JPWO2015152051A1 - Coloring composition, cured film, color filter, method for producing color filter, solid-state imaging device, and image display device - Google Patents

Abstract

Colored composition, cured film, color filter, color filter manufacturing method, solid-state imaging device, and image display capable of forming a colored layer having high luminance and excellent solvent resistance when a colored layer such as a color filter is formed Providing equipment. A salt compound comprising a dye cation and a divalent or higher anion; a solvent capable of dissolving 1.0% by mass or more of the salt compound at 25 ° C .; and at least one selected from a xanthene dye, a pyromethene dye, and a tetraazaporphyrin dye. And a dye cation having 1 to 20 triarylmethane dye structures in one molecule.

Description

  The present invention relates to a colored composition, a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and an image display device.

As one of methods for preparing a colored composition used for producing a color filter used in a liquid crystal display device or a solid-state imaging device (CCD (Charge Coupled Devices), CMOS (Complementary Metal-Oxide Semiconductor), etc.), a pigment dispersion method is used. It has been known.
This pigment dispersion method is a method for producing a color filter by a photolithography method using a colored composition in which a pigment is dispersed in various photosensitive compositions. This is a method suitable for producing a color filter with high positional accuracy, a large screen, and high definition because patterning is performed by a photolithography method. When producing a color filter by a pigment dispersion method, a colored composition is applied by a spin coater or a roll coater to form a coating film, and a colored pattern is formed by exposing and developing the coating film. A color filter can be obtained by repeating for each color.
In recent years, color filters tend to be used not only for monitors but also for televisions (TVs) in liquid crystal display (LCD) applications. Along with this trend of expanding applications, color filters are required to have high color characteristics in terms of chromaticity and contrast. Further, color filters for image sensors (solid-state imaging devices) are also required to further improve color characteristics such as reduction of color unevenness and improvement of color resolution.
In order to satisfy recent chromaticity requirements, techniques using dyes have been developed in place of pigments conventionally used as colorants (for example, Patent Documents 1 to 3). Among these, for a color filter having a blue hue, a technique using a triarylmethane dye as a color material has been proposed (for example, Patent Documents 4 to 6).
In addition, a technique for insolubilizing triarylmethane dyes by multimerization has been proposed (Patent Document 7).

Japanese Patent No. 3387541 (Japanese Patent Laid-Open No. 6-230210) JP 2008-292970 A JP 2009-86375 A International publication WO2011 / 162217 pamphlet JP 2011-70171 A JP 2011-116802 A JP 2013-57053 A

When a dye is used as a colorant, it tends to be poor in solvent resistance because it is more soluble in a solvent than a pigment. This is because the dye develops color in a molecular state, so that the dye molecule can move freely in the film to some extent even after the coating film is cured. For this reason, for example, when another color resist or overcoat is applied over the coating film, the dye tends to easily elute into other colored layers or overcoat layers applied later. A colored layer may be formed.
In particular, in a liquid crystal display device, in addition to the elution of dyes by overcoating with other color resists and overcoats, when an LCD panel is formed, there is a possibility that the dye components are eluted in the liquid crystal. In this case, the insulating property of the liquid crystal layer is easily lowered by the eluted dye.
To solve these problems, for example, in the technique described in Patent Document 7, by insolubilizing the triarylmethane dye, the dye characteristic of color development in the molecular state is lost, and it becomes difficult to obtain a good hue. .
The present invention has been made in view of the above situation. That is, an object of the present invention is to provide a colored composition capable of forming a colored layer having high luminance and excellent solvent resistance when a colored layer such as a color filter is formed. Another object of the present invention is to provide a cured film, a color filter, a method for producing the same, and a solid-state imaging device and an image display device that are provided with the color filter and are capable of displaying good image quality.

一般式（Ａ１）中、Ａｒ⁺はそれぞれ独立にトリアリールメタン色素構造を表し、Ｌ¹は２つ以上のＡｒ⁺を連結する基を表し、ｎ１は１〜２０の整数を表し、ｍは０または１を表す；ｎ１が１を表す場合、ｍは０を表す；
一般式（Ａ２）

一般式（Ａ２）中、Ａｒ⁺はそれぞれ独立にトリアリールメタン色素構造を表し、Ｌ²はそれぞれ独立に２価の連結基を表し、Ｌ³は２価の連結基を表し、ｑは１〜１８の整数を表す。
＜３＞紫色着色剤が、下記一般式（Ｉ−１ａ）で表されるキサンテン色素、下記一般式（ＩＩ）で表されるピロメテン色素、および下記一般式（ＩＩＩ）で表されるテトラアザポルフィリン色素の少なくとも１種を含む、＜１＞または＜２＞に記載の着色組成物；
一般式（Ｉ−１ａ）

一般式（Ｉ−１ａ）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に水素原子、炭素数１〜２０の１価の飽和炭化水素基または炭素数６〜１０の１価の芳香族炭化水素基を表し、上記飽和炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−ＣＯ−または−ＮＲ¹¹−で置換されていてもよい；
Ｒ¹およびＲ²は、互いに結合して窒素原子を含む環を形成してもよい。Ｒ³およびＲ⁴は、互いに結合して窒素原子を含む環を形成してもよい；
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸または−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す；
Ｒ⁶およびＲ⁷は、それぞれ独立に、炭素数１〜６のアルキル基を表す；
ｍ１は、０〜５の整数を表す。ｍ１が２以上のとき、複数のＲ^5Aは同一でも異なってもよい；
ｍ２およびｍ３は、それぞれ独立に、０〜３の整数を表す。ｍ２およびｍ３がそれぞれ独立に、２または３のとき、複数のＲ^5BおよびＲ^5Cはそれぞれ独立に、同一でも異なってもよい；
ａは、０または１を表す；ａが０を表す場合、キサンテン色素構造中のいずれかの基がアニオンを含む；
Ｘ^-は、アニオンを表す；
Ｚ⁺は、Ｎ⁺（Ｒ¹¹）₄、Ｎａ⁺またはＫ⁺を表し、４つのＲ¹¹は同一でも異なってもよい；
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表すし、上記飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい；
Ｒ⁹およびＲ¹⁰は、それぞれ独立に、水素原子または炭素数１〜２０の１価の飽和炭化水素基を表し、上記飽和脂肪族炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＮＨ−または−ＮＲ⁸−で置換されていてもよく、Ｒ⁹およびＲ¹⁰は、互いに結合して窒素原子を含む３〜１０員環の複素環を形成していてもよい；
Ｒ¹¹は、水素原子、炭素数１〜２０の１価の飽和炭化水素基または炭素数７〜１０のアラルキル基を表す；
一般式（ＩＩ）

一般式（ＩＩ）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵およびＲ⁶は、各々独立に、水素原子または１価の置換基を表す；Ｒ⁷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；
一般式（ＩＩＩ）

一般式（ＩＩＩ）中、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、全てが窒素原子を表すか、若しくは、Ｚ¹およびＺ³、Ｚ²およびＺ⁴のいずれか１組が双方ともに窒素原子を表し、他の一組がＣ−Ｒを表し、Ｒがそれぞれ独立に水素原子、アルキル基、またはアリール基を表す；Ａ¹、Ａ²、Ａ³、Ａ⁴、Ａ⁵、Ａ⁶、Ａ⁷およびＡ⁸は、各々独立にアルキル基、アルケニル基、アリール基、アルコキシ基、アルキルチオ基、アリールオキシ基、アリールチオ基、ハロゲン原子、ヒドロキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノ基、カルバモイル基、スルファモイル基、アシル基、シリルオキシ基、シアノ基、ニトロ基またはヘテロ環基を表す；Ａ¹とＡ²、Ａ³とＡ⁴、Ａ⁵とＡ⁶、および、Ａ⁷とＡ⁸は、各々互いに結合して環構造を形成してもよいが、少なくとも１組は環構造を形成しない；Ｍは、２価の金属原子または置換された金属原子であって２価である原子または原子団を表す。
＜４＞染料カチオンが、下記一般式（ＴＰ１）で表されるトリアリールメタン色素構造および下記一般式（ＴＰ２）で表されるトリアリールメタン色素構造の少なくとも１種を含む、＜１＞〜＜３＞のいずれかに記載の着色組成物；

一般式（ＴＰ１）および（ＴＰ２）中、Ｒｔｐ₁〜Ｒｔｐ₄は、それぞれ独立に水素原子、アルキル基、アリール基または架橋性基を有する基を表す；Ｒｔｐ₅、Ｒｔｐ₆、Ｒｔｐ₈、Ｒｔｐ₉およびＲｔｐ₁₁は、それぞれ独立に置換基を表す。Ｒｔｐ₇は、水素原子、アルキル基、アリール基、架橋性基を有する基またはＮＲｔｐ₇₁Ｒｔｐ₇₂を表す。Ｒｔｐ₇₁およびＲｔｐ₇₂は、それぞれ独立に水素原子、アルキル基、アリール基または架橋性基を有する基を表す。Ｒｔｐ₁₀は、水素原子、アルキル基、アリール基または架橋性基を有する基を表す。ａ、ｂおよびｃは、それぞれ独立に０〜４の整数を表す。ａ、ｂおよびｃが２以上の場合、Ｒｔｐ₅同士、Ｒｔｐ₆同士、Ｒｔｐ₈同士およびＲｔｐ₉同士は、それぞれ、互いに連結して環を形成してもよい。
＜５＞染料カチオンが架橋性基を有する、＜１＞〜＜４＞のいずれかに記載の着色組成物。
＜６＞２価以上のアニオンが、−ＳＯ₃ ^-、−ＣＯＯ^-、−ＰＯ₄ ^-、下記一般式（Ｂ２）で表される構造を含む基または下記一般式（Ｂ３）で表される構造を含む基を有する、＜１＞〜＜５＞のいずれかに記載の着色組成物；
一般式（Ｂ２）

一般式（Ｂ２）中、Ｒ¹¹およびＲ¹²はそれぞれ独立に−ＳＯ₂−または−ＣＯ−を表す；
一般式（Ｂ３）

一般式（Ｂ３）中、Ｒ¹³は−ＳＯ₂−または−ＣＯ−を表す；Ｒ¹⁴およびＲ¹⁵はそれぞれ独立に−ＳＯ₂−、−ＣＯ−または−ＣＮを表す。
＜７＞Ｐｉｇｍｅｎｔ Ｂｌｕｅ１、２、１５、１５：１、１５：２、１５：３、１５：４、１５：６、１６、２２、６０、６４、６６、７９、８０およびＰｉｇｍｅｎｔ Ｇｒｅｅｎ ７のＣｌをＯＨに変えたものから選択される少なくとも１種をさらに含む、＜１＞〜＜６＞のいずれかに記載の着色組成物。
＜８＞バインダー樹脂、重合性化合物および光重合開始剤をさらに含有する、＜１＞〜＜７＞のいずれかに記載の着色組成物。
＜９＞カラーフィルタの着色層の形成に用いられる、＜１＞〜＜８＞のいずれかに記載の着色組成物。
＜１０＞＜１＞〜＜９＞のいずれかに記載の着色組成物を硬化してなる硬化膜。
＜１１＞＜１＞〜＜９＞のいずれかに記載の着色組成物を用いたカラーフィルタ。
＜１２＞＜１＞〜＜９＞のいずれかに記載の着色組成物を支持体上に付与して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、未露光部を現像除去して着色パターンを形成する工程とを含むカラーフィルタの製造方法。
＜１３＞＜１１＞に記載のカラーフィルタまたは＜１２＞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。
＜１４＞＜１１＞に記載のカラーフィルタまたは＜１２＞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画像表示装置。Under such circumstances, the inventor of the present application diligently studied. As a result, a salt compound composed of a dye cation and a divalent or higher anion, a solvent capable of dissolving 1.0% by mass or more of the salt compound at 25 ° C., and It has been found that by using a coloring composition containing a specific purple colorant, a coloring composition having high luminance and excellent solvent resistance can be obtained, and the present invention has been completed.
Specifically, the above problem has been solved by the following means <1>, preferably by means <2> to <14>.
<1> a salt compound composed of a dye cation and a divalent or higher anion, a solvent capable of dissolving 1.0% by mass or more of the salt compound at 25 ° C., and at least selected from a xanthene dye, a pyromethene dye and a tetraazaporphyrin dye One violet colorant,
The dye cation has a coloring composition having 1 to 20 triarylmethane dye structures in one molecule.
<2> The colored composition according to <1>, wherein the dye cation is represented by the general formula (A1) or the general formula (A2);
General formula (A1)

In General Formula (A1), Ar ⁺ independently represents a triarylmethane dye structure, L ¹ represents a group connecting two or more Ar ⁺ , n1 represents an integer of 1 to 20, and m represents 0. Or represents 1; when n1 represents 1, m represents 0;
General formula (A2)

In formula (A2), Ar ⁺ each independently represent a triarylmethane dye structure, L ² each independently represent a divalent linking group, L ³ represents a divalent linking group, q is 1 Represents an integer of 18.
<3> A purple colorant is a xanthene dye represented by the following general formula (I-1a), a pyromethene dye represented by the following general formula (II), and a tetraazaporphyrin represented by the following general formula (III) The coloring composition as described in <1> or <2> containing at least 1 sort (s) of pigment | dye;
Formula (I-1a)

In general formula (I-1a), R ^{1 to} R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. And —CH ₂ — contained in the saturated hydrocarbon group may be substituted with —O—, —CO— or —NR ¹¹ —;
R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom. R ³ and R ⁴ may combine with each other to form a ring containing a nitrogen atom;
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰ ;
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms;
m1 represents the integer of 0-5. when m1 is 2 or more, the plurality of R ^5A may be the same or different;
m2 and m3 each independently represents an integer of 0 to 3. when m2 and m3 are each independently 2 or 3, a plurality of R ^5B and R ^5C may be independently the same or different;
a represents 0 or 1; when a represents 0, any group in the xanthene dye structure contains an anion;
X ⁻ represents an anion;
Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different;
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom;
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the saturated aliphatic hydrocarbon group is —O—, -CO -, - NH- or -NR ⁸ - may optionally be substituted with, R ⁹ and R ^10, may form a heterocyclic ring of 3 to 10-membered ring containing a nitrogen atom bonded to each other ;
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms;
Formula (II)

In the general formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a monovalent substituent; R ⁷ represents a hydrogen atom or a halogen atom Represents an alkyl group, an aryl group or a heterocyclic group;
Formula (III)

In general formula (III), Z ¹ , Z ² , Z ³ and Z ⁴ all represent a nitrogen atom, or any one of Z ¹ and Z ³ , Z ² and Z ⁴ is both nitrogen Represents an atom, the other set represents C—R, and each R independently represents a hydrogen atom, an alkyl group or an aryl group; A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently an alkyl group, alkenyl group, aryl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, halogen atom, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, A carbamoyl group, a sulfamoyl group, an acyl group, a silyloxy group, a cyano group, a nitro group or a heterocyclic group; A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ are , Each joined to each other It may form a ring structure Te, but at least one set do not form a ring structure; M represents a divalent and is atom or group a divalent metal atom or a substituted metal atom.
<4> The dye cation includes at least one of a triarylmethane dye structure represented by the following general formula (TP1) and a triarylmethane dye structure represented by the following general formula (TP2): 3> the coloring composition according to any one of the above;

In the general formulas (TP1) and (TP2), Rtp _{1 to} Rtp ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group having a crosslinkable group; Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ And Rtp ₁₁ each independently represents a substituent. Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, a group having a crosslinkable group, or NRtp ₇₁ Rtp ₇₂ . Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group having a crosslinkable group. Rtp ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a group having a crosslinkable group. a, b and c each independently represents an integer of 0 to 4; a, when b and c is 2 or more, Rtp ₅ together, Rtp ₆ together, Rtp ₈ and between Rtp ₉ each other, respectively, may be bonded to each other to form a ring.
<5> The colored composition according to any one of <1> to <4>, wherein the dye cation has a crosslinkable group.
<6> a divalent or higher anion is —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a group containing a structure represented by the following general formula (B2) or a structure represented by the following general formula (B3) The coloring composition in any one of <1>-<5> which has group containing this;
General formula (B2)

In general formula (B2), R ¹¹ and R ¹² each independently represent —SO ₂ — or —CO—;
General formula (B3)

In General Formula (B3), R ¹³ represents —SO ₂ — or —CO—; R ¹⁴ and R ¹⁵ each independently represent —SO ₂ —, —CO—, or —CN.
<7> CI of Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 and Pigment Green 7 The coloring composition according to any one of <1> to <6>, further comprising at least one selected from those changed to OH.
<8> The colored composition according to any one of <1> to <7>, further containing a binder resin, a polymerizable compound, and a photopolymerization initiator.
<9> The colored composition according to any one of <1> to <8>, which is used for forming a colored layer of a color filter.
<10> A cured film obtained by curing the colored composition according to any one of <1> to <9>.
<11> A color filter using the colored composition according to any one of <1> to <9>.
<12> A step of applying the colored composition according to any one of <1> to <9> on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, And a step of developing and removing an unexposed portion to form a colored pattern.
<13> A solid-state imaging device having a color filter according to <11> or a color filter obtained by the method for producing a color filter according to <12>.
<14> An image display device having the color filter according to <11> or the color filter obtained by the method for producing a color filter according to <12>.

  According to the present invention, it is possible to provide a coloring composition having high luminance and excellent solvent resistance. In addition, it has become possible to provide a cured film, a color filter, a method for producing a color filter, a solid-state imaging device, and a liquid crystal display device using the colored composition.

Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In this specification, the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the group which does not have 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).
In addition, “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by 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, “exposure” in this specification is not only exposure with far ultraviolet rays, X-rays, EUV light, etc., typified by mercury lamps and excimer lasers, but also drawing with particle beams such as electron beams and ion beams. Are also included in the exposure.
In this specification, “(meth) acrylate” represents both and / or acrylate and methacrylate, “(meth) acryl” represents both and / or acryl and “(meth) acrylic” ) "Acryloyl" represents both and / or acryloyl and methacryloyl.
In the present specification, “monomer” and “monomer” are synonymous.
The monomer in this specification 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 means a compound having a polymerizable functional group, and may be a monomer or a polymer. The polymerizable functional group refers to a group that participates in a polymerization reaction.
In this 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, Ph represents a phenyl group, and AC represents an acetyl group.
In this specification, the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
The weight average molecular weight in the present invention refers to that measured by gel permeation chromatography (GPC) unless otherwise specified.
In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total composition of the composition. The solid content in the present invention is a solid content at 25 ° C.

[Coloring composition]
The coloring composition of the present invention (hereinafter also referred to as the composition of the present invention) is a solvent comprising a salt compound composed of a dye cation and a divalent or higher anion, and 1.0% by mass or more of the salt compound at 25 ° C. And at least one purple colorant selected from a xanthene dye, a pyromethene dye and a tetraazaporphyrin dye, wherein the dye cation has 1 to 20 triarylmethane dye structures in one molecule, To do.
By setting it as such a structure, the coloring composition with high brightness | luminance and excellent in solvent resistance can be provided. This mechanism is presumed, but when a salt compound composed of a dye cation having a triarylmethane dye structure and a divalent or higher anion is contained, a salt compound in which the dye cation and the anion are monovalent is used. In comparison, since the dye is less likely to elute into the liquid crystal when another colored layer, overcoat layer, or LCD panel is formed, the solvent resistance is improved. In particular, since the elution of the dye into the liquid crystal when the LCD panel is formed can be effectively suppressed, the deterioration of the insulating property of the liquid crystal layer can be suppressed, and the electrical characteristics can be improved. Further, by dissolving the salt compound in a solvent, for example, higher brightness can be obtained as compared with the case where the dye is raked.
Furthermore, light resistance can be improved by using at least one purple colorant selected from a xanthene dye, a pyromethene dye and a tetraazaporphyrin dye in combination with the salt compound. This is thought to be based on the excitation energy of the excited triarylmethane dye cation being received in the form of fluorescence by the purple colorant to relax the excited triarylmethane dye cation.

一般式（ＴＰ１）および（ＴＰ２）中、Ｒｔｐ₁〜Ｒｔｐ₄は、それぞれ独立に水素原子、アルキル基、アリール基または架橋性基を有する基を表す；Ｒｔｐ₅、Ｒｔｐ₆、Ｒｔｐ₈、Ｒｔｐ₉およびＲｔｐ₁₁は、それぞれ独立に置換基を表す。Ｒｔｐ₇は、水素原子、アルキル基、アリール基、架橋性基を有する基またはＮＲｔｐ₇₁Ｒｔｐ₇₂を表す。Ｒｔｐ₇₁およびＲｔｐ₇₂は、それぞれ独立に水素原子、アルキル基、アリール基または架橋性基を有する基を表す。Ｒｔｐ₁₀は、水素原子、アルキル基、アリール基または架橋性基を有する基を表す。ａ、ｂおよびｃは、それぞれ独立に０〜４の整数を表す。ａ、ｂおよびｃが２以上の場合、Ｒｔｐ₅同士、Ｒｔｐ₆同士、Ｒｔｐ₈同士およびＲｔｐ₉同士は、それぞれ、互いに連結して環を形成してもよい。<Salt compound>
The salt compound contained in the composition of the present invention comprises a dye cation and a divalent or higher anion.
<< Dye cation >>
The dye cation has 1 to 20 triarylmethane dye structures in one molecule. The number of triarylmethane dye structures in one molecule of the dye cation is preferably 1 to 4, and more preferably 2 or 3. By setting it as such a structure, the solvent solubility of the salt compound used for this invention can be made more favorable. Therefore, the salt compound used in the present invention can be suitably used as a color material for a color resist, for example. The dye cation may have a crosslinkable group. The crosslinkable group will be described later.
The dye cation preferably contains at least one of a triarylmethane dye structure represented by the following general formula (TP1) and a triarylmethane dye structure represented by the following general formula (TP2).

In the general formulas (TP1) and (TP2), Rtp _{1 to} Rtp ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group having a crosslinkable group; Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ And Rtp ₁₁ each independently represents a substituent. Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, a group having a crosslinkable group, or NRtp ₇₁ Rtp ₇₂ . Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group having a crosslinkable group. Rtp ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a group having a crosslinkable group. a, b and c each independently represents an integer of 0 to 4; a, when b and c is 2 or more, Rtp ₅ together, Rtp ₆ together, Rtp ₈ and between Rtp ₉ each other, respectively, may be bonded to each other to form a ring.

