succinimide, N-phthalimide), phosphino group (preferably, a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethyl phosphino, diphenyl phosphino, methyl phenoxy phosphino), phosphinyl group (preferably, 2 carbon atoms) -30 substituted or unsubstituted phosphinyl groups, for example, phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl),

  A phosphinyl oxy group (preferably a substituted or unsubstituted phosphinyl oxy group having 2 to 30 carbon atoms, for example, diphenoxy phosphinyl oxy, dioctyl oxy phosphinyl oxy), phosphinyl amino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), silyl group (preferably, having 3 to 30 carbon atoms) Or unsubstituted silyl groups such as trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).

  Among the above functional groups, those having a hydrogen atom may have a hydrogen atom portion in the functional group substituted by any of the above groups. Examples of the functional group that can be introduced as a substituent include an alkylcarbonylaminosulfonyl group, an arylcarbonylaminosulfonyl group, an alkylsulfonylaminocarbonyl group, and an arylsulfonylaminocarbonyl group, and specifically, methylsulfonylaminocarbonyl, p-methylphenylsulfonylaminocarbonyl, acetylaminosulfonyl, benzoylaminosulfonyl group can be mentioned.

Hereinafter, specific examples of the dye compound (A) used in the present invention will be shown, but the present invention is not limited thereto. Moreover, the polymer which contains the repeating unit derived from the compound (A-13-A-26) which has a polymeric group among the following compounds shall also be contained in the (A) pigment compound of this invention.

<< Cyanine dye >>
One of the embodiments of the dye compound (A) is one having a partial structure derived from a cyanine dye (cyanine compound). Examples of the (A) dye compound include those having a partial structure derived from a compound (cyanine compound) represented by the following general formula (PM) as a partial structure of a dye moiety. In the present invention, the cyanine compound is a generic term for compounds having a dye moiety containing a cyanine skeleton in the molecule.

（一般式（ＰＭ）中、環Ｚ１および環Ｚ２は、それぞれ独立に置換基を有してもよい複素環を表す。ｌは０以上３以下の整数を表す。） General formula (PM)

(In the general formula (PM), the ring Z1 and the ring Z2 each independently represent a heterocyclic ring which may have a substituent. L represents an integer of 0 or more and 3 or less)

Examples of ring Z1 and ring Z2 each independently include oxazole, benzoxazole, oxazoline, thiazole, thiazoline, benzothiazole, indolenine, benzoindolenine, 1,3-thiadiazine and the like.
The substituents which may be taken by ring Z1 and ring Z2 include the above-mentioned substituent group A.

  The compound represented by Formula (PM) is preferably a compound represented by the following Formula (PM-2).

（一般式（ＰＭ−２）中、環Ｚ⁵および環Ｚ⁶は、それぞれ独立に、置換基を有していてもよいベンゼン環または置換基を有していてもよいナフタレン環を表す。
ｎは、０以上３以下の整数を表す。
Ａ¹およびＡ²は、それぞれ独立に、酸素原子、硫黄原子、セレン原子、炭素原子または窒素原子を表す。
Ｒ¹およびＲ²は、それぞれ独立に、置換基を有していてもよい１価の炭素数１〜２０の脂肪族炭化水素基を表す。
Ｒ³およびＲ⁴は、それぞれ独立に水素原子または１価の炭素数１〜６の脂肪族炭化水素基を表すか、１個のＲ³と１個のＲ⁴とが一緒になって形成された２価の炭素数２〜６の脂肪族炭化水素基を表す。
ａおよびｂは、それぞれ独立に、０以上２以下の整数を表す。） General formula (PM-2)

In General Formula (PM-2), Ring Z ⁵ and Ring Z ⁶ each independently represent a benzene ring which may have a substituent or a naphthalene ring which may have a substituent.
n represents an integer of 0 or more and 3 or less.
Each of A ¹ and A ² independently represents an oxygen atom, a sulfur atom, a selenium atom, a carbon atom or a nitrogen atom.
Each of R ¹ and R ² independently represents a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
R ³ and R ⁴ each independently represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms, or one R ³ and one R ⁴ are formed together And a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms.
Each of a and b independently represents an integer of 0 or more and 2 or less. )

  The following (pm-1) to (pm-17) are examples of the dye structure of the cyanine compound, but the present invention is not limited thereto.

Moreover, although the following A-pm-1 to A-pm-4 are specific examples of the cyanine compound, the present invention is not limited thereto. In addition, a polymer containing a repeating unit derived from a compound having a polymerizable group (A-pm-1, A-pm-2 and A-pm-4) is also included in the (A) dye compound of the present invention Do.

<< squarylium dye >>
The dye compound (A) may have a squarylium dye structure. As the squarylium dye, a dye represented by the following general formula (K) is preferable.

（式中、Ａ及びＤは、それぞれ独立にアリール基又はヘテロ環基を表し、Ｒは、アルキル基又はアリール基を表す。） General formula (K)

(Wherein, A and D each independently represent an aryl group or a heterocyclic group, and R represents an alkyl group or an aryl group)

In general formula (K), A and D each independently represent an aryl group or a heterocyclic group, and D has a cationic structure. The aryl group is preferably an aryl group having a carbon number of 6 to 48, more preferably 6 to 24, and examples thereof include phenyl and naphthyl. The heterocyclic group is preferably a 5- or 6-membered heterocyclic group, and examples thereof include pyroyl, imidazoyl, pyrazolyl, thienyl, pyridyl, pyrimidyl, pyridazyl, triazol-1-yl, thienyl, furyl, thiadiazoyl and the like. . A and B may be a fused ring of an aryl group and a heterocyclic group.
R represents an alkyl group or an aryl group. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group. Groups, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group and the like. The aryl group is preferably an aryl group having a carbon number of 6 to 36, more preferably a carbon number of 6 to 18, and examples thereof include a phenyl group and a naphthyl group.

  The compound represented by General Formula (K) is particularly preferably a compound represented by the following General Formula (K-1), or General Formula (K-2).

（一般式（Ｋ−１）中、Ｍ¹、Ｍ²、Ｍ³およびＭ⁴は、それぞれ独立に酸素原子、硫黄原子、または窒素原子を表し、Ｒ、Ｒ¹、およびＲ²は、それぞれ独立にアルキル基又はアリール基を表す。） General formula (K-1)

(In the general formula (K-1), M ¹ , M ² , M ³ and M ⁴ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, and R, R ¹ and R ² are each independently Represents an alkyl group or an aryl group)

In formula (K-1), M ¹ , M ² , M ³ and M ⁴ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, and a sulfur atom and a nitrogen atom are preferable. M ¹ and M ³ are preferably the same atom, and M ² and M ⁴ are preferably the same atom.
R, R ¹ and R ² in the general formula (K-1) have the same meaning as R in the general formula (K), and preferred ranges are also the same.

（一般式（Ｋ−２）中、Ｍ⁵およびＭ⁶は、それぞれ独立に酸素原子、硫黄原子、または窒素原子を表し、Ｒ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は、それぞれ独立にアルキル基又はアリール基を表す。） General formula (K-2)

(In the general formula (K-2), M ⁵ and M ⁶ each independently represent an oxygen atom, a sulfur atom or a nitrogen atom, and R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R 6 ⁶ each independently represents an alkyl group or an aryl group)

In the formula (K-2), M ⁵ and M ⁶ has the same meaning as the general formula ^{(K-1) M 1 ~M} 4 in the preferred ranges are also the same. M ⁵ and M ⁶ are preferably the same atom.
R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (K-2) have the same meaning as R in the general formula (K), and preferred ranges are also the same.

  The compound represented by General Formula (K-1) is preferably a compound represented by the following General Formula (K-3), and the compound represented by General Formula (K-2) is a compound represented by General Formula (K-2) It is preferable that it is a compound represented by Formula (K-4).

（一般式（Ｋ−３）中、Ｒ、Ｒ¹、およびＲ²は、それぞれ独立にアルキル基又はアリール基を表す。） General formula (K-3)

(In the general formula (K-3), R, R ¹ and R ² each independently represent an alkyl group or an aryl group.)

R, R ¹ and R ² in the general formula (K-3) have the same meaning as R in the general formula (K), and preferred ranges are also the same.

（一般式（Ｋ−４）中、Ｒ、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は、それぞれ独立にアルキル基又はアリール基を表す。） General formula (K-4)

(In the general formula (K-4), R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent an alkyl group or an aryl group.)

R, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (K-4) have the same meaning as R in the general formula (K), and preferred ranges are also the same.

  The following (sm-1) and (sm-2) are examples of dye structures of squarylium compounds, but the present invention is not limited thereto.

Moreover, although the following (sm-3) and (sm-4) are examples of squarylium compounds, the present invention is not limited thereto.

<< Dipyrromethene dye >>
One of the modes of the dye compound (A) is one having a partial structure derived from the dipyrromethene dye shown below as a partial structure of a dye moiety.

As the dipyrromethene dye in the present invention, a dipyrromethene compound and a dipyrromethene metal complex compound obtained from the dipyrromethene compound and a metal or a metal compound are preferable.
In the present invention, a compound having a dipyrromethene structure is referred to as a dipyrromethene compound, and a complex in which a compound having a dipyrromethene structure is coordinated to a metal or a metal compound is referred to as a dipyrromethene metal complex compound.

As a dipyrromethene metal complex compound, a dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the following general formula (M) and a metal or a metal compound and a tautomer thereof are preferable, and among them, the following general formula as a preferable embodiment The dipyrromethene metal complex compound represented by (7) or the dipyrromethene metal complex compound represented by the following general formula (8) is mentioned, and the dipyrromethene metal complex compound represented by the general formula (8) is more preferable.

<<< Dipyrromethene metal complex compound obtained from a dipyrromethene compound represented by the general formula (M) and a metal or a metal compound, and a tautomer thereof>
(A) One of the preferable embodiments of the dye structure in the dye compound is a complex (hereinafter referred to as a compound in which a compound (dipyrromethene compound) represented by the following general formula (M) or a tautomer thereof is coordinated to a metal or a metal compound And a "specific complex", as appropriate, as a dye moiety. In the present invention, the following compounds form a cationic structure, but for example, a hydrogen atom bonded to a nitrogen atom of the general formula (M) can form a cation.

（一般式（Ｍ）において、Ｒ⁴〜Ｒ¹⁰は、各々独立に、水素原子または１価の置換基を表す。但し、Ｒ⁴とＲ⁹とが互いに結合して環を形成することはない。）

(In the general formula (M), R ^{4 to} R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent, provided that R ⁴ and R ⁹ do not combine with each other to form a ring. .)

Introduction when a compound represented by General Formula (M) is introduced into structural units represented by General Formula (A) to General Formula (C) described later, or a polymer represented by General Formula (D) The site is not particularly limited, but is preferably introduced at any one site of R ^{4 to} R ^{9 in} terms of synthetic compatibility, and any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ is preferred. It is more preferably introduced in one, and further preferably introduced in any one of R ⁴ and R ⁹ .

Examples of the monovalent substituent in the case where R ^{4 to} R ⁹ in the general formula (M) represent a monovalent substituent include the substituents listed in the section of Substituent Group A above.

When the monovalent substituent represented by R ^{4 to} R ⁹ in the general formula (M) is a substitutable group, it may further have the substituent described for R ^{4 to} R ⁹ If two or more substituents are present, those substituents may be the same or different.

R ⁴ and R ⁵ in general formula (M), R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁸ and R ⁹ are each independently bonded to each other to be 5, 6, or 7 members Member may form a saturated or unsaturated ring. However, R ⁴ and R ⁹ do not combine with each other to form a ring. When the formed 5-, 6-, and 7-membered rings are further substitutable groups, they may be substituted by the substituents described in R ^{4 to} R ⁹ , and two or more substituents may be substituted. When substituted by groups, the substituents may be the same or different.

R ⁴ and R ⁵ in the general formula (M), R ⁵ and R ⁶ , R ⁷ and R ⁸ , and R ⁸ and R ⁹ are each independently bonded to each other to have no substituent When forming a 6-, 7- or 7-membered saturated or unsaturated ring, examples of the 5-, 6-, or 7-membered saturated or unsubstituted ring having no substituent include a pyrrole ring, Furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyrazine ring, and pyridazine ring are preferable, and preferred Is a benzene ring or a pyridine ring.

R ¹⁰ in the general formula (M) preferably represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. The halogen atom, the alkyl group, the aryl group and the heterocyclic group have the same meanings as the halogen atom, the alkyl group, the aryl group and the heterocyclic group described in the section of Substituent Group A above, and preferred ranges thereof are also It is similar.
When R ¹⁰ represents an alkyl group, an aryl group, or a heterocyclic group, the alkyl group, the aryl group, and the heterocyclic group may be further substitutable groups. The substituents may be substituted with the substituents described in the section, and when substituted with two or more substituents, those substituents may be the same or different.

~ Metal or metal compound ~
The specific complex in the present invention is a complex in which the dipyrromethene compound represented by the general formula (M) described above or the tautomer thereof is coordinated to a metal or a metal compound.
Here, as the metal or metal compound, any metal or metal compound capable of forming a complex may be used, and a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, Or a divalent metal chloride is included. Examples of metals or metal compounds include metals such as Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Pb, Cu, Ni, Co, Fe, etc., AlCl, InCl, FeCl, TiCl, and the like. _And metal chlorides such as SnCl ₂ , SiCl ₂ and GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ .
Among them, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and manufacturing suitability of the complex, etc. VO is preferred, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co or VO is more preferred, and Zn is particularly preferred.

  Next, the further preferable range of the specific complex in the present invention of the compound represented by General Formula (M) will be described.

The preferred range of the specific complex in the present invention is that in the general formula (M), R ⁴ and R ⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a silyl group, a hydroxyl group, Cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group, anilino group, heterocyclic amino group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group , Aryloxycarbonylamino group, sulfonamide group, azo group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group; R ⁵ and R ⁸ each represent Independently, hydrogen atom, halogen atom, alkyl group, alkenyl group, Group, heterocyclic group, hydroxyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino A sulfonamide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group; R ⁶ and R ⁷ each independently represent a hydrogen atom or a halogen atom , Alkyl group, alkenyl group, aryl group, heterocyclic group, silyl group, hydroxyl group, cyano group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, carbamoyl group, anilino group, carbonamide Group, ureido group, imide group, Job aryloxycarbonyl amino group, a sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or be a phosphinoylamino group,; R ¹⁰ is a hydrogen atom A halogen atom, an alkyl group, an aryl group or a heterocyclic group; the metal or the metal compound may be Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, or V = O It is a range.

A more preferable range of the specific complex in the present invention is that in the general formula (M), R ⁴ and R ⁹ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group or an acyl group , Alkoxycarbonyl group, carbamoyl group, amino group, heterocyclic amino group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, azo group, alkylsulfonyl group, arylsulfonyl R ⁵ and R ⁸ each independently represent an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, a nitro group, an acyl group, an alkoxycarbonyl group, an aryloxy group Carbonyl group, carbamoyl group, imide group, alkylsulfonyl group, ant Rusuruhoniru group or be a sulfamoyl group,; R ⁶ and R ⁷ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, carbonamido group, a ureido group, an imido group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or be a sulfamoyl group,; R ¹⁰ is a hydrogen atom Or a halogen atom, an alkyl group, an aryl group or a heterocyclic group; a range in which the metal or the metal compound is Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, or V = O.

A particularly preferable range of the specific complex in the present invention is that in the general formula (M), R ⁴ and R ⁹ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an amino group, a heterocyclic amino group, A carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamide group, an azo group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group; and R ⁵ and R ⁸ are each independently An alkyl group, an aryl group, a heterocyclic group, a cyano group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, or an arylsulfonyl group; R ⁶ and R ⁷ each independently represent a hydrogen atom or an alkyl group , an aryl group or heteroaryl ring group,; R ¹⁰ is a hydrogen atom, an alkyl group, an aryl group or a heteroaryl, A group; metal or metal compound is in the range is Zn, Cu, Co or V = O,.

  Furthermore, a dipyrromethene metal complex compound represented by the general formula (7) or the general formula (8) described in detail below is also a particularly preferred embodiment of the dipyrromethene dye.

<<< Dipyrromethene Metal Complex Compound Represented by General Formula (7) >>
One of the preferable embodiments of the dye structure in the dye multimer (A) is a dye structure derived from a dipyrromethene metal complex compound represented by the following general formula (7).

（一般式（７）中、Ｒ⁴〜Ｒ⁹は、各々独立に、水素原子、または１価の置換基を表し、Ｒ¹⁰は、水素原子、ハロゲン原子、アルキル基、アリール基、またはヘテロ環基を表す。Ｍａは、金属原子、または金属化合物を表す。ただし、Ｒ⁴とＲ⁹とが互いに結合して環を形成することはない。）
なお、一般式（７）で表されるジピロメテン金属錯体化合物は、互変異性体を含む。

(In the general formula (7), R ^{4 to} R ⁹ each independently represent a hydrogen atom or a monovalent substituent, and R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic ring Ma represents a metal atom or a metal compound, provided that R ⁴ and R ⁹ do not combine with each other to form a ring)
In addition, the dipyrromethene metal complex compound represented by General formula (7) contains a tautomer.

The introduction site in the case of introducing the dipyrromethene metal complex compound represented by the general formula (7) into a multimer is not particularly limited, but in terms of synthetic compatibility, any one site of R ^{4 to} R ⁹ Is preferably introduced at any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ , and is further preferably introduced at any one of R ⁴ and R ⁹ preferable.

When the dye structure has an alkali-soluble group, an alkali-soluble group may be added to any one or two or more substituents of R ^{4 to} R ¹⁰ in General Formula (7) as a method of introducing an alkali-soluble group. Can be used. Among these substituents, any ^one of R ^{4 to} R ⁹ and X ¹ is preferable, any one of R ⁴ , R ⁶ , R ⁷ and R ⁹ is more preferable, and any one of R ⁴ and R ⁹ is more preferable.

The dipyrromethene metal complex compound represented by the general formula (7) may have a functional group other than the alkali-soluble group, as long as the effect of the present invention is not impaired.
R ⁴ to R ⁹ in the middle in the general formula (7) has the same meaning as R ⁴ to R ⁹ in the general formula (M), preferable embodiments thereof are also the same.

In the general formula (7), Ma represents a metal atom or a metal compound. The metal atom or metal compound may be any metal atom or metal compound capable of forming a complex, and is a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or It contains divalent metal chlorides.
For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe , etc., and _{AlCl, InCl, FeCl, TiCl 2} , SnCl 2, SiCl 2, GeCl 2 , etc. And metal oxides such as TiO, V の O, and metal hydroxides such as Si (OH) ₂ .

  Among them, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, as a metal atom or a metal compound, from the viewpoints of stability of the complex, spectral characteristics, heat resistance, light resistance, and production suitability. Ni, Co, TiO, and V = O are preferable, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, and V = O are more preferable, Zn, Co, V = O, and Cu are more preferable. And Zn are particularly preferred.

Further, in the general formula (7), R ¹⁰ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group, preferably a hydrogen atom.

As a preferred embodiment of the compound represented by the general formula (7), R ^{4 to} R ⁹ are each independently a preferred embodiment described in the explanation of R ^{4 to} R ⁹ , and R ¹⁰ is described in the explanation of R ¹⁰ Ma is Zn, Cu, Co, or VOO.

<<< Dipyrromethene Metal Complex Compound Represented by General Formula (8) >>
One of the preferable embodiments of the dye structure in the dye compound (A) is a dye structure derived from a dipyrromethene metal complex compound represented by the following general formula (8).

