JP6255505B2 - Coloring composition, inkjet recording ink, and inkjet recording method - Google Patents

Description

  The present invention relates to a coloring composition, an inkjet recording ink, and an inkjet recording method.

As is well known, the ink jet recording method is a method of performing printing by causing a small droplet of ink to fly and adhere to a recording medium such as paper. This printing method is capable of printing high-resolution, high-quality images at high speed and easily with an inexpensive apparatus. In particular, in color printing, technical development has recently been carried out as an image forming method that can replace photographs. .
When forming a color image using an inkjet recording method, it is common to use at least yellow ink, magenta ink, cyan ink, and black ink. These inks have physical properties such as viscosity and surface tension within an appropriate range, nozzle clogging, excellent storage stability, and a high density recording image, light resistance, ozone resistance, Properties such as excellent water resistance and moisture resistance are required.

  These performances often meet the required levels by using water or a water-based ink containing a mixture of water and a water-soluble organic solvent as a main solvent, but in particular, color tone, vividness, light resistance, Ozone properties, water resistance, moisture resistance, and the like largely depend on colorants and additives, and various dyes and additives have been studied in the past.

For example, Patent Document 1 discloses an ink composition containing a xanthene compound having a specific structure and a copper compound having good light resistance, ozone resistance, and hue. Patent Document 2 discloses an ink composition containing a xanthene compound having a specific structure with good light resistance.
For example, Patent Document 1 discloses an ink composition containing a xanthene compound having a specific structure and a copper compound. Patent Document 2 discloses an ink composition containing a xanthene compound having a specific structure.

Japanese Unexamined Patent Publication No. 2014-5462 Japanese Patent No. 5451556

  However, in the field of dyes, further improvement in performance is required, and there is a demand for a coloring composition that has good hue and can further improve image fastness such as light resistance and ozone resistance. Yes.

  This invention is made | formed in view of such a situation, and it aims at providing the coloring composition excellent in light resistance, ozone resistance, and a hue. Another object of the present invention is to provide an ink jet recording ink containing the coloring composition and an ink jet recording method using the ink for ink jet recording.

一般式（１Ａ）及び一般式（２Ａ）中、Ｒ ^１ 、Ｒ ^５ 、Ｒ ^６ 、Ｒ ^１０ 、Ｒ ^１１ 、Ｒ ^１５ 、Ｒ ^１６ 及びＲ ^２０ は各々独立に置換又は無置換のアルキル基を表し、Ｒ ^３ 及びＲ ^８ は各々独立に水素原子、置換若しくは無置換のアルキル基、又はスルホ基を表し、Ｒ ^４ 及びＲ ^９ は各々独立に水素原子、置換若しくは無置換のアシルアミノ基、置換若しくは無置換のアルコキシカルボニルアミノ基、置換若しくは無置換のアルキルスルホニルアミノ基、置換若しくは無置換のアリールスルホニルアミノ基、置換若しくは無置換のアルキルウレイド基、置換若しくは無置換のアリールウレイド基、又はスルホ基を表し、Ｒ ^１２ 、Ｒ ^１４ 、Ｒ ^１７ 及びＲ ^１９ は各々独立に水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のアルコキシ基を表し、Ｘ ^１ 、Ｘ ^２ 、Ｘ ^３ 及びＸ ^４ は各々独立に、置換若しくは無置換のヘテロ環オキシ基、置換若しくは無置換のアルキルアミノ基、置換若しくは無置換のアリールアミノ基、置換若しくは無置換のヘテリルアミノ基、置換若しくは無置換のアシルオキシ基、置換若しくは無置換のアミノカルボニルオキシ基、カルボキシル基で置換されたアリールスルホニルアミノ基、置換若しくは無置換のアルコキシカルボニルアミノ基、置換若しくは無置換のアリールオキシカルボニルアミノ基、置換若しくは無置換のウレイド基、置換若しくは無置換のアルキルチオ基、又は置換若しくは無置換のアリールチオ基を表し、Ｍは水素原子又はアルカリ金属を表し、ｎ１、ｎ２、ｎ３及びｎ４は各々独立に０又は１の整数を表す。
一般式（３）：

一般式（３）中、Ｌ ^１ は置換若しくは無置換のアルキレン基、置換若しくは無置換のアリーレン基、置換若しくは無置換のアルケニレン基、又はこれらから選ばれる２種以上を組み合わせてなる２価の連結基を表し、Ｄ ^１ は下記一般式（１）又は一般式（２）で表される化合物から水素原子を２個取り除いた部分構造を表す。ｎ ^１ は、２〜１００を表す。
一般式（４）：

一般式（４）中、Ｌ ^２ は置換若しくは無置換のアルキレン基、置換若しくは無置換のアリーレン基、置換若しくは無置換のアルケニレン基、トリアジン基、シアヌル基、アミノ基又はこれらから選ばれる２種以上を組み合わせてなる２〜６価の連結基を表し、Ｄ ^２ は下記一般式（１）又は一般式（２）で表される化合物から水素原子を１個取り除いた部分構造を表す。ｎ ^２ は、２〜６の整数を表す。