In general formula (TP1), Rtp _{1 to} Rtp ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group having a crosslinkable group.
In general formula (TP1), 1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The alkyl group may have a substituent, but is preferably unsubstituted. Examples of the substituent that the alkyl group may have include the substituents mentioned in the section of Substituent Group A described later.
6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable. Examples of the substituent that the aryl group may have include the substituents mentioned in the section of the substituent group A described later.
The group having a crosslinkable group may comprise only a crosslinkable group, or may contain a linking group in addition to the crosslinkable group. In particular, a group having a crosslinkable group, a group represented by -L ⁰ -P ⁰ is preferable. Here, L ⁰ represents a single bond or a divalent linking group, and P ¹ represents a crosslinkable group.
As the crosslinkable group, a crosslinkable group that can be crosslinked by a radical, an acid, or heat can be used. Specific examples include a group having an ethylenically unsaturated double bond, a (meth) acryl group, a styrene group, a vinyl group, an allyl group, and a cyclic ether group, and a (meth) acryl group, a styrene group, and a vinyl group. And at least one selected from allyl groups is preferred, at least one selected from (meth) acrylic groups, styrene groups and vinyl groups is more preferred, and (meth) acrylic groups and styrene groups are more preferred. For example, the cyclic ether group is preferably an epoxy group or an oxetanyl group, and more preferably an epoxy group.
The divalent linking group includes an alkylene group, an arylene group, a heterocyclic linking group, —CH═CH—, —O—, —S—, —C (═O) —, —CO—, —NR—, and —CONR. —, —OC—, —SO—, —SO ₂ — and a combination of two or more thereof are preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
In particular, the divalent linking group is preferably an alkylene group.
The alkylene group may be linear, branched or cyclic. 1-30 are preferable, as for carbon number of an alkylene group, 1-20 are more preferable, 5-20 are more preferable, and 5-10 are especially preferable. Specifically, a methylene group, ethylene group, propylene group, butylene group, hexylene group, hepsylene group, cyclopentenylene group, cyclohexylene group and the like are preferable.
6-30 are preferable, as for carbon number of an arylene group, 6-18 are more preferable, and 6-12 are more preferable. Specifically, the arylene group is preferably a phenylene group or a naphthalene group.

In general formula (TP1), Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, a group having a crosslinkable group or NRtp ₇₁ Rtp ₇₂ , preferably a hydrogen atom or NRtp ₇₁ Rtp _{72, and} more preferably NRtp ₇₁ Rtp ₇₂ preferable.
1-10 are preferable, as for carbon number of an alkyl group, 1-5 are more preferable, and 1-3 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear. Examples of the substituent that the alkyl group may have include the substituents mentioned in the section of Substituent Group A described later. 6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable.

Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom or an alkyl group.
1-10 are preferable, as for carbon number of an alkyl group, 1-8 are more preferable, and 1-6 are more preferable. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. The alkyl group is preferably unsubstituted. Examples of the substituent that the alkyl group may have include the substituents mentioned in the section of Substituent Group A described later. 6-18 are preferable, as for carbon number of an aryl group, 6-12 are more preferable, and 6 is more preferable. Examples of the substituent that the aryl group may have include the substituents mentioned in the section of the substituent group A described later.
The group having a crosslinkable group has the same meaning as the group having a crosslinkable group in Rtp _{1 to} Rtp ₄ in the general formula (TP1) described above, and the preferred range is also the same.

In general formula (TP1), Rtp ₅ , Rtp ₆ and Rtp ₈ each independently represent a substituent. Examples of the substituent include the substituents mentioned in the section of the substituent group A described later. In particular, a linear or branched alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, an aryl group having 6 to 15 carbon atoms, a carboxyl group, or a sulfo group is preferable, and a linear chain having 1 to 5 carbon atoms. Alternatively, a branched alkyl group, an alkenyl group having 1 to 5 carbon atoms, a phenyl group, a group having a crosslinkable group, or a carboxyl group is more preferable. In particular, Rtp ₅ and Rtp ₆ are preferably each independently an alkyl group having 1 to 5 carbon atoms. Rtp ₈ preferably has two alkenyl groups bonded to each other to form a ring. The ring is preferably a benzene ring.
The group having a crosslinkable group has the same meaning as the group having a crosslinkable group in Rtp _{1 to} Rtp ₄ in the general formula (TP1) described above, and the preferred range is also the same.

  In the general formula (TP1), a, b and c each independently represent an integer of 0 to 4, and a and b preferably represent 0 or 1, and more preferably represent 0. c preferably represents 0 to 2, more preferably 0 or 1.

In general formula (TP2), Rtp _{1 to} Rtp ₄ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a group having a crosslinkable group, and has the same meaning as Rtp _{1 to} Rtp ₄ in general formula (TP1). The preferred range is also the same. The group having a crosslinkable group has the same meaning as the group having a crosslinkable group in Rtp _{1 to} Rtp ₄ in the general formula (TP1) described above, and the preferred range is also the same.
In general formula (TP2), Rtp ₅ and Rtp ₆ each independently represent a substituent, and are synonymous with Rtp ₅ and Rtp ₆ in general formula (TP1), and their preferred ranges are also the same.
In General Formula (TP2), Rtp ₉ and Rtp ₁₁ each independently represent a substituent, and the substituents exemplified in the section of Substituent Group A described later can be used.
Rtp ₉ is preferably an alkyl group, an alkoxy group, or a halogen atom.
Rtp ₁₁ is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms, and still more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group is preferably linear or branched, and more preferably linear.
In General Formula (TP2), Rtp ₁₀ represents a substituent, and a group having a substituent or a crosslinkable group mentioned in the section of Substituent Group A described later can be used. In particular, Rtp ₁₀ is more preferably an aryl group having 6 to 12 carbon atoms, and more preferably a phenyl group. The group having a crosslinkable group has the same meaning as the group having a crosslinkable group in Rtp _{1 to} Rtp ₄ in the general formula (TP1) described above, and the preferred range is also the same.

  In the general formula (TP2), a, b and c each independently represent an integer of 0 to 4, and a and b preferably represent 0 or 1, and more preferably represent 0. c preferably represents 0 to 2, and more preferably represents 0.

  In the triarylmethane dye structure, cations are present in a delocalized manner as follows, and the following structures are synonymous, and all of them are included in the present invention. The cation moiety may be at any position in the molecule, but is preferably located on the nitrogen atom. When substituted on a nitrogen atom, the color tends to be further improved.

Substituent group A:
Substituents include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxyl groups, nitro groups, carboxyl groups, alkoxy groups, aryloxy groups Silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, 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 arylsulfonyl group Groups, acyl groups, aryloxycarbonyl groups, alkoxycarbonyl groups, carbamoyl groups, aryl or heterocyclic azo groups, imide groups, phosphino groups, phosphinyl groups, phosphinyloxy groups, phosphinylamino groups, silyl groups, etc. It is done. Details are described below.

  A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a linear or branched alkyl group (a linear or branched substituted or unsubstituted alkyl group, preferably an 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 3 to 30 carbon atoms substituted or Examples thereof include unsubstituted cycloalkyl groups such as cyclohexyl and cyclopentyl, and polycycloalkyl groups such as bicycloalkyl groups (preferably substituted or unsubstituted bicycloalkyl groups having 5 to 30 carbon atoms such as 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.)

  Linear or branched alkenyl group (straight or branched substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, such as vinyl, allyl, prenyl, geranyl, oleyl), cycloalkenyl Group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, such as 2-cyclopenten-1-yl and 2-cyclohexen-1-yl, and a polycycloalkenyl group such as bicyclo An alkenyl group (preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms such as bicyclo [2,2,1] hept-2-en-1-yl, bicyclo [2,2,2] Oct-2-en-4-yl) and tricycloalkenyl groups, with monocyclic cycloalkenyl groups being particularly preferred. 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 such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), a heterocyclic group (preferably 5 to 5 7-membered substituted or unsubstituted, saturated or unsaturated, aromatic or non-aromatic, monocyclic or condensed heterocyclic group, more preferably the ring-constituting atom is selected from carbon atom, nitrogen atom and sulfur atom And a heterocyclic group having at least one heteroatom of any one of a nitrogen atom, an oxygen atom and a 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 1 to 30 carbon atoms such as methoxy, ethoxy, isopropoxy, tert-butoxy, n-octyloxy, 2-methoxyethoxy), aryloxy group (preferably Is a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as phenoxy, 2-methylphenoxy, 2,4-di-tert-amylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), a silyloxy group (preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, tert-butyldimethylsilyloxy), a heterocyclic oxy group (preferably having 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, such as formyloxy, acetyloxy , Pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms such as N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably having 2 to 30 carbon atoms) Or an unsubstituted alkoxycarbonyloxy group such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted group having 7 to 30 carbon atoms). Substituted aryloxycarbonyloxy groups such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy),

  An amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a 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), acylamino group (preferably formylamino group, carbon number A substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms, such as formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3, 4,5-tri-n-octyloxyphenylcarbonylamino), amino A rubonylamino 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 such as methoxycarbonylamino, ethoxycarbonylamino, tert-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl- Methoxycarbonylamino),

  Aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino) A sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms such as sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylamino Sulfonylamino), 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, such as 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, such as 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), a heterocyclic thio group (preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms, wherein the heterocyclic portion is the above-described heterocyclic group The heterocyclic moiety described in the above is preferable, 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 substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms, such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl), an alkyl or arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, such as methylsulfonyl , Ethylsulfonyl, phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbocycle having 7 to 30 carbon atoms) D Groups such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl), aryloxycarbonyl groups (preferably substituted or unsubstituted aryloxy having 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, such as methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, n-octadecyloxycarbonyl), a carbamoyl group (preferably having a carbon number) 1-30 substituted or unsubstituted carbamoyl such as carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl or hetero A ring 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 heterocycle portion is the heterocycle described in the above heterocyclic group); Ring portion 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 such as N-succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably 2 carbon atoms). -30 substituted or unsubstituted phosphinyl groups such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl)

  A phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino group ( Preferably, it is a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably substituted with 3 to 30 carbon atoms) Or an unsubstituted silyl group, for example, trimethylsilyl, tert-butyldimethylsilyl, phenyldimethylsilyl).

  Specific examples of the triarylmethane dye structure are given below, but the present invention is not limited thereto.

一般式（Ａ１）中、Ａｒ⁺はそれぞれ独立にトリアリールメタン色素構造を表し、Ｌ¹は２つ以上のＡｒ⁺を連結する基を表し、ｎ１は１〜２０の整数を表し、ｍは０または１を表す；ｎ１が１を表す場合、ｍは０を表す。The dye cation is preferably represented by the general formula (A1) or the general formula (A2).
General formula (A1)

In General Formula (A1), Ar ⁺ independently represents a triarylmethane dye structure, L ¹ represents a group connecting two or more Ar ⁺ , n1 represents an integer of 1 to 20, and m represents 0. Or represents 1; when n1 represents 1, m represents 0.

In the general formula (A1), Ar ⁺ represents a triarylmethane dye structure, which is synonymous with the above-described triarylmethane dye structure, and the preferred range is also the same.
When the triarylmethane dye structure is represented by the general formula (TP1), the bonding position between the triarylmethane dye structure and L ¹ is any _one of Rtp _{1 to} Rtp ₈ , Rtp ₇₁ and Rtp ₇₂ , and Rtp ₇₁ or it is preferably Rtp _72. When the triarylmethane dye structure is represented by the general formula (TP2), the bonding position between the triarylmethane dye structure and L ¹ is any one of Rtp _{1 to} Rtp ₆ and Rtp _{9 to} Rtp ₁₁ . (Rtp _{9 to} Rtp ₁₁ ) is preferable.

In general formula (A1), L ¹ represents a group linking two or more Ar ⁺ . L ¹ is a divalent or higher valent linking group, and preferably a divalent to hexavalent linking group.
L ¹ is a hydrocarbon group, a heterocyclic group, —O—, —S—, —CO—, —NR—, —CONR—, —OC—, —SO—, or a group obtained by combining two or more thereof. preferable. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The hydrocarbon group may be linear, branched or cyclic. 1-30 are preferable, as for carbon number of a hydrocarbon group, 1-18 are more preferable, and 1-12 are more preferable. The hydrogen atom contained in the hydrocarbon group may be substituted with a halogen atom. As the halogen atom, a fluorine atom is preferable.
When a hydrocarbon group is an aliphatic hydrocarbon group, 1-20 are preferable and 1-10 are more preferable. When a hydrocarbon group is an aromatic hydrocarbon group, 6-24 are preferable and, as for carbon number, 6-12 are more preferable.
The heterocyclic group preferably contains a nitrogen atom as a hetero atom. The heterocyclic group is preferably a 3- to 8-membered ring, more preferably a 6-membered ring.
In particular, L ¹ is preferably a group consisting of an aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 1 to 30 carbon atoms, or a combination thereof.
For example, when L ¹ represents a divalent linking group, an alkylene group having 1 to 30 carbon atoms (methylene group, ethylene group, trimethylene group, propylene group, butylene group, etc.), an arylene group having 6 to 30 carbon atoms (phenylene) Group, naphthalene group, etc.), heterocyclic group, -CH = CH-, -O-, -S-, -CO-, -NR-, -CONR-, -OC-, -SO-, or these 2 A combined linking group as described above is preferred. Here, R represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group each independently.
1-20 are preferable and, as for carbon number of a C1-C30 alkylene group, 1-10 are more preferable. When the alkylene group having 1 to 30 carbon atoms has a substituent, examples of the substituent include a halogen atom.
The heterocyclic group preferably contains a nitrogen atom as a hetero atom. The heterocyclic group is preferably a 3- to 8-membered ring, more preferably a 6-membered ring.
6-24 are preferable and, as for carbon number of a C6-C30 arylene group, 6-12 are more preferable.

From the viewpoint of heat resistance, L ¹ preferably contains a cyclic aliphatic hydrocarbon group or aromatic group. 3-8 are preferable and, as for carbon number of a cyclic | annular aliphatic hydrocarbon group, 4-6 are more preferable. The aromatic group may be an aromatic hydrocarbon group or an aromatic heterocyclic group. 6-12 are preferable and, as for carbon number of an aromatic group, 6-10 are more preferable.

The binding site between L ¹ and Ar ⁺ preferably does not contain a conjugated system. By not including a conjugated system at the binding site between L ¹ and Ar ⁺ , the formation of a conjugated system between Ar ⁺ and L ¹ can be suppressed, and the hue of the triarylmethane dye changes. Can be effectively suppressed.

Formula weight of L ¹ portion in the dye cation 1 molecule is preferably from 14 to 800, 50 to 200 is more preferable.

Specific examples of L ¹ include the following structures, but the present invention is not limited to these. In the following structure, * represents a connecting site with Ar ⁺ in the general formula (A1), and a represents an integer of 1 or more.

  In general formula (A1), n1 represents the integer of 1-20, the integer of 1-6 is preferable, the integer of 2-4 is more preferable, and 2 or 3 is more preferable. By setting it as such a structure, the solvent solubility of the salt compound used for this invention can be made favorable.

In general formula (A1), m represents 0 or 1. When n1 represents 1, m represents 0, ie L ¹ does not exist.

一般式（Ａ２）中、Ａｒ⁺はそれぞれ独立にトリアリールメタン色素構造を表し、Ｌ²は２価の連結基を表し、Ｌ³は２価の連結基を表し、ｑは１〜１８の整数を表す。
一般式（Ａ２）中、Ａｒ⁺はトリアリールメタン色素構造を表し、一般式（Ａ１）中のＡｒ⁺と同義であり、好ましい範囲も同様である。
一般式（Ａ２）中、Ｌ²は２価の連結基を表し、一般式（Ａ１）中のＬ¹が２価の連結基を表す場合と同義であり、好ましい範囲も同様である。
一般式（Ａ２）中、Ｌ³は２価の連結基を表し、一般式（Ａ１）中のＬ¹が２価の連結基を表す場合と同義であり、好ましい範囲も同様である。
一般式（Ａ２）中、ｑは１〜１８の整数を表し、１〜１０の整数が好ましく、１〜３の整数がより好ましい。General formula (A2)

In General Formula (A2), Ar ⁺ independently represents a triarylmethane dye structure, L ² represents a divalent linking group, L ³ represents a divalent linking group, and q represents an integer of 1 to 18. Represents.
In General Formula (A2), Ar ⁺ represents a triarylmethane dye structure, and is synonymous with Ar ⁺ in General Formula (A1), and the preferred range is also the same.
In General Formula (A2), L ² represents a divalent linking group, which is synonymous with the case where L ¹ in General Formula (A1) represents a divalent linking group, and the preferred range is also the same.
In General Formula (A2), L ³ represents a divalent linking group, which is synonymous with the case where L ¹ in General Formula (A1) represents a divalent linking group, and the preferred range is also the same.
In general formula (A2), q represents an integer of 1 to 18, an integer of 1 to 10 is preferable, and an integer of 1 to 3 is more preferable.

Specific examples of the dye cation are listed below, but are not limited thereto. In addition, as a specific example in case n1 represents 1 in general formula (A1), the specific example of the triarylmethane dye structure mentioned above is mentioned.

  The molecular weight of the dye cation is preferably 1,000 to 10,000, and more preferably 1,000 to 5,000.

<< Divalent or higher anion >>
The divalent or higher anion may exist as a separate molecule without being bonded to the dye cation via a covalent bond, or may be present in the same molecule as the dye cation.
The divalent or higher valent anion constituting the salt compound of the present invention is not particularly defined, but includes —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , and a group containing a structure represented by the following general formula (B2) And preferably contains at least one selected from groups containing a structure represented by the following general formula (B3), more preferably a group containing a structure represented by —SO ₃ ^— and / or the general formula (B2). preferable. The divalent or higher anion preferably has a fluorine atom.
The salt compound of the present invention may contain only one kind of divalent or more anions, or may contain two or more kinds.

一般式（Ｂ２）中、Ｒ¹¹およびＲ¹²はそれぞれ独立に−ＳＯ₂−または−ＣＯ−を表し、Ｒ¹¹およびＲ¹²の少なくとも１つが−ＳＯ₂−を表すことが好ましく、Ｒ¹¹およびＲ¹²の両方が−ＳＯ₂−を表すことがより好ましい。
一般式（Ｂ２）で表される構造を含む基は、一般式（Ｂ２）中、Ｒ¹¹およびＲ¹²の一方の末端に、フッ素置換アルキル基を有することが好ましく、Ｒ¹¹およびＲ¹²の一方が直接フッ素置換アルキル基と結合していることがより好ましい。フッ素置換アルキル基の炭素数は、１〜１０が好ましく、１〜６がより好ましく、１〜３がさらに好ましく、１または２がよりさらに好ましく、１が特に好ましい。これらのアルキル基は、パーフルオロアルキル基がより好ましい。フッ素置換アルキル基の具体例としては、トリフルオロメチル基が好ましい。General formula (B2)

In the general formula (B2), -SO _2, respectively R ¹¹ and R ¹² are independently - represents or -CO-, at least one of R ¹¹ and R ¹² -SO ₂ - is preferable to represent, R ¹¹ and R and more preferably represents - both ¹² -SO _2.
Group containing a structure represented by the general formula (B2), in the formula (B2), to one end of R ¹¹ and R ^12, preferably has a fluorine-substituted alkyl group, one of R ¹¹ and R ¹² More preferably, is directly bonded to a fluorine-substituted alkyl group. 1-10 are preferable, as for carbon number of a fluorine-substitution alkyl group, 1-6 are more preferable, 1-3 are more preferable, 1 or 2 is further more preferable, and 1 is especially preferable. These alkyl groups are more preferably perfluoroalkyl groups. As a specific example of the fluorine-substituted alkyl group, a trifluoromethyl group is preferable.

一般式（Ｂ３）中、Ｒ¹³は−ＳＯ₂−または−ＣＯ−を表し、Ｒ¹⁴およびＲ¹⁵はそれぞれ独立に−ＳＯ₂−、−ＣＯ−または−ＣＮを表す。
一般式（Ｂ３）中、Ｒ¹³〜Ｒ¹⁵の少なくとも１つが−ＳＯ₂−を表すことが好ましく、Ｒ¹³〜Ｒ¹⁵の少なくとも２つが−ＳＯ₂−を表すことがより好ましい。
一般式（Ｂ３）で表される構造を含む基は、一般式（Ｂ３）中、Ｒ¹³〜Ｒ¹⁵の少なくともいずれかの末端に、フッ素置換アルキル基を有することが好ましく、Ｒ¹³〜Ｒ¹⁵の少なくともいずれかが直接フッ素置換アルキル基と結合していることがより好ましい。特に、Ｒ¹³〜Ｒ¹⁵の少なくとも２つの末端に、フッ素置換アルキル基を有することが好ましい。フッ素置換アルキル基は、一般式（Ｂ２）で表される構造を含む基で説明したものと同義であり、好ましい範囲も同様である。General formula (B3)

In General Formula (B3), R ¹³ represents —SO ₂ — or —CO—, and R ¹⁴ and R ¹⁵ each independently represent —SO ₂ —, —CO—, or —CN.
Preferably representing the, at least two of R ¹³ ~R ¹⁵ -SO ₂ - - in the general formula (B3), at least one of R ¹³ to R ¹⁵ -SO ₂ more preferably represents.
The group including the structure represented by the general formula (B3) preferably has a fluorine-substituted alkyl group at least at any terminal of R ^{13 to} R ^{15 in} the general formula (B3), and R ^{13 to} R ^15. More preferably, at least one of the above is directly bonded to the fluorine-substituted alkyl group. In particular, it is preferable to have a fluorine-substituted alkyl group at at least two ends of R ^{13 to} R ¹⁵ . A fluorine-substituted alkyl group is synonymous with what was demonstrated with group containing the structure represented by general formula (B2), and its preferable range is also the same.

一般式（Ｂ１）中、ｋは２〜２０の整数を表す；ｐは０または１を表す；Ｒは２〜ｋ価の有機基を表す；Ａは２価の連結基を表す；Ｘ^-は、−ＳＯ₃ ^-、−ＣＯＯ^-、−ＰＯ₄ ^-、一般式（Ｂ２）で表される構造を含む基または一般式（Ｂ３）で表される構造を含む基を表す。The divalent or higher anion is preferably an anion represented by the following general formula (B1).
General formula (B1)

In the general formula (B1), k represents an integer of 2 to 20; is A represents a divalent linking group; representing R is 2~k valent organic group; p represents 0 or 1 X ^- is , —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a group containing a structure represented by the general formula (B2) or a group containing a structure represented by the general formula (B3).

In general formula (B1), R represents a k-valent organic group, and examples thereof include the following organic groups (a) to (e). Among these, the organic group (a) or (c) is preferable.
(A) a substituted or unsubstituted non-aromatic hydrocarbon group (b) a group in which a plurality of substituted or unsubstituted non-aromatic hydrocarbon groups are linked by a divalent linking group containing a hetero atom (c) substituted or unsubstituted An unsubstituted aromatic hydrocarbon group (d) a group in which two substituted or unsubstituted aromatic hydrocarbon groups are linked by a divalent linking group containing a hetero atom or a divalent non-aromatic hydrocarbon group ( e) substituted or unsubstituted heterocyclic group

The non-aromatic hydrocarbon group in the organic group (a) is preferably an aliphatic hydrocarbon group, which may be linear, branched or cyclic. In particular, an alkylene group having 1 to 10 carbon atoms is preferable. When the non-aromatic hydrocarbon group has a substituent, the substituent is preferably a halogen atom (particularly a fluorine atom). As an example in case a non-aromatic hydrocarbon group has a substituent, the C1-C10 alkylene group substituted by the fluorine atom is mentioned.
1-40 are preferable and, as for the number of atoms which comprise the non-aromatic hydrocarbon group of (a), 1-20 are more preferable.
Specific examples of the organic group (a) include the following, but the present invention is not limited thereto. In the following structure, * represents a linking site with A or X ⁻ in the general formula (B1).