（一般式（８）中、Ｒ¹¹およびＲ¹⁶は、各々独立に、アルキル基、アルケニル基、アリール基、ヘテロ環基、アルコキシ基、アリールオキシ基、アルキルアミノ基、アリールアミノ基、またはヘテロ環アミノ基を表す。Ｒ¹²〜Ｒ¹⁵は、各々独立に、水素原子、または置換基を表す。Ｒ¹⁷は、水素原子、ハロゲン原子、アルキル基、アリール基、またはヘテロ環基を表す。Ｍａは、金属原子、または金属化合物を表す。Ｘ²およびＸ³は、各々独立に、ＮＲ（Ｒは水素原子、アルキル基、アルケニル基、アリール基、ヘテロ環基、アシル基、アルキルスルホニル基、またはアリールスルホニル基を表す。）、窒素原子、酸素原子、または硫黄原子を表す。Ｙ¹およびＹ²は、各々独立に、ＮＲ^c（Ｒ^cは水素原子、アルキル基、アルケニル基、アリール基、ヘテロ環基、アシル基、アルキルスルホニル基、またはアリールスルホニル基を表す。）、窒素原子または炭素原子を表す。Ｒ¹¹とＹ¹は、互いに結合して５員、６員、または７員の環を形成していてもよく、Ｒ¹⁶とＹ²は、互いに結合して５員、６員、または７員の環を形成していてもよい。）
なお、一般式（８）で表されるジピロメテン金属錯体化合物は、互変異性体を含む。

(In the general formula (8), each of R ¹¹ and R ¹⁶ independently represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic ring R ^{12 to} R ¹⁵ each independently represent a hydrogen atom or a substituent R ¹⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group Ma is an amino group X ² and X ³ each independently represent NR (wherein R represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an aryl) a sulfonyl group.), a nitrogen atom, .Y ¹ and Y ² represents an oxygen atom or a sulfur atom, each independently, NR ^c (R ^c is a hydrogen atom, an alkyl group, an alkenyl group, an Lumpur group, a heterocyclic group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group,.), .R ¹¹ and Y ¹ representing a nitrogen atom or a carbon atom, 5-membered bonded to each other, 6-membered, or It may form a 7-membered ring, and R ¹⁶ and Y ² may combine with each other to form a 5-, 6-, or 7-membered ring.)
In addition, the dipyrromethene metal complex compound represented by General formula (8) contains a tautomer.

Represented the site for introducing an dipyrromethene metal complex compound multimers by formula (8), but unless not particularly limited to impair the effects of the present invention, one of ^{R 11 ~R 17, Y 1 ~Y} 2 1 Is preferred. Among these, in terms of synthetic compatibility, it is preferable to be introduced at any one of R ^{11 to} R ¹⁶ , more preferably at any one of R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁶ It is an embodiment inserted, more preferably an embodiment inserted in any one of R ¹¹ and R ¹⁶ .

When the dye structure has an alkali-soluble group, R ^{11 to} R ¹⁷ in the general formula (8), when a dye monomer or a structural unit having an alkali-soluble group is used as a method for introducing an alkali-soluble group A method in which an alkali-soluble group is provided to any one or two or more substituents of Y ^{1 to} Y ² can be used. Among these substituents, any one of R ^{11 to} R ¹⁶ is preferable, any one of R ¹¹ , R ¹³ , R ¹⁴ and R ¹⁶ is more preferable, and any one of R ¹¹ and R ¹⁶ is more preferable.

  The dipyrromethene metal complex compound represented by the general formula (8) may have a functional group other than the alkali-soluble group as long as the effect of the present invention is not impaired.

In the general formula (8), R ¹² ~R ¹⁵ of the general formula (M) in the same meaning as R ⁵ to R ⁸ of preferred embodiment is also the same. R ¹⁷ has the same meaning as R ¹⁰ in General Formula (M), and preferred embodiments are also the same. Ma is synonymous with Ma in General formula (7), and its preferable range is also the same.

More specifically, among R ^{12 to} R ¹⁵ in the general formula (8), as R ¹² and R ¹⁵ , an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, Imido group or carbamoylsulfonyl group is preferable, and alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group is more preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group Groups, nitrile groups, imide groups and carbamoylsulfonyl groups are more preferred, and alkoxycarbonyl groups, aryloxycarbonyl groups and carbamoyl groups are particularly preferred.
As R ¹³ and R ¹⁴ , a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group is preferable, and a substituted or unsubstituted alkyl group, further preferably a substituted or unsubstituted group Is an aryl group of Here, specific examples of the more preferable alkyl group, aryl group and heterocyclic group can be the same as specific examples listed for R ⁶ and R ⁷ in the general formula (M).

In the general formula (8), R ¹¹ and R ^{16 each} represent an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms), for example, methyl Group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group), alkenyl Group (preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, for example, a vinyl group, an allyl group or a 3-buten-1-yl group), an aryl group (preferably a carbon number of 6 to 6). 36, more preferably an aryl group having 6 to 18 carbon atoms, for example, a phenyl group, a naphthyl group), a heterocyclic group (preferably having a carbon number of 1 to 24, more preferably Or a heterocyclic group having 1 to 12 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 2-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group), alkoxy group (preferably having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms), and examples thereof include a methoxy group, an ethoxy group and a propyloxy group, Butoxy, hexyloxy, 2-ethylhexyloxy, dodecyloxy, cyclohexyloxy), aryloxy (preferably having 6 to 24 carbon atoms, more preferably having 1 to 18 carbon atoms), for example, Phenoxy group, naphthyloxy group), alkylamino group (preferably having 1 to 36 carbon atoms, more preferably 1 to 1 carbon atoms Alkylamino group, for example, methylamino group, ethylamino group, propylamino group, butylamino group, hexylamino group, 2-ethylhexylamino group, isopropylamino group, tert-butylamino group, tert-octylamino group, Cyclohexylamino group, N, N-diethylamino group, N, N-dipropylamino group, N, N-dibutylamino group, N-methyl-N-ethylamino group), arylamino group (preferably having 6 to 36 carbon atoms) And more preferably an arylamino group having a carbon number of 6 to 18, and examples thereof include a phenylamino group, a naphthylamino group, an N, N-diphenylamino group, an N-ethyl-N-phenylamino group) or a heterocyclic amino group Preferably, it is a heterocyclic amino group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, for example, 2-aminopyrrole group, 3-aminopyrazole, 2-aminopyridine group, 3-aminopyridine group).

Among R ¹¹ and R ¹⁶ , among the above, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group and a heterocyclic amino group are preferable, and an alkyl group, an alkenyl group, an aryl group and a hetero The cyclic group is more preferable, the alkyl group, the alkenyl group and the aryl group are more preferable, and the alkyl group is particularly preferable.

In the general formula (8), an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkylamino group, an arylamino group or a heterocyclic amino group represented by R ¹¹ and R ¹⁶ is And when it is a further substitutable group, it may be substituted by the substituents described in the above-mentioned Substituent Group A, and when it is substituted by two or more substituents, The substituents may be the same or different.

In general formula (8), X ² and X ³ each independently represent NR, a nitrogen atom, an oxygen atom or a sulfur atom. Here, R is a hydrogen atom, an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 36 carbon atoms, more preferably 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, dodecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-adamantyl group, alkenyl group (preferably carbon) The alkenyl group is preferably an alkenyl group having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, and, for example, a vinyl group, an allyl group, a 3-buten-1-yl group, an aryl group (preferably 6 to 36 carbon atoms, more preferably An aryl group having 6 to 18 carbon atoms, for example, a phenyl group or a naphthyl group), a heterocyclic group (preferably having a carbon number of 1 to 24, more preferably carbon) 1 to 12 heterocyclic groups, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group , Benzotriazol-1-yl group), an acyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms), such as acetyl, pivaloyl, 2-ethylhexyl, benzoyl, Cyclohexanoyl group), alkylsulfonyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 18 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, isopropylsulfonyl group, cyclohexylsulfonyl group) Or arylsulfonyl group (preferably having 6 to 24 carbon atoms, more preferably 6 to 18 carbon atoms Arylsulfonyl group represented, for example, a phenylsulfonyl group, a naphthylsulfonyl group).

In general formula (8), Y ¹ and Y ² each independently represent NR ^C , a nitrogen atom or a carbon atom, R ^C has the same meaning as R of X ² and X ³ , and preferred embodiments are also the same. It is.

In the general formula (8), R ¹¹ and Y ¹ are bonded to each other to form a 5-membered ring (for example, cyclopentane ring, pyrrolidine ring, tetrahydrofuran ring, dioxolane ring, tetrahydrothiophene ring, pyrrole ring, furan ring) together with carbon atoms Thiophene ring, indole ring, benzofuran ring, benzothiophene ring), 6-membered ring (eg, cyclohexane ring, piperidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, dioxane ring, pentamethylene sulfide ring, dithian ring, benzene ring, A piperidine ring, a piperazine ring, a pyridazine ring, a quinoline ring, a quinazoline ring), or a 7-membered ring (eg, a cycloheptane ring, a hexamethyleneimine ring) may be formed.

In the general formula (8), R ¹⁶ and Y ² are mutually bonded to form a 5-membered ring (for example, cyclopentane ring, pyrrolidine ring, tetrahydrofuran ring, dioxolane ring, tetrahydrothiophene ring, pyrrole ring, furan ring, etc.) together with carbon atoms Thiophene ring, indole ring, benzofuran ring, benzothiophene ring), 6-membered ring (eg, cyclohexane ring, piperidine ring, piperazine ring, morpholine ring, tetrahydropyran ring, dioxane ring, pentamethylene sulfide ring, dithian ring, benzene ring, A piperidine ring, a piperazine ring, a pyridazine ring, a quinoline ring, a quinazoline ring), or a 7-membered ring (eg, a cycloheptane ring, a hexamethyleneimine ring) may be formed.

In the general formula (8), in the case where the 5-, 6-, and 7-membered rings formed by combining R ¹¹ and Y ¹ , and R ¹⁶ and Y ² are substitutable rings, The substituent may be substituted by the substituents described in the section of the substituent group A, and in the case of being substituted by two or more substituents, those substituents may be the same or different. .

In the general formula (8), R ¹¹ and R ¹⁶ are preferably each independently a monovalent substituent having a steric parameter -Es value of 1.5 or more, and 2.0 or more. More preferably, it is more preferably 3.5 or more, and particularly preferably 5.0 or more.
Here, the steric parameter-Es' value is a parameter representing the steric bulk of the substituent, and the document (JA Macphee, et al, Tetrahedron, Vol. 34, pp 3553 to 3562, Toshio Fujita, Chemical special edition 107, Structure activity relationship And Druck Design, published Feb. 20, 1986 (Chem. Dojin)-using the Es' value.

As a preferred embodiment of the compound represented by the general formula (8), R ^{12 to} R ¹⁵ are each independently the preferred embodiments described in the explanation of R ^{5 to} R ⁸ in the general formula (M), R ¹⁷ is a preferred embodiment described in the explanation of R ^{10 in} the general formula (M), Ma is Zn, Cu, Co or VVO, X ² is NR (R is a hydrogen atom, an alkyl group), A nitrogen atom or an oxygen atom, X ³ is NR (R is a hydrogen atom or an alkyl group), or an oxygen atom, Y ¹ is NR ^C (R ^C is a hydrogen atom or an alkyl group), a nitrogen atom or carbon an atom, Y ² is a nitrogen atom or a carbon atom, each independently R ¹¹ and R ¹⁶ are an alkyl group, an aryl group, a heterocyclic group, an alkoxy group or alkylamino group, X ¹ is oxygen A group bonded through an atom, a is 0 or 1. R ¹¹ and Y ¹ may be bonded to each other to form a 5- or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5- or 6-membered ring.

As a further preferred embodiment of the compounds represented by the general formula (8), R ¹² ~R ¹⁵ each independently preferably described in the compound represented by formula (M) in the description of R ⁵ to R ⁸ aspects R ¹⁷ is a preferred embodiment described in the description of R ^{10 in} the general formula (M), Ma is Zn, X ² and X ³ are oxygen atoms, Y ¹ is NH, Y ² is a nitrogen atom, and R ¹¹ and R ¹⁶ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, and X ¹ is a group bonded via an oxygen atom Yes, a is 0 or 1. R ¹¹ and Y ¹ may be bonded to each other to form a 5- or 6-membered ring, or R ¹⁶ and Y ² may be bonded to each other to form a 5- or 6-membered ring.

  The molar absorption coefficient of the dipyrromethene metal complex compound represented by the general formula (7) and the general formula (8) is preferably as high as possible from the viewpoint of coloring power. The maximum absorption wavelength λmax is preferably 520 nm to 580 nm, and more preferably 530 nm to 570 nm, from the viewpoint of improving color purity. By being in this region, a color filter having good color reproducibility can be produced using the coloring composition of the present invention.

  Furthermore, the dye multimer (A) having a dye structure derived from a dipyrromethene dye preferably has an absorbance of 1,000 times or more of the maximum absorption wavelength (λmax) relative to the absorbance at 450 nm, and is 10,000 times or more Is more preferably, and more preferably 100,000 times or more. When the ratio is in this range, it is possible to form a color filter with higher transmittance, particularly when producing a blue color filter, using the coloring composition of the present invention. The maximum absorption wavelength and the molar absorption coefficient are measured by a spectrophotometer cary 5 (manufactured by Varian).

  The melting point of the dipyrromethene metal complex compound represented by the general formula (7) and the general formula (8) should not be too high from the viewpoint of solubility.

  The dipyrromethene metal complex compounds represented by the general formula (7) and the general formula (8) are disclosed in U.S. Patent Nos. 4,774,339, 5,433,896, and JP-A-2001-240761. Publication No. 2002-155052, Japanese Patent No. 3614586, Aust. J. Chem, 1965, 11, 1835-1845, J. Am. H. Boger et al, Heteroatom Chemistry, Vol. 1, No. 5, 389 (1990) and the like. Specifically, the method described in paragraphs 0131 to 0157 of JP-A-2008-292970 can be applied.

  The following (PM-1) to (PM-10) are examples of the dye structure of the dipyrromethene compound, but the present invention is not limited thereto. In specific examples (PM-1) to (PM-10), Zn is a cation.

Moreover, although the following (A-PM-1)-(A-PM-4) are specific examples of a dipyrromethene compound, this invention is not limited to this. In addition, a polymer containing a repeating unit derived from a compound having a polymerizable group (A-PM-1, A-PM-3 and A-PM-4) is also included in the (A) dye compound of the present invention Do.

  When the coloring compound used in the present invention is a xanthene dye, azo dye or squarylium dye (preferably xanthene dye), combined use with a red colorant (preferably red pigment) or a yellow colorant (preferably yellow pigment) Thus, it is possible to make a red colored composition. In this case, the weight ratio of the dye compound to the red and / or yellow colorant used in the present invention is preferably 10:90 to 90:10.

The coloring composition of the present invention is used to form a coloring layer of a color filter. The coloring composition used in the present invention contains (B) a curable compound and (C) a solvent in addition to the above-mentioned (A) dye compound, and may further contain other components.
For example, when a colored layer is formed by a photoresist, the colored composition of the present invention comprises (A) a dye compound, an alkali-soluble resin as a curable compound and a solvent, and a pigment and a photopolymerization initiator. Are preferred. Furthermore, components such as surfactants may be included.
When the colored layer is formed by dry etching, a composition containing a pigment and a photopolymerization initiator in addition to the (A) dye compound, the polymerizable compound as the curable compound, and the solvent is preferable. Furthermore, components such as surfactants may be included.
The details of these will be described below.

<Curable compound>
The coloring composition of the present invention contains a curable compound. As the curable compound, a known polymerizable compound which can be crosslinked by a radical, an acid or heat can be used. For example, a polymerizable compound containing an ethylenically unsaturated bond, a cyclic ether (epoxy, oxetane), methylol or the like It can be mentioned. The polymerizable compound is suitably selected from compounds having at least one, preferably two or more terminal ethylenically unsaturated bonds, from the viewpoint of sensitivity. Among them, tetrafunctional or higher polyfunctional polymerizable compounds are preferable, and pentafunctional or higher polyfunctional polymerizable compounds are more preferable.

  Such compounds are widely known in the industrial field, and they can be used in the present invention without particular limitation. These may be, for example, any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers or mixtures thereof and multimers thereof. The polymerizable compound in the present invention may be used alone or in combination of two or more.

More specifically, examples of monomers and prepolymers thereof include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid etc.) and esters thereof, amides, etc. And multimers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and multimers thereof. is there. Also, addition reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group etc. with monofunctional or polyfunctional isocyanates or epoxies, monofunctional or multifunctional Dehydration condensation products with functional carboxylic acids and the like are also suitably used. Also, addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as isocyanate group and epoxy group with monofunctional or polyfunctional alcohols, amines and thiols, and halogen groups Also suitable are substitution reaction products of unsaturated carboxylic acid esters or amides having a leaving substituent such as tosyloxy group with monofunctional or polyfunctional alcohols, amines and thiols. As another example, instead of the above unsaturated carboxylic acid, it is also possible to use unsaturated phosphonic acid, a vinyl benzene derivative such as styrene, a vinyl ether, an allyl ether or the like, and a group of compounds replaced.
As these specific compounds, compounds described in Paragraph Nos. [0095] to [0108] of JP-A-2009-288705 can be suitably used in the present invention.

Further, as the polymerizable compound, a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or more under normal pressure is also preferable. Examples thereof include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol ( Meta) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanate Those obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as nurate, glycerin or trimethylolethane and then forming (meth) acrylate, JP-B-48-41708, JP-B-50-6034, Urethane (meth) acrylates as described in JP-A-51-37193, polyester acrylates described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490 And polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof.
Polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group such as glycidyl (meth) acrylate and an ethylenically unsaturated group with a polyfunctional carboxylic acid can also be mentioned.
Moreover, as another preferable polymerizable compound, it has a fluorene ring and is described in, for example, JP-A-2010-160418, JP-A-2010-129825, and JP-A-4364216, and an ethylenically unsaturated group is described. It is also possible to use a compound having two or more functions, a cardo resin.

  Moreover, as a compound which has a boiling point of 100 degreeC or more under a normal pressure, and has at least 1 addition polymerizable ethylenic unsaturated group, Paragraph No. [0254]-[0257] of Unexamined-Japanese-Patent No. 2008-292970. The compounds described in are also suitable.

  In addition to the above, radically polymerizable monomers represented by the following formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R.

In the general formula, n is 0-14 and m is 1-8. A plurality of R and T in one molecule may be identical to or different from each other.
In each of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), at least one of a plurality of R is -OC (= O) CH = CH ₂ , or -OC ( OO) represents a group represented by C (CH ₃ ) = CH ₂ .
As specific examples of the polymerizable compounds represented by the general formulas (MO-1) to (MO-5), the compounds described in Paragraph No. 0248 to Paragraph No. 0251 of JP-A-2007-269779 are referred to as the present invention. Can also be suitably used.

  Further, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol described in JP-A No. 10-62986 as general formulas (1) and (2) together with specific examples thereof are also polymerized, It can be used as a sex compound.

  Among them, as a polymerizable compound, dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd. Dipentaerythritol penta (meth) acrylate (commercially available as KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; Nippon Kayaku Co., Ltd.) Made of ethyleneoxy-modified dipentaerythritol hexaacrylate (commercially available as A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), pentaerythritol ethoxylate tetraacrylate (commercially available as KAYARAD RP) -104; Nippon Kayaku Co., Ltd.) and the structure where these (meth) acryloyl groups intervene ethylene glycol and a propylene glycol residue are preferable. These oligomer types can also be used.

  The polymerizable compound is a polyfunctional monomer, and may have an acid group such as a carboxyl group, a sulfonic acid group or a phosphoric acid group. If the ethylenic compound has an unreacted carboxyl group as in the case of a mixture as described above, this can be used as it is, but, if necessary, to the hydroxyl group of the above ethylenic compound Non-aromatic carboxylic acid anhydride may be reacted to introduce an acid group. In this case, specific examples of non-aromatic carboxylic acid anhydrides used include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, anhydride Maleic acid is mentioned.

  In the present invention, the monomer having an acid group is an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound. Polyfunctional monomers having an acid group are preferred, and particularly preferred in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. As a commercial item, M-510, M-520 etc. are mentioned, for example as a polybasic acid modified | denatured acryl oligomer by Toagosei Co., Ltd. make.