一般式（１）及び一般式（２）中、Ｒ ^１ 、Ｒ ^５ 、Ｒ ^６ 、Ｒ ^１０ 、Ｒ ^１１ 、Ｒ ^１５ 、Ｒ ^１６ 及びＲ ^２０ は各々独立に置換又は無置換のアルキル基を表し、Ｒ ^３ 及びＲ ^８ は各々独立に水素原子、置換若しくは無置換のアルキル基、又はスルホ基を表し、Ｒ ^４ 及びＲ ^９ は各々独立に水素原子、置換若しくは無置換のアシルアミノ基、置換若しくは無置換のアルコキシカルボニルアミノ基、置換若しくは無置換のアルキルスルホニルアミノ基、置換若しくは無置換のアリールスルホニルアミノ基、置換若しくは無置換のアルキルウレイド基、置換若しくは無置換のアリールウレイド基、又はスルホ基を表し、Ｒ ^１２ 、Ｒ ^１４ 、Ｒ ^１７ 及びＲ ^１９ は各々独立に水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のアルコキシ基を表し、Ｘ ^１ 、Ｘ ^２ 、Ｘ ^３ 及びＸ ^４ は各々独立に、ヒドロキシル基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアリールオキシ基、置換若しくは無置換のヘテロ環オキシ基、置換若しくは無置換のアルキルアミノ基、置換若しくは無置換のアリールアミノ基、置換若しくは無置換のヘテリルアミノ基、置換若しくは無置換のカルボニルアミノ基、置換若しくは無置換のアシルオキシ基、置換若しくは無置換のアミノカルボニルオキシ基、置換若しくは無置換のスルホニルアミノ基、置換若しくは無置換のアルコキシカルボニルアミノ基、置換若しくは無置換のアリールオキシカルボニルアミノ基、置換若しくは無置換のウレイド基、置換若しくは無置換のアルキルチオ基、又は置換若しくは無置換のアリールチオ基を表し、Ｍは水素原子又はアルカリ金属を表し、ｎ１、ｎ２、ｎ３及びｎ４は各々独立に０又は１の整数を表す。
上記一般式（１Ａ）で表される化合物、一般式（２Ａ）で表される化合物、一般式（３）で表される繰り返し単位を有する化合物、一般式（４）で表される化合物、一般式（１）で表される化合物、及び一般式（２）で表される化合物における上記各基が置換基を有する場合、ハロゲン原子、アルキル基、アラルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキル又はアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、アルキル又はアリールスルフィニル基、アルキル又はアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリール又はヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、シリル基、スルホ基及びカルボキシル基から選ばれる置換基を有する。
＜２＞
上記一般式（１Ａ）、一般式（２Ａ）、一般式（１）又は一般式（２）で表される化合物が下記一般式（１−１）又は一般式（２−１）で表される化合物である＜１＞に記載の着色組成物。

一般式（１−１）及び一般式（２−１）中、Ｒ ^１ 、Ｒ ^５ 、Ｒ ^６ 、Ｒ ^１０ 、Ｒ ^１１ 、Ｒ ^１５ 、Ｒ ^１６ 及びＲ ^２０ は各々独立に置換又は無置換のアルキル基を表し、Ｒ ^３ 及びＲ ^８ は各々独立に水素原子、置換若しくは無置換のアルキル基、又はスルホ基を表し、Ｒ ^４ 及びＲ ^９ は各々独立に水素原子、置換若しくは無置換のアシルアミノ基、置換若しくは無置換のアルコキシカルボニルアミノ基、置換若しくは無置換のアルキルスルホニルアミノ基、置換若しくは無置換のアリールスルホニルアミノ基、置換若しくは無置換のアルキルウレイド基、置換若しくは無置換のアリールウレイド基、又はスルホ基を表し、Ｒ ^１２ 、Ｒ ^１４ 、Ｒ ^１７ 及びＲ ^１９ は各々独立に水素原子、置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、又は置換若しくは無置換のアルコキシ基を表し、Ｒ ^１０１ 、Ｒ ^１０２ 、Ｒ ^１０３ 及びＲ ^１０４ は各々独立に置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、カルボキシル基で置換されたアリールスルホニル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、カルバモイル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、又は置換若しくは無置換のアルキルアリールアミノカルボニル基を表し、Ｍは水素原子又はアルカリ金属を表し、ｎ１、ｎ２、ｎ３及びｎ４は各々独立に０又は１の整数を表す。
上記一般式（１−１）で表される化合物及び一般式（２−１）で表される化合物における上記各基が置換基を有する場合、ハロゲン原子、アルキル基、アラルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキル又はアリールスルホニルアミノ基、メルカプト基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、アルキル又はアリールスルフィニル基、アルキル又はアリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、アリール又はヘテロ環アゾ基、イミド基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、シリル基、スルホ基及びカルボキシル基から選ばれる置換基を有する。
＜３＞
一般式（１Ａ）で表される化合物、一般式（２Ａ）で表される化合物、一般式（３−１）で表される繰り返し単位を有する化合物、及び一般式（４−１）で表される化合物のいずれかと、水に可溶な銅化合物とを含む着色組成物。