The non-aromatic hydrocarbon group in the organic group (b) is preferably an aliphatic hydrocarbon group, and may be linear, branched or cyclic. When the non-aromatic hydrocarbon group has a substituent, examples of the substituent include a polymerizable group (for example, a (meth) acryloyl group, a vinyl group). Examples of the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.
The divalent linking group containing a hetero atom is preferably —O—, —N—, —S—, —CO—, or a group comprising a combination of these with an alkylene group.
6-100 are preferable and, as for the number of atoms which comprise the organic group of (b), 8-60 are more preferable.
Specific examples of the (b) non-aromatic hydrocarbon group include the following, but the present invention is not limited thereto. In the following structure, * represents a linking site with A or X ⁻ in the general formula (B1).

The aromatic hydrocarbon group in the organic group (c) is preferably an arylene group. 6-18 are preferable and, as for carbon number of an arylene group, 6-12 are more preferable. The aromatic hydrocarbon group may be monocyclic or polycyclic.
6-60 are preferable and, as for the number of atoms which comprise the organic group of (c), 6-30 are more preferable.
Specific examples of the organic group (c) include the following, but the present invention is not limited thereto. In the following structure, * represents a linking site with A or X ⁻ in the general formula (B1).

The aromatic hydrocarbon group in the organic group (d) has the same meaning as the aromatic hydrocarbon group (c).
Examples of the hetero atom constituting the divalent linking group containing a hetero atom in the organic group (d) include an oxygen atom, a nitrogen atom, and a sulfur atom. The bivalent coupling group containing a hetero atom is synonymous with the bivalent coupling group containing the hetero atom in the organic group of the said (b). Examples of the divalent non-aromatic hydrocarbon group include the non-aromatic hydrocarbon group in the organic group (a).
6-60 are preferable and, as for the number of atoms which comprise the organic group of (d), 6-50 are more preferable.
Specific examples of the organic group (d) include the following, but the present invention is not limited thereto. In the following structure, * represents a linking site with A or X ⁻ in the general formula (B1).

The heterocyclic group in the organic group (e) may be an aromatic heterocyclic group or a non-aromatic heterocyclic group. The hetero atom contained in the heterocyclic group is preferably a nitrogen atom. The heterocyclic group is preferably a 3- to 8-membered ring, and more preferably a 4- to 6-membered ring. The number of carbon atoms constituting the heterocyclic group is preferably 2-6.
6-50 are preferable and, as for the number of atoms which comprise the organic group of (e), 6-30 are more preferable.
Specific examples of the organic group (e) include the following, but the present invention is not limited thereto. In the following structure, * represents a linking site with A or X ⁻ in the general formula (B1).

In general formula (B1), the divalent linking group represented by A is an alkylene group, an arylene group, a heterocyclic group, —CH═CH—, —O—, —S—, —C (═O) —. , —CO—, —NR—, —CONR—, —OC—, —SO—, —SO ₂ — and a combination of two or more thereof are preferred.

Specific examples of divalent or higher anions are listed below, but are not limited thereto.

  The weight average molecular weight (Mw) of the salt compound used in the present invention is preferably 1,000 or more and 10,000 or less, more preferably 1,000 or more and 7,500 or less, and particularly preferably 1,000 or more and 6,000 or less. . Although there are changes depending on the structure of the dye cation and the type of anion, the solvent solubility of the salt compound can be further improved by setting Mw to 10,000 or less. Moreover, electrical characteristics can be made more favorable by setting Mw to 1,000 or more.

  10-60 mass% is preferable with respect to the total solid of the composition of this invention, and, as for content of the salt compound in the composition of this invention, 10-40 mass% is more preferable. The salt compound may be used alone or in combination of two or more.

<Solvent that dissolves 1.0% by mass or more of the salt compound at 25 ° C.>
The coloring composition of this invention contains the solvent which melt | dissolves the said salt compound 1.0 mass% or more at 25 degreeC. By using the salt compound dissolved in such a solvent, the dye can be easily dispersed in a molecular state when used as a color material for a color filter, and a good hue and high luminance can be obtained.
The solubility of the salt compound in the solvent is preferably 3.0% by mass or more at 25 ° C., more preferably 5.0% by mass or more. Moreover, the upper limit of the solubility of the salt compound in the solvent is usually 50% by mass or less at 25 ° C. When the solubility of the salt compound in the solvent satisfies the above range, the storage stability when the colored composition is formed, and the precipitation of the dye during the color filter preparation step can be more effectively suppressed.
As the solvent, organic solvents such as esters, ethers, ketones, and aromatic hydrocarbons are preferable from the viewpoint of use in resists for color filters.
Esters include, for example, 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 (specific examples include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3- Oxypropionic acid alkyl esters, 2-oxypropionic acid alkyl esters, methyl 2-oxy-2-methylpropionate, ethyl 2-oxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, DOO ethyl acetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and the like.
Examples of ethers include diethylene glycol dimethyl ether, cyclohexyl acetate, 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, diethylene glycol ethyl methyl. Examples include ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like.
Examples of ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Preferable examples of aromatic hydrocarbons include toluene and xylene.
Solvents that satisfy the requirement of dissolving 1.0% by mass or more of the salt compound at 25 ° C. and are preferable as a coloring composition for a color filter include methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl. Cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene Examples include glycol methyl ether acetate.
It is also preferable to mix two or more of these organic solvents from the viewpoints of solubility of each component in the coloring composition, improvement of the coated surface, and the like. In this case, a mixed solvent composed of two or more of the above-mentioned solvents is preferable, and diethylene glycol ethyl methyl ether and propylene glycol methyl ether acetate are more preferable.
The content of the solvent for dissolving the salt compound at 1.0% by mass or more at 25 ° C. is preferably such that the total solid concentration in the composition of the present invention is 10 to 30% by mass, and 10 to 20% by mass. Is more preferred. Only 1 type may be used for the said salt compound which melt | dissolves 1.0 mass% or more at 25 degreeC, and 2 or more types may be used together. When using 2 or more types of the solvent which melt | dissolves the said salt compound 1.0 mass% or more at 25 degreeC, it is preferable that the sum total is the said range.

<Purple colorant>
The composition of the present invention contains at least one purple colorant selected from a xanthene dye, a pyromethene dye and a tetraazaporphyrin dye together with the salt compound. By setting it as such a structure, the brightness | luminance and contrast of the formed colored cured film can be improved effectively. The purple colorant is preferably dissolved in a solvent capable of dissolving the salt compound at 25 ° C. by 1.0% by mass or more.
1-90 mass% is preferable with respect to the total amount of the said salt compound, and, as for the total amount of the said purple colorant in the composition of this invention, 5-80 mass% is more preferable. The purple colorant may be used alone or in combination of two or more.
Hereinafter, xanthene dyes, pyromethene dyes, and tetraazaporphyrin dyes will be described.

<< Xanthene dye >>
A xanthene pigment is a dye containing a compound having a xanthene skeleton in the molecule. The xanthene dye is preferably dissolved in an organic solvent. For example, the solubility of the xanthene dye in propylene glycol monomethyl ether acetate is preferably 1% by mass or more, and more preferably 3% by mass or more.

  As the xanthene pigment, a dye containing a compound represented by the general formula (I-1a) (hereinafter sometimes referred to as “compound (1a)”) is preferable. Compound (1a) may be a tautomer thereof. In the case of using the compound (1a), the content of the compound (1a) in the xanthene dye is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more. In particular, it is preferable to use only the compound (1a) as the xanthene dye.

一般式（Ｉ−１ａ）中、Ｒ¹〜Ｒ⁴は、それぞれ独立に水素原子、炭素数１〜２０の１価の飽和炭化水素基または炭素数６〜１０の１価の芳香族炭化水素基を表し、上記飽和炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−ＣＯ−または−ＮＲ¹¹−で置換されていてもよい；
Ｒ¹およびＲ²は、互いに結合して窒素原子を含む環を形成してもよい。Ｒ³およびＲ⁴は、互いに結合して窒素原子を含む環を形成してもよい；
Ｒ⁵は、−ＯＨ、−ＳＯ₃ ^-、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ⁺、−ＣＯ₂Ｈ、−ＣＯ₂ ^-Ｚ⁺、−ＣＯ₂Ｒ⁸、−ＳＯ₃Ｒ⁸または−ＳＯ₂ＮＲ⁹Ｒ¹⁰を表す；
Ｒ⁶およびＲ⁷は、それぞれ独立に、炭素数１〜６のアルキル基を表す；
ｍ１は、０〜５の整数を表す。ｍ１が２以上のとき、複数のＲ⁵は同一でも異なってもよい；
ｍ２およびｍ３は、それぞれ独立に、０〜３の整数を表す。ｍ２およびｍ３がそれぞれ独立に、２または３のとき、複数のＲ⁶およびＲ⁷はそれぞれ独立に、同一でも異なってもよい；
ａは、０または１を表す；ａが０を表す場合、キサンテン色素構造中のいずれかの基がアニオンを含む；
Ｘ^-は、アニオンを表す；
Ｚ⁺は、Ｎ⁺（Ｒ¹¹）₄、Ｎａ⁺またはＫ⁺を表し、４つのＲ¹¹は同一でも異なってもよい；
Ｒ⁸は、炭素数１〜２０の１価の飽和炭化水素基を表し、上記飽和炭化水素基に含まれる水素原子は、ハロゲン原子で置換されていてもよい；
Ｒ⁹およびＲ¹⁰は、それぞれ独立に、水素原子または炭素数１〜２０の１価の飽和炭化水素基を表し、上記飽和脂肪族炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−ＣＯ−、−ＮＨ−または−ＮＲ⁸−で置換されていてもよく、Ｒ⁹およびＲ¹⁰は、互いに結合して窒素原子を含む３〜１０員環の複素環を形成していてもよい；
Ｒ¹¹は、水素原子、炭素数１〜２０の１価の飽和炭化水素基または炭素数７〜１０のアラルキル基を表す。Formula (I-1a)

In general formula (I-1a), R ^{1 to} R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. And —CH ₂ — contained in the saturated hydrocarbon group may be substituted with —O—, —CO— or —NR ¹¹ —;
R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom. R ³ and R ⁴ may combine with each other to form a ring containing a nitrogen atom;
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰ ;
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms;
m1 represents the integer of 0-5. when m1 is 2 or more, the plurality of R ⁵ may be the same or different;
m2 and m3 each independently represents an integer of 0 to 3. when m2 and m3 are each independently 2 or 3, a plurality of R ⁶ and R ⁷ may be independently the same or different;
a represents 0 or 1; when a represents 0, any group in the xanthene dye structure contains an anion;
X ⁻ represents an anion;
Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different;
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom;
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the saturated aliphatic hydrocarbon group is —O—, -CO -, - NH- or -NR ⁸ - may optionally be substituted with, R ⁹ and R ^10, may form a heterocyclic ring of 3 to 10-membered ring containing a nitrogen atom bonded to each other ;
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms.

Examples of the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{1 to} R ⁴ include a phenyl group, a toluyl group, a xylyl group, a mesityl group, a propylphenyl group, and a butylphenyl group. Among them, a toluyl group, a xylyl group, a mesityl group, and a propylphenyl group are preferable, and a toluyl group and a xylyl group are particularly preferable, and among these, a 2,6-xylyl group is preferable.

The aromatic hydrocarbon group substituent which may have a halogen ^{atom, -R 8, -OH, -OR 8} , -SO 3 -, - SO 3 H, -SO 3 - Z +, -CO ₂ H, —CO ₂ R ⁸ , —SR ⁸ , —SO ₂ R ⁸ , —SO ₃ R ⁸ or —SO ₂ NR ⁹ R ¹⁰ may be mentioned. Among them, as the _{substituent, -SO 3 -, - SO 3} H, -SO 3 - Z + and -SO ₂ NR ⁹ R ¹⁰ is preferably, -SO ₃ ^- Z ⁺ and -SO ₂ NR ⁹ R ¹⁰ Is more preferable. The _{^{Z +, -SO 3 - - -SO}} 3 in this case N ⁺ (R ¹¹⁾ ₄ are preferred. When R ^{1 to} R ⁴ are these groups, the color composition of the present invention containing the compound (1a) can form a color filter with less generation of foreign matters and excellent heat resistance.

Examples of the ring formed by combining R ¹ and R ² with each other and the ring formed by combining R ³ and R ⁴ with each other include the following.

Examples of the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ^{8 to} R ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. Linear alkyl groups such as decyl group, dodecyl group, hexadecyl group, icosyl group; branched alkyl groups such as isopropyl group, isobutyl group, isopentyl group, neopentyl group, 2-ethylhexyl group; cyclopropyl group, cyclopentyl group , An alicyclic saturated hydrocarbon group having 3 to 20 carbon atoms such as a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a tricyclodecyl group.
Among them, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group are preferable, and in particular, a propyl group, an isopropyl group, a butyl group, a hexyl group, A 2-ethylhexyl group is preferred.
The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms may be substituted with, for example, an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom.

Examples of —OR ⁸ include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group and icosyloxy group. Of these, a methoxy group, an ethoxy group, a propoxy group, and a butoxy group are preferable.

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

Examples of —SR ⁸ include a methylsulfanyl group, an ethylsulfanyl group, a butylsulfanyl group, a hexylsulfanyl group, a decylsulfanyl group, and an icosylsulfanyl group.
Examples of —SO ₂ R ⁸ include a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a decylsulfonyl group, and an icosylsulfonyl group.
Examples of —SO ₃ R ⁸ include a methoxysulfonyl group, an ethoxysulfonyl group, a propoxysulfonyl group, a tert-butoxysulfonyl group, a hexyloxysulfonyl group, and an icosyloxysulfonyl group.

—SO ₂ NR ⁹ R ¹⁰ includes, for example, a sulfamoyl group;
N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-isobutylsulfamoyl group, N- sec-butylsulfamoyl group, N-tert-butylsulfamoyl group, N-pentylsulfamoyl group, N- (1-ethylpropyl) sulfamoyl group, N- (1,1-dimethylpropyl) sulfamoyl group, N- (1,2-dimethylpropyl) sulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (2,2-dimethylpropyl) sulfamoyl group, N- (1-methylbutyl) sulfamoyl group, N- (2 -Methylbutyl) sulfamoyl group, N- (3-methylbutyl) sulfamoyl group, N-cyclopentyl Rufamoyl group, N-hexylsulfamoyl group, N- (1,3-dimethylbutyl) sulfamoyl group, N- (3,3-dimethylbutyl) sulfamoyl group, N-heptylsulfamoyl group, N- (1- Methylhexyl) sulfamoyl group, N- (1,4-dimethylpentyl) sulfamoyl group, N-octylsulfamoyl group, N- (2-ethylhexyl) sulfamoyl group, N- (1,5-dimethyl) hexylsulfamoyl group An N-1 substituted sulfamoyl group such as a group, N- (1,1,2,2-tetramethylbutyl) sulfamoyl group;
N, N-dimethylsulfamoyl group, N, N-ethylmethylsulfamoyl group, N, N-diethylsulfamoyl group, N, N-propylmethylsulfamoyl group, N, N-isopropylmethylsulfa Moyl group, N, N-tert-butylmethylsulfamoyl group, N, N-butylethylsulfamoyl group, N, N-bis (1-methylpropyl) sulfamoyl group, N, N-heptylmethylsulfamoyl And N, N-2-substituted sulfamoyl groups such as a group.
Among them, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-isopropylsulfamoyl group, N-butylsulfamoyl group, N-pentylsulfamoyl group, N -(2-ethylhexyl) sulfamoyl group is preferred, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N- (2-ethylhexyl) A sulfamoyl group is more preferred.

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

R ^{5 _{is, -CO 2 H, -CO 2 -}} Z +, -CO 2 R 8, -CO 2 NHR 9, -SO 3 -, -SO 3 - Z +, -SO 3 H, -SO 2 R 8 or -SO ₂ NHR ⁹ is _{^{preferably,, -SO 3 -, -SO 3}} - Z +, -SO 3 H or -SO ₂ NHR ⁹ is more preferable.
m1 is preferably an integer of 1 to 4, and more preferably 1 or 2.
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms, and among the alkyl groups mentioned as the monovalent saturated hydrocarbon group having 1 to 20 carbon atoms described above, 1 to 6 carbon atoms Of the alkyl group.
m2 and m3 each independently represents an integer of 0 to 3, and 0 is preferable.
Examples of the aralkyl group having 7 to 10 carbon atoms in R ¹¹ include a benzyl group, a phenylethyl group, and a phenylbutyl group.

a represents 0 or 1, and when a represents 0, any group in the xanthene dye structure preferably has an anion, and R ^5A preferably contains an anion.
X ⁻ is included depending on the valence of the cation contained in the xanthene dye represented by the general formula (I-1a), and is usually monovalent or divalent, and monovalent is preferable. Examples of the anion X ⁻ include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a low nucleophilic anion. A fluorine anion, a chlorine anion, a bromine anion or an iodine anion is preferable. . The low nucleophilic anion indicates an anion structure in which an organic acid having a pKa lower than that of sulfuric acid is dissociated. Examples of anions include a low nucleophilic anion described in paragraph No. 0075 of JP2007-310315A, anions described in paragraphs 0016 to 0025 of JP2012-173399A, and JP2013-033731A. Examples include the anion moiety described in paragraphs 0025 to 0033, the contents of which are incorporated herein.
Z ⁺ is N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , preferably N ⁺ (R ¹¹ ) ₄ .
N ⁺ (R ¹¹ ) ₄ is preferably a monovalent saturated hydrocarbon group having 5 to 20 carbon atoms, at least two of the four R ¹¹ . The total number of carbon atoms of the four R ¹¹ is preferably 20 to 80, 20 to 60 is more preferable. When N ⁺ (R ¹¹ ) ₄ is present in the compound (1a), R ¹¹ is any of these groups, so that the color composition containing the compound (1a) has less foreign matter from the colored composition of the present invention. A filter can be formed.

  In addition, the xanthene dye represented by the general formula (I-1a) has a cation delocalized as follows, and the following structures are synonymous, and all are included in the present invention. To do. The cation moiety may be at any position in the molecule, but is preferably located on the nitrogen atom.

一般式（Ｉ−２ａ）
一般式（Ｉ−２ａ）中、Ｒ²¹〜Ｒ²⁴は、互いに独立に、水素原子、−Ｒ²⁶または置換基を有していてもよい炭素数６〜１０の１価の芳香族炭化水素基を表す。Ｒ²¹およびＲ²²は、互いに結合して窒素原子を含む環を形成してもよく、Ｒ²³およびＲ²⁴は、互いに結合して窒素原子を含む環を形成してもよい。
Ｒ²⁵は、−ＳＯ₃−、−ＳＯ₃Ｈ、−ＳＯ₃ ^-Ｚ¹⁺または−ＳＯ₂ＮＨＲ²⁶を表す。
ｍ４は、０〜５の整数を表す。ｍ４が２以上のとき、複数のＲ²⁵は同一でも異なってもよい。
ａ１は、０または１の整数を表す。ａが０を表す場合、キサンテン色素構造中のいずれかの基がアニオンを含む；
Ｘ１^-は、アニオンを表す。
Ｒ²⁶は、炭素数１〜２０の１価の飽和炭化水素基を表す。
Ｚ¹⁺は、⁺Ｎ（Ｒ²⁷）₄、Ｎａ⁺またはＫ⁺を表し、４つのＲ²⁷は同一でも異なってもよい。
Ｒ²⁷は、炭素数１〜２０の１価の飽和炭化水素基またはベンジル基を表す。The compound (1a) is preferably a compound represented by the general formula (I-2a) (hereinafter sometimes referred to as “compound (2a)”). Compound (2a) may be a tautomer thereof.

Formula (I-2a)
In general formula (I-2a), R ^{21 to} R ²⁴ are each independently a hydrogen atom, —R ²⁶ or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms which may have a substituent. Represents. R ²¹ and R ²² may be bonded to each other to form a ring containing a nitrogen atom, and R ²³ and R ²⁴ may be bonded to each other to form a ring containing a nitrogen atom.
R ²⁵ is, -SO ₃ - represents a Z ¹⁺ or _{^{-SO 2 NHR 26 -, - SO}} 3 H, -SO 3.
m4 represents an integer of 0 to 5. When m4 is 2 or more, the plurality of R ²⁵ may be the same or different.
a1 represents an integer of 0 or 1. when a represents 0, any group in the xanthene dye structure contains an anion;
X1 ⁻ represents an anion.
R ²⁶ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms.
Z ¹⁺ represents ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , and four R ^{27 s} may be the same or different.
R ²⁷ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a benzyl group.

The monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms in R ^{21 to} R ²⁴ has the same meaning as the aromatic hydrocarbon group represented by R ^{1 to} R ^{4 in} the general formula (I-1a). is there. Hydrogen atoms contained in the monovalent aromatic hydrocarbon group having 6 to 10 carbon _{^{atoms, -SO 3 -, -SO 3 H}} , -SO 3 - Z 1+, -SO 3 R 26 or -SO ₂ NHR ²⁶ May be substituted.
As a combination of R ^{21 to} R ²⁴ , R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and the above aromatic hydrocarbons hydrogen atoms contained in the _{^{groups, -SO 3 -, -SO 3 H}} , -SO 3 - Z 1+, what is preferably substituted by -SO ₃ R ²⁶ or -SO ₂ NHR ^26. A more preferred combination is that R ²¹ and R ²³ are hydrogen atoms, R ²² and R ²⁴ are monovalent aromatic hydrocarbon groups having 6 to 10 carbon atoms, and hydrogen contained in the aromatic hydrocarbon group. atom, -SO ₃ ^- in which are substituted with Z ¹⁺ or -SO ₂ NHR ^26. When R ^{21 to} R ²⁴ have such a configuration, a color filter having more excellent heat resistance can be formed from the colored composition of the present invention containing the compound (2a).

Examples of the ring containing a nitrogen atom formed by combining R ²¹ and R ²² with each other and the ring containing a nitrogen atom formed by combining R ²³ and R ²⁴ with each other include R in the general formula (I-1a). Examples of the ring formed by combining ¹ and R ² with each other include aliphatic heterocyclic rings. Examples of the aliphatic heterocycle include the following.

The monovalent saturated hydrocarbon group having 1 to 20 carbon atoms in R ²⁶ and R ²⁷ has the same meaning as that described as the saturated hydrocarbon group in R ^{8 to} R ¹¹ .
If R ²¹ to R ²⁴ represents -R ^26, -R ²⁶ each independently is preferably a methyl group or an ethyl group. As the R ²⁶ in -SO ₃ R ²⁶ and -SO ₂ NHR ^26, preferably branched alkyl group having 3 to 20 carbon atoms, more preferably a branched alkyl group having 6 to 12 carbon atoms, A 2-ethylhexyl group is more preferred. When R ²⁶ is such a group, a color filter with less generation of foreign matters can be formed from the colored composition of the present invention containing the compound (2a).

a1 represents 0 or 1, and when a1 represents 0, any group in the xanthene dye structure preferably has an anion, and R ²⁵ preferably contains an anion.
X1 ^- the general formula is included in accordance with the valence of the cation contained in the xanthene dye represented by (I-2a), usually a monovalent or divalent, monovalent preferred. Anion X ^- is the general formula of (I-1a) X ^- in the above formula, the preferable range is also the same.
Z ¹⁺ is ⁺ N (R ²⁷ ) ₄ , Na ⁺ or K ⁺ , preferably ⁺ N (R ²⁷ ) ₄ . ^{+ As} N (R ²⁷ ) ₄ , at least two of four R ²⁷ are preferably monovalent saturated hydrocarbon groups having 5 to 20 carbon atoms. The total number of carbon atoms of the four R ²⁷ is preferably 20 to 80, 20 to 60 is more preferable. When ⁺ N (R ²⁷ ) ₄ is present in the compound (2a), when R ²⁷ is any of these groups, the color composition of the present invention containing the compound (2a) produces less foreign matter. Can be formed.
m4 is preferably 1 to 4, and more preferably 1 or 2.