One of these monomers may be used alone, but two or more of these monomers may be used in combination because it is difficult to use a single compound in production. If necessary, a polyfunctional monomer having no acid group and a polyfunctional monomer having an acid group may be used in combination as monomers.
The acid value of the polyfunctional monomer having an acid group is preferably 0.1 mg KOH / g to 40 mg KOH / g, particularly preferably 5 mg KOH / g to 30 mg KOH / g. When the acid value of the polyfunctional monomer is too low, the development dissolution property is deteriorated, and when too high, the production and handling become difficult, the photopolymerization performance is deteriorated, and the curability such as the surface smoothness of the pixel is deteriorated. Therefore, in the case of using two or more kinds of polyfunctional monomers having different acid groups in combination, or in the case of using a polyfunctional monomer having no acid group, the acid group as the entire polyfunctional monomer is adjusted to fall within the above range. Is preferred.

Moreover, it is also a preferable aspect to contain the polyfunctional monomer which has a caprolactone structure as a polymeric compound.
The polyfunctional monomer having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule, and examples thereof include trimethylol ethane, ditrimethylol ethane, trimethylol propane, ditrimethylol propane and penta An ε-caprolactone modified polyfunctional (ε) obtained by esterifying (meth) acrylic acid and ε-caprolactone with a polyhydric alcohol such as erythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine Mention may be made of meta) acrylates. Among them, polyfunctional monomers having a caprolactone structure represented by the following general formula (Z-1) are preferable.

  In the general formula (Z-1), all six Rs are groups represented by the following general formula (Z-2), or 1 to 5 of the six Rs have the following general formula (Z And the remainder is a group represented by the following general formula (Z-3).

In general formula (Z-2), R ¹ represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and “*” represents a bond.

In general formula (Z-3), R ¹ represents a hydrogen atom or a methyl group, and “*” represents a bond. )

Such multifunctional monomers having a caprolactone structure are commercially available, for example, from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and DPCA-20 (the above formulas (Z-1) to (Z-3) Where m = 1, the number of groups represented by formula (Z-2) = 2, and a compound wherein all R ¹ are hydrogen atoms, DPCA-30 (the same formula, m = 1, formula (Z-2) Compound represented by the number of groups = 3, a compound wherein all R ¹ are hydrogen atoms, DPCA-60 (in the formula, m = 1, the number of groups represented by the formula (Z-2) = 6, R ¹ is Examples include compounds in which all are hydrogen atoms, DPCA-120 (the number of groups represented by m = 2 and formula (Z-2) = 6 in the same formula, compounds in which all R ¹ are hydrogen atoms), etc. it can.
In the present invention, polyfunctional monomers having a caprolactone structure can be used alone or in combination of two or more.

  Moreover, as a specific monomer in this invention, it is also preferable that it is at least 1 sort (s) selected from the group of the compound represented by the following general formula (Z-4) or (Z-5).

In the formula (Z-4) and (Z-5), E are each _{independently, - ((CH 2) yCH} 2 O) -, or _{- ((CH 2) yCH (} CH 3) O) - a And y each independently represents an integer of 0 to 10, and each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
In the general formula (Z-4), the total of acryloyl group and methacryloyl group is 3 or 4, m each independently represents an integer of 0 to 10, and the sum of each m is an integer of 0 to 40 . However, when the sum of each m is 0, any one of X is a carboxyl group.
In general formula (ii), the total of acryloyl group and methacryloyl group is 5 or 6, n each independently represents an integer of 0 to 10, and the sum of each n is an integer of 0 to 60. However, when the sum of each n is 0, any one of X is a carboxyl group.

In general formula (Z-4), m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4. Moreover, the integer of 2-40 is preferable, the integer of 2-16 is more preferable, and, as for the sum of each m, the integer of 4-8 is especially preferable.
In general formula (Z-5), n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
Moreover, the integer of 3-60 is preferable, the integer of 3-24 is more preferable, and, as for the sum of each n, the integer of 6-12 is especially preferable.
In general formula (Z-4) or general formula (Z-5) in the _{- ((CH 2) yCH 2} O) - or _{- ((CH 2) yCH (} CH 3) O) - , the oxygen atom side Preferred is a form in which the terminus of X is attached to X.

  The compounds represented by General Formula (Z-4) or General Formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (ii), a form in which all six X's are an acryloyl group is preferable.

  Moreover, as a total content in the polymeric compound of a compound represented by general formula (Z-4) or general formula (Z-5), 20 mass% or more is preferable, and 50 mass% or more is more preferable.

  The compounds represented by the general formula (Z-4) or the general formula (Z-5) are obtained by ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol which is a conventionally known step. The compound can be synthesized from the step of binding the ring-opened skeleton by reaction, and the step of reacting the terminal hydroxyl group of the ring-opened skeleton with, for example, (meth) acryloyl chloride to introduce a (meth) acryloyl group. Each step is a well-known step, and those skilled in the art can easily synthesize a compound represented by general formula (i) or (ii).

Among the compounds represented by General Formula (Z-4) or General Formula (Z-5), pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
Specific examples thereof include compounds represented by the following formulas (a) to (f) (hereinafter, also referred to as “exemplified compounds (a) to (f)”), and among them, exemplified compounds (a) and (f) b), (e) and (f) are preferred.

  As commercial products of the polymerizable compounds represented by the general formulas (Z-4) and (Z-5), for example, SR-494 which is a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartmar, Nippon Kayaku Co., Ltd. Examples thereof include DPCA-60, which is a hexafunctional acrylate having 6 pentylene oxy chains, and TPA-330, which is a trifunctional acrylate having 3 isobutylene oxy chains.

In addition, as polymerizable compounds, urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765. Further, urethane compounds having an ethylene oxide-based skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, JP-A-1-105238 as a polymerizable compound By using the compounds, it is possible to obtain a curable composition which is very excellent in photosensitive speed.
As commercially available products of the polymerizable compound, urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha) etc. are mentioned.

  As cyclic ether (epoxy, oxetane), as what has an epoxy group, it is JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, as a bisphenol A epoxy resin, for example. JER-1055, JER-1007, JER-1009, JER-1010 (above, made by Japan Epoxy Resins Co., Ltd.), EPICLON 840, EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, made by DIC Corporation), etc. As bisphenol F-type epoxy resin, JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (all manufactured by Japan Epoxy Resins Co., Ltd.) EPICLON 830, EPICLON 835 (all, DIC Corporation), LCE-21, RE-602S (all, Nippon Kayaku Co., Ltd.) and the like, and as phenol novolac epoxy resins, JER-152, JER-154, JER-157S70, JER-157S65, (above, Japan Epoxy Resins Co., Ltd.), EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation), etc. Yes, as cresol novolac type epoxy resin, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 As described above, DIC Corporation, as a dicyclopentadiene type epoxy resin, EPICLON HP-7200 (DIC Corporation), EOCN-1020 (Nippon Kayaku Co., Ltd.), as an aliphatic epoxy resin ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (above, manufactured by ADEKA) Celloxide 2021 P, Celloxide 2081, Celloxide 2083, Celloxide 2085, EHPE-3150 (2, 2-Bis (hydroxymethyl)- 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 1-butanol), EPOLEAD PB 3600, PB 4700 (all manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211L, EX-212L, EX-214L, EX -216L, EX-321L, EX-850L (all manufactured by Nagase ChemteX Co., Ltd.), ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (all, manufactured by ADEKA) ), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (all manufactured by ADEKA Corporation), JER-1031 S (manufactured by Japan Epoxy Resins Corporation), etc. Be Such a polymerizable compound is suitable when forming a pattern by a dry etching method.

With regard to these polymerizable compounds, the details of the structure, single use or combined use, details of usage methods such as addition amount can be arbitrarily set in accordance with the final performance design of the coloring composition. For example, from the viewpoint of sensitivity, a structure having a high unsaturated group content per molecule is preferable, and in many cases, a bifunctional or more functional is preferable. In addition, from the viewpoint of enhancing the strength of the cured film formed by the coloring composition, trifunctional or higher functional groups are preferable, and further, different functional group number and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrenic compound, It is also effective to control both sensitivity and intensity by using vinyl ether compounds in combination. Furthermore, it is preferable to use a polymerizable compound having a trifunctional or higher functional group and having a different ethylene oxide chain length in combination, since the developability of the colored composition can be controlled and excellent pattern forming ability can be obtained.
In addition, the selection and use method of the polymerizable compound is also for compatibility and dispersibility with other components (for example, a photopolymerization initiator, a material to be dispersed, an alkali-soluble resin, etc.) contained in the coloring composition It is an important factor, and it may be possible to improve the compatibility, for example, by the use of a low purity compound or a combination of two or more. In addition, a specific structure may be selected from the viewpoint of improving the adhesion to a hard surface such as a support.

When mix | blending a polymeric compound in the coloring composition of this invention, 5-40 mass% is preferable with respect to the total solid in a coloring composition, and, as for content of a polymeric compound, 7-35 mass% is further more preferable Preferably, 8 to 30% by mass is particularly preferable.
The composition of the present invention may contain only one type of polymerizable compound, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<Multifunctional thiol compound>
The coloring composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of accelerating the reaction of the above-mentioned polymerizable compound. The polyfunctional thiol compound is preferably a secondary alkanethiol, and in particular, a compound represented by the following general formula (I) is preferable.

一般式（Ｉ）中、ｎは２〜４の整数を表し、Ｌ¹は２〜４価の連結基を表し、Ｌ²は単結合または２価の連結基を表す。 General formula (I)

In general formula (I), n represents an integer of 2 to 4, L ¹ represents a divalent to tetravalent linking group, and L ² represents a single bond or a divalent linking group.

L ¹ is preferably an aliphatic group having 2 to 12 carbon atoms, or a group consisting of a combination of an aliphatic group having 2 to 12 carbon atoms and a heterocyclic group. The heterocyclic group may be monocyclic or polycyclic, but is preferably monocyclic. The heterocyclic group preferably contains a nitrogen atom as a hetero atom.
When L ² represents a divalent linking group, an alkylene group having 1 to 3 carbon atoms is preferable, and a methylene group is more preferable.
Specific examples of the polyfunctional thiol compound include the following compounds.

The content of the polyfunctional thiol compound in the coloring composition of the present invention is preferably 0.01 to 8.9% by mass, and more preferably 0.1 to 6.4% by mass with respect to the total solid content excluding the solvent. preferable.
The polyfunctional thiol can be used singly or in combination of two or more. When two or more types of polyfunctional thiol compounds are contained, the total amount thereof is preferably in the above range.

<Solvent>
The coloring composition of the present invention contains a solvent.
The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the coloring composition, but in particular, the solubility, coatability and safety of UV absorbers, alkali soluble resins and dispersants, etc. It is preferable to be selected in consideration of Moreover, when preparing the coloring composition in this invention, it is preferable to contain at least 2 types of solvent.

  As the solvent, for example, esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, Alkyl oxyacetate (eg methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc)), 3-oxypropionic acid alkyl ester (Eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.) ), 2-Oki Propionic acid alkyl esters (eg, methyl 2-hydroxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc. (eg, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, 2-methoxypropion) Propyl, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (eg 2-methoxy-2-methyl) Methyl propionate, ethyl 2-ethoxy-2-methyl propionate etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate etc. And as ethers, For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, Propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like, and as ketones, for example, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, cyclopentanone and the like, and as aromatic hydrocarbons, examples For example, toluene, xylene and the like are preferably mentioned.

  It is also preferable to mix two or more of these solvents from the viewpoint of the solubility of the ultraviolet absorber and the alkali-soluble resin, the improvement of the coated surface condition, and the like. In this case, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl are particularly preferable in this case. It is a mixed solution composed of two or more selected from carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.

The content of the solvent in the coloring composition is preferably such that the total solid concentration of the composition is 5 to 80% by mass, more preferably 5 to 60% by mass, from the viewpoint of coatability. An amount of 50% by mass is particularly preferred.
The composition of the present invention may contain only one type of solvent, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.
<Pigment>
The coloring composition of the present invention preferably further contains a pigment, and more preferably contains a pigment having a phthalocyanine skeleton.
As the pigment used in the present invention, various conventionally known inorganic pigments or organic pigments can be used, and it is preferable to use an organic pigment. The pigment preferably has high transmittance.

  Examples of inorganic pigments include metal compounds represented by metal oxides, metal complex salts, etc. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And metal complex oxides.

As an organic pigment, for example,
C. I. Pigment yellow 11, 24, 31, 53, 83, 93, 99, 108, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 179, 209, 220, 224, 242, 254, 255, 264, 270;
C. I. Pigment violet 19, 23, 32, 39;
C. I. Pigment blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37, 58;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1;
Etc. can be mentioned.

  The following can be mentioned as a pigment which can be preferably used in the present invention. However, the present invention is not limited to these.

C. I. Pigment yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185,
C. I. Pigment orange 36, 71,
C. I. Pigment red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264,
C. I. Pigment violet 19, 23, 32,
C. I. Pigment blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment green 7, 36, 37, 58;
C. I. Pigment black 1

  These organic pigments can be used alone or in various combinations in order to adjust the spectrum and to improve the color purity. The specific example of the said combination is shown below. For example, as red pigments, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments And the like can be used. For example, as anthraquinone pigments, C.I. I. Pigment red 177, and examples of perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment red 224, and examples of the diketopyrrolopyrrole pigment include C.I. I. Pigment red 254, and C.I. I. The mixing with pigment yellow 139 is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. If it is 100: 4 or less, it is difficult to suppress the light transmittance of 400 nm to 500 nm, and if it is 100: 51 or more, the main wavelength tends to be a short wavelength and color resolution may not be able to be improved. In particular, the range of 100: 10 to 100: 30 is optimum as the above mass ratio. In addition, in the case of the combination of red pigments, it can adjust according to the spectroscopy to be calculated | required.

  Further, as the green pigment, it is possible to use a halogenated phthalocyanine-based pigment alone or a mixture thereof with a disazo-based yellow pigment, a quinophthalone-based yellow pigment, an azomethine-based yellow pigment or an isoindoline-based yellow pigment. For example, as such an example, C.I. I. Pigment greens 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. The mixing with pigment yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. As said mass ratio, the range of 100: 30-100: 120 is especially preferable.

  As a blue pigment, a phthalocyanine-based pigment can be used alone, or a mixture of this with a dioxazine-based purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 and C.I. I. The mixing with pigment violet 23 is preferred. The mass ratio of the blue pigment to the purple pigment is preferably 100: 0 to 100: 100, more preferably 100: 10 or less.

  In addition, carbon, titanium black, iron oxide, titanium oxide alone or in combination is used as a pigment for the black matrix, and a combination of carbon and titanium black is preferable. The mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.

  The coloring composition of the present invention is preferably blended with a pigment other than black, and is suitable for a blue pigment.

When used for color filters, the primary particle size of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. The primary particle size of the pigment is more preferably 5 to 75 nm, still more preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
The primary particle size of the pigment can be measured by a known method such as an electron microscope.

  Among them, the pigment is preferably a pigment selected from anthraquinone pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, quinophthalone pigments, isoindoline pigments, azomethine pigments, and dioxazine pigments. In particular, C.I. I. Pigment red 177 (anthraquinone pigment), C.I. I. Pigment red 254 (diketopyrrolopyrrole pigment), C.I. I. Pigment green 7, 36, 58, C.I. I. Pigment blue 15: 6 (phthalocyanine pigment), C.I. I. Pigment yellow 138 (quinophthalone pigment), C.I. I. Pigment yellow 139, 185 (isoindoline pigment), C.I. I. Pigment yellow 150 (azomethine pigment), C.I. I. Pigment Violet 23 (dioxazine pigment) is particularly preferred.

When a pigment is added to the composition of the present invention, the content of the pigment is preferably 10 to 70% by mass, more preferably 20 to 60% by mass with respect to all the components excluding the solvent contained in the coloring composition. %, More preferably 25 to 50% by mass.
The composition of the present invention may contain only one type of pigment, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

The coloring composition of the present invention may contain known dyes. For example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, JP-B-2592207, U.S. Pat. No. 4,808,501, U.S. Pat. Specification, U.S. Pat. No. 505,950, U.S. Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, etc. The dyes disclosed in can be used. Chemical structures include pyrazole azo, pyrromethene, anilinoazo, triphenylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine Dye can be used.
Further, as the dye, a dye multimer may be used. As a pigment | dye multimer, the compound described in Unexamined-Japanese-Patent No. 2011-213925, Unexamined-Japanese-Patent No. 2013-041097 grade | etc., Is mentioned.

<Photoinitiator>
It is preferable that the coloring composition of this invention contains a photoinitiator from a viewpoint of a further sensitivity improvement.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to light rays visible from the ultraviolet region are preferable. In addition, it may be an activator that produces an action with a photoexcited sensitizer and generates active radicals, or may be an initiator that initiates cationic polymerization depending on the type of monomer.
The photopolymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (330 nm to 500 nm is more preferable).

  As the photopolymerization initiator, for example, a halogenated hydrocarbon derivative (for example, one having a triazine skeleton, one having an oxadiazole skeleton, etc.), an acylphosphine compound such as an acyl phosphine oxide, a hexaarylbiimidazole, an oxime derivative And oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenones and the like, with preference given to oxime compounds.

  From the viewpoint of exposure sensitivity, trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallyl imidazole dimers, oniums Compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.

トリアリールイミダゾール化合物、ベンゾイミダゾール化合物としては、以下の化合物が例示される。

More preferably, trihalomethyl triazine compounds, α-amino ketone compounds, acyl phosphine compounds, phosphine oxide compounds, oxime compounds, triallyl imidazole dimers, triaryl imidazole compounds, benzimidazole compounds, onium compounds, benzophenone compounds, acetophenone compounds Particularly preferred is at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, oxime compounds, triallylimidazole compounds, benzophenone compounds, triarylimidazole compounds and benzimidazole compounds. The triarylimidazole compound may also be a mixture with benzimidazole.
Specifically, the following compounds are exemplified as the trihalomethyl triazine compound. Ph is a phenyl group.

The following compounds are illustrated as a triaryl imidazole compound and a benzimidazole compound.

A commercial item can also be used as a trihalomethyl triazine compound, for example, TAZ-107 (made by Midori-Chemical company) can also be used.
In particular, when the coloring composition of the present invention is used for the preparation of a color filter provided in a solid-state imaging device, since it is necessary to form a fine pattern in a sharp shape, there are residues on the unexposed area together with curability. Development is important. From such a viewpoint, it is particularly preferable to use an oxime compound as the polymerization initiator. In particular, when forming a fine pattern in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of addition of the polymerization initiator also needs to be suppressed low. In consideration of these points, it is particularly preferable to use an oxime compound as the photopolymerization initiator (D) for forming a fine pattern as in a solid-state imaging device.

  As a halogenated hydrocarbon compound having a triazine skeleton, for example, Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), compounds described in GB 1 388 492, compounds described in JP-A 53-133428, compounds described in DE 33 37 024, F. C. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-58241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Patent No. 4212976 And compounds described in paragraph 0075 of JP-A-2013-077009, and the like.

  Moreover, an acridine derivative is illustrated as a photoinitiator other than the above. Specifically, the compound etc. which are described in Paragraph No. 0076 of Unexamined-Japanese-Patent No. 2013-077009 are mentioned, These content is integrated in this-application specification.

  As a ketone compound, the compound as described in stage No. 0077 of Unexamined-Japanese-Patent No. 2013-077009 etc. are mentioned, for example, These content is integrated in this-application specification.

As the photopolymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acyl phosphine compound can also be suitably used. More specifically, for example, an aminoacetophenone-based initiator described in JP-A-10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can also be used.
As a hydroxyacetophenone type initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (brand name: all are BASF Corporation make) can be used. As aminoacetophenone initiators, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF Corporation) can be used. As the aminoacetophenone initiator, a compound described in JP-A-2009-191179 in which the absorption wavelength is matched to a long wave light source such as 365 nm or 405 nm can also be used. Moreover, IRGACURE-819 and DAROCUR-TPO (brand name: all are BASF Corporation make) which are commercial items can be used as an acyl phosphine type initiator.

  As a photoinitiator, More preferably, an oxime compound is mentioned. As a specific example of an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-80068, and the compound of Unexamined-Japanese-Patent No. 2006-342166 can be used.

  Examples of oxime compounds such as oxime derivatives suitably used as a photopolymerization initiator in the present invention include 3-benzoximinobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimino Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoximino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like can be mentioned.