一般式（１Ａ）及び一般式（２Ａ）中、Ｒ ^１ 、Ｒ ^５ 、Ｒ ^６ 、Ｒ ^１０ 、Ｒ ^１１ 、Ｒ ^１５ 、Ｒ ^１６ 及びＲ ^２０ は各々独立に無置換のアルキル基を表し、Ｒ ^３ 及びＲ ^８ は各々独立に水素原子、無置換のアルキル基、又はスルホ基を表し、Ｒ ^４ 及びＲ ^９ は各々独立に水素原子、又はスルホ基を表し、Ｒ ^１２ 、Ｒ ^１４ 、Ｒ ^１７ 及びＲ ^１９ は各々独立に水素原子、又は無置換のアルキル基を表し、Ｘ ^１ 、Ｘ ^２ 、Ｘ ^３ 及びＸ ^４ は各々独立に、下記置換基群Ａ’から選ばれる少なくとも１つの置換基で置換された若しくは無置換のアルキルアミノ基、下記置換基群Ａ’から選ばれる少なくとも１つの置換基で置換された若しくは無置換のアリールアミノ基、カルボキシル基で置換されたアリールスルホニルアミノ基、下記置換基群Ａ’から選ばれる少なくとも１つの置換基で置換された若しくは無置換のアルコキシカルボニルアミノ基、下記置換基群Ａ’から選ばれる少なくとも１つの置換基で置換された若しくは無置換のアリールオキシカルボニルアミノ基、下記置換基群Ａ’から選ばれる少なくとも１つの置換基で置換されたアルキル基若しくは無置換のアルキル基で置換されたウレイド基、又は下記置換基群Ａ’から選ばれる少なくとも１つの置換基で置換されたアリール基若しくは無置換のアリール基で置換されたウレイド基を表し、Ｍは水素原子又はアルカリ金属を表し、ｎ１、ｎ２、ｎ３及びｎ４は各々独立に０又は１を表す。
置換基群Ａ’：ヒドロキシル基、カルボキシル基、スルホ基
一般式（１Ａ）中のｎ１及びｎ２の少なくとも１つが１を表すか、又は一般式（１Ａ）中のＲ ^３ 、Ｒ ^４ 、Ｒ ^８ 、Ｒ ^９ 、Ｘ ^１ 、及びＸ ^２ の少なくとも１つがカルボキシル基又はスルホ基を有する。
一般式（２Ａ）中のｎ３及びｎ４の少なくとも１つが１を表すか、又は一般式（２Ａ）中のＸ ^３ 及びＸ ^４ の少なくとも１つがカルボキシル基又はスルホ基を有する。
一般式（３−１）：

一般式（３−１）中、Ｒ ^１ 、Ｒ ^５ 、Ｒ ^６ 、及びＲ ^１０ は各々独立に無置換のアルキル基を表し、Ｒ ^３ 及びＲ ^８ は各々独立に水素原子、無置換のアルキル基、又はスルホ基を表し、Ｒ ^４ 及びＲ ^９ は各々独立に水素原子又はスルホ基を表し、Ｒ ^３０１ 、Ｒ ^３０２ 、Ｒ ^３０３ 及び ^３０４ は水素原子を表し、Ｌ ^１０１ は下記連結基群Ｌより選択される２価の連結基を表し、Ｍは水素原子、又はアルカリ金属を表し、ｎ１及びｎ２は０又は１を表し、ｎ１０１は２〜１５を表す。
連結基群Ｌ：

一般式（３−１）中のｎ１及びｎ２の少なくとも１つが１を表すか、又は一般式（３−１）中のＲ ^３ 、Ｒ ^４ 、Ｒ ^８ 、及びＲ ^９ の少なくとも１つがスルホ基を表す。
一般式（４−１）：

一般式（４−１）中、Ｒ ^１ 、Ｒ ^５ 、Ｒ ^６ 、及びＲ ^１０ は各々独立に無置換のアルキル基を表し、Ｒ ^３ 及びＲ ^８ は各々独立に水素原子、無置換のアルキル基、又はスルホ基を表し、Ｒ ^４ 及びＲ ^９ は各々独立に水素原子又はスルホ基を表し、Ｘ ^１ａ は、無置換のアルキルカルボニル基又は無置換のアリールカルボニル基を表し、Ｍは水素原子又はアルカリ金属を表し、ｎ１及びｎ２は各々独立に０又は１を表し、ｎ２０１は２を表し、Ｌ ^２０１ は上記連結基群Ｌより選択される２価の連結基を表す。
一般式（４−１）中のｎ１及びｎ２の少なくとも１つが１を表すか、又は一般式（４−１）中のＲ ^３ 、Ｒ ^４ 、Ｒ ^８ 、及びＲ ^９ の少なくとも１つがスルホ基を表す。
＜４＞
上記一般式（１Ａ）、一般式（２Ａ）、一般式（１）、一般式（２）、一般式（１−１）、一般式（２−１）、一般式（３−１）又は一般式（４−１）中のＲ ^１ 、Ｒ ^５ 、Ｒ ^６ 、Ｒ ^１０ 、Ｒ ^１１ 、Ｒ ^１５ 、Ｒ ^１６ 及びＲ ^２０ が各々独立に無置換の炭素数１〜６のアルキル基を表す＜１＞〜＜３＞のいずれか１項に記載の着色組成物。
＜５＞
上記一般式（１Ａ）、一般式（１）、一般式（１−１）、一般式（３−１）又は一般式（４−１）中のＲ ^４ 及びＲ ^９ が各々独立にスルホ基を表す＜１＞〜＜４＞のいずれか１項に記載の着色組成物。
＜６＞
上記銅化合物が、塩素酸銅（ＩＩ）、塩化銅（ＩＩ）、サリチル酸銅（ＩＩ）、グルコン酸銅（ＩＩ）、蟻酸銅（ＩＩ）、エチレンジアミン四酢酸二ナトリウム銅（ＩＩ）、及び酢酸銅（ＩＩ）からなる群から選択される少なくとも一種である、＜１＞〜＜５＞のいずれか１項に記載の着色組成物。
＜７＞
上記一般式（１Ａ）で表される化合物、一般式（２Ａ）で表される化合物、一般式（３）で表される繰り返し単位を有する化合物、一般式（４）で表される化合物、一般式（３−１）で表される繰り返し単位を有する化合物、及び一般式（４−１）で表される化合物のいずれかを１〜２０質量％含有する＜１＞〜＜６＞のいずれか１項に記載の着色組成物。
＜８＞
上記一般式（１Ａ）で表される化合物、一般式（２Ａ）で表される化合物、一般式（３）で表される繰り返し単位を有する化合物、一般式（４）で表される化合物、一般式（３−１）で表される繰り返し単位を有する化合物、及び一般式（４−１）で表される化合物のいずれかの含有量と上記水に可溶な銅化合物の含有量との質量比が３５０／１〜７／３である＜１＞〜＜７＞のいずれか一項に記載の着色組成物。
＜９＞
＜１＞〜＜８＞のいずれか１項に記載の着色組成物を含有するインクジェット記録用インク。
＜１０＞
＜１＞〜＜８＞のいずれか１項に記載の着色組成物又は＜９＞に記載のインクジェット記録用インクを用いて、画像形成するインクジェット記録方法。
本発明は、上記＜１＞〜＜１０＞に係る発明であるが、以下、それ以外の事項についても参考のため記載している。 As a result of intensive studies, the present inventors have found that the above problem can be solved by combining the following specific xanthene compounds and copper compounds.
That is, the present invention is as follows.
<1>
Any of the compound represented by the general formula (1A), the compound represented by the general formula (2A), the compound having a repeating unit represented by the general formula (3), and the compound represented by the general formula (4) A coloring composition comprising a copper compound soluble in water.