  Further, as the compound (1a), a compound represented by the general formula (I-3a) (hereinafter sometimes referred to as “compound (3a)”) is also preferable. Compound (3a) may be a tautomer thereof.

一般式（Ｉ−３ａ）中、Ｒ³¹およびＲ³²は、それぞれ独立に、炭素数１〜１０の１価の飽和炭化水素基を表す。炭素数１〜１０の１価の飽和炭化水素基に含まれる水素原子は、炭素数６〜１０の芳香族炭化水素基またはハロゲン原子で置換されていてもよい。炭素数６〜１０の芳香族炭化水素基に含まれる水素原子は、炭素数１〜３のアルコキシ基で置換されていてもよく、炭素数１〜１０の１価の飽和炭化水素基に含まれる−ＣＨ₂−は、−Ｏ−、−ＣＯ−または−ＮＲ¹¹−で置換されていてもよい。
Ｒ³³およびＲ³⁴は、それぞれ独立に、炭素数１〜４のアルキル基、炭素数１〜４のアルキルスルファニル基または炭素数１〜４のアルキルスルホニル基を表す。
Ｒ³¹およびＲ³³は、互いに結合して窒素原子を含む環を形成してもよく、Ｒ³²およびＲ³⁴は、互いに結合して窒素原子を含む環を形成してもよい。
ｐおよびｑは、それぞれ独立に、０〜５の整数を表す。ｐが２以上のとき、複数のＲ³³は同一でも異なってもよい。ｑが２以上のとき、複数のＲ³⁴は同一でも異なってもよい。
Ｒ¹¹は、式（１ａ）中のＲ¹¹と同義である。）Formula (I-3a)

In general formula (I-3a), R ³¹ and R ³² each independently represent a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. The hydrogen atom contained in the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms may be substituted with an aromatic hydrocarbon group having 6 to 10 carbon atoms or a halogen atom. The hydrogen atom contained in the aromatic hydrocarbon group having 6 to 10 carbon atoms may be substituted with an alkoxy group having 1 to 3 carbon atoms, and is contained in a monovalent saturated hydrocarbon group having 1 to 10 carbon atoms. —CH ₂ — may be substituted with —O—, —CO— or —NR ¹¹ —.
R ³³ and R ³⁴ each independently represents an alkyl group, an alkylsulfanyl group, or an alkylsulfonyl group having 1 to 4 carbon atoms having 1 to 4 carbon atoms having 1 to 4 carbon atoms.
R ³¹ and R ³³ may be bonded to each other to form a ring containing a nitrogen atom, and R ³² and R ³⁴ may be bonded to each other to form a ring containing a nitrogen atom.
p and q represent the integer of 0-5 each independently. When p is 2 or more, the plurality of R ³³ may be the same or different. When q is 2 or more, the plurality of R ³⁴ may be the same or different.
R ¹¹ has the same meaning as R ¹¹ in the formula (1a). )

The monovalent saturated hydrocarbon group having 1 to 10 carbon atoms in R ³¹ and R ^32, the carbon number of the monovalent saturated hydrocarbon group having 1 to 10 carbon atoms described in R ⁸ in the formula (1a) Examples thereof include 1 to 10 monovalent saturated hydrocarbon groups. Of these, methyl, ethyl, propyl, butyl, hexyl and 2-ethylhexyl are preferred. Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms which may be present as a substituent include the monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms described for R ¹ in formula (1a). It is done.
As a C1-C3 alkoxy group in which the hydrogen atom contained in a C6-C10 aromatic hydrocarbon group may be substituted, a methoxy group, an ethoxy group, a propoxy group etc. are mentioned, for example.
R ³¹ and R ³² are preferably each independently a monovalent saturated hydrocarbon group having 1 to 3 carbon atoms.

Examples of the alkyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Of these, a methyl group, an ethyl group, and a propyl group are preferable.
Examples of the alkylsulfanyl group having 1 to 4 carbon atoms in R ³³ and R ³⁴ include a methylsulfanyl group, an ethylsulfanyl group, a propylsulfanyl group, a butylsulfanyl group, and an isopropylsulfanyl group.
Examples of the alkylsulfonyl group having 1 to 4 carbon atoms for R ³³ and R ³⁴ include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group.
p and q are preferably an integer of 0 to 2, and preferably 0 or 1.

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

Examples of xanthene dyes include C.I. I. Acid Red 51 (hereinafter, the description of CI Acid Red is omitted and only the number is described. Others are also the same), 52, 87, 92, 94, 289, 388, C.I. I. Acid Violet 9, 30, 102, C.I. I. Basic Red 1 (Rhodamine 6G), 2, 3, 4, 8, C.I. I. Basic Red 10 (Rhodamine B), 11, C.I. I. Basic violet 10, 11, 25, C.I. I. Solvent Red 218, C.I. I. Modern Tread 27, C.I. I. Reactive red 36 (rose bengal B), sulforhodamine G, xanthene dyes described in JP 2010-32999 A and xanthene dyes described in Japanese Patent No. 4492760.
As the xanthene pigment, commercially available xanthene dyes (for example, “Chugai Aminol Fast Pink RH / C” manufactured by Chugai Kasei Co., Ltd., “Rhodamin 6G” manufactured by Taoka Chemical Industry Co., Ltd.) can be used. Moreover, it can also synthesize | combine with reference to Unexamined-Japanese-Patent No. 2010-32999 using the commercially available xanthene dye as a starting material, The content is integrated in this-application specification.

  Xanthene dyes may be used alone or in combination of two or more. When two or more kinds of xanthene dyes are used in combination, the total amount preferably satisfies the above range.

<< Pyromethene Dye >>
The pyromethene dye is preferably a dipyrromethene metal complex compound in which the compound represented by the general formula (I) is coordinated to a metal atom or a metal compound.

Formula (II)

In general formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent substituent. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group.

In the general formula (II), when R ^{1 to} R ⁶ represent a monovalent substituent, examples of the monovalent substituent include the substituents in the substituent group A described above. When the monovalent substituent is a further substitutable group, it may be further substituted with any of the groups described above. In addition, when it has two or more substituents, those substituents may be the same or different.

In general formula (II), R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ⁶ are each independently bonded to each other to form a 5-membered, 6-membered or 7-membered member. A ring may be formed. Examples of the ring formed include a saturated ring and an unsaturated ring. Examples of the 5-membered, 6-membered or 7-membered saturated ring or unsaturated ring include a pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, Examples include a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, a pyridine ring, a pyrazine ring and a pyridazine ring, and preferably a benzene ring and a pyridine ring.
In addition, when the 5-membered, 6-membered and 7-membered rings formed are further substitutable groups, they may be substituted with any of the above-mentioned substituent group A, and two or more substituents In the case where the substituent is substituted, the substituents may be the same or different.
The preferable range of R ^{7 in} the general formula (II) is the same as the case where R ^{1 to} R ⁶ are a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and the preferable range is also the same.

In general formula (II), R ¹ and R ⁶ are preferably an alkylamino group, an arylamino group, a carbonamido group, a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, a carbonamido group, a ureido group, An alkoxycarbonylamino group and a sulfonamide group are more preferable, a carbonamide group, a ureido group, an alkoxycarbonylamino group, and a sulfonamide group are more preferable, and a carbonamide group and a ureido group are particularly preferable.

In general formula (II), R ² and R ⁵ are preferably an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a nitrile group, an imide group, a carbamoylsulfonyl group, an alkoxycarbonyl group, Aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, nitrile group, imide group, carbamoylsulfonyl group are more preferable, An alkoxycarbonyl group, an aryloxycarbonyl group, and a carbamoyl group are particularly preferable.
In general formula (II), R ³ and R ⁴ are preferably an alkyl group, an aryl group or a heterocyclic group, and more preferably an alkyl group or an aryl group.

In the general formula (II), when R ³ and R ⁴ represent an alkyl group, the alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, such as methyl group, ethyl Group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, i-butyl group, tert-butyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, and benzyl group. Moreover, it is more preferable than a C1-C12 branched or cyclic alkyl group, for example, an isopropyl group, a cyclopropyl group, i-butyl group, a tert-butyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group are mentioned. Further, a secondary or tertiary alkyl group having 1 to 12 carbon atoms is preferable, and examples thereof include an isopropyl group, a cyclopropyl group, an i-butyl group, a tert-butyl group, a cyclobutyl group, and a cyclohexyl group.

In the general formula (II), when R ³ and R ⁴ represent an aryl group, the aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
When R ³ and R ⁴ represent a heterocyclic group, the heterocyclic group includes a 2-thienyl group, 4-pyridyl group, 3-pyridyl group, 2-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 2 -A benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group or benzotriazol-1-yl group is preferable, and a 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group or 1-pyridyl group is more preferable. preferable.

Next, the metal atom or metal compound that forms the dipyrromethene-based metal complex compound will be described.
The metal or metal compound may be any metal atom or metal compound capable of forming a complex, a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or 2 Valent metal chlorides are included. For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, in addition to B, such as, AlCl, InCl, FeCl, TiCl 2, SnCl 2, SiCl 2 Further, metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ are also included.
Among these, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoint of the stability, spectral characteristics, heat resistance, light resistance, and production suitability of the complex Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is more preferable. Particularly preferred. Among these, Zn is particularly preferable.

In the dipyrromethene metal complex compound in which the compound represented by the general formula (II) is coordinated to a metal atom or a metal compound, preferred embodiments are shown below. That is, in the general formula (II), R ¹ and R ⁶ are each independently a hydrogen 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, amino group, anilino group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfone An amide group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a phosphinoylamino group, wherein R ² and R ⁵ are each independently a hydrogen atom, a halogen atom, Atom, alkyl group, alkenyl group, aryl group, heterocyclic group, hydride Xyl group, cyano group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group, alkoxycarbonylamino group, sulfonamide group, azo group , An alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, and R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, an 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, carbonamido group, ureido group, imide group , Alkoxycarbonylamino , A sulfonamido group, an azo group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, represented by a sulfamoyl group or a phosphinoylamino group,, R ⁷ is a hydrogen atom, a halogen atom, Represented by an alkyl group, aryl group, or heterocyclic group, the metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B, or VO. The embodiment is mentioned.

The more preferable aspect of a dipyrromethene type metal complex compound is shown below. That is, in the general formula (II), R ¹ and R ⁶ are each independently a hydrogen atom, alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, acyl group, alkoxycarbonyl group, carbamoyl group, amino group. Group, heterocyclic amino group, carbonamido group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamido group, azo group, alkylsulfonyl group, arylsulfonyl group, or phosphinoylamino group R ² and R ⁵ are each independently an alkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, imide group , Alkylsulfonyl group, arylsulfonyl group, or sulf Represented by moil group, R ³ and R ⁴ are each independently 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, a carbonamide group, Represented by a ureido group, an imide group, an alkoxycarbonylamino group, a sulfonamido group, an alkylthio group, an arylthio group, a heterocyclic thio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfamoyl group, R ⁷ is a hydrogen atom, a halogen atom , An alkyl group, an aryl group, or a heterocyclic group, and the metal atom or metal compound is represented by Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO.

  A preferred embodiment of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (II) is coordinated to a metal atom or a metal compound is the following general formula (II-1), (II-2) or (II-3) It is a complex compound represented by these.

Formula (II-1)

In general formula (II-1), R < ¹ > -R < ⁶ > represents a hydrogen atom or a substituent each independently. R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Ma represents a metal atom or a metal compound, X ¹ represents a group capable of binding to Ma, and X ² represents a group necessary for neutralizing the charge of Ma. X ¹ and X ² may be bonded to each other to form a 5-membered, 6-membered or 7-membered ring.

R < ¹ > -R < ⁶ > in General formula (II-1) is synonymous with R < ¹ > -R < ⁶ > in General formula (II), and its preferable aspect is also the same.
Ma in the general formula (II-1) represents a metal atom or a metal compound, and the metal atom or metal compound in the “complex in which the compound represented by the general formula (II) is coordinated to the metal atom or metal compound” It is synonymous and the preferable range is also the same.
R ⁷ in the general formula (II-1) has the same meaning as R ⁷ in formula (II), preferable embodiments thereof are also the same.

X ¹ in the general formula (II-1) may be any group as long as it is capable of binding to Ma, such as water, alcohols (for example, methanol, ethanol, propanol), and further “metal chelate” [ 1] Groups derived from the compounds described in Takeichi Sakaguchi and Keihei Ueno (1995 Nanedou), [2] (1996), [3] (1997), and the like. Among these, water, carboxylic acid compounds, alcohols, amine compounds, and amide compounds are preferable from the viewpoint of production, and water, carboxylic acid compounds, and amide compounds are more preferable.

X ² in the general formula (II-1) represents a group necessary for neutralizing the electric charge of Ma, such as a halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxyl group, aliphatic imide A monovalent group derived from (for example, succinimide, maleimide, glutarimide, diacetamide, etc., preferably succinimide, maleimide), an aromatic imide group or a heterocyclic imide (for example, phthalimide, Naphthalimide, 4-bromophthalimide, 4-methylphthalimide, 4-nitrophthalimide, naphthalenecarboximide, tetrabromophthalimide, etc., preferably phthalimide, 4-bromophthalimide, 4-methylphthalimide) Valent groups, aromatic carboxylic acids (eg benzoic acid, 2-methoxy Benzoic acid, 3-methoxybenzoic acid, 4-methoxybenzoic acid, 4-chlorobenzoic acid, 2-naphthoic acid, salicylic acid, 3,4,5-trimethoxybenzoic acid, 4-heptyloxybenzoic acid, 4-tert- Butyl benzoic acid and the like, preferably monovalent groups derived from benzoic acid, 4-methoxybenzoic acid, salicylic acid and the like, aliphatic carboxylic acids (for example, formic acid, acetic acid, acrylic acid, methacrylic acid, ethane) Acid, propanoic acid, lactic acid, pivalic acid, hexanoic acid, octanoic acid, 2-ethylhexanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, 2-hexadecyloctadecanoic acid, 2-hexyldecanoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, 5-norbornene-2 A monovalent group derived from -carboxylic acid, 1-adamantanecarboxylic acid and the like, preferably acetic acid, methacrylic acid, lactic acid, pivalic acid, 2-ethylhexanoic acid, stearyl acid and the like, dithiocarbamic acid (for example, Monovalent groups derived from dimethyldithiocarbamic acid, diethyldithiocarbamic acid, dibenzyldithiocarbamic acid), sulfonamides (eg, benzenesulfonamide, 4-chlorobenzenesulfonamide, 4-methoxybenzenesulfonamide, 4-methyl) Benzenesulfonamide, 2-methylbenzenesulfonamide, and methanesulfonamide, preferably benzenesulfonamide and methanesulfonamide), a monovalent group derived from hydroxamic acid (for example, acetohydroxamic acid, Monovalent groups derived from kutanohydroxamic acid and benzohydroxamic acid, nitrogen-containing ring compounds (hydantoin, 1-benzyl-5-ethoxyhydantoin, 1-allylhydantoin, 5,5-diphenylhydantoin, 5,5 -Dimethyl-2,4-oxazolidinedione, barbituric acid, imidazole, pyrazole, 4,5-dicyanoimidazole, 4,5-dimethylimidazole, benzimidazole, diethyl 1H-imidazole-4,5-dicarboxylate, etc. And preferably 1-benzyl-5-ethoxyhydantoin, 5,5-dimethyl-2,4-oxazolidinedione, 4,5-dicyanoimidazole, diethyl 1H-imidazole-4,5-dicarboxylate) Represents a valent group.
Among them, in terms of production, a halogen atom, an aliphatic carboxylic acid group, an aromatic carboxylic acid group, an aliphatic imide group, an aromatic imide group, a sulfonic acid group, and a nitrogen-containing ring compound are preferable, and a hydroxyl group and an aliphatic carboxylic acid group An aromatic imide group and a nitrogen-containing ring compound are more preferable.

In the general formula (II-1), when X ¹ and X ² are bonded to each other to form a 5-membered, 6-membered, or 7-membered ring with Ma, 5-membered, 6-membered, and 7-membered are formed. The ring may be a saturated ring or an unsaturated ring. The 5-membered, 6-membered, and 7-membered rings are heterocycles having at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, which may be composed of only carbon and hydrogen atoms. There may be.

Formula (II-2)

In general formula (II-2), R < ¹ > -R < ¹³ > represents a hydrogen atom or a substituent each independently. R ⁷ and R ¹⁴ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ma represents a metal atom or a metal compound.

R < ¹ > -R < ⁶ > in General formula (II-2) is synonymous with R < ¹ > -R < ⁶ > in General formula (II), and its preferable aspect is also the same.
The substituent represented by R ^{8 to} R ¹³ in the general formula (II-2) has the same meaning as the substituent represented by R ^{1 to} R ⁶ of the compound represented by the general formula (II). The preferred embodiment is also the same. When the substituent represented by R ^{8 to} R ¹³ of the compound represented by the general formula (I-2) is a further substitutable group, it is substituted with any of the substituent group A described above. In the case where it is substituted with two or more substituents, these substituents may be the same or different.

R ⁷ in the formula (II-2) has the same meaning as R ⁷ in formula (I), preferable embodiments thereof are also the same.
R ¹⁴ in the general formula (II-2) represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group, and has the same meaning as R ⁷ in the general formula (II). It is. When R ¹⁴ is a further substitutable group, it may be substituted with any of the aforementioned substituents R, and when it is substituted with two or more substituents, those substituents are They may be the same or different.

  Ma in the general formula (II-2) represents a metal or a metal compound, and the metal atom or metal compound in the above-described “complex in which the compound represented by the general formula (II) is coordinated to the metal atom or metal compound” The preferred range is also the same.

R ⁸ and R ⁹ , R ⁹ and R ¹⁰ , R ¹¹ and R ¹² , R ¹² and R ¹³ in the general formula (II-2) are independently bonded to each other to form a 5-membered, 6-membered, or 7-membered compound. A membered saturated ring or an unsaturated ring may be formed. The saturated or unsaturated ring formed is synonymous with the saturated or unsaturated ring formed by R ¹ and R ² , R ² and R ³ , R ⁴ and R ⁵ , and R ⁵ and R ^6. There are also preferred examples.

Formula (II-3)

In General Formula (II-3), R ^{2 to} R ⁵ each independently represent a hydrogen atom or a substituent, and R ⁷ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. . R ⁸ and R ⁹ each 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 amino group. Ma represents a metal atom or a metal compound. X ³ and X ⁴ each independently represent NRa (Ra represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, or Represents a sulfur atom. Y ¹ and Y ² each independently represent NRb (Rb represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group), an oxygen atom, Represents a sulfur atom or a carbon atom. X ⁵ represents a group capable of binding to Ma, and a represents 0, 1 or 2. R ⁸ and Y ¹ may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5-, 6-, or 7-membered ring. The ring may be formed.

R ² to R ⁵ and R ⁷ in Formula (II-3), the general formula (II) in the same meaning as R ² to R ⁵ and R ^7, the preferred embodiment is also the same.
Ma in the general formula (II-3) represents a metal or a metal compound, and is synonymous with the metal atom or the metal compound in the complex in which the compound represented by the general formula (II) is coordinated to the metal atom or the metal compound. The preferred range is also the same.

In general formula (II-3), R ⁸ and R ⁹ are each independently 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), an 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, a 3-buten-1-yl group), an aryl group (preferably a carbon number). An aryl group having 6 to 36, more preferably 6 to 18, for example, a phenyl group or a naphthyl group, a heterocyclic group (preferably having 1 to 24 carbon atoms, and more preferable) Or a heterocyclic group of 1 to 12, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1- A pyrazolyl group, a benzotriazol-1-yl group), an alkoxy group (preferably an alkoxy group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms such as a methoxy group, an ethoxy group, a propyloxy group, a butoxy group, and a hexyl group. An oxy group, a 2-ethylhexyloxy group, a dodecyloxy group, a cyclohexyloxy group), an aryloxy group (preferably an aryloxy group having 6 to 24 carbon atoms, more preferably 1 to 18 carbon atoms such as a phenoxy group and a naphthyloxy group. ), An alkylamino group (preferably an alkylamino group having 1 to 36 carbon atoms, more preferably 1 to 18 carbon atoms, 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 6 to 36 carbon atoms, more preferably 6 to 6 carbon atoms) 18 arylamino groups, for example, phenylamino group, naphthylamino group, N, N-diphenylamino group, N-ethyl-N-phenylamino group), or heterocyclic amino group (preferably having 1 to 24 carbon atoms, More preferably, it is a 1-12 heterocyclic amino group, for example, 2-aminopyrrole group, 3-aminopyra Lumpur group, 2-aminopyridine group or a 3-aminopyridine group).

In general formula (II-3), an alkyl group, alkenyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, alkylamino group, arylamino group, or heterocyclic amino group represented by R ⁸ and R ⁹ Is a further substitutable group, it may be substituted with any of the above-mentioned substituent group A, and when it is substituted with two or more substituents, these substituents are They may be the same or different.

In General Formula (II-3), X ³ and X ⁴ each independently represent NRa, an oxygen atom, or a sulfur atom. Ra 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, such as a methyl group, an ethyl group, a propyl group, an 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 having 2 to 24 carbon atoms, more Preferably it is a 2-12 alkenyl group, for example, a vinyl group, an allyl group, 3-buten-1-yl group), an aryl group (preferably a C6-C36, more preferably a 6-18 aryl group, For example, a phenyl group, a naphthyl group), a heterocyclic group (preferably a heterocyclic group having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, 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), acyl A group (preferably an acyl group having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, for example, acetyl group, pivaloyl group, 2-ethylhexyl group, benzoyl group, cyclohexanoyl group), alkylsulfonyl group (preferably carbon An alkylsulfonyl group having 1 to 24, more preferably 1 to 18, for example, a methylsulfonyl group, an ethylsulfonyl group, an isopropylsulfonyl group, a cyclohexylsulfonyl group, an arylsulfonyl group (preferably having 6 to 24 carbon atoms, more preferably Is an arylsulfonyl group of 6 to 18, for example, phenylsulfonyl Group, a naphthylsulfonyl group). Further, when Ra can be substituted, it may be further substituted with a substituent, and when it is substituted with a plurality of substituents, these substituents may be the same or different.
X ³ and X ⁴ are each independently preferably an oxygen atom or a sulfur atom, and more preferably an oxygen atom.