As oxime compounds, J.I. C. S. Perkin II (1979) pp. 1653-1660), J.F. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. The compounds described in JP-A-2000-80068, JP-A-2000-80068, JP-A-2004-534797, JP-A-2006-342166, and the like can be given.
Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also suitably used.
Also, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (above, made by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), Adeka ARKRUZ It is also possible to use commercially available products such as NCI-831 and Adeka ARKLS NCI-930 (manufactured by Adeka).

  Further, as oxime compounds other than those described above, compounds described in JP-T-2009-519904, in which an oxime is linked to the carbazole N-position, and compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced in the benzophenone moiety, Compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039, in which a nitro group is introduced into a dye structure, ketooxime compounds described in WO2009-131189, triazine skeleton and oxime skeleton have the same molecule The compound described in U.S. Pat. No. 7,556,910, which is contained in the inside, the compound described in JP-A 2009-221114 having an absorption maximum at 405 nm and good sensitivity to a g-line light source, or the like may be used.

Preferably, the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A can also be suitably used. Among cyclic oxime compounds, cyclic oxime compounds fused to a carbazole dye described in JP-A-2010-32985 and JP-A-2010-185072 have high light absorption and high sensitivity. preferable.
In addition, the compound described in JP-A-2009-242469, which has an unsaturated bond at a specific site of the oxime compound, can also be suitably used, since high sensitivity can be achieved by regenerating the active radical from the polymerization inactive radical. it can.

Especially preferably, the oxime compound which has a specific substituent shown by Unexamined-Japanese-Patent No. 2007-269779, and the oxime compound which has a thioaryl group shown by Unexamined-Japanese-Patent No. 2009-191061 are mentioned.
Specifically, as an oxime compound which is a photopolymerization initiator, a compound represented by the following general formula (OX-1) is preferable. In addition, the N—O bond of the oxime may be an oxime compound of (E) form, an oxime compound of (Z) form, or a mixture of (E) form and (Z) form. .

In General Formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent nonmetal atomic group.
Examples of the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group and an arylthiocarbonyl group. Also, these groups may have one or more substituents. Moreover, the substituent mentioned above may be further substituted by the other substituent.
Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, an aryl group and the like.

  The alkyl group is preferably an alkyl group having a carbon number of 1 to 30, and specifically, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, octadecyl group, isopropyl group , Isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl, 2-ethylhexyl, phenacyl, 1-naphthoylmethyl, 2-naphthoyl Methyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group, 3-fluorophena group Sill, 3-trifluoromethylphenacyl and 3-nitrof Nasir group can be exemplified.

  The aryl group is preferably an aryl group having a carbon number of 6 to 30, and specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group Group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 9-fluorenyl group, terphenyl group, quarter phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group, o- Cumenyl group, m-cumenyl group and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, ternaphthalenyl group, quarternaphthalenyl group, heptalenyl group, biphenylenyl group, indasenyl group, fluoranthenyl group, acenaphthyrenyl group, aceanthrilele Group, phenalenyl group, fluorenyl group, anthryl group, Biantrase Group, teranthracenyl group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, Examples include tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, trinaphthyrenyl group, heptaphenyl group, heptacenyl group, pyranthrenyl group, and ovalenyl group.

  The acyl group is preferably an acyl group having a carbon number of 2 to 20. Specifically, acetyl group, propanoyl group, butanoyl group, trifluoroacetyl group, pentanoyl group, benzoyl group, 1-naphthoyl group, 2-naphthoyl group , 4-Methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxybenzoyl group, 2-butoxybenzoyl group Group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, and 4-methoxybenzoyl group can be exemplified. .

  The alkoxycarbonyl group is preferably an alkoxycarbonyl group having a carbon number of 2 to 20, and specifically, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, decyl Examples thereof include an oxycarbonyl group, an octadecyloxycarbonyl group, and a trifluoromethyloxycarbonyl group.

  Specific examples of the aryloxycarbonyl group include phenoxy carbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4-phenylsulfanylphenyloxycarbonyl group, 4-dimethylamino Phenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group , 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyl Alkoxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and a 4-methoxy phenyloxy carbonyl group can be exemplified.

The heterocyclic group is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom.
Specifically, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thianthrenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxatyi. Group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group 4H-quinolizinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group Group Midinyl, phenanthrolinyl, phenazinyl, phenalzazinyl, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl, phenoxazinyl, isochromanyl, chromanyl, pyrrolidinyl, pyrrolinyl, imidazolidinyl, imidazolinyl, pyrazolidinyl And pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, and thioxantholyl group can be exemplified.

  Specific examples of the alkylthiocarbonyl group include methylthiocarbonyl group, propylthiocarbonyl group, butylthiocarbonyl group, hexylthiocarbonyl group, octylthiocarbonyl group, decylthiocarbonyl group, octadecylthiocarbonyl group, and trifluoromethylthiocarbonyl group. Can be illustrated.

  Specifically as the arylthiocarbonyl group, 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethylaminophenylthiocarbonyl group , 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group, 3-triphenylthiocarbonyl group Fluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group, And, and a 4-methoxyphenylthiocarbonyl group.

  In Formula (OX-1), the monovalent substituent represented by B represents an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. Also, these groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified. Moreover, the substituent mentioned above may be further substituted by the other substituent.

Among them, particularly preferred is the structure shown below.
In the following structures, Y, X and n are respectively synonymous with Y, X and n in General Formula (OX-2) described later, and preferred examples are also the same.

As a bivalent organic group represented by A in Formula (OX-1), a C1-C12 alkylene group, a cycloalkylene group, an alkynylene group is mentioned. Also, these groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified. Moreover, the substituent mentioned above may be further substituted by the other substituent.
Among them, as A in the formula (OX-1), from the viewpoint of enhancing sensitivity and suppressing coloring due to heating and aging, unsubstituted alkylene group, alkyl group (for example, methyl group, ethyl group, tert-butyl group, dodecyl) Group) substituted alkylene group, alkenyl group (eg, vinyl group, allyl group) substituted alkylene group, aryl group (eg, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group) Groups, phenanthryl groups, styryl groups) -substituted alkylene groups are preferred.

The aryl group represented by Ar in the formula (OX-1) is preferably an aryl group having a carbon number of 6 to 30, and may have a substituent. As the substituent, those similar to the substituents introduced into the substituted aryl group mentioned as the specific example of the aryl group which may have a substituent can be exemplified.
Among them, a substituted or unsubstituted phenyl group is preferable from the viewpoint of enhancing sensitivity and suppressing coloring due to heating and aging.

  In formula (OX-1), the structure of “SAr” formed of Ar in formula (OX-1) and S adjacent thereto is preferably a structure shown below in view of sensitivity. Me represents a methyl group, and Et represents an ethyl group.

  The oxime compound is preferably a compound represented by the following general formula (OX-2).

  In general formula (OX-2), R and X each independently represent a monovalent substituent, A and Y each independently represent a divalent organic group, Ar represents an aryl group, and n is 0 to 0. It is an integer of five. R, A and Ar in General Formula (OX-2) have the same meanings as R, A and Ar in General Formula (OX-1), and preferred examples are also the same.

  As the monovalent substituent represented by X in General Formula (OX-2), an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyloxy group, an acyl group, an alkoxycarbonyl group, an amino group, a heterocyclic ring And halogen atoms. Also, these groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified. Moreover, the substituent mentioned above may be further substituted by the other substituent.

Among these, as X in the general formula (OX-2), an alkyl group is preferable from the viewpoint of solvent solubility and improvement of absorption efficiency in a long wavelength region.
Moreover, n in Formula (2) represents the integer of 0-5, and the integer of 0-2 is preferable.

  Examples of the divalent organic group represented by Y in General Formula (OX-2) include the structures shown below. In the groups shown below, "*" represents a bonding position between Y and the adjacent carbon atom in formula (OX-2).

  Among them, the following structure is preferable from the viewpoint of high sensitivity.

  Furthermore, it is preferable that an oxime compound is a compound represented by the following general formula (OX-3) or (OX-4).

In the general formulas (OX-3) or (OX-4), R and X each independently represent a monovalent substituent, A represents a divalent organic group, Ar represents an aryl group, and n is 0 It is an integer of ~ 5. )
R, X, A, Ar and n in the general formula (OX-3) or (OX-4) have the same meanings as R, X, A, Ar and n in the general formula (OX-2) Preferred examples are also the same.

  Specific examples (C-4) to (C-13) of oxime compounds suitably used below are shown below, but the present invention is not limited thereto.

  The oxime compound has a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, preferably an absorption wavelength in a wavelength range of 360 nm to 480 nm, and particularly preferably one having a high absorbance at 365 nm and 455 nm.

The oxime compound preferably has a molar absorption coefficient at 365 nm or 405 nm of 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, from the viewpoint of sensitivity. And particularly preferably 1,000.
The molar absorption coefficient of the compound may be a known method, and specifically, for example, 0.01 g of ethyl acetate solvent is used in an ultraviolet-visible spectrophotometer (Varry Carry-5 spctrophotometer) It is preferable to measure at a concentration of / L.

When the coloring composition of the present invention contains a photopolymerization initiator, the content of the photopolymerization initiator is preferably 0.1 to 50% by mass based on the total solid content of the coloring composition, and more preferably It is 0.5-30 mass%, More preferably, it is 1-20 mass%. Within this range, better sensitivity and patternability can be obtained.
The composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<Dispersing resin agent>
When the colored composition of the present invention has a pigment, a dispersing resin agent (pigment dispersing agent) can be used in combination as desired.
As a dispersing resin agent which can be used in the present invention, polymer dispersing agents [eg, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate (Meth) acrylic copolymers, naphthalene sulfonic acid formalin condensates], and surfactants such as polyoxyethylene alkyl phosphates, polyoxyethylene alkyl amines, alkanolamines, and pigment derivatives etc. Can.
Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.

  Examples of terminal-modified polymers having anchor sites on the pigment surface include polymers having a phosphoric acid group at the ends described in JP-A-3-112992 and JP-A-2003-533455, etc., JP-A-2002 Examples thereof include polymers having a sulfonic acid group at the terminal as described in JP-273191 and the like, and polymers having a partial skeleton and a heterocyclic ring of an organic dye described in JP-A-9-77994 and the like. In addition, polymers described in JP-A-2007-277514 in which two or more anchor sites (acid group, basic group, partial skeleton of organic dye, heterocyclic ring, etc.) are introduced at the polymer end are also used. It is excellent in dispersion stability and preferable.

  As a graft type polymer having an anchor site to the pigment surface, for example, polyester type dispersants and the like can be mentioned. Specifically, JP-A-54-37082, JP-A-8-507960, and JP 2009-258668, etc., reaction product of poly (lower alkylenimine) and polyester, JP-A 9-169821, reaction product of polyallylamine and polyester, JP 10-339949 Copolymers of macromonomers and nitrogen atom monomers described in JP-A 2004-37986, International Publication Pamphlet WO 2010/110491, etc., JP-A 2003-238837, JP-A 2008-9426, JP-A Graft having a partial skeleton or a heterocyclic ring of the organic dye described in JP-A-2008-81732, etc. Polymer, and a copolymer of a macromonomer and acid group-containing monomers described in JP 2010-106268 Publication. In particular, the amphoteric dispersion resin having a basic group and an acidic group described in JP-A-2009-203462 has the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored composition using the pigment dispersion. Particularly preferred from the viewpoint of

  A known macromonomer can be used as a macromonomer to be used when producing a graft type polymer having an anchor site to a pigment surface by radical polymerization, and a macromonomer AA-6 (terminally manufactured by Toagosei Co., Ltd.) Poly (methyl methacrylate) in which the group is methacryloyl, AS-6 (polystyrene in which the terminal group is methacryloyl), AN-6S (copolymer of styrene and acrylonitrile in which the terminal is methacryloyl), AB-6 Butyl acrylate having a methacryloyl group as the terminal group, Plaxel FM 5 (ε-caprolactone 5 molar equivalent adduct of 2-hydroxyethyl methacrylate) manufactured by Daicel Chemical Industries, Ltd., FA 10 L (2-hydroxyethyl acrylate) ε-caprolactone (10 molar equivalent adducts), and JP-A-2-272 The polyester type macromonomer etc. which are described in the 009 gazette are mentioned. Among these, polyester-based macromonomers that are particularly excellent in flexibility and lipophilicity are particularly preferable from the viewpoint of the dispersibility of the pigment dispersion, the dispersion stability, and the developability exhibited by the colored composition using the pigment dispersion, Furthermore, polyester-based macromonomers represented by polyester-based macromonomers described in JP-A-2-272009 are particularly preferable.

  As a block type polymer which has an anchor site | part to the pigment surface, the block type polymer of Unexamined-Japanese-Patent No. 2003-49110, 2009-52010 grade | etc., Is preferable.

As a dispersing resin agent, an oligoimine resin containing a nitrogen atom in at least one of the main chain and the side chain is also preferable. The oligoimine resin has a repeating unit having a partial structure X having a functional group having a pKa of 14 or less and a side chain containing a side chain Y having 40 to 10,000 atoms, and at least a main chain and a side chain Resins having a basic nitrogen atom on one side are preferred.
The oligoimine resin can be referred to, for example, the description in paragraphs 0225 to 0267 of JP-A-2014-063125, the contents of which are incorporated herein.

  The dispersion resin agent which can be used in the present invention is also available as a commercial product, and specific examples thereof include “DA-7301” manufactured by Tochigi Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate) manufactured by BYK Chemie ), 107 (carboxylic acid ester), 110, 111 (copolymer containing an acid group), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) "," BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid), EFKA "EFKA 4047, 4050 to 4010 to 4165 (polyurethane type), EFKA 4330 to 4340 (block copolymer), 4400 to 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylic acid ), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," ADISPAR PB 821, PB 822, PB 880, PB 881 "manufactured by Ajinomoto Fan Techno Co., Ltd. "", "Poly flow No. 50E, No. 300 (acrylic copolymer)", manufactured by Kushimoto Chemical Co., Ltd. "Disparone KS-860, 873 SN, 874, # 2150 (aliphatic polyvalent carboxylic acid), # 7004 (poly Ether ester), DA-703-50, DA-705, DA-725 ”, Kao Corporation“ Demol RN, N (naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin) "Polycondensates" "," Hogenol L-18 (polymer polycarbo) Acid), "Emulgen 920, 930, 935, 985 (polyoxyethylene nonyl phenyl ether)", "Acetamine 86 (stearylamine acetate)", manufactured by Nippon Lubrizol Co., Ltd. "Sol Sparse 5000 (phthalocyanine derivative), 22000 ( Azo pigment derivative), 13240 (polyester amine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ", manufactured by Nikko Chemical Co., Ltd." NIKKOL T106 (Polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate), manufactured by Kawaken Fine Chemicals Co., Ltd. Hinoacto T-8000 E, etc., Shin-Etsu Chemical Co., Ltd. manufactured, organosiloxane polymer P341, Yusho Co., Ltd. “W001: cationic surfactant”, polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, Nonionic surfactants such as polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", manufactured by Morishita Sangyo Co., Ltd. "EFKA-46, EFKA-47" , EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450 ", Sannopco Co., Ltd." Dispers Aid 6, Dispers Aid , Disperse Aid 15, Dispers Aid 9100, etc., "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, P72, P95, F77, P84, F87, manufactured by ADEKA Corporation. P94, L101, P103, F108, L121, P-123 "and" Ionette (trade name) S-20 "manufactured by Sanyo Chemical Industries, Ltd., etc. may be mentioned.

  These dispersion resin agents may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant. The dispersing resin agent may be used in combination with an alkali-soluble resin together with a terminal-modified polymer having an anchor site on the pigment surface, a graft polymer, and a block polymer. As the alkali-soluble resin, (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain And the like, and particularly preferred is (meth) acrylic acid copolymer. Also, an N-substituted maleimide monomer copolymer described in JP-A-10-300922, an ether dimer copolymer described in JP-A-2004-300204, and a polymerizable group described in JP-A-7-319161. Also preferred are alkali-soluble resins containing

The following compounds can also be used as a dispersing resin agent.

In the coloring composition, when the dispersion resin agent is contained, the total content of the dispersion resin agent is preferably 1 to 80 parts by mass, and more preferably 5 to 70 parts by mass with respect to 100 parts by mass of the pigment. 10 to 60 parts by mass is more preferable.
The composition of the present invention may contain only one type of dispersing resin agent, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

Specifically, if a polymer dispersant is used, the amount thereof is preferably in the range of 5 to 100 parts by mass and 10 to 80 parts by mass in terms of mass with respect to 100 parts by mass of the pigment. It is more preferable that
When a pigment derivative is used in combination, the amount of the pigment derivative used is preferably in the range of 1 to 30 parts by mass in terms of mass and preferably in the range of 1 to 25 parts by mass with respect to 100 parts by mass of the pigment. Is more preferable, and the range of 1 to 20 parts by mass is particularly preferable.

  In the coloring composition, from the viewpoint of curing sensitivity and color density, the total content of the dye and the dispersant component is preferably 30 to 90 mass% with respect to the total solid content of the coloring composition, 35 It is more preferable that it is -80 mass%, and it is further more preferable that it is 40-75 mass%.

<< Alkali-soluble resin >>
The coloring composition of the present invention preferably further contains an alkali soluble resin.
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain) It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable. From the viewpoint of control of developability, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.

  Examples of groups promoting alkali solubility (hereinafter, also referred to as acid groups) include, for example, carboxyl groups, phosphoric acid groups, sulfonic acid groups, and phenolic hydroxyl groups, but they are soluble in organic solvents and developed with weak alkaline aqueous solutions. Possible are preferred, and (meth) acrylic acid is mentioned as being particularly preferred. These acid groups may be of only one type, or of two or more types.

As a monomer capable of providing an acid group after polymerization, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, 2-isocyanatoethyl (meth) The monomer etc. which have isocyanate groups, such as an acrylate, are mentioned. The monomers for introducing these acid groups may be only one type or two or more types. In order to introduce an acid group into an alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of providing an acid group after polymerization (hereinafter, may be referred to as "monomer for introducing an acid group"). ) May be polymerized as a monomer component.
In addition, when introduce | transducing an acidic radical by using as a monomer component the monomer which can provide an acidic radical after superposition | polymerization, the process for providing an acidic radical which is mentioned later after superposition | polymerization is needed.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. The polymerization conditions such as temperature, pressure, type of radical initiator and amount thereof, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization method can be easily set by those skilled in the art, and the conditions are determined experimentally. You can also do so.

  As the linear organic polymer used as the alkali-soluble resin, a polymer having a carboxylic acid in a side chain is preferable, and a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer Maleic acid copolymer, partially esterified maleic acid copolymer, alkali-soluble phenol resin such as novolak resin, etc., acid cellulose derivative having carboxylic acid in side chain, acid anhydride added to polymer having hydroxyl group Are listed. In particular, copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin. Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. As alkyl (meth) acrylate and aryl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, etc., vinyl compounds such as styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene Macromonomer, polymethylmethacrylate macromonomer, as N-position-substituted maleimide monomer described in JP-A-10-300922, may be mentioned N- phenylmaleimide, an N- cyclohexyl maleimide and the like. These other monomers copolymerizable with (meth) acrylic acid may be only one type, or two or more types.

  As the alkali-soluble resin, a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer") is essential. It is also preferable to include a polymer (a) formed by polymerizing monomer components to be used.

General formula (ED)

In formula (ED), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
General formula (ED2)

Thereby, the colored composition of the present invention can form a cured coating film which is extremely excellent not only in heat resistance but also in transparency. The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² in the general formula (ED) representing an ether dimer is not particularly limited, and, for example, methyl , Linear or branched alkyl groups such as ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; Alicyclic groups such as tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, 2-methyl-2-adamantyl; and the like; substituted with alkoxy such as 1-methoxyethyl or 1-ethoxyethyl An alkyl group; an alkyl group substituted with an aryl group such as benzyl; and the like. Among these, an acid such as methyl, ethyl, cyclohexyl, benzyl and the like, and a primary or secondary carbon substituent which is not easily released by heat is preferable in view of heat resistance.
In general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of general formula (ED2), the description of Unexamined-Japanese-Patent No. 2010-168539 can be considered into consideration.