In general formula (1A) and general formula (2A), R ¹ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ and R ²⁰ each independently represents a substituted or unsubstituted alkyl group, R ³ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a sulfo group, and R ⁴ and R ⁹ each independently represent a hydrogen atom, a substituted or unsubstituted acylamino group, substituted or unsubstituted An alkoxycarbonylamino group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted alkylureido group, a substituted or unsubstituted arylureido group, or a sulfo group, ^{R 12,} R 14, R ¹⁷ and ^{R 19} each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted a It represents Lumpur group, or a substituted or unsubstituted alkoxy group, X ^{1, X 2,} the X ³ and X ⁴ each independently represent a substituted or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylamino group, Substituted or unsubstituted arylamino group, substituted or unsubstituted heterylamino group, substituted or unsubstituted acyloxy group, substituted or unsubstituted aminocarbonyloxy group, arylsulfonylamino group substituted by carboxyl group, substituted or unsubstituted Represents an alkoxycarbonylamino group, a substituted or unsubstituted aryloxycarbonylamino group, a substituted or unsubstituted ureido group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, M is a hydrogen atom or an alkali Represents metal, n1, n2, n3 and n4 are each Independently represents an integer of 0 or 1.
General formula (3):

In general formula (3), L ¹ is a divalent linkage formed by combining a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, or a combination of two or more thereof. D ¹ represents a partial structure obtained by removing two hydrogen atoms from a compound represented by the following general formula (1) or general formula (2). n ¹ represents 2 to 100.
General formula (4):

In General Formula (4), L ² represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, a triazine group, a cyanuric group, an amino group, or two or more selected from these Represents a divalent to hexavalent linking group, and D ² represents a partial structure in which one hydrogen atom is removed from a compound represented by the following general formula (1) or general formula (2). n ² represents an integer of 2 to 6.

In general formula (1) and general formula (2), R ¹ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ and R ²⁰ each independently represents a substituted or unsubstituted alkyl group, R ³ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a sulfo group, and R ⁴ and R ⁹ each independently represent a hydrogen atom, a substituted or unsubstituted acylamino group, substituted or unsubstituted An alkoxycarbonylamino group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted alkylureido group, a substituted or unsubstituted arylureido group, or a sulfo group, ^{R 12,} R 14, R ¹⁷ and ^{R 19} each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl Group, or a substituted or unsubstituted alkoxy group, a X ^{1, X 2,} X ³ and X ⁴ are each independently a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted Or an unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heterylamino group, a substituted or unsubstituted carbonylamino group, a substituted or unsubstituted acyloxy Group, substituted or unsubstituted aminocarbonyloxy group, substituted or unsubstituted sulfonylamino group, substituted or unsubstituted alkoxycarbonylamino group, substituted or unsubstituted aryloxycarbonylamino group, substituted or unsubstituted ureido group, A substituted or unsubstituted alkylthio group, Represents a substituted or unsubstituted arylthio group, M represents a hydrogen atom or an alkali metal, n1, n2, n3 and n4 each independently represent an integer of 0 or 1.
Compound represented by general formula (1A), compound represented by general formula (2A), compound having a repeating unit represented by general formula (3), compound represented by general formula (4), general When each of the above groups in the compound represented by the formula (1) and the compound represented by the general formula (2) has a substituent, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, Heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino Group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfur Moylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group , A carbamoyl group, an aryl or heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, a sulfo group, and a carboxyl group.
<2>
The compound represented by the general formula (1A), general formula (2A), general formula (1), or general formula (2) is represented by the following general formula (1-1) or general formula (2-1). The coloring composition as described in <1> which is a compound.