In General Formula (II-3), Y ¹ and Y ² each independently represent NRb, a sulfur atom, or a carbon atom, and Rb has the same meaning as Ra in X ³ .
Y ¹ and Y ² are preferably each independently NRb (Rb is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), and Y ¹ and Y ² are particularly preferably both NH.

In general formula (II-3), R ⁸ and Y ¹ are bonded to each other, and together with R ⁸ , Y ¹ and the carbon atom, a 5-membered ring (for example, cyclopentane, pyrrolidine, tetrahydrofuran, dioxolane, tetrahydrothiophene, pyrrole) , Furan, thiophene, indole, benzofuran, benzothiophene), 6-membered ring (eg, cyclohexane, piperidine, piperazine, morpholine, tetrahydropyran, dioxane, pentamethylene sulfide, dithiane, benzene, piperidine, piperazine, pyridazine, quinoline, quinazoline) Or a 7-membered ring (eg, cycloheptane, hexamethyleneimine).

In General Formula (II-3), R ⁹ and Y ² may be bonded to each other to form a 5-membered, 6-membered, or 7-membered ring together with R ⁹ , Y ² , and the carbon atom. The 5-membered, 6-membered, and 7-membered rings that are formed include rings in which one bond in the ring formed by R ⁸ , Y ^1, and a carbon atom is changed to a double bond.

In the general formula (II-3), when the 5-membered, 6-membered, and 7-membered rings formed by combining R ⁸ and Y ¹ and R ⁹ and Y ² are further substitutable rings May be substituted with the group described in any of the above-mentioned substituent groups A, and when substituted with two or more substituents, these substituents may be the same or different. May be.

In General Formula (II-3), X ⁵ represents a group capable of binding to Ma, and examples thereof include the same groups as X ^{2 in} General Formula (II-1). a represents 0, 1, or 2.

Preferred embodiments of the compound represented by formula (II-3) are shown below. That is, R ^{2 to} R ⁵ , R ⁷ , and Ma are each a preferred embodiment of a complex containing a compound represented by the general formula (II) and a metal atom or a metal compound, and X ³ and X ⁴ are Each independently NRa (Ra is a hydrogen atom, an alkyl group, a heterocyclic group) or an oxygen atom, and Y ¹ and Y ² are each independently NRb (Rb is a hydrogen atom or an alkyl group), a nitrogen atom, or A carbon atom, X ⁵ is a group bonded through an oxygen atom or a nitrogen atom, and R ⁸ and R ⁹ are each independently an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group. R ⁸ and Y ¹ are bonded to each other to form a 5- or 6-membered ring, and R ⁹ and Y ² are bonded to each other to form a 5- or 6-membered ring, a is 0 Or it is an aspect represented by 1.

The more preferable aspect of the compound represented by general formula (II-3) is shown below. That is, R ^{2 to} R ⁵ , R ⁷ and Ma are each a preferred embodiment of a complex containing a compound represented by the general formula (II) and a metal atom or a metal compound, and X ³ and X ⁴ are oxygen atoms. Y ¹ is NH, Y ² is a nitrogen atom, X ⁵ is an oxygen atom or a group bonded through a nitrogen atom, and R ⁸ and R ⁹ are each independently an alkyl group, Represents an aryl group, a heterocyclic group, an alkoxy group, or an alkylamino group, or R ⁸ and Y ¹ are bonded to each other to form a 5-membered or 6-membered ring, and R ⁹ and Y ² are bonded to each other A forms a 5-membered or 6-membered ring, and a is an embodiment represented by 0 or 1.

  The general formula (II-1), (II-2) or (II-3) is a preferred embodiment of the dipyrromethene-based metal complex compound in which the compound represented by the general formula (II) is coordinated to a metal atom or a metal compound. Of the complex compounds represented by formula (II-3), the complex compound represented by formula (II-3) is particularly preferred.

  Specific examples of the dipyrromethene metal complex compound in which the compound represented by the general formula (II) used in the present invention is coordinated to a metal atom or a metal compound are described in paragraphs 0179 to 0188 of JP2012-237985A. Which is incorporated herein by reference.

  Only one type of pyromethene dye may be used, or two or more types may be used in combination. When two or more types of pyromethene dyes are used in combination, the total amount preferably satisfies the above range.

一般式（ＩＩＩ）中、Ｚ¹、Ｚ²、Ｚ³およびＺ⁴は、全てが窒素原子を表すか、若しくは、Ｚ¹およびＺ³、Ｚ²およびＺ⁴のいずれか１組が双方ともに窒素原子を表し、他の一組がＣ−Ｒを表し、Ｒがそれぞれ独立に水素原子、アルキル基、またはアリール基を表す；Ａ¹、Ａ²、Ａ³、Ａ⁴、Ａ⁵、Ａ⁶、Ａ⁷およびＡ⁸は、各々独立にアルキル基、アルケニル基、アリール基、アルコキシ基、アルキルチオ基、アリールオキシ基、アリールチオ基、ハロゲン原子、ヒドロキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アミノ基、カルバモイル基、スルファモイル基、アシル基、シリルオキシ基、シアノ基、ニトロ基またはヘテロ環基を表す；Ａ¹とＡ²、Ａ³とＡ⁴、Ａ⁵とＡ⁶、および、Ａ⁷とＡ⁸は、各々互いに結合して環構造を形成してもよいが、少なくとも１組は環構造を形成しない；Ｍは、２価の金属原子または置換された金属原子であって２価である原子または原子団を表す。<< tetraazaporphyrin dye >>
The tetraazaporphyrin dye is preferably a compound represented by the general formula (III).
Formula (III)

In general formula (III), Z ¹ , Z ² , Z ³ and Z ⁴ all represent a nitrogen atom, or any one of Z ¹ and Z ³ , Z ² and Z ⁴ is both nitrogen Represents an atom, the other set represents C—R, and each R independently represents a hydrogen atom, an alkyl group or an aryl group; A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently an alkyl group, alkenyl group, aryl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, halogen atom, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, A carbamoyl group, a sulfamoyl group, an acyl group, a silyloxy group, a cyano group, a nitro group or a heterocyclic group; A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ are , Each joined to each other It may form a ring structure Te, but at least one set do not form a ring structure; M represents a divalent and is atom or group a divalent metal atom or a substituted metal atom.

In general formula (III), A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ may be bonded to each other to form a ring structure, One set is an embodiment in which no ring structure is formed.
Also, in one set forming a ring structure, an alicyclic structure may be formed, but it is preferable not to form an aromatic ring structure, more preferably A ¹ and A ² , A ³ and A ⁴ , A ⁵ and In this embodiment, A ⁶ and any of A ⁷ and A ⁸ do not form a ring structure.

The substituents represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ will be described.
The alkyl group is preferably a linear, branched, or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples include a methyl group, an ethyl group, Propyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, dodecyl group, hexadecyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl Group, 1-adamantyl group and the like. The alkenyl group is preferably an alkenyl group having 2 to 48 carbon atoms, more preferably 2 to 18 carbon atoms. Specific examples include a vinyl group, an allyl group, and a 3-buten-1-yl group. The aryl group is preferably an aryl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and specific examples include a phenyl group and a naphthyl group. The alkoxy group is preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, a 1-butoxy group, a 2-butoxy group, and an isopropoxy group. Group, tert-butoxy group, dodecyloxy group, and cycloalkyloxy group include, for example, cyclopentyloxy group, cyclohexyloxy group and the like. The alkylthio group is preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and specific examples include a methylthio group, an ethylthio group, an octylthio group, and a cyclohexylthio group. The aryloxy group is preferably an aryloxy group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, and specific examples include a phenoxy group and 1-naphthoxy group. The arylthio group is preferably an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, specifically, for example, a phenylthio group. As a halogen atom, Preferably, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, Preferably a fluorine atom, a chlorine atom, and a bromine atom are mentioned. The alkoxycarbonyl group is preferably an alkoxycarbonyl group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, and a cyclohexyloxycarbonyl group. Group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group, and the like.

  The aryloxycarbonyl group is preferably an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, and specific examples include a phenoxycarbonyl group. The amino group is preferably an amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. Specific examples include an amino group, a methylamino group, an N, N-dibutylamino group, and a tetradecylamino group. , 2-ethylhexylamino group, cyclohexylamino group and the like. The carbamoyl group is preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specifically, for example, a carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N -Octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group, alkoxycarbonyl group, etc. . The sulfamoyl group is preferably a sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms. Specific examples include a sulfamoyl group, N, N-dipropylsulfamoyl group, and N-ethyl-N-dodecyl. A sulfamoyl group, an N-ethyl-N-phenylsulfamoyl group, an N-cyclohexylsulfamoyl group and the like can be mentioned. The acyl group is preferably an acyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specifically, for example, a formyl group, an acetyl group, a pivaloyl group, a benzoyl group, a tetradecanoyl group, A cyclohexanoyl group etc. are mentioned. The silyloxy group is preferably a silyloxy group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms. Specific examples include a trimethylsilyloxy group, a tert-butyldimethylsilyloxy group, and a diphenylmethylsilyloxy group. Etc. The heterocyclic group is preferably a heterocyclic group having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms. Specifically, for example, a 2-thienyl group, a 4-pyridyl group, a 2-furyl group, Examples include 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazol-1-yl group and the like.

These substituents represented by A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ may be further substituted. Examples of the substituents that can be introduced include halogen atoms (for example, , A fluorine atom, a chlorine atom, a bromine atom, etc.), an alkyl group (preferably a linear, branched or cyclic alkyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, specifically For example, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, dodecyl, hexadecyl, cyclopropyl Group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group, etc.), alkenyl group (preferably having 2 to 48 carbon atoms, more preferably 2 to 2 carbon atoms). 18 alkenyl groups are mentioned, specifically, for example, vinyl group, allyl group, 3-buten-1-yl group, etc., aryl group (preferably having 6 to 48 carbon atoms, more preferably having 6 to 48 carbon atoms). 24 aryl groups, specifically, for example, a phenyl group, a naphthyl group, etc., a heterocyclic group (preferably a C1-C32, more preferably a C1-C18 heterocyclic group). Specifically, 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, benzotriazole -1-yl group, etc.), a silyl group (preferably a silyl group having 3 to 38 carbon atoms, more preferably 3 to 18 carbon atoms, specifically, for example, trimethylsilyl group, triethyl Silyl group, tributyl silyl group, tert- butyldimethylsilyl group, tert- hexyl dimethyl silyl group), a hydroxyl group, a cyano group, a nitro group,

An alkoxy group (preferably an alkoxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, specifically, for example, methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, In the case of propoxy group, tert-butoxy group, dodecyloxy group, and cycloalkyloxy group, for example, cyclopentyloxy group, cyclohexyloxy group, etc., aryloxy group (preferably having 6 to 48 carbon atoms, more preferably carbon Examples thereof include aryloxy groups having 6 to 24, specifically, for example, phenoxy group, 1-naphthoxy group and the like, and heterocyclic oxy groups (preferably having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms). Specific examples thereof include, for example, 1-phenyltetrazol-5-oxy group, 2-tetrahydro Ranyloxy groups, etc.), silyloxy groups (preferably silyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, specifically, for example, trimethylsilyloxy group, tert-butyldimethylsilyloxy group, A diphenylmethylsilyloxy group), an acyloxy group (preferably an acyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms). Specific examples include an acetoxy group, a pivaloyloxy group, and a benzoyloxy group. , A dodecanoyloxy group, etc.), an alkoxycarbonyloxy group (preferably an alkoxycarbonyloxy group having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, specifically, for example, an ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, Examples of the alkyloxycarbonyloxy group include a cyclohexyloxycarbonyloxy group and the like, and an aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms). Specifically, for example, a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, and the like), For example, an N, N-dimethylcarbamoyloxy group, an N-butylcarbamoyloxy group, an N-phenylcarbamoyloxy group, an N-ethyl-N-phenylcarbamoyloxy group, etc., a sulfamoyloxy group (preferably having a carbon number of 1 to 32, more preferably 1 to 24 carbon sulfa Specific examples include N, N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group and the like, alkylsulfonyloxy group (preferably having 1 to 38 carbon atoms, and more preferable). Includes an alkylsulfonyloxy group having 1 to 24 carbon atoms. Specifically, for example, a methylsulfonyloxy group, a hexadecylsulfonyloxy group, a cyclohexylsulfonyloxy group, and the like, an arylsulfonyloxy group (preferably having 6 carbon atoms) To 32, more preferably an arylsulfonyloxy group having 6 to 24 carbon atoms. Specifically, for example, a phenylsulfonyloxy group, etc., an acyl group (preferably 1 to 48 carbon atoms, more preferably a carbon number). 1 to 24 acyl groups, specifically, for example, formyl group, ace Group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group, etc.), alkoxycarbonyl group (preferably C2-C48, more preferably C2-C24 alkoxycarbonyl group) Specifically, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an octadecyloxycarbonyl group, a cyclohexyloxycarbonyl group, a 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group, etc.), an aryloxycarbonyl group (preferably Is an aryloxycarbonyl group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, specifically, for example, a phenoxycarbonyl group),

A carbamoyl group (preferably a carbamoyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, specifically, for example, carbamoyl group, N, N-diethylcarbamoyl group, N-ethyl-N- Octylcarbamoyl group, N, N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N, N-dicyclohexylcarbamoyl group, etc.), amino group (preferably An amino group having 32 or less carbon atoms, more preferably 24 or less carbon atoms can be mentioned. Specific examples include amino group, methylamino group, N, N-dibutylamino group, tetradecylamino group, and 2-ethyl. Xylamino group, cyclohexylamino group, etc.), anilino group (preferably having 6 to 32 carbon atoms, more preferably 6-24 anilino group is mentioned, Specifically, for example, anilino group, N-methylanilino group, etc., heterocyclic amino group (preferably C1-C32, more preferably 1-18 heterocyclic amino Groups, specifically, for example, 4-pyridylamino group, etc., carbonamide groups (preferably C2-C48, more preferably 2-24 carbonamide groups, specifically, For example, an acetamido group, a benzamide group, a tetradecanamide group, a pivaloylamide group, a cyclohexaneamide group, etc.), a ureido group (preferably having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms are exemplified, Are, for example, ureido group, N, N-dimethylureido group, N-phenylureido group, etc.), imide group (preferably having 3 carbon atoms) Hereinafter, an imide group having 24 or less carbon atoms is more preferable. Specifically, for example, an N-succinimide group, an N-phthalimide group, or the like, an alkoxycarbonylamino group (preferably having 2 to 48 carbon atoms, and more preferably). Includes an alkoxycarbonylamino group having 2 to 24 carbon atoms. Specifically, for example, a methoxycarbonylamino group, an ethoxycarbonylamino group, a tert-butoxycarbonylamino group, an octadecyloxycarbonylamino group, a cyclohexyloxycarbonylamino group Etc.), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, specifically, for example, a phenoxycarbonylamino group), sulfone, etc. An amide group (preferably Examples thereof include a sulfonamide group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples include a methanesulfonamide group, a butanesulfonamide group, a benzenesulfonamide group, a hexadecanesulfonamide group, and cyclohexane. Sulfonamido groups, etc.), sulfamoylamino groups (preferably sulfamoylamino groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms), specifically, for example, N, N-dipro A pyrsulfamoylamino group, an N-ethyl-N-dodecylsulfamoylamino group, etc.), an azo group (preferably an azo group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms), specifically Are, for example, phenylazo group, 3-pyrazolylazo group),

An alkylthio group (preferably an alkylthio group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, specifically, for example, a methylthio group, an ethylthio group, an octylthio group, a cyclohexylthio group, etc.), an arylthio group (Preferably includes an arylthio group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, specifically, for example, a phenylthio group), a heterocyclic thio group (preferably having 1 to 32 carbon atoms, and more. Preferably, a C1-C18 heterocyclic thio group is mentioned, Specifically, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group etc.), alkylsulfinyl group ( Preferably an alkylsulfinyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, specifically, for example, Dodecanesulfinyl group etc.), arylsulfinyl group (preferably arylsulfinyl group having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, specifically phenylsulfinyl group etc.), alkylsulfonyl group (Preferably includes an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms. Specific examples include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, a butylsulfonyl group, and an isopropylsulfonyl group. Group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group, etc.), arylsulfonyl group (preferably having 6 to 48 carbon atoms, more preferably having 6 to 24 carbon atoms). , Specifically , For example, phenylsulfonyl group, 1-naphthylsulfonyl group and the like, sulfamoyl group (preferably sulfamoyl group having 32 or less carbon atoms, more preferably 24 or less carbon atoms, specifically, for example, sulfamoyl group, N N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group, etc.), sulfo group, phosphonyl group (preferably Includes a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms. Specifically, for example, a phenoxyphosphonyl group, an octyloxyphosphonyl group, a phenylphosphonyl group, etc.), phosphinoyl Amino group (preferably phosphinoyla having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms) And a mino group, specifically, a diethoxyphosphinoylamino group, a dioctyloxyphosphinoylamino group, and the like.

In C—R represented by Z ¹ , Z ² , Z ³ and Z ⁴ , the alkyl group and aryl group represented by R include A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ^7. and alkyl groups described as the substituent a ⁸ represents, and is synonymous with an aryl group.

In the general formula (III), the metal atom represented by M is preferably Al, Si, Ca, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Ge, Mo, Ru, Rh, Pd, In, Represents Sn, Pt, Pb, Mg, more preferably represents Al, V, Mn, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Pt, Mg, and more preferably Al, V, Mn, Fe, Co, Ni, Cu, Zn, and Mg are represented, and V, Co, Ni, Cu, and Zn are particularly preferably represented.
Specific examples of the substituted metal atom represented by M in the general formula (III), which is a divalent atom or atomic group, include metal halide atoms (for example, Al-F, Al-Cl, Al -Br, Al-I, In- F, In-Cl, Fe-Cl, In-Br, In-I, SiF 2, SiCl 2, SiBr 2, SiI 2, TiF 2, TiCl 2, TiBr 2, TiI 2 Etc.), MB (B is a substituent such as an alkyl group, an aryl group, a naphthyl group, an alkoxy group, a hydroxyl group, and the like. Specifically, for example, Si (CH ₃ ) ₃ , Si (C ₂ H ₅ ) ₃ , Al—C ₆ H ₅ , In—C ₆ H ₅ , Al (OH), Mn (OH), Si (OH) ₂ , Zr (OH) ₂ , Al—OCH ₃ , Al—O (C ₆ H ₅ Etc.) and metal oxide atoms (for example, TiO, MnO, VO, etc.).

一般式（ＩＩＩ−２）中、Ａ¹、Ａ²、Ａ³、Ａ⁴、Ａ⁵、Ａ⁶、Ａ⁷、Ａ⁸およびＭは、一般式（ＩＩＩ）におけるＡ¹、Ａ²、Ａ³、Ａ⁴、Ａ⁵、Ａ⁶、Ａ⁷、Ａ⁸およびＭと各々同義である。
一般式（ＩＩＩ）で表される化合物の吸収スペクトルの極大値は、カラーフィルタの透過率の観点から５５０ｎｍから６５０ｎｍが好ましく、より好ましくは５７０ｎｍから６３０ｎｍ、特に好ましくは５７０ｎｍから６１０ｎｍが好ましい。The tetraazaporphyrin dye is preferably a tetraazaporphyrin compound in which all of Z ¹ , Z ² , Z ³ and Z ⁴ represent a nitrogen atom, preferably a compound represented by the general formula (III-2).
Formula (III-2)

In the general formula ^{(III-2), A 1} , A 2, A 3, A 4, A 5, A 6, A 7, A 8 and M, A ¹ in the general formula ^{(III), A 2, A} 3 , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ and M are respectively synonymous.
The maximum value of the absorption spectrum of the compound represented by formula (III) is preferably from 550 nm to 650 nm, more preferably from 570 nm to 630 nm, particularly preferably from 570 nm to 610 nm, from the viewpoint of the transmittance of the color filter.

As specific examples of the compound represented by the general formula (III), description in paragraphs 0124 to 0141 of JP2013-210577A can be referred to, and the contents thereof are incorporated in the present specification.
Only one tetraazaporphyrin dye may be used, or two or more tetraazaporphyrin dyes may be used in combination. When two or more tetraazaporphyrin dyes are used in combination, the total amount preferably satisfies the above range.

<Pigment>
The coloring composition of the present invention may further contain a pigment. By including the pigment, not only the hue can be adjusted, but also the heat resistance, light resistance, patterning characteristics and the like can be further improved.

In the salt compound contained in the composition of the present invention, since the triarylmethane dye has a bluish hue, the pigment to be combined is preferably a pigment having a purple to blue hue, more preferably a blue pigment, Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80, and Pigment Green 7 in which Cl is changed to OH At least one selected from is more preferred. Among these pigments, Pigment Blue 1, 15: 3, 15: 6, 66 and 79 are preferable, and Pigment Blue 15: 3 and 15: 6 are more preferable.
When blending a pigment having a purple to blue hue in the composition of the present invention, the total amount of the pigment having a purple to blue hue is preferably 0.1 to 20 mass relative to the total amount of the salt compound. 1 to 15% by mass is more preferable.

  The content of the pigment in the composition of the present invention is preferably 30% by mass or less, more preferably 15% by mass or less, and still more preferably 10% by mass or less with respect to the total mass of the coloring material in the composition of the present invention. By setting it as such a range, the fall of the transmittance | permeability can be suppressed and the fall of a brightness | luminance can be suppressed.

The composition of the present invention preferably contains a curable compound in addition to the components described above. Examples of the curable compound include a polymerizable compound and an alkali-soluble binder (including an alkali-soluble binder containing a polymerizable group), and the curable compound is appropriately selected depending on the application and production method. Furthermore, the composition of the present invention preferably contains a photopolymerization initiator.
For example, when a colored layer is formed by a photoresist, the composition of the present invention is added to the salt compound, a solvent that dissolves the salt compound at 1.0% by mass or more at 25 ° C., and the purple colorant. It preferably contains a polymerizable compound as a pigment, a curable compound, an alkali-soluble binder, and a photopolymerization initiator. Furthermore, a surfactant may be included.
When the colored layer is formed by dry etching, the composition of the present invention is added to the salt compound, a solvent that dissolves the salt compound at 1.0% by mass or more at 25 ° C., and the purple colorant. It preferably contains a polymerizable compound as a curable compound, a solvent and a photopolymerization initiator. Furthermore, a surfactant may be included.
Details of these will be described below.

<Curable compound>
The colored composition of the present invention preferably contains a curable compound. The curable compound preferably contains at least a polymerizable compound.
<< polymerizable compound >>
The colored composition of the present invention preferably contains at least one polymerizable compound.
The polymerizable compound is, for example, a polymerizable compound having at least one ethylenically unsaturated double bond, and can be selected and used from components constituting a known composition, as disclosed in JP-A-2006-23696. Examples include the components described in paragraph numbers [0010] to [0020] and the components described in paragraph numbers [0027] to [0053] of JP-A-2006-64921. The polymerizable compound is preferably a compound having a terminal ethylenically unsaturated bond, and more preferably selected from compounds having two or more terminal ethylenically unsaturated bonds.
Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers, or mixtures thereof and multimers thereof.