  Specific examples of the ether dimer include, for example, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, n-Propyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) 2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl) -2,2 '-[Oxybis (methylene)] bis-2-propenoate, di (tert-amyl) -2,2'-[oxybis (methylene)] bis-2-propenoe Di (stearyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (2- Ethylhexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxy) Ethyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2'-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 '-[oxybis (methylene) )] Bis-2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tert-butyl ester) Lohexyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, di (tricyclodi) Decanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 ' And-[oxybis (methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate and the like. Among these, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 '-[oxybis (methylene)] bis-2-propenoate are preferred. One of these ether dimers may be used alone, or two or more thereof may be used. The structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.

（式（Ｘ）において、Ｒ¹は、水素原子またはメチル基を表し、Ｒ²は炭素数２〜１０のアルキレン基を表し、Ｒ³は、水素原子またはベンゼン環を含んでもよい炭素数１〜２０のアルキル基を表す。ｎは１〜１５の整数を表す。） In addition to the above, it is preferable to include an ethylenically unsaturated monomer (a) represented by the following formula (X) as a monomer to be copolymerized to the alkali-soluble resin.
Formula (X)

(In formula (X), R ¹ represents a hydrogen atom or a methyl group, R ² represents an alkylene group having 2 to 10 carbon atoms, and R ³ represents a hydrogen atom or a carbon atom having 1 to 7 carbon atoms which may contain a benzene ring. Represents an alkyl group of 20. n represents an integer of 1 to 15.)

In the formula (X), the number of carbon atoms of the alkylene group R ² is preferably 2-3. Although the carbon number of the alkyl group of R ³ is 1 to 20, more preferably 1 to 10, alkyl group of R ³ may include a benzene ring. Examples of the alkyl group containing a benzene ring represented by R ³ include a benzyl group and a 2-phenyl (iso) propyl group.

  As the ethylenically unsaturated monomer (a), ethylene oxide (EO) modified (meth) acrylate of phenol, EO of paracumyl phenol or propylene oxide (PO) modified (meth) acrylate, EO modified (meth) of nonyl phenol Acrylate, PO modified (meth) acrylate of nonylphenol, etc. are mentioned. Among these compounds, paracumylphenol-modified EO or PO (meth) acrylate has a higher dispersion effect.

  Moreover, in order to improve the crosslinking efficiency of the coloring composition in this invention, you may use alkali-soluble resin which has a polymeric group. As an alkali-soluble resin having a polymerizable group, an alkali-soluble resin containing an allyl group, a (meth) acrylic group, an allyloxyalkyl group or the like in a side chain is useful. Examples of the above-mentioned polymer containing a polymerizable group include Dianor NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (containing COOH containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd.,), Viscote R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF 200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UBC Co., Ltd.), and the like. As an alkali-soluble resin containing these polymerizable groups, an isocyanate group and an OH group are reacted in advance to leave one unreacted isocyanate group, and a compound containing a (meth) acryloyl group and an acrylic resin containing a carboxyl group And an unsaturated group-containing acrylic resin obtained by the reaction of an acrylic resin containing a carboxyl group and a compound having both an epoxy group and a polymerizable double bond in the molecule. Resin, acid pendant epoxy acrylate resin, polymerizable double bond-containing acrylic resin obtained by reacting acrylic resin containing OH group with dibasic acid anhydride having polymerizable double bond, acrylic resin containing OH group and isocyanate Resin in which a compound having a polymerizable group is reacted, JP-A-2002-229207 Resin obtained by basic treatment of a resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the α position or β position described in JP-A No. 2003-358814 and JP-A No. 2003-335814 And the like.

  As the alkali-soluble resin, in particular, a multicomponent copolymer comprising benzyl (meth) acrylate / (meth) acrylic acid copolymer and benzyl (meth) acrylate / (meth) acrylic acid / other monomers is suitable . In addition, benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer obtained by copolymerizing 2-hydroxyethyl methacrylate, as described in JP-A-7-140654. -Hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl Methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Are particularly preferred examples include a copolymer of benzyl methacrylate / methacrylic acid.

JP-A-2012-208494, paragraphs 0558 to 0571 (corresponding to [0685] to [0700] of corresponding US Patent Application Publication No. 2012/0235099) can be referred to as the alkali-soluble resin, and the contents thereof can be referred to. Are incorporated herein by reference.
Furthermore, the copolymer (B) described in paragraphs 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in the examples, paragraph 0088 to JP 2012-208474 A The binder resin described in 0098 and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP 2012-137531 A and the binder resin used in the examples, JP 2013- Binder resins described in paragraphs 0132 to 0143 of 024 934 and binder resins used in the examples, binder resins used in paragraphs 0092 to 0098 of JP 2011-242752 A and examples, Paragraph number of the open 2012-032770 gazette It preferred to use a binder resin according to 030-0072. The contents of these are incorporated herein. More specifically, the following resins are preferred.

The acid value of the alkali-soluble resin is preferably 30 mg KOH / g to 200 mg KOH / g, more preferably 50 mg KOH / g to 150 mg KOH / g, and particularly preferably 70 mg KOH / g to 120 mg KOH / g.
Moreover, as a weight average molecular weight (Mw) of alkali-soluble resin, 2,000-50,000 are preferable, 5,000-30,000 are more preferable, and 7,000-20,000 are especially preferable.

When the alkali-soluble resin is contained in the coloring composition, the content of the alkali-soluble resin is preferably 1 to 30% by mass, more preferably 1 to 25% by mass, with respect to the total solid content of the coloring composition. Particularly preferably, it is 1 to 20% by mass.
The composition of the present invention may contain only one alkali-soluble resin, or two or more alkali-soluble resins. When it contains two or more types, it is preferable that the total amount becomes the said range.

<< Crosslinking agent >>
A crosslinking agent may be additionally used in the coloring composition of the present invention to further increase the hardness of a cured film obtained by curing the coloring composition.
The crosslinking agent is not particularly limited as long as it can perform film curing by a crosslinking reaction, and for example, at least at least one selected from (a) epoxy resin, (b) methylol group, alkoxymethyl group, and acyloxymethyl group At least one substituent selected from melamine compounds, guanamine compounds, glycoluril compounds or urea compounds, (c) methylol groups, alkoxymethyl groups, and acyloxymethyl groups, which are substituted by one substituent; A phenol compound, a naphthol compound or a hydroxyanthracene compound is mentioned. Among them, polyfunctional epoxy resins are preferred.
For details of the specific example of the crosslinking agent and the like, the description in paragraphs [0134] to [0147] of JP-A-2004-295116 can be referred to.
When a crosslinking agent is contained in the coloring composition of the present invention, the compounding amount of the crosslinking agent is not particularly limited, but preferably 1 to 30% by mass, and 1 to 25% by mass of the total solid content of the composition. More preferable.
The composition of the present invention may contain only one type of crosslinking agent, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<< polymerization inhibitor >>
In the coloring composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during production or storage of the coloring composition.
As a polymerization inhibitor which can be used in the present invention, hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-) tert-Butylphenol), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), N-nitrosophenylhydroxyamine cerous salt and the like.
When the polymerization inhibitor is contained in the coloring composition of the present invention, the addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the entire composition.
The composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<< Surfactant >>
Various surfactants may be added to the coloring composition of the present invention from the viewpoint of further improving the coating properties. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone surfactant and the like can be used.

In particular, since the coloring composition of the present invention further improves the liquid properties (in particular, the fluidity) when prepared as a coating liquid by containing a fluorine-based surfactant, the uniformity of the coating thickness and the saving of the coating Liquidity can be further improved.
That is, in the case of forming a film using a coating liquid to which a coloring composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced to wet the surface to be coated The properties are improved, and the coatability on the surface to be coated is improved. For this reason, even in the case where a thin film of about several μm is formed with a small amount of liquid, it is effective in that film formation with a uniform thickness with small thickness unevenness can be more suitably performed.

  The fluorine content in the fluorine-based surfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass. The fluorine-based surfactant having a fluorine content in this range is effective in terms of the uniformity of the thickness of the coating film and the liquid saving property, and the solubility in the coloring composition is also good.

  Examples of fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F44, R30, F437, F475, F479, and the like. The F482, the F554, the F780, the F781 (above, made by DIC Corporation), the Florard FC430, the same FC431, the same FC171 (above, Sumitomo 3M Co., Ltd.), Surfron S-382, the same SC-101 The SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all manufactured by Asahi Glass Co., Ltd.) and the like can be mentioned.

  Specific examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerine ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Rusupasu 20000 (Lubrizol Japan Co., Ltd.), and the like.

  Specific examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid Co) polymer poly flow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.

  Specific examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), and the like.

As silicone type surfactant, for example, Toray Dow Corning Co., Ltd. product "Tore silicone DC3PA", "Tore silicone SH7PA", "Tore silicone DC11PA", "Tore silicone SH21PA", "Tore silicone SH28PA", "Tore silicone SH21PA" Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400, Momentive Performance Materials, Inc. "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", "TSF “4452”, “KP341”, “KF6001”, “KF6002” manufactured by Shin-Etsu Silicone Co., Ltd., “BYK307”, “BYK323”, “BYK330” manufactured by BIC Chemie, and the like.
When the coloring composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001% by mass to 2.0% by mass, more preferably the total solid content of the coloring composition. Is 0.005% by mass to 1.0% by mass.
The composition of the present invention may contain only one surfactant, or two or more surfactants. When it contains two or more types, it is preferable that the total amount becomes the said range.

<< Organic Carboxylic Acid, Organic Carboxylic Anhydride >>
The coloring composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride.
Specifically as an organic carboxylic acid compound, aliphatic carboxylic acid or aromatic carboxylic acid is mentioned. Examples of aliphatic carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, glycolic acid, acrylic acid and methacrylic acid, oxalic acid, malonic acid, succinic acid, Glutaric acid, adipic acid, pimelic acid, cyclohexanedicarboxylic acid, cyclohexene dicarboxylic acid, itaconic acid, citraconic acid, dicarboxylic acids such as maleic acid and fumaric acid, and tricarboxylic acids such as tricarballylic acid and aconic acid. Examples of aromatic carboxylic acids include carboxylic acids such as benzoic acid and phthalic acid in which a carboxyl group is directly bonded to a phenyl group, and carboxylic acids in which a carboxyl group is bonded from a phenyl group via a carbon bond. Among these, those having a molecular weight of 600 or less, particularly 50 to 500, and specifically, for example, maleic acid, malonic acid, succinic acid and itaconic acid are preferable.

  Examples of organic carboxylic acid anhydrides include aliphatic carboxylic acid anhydrides and aromatic carboxylic acid anhydrides. Specifically, for example, acetic acid anhydride, trichloroacetic acid anhydride, trifluoroacetic acid anhydride, tetrahydrophthalic acid anhydride Succinic anhydride, maleic anhydride, citraconic anhydride, itaconic anhydride, glutaric anhydride, 1,2-cyclohexene dicarboxylic acid anhydride, n-octadecyl succinic anhydride, 5-norbornene-2,3-dicarboxylic acid anhydride, etc. Aliphatic carboxylic anhydrides may be mentioned. Examples of the aromatic carboxylic anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, naphthalic anhydride and the like. Among these, those having a molecular weight of 600 or less, particularly 50 to 500, and specifically, for example, maleic anhydride, succinic anhydride, citraconic anhydride and itaconic anhydride are preferable.

When the coloring composition of the present invention contains an organic carboxylic acid or an organic carboxylic acid anhydride, the amount of the organic carboxylic acid and / or the organic carboxylic acid anhydride added is usually 0.01 to 10% by mass based on the total solids. Preferably it is 0.03-5 mass%, More preferably, it is the range of 0.05-3 mass%.
The composition of the present invention may contain only one type of organic carboxylic acid and / or organic carboxylic acid anhydride, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.
By adding the organic carboxylic acid having a molecular weight of 1000 or less and / or the organic carboxylic acid anhydride, it is possible to further reduce the undissolved matter of the coloring composition while maintaining high pattern adhesion. .

In addition to the above, various additives, for example, fillers, adhesion promoters, antioxidants, ultraviolet light absorbers, aggregation inhibitors and the like can be added to the coloring composition, if necessary. Examples of these additives include those described in paragraphs [0155] to [0156] of JP-A-2004-295116, the contents of which are incorporated in the present specification.
The coloring composition of the present invention may contain the sensitizer and the light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the same publication.
The composition of the present invention may contain only one type of each of the above components, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.

<Method of Preparing Colored Composition>
The coloring composition of the present invention is prepared by mixing the above-mentioned components.
In addition, when preparing a coloring composition, each component which comprises a coloring composition may be mix | blended collectively, and it may mix | blend sequentially, after melt | dissolving and disperse | distributing each component in a solvent. In addition, the order of introduction and working conditions at the time of blending are not particularly limited. For example, the composition may be prepared by dissolving and dispersing all the components simultaneously in a solvent, or, if necessary, appropriately setting each component as two or more solutions / dispersions at the time of use ) And these may be mixed to prepare a composition.

The colored composition of the present invention is preferably filtered with a filter for the purpose of removing foreign matter and reducing defects. It can be used without particular limitation as long as it is conventionally used for filtration applications and the like. For example, a fluorine resin such as PTFE (polytetrafluoroethylene), a polyamide-based resin such as nylon-6 or nylon-6, 6, a polyolefin resin such as polyethylene or polypropylene (PP) (including high density and ultrahigh molecular weight) Filter by Among these materials, polypropylene (including high density polypropylene) is preferable.
The pore size of the filter is suitably about 0.01 to 7.0 μm, preferably 0.01 to 3.0 μm, more preferably 0.01 to 2.5 μm, even more preferably 0.01 to 2.0 μm. And 0.05 to 0.5 μm are particularly preferred. By setting this range, it is possible to reliably remove fine foreign substances that inhibit the preparation of uniform and smooth colored radiation-sensitive compositions in the subsequent steps.
When using filters, different filters may be combined. At this time, the filtering with the first filter may be performed only once or may be performed twice or more.
Moreover, you may combine the 1st filter of the hole diameter which is different within the range mentioned above. The pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it is possible to select from various filters provided by Nippon Pall Ltd., Advantech Toyo Ltd., Nippon Entegris Ltd. (old Japan Microlith Ltd.) or Kitz Micro Filter Inc. .
The second filter can be formed of the same material as the first filter described above.
For example, the filtering with the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.

  The colored composition of the present invention is preferably used for forming a colored layer of a color filter. More specifically, since the colored composition of the present invention can form a cured film excellent in heat resistance and color characteristics, it is suitably used to form a colored pattern (colored layer) of a color filter. . In addition, the coloring composition of the present invention is suitably used for forming a coloring pattern such as a color filter used in an image display device such as a solid-state imaging device (for example, CCD, CMOS etc.) or a liquid crystal display (LCD). Can. Furthermore, it can be used suitably also as preparation applications, such as printing ink, inkjet ink, and a paint. Among them, color filters for solid-state imaging devices such as CCD and CMOS can be suitably used as a production application.

  The present invention also relates to a polymer having a repeating unit represented by the above general formula (A4-1) and / or the above general formula (A4-3). The present invention also relates to xanthene dyes represented by the above general formula (A5).

Cured Film, Pattern Forming Method, Color Filter, and Color Filter Manufacturing Method
Next, the cured film, the pattern formation method and the color filter in the present invention will be described in detail through the manufacturing method.
The cured film of the present invention is formed by curing the colored composition of the present invention. Such a cured film is preferably used for a color filter.

In the pattern forming method of the present invention, a colored composition layer is formed on a support using the colored composition of the present invention, and unnecessary portions are removed to form a colored pattern.
The pattern formation method of the present invention can be suitably applied to the formation of a colored pattern (pixel) of a color filter.
In the composition of the present invention, a color filter may be produced by patterning by a so-called photolithography method, or a pattern may be formed by dry etching.
That is, as a first production method of the color filter of the present invention, a step of applying a coloring composition on a support to form a coloring composition layer, a step of exposing the coloring composition layer in a pattern, and And a step of developing and removing the exposed portion to form a colored pattern.
In addition, as a second method for producing the color filter of the present invention, a step of forming a colored composition layer by applying a colored composition on a support and curing it to form a colored layer, a photoresist on a colored layer A method of manufacturing a color filter is exemplified, which includes a step of forming a layer, a step of patterning a photoresist layer by exposure and development to obtain a resist pattern, and a step of dry etching a colored layer using the resist pattern as an etching mask. Ru.
In the present invention, the photolithographic method is more preferable.
The details of these will be described below.

  Hereinafter, although each process in the pattern formation method of this invention is demonstrated in detail through the manufacturing method of the color filter for solid-state image sensors, this invention is not limited to this method. Hereinafter, the color filter for solid-state imaging device may be simply referred to as “color filter”.

<< Step of Forming a Colored Composition Layer >>
At the process of forming a coloring composition layer, the coloring composition of this invention is applied on a support body, and a coloring composition layer formation process is formed.

As a support that can be used in this process, for example, solid-state imaging in which an imaging element (light receiving element) such as a charge coupled device (CCD) or a complementary metal oxide semiconductor (CMOS) is provided on a substrate (for example, a silicon substrate) An element substrate can be used.
The colored pattern in the present invention may be formed on the imaging device forming surface side (front surface) of the substrate for a solid-state imaging device, or may be formed on the imaging device non-forming surface side (rear surface).
A light shielding film may be provided between colored patterns in the solid-state imaging device or on the back surface of the substrate for the solid-state imaging device.
In addition, if necessary, a subbing layer may be provided on the support to improve the adhesion with the upper layer, to prevent the diffusion of substances, or to planarize the substrate surface. The subbing layer may contain a solvent, an alkali-soluble resin, a polymerizable compound, a polymerization inhibitor, a surfactant, a photopolymerization initiator and the like, and each of these components may be added to the composition of the present invention described above. It is preferable to select suitably.

  As a method of applying the coloring composition of the present invention onto a support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing can be applied.

  Drying (pre-baking) of the colored composition layer applied on the support can be carried out at a temperature of 50 ° C. to 140 ° C. for 10 seconds to 300 seconds with a hot plate, an oven or the like.

<Step of forming a pattern by photolithography method>
<< Process to expose>
In the exposure step, the colored composition layer formed in the colored composition layer forming step is pattern-exposed through a mask having a predetermined mask pattern, using an exposure apparatus such as a stepper, for example. Thereby, a cured film is obtained.
As radiation (light) which can be used at the time of exposure, ultraviolet light such as g-ray and i-ray is particularly preferably used (particularly preferably i-ray). Irradiation dose (exposure dose) is more preferably 30mJ / cm ² ~1500mJ / cm ² is preferably ^{50mJ / cm 2 ~1000mJ / cm 2} , 80mJ / cm 2 ~500mJ / cm 2 is particularly preferred.

The thickness of the cured film (colored film) is preferably 1.0 μm or less, more preferably 0.1 μm to 0.9 μm, and still more preferably 0.2 μm to 0.8 μm.
By setting the film thickness to 1.0 μm or less, high resolution and high adhesion can be obtained, which is preferable.
Further, in this step, a cured film having a thin film thickness of 0.7 μm or less can also be suitably formed, and the obtained cured film is developed in a pattern forming step to be described later to form a thin film. Although it is possible to obtain a colored pattern excellent in developability, surface roughness suppression and pattern shape.

<< Development Process >>
Then, by performing an alkali development treatment, the colored composition layer in the non-light-irradiated portion in the exposure step is eluted in the aqueous alkali solution, and only the photocured portion remains.
As the developing solution, an organic alkaline developing solution which does not cause damage to the underlying imaging element or circuit is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is conventionally 20 seconds to 90 seconds. In order to remove the residue more, it may be implemented in 120 seconds to 180 seconds in recent years. Furthermore, in order to further improve the residue removability, the process of shaking off the developer every 60 seconds and further supplying the developer anew may be repeated several times.