In general formula (1-1) and general formula (2-1), R ¹ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ and R ²⁰ are each independently substituted or unsubstituted alkyl. R ³ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a sulfo group, and R ⁴ and R ⁹ each independently represent a hydrogen atom, a substituted or unsubstituted acylamino group, Substituted or unsubstituted alkoxycarbonylamino group, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group, substituted or unsubstituted alkylureido group, substituted or unsubstituted arylureido group, or sulfo It represents a ^{group, R 12, R 14, R} 17 and ^{R 19} each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted Represents an aryl group, or a substituted or unsubstituted alkoxy ^{group, R 101, R 102, R} 103 and ^{R 104} each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted Heterocyclic group, arylsulfonyl group substituted with a carboxyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted Represents a substituted dialkylaminocarbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, or a substituted or unsubstituted alkylarylaminocarbonyl group, and M represents a hydrogen atom or an alkali metal. And, n1, n2, n3 and n4 each independently represent an integer of 0 or 1.
When each group in the compound represented by the general formula (1-1) and the compound represented by the general formula (2-1) has a substituent, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl Group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group Amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, Sulfamoyl group, Alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphine group It has a substituent selected from a finylamino group, a silyl group, a sulfo group and a carboxyl group.
<3>
The compound represented by the general formula (1A), the compound represented by the general formula (2A), the compound having a repeating unit represented by the general formula (3-1), and the general formula (4-1). A coloring composition comprising any one of the above compounds and a water-soluble copper compound.

In general formula (1A) and general formula (2A), R ¹ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ and R ²⁰ each independently represents an unsubstituted alkyl group, and R ³ And R ⁸ each independently represents a hydrogen atom, an unsubstituted alkyl group, or a sulfo group, R ⁴ and R ⁹ each independently represent a hydrogen atom or a sulfo group, and R ¹² , R ¹⁴ , R ¹⁷ and R ¹⁹ each independently represents a hydrogen atom or an unsubstituted alkyl group, and X ¹ , X ² , X ³ and X ⁴ are each independently substituted with at least one substituent selected from the following substituent group A ′. Or an unsubstituted alkylamino group, an arylamino group substituted or substituted with at least one substituent selected from the following substituent group A ′, an arylsulfonylamino group substituted with a carboxyl group, and the following substituent group Selected from A ' Substituted or unsubstituted alkoxycarbonylamino group substituted by at least one substituent selected from the following substituent group A ′ or unsubstituted aryloxycarbonylamino group substituted by the following substituent: An alkyl group substituted with at least one substituent selected from group A ′ or a ureido group substituted with an unsubstituted alkyl group, or aryl substituted with at least one substituent selected from the following substituent group A ′ Represents a ureido group substituted with a group or an unsubstituted aryl group, M represents a hydrogen atom or an alkali metal, and n1, n2, n3 and n4 each independently represents 0 or 1.
Substituent group A ′: hydroxyl group, carboxyl group, sulfo group
At least one of n1 and n2 in the general formula (1A) represents 1, or at least one of R ³ , R ⁴ , R ⁸ , R ⁹ , X ¹ , and X ^{2 in} the general formula (1A) is carboxyl Group or sulfo group.
Or at least one of n3 and n4 in formula (2A) represents a 1, or the general formula (2A) ^{X 3} and ^{X 4} in at least one having a carboxyl group or a sulfo group.
General formula (3-1):

In General Formula (3-1), R ¹ , R ⁵ , R ⁶ , and R ¹⁰ each independently represent an unsubstituted alkyl group, and R ³ and R ⁸ are each independently a hydrogen atom or an unsubstituted alkyl group. Or a sulfo group, R ⁴ and R ⁹ each independently represents a hydrogen atom or a sulfo group, R ³⁰¹ , R ³⁰² , R ³⁰³ and ³⁰⁴ each represents a hydrogen atom, and L ¹⁰¹ is selected from the following linking group L Represents a divalent linking group, M represents a hydrogen atom or an alkali metal, n1 and n2 represent 0 or 1, and n101 represents 2 to 15.
Linking group L:

At least one of n1 and n2 in the general formula (3-1) represents 1, or at least one of R ³ , R ⁴ , R ⁸ , and R ^{9 in} the general formula (3-1) represents a sulfo group. Represent.
Formula (4-1):