In addition, a urethane-added polymerizable compound produced by using an addition reaction between an isocyanate and a hydroxyl group is also suitable. And the ethylene oxide skeletons described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418. Urethane compounds having them are also suitable.
Other examples include polyester acrylates, epoxy resins and (meth) described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates obtained by reacting with acrylic acid. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  Specific examples include pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri ((meth) acryloyloxyethyl) isocyanurate. , Pentaerythritol tetra (meth) acrylate EO modified product, dipentaerythritol hexa (meth) acrylate EO modified product, etc., and commercially available products include NK ester A-TMMT, NK ester A-TMM-3, NK oligo UA -32P, NK Oligo UA-7200 (above, manufactured by Shin-Nakamura Chemical Co., Ltd.), Aronix M-305, Aronix M-306, Aronix M-309, Aronix M-450, Aronic M-402, TO-1382, TO-2349 (above, manufactured by Toagosei Co., Ltd.), V # 802 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), KAYARAD D-330, D-320, D-310, DPHA (Nippon Kayaku Co., Ltd.) can be mentioned as a preferred example.

  Moreover, as said (C) polymeric compound, the component as described in Paragraph No. [0031]-[0061] of Unexamined-Japanese-Patent No. 2009-265630 can be mentioned from a viewpoint of low-temperature curability. Especially, as said (C) polymeric compound, (1)-(20) and (M-1)-(M-8) shown below are preferable. In particular, a colored film formed using a polymerizable monomer having two ethylenically unsaturated bonds in the molecule is excellent from the viewpoint of low-temperature curability.

When the polymerizable compound is used for the coloring composition, the content of the polymerizable compound relative to the total solid content of the composition is preferably 10% by mass to 80% by mass, more preferably 15% by mass to 75% by mass, and 20% by mass. -60 mass% is particularly preferred.
Only 1 type may be used for a polymeric compound and it may use 2 or more types together. When two or more polymerizable compounds are used in combination, the total amount preferably satisfies the above range.

<Photopolymerization initiator>
The colored composition of the present invention preferably contains at least one photopolymerization initiator.
The photopolymerization initiator is not particularly limited as long as it can polymerize the polymerizable compound, and is preferably selected from the viewpoints of characteristics, initiation efficiency, absorption wavelength, availability, cost, and the like.
The photopolymerization initiator is a compound that is exposed to exposure light and starts and accelerates polymerization of the polymerizable compound. A compound that responds to actinic rays having a wavelength of 300 nm or longer and initiates and accelerates polymerization of the polymerizable compound is preferable. In addition, a photopolymerization initiator that does not directly respond to actinic rays having a wavelength of 300 nm or longer can also be preferably used in combination with a sensitizer.

Specifically, for example, oxime ester compounds, organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxides, azo compounds, coumarin compounds, azide compounds, metallocene compounds, Examples include hexaarylbiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, onium salt compounds, acylphosphine (oxide) compounds, benzophenone compounds, acetophenone compounds, benzimidazole compounds, and derivatives thereof.
Among these, oxime ester compounds and hexaarylbiimidazole compounds are preferable from the viewpoint of sensitivity.

  Examples of the oxime ester compound include JP 2000-80068, JP 2001-233842, JP 2004-534797, WO 2005/080337, WO 2006/018933, JP The compounds described in JP 2007-210991 A, JP 2007-231000 A, JP 2007-2699779 A, JP 2009-191061 A, and International Publication No. 2009/131189 can be used.

  Specific examples include 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl]. -1,2-pentanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-hexanedione, 2- (O-benzoyloxime) -1- [4- ( Phenylthio) phenyl] -1,2-heptanedione, 2- (O-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 2- (O-benzoyloxime) -1- [4- (Methylphenylthio) phenyl] -1,2-butanedione, 2- (O-benzoyloxime) -1- [4- (ethylphenylthio) phenyl] -1,2- Tandione, 2- (O-benzoyloxime) -1- [4- (butylphenylthio) phenyl] -1,2-butanedione, 1- (O-acetyloxime) -1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-methyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-propyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl -6- (2-ethylbenzoyl) -9H-carbazol-3-yl] ethanone, 1- (O-acetyloxime) -1- [9-ethyl-6- (2-butylbenzoyl) -9 - carbazol-3-yl] ethanone, 1-(O-acetyl oxime) -1- [9-ethyl-6- (thiophenoyl) -9H- carbazol-3-yl] such as propanone and the like. However, it is not limited to these.

  In the present invention, a compound represented by the following general formula (A) is also suitable as an oxime ester compound that is a photopolymerization initiator from the viewpoint of sensitivity, stability over time, and coloring during post-heating.

一般式（Ａ）中、Ｘ¹、Ｘ²、およびＸ³はそれぞれ独立に、水素原子、ハロゲン原子、またはアルキル基を表し、Ｒ¹は−Ｒ、−ＯＲ、−ＣＯＲ、−ＳＲ、−ＣＯＮＲＲ'、または−ＣＮを表し、Ｒ²およびＲ³はそれぞれ独立に。−Ｒ、−ＯＲ、−ＣＯＲ、−ＳＲ、または−ＮＲＲ'を表す。ＲおよびＲ'は、それぞれ独立に、アルキル基、アリール基、アラルキル基、または、複素環基を表し、これらの基は、ハロゲン原子および複素環基からなる群より選択される１以上で置換されていてもよく、上記アルキル基、およびアラルキル基におけるアルキル鎖を構成する炭素原子の１以上が、不飽和結合、エーテル結合、またはエステル結合に置き換わっていてもよく、ＲおよびＲ'は互いに結合して環を形成していてもよい。

In general formula (A), X ¹ , X ² , and X ³ each independently represent a hydrogen atom, a halogen atom, or an alkyl group, and R ¹ is —R, —OR, —COR, —SR, —CONRR. ', Or -CN, and R ² and R ³ are each independently. -R, -OR, -COR, -SR, or -NRR 'is represented. R and R ′ each independently represents an alkyl group, an aryl group, an aralkyl group, or a heterocyclic group, and these groups are substituted with one or more selected from the group consisting of a halogen atom and a heterocyclic group. One or more of carbon atoms constituting the alkyl chain in the alkyl group and the aralkyl group may be replaced with an unsaturated bond, an ether bond, or an ester bond, and R and R ′ are bonded to each other. May form a ring.

In the general formula (A), when X ¹ , X ² , and X ³ represent a halogen atom, examples of the halogen atom include fluorine, chlorine, bromine, and iodine, and X ¹ , X ² , and X ³ are alkyl Examples of the alkyl group in the case of representing a group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, hexyl, heptyl, octyl, isooctyl, 2- Ethylhexyl, tert-octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxyethoxyethyl, ethoxyethoxyethyl, propoxyethoxyethyl, methoxypropyl, Monofluoromethyl, difluoromethyl, tri Fluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like can be mentioned.
Especially, it is preferable that all of X < ¹ >, X < ² > and X < ³ > represent a hydrogen atom, or X < ¹ > represents an alkyl group and X < ² > and X < ³ > both represent a hydrogen atom.

In general formula (A), examples of the alkyl group represented by R and R ′ include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, amyl, isoamyl, tert-amyl, Hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tertiary octyl, nonyl, isononyl, decyl, isodecyl, vinyl, allyl, butenyl, ethynyl, propynyl, methoxyethyl, ethoxyethyl, propyloxyethyl, methoxyethoxyethyl, ethoxyethoxy Examples include ethyl, propyloxyethoxyethyl, methoxypropyl, monofluoromethyl, difluoromethyl, trifluoromethyl, trifluoroethyl, perfluoroethyl, 2- (benzoxazol-2′-yl) ethenyl and the like.
Examples of the aryl group represented by R and R ′ include phenyl, tolyl, xylyl, ethylphenyl, chlorophenyl, naphthyl, anthryl, phenanthrenyl and the like.
Examples of the aralkyl group represented by R and R ′ include benzyl, chlorobenzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, phenylethenyl and the like.
Examples of the heterocyclic group represented by R and R ′ include pyridyl, pyrimidyl, furyl, thiophenyl and the like.
Examples of the ring formed by bonding R and R ′ to each other include a piperidine ring and a morpholine ring.

R ² and R ^{3 including} R and R ′ are each independently a methyl group, a hexyl group, a cyclohexyl group, —S—Ph, —S—Ph—Cl, and —S—Ph—. Br is a particularly preferred embodiment.

Among photopolymerization initiators, in general formula (A), X ¹ , X ² , and X ³ are all hydrogen atoms; R ¹ is an alkyl group, particularly a methyl group; R ² is alkyl Particularly preferred as photoinitiators are those which are groups, in particular methyl groups; those in which R ³ is an alkyl group, in particular ethyl group.

  Accordingly, preferred specific examples of the photopolymerization initiator represented by the general formula (A) include compounds A to G exemplified below. However, the present invention is not limited by the following compounds.

The photopolymerization initiator represented by the general formula (A) can be synthesized, for example, by the method described in JP-A-2005-220097.
The compound represented by the general formula (A) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

一般式（Ｂ）中、Ｒ²²は１価の置換基を表す。Ａ²²は２価の連結基を表し、Ａｒは、アリール基を表す。ｎは、０〜５の整数である。Ｘ²²は１価の置換基を表し、ｎが２〜４の整数である場合複数存在するＸ²²は、同一であっても異なってもよい。In the present invention, a compound represented by the following general formula (B) is also suitable as an oxime ester compound that is a photopolymerization initiator from the viewpoint of sensitivity, stability over time, and coloring during post-heating.

In the general formula (B), R ²² represents a monovalent substituent. A ²² represents a divalent linking group, and Ar represents an aryl group. n is an integer of 0-5. X ²² represents a monovalent substituent, and when n is an integer of 2 to 4, a plurality of X ²² may be the same or different.

The monovalent substituent represented by R ²² is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R ²² include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkylsulfonyl group which may have a substituent, Examples include an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, a heterocyclic group which may have a substituent, and the like.

The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a cyclopentyl group, a cyclohexyl group, or a trifluoromethyl group. , Etc.
The aryl group that may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and examples thereof include a phenyl group, a biphenyl group, a 1-naphthyl group, and a 2-naphthyl group.
The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, and examples thereof include a methylsulfonyl group and an ethylsulfonyl group.
The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, and examples thereof include a phenylsulfonyl group and a 1-naphthylsulfonyl group.
The acyl group which may have a substituent is preferably an acyl group having 2 to 20 carbon atoms, for example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl 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, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxybenzoyl Groups and the like.
The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, a thienyl group, a furyl group, a pyranyl group, etc. are mentioned.
R ²² is more preferably an unsubstituted or substituted acyl group from the viewpoint of high sensitivity, and specifically, an unsubstituted or substituted acetyl group, propionyl group, benzoyl group, toluyl group Is preferred.
Examples of the substituent include groups represented by the following structural formulas, and among them, any of (d-1) (d-4) and (d-5) is preferable.

Examples of the divalent linking group represented by A ²² include an alkylene having 1 to 12 carbon atoms which may have a substituent, cyclohexylene which may have a substituent, and alkynylene which may have a substituent. Is mentioned.
Examples of the substituent that can be introduced into these groups include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Examples include aryloxy groups such as a tolyloxy group, alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group.

Among them, the A ²² is substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Alkylene group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, An alkylene group substituted with a styryl group) is preferred.

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms and may have a substituent.
Specifically, Ar is a phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m. -, P-cumenyl group, mesityl group and the like. Among them, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen atoms such as a fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy such as methoxy group, ethoxy group and tert-butoxy group. Groups, phenoxy groups, aryloxy groups such as p-tolyloxy groups, methoxycarbonyl groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acetoxy groups, propionyloxy groups, acyloxy groups such as benzoyloxy groups, acetyl groups, Benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, methacrylyl group and other acyl groups, methylamino group, cyclohexylamino group and other alkylamino groups, dimethylamino group, diethylamino group, morpholino group, piperidino group and other dialkylamino groups, Fe Arylamino group, a methyl group, an ethyl group, tert- butyl group, an alkyl group such as a dodecyl group, a hydroxy group, a carboxy group, and the like.

  In the general formula (B), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

Examples of the monovalent substituent represented by X ²² include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthiooxy group which may have a substituent, and a substituent. Good arylthiooxy groups, halogen atoms and the like can be mentioned.
The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl. Group, 2-ethylhexyl group, phenacyl group, and the like.
As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable. For example, a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a terphenyl group, a quarterphenyl group, o-, m-, and p-tolyl groups, xylyl groups, and the like.
As an alkenyl group which may have a substituent, a C2-C10 alkenyl group is preferable, for example, a vinyl group, an allyl group, a styryl group etc. are mentioned.
The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.
The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a butoxy group, and a benzyloxy group. .
The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 2-chlorophenyloxy group, 2-methylphenyloxy group, 2-methoxyphenyloxy group, etc. are mentioned.
The alkylthiooxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms. For example, a methylthiooxy group, an ethylthiooxy group, a propylthiooxy group, an isopropylthiooxy group, a butylthiooxy group Group, isobutylthiooxy group, sec-butylthiooxy group, tert-butylthiooxy group, pentylthiooxy group, isopentylthiooxy group, hexylthiooxy group, heptylthiooxy group, octylthiooxy group, 2-ethylhexyl Examples include a thiooxy group, a decylthiooxy group, a dodecylthiooxy group, an octadecylthiooxy group, and a benzylthiooxy group.
The arylthiooxy group which may have a substituent is preferably an arylthiooxy group having 6 to 30 carbon atoms, such as a phenylthiooxy group, a 1-naphthylthiooxy group, a 2-naphthylthiooxy group, 2 -Chlorophenylthiooxy group, 2-methylphenylthiooxy group, 2-methoxyphenylthiooxy group, 2-butoxyphenylthiooxy group, 3-chlorophenylthiooxy group, 3-trifluoromethylphenylthiooxy group, 3-cyano Phenylthiooxy group, 3-nitrophenylthiooxy group, 4-fluorophenylthiooxy group, 4-cyanophenylthiooxy group, 4-methoxyphenylthiooxy group, 4-dimethylaminophenylthiooxy group, 4-methylsulfanyl Phenylthiooxy group, 4-phenylsulfanylphenyl There is thiooxyacids group, and the like.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Examples of the halogenated alkyl group which may have a substituent include a monofluoromethyl group, a difluoromethyl group, a trifluoromethyl group, a dichloromethyl group, a trichloromethyl group, a monobromomethyl group, a dibromomethyl group, and a tribromomethyl group. Etc.
Examples of the amide group which may have a substituent on N include N, N-dimethylamide group and N, N-diethylamide group.

Among these, X ²² has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of solvent solubility and improvement in absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthio which may have a substituent An oxy group, an arylthiooxy group which may have a substituent, a halogenated alkyl group which may have a substituent, an amino group which may have a substituent, or a substituent on N A good amide group is preferable, and an alkyl group which may have a substituent is more preferable.

Moreover, although n in general formula (B) represents the integer of 0-5, the integer of 0-3 is preferable from a viewpoint of the ease of a synthesis | combination, and the integer of 0-2 is more preferable.
In Formula (B), if X ²² there are a plurality, the plurality of X ²² may be the same or may be different.

Specific examples of the oxime photopolymerization initiator represented by the general formula (B) are shown below.

  The compound represented by the general formula (B) used in the present invention has an absorption wavelength in a wavelength region of 250 nm to 500 nm. More preferably, the thing which has an absorption wavelength in the wavelength range of 300 nm-380 nm can be mentioned. In particular, those having high absorbance at 308 nm and 355 nm are preferable.

  Specific examples of the organic halogenated compound include Wakabayashi et al., “Bull Chem. Soc. Japan” 42, 2924 (1969), US Pat. No. 3,905,815, and Japanese Patent Publication No. 46-4605. JP, 48-34881, JP 55-3070, JP 60-239736, JP 61-169835, JP 61-169837, JP 62-58241, JP-A 62-212401, JP-A 63-70243, JP-A 63-298339, M.S. P. Examples include compounds described in Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970), and in particular, oxazole compounds substituted with a trihalomethyl group and s-triazine compounds.

  Examples of hexaarylbiimidazole compounds include, for example, JP-B-6-29285, US Pat. Nos. 3,479,185, 4,311,783, and 4,622,286. Various compounds described in the specification, specifically 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o- Bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2, 2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) biimidazole, 2,2′-bis (o, o′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2 '-Bis (o-nitrophenyl) -4,4', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,4 ', 5,5'-tetraphenyl Examples include biimidazole and 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole.

  A photoinitiator can be used 1 type or in combination of 2 or more types. When using 2 or more types, multiple types of compounds represented by general formula (A) may be used, and multiple types of compounds represented by general formula (B) may be used. Moreover, you may use at least 1 sort (s) from the compound represented by general formula (A) and (B), respectively. Further, at least one compound represented by the general formulas (A) and (B) and an oxime compound other than the compounds represented by the general formulas (A) and (B) or a photopolymerization initiator other than the oxime compound, respectively. It may be used. Moreover, you may use a sensitizer together.

  The total content of the photopolymerization initiator is preferably 0.1% by mass to 20% by mass, and preferably 0.5% by mass to 10% by mass with respect to the total solid content in the colored composition. More preferably, 1% by mass to 5% by mass is most preferable. Within this range, the sensitivity during exposure is high and the color characteristics are also good.

<Binder resin>
The colored composition of the present invention may further contain a binder resin in order to improve the film forming property. As the binder resin, an alkali-soluble binder is preferably used from the viewpoint of pattern formation.
The alkali-soluble binder is not particularly limited except that it has alkali solubility, and can be preferably selected from the viewpoints of heat resistance, developability, availability, and the like.
The alkali-soluble binder is preferably a linear organic high molecular polymer that is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution. Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful.

  In addition to those described above, the alkali-soluble binder includes, for example, those obtained by adding an acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly (2-hydroxyethyl (meth) acrylate), Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include chain butyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

  The alkali-soluble binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, and includes, for example, an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Polymers and the like are also useful. Examples of the above-described polymer containing a polymerizable group include: NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., biscort R-264), Examples thereof include KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like. In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  Among these various alkali-soluble binders, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable, and from the viewpoint of development control. Are preferably acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins. An allyl methacrylate / methacrylic acid copolymer is also preferred.

  Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, the above Photomer 6173, and KS resist-106. Cyclomer P series and the like are preferable.

The alkali-soluble binder is preferably a polymer having a weight average molecular weight (polystyrene equivalent value measured by GPC method) of 1,000 to 200,000 from the viewpoint of developability, liquid viscosity, etc., and 2,000 to 100,000. More preferably, the polymer of 5,000-50,000 is especially preferable.
The alkali-soluble binder can be used alone or in combination of two or more.

<Other ingredients>
In the coloring composition of the present invention, if necessary, a known additive such as a polyfunctional thiol compound, a chain transfer agent, a polymerization inhibitor, an organic solvent, a surface active agent is used as long as the effects of the present invention are not impaired. Agents, adhesion improvers, crosslinking agents, development accelerators, and other additives.
Below, these components are demonstrated.

<Multifunctional thiol compound>
The coloring composition of the present invention may contain a polyfunctional thiol compound.
The coloring composition of the present invention contains a polyfunctional thiol compound, so that the sensitivity is enhanced, ion elution caused by a coloring material such as a dye is suppressed, and the coloring composition of the present invention is used for producing a color filter of a liquid crystal display device. When used, deterioration in image quality such as crosstalk can be prevented, and a clear display with high image quality becomes possible.
In the present invention, the “polyfunctional thiol compound” means a compound having two or more thiol groups in the molecule. As the polyfunctional thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable, specifically, a molecular weight of 100 to 1500 is preferable, and 150 to 1000 is more preferable. The polyfunctional thiol compound preferably has 2 to 10 thiol groups in the molecule, more preferably 2 to 6, and particularly preferably 2 to 4. In addition, these compounds are preferably used as a system that is used auxiliary when the radical polymerizable monomer is polymerized. Specifically, the addition amount of the polyfunctional thiol compound is 1 to 20% by mass relative to the total solid content of the composition, or less than the addition amount of the radical polymerizable monomer contained at the same time. It is preferable to make it an addition amount.

  Specific examples of the polyfunctional thiol compound that can be used in the present invention include, for example, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercapto). Propionate), dipentaerythritol hexakis (3-mercaptopropionate), pentaerythritol tetrakis (thioglycolate), pentaerythritol tetrakis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Multifunctional thiols, such as trione, etc. And the like as compounds. Particularly preferred is a compound containing secondary SH, and it is preferred to have a triazine skeleton from the viewpoint of liquid stability. Specific examples include Karenz MT series (manufactured by Showa Denko KK).

  The content of the polyfunctional thiol compound is preferably 0.01% by mass to 20% by mass and more preferably 0.1% by mass to 10% by mass with respect to the total solid content in the colored composition. . When the content of the polyfunctional thiol compound is within this range, the sensitivity of the colored composition is good, the storage stability is good, the pixel adhesion in the obtained color filter is good, there is no pattern defect, and the liquid crystal When used in a display device, a colored composition having good electrical characteristics can be provided.

<Sensitizer>
A sensitizer can also be added to the coloring composition of the present invention. Typical sensitizers used in the present invention include Krivello [J. V. Crivello, Adv. in Polymer Sci, 62, 1 (1984)]. Specific examples include pyrene, perylene, acridine, thioxanthone, 2-chlorothioxanthone, benzoflavine, N-vinylcarbazole, 9,10. -Dibutoxyanthracene, anthraquinone, benzophenone, coumarin, ketocoumarin, phenanthrene, camphorquinone, phenothiazine derivatives and the like. The sensitizer is preferably added in a proportion of 50 to 200% by mass with respect to the photopolymerization initiator.

<Chain transfer agent>
A chain transfer agent can also be added to the coloring composition of the present invention. Examples of the chain transfer agent used in the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercapto. And mercapto compounds having a heterocyclic ring such as benzimidazole and N-phenylmercaptobenzimidazole.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.
The addition amount of the chain transfer agent is preferably in the range of 0.01% by mass to 15% by mass with respect to the total solid content of the coloring composition of the present invention, from the viewpoint of reducing the sensitivity variation. 1 mass%-10 mass% are more preferable, and 0.5 mass%-5 mass% are especially preferable.

<Polymerization inhibitor>
The coloring composition of the present invention may contain a polymerization inhibitor.
A polymerization inhibitor means hydrogen donation (or hydrogen donation), energy donation (or energy donation), electron donation (or electron donation) to polymerization initiation species such as radicals generated in the colored composition by light or heat. A substance that plays a role of suppressing the initiation of polymerization unintentionally by deactivating the polymerization initiating species. The polymerization inhibitors described in paragraphs [0154] to [0173] of JP-A-2007-334322 can be used.
Among these, p-methoxyphenol is preferably exemplified as the polymerization inhibitor.
The content of the polymerization inhibitor in the colored composition of the present invention is preferably 0.0001% by mass to 5% by mass, more preferably 0.001% by mass to 5% by mass, based on the total mass of the polymerizable compound. 0.001% by mass to 1% by mass is particularly preferable.