As an alkaline agent used for a developing solution, for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide Organic alkaline compounds such as choline, pyrrole, piperidine and 1,8-diazabicyclo- [5,4,0] -7-undecene, and the concentration of these alkali agents is 0.001% to 10% by mass, An alkaline aqueous solution diluted with pure water so as to be preferably 0.01% by mass to 1% by mass is preferably used as a developer.
An inorganic alkali may be used for the developer, and as the inorganic alkali, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium borate, sodium metaborate and the like are preferable.
In addition, when using the developing solution which consists of such alkaline aqueous solution, generally it wash | cleans (rinses) with a pure water after image development.

Next, it is preferable to perform heat treatment (post bake) after drying. If a multicolored coloring pattern is to be formed, the above-described steps can be sequentially repeated for each color to produce a cured film. Thereby, a color filter is obtained.
Post-baking is a heat treatment after development to complete curing, and is usually heat-cured at 100 ° C. to 240 ° C., preferably 200 ° C. to 240 ° C.
This post-baking treatment is carried out continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulation dryer), high frequency heater or the like so that the coated film after development is under the above conditions. be able to.

<When forming a pattern by dry etching method>
When patterning by dry etching, the above-mentioned coloring composition is applied on a support to form a coloring composition layer, and a step of curing to form a coloring layer, and forming a photoresist layer on the coloring layer Preferably, the method includes the steps of: patterning the photoresist layer by exposure and development to obtain a resist pattern; and dry etching the colored layer using the resist pattern as an etching mask.
The dry etching can be performed using an etching gas with the colored layer as a mask and the patterned photoresist layer as a mask. Specifically, a positive or negative radiation sensitive composition is applied onto the colored layer and dried to form a photoresist layer. In the formation of the photoresist layer, it is preferable to further perform a pre-bake treatment. In particular, as a process for forming a photoresist, it is desirable that the heat treatment (PEB) after exposure and the heat treatment (post-bake treatment) after development be performed.

As a photoresist, for example, a positive type radiation sensitive composition is used. The positive type radiation sensitive composition may be a positive type photosensitive to radiation such as ultraviolet (g ray, h ray, i ray), far ultraviolet ray including excimer laser, etc., electron beam, ion beam and X ray. Positive resist compositions suitable for resists can be used. Among the radiation, g-ray, h-ray and i-ray are preferable, and i-ray is more preferable among them.
Specifically, a composition containing a quinone diazide compound and an alkali-soluble resin is preferable as the positive type radiation sensitive composition. The positive radiation-sensitive composition containing a quinonediazide compound and an alkali-soluble resin is that the quinonediazide group is decomposed by irradiation with light having a wavelength of 500 nm or less to form a carboxyl group, and as a result, it becomes alkaline soluble to alkaline insoluble. It is used. Since this positive photoresist has extremely excellent resolution, it is used for the fabrication of integrated circuits such as ICs and LSIs. A naphthoquinone diazide compound is mentioned as a quinone diazide compound. Examples of commercially available products include FHi 622 BC "(manufactured by Fujifilm Electronics Materials Co., Ltd.).

  The thickness of the photoresist layer is preferably 0.1 to 3 μm, more preferably 0.2 to 2.5 μm, and still more preferably 0.3 to 2 μm. In addition, application | coating of a photoresist layer can be suitably performed using the application method in a colored layer as stated above.

  Next, the photoresist layer is exposed and developed to form a resist pattern (patterned photoresist layer) provided with a group of resist through holes. The formation of the resist pattern can be carried out by appropriately optimizing the conventionally known photolithography technology without any particular limitation. By providing a resist through hole group in the photoresist layer by exposure and development, a resist pattern as an etching mask used in the next etching is provided on the colored layer.

  Exposure of the photoresist layer is carried out by subjecting a positive or negative radiation sensitive composition to exposure through g-ray, h-ray, i-ray or the like, preferably i-ray, through a predetermined mask pattern. Can. After exposure, development processing with a developer is performed to remove the photoresist in accordance with the area where the colored pattern is to be formed.

  Any developer can be used as the developer as long as it does not affect the coloring layer containing the dye and dissolves the exposed part of the positive resist and the uncured part of the negative resist, for example, various organic solvents. A combination or alkaline aqueous solution can be used. As the alkaline aqueous solution, an alkaline aqueous solution prepared by dissolving an alkaline compound so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 5% by mass, is suitable. Examples of the alkaline compound include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium borate, sodium metaborate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and the like can be mentioned. When an alkaline aqueous solution is used as a developing solution, washing treatment with water is generally performed after development.

  Next, using the resist pattern as an etching mask, patterning is performed by dry etching so that through holes are formed in the colored layer. Thereby, a coloring pattern is formed. The through hole group is provided in a checkered manner in the colored layer. Therefore, the first colored pattern in which the through holes are provided in the colored layer has a plurality of square-shaped first colored pixels in a checkered manner.

  Specifically, in the dry etching, the colored layer is dry etched using the resist pattern as an etching mask. Representative examples of dry etching include, for example, JP-A-59-126506, JP-A-59-46628, JP-A-58-9108, JP-A-58-2809, JP-A-57-148706, and JP-A-61-411102. There are methods described in each of the publications.

The dry etching is preferably performed in the following manner from the viewpoint of forming the pattern cross section closer to a rectangle or from the viewpoint of reducing damage to the support.
Using a mixed gas of fluorine-based gas and oxygen gas (O ₂ ), etching is performed to a region (depth) where the support is not exposed, and after this first-stage etching, nitrogen gas ( Second step etching using a mixed gas of N ₂ ) and oxygen gas (O ₂ ), preferably to the vicinity of the region (depth) where the support is exposed, and over-etching performed after the support is exposed And the form containing is preferable. Hereinafter, the specific method of dry etching, and the etching of the first stage, the etching of the second stage, and the over-etching will be described.

Dry etching is performed by obtaining etching conditions in advance by the following method.
(1) The etching rate (nm / min) in the first stage etching and the etching rate (nm / min) in the second stage etching are respectively calculated. (2) The time for etching the desired thickness in the first stage etching and the time for etching the desired thickness in the second stage etching are respectively calculated. (3) The first stage of etching is performed in accordance with the etching time calculated in (2) above. (4) The second stage of etching is performed in accordance with the etching time calculated in (2) above. Alternatively, the etching time may be determined by end point detection, and the second etching may be performed according to the determined etching time. (5) The over-etching time is calculated with respect to the total time of the above (3) and (4), and the over-etching is performed.

The mixed gas used in the etching step of the first step preferably contains a fluorine-based gas and an oxygen gas (O ₂ ) from the viewpoint of processing the organic material to be etched into a rectangular shape. In the first etching process, damage to the support can be avoided by etching to the area where the support is not exposed. Further, in the etching step of the second step and the over-etching step, damage to the support is performed after etching is performed to a region where the support is not exposed by the mixed gas of fluorine gas and oxygen gas in the etching step of the first step. From the viewpoint of avoidance, it is preferable to perform the etching process using a mixed gas of nitrogen gas and oxygen gas.

  It is important to determine the ratio of the amount of etching in the first step etching process to the amount of etching in the second step etching process so as not to lose the rectangularity due to the etching process in the first step etching step. It is. The ratio of the latter in the total etching amount (the sum of the etching amount in the first step etching step and the etching amount in the second step etching step) is preferably in the range of more than 0% and 50% or less 10 to 20% is more preferable. The etching amount refers to an amount calculated from the difference between the remaining film thickness of the film to be etched and the film thickness before etching.

  Also, the etching preferably includes an over-etching process. The over-etching process is preferably performed with the over-etching ratio set. Moreover, it is preferable to calculate the over-etching ratio from the etching processing time to be performed first. Although the over-etching ratio can be set arbitrarily, it is preferably 30% or less of the etching processing time in the etching step, and is 5 to 25% in terms of etching resistance of the photoresist and maintaining the rectangularity of the pattern to be etched. Is more preferable, and 10 to 15% is particularly preferable.

   Next, the resist pattern (ie, the etching mask) remaining after the etching is removed. The removal of the resist pattern preferably includes the steps of: applying a stripping solution or a solvent onto the resist pattern to make the resist pattern removable; and removing the resist pattern using cleaning water.

  As a step of applying a stripping solution or a solvent on the resist pattern to make the resist pattern removable, for example, a step of applying a stripping solution or a solvent on at least a resist pattern, and stagnating for a predetermined time for paddle development Can be mentioned. The time for which the stripping solution or solvent is stagnated is not particularly limited, but is preferably several tens of seconds to several minutes.

  Further, as a process of removing the resist pattern using cleaning water, for example, a process of removing the resist pattern by spraying cleaning water onto the resist pattern from a spray type or shower type spray nozzle can be mentioned. As washing water, pure water can be preferably used. In addition, examples of the injection nozzle include an injection nozzle in which the entire support is included in the injection range, and an injection nozzle which is a movable injection nozzle and whose movable range includes the entire support. When the spray nozzle is movable, the resist pattern can be removed more effectively by moving the support from the center to the end of the support twice or more during the process of removing the resist pattern to spray the washing water. be able to.

  The stripping solution generally contains an organic solvent, but may further contain an inorganic solvent. As the organic solvent, for example, 1) hydrocarbon compound, 2) halogenated hydrocarbon compound, 3) alcohol compound, 4) ether or acetal compound, 5) ketone or aldehyde compound, 6) ester compound 7) Polyhydric alcohol compounds, 8) carboxylic acids or acid anhydride compounds thereof, 9) phenolic compounds, 10) nitrogen-containing compounds, 11) sulfur-containing compounds, 12) fluorine-containing compounds. The stripping solution preferably contains a nitrogen-containing compound, and more preferably contains a non-cyclic nitrogen-containing compound and a cyclic nitrogen-containing compound.

The non-cyclic nitrogen-containing compound is preferably a non-cyclic nitrogen-containing compound having a hydroxyl group. Specifically, for example, monoisopropanolamine, diisopropanolamine, triisopropanolamine, N-ethylethanolamine, N, N-dibutylethanolamine, N-butylethanolamine, monoethanolamine, diethanolamine, triethanolamine and the like It is preferably monoethanolamine, diethanolamine or triethanolamine, more preferably monoethanolamine (H ₂ NCH ₂ CH ₂ OH). Further, as cyclic nitrogen-containing compounds, isoquinoline, imidazole, N-ethylmorpholine, ε-caprolactam, quinoline, 1,3-dimethyl-2-imidazolidinone, α-picoline, β-picoline, γ-picoline, 2- Pipecoline, 3-pipecoline, 4-pipecoline, piperazine, piperidine, pyrazine, pyridine, pyrrolidine, N-methyl-2-pyrrolidone, N-phenylmorpholine, 2,4-lutidine, 2,6-lutidine and the like, with preference given to Is N-methyl-2-pyrrolidone, N-ethyl morpholine, more preferably N-methyl-2-pyrrolidone (NMP).

  The stripping solution preferably contains a non-cyclic nitrogen-containing compound and a cyclic nitrogen-containing compound. Among them, as the non-cyclic nitrogen-containing compound, at least one selected from monoethanolamine, diethanolamine, and triethanolamine, and cyclic It is more preferable to contain at least one selected from N-methyl-2-pyrrolidone and N-ethyl morpholine as the nitrogen-containing compound, and it is further preferable to include monoethanolamine and N-methyl-2-pyrrolidone.

  When removing with the stripping solution, the resist pattern 52 formed on the first colored pattern 12 only needs to be removed, and the deposit as the etching product adheres to the side wall of the first colored pattern 12 However, the deposit may not be completely removed. The deposit means an etching product adhering to and deposited on the side wall of the colored layer.

  As the stripping solution, the content of the non-cyclic nitrogen-containing compound is 9 parts by mass to 11 parts by mass with respect to 100 parts by mass of the stripping solution, and the content of the cyclic nitrogen-containing compound is 100 parts by mass of the stripping solution. On the other hand, those which are 65 parts by mass or more and 70 parts by mass or less are desirable. The stripping solution is preferably one obtained by diluting a mixture of a non-cyclic nitrogen-containing compound and a cyclic nitrogen-containing compound with pure water.

  In addition, the manufacturing method of this invention may have a well-known process as a manufacturing method of the color filter for solid-state image sensors as processes other than the above as needed. For example, after performing the colored composition layer forming step, the exposure step and the pattern forming step described above, a curing step of curing the formed colored pattern by heating and / or exposure may be included, if necessary.

In addition, when the coloring composition according to the present invention is used, for example, clogging of the nozzle or piping of the discharge unit of the coating device or contamination due to adhesion, sedimentation or drying of the coloring composition or pigment in the coating device may occur. is there. Therefore, in order to efficiently clean the contamination caused by the coloring composition of the present invention, it is preferable to use the solvent for the above-mentioned composition as a cleaning solution. Also, JP-A-7-128867, JP-A-7-146562, JP-A-8-278637, JP-A-2000-273370, JP-A-2006-85140, JP-A-2006-291191, and the like. The washing | cleaning liquid as described in Unexamined-Japanese-Patent 2007-2101, 2007-2102, 2007-281523 etc. can also be used suitably as washing | cleaning removal of the coloring composition which concerns on this invention.
Among the above, alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferable.
These solvents may be used alone or in combination of two or more. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent having a hydroxyl group to the solvent having no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 80/20. A mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME), the ratio of which is particularly preferably 60/40. In addition, in order to improve the permeability of the cleaning solution to contaminants, the surfactant related to the composition described above may be added to the cleaning solution.

Since the color filter of the present invention uses the coloring composition of the present invention, it can perform exposure with an excellent exposure margin, and the formed coloring pattern (colored pixel) is excellent in the pattern shape and the surface of the pattern is rough Since the residue in the developing unit is suppressed, the color characteristic is excellent.
The color filter of the present invention can be suitably used for solid-state imaging devices such as CCDs and CMOSs, and is particularly suitable for high-resolution CCDs and CMOSs having one million pixels or more. The color filter for solid-state imaging device of the present invention can be used, for example, as a color filter disposed between a light receiving portion of each pixel constituting a CCD or a CMOS and a microlens for collecting light.

The film thickness of the colored pattern (colored pixel) in the color filter of the present invention is preferably 2.0 μm or less, more preferably 1.0 μm or less, and still more preferably 0.7 μm or less.
The size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less.

<Solid-state imaging device>
The solid-state imaging device of the present invention includes the color filter of the present invention described above. The configuration of the solid-state imaging device according to the present invention is the configuration provided with the color filter according to the present invention, and is not particularly limited as long as it functions as a solid-state imaging device. .

On a support, there are provided a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like, It has a light shielding film made of tungsten or the like in which only the light receiving portion of the photodiode is opened, and has a device protective film made of silicon nitride or the like formed on the light shielding film to cover the entire light shielding film and the photodiode light receiving portion It is a structure which has a color filter for solid-state image sensors of this invention on a device protective film.
Furthermore, a configuration having a condensing means (for example, a micro lens etc. hereinafter the same) on the device protective layer and under the color filter (closer to the support), or a constitution having a condensing means on the color filter Or the like.

<Image display device>
The color filter of the present invention can be used not only for the above solid-state imaging device but also for image display devices such as liquid crystal display devices and organic EL display devices, and is particularly suitable for use in liquid crystal display devices. The liquid crystal display device provided with the color filter of the present invention can display a high quality image excellent in display characteristics with good color tone of the display image.

  For the definition of the display device and details of each display device, for example, “Electronic display device (authored by Akio Sasaki, published by Industry Research Association, 1990)”, “Display device (authored by Ibuki, authored by Sangyo Tosho Co., Ltd.) It is described in the "New Year" issue. The liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industry Research Association, 1994)”. There is no restriction | limiting in particular in the liquid crystal display device which can apply this invention, For example, it can apply to the liquid crystal display device of various systems described in said "next-generation liquid crystal display technology."

The color filter of the present invention may be used in a color TFT liquid crystal display device. The color TFT liquid crystal display device is described, for example, in “Color TFT liquid crystal display (Kyoritsu Publishing Co., Ltd., published in 1996)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as IPS or other horizontal electric field drive method, MVA or other pixel division method, STN, TN, VA, OCS, FFS, R-OCB, etc. it can.
Further, the color filter in the present invention can also be used for a bright and high-definition color-filter on array (COA) system. In the COA type liquid crystal display device, the required characteristics for the color filter layer are required to have the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance, in addition to the usual required characteristics as described above. There is a thing. In the color filter of the present invention, since a pigment having excellent hue is used, the color purity, light transmittance, etc. are good and the coloration of the colored pattern (pixel) is excellent. Liquid crystal display device. In order to satisfy the required characteristics of low dielectric constant, a resin film may be provided on the color filter layer.
These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest trends in technology and market-(Toray Research Center, Research Division, 2001)".
Moreover, in this invention, it can use preferably also for the display of a micro-a red system (micro OLED). These image display methods are described, for example, on page 43 of "EL, PDP, LCD display-latest trends in technology and market-(Toray Research Center, Research Division, 2001)".

The liquid crystal display device provided with the color filter in the present invention is composed of various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, a viewing angle ensuring film, in addition to the color filter in the present invention. The color filter of the present invention can be applied to a liquid crystal display composed of these known members. For these members, for example, “'94 Liquid crystal display peripheral materials and chemicals market (Kentaro Shima, Inc., CMSC Co., Ltd. 1994 issue),” “Present state and future prospects of liquid crystal related market in 2003 (second volume) Co., Ltd. Fuji Chimera Research Institute, published in 2003).
For backlight, see SID meeting Digest 1380 (2005) (A. Konno et. Al), 18 to 24 pages of the monthly display, December 2005 (Yasuhiro Shima), 25 to 30 pages (Takaaki Yagi), etc. Have been described.

  When the color filter according to the present invention is used in a liquid crystal display device, high contrast can be realized when it is combined with a conventionally known cold cathode tube three wavelength tube, but red, green and blue LED light sources (RGB-LED) By using as a backlight, it is possible to provide a liquid crystal display device having high luminance and high color purity and good color reproducibility.

  Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples within the scope of the present invention. In addition, unless there is particular notice, "%" and "part" are mass references.

Synthesis Example of Dye Compound A-1

<Synthesis of Intermediate 1>
50 parts of DCSF (manufactured by Chuo Kasei Kagaku Co., Ltd.), 74.76 parts of 2,6-dimethylaniline, 27.58 parts of zinc chloride and 200 parts of sulfolane were added to a flask and stirred at an external temperature of 200 ° C. for 4 hours. Thereafter, the reaction solution obtained was allowed to cool to room temperature, and added dropwise to 500 parts of 2N hydrochloric acid, and the precipitated crystals were separated by filtration. The crystals were dispersed and washed with 300 parts of acetonitrile at 40 ° C., collected by filtration and air-dried for 10 hours to obtain 46.5 parts of an intermediate 1 (yield: 65.6%).

<Synthesis of Intermediate 2>
20 parts of Intermediate 1 and 106 parts of phosphorus oxychloride were charged into a flask and stirred at 60 ° C. for 2 hours. The resulting reaction solution was allowed to cool to room temperature, and the reaction solution was added dropwise to 1500 parts of ice water and stirred for 30 minutes. The obtained crystals were separated by filtration, washed with 200 parts of water, and blow-dried for 10 hours to obtain 18.5 parts (yield: 89.4%) of an intermediate 2.

<Synthesis of Dye Compound A-1>
7 parts of Intermediate 2 and 1.94 parts of trifluoromethyl sulfonamide were dissolved in 40 parts of chloroform, and 1.55 parts of triethylamine was added dropwise and stirred at room temperature for 1 hour. Thereafter, 100 parts of water was added to the obtained reaction solution and washed with water, and then the organic layer was separated. The organic layer was dried over sodium sulfate, purified by column chromatography, and concentrated under reduced pressure to obtain a dye compound A-1 (3 parts (yield: 36%)).
The ¹ H NMR spectrum was measured for the dye compound A-1. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 2.15-2.25 (12 H, m), 5.95-6.31 (4 H, m), 6.95-7.4 (8 H, m), 7.4-7.53 (1 H, m) ), 7.7-7.9 (2H, m), 8.11-8.25 (1H, m), 9.93-10.12 (2H, m).

Synthesis Example of Dye Compound A-2
A dye compound A-2 was prepared in the same manner as the above-mentioned dye compound A-1 except that trifluoromethylsulfonamide was changed to an equimolar bistrifluoromethylsulfonylmethane in the method of synthesizing the dye compound A-1. Synthesized.