In General Formula (4-1), R ¹ , R ⁵ , R ⁶ , and R ¹⁰ each independently represent an unsubstituted alkyl group, and R ³ and R ⁸ each independently represent a hydrogen atom or an unsubstituted alkyl group. Or R ⁴ and R ⁹ each independently represent a hydrogen atom or a sulfo group, X ^1a represents an unsubstituted alkylcarbonyl group or an unsubstituted arylcarbonyl group, and M represents a hydrogen atom or an alkali group. represents a metal, n1 and n2 each independently represent 0 or 1, n201 represents ^{2, L 201} represents a divalent linking group selected from the group of linkage groups L.
At least one of n1 and n2 in the general formula (4-1) represents 1, or at least one of R ³ , R ⁴ , R ⁸ , and R ^{9 in} the general formula (4-1) represents a sulfo group. Represent.
<4>
General formula (1A), general formula (2A), general formula (1), general formula (2), general formula (1-1), general formula (2-1), general formula (3-1) or general formula R ¹ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ and R ^{20 in} formula (4-1) each independently represent an unsubstituted alkyl group having 1 to 6 carbon atoms <1 The coloring composition according to any one of> to <3>.
<5>
R ⁴ and R ^{9 in the} general formula (1A), general formula (1), general formula (1-1), general formula (3-1), or general formula (4-1) are each independently a sulfo group. The colored composition according to any one of <1> to <4>.
<6>
The copper compound is copper (II) chlorate, copper (II) chloride, copper (II) salicylate, copper (II) gluconate, copper (II) formate, disodium copper (II) ethylenediaminetetraacetate, and copper acetate The coloring composition according to any one of <1> to <5>, which is at least one selected from the group consisting of (II).
<7>
Compound represented by general formula (1A), compound represented by general formula (2A), compound having a repeating unit represented by general formula (3), compound represented by general formula (4), general Any one of <1> to <6> containing 1 to 20% by mass of any one of a compound having a repeating unit represented by formula (3-1) and a compound represented by formula (4-1) 2. A coloring composition according to item 1.
<8>
Compound represented by general formula (1A), compound represented by general formula (2A), compound having a repeating unit represented by general formula (3), compound represented by general formula (4), general The mass of the content of any of the compound having a repeating unit represented by formula (3-1) and the compound represented by formula (4-1) and the content of the water-soluble copper compound The coloring composition as described in any one of <1>-<7> whose ratio is 350/1-7/3.
<9>
<1>-<8> The inkjet recording ink containing the coloring composition of any one of <8>.
<10>
An inkjet recording method for forming an image using the colored composition according to any one of <1> to <8> or the inkjet recording ink according to <9>.
The present invention is an invention according to the above <1> to <10>, but other matters are described below for reference.

一般式（１）及び一般式（２）中、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１９及びＲ^２０は各々独立に水素原子又は置換基を表し、Ｘ^１、Ｘ^２、Ｘ^３及びＸ^４は各々独立に、ヒドロキシル基、置換若しくは無置換のアルコキシ基、置換若しくは無置換のアリールオキシ基、置換若しくは無置換のヘテロ環オキシ基、置換若しくは無置換のアルキルアミノ基、置換若しくは無置換のアリールアミノ基、置換若しくは無置換のヘテリルアミノ基、置換若しくは無置換のカルボニルアミノ基、置換若しくは無置換のアシルオキシ基、置換若しくは無置換のアミノカルボニルオキシ基、置換若しくは無置換のスルホニルアミノ基、置換若しくは無置換のアルコキシカルボニルアミノ基、置換若しくは無置換のアリールオキシカルボニルアミノ基、置換若しくは無置換のウレイド基、置換若しくは無置換のアルキルチオ基、又は置換若しくは無置換のアリールチオ基を表し、Ｍは水素原子又はアルカリ金属を表し、ｎ１、ｎ２、ｎ３及びｎ４は各々独立に０又は１の整数を表す。
一般式（３）：

一般式（３）中、Ｌ^１は２価の連結基を表し、Ｄ^１は一般式（１）又は一般式（２）で表される化合物から水素原子を２個取り除いた部分構造を表す。ｎ^１は、２〜１００を表す。
一般式（４）：

一般式（４）中、Ｌ^２はｎ^２価の連結基を表し、Ｄ^２は一般式（１）又は一般式（２）で表される化合物から水素原子を１個取り除いた部分構造を表す。ｎ^２は、２〜６の整数を表す。
〔２〕
上記一般式（１）又は一般式（２）で表される化合物が下記一般式（１−１）又は一般式（２−１）で表される化合物である〔１〕に記載の着色組成物。