<Surfactant>
The coloring composition of the present invention may contain a surfactant.
As the surfactant, any of anionic, cationic, nonionic, or amphoteric surfactants can be used, but a preferred surfactant is a nonionic surfactant. Specific examples include nonionic surfactants described in paragraph 0058 of JP-A-2009-098616, and among these, fluorosurfactants are preferable.
Other surfactants that can be used in the present invention include, for example, commercially available products such as MegaFuck F142D, F172, F173, F176, F177, F183, F479, F482, and F554. F780, F781, F781-F, R30, R08, F-472SF, BL20, R-61, R-90 (made by DIC Corporation), Florard FC-135, FC -170C, FC-430, FC-431, Novec FC-4430 (manufactured by Sumitomo 3M), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131 S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), F-top EF351, 352, 801, 802 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Footgent 250 (manufactured by Neos Co., Ltd.), etc. Is mentioned.
Further, the surfactant includes a structural unit A and a structural unit B represented by the following formula (W), and has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography using tetrahydrofuran as a solvent. A copolymer having a molecular weight of 000 or more and 10,000 or less can be given as a preferred example.

（式（Ｗ）中、Ｒ¹およびＲ³はそれぞれ独立に、水素原子またはメチル基を表し、Ｒ²は炭素数１以上４以下の直鎖アルキレン基を表し、Ｒ⁴は水素原子または炭素数１以上４以下のアルキル基を表し、Ｌは炭素数３以上６以下のアルキレン基を表し、ｐおよびｑは重合比を表す質量百分率であり、ｐは１０質量％以上８０質量％以下の数値を表し、ｑは２０質量％以上９０質量％以下の数値を表し、ｒは１以上１８以下の整数を表し、ｎは１以上１０以下の整数を表す。）

(In the formula (W), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group, R ² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴ represents a hydrogen atom or carbon number. 1 represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, and n represents an integer of 1 to 10.

L is preferably a branched alkylene group represented by the following formula (W-2). R ⁵ in Formula (W-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability with respect to the coated surface. Two or three alkyl groups are more preferred.
The sum (p + q) of p and q in the formula (W) is preferably p + q = 100, that is, 100% by mass.
The weight average molecular weight (Mw) of the copolymer is more preferably 1,500 or more and 5,000 or less.

These surfactants can be used alone or in combination of two or more.
0.01-2.0 mass% is preferable in the total solid of a coloring composition, and, as for the addition amount of surfactant in the coloring composition of this invention, 0.02-1.0 mass% is especially preferable. Within this range, the coatability and the uniformity of the cured film are good.

<Adhesion improver>
The coloring composition of the present invention may contain an adhesion improving agent.
The adhesion improver is an inorganic substance that serves as a support, for example, a compound that improves adhesion between a silicon compound such as glass, silicon, silicon oxide, and silicon nitride, gold, copper, aluminum, and the cured film of the colored composition layer. is there. Specific examples include silane coupling agents. The silane coupling agent as the adhesion improving agent is for the purpose of modifying the interface, and any known silane coupling agent can be used without any particular limitation.
As the silane coupling agent, a silane coupling agent described in paragraph 0048 of JP-A-2009-98616 is preferable, and among them, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable. Also, 3-methacryloxypropyltrimethoxysilane can be used.
The adhesion improver can be used alone or in combination of two or more.
The content of the adhesion improving agent in the colored composition of the present invention is preferably 0.1% by mass to 20% by mass and more preferably 0.2% by mass to 5% by mass with respect to the total solid content of the colored composition. .

<Crosslinking agent>
A supplementary crosslinking agent may be used in the colored composition of the present invention to further increase the hardness of the colored layer obtained by curing the colored composition.
The crosslinking agent is not particularly limited as long as the film can be cured by a crosslinking reaction. For example, at least selected from (a) an epoxy resin, (b) a methylol group, an alkoxymethyl group, and an acyloxymethyl group. Substituted with at least one substituent selected from a melamine compound, a guanamine compound, a glycoluril compound or a urea compound, (c) a methylol group, an alkoxymethyl group, and an acyloxymethyl group, substituted with one substituent, Phenol compounds, naphthol compounds or hydroxyanthracene compounds.
Among these, an epoxy resin is particularly preferable because a stronger film can be formed by a reaction with an acid (resin, monomer, etc.) present in the resist system as a curing agent and an SH compound. From the viewpoint of low viscosity, heat resistance, and stability, alicyclic epoxy is preferable.
For details such as specific examples of the crosslinking agent, the description in paragraphs [0134] to [0147] of JP-A No. 2004-295116 can be referred to.
A crosslinking agent can be used alone or in combination of two or more.

<Development accelerator>
A development accelerator can also be added in order to promote the alkali solubility of the non-exposed area when the colored composition layer is exposed and to further improve the developability of the colored composition. The development accelerator is preferably a low molecular weight organic carboxylic acid compound having a molecular weight of 1000 or less and a low molecular weight phenol compound having a molecular weight of 1000 or less.
Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, and umbellic acid.
The development accelerator can be used alone or in combination of two or more.

If necessary, the colored composition of the present invention may further contain various additives such as fillers, polymer compounds other than those described above, ultraviolet absorbers, antioxidants and the like. Examples of these additives include those described in paragraphs 0155 to 0156 of JP-A No. 2004-295116.
The coloring composition of the present invention may contain a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph 0081 of the publication.

<Method for preparing colored composition>
The coloring composition of the present invention is prepared by mixing the above-described components and optional components as necessary.
In preparing the colored composition, the components constituting the colored composition may be mixed together, or may be sequentially added after each component is dissolved and dispersed in a solvent. In addition, there are no particular restrictions on the charging order and working conditions when blending. For example, the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a colored composition.
The colored composition prepared as described above can preferably be used after being filtered using a filter having a pore size of about 0.01 μm to 3.0 μm.
Since the colored composition of the present invention can form a colored cured film excellent in luminance and contrast, for forming colored pixels such as a color filter used in a liquid crystal display device, printing ink, inkjet ink, and It can be suitably used as a production application for paints and the like.

<Color filter and manufacturing method thereof>
The color filter of the present invention includes a substrate and a colored pixel composed of a colored film formed on the substrate with the colored composition of the present invention. The colored region on the substrate is composed of colored layers such as red (R), green (G), and blue (B) that form each pixel of the color filter.
The method for producing a color filter of the present invention includes a colored layer forming step (A) in which a colored layer (colored composition layer) is formed by applying the above-described colored composition on a support, and step (A). An exposure step (B) for pattern-like exposure to the formed colored layer and a development step (C) for developing the exposed colored layer to form a pattern are included.
Moreover, in the manufacturing method of the color filter of this invention, the aspect which further provided the post-baking (post-heating process) (D) which heat-processes with respect to the coloring pattern obtained at the process (C) is preferable.
Furthermore, it is also possible to provide a step (post-exposure) for irradiating the colored pattern with ultraviolet rays between the development step and the post-bake step.
The method for producing a color filter of the present invention comprises a step of applying the composition of the present invention on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, and an unexposed portion. It is also preferable to include a step of developing and removing to form a colored pattern.
Hereinafter, the manufacturing method of the color filter of the present invention will be described more specifically. A color filter on array (COA) type color filter manufacturing method that is effective from the viewpoint of improving luminance and yield will be described in addition to the manufacturing method that has been mainly used conventionally.

<< Conventional Color Filter Manufacturing Method >>
-Process (A)-
In the method for producing a color filter of the present invention, first, the above-described colored composition of the present invention is applied onto a support by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, and inkjet. Then, a colored layer is formed, and then the colored layer is dried by heating (prebaking) or vacuum drying.
Examples of the support include sodium glass, alkali-free glass, borosilicate glass, quartz glass, silicon substrate, and resin substrate used for liquid crystal display devices.
For a COA liquid crystal display device, a driving substrate for a thin film transistor (TFT) liquid crystal display device is used.
Further, an undercoat layer, an interlayer insulating film, or the like may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the surface.
Examples of the pre-baking condition include a condition of heating at 70 ° C. to 130 ° C. for about 0.5 minutes to 15 minutes using a hot plate or an oven.
Moreover, the thickness of the colored layer formed with a coloring composition is suitably selected according to the objective. In the color filter for liquid crystal display devices, the range of 0.2 μm to 5.0 μm is preferable, and the range of 1.0 μm to 4.0 μm is more preferable. In the COA type color filter for liquid crystal display devices, the thickness of the pixel film is preferably in the range of 0.3 μm to 5.0 μm, and more preferably in the range of 0.5 μm to 3.5 μm. In addition, the thickness of a colored layer is a film thickness after prebaking.

-Process (B)-
Subsequently, in the method for producing a color filter of the present invention, pattern-like exposure is performed on the colored layer formed on the support. As light or radiation applicable to exposure, g-line, h-line, i-line and various laser beams are preferable, and i-line is particularly preferable. When using the i-line to the irradiation light is preferably irradiated at an exposure dose of ^{5mJ / cm 2 ~500mJ / cm 2} .
In addition, as other exposure light sources, ultra-high pressure, high pressure, medium pressure, and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, various laser light sources, and the like can be used.

-Process (C)-
Subsequently, the colored layer after exposure is developed with a developer. Thereby, a colored pattern can be formed. As long as the developing solution dissolves the uncured portion of the colored layer and does not dissolve the cured portion, a combination of various organic solvents or an alkaline aqueous solution can be used. When the developer is an alkaline aqueous solution, the alkali concentration is preferably adjusted to pH 10-13. Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethyl. Examples include alkaline aqueous solutions such as ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene.
In a color filter used in a COA type liquid crystal display device, an organic alkaline developer is particularly desirable as the developer from the viewpoint of not causing damage to the underlying circuit.
The development time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 120 seconds. The development temperature is preferably 20 ° C to 40 ° C, more preferably 20 ° C to 30 ° C.
Development can be performed by a paddle method, a shower method, a spray method, or the like.
Moreover, after developing using alkaline aqueous solution, it is preferable to wash | clean with water.
In the method for producing a color filter of the present invention, it is particularly preferable to perform post-exposure by ultraviolet irradiation on a colored pattern (pixel) formed using a colored composition.

-Process (D)-
It is preferable to further heat-treat the colored pattern after development or the colored pattern subjected to post-exposure by ultraviolet irradiation as described above. The colored pattern can be further cured by subjecting the formed colored pattern to heat treatment (so-called post-bake treatment). This heat treatment can be performed by, for example, a hot plate, various heaters, an oven, or the like.
As temperature in the case of heat processing, it is preferable that it is 100 to 300 degreeC, More preferably, it is 150 to 250 degreeC. The heating time is preferably about 10 minutes to 120 minutes.

The colored pattern thus obtained constitutes a pixel in the color filter. In manufacturing a color filter having a plurality of hue pixels, the above-described step (A), step (B), step (C), and step (D) may be repeated according to the desired number of colors.
In addition, whenever formation, exposure, and development of a single color layer are completed (for each color), the step (D) may be performed, or formation, exposure, and exposure of all the color layers having a desired number of colors. After the development is completed, the step (D) may be performed collectively.
Hereinafter, a color filter which is a more preferable aspect as a color filter constituted using the colored composition of the present invention, a method for producing the color filter, and details relating to the production of COA using these will be described.

<< Production Method and Usage Method of COA Color Filter >>
In producing the color filter of the present invention by the COA method, it can be produced as follows. After applying the composition of the present invention containing a colorant on the TFT substrate to form a coating film of the composition, the coating film is subjected to pattern exposure, alkali development, post-baking treatment, etc. to form each pixel. . Next, after sputtering a transparent electrode (ITO) film on each of the pixels, a positive photoresist coating film is formed, pattern exposure and development are performed on the photoresist film, and the necessary ITO is etched to form a pixel electrode pattern. After the formation, the photoresist film remaining on the pixel electrode pattern is removed with a stripping solution to obtain a COA color filter.

  In order to form a coating film by applying the composition of the present invention, it is applied to a substrate directly or via another layer by spin coating (spin coating), slit coating, casting coating, roll coating, or the like, What is necessary is just to dry (pre-bake). The composition layer applied on the substrate can be dried (prebaked) at a temperature of 50 ° C. to 140 ° C. for 10 to 300 seconds using a hot plate, oven, or the like. In recent years, since the substrate has been increased in size, slit coating is also effective as a method for forming a coating film, and this coating method is becoming common.

Further, the pattern exposure of the coating film is made up of pixels of each color (three colors or four colors) by exposing through a predetermined mask pattern, curing only the coating film portion irradiated with light, and developing with a developer. This can be done by forming a patterned film. As radiation that can be used in exposure, ultraviolet rays such as g-line and i-line are particularly preferably used.
Next, by carrying out an alkali development treatment, in the case of the negative type, the uncured portion that has not been exposed is eluted in the alkaline aqueous solution, and only the photocured portion remains. As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.
Examples of the alkali include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, The concentration of an organic alkaline compound such as piperidine or 1,8-diazabicyclo- [5,4,0] -7-undecene is 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass. Thus, an alkaline aqueous solution diluted with pure water can be used. In the case where a developer composed of such an alkaline aqueous solution is used, the developer is generally washed (rinsed) with pure water after development.
Next, excess developer is washed away and dried, followed by heat treatment (post-bake). In this way, the above process can be repeated sequentially for each color to produce a cured coating. Thereby, a color filter is obtained.

The post-baking is a heat treatment after development for complete curing, and usually a heat curing treatment at 200 ° C. to 240 ° C. is performed.
This post-bake treatment is performed continuously or batchwise by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, or the like so that the coating film after development is in the above-described condition. be able to.

Then, a transparent electrode (ITO) film is formed on the formed pixel by sputtering, a positive photoresist film is further formed thereon, pattern exposure and development are performed, and unnecessary with chemicals such as hydrofluoric acid. ITO is etched to form pixel electrodes. As the photoresist used at this time, a positive photoresist having etching resistance is required. Moreover, a well-known method can be normally used for pattern exposure, image development, and etching without a restriction | limiting.
Next, the positive resist remaining on the formed pixel electrode is quickly stripped and removed with a stripping solution. There is no restriction | limiting in particular as this stripping solution, A conventionally well-known stripping solution can be used. For example, various publications disclosed in JP-A-51-72503, JP-A-57-84456, JP-A-6-222573, etc., and U.S. Pat. No. 4,165,294 and European Patent No. 0119337. These organic solvents can be used. A typical stripping solution includes a mixed solvent of monoethanolamine (MEA) and dimethyl sulfoxide (DMSO). Further, by using an organic solvent heated to 60 ° C. or higher as the stripping solution, the stripping process can be shortened, and further, there can be no problem of development residue. Since the composition in the present invention is particularly excellent in stripping liquid resistance, even when an organic solvent heated to 60 ° C. or higher is used, the coating film of the color filter may peel off, swell or expand. The resist film can be removed.

The color filter of the present invention is usually used in various display devices such as a TFT liquid crystal display device having a structure as disclosed in FIG. 1 of JP-A-9-31347.
The color filter obtained as described above is suitable for a COA type image display device because it can be easily aligned and can increase the aperture ratio. In addition, since the pixel is formed using the composition of the present invention, the resistance to the stripping solution is high, so that the yield rate is high and the production efficiency is also high. In addition, heat discoloration, low dielectric constant, film thickness uniformity, resolution, voltage holding ratio, light resistance and the like normally required for color filters are also good.

The structure of the color filter is composed of a pixel film formed of a coating film of a pixel composition and the pixel protective film composition formed on the pixel film, in contrast to the form in which the pixel has only one layer as described above. Two layers of a pixel protective film are provided between the substrate and the pixel electrode.
The film thickness of the pixel film is preferably 0.3 μm to 5.0 μm, more preferably 0.5 μm to 3.5 μm. The higher the coating thickness, the higher the chromaticity can be achieved. However, the thicker the coating thickness, the lower the resolution of the contact hole. The film thickness of the pixel protective film is preferably 0.2 μm to 5.0 μm, and more preferably 0.2 μm to 3.0 μm. Further, it is desirable that the unevenness of the underlying pixel is flattened so that the surface is smooth.

<Display device>
The color filter obtained by the method for producing a color filter of the present invention (the color filter of the present invention) is excellent in luminance and contrast because it uses the colored composition of the present invention.
The display device of the present invention includes the color filter of the present invention.
Specifically, as a display device of the present invention, a liquid crystal display (liquid crystal display device; LCD), an organic EL display (organic EL display device), a liquid crystal projector, a display device for a game machine, a display device for a portable terminal such as a mobile phone. Display devices such as digital camera display devices and car navigation display devices, particularly color display devices are suitable.
When the color filter of the present invention is used in an organic EL display device, a liquid crystal display device or the like, it is possible to display an image with high luminance and excellent spectral characteristics and contrast.

<Liquid crystal display device>
A liquid crystal display device using the color filter of the present invention will be described. For the definition of organic EL display devices and liquid crystal display devices and details of each display device, refer to, for example, “Electronic Display Devices (Akio Sasaki, published by Kogyo Kenkyukai 1990)”, “Display Devices (written by Junaki Ibuki, Sangyo Tosho (issued in 1989) ”. The liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Kenkyukai 1994)”. The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
The color filter of the present invention is particularly effective for a color TFT liquid crystal display device. The color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”. Furthermore, the present invention is applied to a liquid crystal display device with a wide viewing angle such as a horizontal electric field driving method such as IPS and a pixel division method such as MVA, STN, TN, VA, OCS, FFS, and R-OCB. it can. Further, as described above, the color filter of the present invention can be used for a COA (Color-filter On Array) system.

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

<Solid-state imaging device>
The composition of the present invention can be preferably used as a solid-state imaging device. The solid-state imaging device of the present invention includes the color filter of the present invention.
The configuration of the solid-state imaging device is a configuration provided with a color filter manufactured using the composition of the present invention, and is not particularly limited as long as the configuration functions as a solid-state imaging device. Can be mentioned.
A transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD image sensor, CMOS image sensor, etc.) is provided on a support, and the photodiode and the transfer electrode are provided on the support. A light-shielding film made of tungsten or the like having an opening only in the light-receiving portion of the photodiode, and a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving portion. It is the structure which has the color filter for solid-state image sensors of this invention on a device protective film.
Further, a configuration having a light condensing means (for example, a microlens, etc., the same applies hereinafter) on the device protective layer and under the color filter (on the side close to the support), or a structure having the light condensing means on the color filter. Etc.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “%” and “parts” are based on mass.

Dye 1A

Dye 2A

Dye 3A

Dye 4A

Dye 5A

Dye 6A

Dye 7A

Dye 8A

Dye 1B

Dye 2B

Dye 3B

Dye 4B

Dye 5B

Dye 6B

<Example 1>
-Preparation of coloring composition 1-
The following components were mixed and dissolved to prepare a colored composition.
Organic solvent 1 (propylene glycol monomethyl ether acetate: PGMEA) 27.4 parts Organic solvent 2 (diethylene glycol ethyl methyl ether: MEDG)
12.6 parts, alkali-soluble binder (allyl methacrylate / methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 6.6 parts, polymerizable compound (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 6 .3 parts-polymerization inhibitor (p-methoxyphenol) 0.003 parts-photopolymerization initiator (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazole-3 -Il] propanone)
0.3 part ・ Polyfunctional thiol compound 1 (1,4-bis (3-mercaptobutyryloxy) butane) 0.2 part ・ Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.2 part ・ Fluorine -Based surfactant (Megafac F-554 manufactured by DIC, 2% propylene glycol monomethyl ether acetate solution) 0.6 part Dye A: 41.6 parts of 5% propylene glycol monomethyl ether acetate solution of (1A above) dye B: 4.2 parts of 5% propylene glycol monomethyl ether acetate solution of (1B above)

<Examples 2 to 21>
Colored compositions 2 to 21 were prepared in the same manner as in Example 1 except that the dyes (1A) and (1B) used in Example 1 were changed as described in the following table.

なお、上記例示化合物Ａは特開２０１１−１７８８６５号公報に記載の方法に従い合成した。<Example 22>
-Preparation of blue pigment dispersion-
-Adjustment of pigment-
C. I. 100 parts of Pigment Blue 15: 6 (product name: Fastogen Blue EP-193), 400 parts of sodium chloride and 140 parts of diethylene glycol were charged into a table kneader (manufactured by Irie Shokai Co., Ltd.) and kneaded for 10 hours. Next, this kneaded product was stirred and mixed with water using a dissolver (manufactured by Nippon Seiki Seisakusho Co., Ltd.), and then filtered and washed repeatedly to remove sodium chloride and the solvent to obtain a water cake of a coloring material. Thereafter, the water cake was dried in an oven at 80 ° C. for 6 hours.
-Coarse dispersion-
After preparing the following composition using the above pigment, the mixture was dispersed using Eiger mill (manufactured by Eiger Japan Co., Ltd.) and zirconia beads having a diameter of 0.8 mm.
-100 parts of the above blue pigment-10 parts of the pigment derivative (I) described in paragraph 0388 of JP2011-178865A-120 parts of a polymer dispersant (the following exemplary compound A)-220 parts of propylene glycol monomethyl ether acetate (Exemplary Compound A)

The exemplified compound A was synthesized according to the method described in JP2011-178865A.

<Precise dispersion>
The dispersion after the coarse dispersion was taken out, and 30 parts of propylene glycol monomethyl ether acetate was added to 100 parts of the dispersion and mixed. Then, it disperse | distributed using the Eiger mill (Eiger Japan Co., Ltd. product) and the zirconia bead of diameter 0.1mm.

<Density adjustment>
The pigment dispersion after precision dispersion was taken out and diluted by adding propylene glycol monomethyl ether acetate so that the pigment concentration was 10% by mass to obtain a blue pigment dispersion.

-Preparation of coloring composition 22-
The following components were mixed and dissolved to prepare a colored composition.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate)
29.5 parts · Organic solvent 2 (diethylene glycol ethyl methyl ether) 12.6 parts · Alkali-soluble binder (allyl methacrylate / methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 6.6 parts · Polymerizability Compound (Nippon Kayaku Co., Ltd., KAYARAD DPHA)
6.3 parts-polymerization inhibitor (p-methoxyphenol) 0.003 parts-photopolymerization initiator (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazole- 3-Il] propanone)
0.3 part ・ Polyfunctional thiol compound 1 (1,4-bis (3-mercaptobutyryloxy) butane 0.2 part ・ Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.2 part ・ Fluorine Surfactant (manufactured by DIC, MegaFac F-554, 2% propylene glycol monomethyl ether acetate solution) 0.6 parts / dye A: 37.4 parts of 5% propylene glycol monomethyl ether acetate solution (2A above) / dye B : 5% propylene glycol monomethyl ether acetate solution of (1B above) 4.2 partsPigment: 2.1 parts of the above blue pigment dispersion

<Examples 23 and 24>
In Example 22, coloring compositions 23 and 24 were prepared in the same manner as in Example 22 except that the dye (2A) and the dye (1B) were changed as shown in the following table.