＜化合物Ａ−１３＞
中間体３（３部）、トリエチルアミン０．７部を塩化メチレン１２部に溶解させ、ここに４．６部の中間体２を加え室温下で１時間撹拌させた。得られた反応液に水５０部を加えて水洗し、水洗後の反応溶液を硫酸マグネシウムにて乾燥後、シリカゲルカラムクロマトグラフィー（クロロホルム／メタノール＝８／２の展開溶媒）にて精製し、Ａ−１３を０．８部得た。

<Synthesis of Intermediate 3>
50 parts of p-acetoxystyrene, 150 parts of ethyl acetate, and 89.2 parts of a 28% methanol solution of sodium methoxide were charged in a flask and stirred at room temperature for 1 hour. To the resulting reaction solution was added 500 parts of 1 N hydrochloric acid water, and then the ethyl acetate layer was separated. The ethyl acetate layer was washed, and the washed ethyl acetate layer was dried over magnesium sulfate. The solution after drying was added with 4.63 parts of triethylamine, cooled to 0 ° C., and 1,3-bis (fluorosulfonyl) -1,1,2,2,3,3-hexafluorobutane (manufactured by Mitsubishi Materials Corporation) 13.8 parts of EF-3000) were dropped under cooling, and stirred for 30 minutes. Thereafter, 500 parts of an aqueous ammonia solution was added thereto and stirred for 30 minutes. The reaction solution was neutralized with 1 N hydrochloric acid water, then washed with 500 parts of saturated brine, dried over magnesium sulfate, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (chloroform / methanol = 8/2 developing solvent) to obtain 3.0 parts of Intermediate 3.
Intermediate 3

<Compound A-13>
Intermediate 3 (3 parts) and 0.7 parts of triethylamine were dissolved in 12 parts of methylene chloride, and 4.6 parts of Intermediate 2 were added thereto, and the mixture was stirred at room temperature for 1 hour. 50 parts of water is added to the obtained reaction solution and washed with water, and after washing with water, the reaction solution is dried with magnesium sulfate and then purified by silica gel column chromatography (developing solvent of chloroform / methanol = 8/2) to obtain A 0.8 parts of -13 were obtained.

<Synthesis of Dye Compound P-1>
2.7 parts of cyclohexanone are stirred at 90 ° C., 2 parts of A-13, 0.43 parts of methacrylic acid, and V601 (0.42 parts) manufactured by Wako Pure Chemical Industries, Ltd. are added to 6.4 parts of cyclohexanone with respect to the solution The solution was added dropwise over 1 hour and then stirred at 90.degree. C. for 3 hours. The resulting reaction solution was allowed to cool to room temperature. Thereafter, this reaction solution was dropped to 100 parts of methanol. The obtained crystals were separated by filtration, washed with 30 parts of methanol and dried under reduced pressure at 40 ° C. to obtain 1.8 parts of P-1.
The ¹ H NMR spectrum was measured for the dye compound P-1. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400. The measurement results are shown in FIG.

Synthesis Example of Dye Compounds P-2 to P-44
Dye compounds P-2 to P-44 were synthesized in the same manner as in the synthesis of dye compound P-1, except that the repeating units in dye compound P-1 were changed to those described in the following table.
¹ H NMR spectra were measured for dye compounds P-25 and P-29. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400. The measurement results are shown in FIGS.

比較化合物−２

比較化合物−３

The following compounds were used as comparative compound-1-comparative compound-3.
Comparative compound-1

Comparative compound-2

Comparative compound-3

Synthetic Example of Intermediate 4
10 parts of the above DCSF (manufactured by Chuo Kasei Kagaku Co., Ltd.), 10.5 parts of 2,6-diisopropylaniline and 40 parts of sulfolane were placed in a flask and stirred at an internal temperature of 80 ° C. for 5 hours. Then, 33.2 parts of 2, 6- diisopropyl aniline and 3.88 parts of magnesium chloride were added with respect to the reaction liquid, and it stirred at 125 degreeC for 48 hours. The resulting reaction solution was allowed to cool to room temperature, dropped into 400 parts of 2N hydrochloric acid, and the precipitated crystals were separated by filtration. The crystals were dispersed and washed with 200 parts of acetonitrile, collected by filtration, and the crystals obtained were subjected to air-drying for 10 hours to obtain 12 parts of an intermediate 4 (yield: 70.8%).
Synthetic Example of Intermediate 5
An intermediate 5 was synthesized in the same manner as the intermediate 2 except that the above intermediate 4 was used instead of the intermediate 1 used for the synthesis of the intermediate 2.

Synthesis Example of Dye Compound (A-40)
A dye compound (A-40) was synthesized in the same manner as the dye compound (A-1) except that Intermediate 5 was used instead of Intermediate 2 used for the synthesis of the dye compound (A-1).

Synthesis Example of Dye Compound A-41
The dye compound (A-40) was synthesized in the same manner as in the dye compound (A-40) except that DCSF, which is a starting material of the dye compound (A-40), was changed to fluorescein chloride.

Synthesis Example of Dye Compound A-42
The dye was synthesized by the same operation as the dye compound (A-40) except that pentafluorobenzenesulfonylamide was used instead of trifluoromethanesulfonylamide used for the synthesis of the dye compound (A-40). Pentafluorobenzenesulfonylamide is described, for example, in Bioorganic and Medicinal Chemistry, 2013, vol. 21, # 7 p. It synthesize | combined by the method as described in 2093-2106.
The ¹ H NMR spectrum was measured for the dye compound A-42. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 0.93 to 1.35 (24 H, m), 2.85 to 3.13 (4 H, m), 5.98 to 6.28 (2 H, m), 7.02 to 7.43 (11 H, m) ), 7.44-8.28 (3 H, m), 9.87-10.08 (2 H, m).

Synthesis Example of Dye Compound A-43
In place of trifluoromethanesulfonylamide used in the synthesis of the dye compound (A-40), benzenesulfonylamide is used, and in place of triethylamine, DBU (1, 8-diazabicyclo [5.4.0] undec-7-ene) The dye was synthesized in the same manner as the dye compound (A-40) except that
The ¹ H NMR spectrum was measured for the dye compound A-43. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 0.9-1.34 (24 H, m), 2.87-3.18 (4 H, m), 5.88-6.14 (2 H, m), 7.07-7.53 (16 H, m ), 7.53-8.21 (3H, m), 9.88-10.04 (2H, m).

Synthesis Example of Dye Compound A-44
Three parts of the dye compound (A-48) and 15 parts of N, N-dimethylacetamide were added to a three-necked flask, and stirred at room temperature, 0.3 part of acrylic acid chloride was added dropwise, and stirred at room temperature for 1 hour. Thereafter, the reaction solution was added dropwise to 100 parts of 1 M hydrochloric acid water, and the obtained crystals were separated by filtration. The crystals were washed with 50 parts of acetonitrile, and after filtration, the obtained crystals were dried for 10 hours with a blower drier set at 40 ° C. 3 parts (yield 95%) of pigment compounds (A-44) were obtained.
The ¹ H NMR spectrum was measured for the dye compound A-44. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 0.94-1.34 (24H, m), 2.82-3.14 (6H, m), 4.24-4.29 (2H, t) 5.76-6.14 (7H, m) 7.04-7.53 (8 H, m), 7.54-8.16 (4 H, m), 9.88-10.06 (2 H, m).

Synthesis Example of Dye Compound A-45
In a three-necked flask, 150 parts of pentafluorobenzenesulfonylamide, 49.8 parts of 2-mercaptoethanol and 1000 parts of methanol were added and stirred at room temperature, 64.5 parts of triethylamine was added dropwise, and stirred at room temperature for one hour. The methanol was concentrated under reduced pressure, and 900 parts of ethyl acetate, 900 parts of saturated brine and 100 parts of saturated aqueous sodium hydrogen carbonate solution were added to the residue for extraction. The organic layer is dried over magnesium sulfate, and the filtrate is concentrated to give 169 parts of 2,3,5,6-tetrafluoro-4-((2-hydroxyethyl) thio) benzenesulfonamide (yield 91). %)Obtained.
In a three-necked flask, 50 parts of 2,3,5,6-tetrafluoro-4-((2-hydroxyethyl) thio) benzenesulfonamide, 165 parts of N, N-dimethylacetamide, 2-isocyanatoethyl methacrylate (Showa Twenty-eight parts of electric lens Karenz MOI and 0.01 parts of neostan U-600 (manufactured by Nitto Kasei Co., Ltd.) were added, and the mixture was stirred at 60 ° C. for 2 hours. The reaction solution is allowed to cool to room temperature, and the mixture is partitioned with 600 parts of ethyl acetate and 600 parts of water, the organic layer is dried over magnesium sulfate, and the filtrate is concentrated under reduced pressure. To the obtained residue, 200 parts of chloroform is added and stirred, and the obtained crystal is filtered and dried by blowing at 40 ° C. for 10 hours to give 3-((((2-((2,3,5,6, -Tetrafluoro-4-sulfamoylphenyl) thio) carbonyl) amino) propyl methacrylate was obtained in 62.3 parts (yield 86%).
3-(((2-((2,3,5,6-tetrafluoro-4-sulfamoylphenyl) thio) in place of trifluoromethanesulfonylamide used for the synthesis of dye compound (A-40) The dye compound (A-45) was synthesized in the same manner as the compound (A-40) using (carbonyl) amino) propyl methacrylate.
The ¹ H NMR spectrum was measured for the dye compound A-45. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 0.95 to 1.35 (24 H, m), 1.84 to 1.9 (3 H, s), 2.85 to 3.15 (4 H, m), 3.15 to 3.3 (4 H, m) ), 4.0-4.18 (4H, m), 5.62-6.18 (4H, m), 7.03-7.43 (11H, m), 7.43-8.18 (3H) , M), 9.89-10.08 (2 H, m).

Synthesis Example of Dye Compound A-46
It synthesize | combined similarly to the pigment compound (A-13) except having changed the intermediate body 2 which is a raw material of a pigment compound (A-13) into the intermediate body 5.
The ¹ H NMR spectrum was measured for the dye compound A-46. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 0.95 to 1.38 (24 H, m), 2.83 to 3.12 (4 H, m), 5.33 to 5.39 (1 H, d), 5.85 to 6.16 (3 H, m) ), 6.73-7.52 (14H, m), 7.6-7.68 (2H, m), 7.7-7.9 (3H, m), 9.9-10.08 (2H) , M).

Synthesis Example of Dye Compound A-47
Add 20 parts of the dye compound (A-42), 3.08 parts of 6-mercaptohexanol, and 70 parts of N, N-dimethylformamide to a three-necked flask and stir with ice solution, and add 11 parts of DBU dropwise to the solution. It stirred. After extraction with 200 parts of 1 M hydrochloric acid water and 300 parts of ethyl acetate and then extraction with 400 parts of water, the organic layer was dried over magnesium sulfate, and then the filtrate was concentrated under reduced pressure. 80 parts of acetonitrile is added to the residue and stirred at 70 ° C. for 1 hour, followed by filtration, and the obtained crystals are air-dried at 40 ° C. for 10 hours to obtain 18 parts of an analogous intermediate of the dye compound (A-54) (yield 80 %) Got.
In a three-necked flask, 52 parts of a similar intermediate of the dye compound (A-54) and 390 parts of pyridine were added and stirred in an ice bath, and 28.8 parts of tosyl chloride was added in powder form. Thereafter, liquid separation is performed with 600 parts of 2 M hydrochloric acid water and 400 parts of chloroform, pyridine is removed from the organic layer, liquid separation is performed with 600 parts of saturated aqueous sodium hydrogen carbonate solution, and the organic layer is dried with magnesium sulfate The filtrate after filtration was concentrated. The residue is added with 500 parts of acetonitrile, stirred under heating reflux, filtered, and the obtained crystals are blown and dried at 40 ° C. for 10 hours, and 51 parts of the dye compound (A-47) (yield: 85.3%) Obtained in
The ¹ H NMR spectrum was measured for the dye compound A-47. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 0.95 to 1.33 (28 H, m), 1.33 to 1.55 (4 H, m), 2.83 to 3.12 (6 H, m), 4.0 to 4.04 (2 H, m) ), 5.89-6.14 (2H, m), 7.01-7.82 (17H, m), 8.06-8.17 (1H, m), 9.9-10.08 (2H) , M).

Synthesis Example of Dye Compound A-48
Dye compound (A-54) except that 6-mercaptohexanol used in the synthesis of an analogous intermediate of the dye compound (A-54) described in the synthesis example of the dye compound (A-47) is changed to 2-mercaptoethanol The compound was synthesized in the same manner as the synthesis of the analogous intermediate of
The ¹ H NMR spectrum was measured for the dye compound A-48. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 0.95 to 1.36 (24 H, m), 2.83 to 3.15 (6 H, m), 3.45 to 3.58 (3 H, m), 5.89 to 6.14 (2 H, m) ), 7.01 to 7.55 (11 H, m), 7.63 to 8.17 (3 H, m), 9.95 to 10.09 (2 H, m).

Synthesis Example of Dye Compound A-49
Dye compound (A-47) except that 6-mercaptohexanol used in the synthesis of the analogous intermediate of the dye compound (A-54) described in the synthesis example of the dye compound (A-47) is changed to 1,6-hexanedithiol It was synthesized in the same manner as the synthesis of the analogous intermediate of 54).

Synthesis Example of Dye Compound A-50
Tetrabutyl ammonium chloride was added to the dye compound (A-47), and the tosyl group was substituted with a chloride ion to obtain a dye compound (A-50).

Synthesis Example of Dye Compound A-51
Dye compound (A) is prepared according to the method described in Chem. Eur. J. 2010, 16, 10021-10029 in which potassium phthalimide is added to dye compound (A-47) or dye compound (A-50) and then deprotected with hydrazine. -51) was obtained.

Synthesis Example of Dye Compound A-52
The compound was synthesized in the same manner as in the compound (A-40) except that methanesulfonylamide was used instead of trifluoromethanesulfonylamide used for the synthesis of the dye compound (A-40) and DBU was used instead of triethylamine. did.
The ¹ H NMR spectrum was measured for the dye compound A-52. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 0.96-1.36 (24 H, m), 2.58-2.64 (3 H, s), 2.85-3. 15 (4 H, m), 5. 9-6. 14 (2 H, m) ), 7.07-7.52 (11 H, m), 7.58-8.22 (3 H, m), 9.85-10.04 (2 H, m).

Synthesis Example of Dye Compound A-53
Dye compound (A-54) except that 6-mercaptohexanol used in the synthesis of the analogous intermediate of the dye compound (A-54) described in the synthesis example of the dye compound (A-47) is changed to 4-mercaptobutyric acid The compound was synthesized in the same manner as the synthesis of the analogous intermediate of

Synthesis Example of Dye Compound A-54
Dye compound except that 6-mercaptohexanol used in the synthesis of an analogous intermediate of the dye compound (A-54) described in the synthesis example of the dye compound (A-47) is changed to 2- (3-mercaptopropoxy) ethanol It synthesize | combined by the same operation as the synthesis | combination of the similar intermediate of (A-54).
The ¹ H NMR spectrum was measured for the dye compound A-54. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 0.96-1.36 (26 H, m), 1.63-1.8 (2 H, m), 2.83-3.11 (6 H, m), 3.4-3.5 (4 H, m) ), 4.46 to 4.55 (1 H, s), 5.84 to 6.17 (2 H, m), 6.93 to 7.53 (11 H, m), 7.63 to 8.18 (3 H) , M), 9.85-10.15 (2H, br).

Synthesis Example of Dye Compound A-55
Dye compound (A-45) except that 2-isocyanatoethyl methacrylate (Kalenz MOI manufactured by Showa Denko) used in the synthesis of pigment compound (A-45) is changed to 2-isocyanatoethyl acrylate (Kalenz AOI manufactured by Showa Denko) It synthesize | combined by the same operation as the synthesis | combination of.
The ¹ H NMR spectrum was measured for the dye compound A-55. The measurement was performed using 400 MHz and DMSO (dimethyl sulfoxide). The measuring apparatus used Bruker make, product name: AV-400.
δ 0.95 to 1.35 (24 H, m), 2.85 to 3.15 (4 H, m), 3.15 to 3.28 (4 H, m), 4.0 to 4.16 (4 H, m) ), 5.88-6.36 (5H, m), 7.03-7.54 (11H, m), 7.63-8.18 (3H, m), 9.91-10.08 (2H) , M).

[Example and Comparative Example]
1. Preparation of Resist Solution The components of the following composition were mixed and dissolved to prepare a resist solution for undercoat layer.
<Composition of resist solution for undercoat layer>
Solvent: propylene glycol monomethyl ether acetate 19.20 parts Solvent: ethyl lactate 36.67 parts Alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22 / 18, weight average molecular weight 15,000, number average molecular weight 9,000) 40% PGMEA solution 30.51 parts · Ethylenically unsaturated double bond-containing compound: dipentaerythritol hexaacrylate
12.20 parts Polymerization inhibitor: 0.0061 parts of p-methoxyphenol Fluorosurfactant: F-475, manufactured by DIC Co., Ltd. 0.83 parts Photopolymerization initiator: photopolymerization of trihalomethyl triazine type 0.586 parts of an initiator (TAZ-107, manufactured by Midori Kagaku Co., Ltd.)

2. Preparation of Subbing Layer-Containing Silicon Wafer Substrate A 6 inch silicon wafer was heat treated in an oven at 200 ° C. for 30 minutes. Next, the above resist solution is coated on this silicon wafer to a dry film thickness of 1.5 μm, and further dried by heating in an oven at 220 ° C. for 1 hour to form an undercoat layer, and a silicon wafer with an undercoat layer I got the substrate.

3. Preparation of coloring composition 3-1. Preparation of Blue Pigment Dispersion <Preparation of Blue Pigment Dispersion P1>
Blue pigment dispersion P1 was prepared as follows.
C. I. Pigment Blue 15: 6 (blue pigment; hereinafter, also referred to as “PB 15: 6”) 13.0 parts (blue pigment, average particle diameter 55 nm), 5.0 parts of Disperbyk 111 which is a dispersing resin agent, 82.0 parts of PGMEA The resultant mixture was mixed and dispersed for 3 hours by a beads mill (zirconia beads 0.3 mm in diameter) to prepare a pigment dispersion. Thereafter, dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a blue pigment dispersion P1 (C.I. Pigment Blue 15: 6 dispersion, 13% pigment concentration) used for the coloring composition of the example or the comparative example.
It was 24 nm when the particle diameter of the pigment was measured by dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (made by Nikkiso Co., Ltd.)) about the obtained blue pigment dispersion liquid P1.

In the above-mentioned "3-1. Preparation of blue pigment dispersion", C.I. I. A red pigment dispersion liquid is prepared in the same manner as the preparation of the blue pigment dispersion liquid P1 except that the combination of the pigment shown below and the dispersion resin agent Disperbyk 111 is used instead of the combination of Pigment Blue 15: 6 and the dispersion resin agent Disperbyk 111. , Green pigment dispersion, and yellow pigment dispersion were prepared.
Pigment for Red Pigment Dispersion: C.I. I. Pigment red 246 (PR246)
Pigment for Red Pigment Dispersion: C.I. I. Pigment yellow 139 (PY 139)
Pigment for Green Pigment Dispersion: C.I. I. Pigment green 58 (PG 58)
Pigment for Green Pigment Dispersion: C.I. I. Pigment Yellow Pigment Dispersion Pigment: C.I. I. Pigment yellow 139 (PY 139)

Preparation of Blue Pigment Dispersion P2
19.4 parts by mass of PB 15: 6 (average primary particle diameter 55 nm), 2.95 parts by mass of dispersing resin agent BYK-161 (manufactured by BYK), alkali-soluble resin 1 (co-weight of benzyl methacrylate / methacrylic acid) A mixed solution consisting of 2.95 parts by mass (a solution of 9.93 parts by mass) and 30. 5 parts by mass of PGMEA (solid solution) of 30% PGMEA solution, beads mill (zirconia beads 0.3 mm diameter) The mixture was mixed and dispersed for 3 hours. Thereafter, dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a PB 15: 6 dispersion as a pigment dispersion. The average primary particle diameter of the pigment of the obtained PB 15: 6 dispersion was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX 150 (manufactured by Nikkiso Co., td.)). there were.