一般式（１−１）及び一般式（２−１）中、Ｒ^１、Ｒ^３、Ｒ^４、Ｒ^５、Ｒ^６、Ｒ^８、Ｒ^９、Ｒ^１０、Ｒ^１１、Ｒ^１２、Ｒ^１４、Ｒ^１５、Ｒ^１６、Ｒ^１７、Ｒ^１９及びＲ^２０は各々独立に水素原子又は置換基を表し、Ｒ^１０１、Ｒ^１０２、Ｒ^１０３及びＲ^１０４は各々独立に置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のカルボニル基、置換若しくは無置換のスルホニル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、カルバモイル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、又は置換若しくは無置換のアルキルアリールアミノカルボニル基を表し、Ｍは水素原子又はアルカリ金属を表し、ｎ１、ｎ２、ｎ３及びｎ４は各々独立に０又は１の整数を表す。
〔３〕
上記Ｒ^１０１、Ｒ^１０２、Ｒ^１０３及びＲ^１０４が各々独立に置換若しくは無置換のアルキル基、置換若しくは無置換のアリール基、置換若しくは無置換のヘテロ環基、置換若しくは無置換のスルホニル基、置換若しくは無置換のアルコキシカルボニル基、置換若しくは無置換のアリールオキシカルボニル基、カルバモイル基、置換若しくは無置換のモノアルキルアミノカルボニル基、置換若しくは無置換のジアルキルアミノカルボニル基、置換若しくは無置換のモノアリールアミノカルボニル基、置換若しくは無置換のジアリールアミノカルボニル基、又は置換若しくは無置換のアルキルアリールアミノカルボニル基を表す、〔２〕に記載の着色組成物。
〔４〕
上記一般式（１）、一般式（２）、一般式（１−１）又は一般式（２−１）中のＲ^１、Ｒ^５、Ｒ^６、Ｒ^１０、Ｒ^１１、Ｒ^１５、Ｒ^１６及びＲ^２０が各々独立に炭素数１〜６のアルキル基を表す〔１〕〜〔３〕のいずれか１項に記載の着色組成物。
〔５〕
上記一般式（１）又は一般式（１−１）中のＲ^４及びＲ^９が各々独立にスルホ基を表す〔１〕〜〔４〕のいずれか１項に記載の着色組成物。
〔６〕
上記銅化合物が、塩素酸銅（ＩＩ）、塩化銅（ＩＩ）、サリチル酸銅（ＩＩ）、グルコン酸銅（ＩＩ）、蟻酸銅（ＩＩ）、エチレンジアミン四酢酸二ナトリウム銅（ＩＩ）、及び酢酸銅（ＩＩ）からなる群から選択される少なくとも一種である、〔１〕〜〔５〕のいずれか１項に記載の着色組成物。
〔７〕
上記一般式（１）で表される化合物、一般式（２）で表される化合物、一般式（３）で表される繰り返し単位を有する化合物、及び一般式（４）で表される化合物のいずれかを１〜２０質量％含有する〔１〕〜〔６〕のいずれか１項に記載の着色組成物。
〔８〕
上記一般式（１）で表される化合物、一般式（２）で表される化合物、一般式（３）で表される繰り返し単位を有する化合物、及び一般式（４）で表される化合物のいずれかの含有量と上記水に可溶な銅化合物の含有量との質量比が３５０／１〜７／３である〔１〕〜〔７〕のいずれか一項に記載の着色組成物。
〔９〕
〔１〕〜〔８〕のいずれか１項に記載の着色組成物を含有するインクジェット記録用インク。
〔１０〕
〔１〕〜〔８〕のいずれか１項に記載の着色組成物又は〔９〕に記載のインクジェット記録用インクを用いて、画像形成するインクジェット記録方法。[1]
Any of the compound represented by the general formula (1), the compound represented by the general formula (2), the compound having a repeating unit represented by the general formula (3), and the compound represented by the general formula (4) A coloring composition comprising a copper compound soluble in water.

In the general formula (1) and the general formula ^{(2), R 1, R} 3, R 4, R 5, R 6, R 8, R 9, R 10, R 11, R 12, R 14, R 15, R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a substituent, and X ¹ , X ² , X ³ and X ⁴ each independently represent a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted group Or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted heterylamino group, substituted or unsubstituted carbonyl Amino group, substituted or unsubstituted acyloxy group, substituted or unsubstituted aminocarbonyloxy group, substituted or unsubstituted sulfonylamino group, substituted or unsubstituted An alkoxycarbonylamino group, a substituted or unsubstituted aryloxycarbonylamino group, a substituted or unsubstituted ureido group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, M represents a hydrogen atom or an alkali metal N1, n2, n3 and n4 each independently represents an integer of 0 or 1.
General formula (3):

In General Formula (3), L ¹ represents a divalent linking group, and D ¹ represents a partial structure in which two hydrogen atoms are removed from the compound represented by General Formula (1) or General Formula (2). n ¹ represents 2 to 100.
General formula (4):

In the general formula (4), L ² represents a n ² divalent linking group, D ² represents a removing one partial structures a hydrogen atom from the general formula (1) or the compound represented by the general formula (2) . n ² represents an integer of 2 to 6.
[2]
The colored composition according to [1], wherein the compound represented by the general formula (1) or the general formula (2) is a compound represented by the following general formula (1-1) or the general formula (2-1). .

In the general formula (1-1) and the general formula ^{(2-1), R 1, R} 3, R 4, R 5, R 6, R 8, R 9, R 10, R 11, R 12, R 14, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent, and R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ each independently represent a substituted or unsubstituted alkyl group or substituted Or an unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted sulfonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group Carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted mono Represents a reelaminocarbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, or a substituted or unsubstituted alkylarylaminocarbonyl group, M represents a hydrogen atom or an alkali metal, and n1, n2, n3 and n4 each independently An integer of 0 or 1 is represented.
[3]
R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ are each independently substituted or unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted sulfonyl group, substituted Or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylamino The colored composition according to [2], which represents a carbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, or a substituted or unsubstituted alkylarylaminocarbonyl group.
[4]
R < ¹ >, R < ⁵ >, R < ⁶ >, R < ¹⁰ >, R < ¹¹ >, R <^15> , R < ¹⁶ > in the above general formula (1), general formula (2), general formula (1-1) or general formula (2-1). And R ²⁰ each independently represents an alkyl group having 1 to 6 carbon atoms, [1] to [3].
[5]
The colored composition according to any one of [1] to [4], wherein R ⁴ and R ^{9 in the} general formula (1) or the general formula (1-1) each independently represent a sulfo group.
[6]
The copper compound is copper (II) chlorate, copper (II) chloride, copper (II) salicylate, copper (II) gluconate, copper (II) formate, disodium copper (II) ethylenediaminetetraacetate, and copper acetate The coloring composition according to any one of [1] to [5], which is at least one selected from the group consisting of (II).
[7]
Of the compound represented by the general formula (1), the compound represented by the general formula (2), the compound having a repeating unit represented by the general formula (3), and the compound represented by the general formula (4) The coloring composition according to any one of [1] to [6], which contains any one of 1 to 20% by mass.
[8]
Of the compound represented by the general formula (1), the compound represented by the general formula (2), the compound having a repeating unit represented by the general formula (3), and the compound represented by the general formula (4) The coloring composition according to any one of [1] to [7], wherein a mass ratio between any one content and the content of the water-soluble copper compound is 350/1 to 7/3.
[9]
[1] to [8] An inkjet recording ink containing the colored composition according to any one of [8].
[10]
An inkjet recording method for forming an image using the colored composition according to any one of [1] to [8] or the inkjet recording ink according to [9].