<Comparative Example 1>
-Preparation of coloring composition-
The following components were mixed and dissolved to prepare a colored composition of Comparative Example 1.
・ Organic solvent 1 (propylene glycol monomethyl ether acetate)
27.4 parts, organic solvent 2 (diethylene glycol ethyl methyl ether) 12.6 parts, alkali-soluble binder (allyl methacrylate / methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 6.6 parts, polymerizable Compound (Nippon Kayaku Co., Ltd., KAYARAD DPHA) 6.3 parts Polymerization inhibitor (p-methoxyphenol) 0.003 parts Photopolymerization initiator (1- (O-acetyloxime) -1- [9 -Ethyl-6- (thiophenoyl) -9H-carbazol-3-yl] propanone)
0.3 part polyfunctional thiol compound 1 (1,4-bis (3-mercaptobutyryloxy) butane) 0.2 part adhesion improver (3-methacryloxypropyltrimethoxysilane)
0.2 parts · Fluorosurfactant (manufactured by DIC MegaFuck F-554, 2% propylene glycol monomethyl ether acetate solution) 0.6 parts · Dye A: 5% propylene glycol monomethyl ether acetate of (dye 7A above) Solution 41.6 parts Dye B: 5 parts propylene glycol monomethyl ether acetate solution of (1B) 4.2 parts

<Comparative Examples 2 and 3>
Colored compositions of Comparative Examples 2 and 3 were prepared in the same manner as Comparative Example 1 except that the dyes (7A) and (1B) used in Comparative Example 1 were changed as described in the following table.

<Comparative example 4>
-Preparation of coloring composition-
The following components were mixed and dissolved to prepare a colored composition of Comparative Example 4. Dyes 1A and 1B were used in a dispersed state because they were not completely dissolved in PGME.
・ Organic solvent 1 (propylene glycol monomethyl ether: PGME)
27.4 parts, organic solvent 2 (diethylene glycol ethyl methyl ether: MEDG)
12.6 parts, alkali-soluble binder (allyl methacrylate / methacrylic acid copolymer = molar ratio 70/30, weight average molecular weight 26800) 6.6 parts, polymerizable compound (manufactured by Nippon Kayaku Co., Ltd., KAYARAD DPHA) 6 .3 parts-polymerization inhibitor (p-methoxyphenol) 0.003 parts-photopolymerization initiator (1- (O-acetyloxime) -1- [9-ethyl-6- (thiophenoyl) -9H-carbazole-3 -Il] propanone)
0.3 part ・ Polyfunctional thiol compound 1 (1,4-bis (3-mercaptobutyryloxy) butane) 0.2 part ・ Adhesion improver (3-methacryloxypropyltrimethoxysilane) 0.2 part ・ Fluorine -Based surfactant (Megafac F-554 manufactured by DIC, 2% propylene glycol monomethyl ether acetate solution) 0.6 parts Dye A: 5% propylene glycol monomethyl ether solution of (1A)
41.6 parts Dye B: 5% propylene glycol monomethyl ether solution of (1B)
4.2 parts

  In the above table, 1A to 8A and 1B to 6B described in the dye A and the dye B represent the dyes 1A to 8A and 1B to 6B described above.

The performance of the produced colored composition was evaluated as follows.
-Formation of colored composition layer (colored layer)-
On the glass (# 1737; made by Corning) board | substrate, after apply | coating the coloring composition prepared above by the spin coat method, the volatile component was volatilized by making it dry at room temperature for 30 minutes. This colored layer was irradiated with i-rays (wavelength 365 nm) exposed on the entire surface without using a photomask to form a latent image. An ultra-high pressure mercury lamp was used as the i-line light source, and it was irradiated as parallel light. At this time, the irradiation light quantity was 40 mJ / cm ² .
Subsequently, the colored layer on which the latent image was formed was shower-developed for 45 seconds using an aqueous solution of sodium carbonate / sodium bicarbonate (concentration: 2.4 mass%, 26 ° C.), and then rinsed with running water for 20 seconds. And then air blow dried. The dried film was baked at 230 ° C. for 20 minutes in a clean oven to obtain a colored layer. The thickness of the colored layer was adjusted so that the chromaticity (x, y) = (0.150, 0.06) in the CIE 1931 color system (C light source), that is, a hue corresponding to sRGB.

-Evaluation-
(1) Spectral characteristics The transmission spectrum of the colored layer obtained above was measured using a photometric system (MCPD-3700 manufactured by Otsuka Electronics Co., Ltd.). The luminance at the chromaticity was determined from the obtained transmission spectrum.

(2) Liquid crystal specific resistance (electrical characteristics)
The colored layer obtained above was scraped from the substrate, and 9.0 mg of the scraped material was added to 2.00 g of a liquid crystal material ZLI-4792 (manufactured by Merck) and heated at 120 ° C. for 5 hours. Then, it filtered and the specific resistance of liquid crystal material was measured with the liquid crystal specific resistance measuring apparatus (model number ADVANTEST R8340 ULTRA HIGH RESISTANCE ME Co., Ltd. product made by Advantest).
<Evaluation criteria>
A: Specific resistance ≧ 1.0 × 10 ¹¹ MΩ, and when incorporated into a liquid crystal display device as a panel, no deterioration in display performance such as color unevenness, response speed reduction, long-term afterimage was observed.
B: Specific resistance ≧ 1.0 × 10 ¹⁰ MΩ, and there is almost no deterioration in display performance such as color unevenness, response speed reduction, long-term afterimage, etc. when a panel is incorporated in a liquid crystal display device, and there is no problem in performance. It was.
C: Specific resistance <1.0 × 10 ¹⁰ MΩ, and when incorporated into a liquid crystal display device as a panel, display performance such as color unevenness, response speed decrease, long-term afterimage, etc. was observed.

(3) PGMEA resistance One drop of propylene glycol monomethyl ether acetate (PGMEA) was dropped on the colored film obtained above, and the mixture was allowed to stand at 25 ° C. for 10 minutes, and then dropped with a clean wiper (Bencot TR-7F, manufactured by Asahi Kasei Fibers). PGMEA was sucked up. Then, it rinsed with the pure water and air blow dried.
The color difference ΔE ^* ab before and after dropping was evaluated using the same haste system as in (1). The smaller the color difference, the less elution by PGMEA, and it can be said that the color difference is stronger against overcoat layer and other resist coating.

(4) Light resistance The transmission spectrum of the colored layer obtained above and the colored layer A after irradiating the colored layer with a xenon fade meter (XL-75 manufactured by Suga Test Instruments Co., Ltd.) for 48 hours at an illuminance of 390 W / m ² . The color difference ΔE ^* ab of the transmission spectrum of was calculated. If the color difference after irradiation for 48 hours is 3.0 or less, it can be said that the light resistance is suitable as a color material for a color filter.

From the result of the said table | surface, it turned out that the coloring composition used in the Example has high brightness | luminance and is excellent in PGMEA tolerance (solvent resistance). Moreover, it turned out that it is excellent also in the liquid crystal specific resistance and light resistance.
Moreover, it turned out that liquid crystal specific resistance, PGMEA tolerance, and light resistance can be improved more by containing a blue pigment further.
On the other hand, it was found that Comparative Example 1 in which the anion in the salt compound is monovalent has low liquid crystal specific resistance and PGMEA resistance, and cannot withstand liquid crystal panel applications.
Further, in Comparative Example 2 in which dye A was not completely dissolved and evaluated in a dispersed state, there was no problem with respect to liquid crystal specific resistance, PGMEA resistance and light resistance, but the dye used was propylene glycol which is generally used for color resists Since it was insoluble in monomethyl ether acetate, it was found that the luminance was greatly reduced.
In Comparative Example 3 using a coloring composition not containing at least one violet colorant selected from a xanthene dye, a pyromethene dye and a tetraazaporphyrin dye, the light resistance and liquid crystal specific resistance are low, and the hue is sRGB. It turned out that it was difficult to match such a general color. In Comparative Example 3, the violet taste was insufficient compared to other dyes, and the chromaticity (x, y) = (0.150, 0.06) could not be adjusted, so the luminance could not be obtained. It was.
In Comparative Example 4 using a solvent in which the dye does not dissolve, it was found that the luminance reduction was large as in Comparative Example 2.

<Example 25>
-Production of liquid crystal display device-
A color filter was manufactured by the following method, a liquid crystal display device using the color filter was manufactured, and display characteristics were evaluated.
-Preparation of red coloring composition R-
The following red pigment dispersion composition was mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. For 3 hours. The mixed solution thus obtained was further subjected to a dispersion treatment for 12 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO-3000-10 with a decompression mechanism. (Nippon BEE Co., Ltd.) was used, and the dispersion process was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ . This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

[Red pigment dispersion composition]
・ C. I. Pigment Red 254 75 parts C.I. I. Pigment Red 177 50 parts benzyl methacrylate / methacrylic acid copolymer 70 parts (copolymerization composition ratio 70/30, weight average molecular weight 30000, acid value 40 mg / KOH)
・ Propylene glycol monomethyl ether acetate 800 parts

Components of the following composition were further added to the obtained pigment dispersion to prepare a red colored composition R.
[Red coloring composition R composition]
・ 100 parts of the above red pigment dispersion ・ Propylene glycol monomethyl ether acetate solution of benzyl methacrylate / methacrylic acid (= 70/30 [molar ratio]) copolymer (Mw: 30,000) (solid content 50%) 12 parts Polymerizable compound 1: KAYARAD DPHA manufactured by Nippon Kayaku Co., Ltd.
12.1 parts Photopolymerization initiator: 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer) 3.1 parts sensitizing dye: 4,4′-bis (diethylamino) benzophenone 4.2 Parts / hydrogen donating compound: 2.1 parts / mercaptobenzothiazole 2.1 parts / polymerization inhibitor: p-methoxyphenol 0.001 parts / fluorinated surfactant (trade name: Megafac R08 manufactured by DIC Corporation) 0.5 Parts ・ Propylene glycol monomethyl ether acetate 60 parts

-Preparation of green coloring composition G-
In preparation of the red coloring composition R, C.I. I. Pigment Red 254 instead of C.I. I. Pigment Green 58 (103 copies), C.I. I. Pigment Red 177 instead of C.I. I. A green coloring composition G was prepared in the same manner except that 19 parts of Pigment Yellow 150 was used.

-Preparation of black coloring composition K-
The pigment dispersion composition was changed to the following composition, and a black pigment dispersion was prepared by performing a dispersion treatment in the same manner as the preparation of the red pigment dispersion.
[Black pigment dispersion composition]
・ Carbon black: Product name: Nippon 35, manufactured by Degussa Japan
13.1 parts Polymer: benzyl methacrylate / methacrylic acid = 72/28 molar ratio random copolymer (molecular weight 37,000) 6.7 parts Propylene glycol monomethyl ether acetate 79.1 parts Dispersant (the following compound) ) 0.65 parts

Using the obtained black pigment dispersion composition, a black colored composition K was prepared with the following composition.
[Black coloring composition K composition]
-Black pigment dispersion 25 parts-Propylene glycol monomethyl ether acetate 8.5 parts-Methyl ethyl ketone 53 parts-Polymer: benzyl methacrylate / methacrylic acid = 78/22 molar ratio random copolymer, molecular weight 38,000) 27 parts 9.1 parts of a mixture of propylene glycol monomethyl ether acetate and polymerization inhibitor: 0.002 part of hydroquinone monomethyl ether, polymerizable compound: KAYARAD DPHA 12 parts manufactured by Nippon Kayaku Co., Ltd., polymerization initiator: 2,4-bis 0.16 parts of (trichloroethyl) -6- [4 ′ (N, N-bisethoxycarbonylmethyl) amino-3′-bromophenyl] -s-triazine 30% solution of surfactant (the following compound) in methyl ethyl ketone
0.042 parts

-Fabrication of color filter-
-Formation of black matrix-
The alkali-free glass substrate was cleaned with a UV cleaning apparatus, then brush-cleaned with a cleaning agent, and further ultrasonically cleaned with ultrapure water. The substrate was heat treated at 120 ° C. for 3 minutes to stabilize the surface state, and then the substrate was cooled and adjusted to 23 ° C.
The black colored composition K was applied using a glass substrate coater (trade name: MH-1600, manufactured by FS Asia Co., Ltd.) having a slit nozzle on the substrate. Subsequently, a part of the solvent was dried by VCD (vacuum drying apparatus; manufactured by Tokyo Ohka Kogyo Co., Ltd.) for 30 seconds to eliminate the fluidity of the coating layer, and then pre-baked at 120 ° C. for 3 minutes to obtain a film thickness of 2. A 4 μm black photosensitive composition layer was obtained.
With a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, with the substrate and mask (quartz exposure mask having an image pattern) standing vertically, the exposure mask surface and the above photosensitive The distance between the conductive resin layers was set to 200 μm, and pattern exposure was performed with an exposure amount of 300 mJ / cm ² .

  Next, after spraying pure water with a shower nozzle and uniformly moistening the surface of the black photosensitive composition layer, KOH developer (KOH, containing nonionic surfactant, trade name: CDK-1, (Fujifilm Electronics Materials Co., Ltd.) was subjected to shower development at 23 ° C. for 80 seconds and a flat nozzle pressure of 0.04 MPa to obtain a patterning image. Subsequently, ultrapure water was sprayed at a pressure of 9.8 MPa with an ultrahigh pressure washing nozzle to remove residues. Finally, heat treatment was performed at 220 ° C. for 30 minutes to form a black matrix.

-RGB pixel formation-
The red colored composition R, the green colored composition G, and the blue photosensitive composition prepared in Example 22 were sequentially laminated and patterned on the glass substrate on which the black matrix was formed, in the same process as when the black matrix was formed. Thus, a color filter of RGB three-color pixels was obtained. At this time, the thickness of the colored portion of each color of RGB was 1.6 μm.
-Formation of ITO electrode-
The glass substrate on which the color filter was formed was placed in a sputtering apparatus, and 1300 mm thick ITO was vacuum-deposited at 100 ° C., and then annealed at 240 ° C. for 90 minutes to crystallize the ITO to form an ITO transparent electrode.
-Spacer formation-
A spacer was formed on the ITO transparent electrode prepared above by the same method as the spacer forming method described in [Example 1] of JP-A-2004-240335.

-Formation of liquid crystal alignment control protrusions-
Protrusions for controlling the alignment of liquid crystals were formed on the ITO transparent electrode on which the spacers were formed, using the following coating liquid for positive photosensitive resin layer.
However, the following methods were used for exposure, development, and baking.
A proximity exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) is arranged so that the predetermined photomask is at a distance of 100 μm from the surface of the photosensitive resin layer, and the irradiation energy is 150 mJ / Proximity exposure was performed at cm ² .
Subsequently, a 2.38% tetramethylammonium hydroxide aqueous solution was developed by spraying it on a substrate at 33 ° C. for 30 seconds in a shower type developing device. In this way, by removing the unnecessary portion (exposed portion) of the photosensitive resin layer by developing and removing the liquid crystal, the liquid crystal alignment control protrusions made of the photosensitive resin layer patterned into a desired shape are formed on the color filter side substrate. A display device substrate was obtained.
Subsequently, the liquid crystal display device substrate on which the liquid crystal alignment control protrusion was formed was baked at 230 ° C. for 30 minutes to form a cured liquid crystal alignment control protrusion on the liquid crystal display device substrate.

[Coating liquid formulation for positive photosensitive resin layer]
・ Positive resist solution (FH-2413F manufactured by Fujifilm Electronics Materials Co., Ltd.) 53.0 parts ・ Methyl ethyl ketone 46.5 parts ・ Megafac F-780F (manufactured by DIC Corporation) 0.05 parts

-Production of liquid crystal display device-
An alignment film made of polyimide was further provided on the liquid crystal display device substrate obtained above. After that, an epoxy resin sealant is printed at a position corresponding to a black matrix outer frame provided around the pixel group of the color filter, and MVA mode liquid crystal is dropped and bonded to the counter substrate. The bonded substrate was heat treated to cure the sealant.
A polarizing plate HLC2-2518 manufactured by Sanritsu Co., Ltd. was attached to both surfaces of the liquid crystal cell thus obtained. Next, as a light source, an LED light source (a liquid crystal television manufactured by SONY, a backlight light source of KDL-40ZX1) was disposed on the back side of the liquid crystal cell provided with the polarizing plate to obtain a liquid crystal display (LCD).
The liquid crystal display device produced as described above has high contrast and brightness, and is found to be suitable as a display device. In this example, the evaluation was performed using an MVA mode liquid crystal display device. However, by using the colored composition of the present invention for a liquid crystal display device of another mode or a color filter of an organic EL display, it is equally good. It seems that image quality can be obtained.

Claims (14)

At least one selected from a salt compound comprising a dye cation and a divalent or higher anion; a solvent capable of dissolving 1.0% by mass or more of the salt compound at 25 ° C .; and a xanthene dye, a pyromethene dye, and a tetraazaporphyrin dye. A purple colorant,
The dye cation has a coloring composition having 1 to 20 triarylmethane dye structures in one molecule. The coloring composition according to claim 1, wherein the dye cation is represented by the general formula (A1) or the general formula (A2);
General formula (A1)

In general formula (A1), Ar ^<+> independently represents a triarylmethane dye structure, L ^{< 1} > independently represents a group connecting two or more Ar ^<+> , n1 represents an integer of 1-20, m represents 0 or 1; when n1 represents 1, m represents 0;
General formula (A2)

In General Formula (A2), Ar ⁺ independently represents a triarylmethane dye structure, L ² represents a divalent linking group, L ³ represents a divalent linking group, and q represents an integer of 1 to 18. Represents. The purple colorant is a xanthene dye represented by the following general formula (I-1a), a pyromethene dye represented by the following general formula (II), and a tetraazaporphyrin dye represented by the following general formula (III). The coloring composition according to claim 1 or 2, comprising at least one;
Formula (I-1a)

In general formula (I-1a), R ^{1 to} R ⁴ are each independently a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms. And —CH ₂ — contained in the saturated hydrocarbon group may be substituted with —O—, —CO— or —NR ¹¹ —;
R ¹ and R ² may be bonded to each other to form a ring containing a nitrogen atom. R ³ and R ⁴ may combine with each other to form a ring containing a nitrogen atom;
R ^{5 _{is, -OH, -SO 3 -, -SO}} 3 H, -SO 3 - Z +, -CO 2 H, -CO 2 - Z +, -CO 2 R 8, -SO 3 R 8 or -SO ₂ represents NR ⁹ R ¹⁰ ;
R ⁶ and R ⁷ each independently represents an alkyl group having 1 to 6 carbon atoms;
m1 represents the integer of 0-5. when m1 is 2 or more, the plurality of R ^5A may be the same or different;
m2 and m3 each independently represents an integer of 0 to 3. when m2 and m3 are each independently 2 or 3, a plurality of R ^5B and R ^5C may be independently the same or different;
a represents 0 or 1; when a represents 0, any group in the xanthene dye structure contains an anion;
X ⁻ represents an anion;
Z ⁺ represents N ⁺ (R ¹¹ ) ₄ , Na ⁺ or K ⁺ , and four R ¹¹ may be the same or different;
R ⁸ represents a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and the hydrogen atom contained in the saturated hydrocarbon group may be substituted with a halogen atom;
R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms, and —CH ₂ — contained in the saturated aliphatic hydrocarbon group is —O—, -CO -, - NH- or -NR ⁸ - may optionally be substituted with, R ⁹ and R ^10, may form a heterocyclic ring of 3 to 10-membered ring containing a nitrogen atom bonded to each other ;
R ¹¹ represents a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 20 carbon atoms or an aralkyl group having 7 to 10 carbon atoms;
Formula (II)

In the general formula (II), R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represents a hydrogen atom or a monovalent substituent; R ⁷ represents a hydrogen atom or a halogen atom Represents an alkyl group, an aryl group or a heterocyclic group;
Formula (III)

In general formula (III), Z ¹ , Z ² , Z ³ and Z ⁴ all represent a nitrogen atom, or any one of Z ¹ and Z ³ , Z ² and Z ⁴ is both nitrogen Represents an atom, the other set represents C—R, and each R independently represents a hydrogen atom, an alkyl group or an aryl group; A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ and A ⁸ are each independently an alkyl group, alkenyl group, aryl group, alkoxy group, alkylthio group, aryloxy group, arylthio group, halogen atom, hydroxy group, alkoxycarbonyl group, aryloxycarbonyl group, amino group, A carbamoyl group, a sulfamoyl group, an acyl group, a silyloxy group, a cyano group, a nitro group or a heterocyclic group; A ¹ and A ² , A ³ and A ⁴ , A ⁵ and A ⁶ , and A ⁷ and A ⁸ are , Each joined to each other It may form a ring structure Te, but at least one set do not form a ring structure; M represents a divalent and is atom or group a divalent metal atom or a substituted metal atom. The dye cation includes at least one of a triarylmethane dye structure represented by the following general formula (TP1) and a triarylmethane dye structure represented by the following general formula (TP2). Or a coloring composition according to claim 1;

In the general formulas (TP1) and (TP2), Rtp _{1 to} Rtp ₄ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group having a crosslinkable group; Rtp ₅ , Rtp ₆ , Rtp ₈ , Rtp ₉ And Rtp ₁₁ each independently represents a substituent. Rtp ₇ represents a hydrogen atom, an alkyl group, an aryl group, a group having a crosslinkable group, or NRtp ₇₁ Rtp ₇₂ . Rtp ₇₁ and Rtp ₇₂ each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group having a crosslinkable group. Rtp ₁₀ represents a hydrogen atom, an alkyl group, an aryl group or a group having a crosslinkable group. a, b and c each independently represents an integer of 0 to 4; a, when b and c is 2 or more, Rtp ₅ together, Rtp ₆ together, Rtp ₈ and between Rtp ₉ each other, respectively, may be bonded to each other to form a ring. The coloring composition of any one of Claims 1-4 in which the said dye cation has a crosslinkable group. The divalent or higher anion includes —SO ₃ ⁻ , —COO ⁻ , —PO ₄ ⁻ , a group including a structure represented by the following general formula (B2), or a structure represented by the following general formula (B3). The coloring composition of any one of Claims 1-5 which has group;
General formula (B2)

In general formula (B2), R ¹¹ and R ¹² each independently represent —SO ₂ — or —CO—;
General formula (B3)

In General Formula (B3), R ¹³ represents —SO ₂ — or —CO—; R ¹⁴ and R ¹⁵ each independently represent —SO ₂ —, —CO—, or —CN. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 80 and CI of Pigment Green 7 are changed to OH The coloring composition of any one of Claims 1-6 which further contains at least 1 sort (s) selected from the thing. The coloring composition of any one of Claims 1-7 which further contains binder resin, a polymeric compound, and a photoinitiator. The coloring composition of any one of Claims 1-8 used for formation of the colored layer of a color filter. The cured film formed by hardening | curing the coloring composition of any one of Claims 1-9. The color filter using the coloring composition of any one of Claims 1-9. A step of applying the colored composition according to any one of claims 1 to 9 on a support to form a colored composition layer, a step of exposing the colored composition layer in a pattern, and an unexposed state And a step of developing and removing the portion to form a colored pattern. The solid-state image sensor which has a color filter obtained by the color filter of Claim 11, or the manufacturing method of the color filter of Claim 12. An image display device comprising the color filter according to claim 11 or the color filter obtained by the method for producing a color filter according to claim 12.