分散樹脂剤Ｄ１の酸価は１００ｍｇＫＯＨ／ｇであった。また、分散樹脂剤Ｄ１の重量平均分子量は２００００であった。また、分散樹脂剤Ｄ１の構造中、ｘとｙの質量比は５０：５０であり、ｎは２０であった。 Preparation of Blue Pigment Dispersion P3
In the preparation of the blue pigment dispersion liquid P2, a blue pigment dispersion liquid P2 was prepared in the same manner as the dispersion resin agent except that the following dispersion resin agent D1 was used.
Dispersion resin agent D1

The acid value of the dispersing resin agent D1 was 100 mg KOH / g. Moreover, the weight average molecular weight of the dispersion resin agent D1 was 20000. Further, in the structure of the dispersing resin agent D1, the mass ratio of x to y was 50:50, and n was 20.

分散樹脂剤Ｄ２の酸価は１００ｍｇＫＯＨ／ｇであった。また、分散樹脂剤Ｄ２の重量平均分子量は２００００であった。また、分散樹脂剤Ｄ２の構造中、ｘとｙの質量比は１５：８５であり、ｎは２０であった。 Preparation of Blue Pigment Dispersion P4
A pigment dispersion liquid P4 was prepared in the same manner as in the preparation of the blue pigment dispersion liquid P2, except that the following dispersion resin agent D2 was used as a dispersion resin agent.

The acid value of the dispersing resin agent D2 was 100 mg KOH / g. Moreover, the weight average molecular weight of the dispersion resin agent D2 was 20000. Further, in the structure of the dispersing resin agent D2, the mass ratio of x to y was 15:85, and n was 20.

Preparation of Red Pigment Dispersion P5
In the preparation of the blue pigment dispersion P2, instead of PB15: 6 as a pigment, C.I. I. A pigment dispersion P5 was prepared in the same manner as in the preparation of the pigment dispersion P2, except that Pigment Red 254 was used. The average primary particle size of the pigment (CI Pigment Red 254) was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX 150 (manufactured by Nikkiso Co., td.)) To be 26 nm .

3-2. Preparation of Colored Composition <Colored Composition of Examples 1 to 27 and Comparative Examples 1 to 3>
The following components were mixed, dispersed and dissolved to obtain colored compositions of Examples and Comparative Examples.
・ (A) Dye compound (compound described in the following table)
Solid content: 0.04 parts • Solvent (PGMEA) 1.133 parts • Alkali-soluble resin (compound of J1 or J2 below) 0.03 parts • Dispersant (Sol spar 20000: (1% cyclohexane solution, Nippon Lubrizol (stock) ))
0.125 parts of a photopolymerization initiator (compound of C-4 to C-13 below) 0.012 parts of the above pigment dispersion P1 (pigment concentration 13%) 0.615 parts of a curable compound 0.07 parts Surfactant (glycerol propoxide: (1% solution in cyclohexane))
0.048 copies

<Colored compositions of Examples 28 to 93 and Comparative Examples 4 to 6>
The following components were mixed, dispersed and dissolved to obtain coloring compositions of Examples and Comparative Examples.
Solvent (Cyclohexanone) 17.12 parts Alkali-soluble resin 1 (copolymer of benzyl methacrylate (BzMA) and methacrylic acid (MAA), 30% PGMEA solution) 1.23 parts Alkali-soluble resin 2 (Acrycure-RD- F8 (manufactured by Nippon Shokubai Co., Ltd.)
0.23 parts of a photopolymerization initiator I-2 (IRGACURE OXE-02) 0.975 parts of a dye multimer in cyclohexanone solution (solid content concentration 12.3%) 24.57 parts of a pigment dispersion (solid content concentration 12.8%) 51.40 parts Curable compound 1.96 parts Polymerization inhibitor (p-methoxyphenol) 0.0007 parts Fluorinated surfactant (F475 manufactured by DIC, 1% PGMEA solution) 50 copies

Curable compound dipentaerythritol hexaacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.)
NK Ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.)
KAYARAD RP-1040 (made by Nippon Kayaku Co., Ltd.)

Polyfunctional thiol compound (chain transfer agent): Compound of the following S-1 to S-5

Epoxy compound E-1: EHPE 3150, manufactured by Daicel Chemical Industries, Ltd. E-2: EPICLON 840 (manufactured by DIC Corporation)
E-3: EPICLON N660 (manufactured by DIC Corporation)
E-4: EPICLON HP 7200 (manufactured by DIC Corporation)

4. Preparation of color filter by coloring composition <Preparation of color filter using coloring composition by photolithography method>
<< Pattern formation >>
Each of the coloring compositions of the examples and comparative examples prepared as described above is referred to the above 2. It apply | coated on the undercoat layer of the silicon wafer board | substrate with an undercoat layer obtained above, and formed the coloring composition layer (coating film). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry thickness of the coating film was 0.6 μm.

Subsequently, it was exposed at various exposure amounts of 50 to 1200 mJ / cm ² through a 1.0 μm square Island pattern mask at a wavelength of 365 nm using an i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.) .
After that, the silicon wafer substrate on which the irradiated coating film is formed is placed on the horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film) Paddling development was carried out at 23 ° C. for 60 seconds using Electronic Materials (manufactured by KK) to form a colored pattern on a silicon wafer substrate.

The silicon wafer on which the coloring pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotational speed of 50 r. p. m. While rotating at the same time, pure water was supplied in the form of a shower from a jet nozzle from above the rotation center to perform a rinse process, and then spray drying was performed.
As described above, a monochrome color filter having a coloring pattern formed of the coloring composition of the example or the comparative example was produced.
Thereafter, the size of the colored pattern was measured using a length measurement SEM “S-9260A” (manufactured by Hitachi High-Technologies Corporation). The exposure amount at which the pattern size becomes 1.0 μm was taken as the optimum exposure amount.

<Fabrication of color filter using colored curable composition by dry etching method>
The colored compositions of the examples and comparative examples prepared as described above are coated on a 7.5 cm × 7.5 cm glass substrate to a film thickness of 0.5 μm using a spin coater, and a hot plate is prepared. Using this, heating was carried out at 200 ° C. for 5 minutes to cure the coating film to produce a colored layer. The thickness of this colored layer was 0.5 μm.
Next, a positive photoresist "FHi 622 BC" (manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied and prebaked at 90 ° C. for 1 minute to form a photoresist layer having a thickness of 0.8 μm.
Subsequently, the photoresist layer is pattern-exposed at an exposure dose of 350 mJ / cm ² using an i-line stepper (manufactured by Canon Inc.), and the temperature of the photoresist layer or the ambient temperature is 90 ° C. for 1 minute. Heat treatment was performed. Thereafter, development was performed for 1 minute with a developing solution "FHD-5" (manufactured by Fujifilm Electronics Materials Co., Ltd.), and a post-baking treatment was further performed at 110 ° C for 1 minute to form a resist pattern. The resist pattern was formed to have a side of 1.0 μm in consideration of the etching conversion difference (reduction of pattern width due to etching).
Next, the obtained glass substrate is attached to an 8-inch silicon wafer, and RF power: 800 W, antenna bias: 400 W, wafer bias: 200 W, in a dry etching apparatus (U-621, manufactured by Hitachi High-Technologies Corporation). Internal pressure of the chamber: 4.0 Pa, substrate temperature: 50 ° C., gas species and flow rate of mixed gas: CF ₄ : 80 mL / min, O ₂ : 40 mL / min, Ar: 800 mL / min. The first stage etching process was performed for 80 seconds.
Then, in the same etching chamber, RF power: 600 W, antenna bias: 100 W, wafer bias: 250 W, chamber internal pressure: 2.0 Pa, substrate temperature: 50 ° C., mixed gas gas species and flow rate N ₂ : The second-step etching process and the over-etching process were performed for 28 seconds, with 500 mL / min, O ₂ : 50 mL / min, Ar: 500 mL / min (N ₂ / O ₂ / Ar = 10/1/10).
After dry etching under the above conditions, the photoresist stripping solution "MS230C" (Fujifilm Electronics Materials Co., Ltd.) is used to carry out stripping treatment at 50 ° C. for 120 seconds to remove the resist, and the green color is colored. Formed a pattern. Furthermore, washing with pure water and spin drying were performed, and then dehydration baking was performed at 100 ° C. for 2 minutes. Thus, a color filter was obtained.

5. Performance evaluation 5-1. Heat resistance The glass substrate coated with the coloring composition obtained above is placed on a hot plate at 200 ° C. to be in contact with the substrate surface and heated for 1 hour, and then a chromaticity meter MCPD-1000 (Otsuka Electronics (stock The color fastness (.DELTA.E * ab value) before and after heating was measured to be an index for evaluating heat fastness. The ΔE * ab value indicates that the smaller the value, the better the heat resistance. The ΔE * ab value is a value determined from the following color difference formula based on the CIE 1976 (L *, a *, b *) space color system (Japanese Color Science Handbook, New Edition Color Science Handbook (Showa 60)) p. 266).
ΔE * ab = {(ΔL *) 2+ (Δa *) 2+ (Δb *) 2} 1/2
The following criteria were evaluated.
A: The value of ΔE * ab is 0 or more and less than 1.0 B: The value of ΔE * ab is 1.0 or more and less than 3.0 C: The value of ΔE * ab is 3.0 or more

5-2. PGMEA Solubility The solvent solubility of the obtained colored composition in PGMEA was evaluated based on the following criteria.
A: A solubility of 20% by mass or more B: A solubility of 10% by mass or more and less than 20% by mass C: A solubility of 5% by mass or more and less than 10% by mass D : When the solubility is less than 5% by mass

5-3. Solubility in cyclohexanone The solvent solubility of the obtained colored composition in cyclohexanone was evaluated based on the following criteria.
A: A solubility of 20% by mass or more B: A solubility of 10% by mass or more and less than 20% by mass C: A solubility of 5% by mass or more and less than 10% by mass D : When the solubility is less than 5% by mass

5-4. Evaluation of color transfer The absorbance of the colored pattern in each color filter was measured with MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (Absorbance A).
A CT-2000L solution (Fuji Film Electronics Materials Co., Ltd. product; transparent base agent) was applied to the colored pattern forming surface of the color filter so that the dry film thickness was 1 μm, and dried to form a transparent film. After that, heat treatment was performed at 280 ° C. for 5 minutes.
After the completion of heating, the absorbance of the transparent film adjacent to the colored pattern was measured by MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.) (absorbance B).
About the value of the light absorbency B of the obtained transparent film, the ratio [%] to the value of the light absorbency A of the coloring pattern measured before heating was calculated [following (formula A)]. This was used as an index for evaluating color transfer to adjacent pixels.
(Formula A) Color transfer (%) = absorbance B / absorbance A × 100
A: The value of Formula A is 0 or more and less than 2 B: The value of Formula A is 2 or more and less than 5 C: The value of Formula A is 5 or more

5-5. Spectral evaluation before and after development On a glass wafer, apply a CT-4000L solution (Fuji Film Electronics Materials Co., Ltd .; transparent base agent) to a dry film thickness of 0.1 μm, dry it, and transparent film. Heat treatment at 220.degree. C. for 5 minutes.
The above-mentioned coloring composition was applied using a spin coater so that the film thickness would be 0.6 μm, and heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C.
Subsequently, it exposed by 500 mJ / cm < ² > exposure amount with the wavelength of 365 nm using i-line stepper exposure apparatus FPA-3000i5 + (made by Canon Co., Ltd.).
The transmittance of the color filter thus obtained was measured in the wavelength range of 300 nm to 800 nm with a spectrophotometer (reference: glass substrate) of an ultraviolet visible near infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation).
The color filter after transmittance measurement is placed on the horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Inc.), and CD-2000 (manufactured by Fujifilm Electronics Materials Inc.) And paddle development at 23 ° C. for 60 seconds, and the silicon wafer substrate is rotated at a number of revolutions of 50 r. p. m. While rotating at the same time, pure water was supplied in the form of a shower from a jet nozzle from above the rotation center to perform a rinse process, and then spray drying was performed. After drying, spectroscopic measurement is performed again, and the transmittance fluctuation before and after development (when the transmittance before development is T0 and the transmittance after development is T1, represented by the formula | T0−T1 | The values were evaluated as follows.

AA: Good The transmittance fluctuation before and after development is less than 2% in the entire region of 300 nm to 800 nm A: Slightly favorable The transmittance fluctuation before and after development is 2% to less than 5% in the entire region of 300 nm to 800 nm Variation of transmittance before and after development is 5% or more and less than 10% in the entire region of ~ 800 nm C: Insufficient In the entire region of 300 nm to 800 nm, variation of transmittance before and after development is 10% or more

  When a color filter was produced using the composition of an Example, it turned out that it is excellent in heat resistance. The compositions of the examples were found to be excellent in solvent resistance and color transfer, and the spectral change before and after development was small, while the compositions of the comparative examples were found to be inferior. The

Claims (22)

It has a dye structure having a cationic site, and an anionic site containing at least one of a structure represented by the following general formula (A1), a structure represented by the following general formula (A2), and a structure containing a boron atom A dye compound in which the anionic site and the cationic site are linked via a covalent bond to be present in the same molecule,
A curable compound,
A coloring composition containing a solvent,
The dye compound is at least selected from a fluorine atom, an aliphatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a nitro group and an aromatic hydrocarbon group containing a cyano group. Any one of them includes a structure which is directly covalently bonded to at least one of R ^{1 to} R ^{5 in} the structure represented by the general formula (A1) or the general formula (A2),
The dye structure having a cationic site is a dye structure selected from xanthene dyes, cyanine dyes, squarylium dyes and dipyrromethene dyes,
A coloring composition;
General formula (A1)

In general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-;
General formula (A2)

In formula (A2), R ³ is, -SO ₂ - or an -CO-; R ⁴ and R ⁵ each independently -SO ₂ -, - CO- or an -CN. It has a dye structure having a cationic site, and an anionic site containing at least one of a structure represented by the following general formula (A1), a structure represented by the following general formula (A2), and a structure containing a boron atom A dye compound in which the anionic site and the cationic site are linked via a covalent bond to be present in the same molecule,
A curable compound,
A coloring composition containing a solvent,
The dye compound is a dye multimer having two or more dye structures each having a cation site in a molecule, and a fluorine atom, an aliphatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a fluorine atom, R ^{1 to} R in the structure in which at least one of an aromatic hydrocarbon group containing a nitro group and an aromatic hydrocarbon group containing a cyano group is represented by the general formula (A1) or the general formula (A2) ^A colored composition comprising a structure directly covalently linked to at least one of ⁵ ;
General formula (A1)

In general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-;
General formula (A2)

In formula (A2), R ³ is, -SO ₂ - or an -CO-; R ⁴ and R ⁵ each independently -SO ₂ -, - CO- or an -CN. It has a dye structure having a cationic site, and an anionic site containing at least one of a structure represented by the following general formula (A1), a structure represented by the following general formula (A2), and a structure containing a boron atom A dye compound in which the anionic site and the cationic site are linked via a covalent bond to be present in the same molecule,
A curable compound,
A coloring composition containing a solvent,
The dye compound has an alkali-soluble group selected from a phenolic hydroxyl group and a carboxylic acid group,
The dye compound is at least selected from a fluorine atom, an aliphatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a nitro group and an aromatic hydrocarbon group containing a cyano group. A colored composition comprising a structure in which any one is directly covalently bonded to at least one of R ^{1 to} R ^{5 in} the structure represented by the general formula (A1) or the general formula (A2);
General formula (A1)

In general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-;
General formula (A2)

In formula (A2), R ³ is, -SO ₂ - or an -CO-; R ⁴ and R ⁵ each independently -SO ₂ -, - CO- or an -CN. It has a dye structure having a cationic site, and an anionic site containing at least one of a structure represented by the following general formula (A1), a structure represented by the following general formula (A2), and a structure containing a boron atom A dye compound in which the anionic site and the cationic site are linked via a covalent bond to be present in the same molecule,
A curable compound,
Solvent,
A photopolymerization initiator,
A colored composition comprising
The dye compound is at least selected from a fluorine atom, an aliphatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a fluorine atom, an aromatic hydrocarbon group containing a nitro group and an aromatic hydrocarbon group containing a cyano group. Any one of them includes a structure which is directly covalently bonded to at least one of R ^{1 to} R ^{5 in} the structure represented by the general formula (A1) or the general formula (A2),
The coloring composition, wherein the photopolymerization initiator comprises an oxime compound;
General formula (A1)

In general formula (A1), R ¹ and R ² each independently represent -SO ₂ -or -CO-;
General formula (A2)

In formula (A2), R ³ is, -SO ₂ - or an -CO-; R ⁴ and R ⁵ each independently -SO ₂ -, - CO- or an -CN.   The coloring composition according to any one of claims 1 to 4, wherein the dye compound has a betaine structure formed by an anion at the anion site and a cation at the cation site. When the anion moiety in the dye compound has a structure represented by the general formula (A1), R ¹ or R ² in the general formula (A1) is directly covalently bonded to the dye structure of the dye compound,
When the anion moiety in the dye compound is a structure represented by the general formula (A2), R ³ , R ⁴ or R ⁵ in the general formula (A2) is directly covalently bonded to the dye structure of the dye compound The coloring composition of any one of Claims 1-5. When the anion moiety in the dye compound has a structure represented by the general formula (A1), R ¹ and R ² in the general formula (A1) are each bonded to an aliphatic hydrocarbon group containing a fluorine atom Yes,
When the anion moiety in the dye compound has a structure represented by the general formula (A2), R ^{3 to} R ⁵ in the general formula (A2) are each bonded to an aliphatic hydrocarbon group containing a fluorine atom The coloring composition of any one of Claims 1-6. R ¹ and R ² in the general formula (A1) are —SO ₂ —,
Wherein R ³ to R ⁵ in the general formula (A2) is -SO ₂ - is a coloring composition according to claim 7.   The coloring composition according to any one of claims 1 to 8, wherein the anion site includes a structure represented by the general formula (A1).   The coloring composition according to any one of claims 2 to 4, wherein the dye structure having a cationic site has a dye structure selected from xanthene dyes, cyanine dyes, squarylium dyes and dipyrromethene dyes.   The coloring composition of Claim 1 or 10 whose pigment structure which has the said cation site | part is a xanthene structure. The coloring composition according to any one of claims 1 to 11, wherein the anion site includes a structure represented by the following general formula (A3-1):
General formula (A3-1)

In general formula (A3-1), L ¹ represents -SO ₂ -or -CO-. G represents a carbon atom or a nitrogen atom; n1 represents 2 when G is a carbon atom and 1 when G is a nitrogen atom; R ⁶ represents an alkyl group containing a fluorine atom or an aryl containing a fluorine atom Group, an aryl group including a nitro group or an aryl group including a cyano group; when n1 is 2, two R ⁶ may be the same or different; * represents a binding site to another site .   The coloring composition according to claim 2, wherein the dye multimer has a structural unit derived from a dye monomer having an ethylenically unsaturated bond.   Furthermore, the coloring composition of any one of Claims 1-3 containing a photoinitiator.   Furthermore, the coloring composition of any one of Claims 1-14 containing the pigment which has a phthalocyanine skeleton.   The coloring composition of any one of Claims 1-15 used for colored layer formation of a color filter.   The cured film obtained by hardening | curing the coloring composition of any one of Claims 1-16.   The color filter which has a cured film of Claim 17.   A process of forming a colored composition layer on a support using the colored composition according to any one of claims 1 to 16, a process of exposing the colored composition layer in a pattern, and an exposed process Developing the unexposed area of the colored composition layer. A step of applying a coloring composition according to any one of claims 1 to 16 on a support to form a coloring composition layer and curing to form a coloring layer,
Forming a photoresist layer on the colored layer,
A method for producing a color filter, comprising the steps of: patterning the photoresist layer by exposure and development to obtain a resist pattern; and dry etching the colored layer using the resist pattern as an etching mask.   A solid-state imaging device comprising the color filter according to claim 18. An image display apparatus comprising the color filter according to claim 18.

Images