  ADVANTAGE OF THE INVENTION According to this invention, the coloring composition excellent in light resistance, ozone resistance, and a hue can be provided. Moreover, the inkjet recording ink containing the said coloring composition and the inkjet recording method using the inkjet recording ink can be provided.

Hereinafter, the present invention will be described in detail.
First, specific examples of the substituent in the present invention are defined as a substituent group A.

(Substituent group A)
Halogen atom, alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto Group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, Job aryloxycarbonyl group, a carbamoyl group, an aryl or heterocyclic azo group, an imido group, a phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, a silyl group, an ionic hydrophilic group mentioned as an example. These substituents may be further substituted, and examples of the further substituent include a group selected from the substituent group A described above.

  As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom is mentioned, for example.

Examples of the alkyl group include linear, branched, and cyclic substituted or unsubstituted alkyl groups, and include cycloalkyl groups, bicycloalkyl groups, and tricyclo structures having many ring structures. An alkyl group (for example, an alkyl group of an alkoxy group or an alkylthio group) in a substituent described below also represents such an alkyl group.
As the alkyl group, an alkyl group having 1 to 30 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group, an n-octyl group, an eicosyl group, 2- Examples thereof include a chloroethyl group, a 2-cyanoethyl group, a 2-ethylhexyl group, etc. The cycloalkyl group is preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, such as a cyclohexyl group, a cyclopentyl group, 4 -N-dodecylcyclohexyl group and the like, and the bicycloalkyl group is preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, that is, one hydrogen atom from a bicycloalkane having 5 to 30 carbon atoms. Removed monovalent groups such as bicyclo [1,2,2] heptan-2-yl group, bicyclo [2,2 2] octan-3-yl group.

  Examples of the aralkyl group include a substituted or unsubstituted aralkyl group, and the substituted or unsubstituted aralkyl group is preferably an aralkyl group having 7 to 30 carbon atoms. For example, a benzyl group and a 2-phenethyl group can be mentioned.

Examples of the alkenyl group include linear, branched, and cyclic substituted or unsubstituted alkenyl groups, and include cycloalkenyl groups and bicycloalkenyl groups.
Preferred examples of the alkenyl group include substituted or unsubstituted alkenyl groups having 2 to 30 carbon atoms such as vinyl group, allyl group, prenyl group, geranyl group, and oleyl group. Preferred examples of the cycloalkenyl group include Is a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group obtained by removing one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms, such as a 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group and the like. As the bicycloalkenyl group, a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a double bond A monovalent group obtained by removing one hydrogen atom from a bicycloalkene having one of, for example, bicyclo [2,2,1] Hept-2-en-1-yl group, a bicyclo [2,2,2] oct-2-en-4-yl group and the like.

  The alkynyl group is preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as an ethynyl group, a propargyl group, and a trimethylsilylethynyl group.

  The aryl group is preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as a phenyl group, a p-tolyl group, a naphthyl group, an m-chlorophenyl group, an o-hexadecanoylaminophenyl group, and the like. Can be mentioned.

  The heterocyclic group is preferably a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound, and more preferably a carbon number. Examples thereof include 3 to 30 5- or 6-membered aromatic heterocyclic groups such as a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group. Examples of non-aromatic heterocyclic groups include morpholinyl groups.

  The alkoxy group is preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group, a t-butoxy group, an n-octyloxy group, or a 2-methoxyethoxy group. Etc.

  The aryloxy group is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, such as a phenoxy group, 2-methylphenoxy group, 4-t-butylphenoxy group, 3-nitrophenoxy group, 2 -Tetradecanoylaminophenoxy group etc. are mentioned.

  Preferred examples of the silyloxy group include substituted or unsubstituted silyloxy groups having 0 to 20 carbon atoms such as a trimethylsilyloxy group and a diphenylmethylsilyloxy group.

  Preferred examples of the heterocyclic oxy group include substituted or unsubstituted heterocyclic oxy groups having 2 to 30 carbon atoms, such as a 1-phenyltetrazole-5-oxy group and a 2-tetrahydropyranyloxy group.

  The acyloxy group is 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 an acetyloxy group, Examples include a pivaloyloxy group, a stearoyloxy group, a benzoyloxy group, and a p-methoxyphenylcarbonyloxy group.

  The carbamoyloxy group is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, such as N, N-dimethylcarbamoyloxy group, N, N-diethylcarbamoyloxy group, morpholinocarbonyloxy group, N , N-di-n-octylaminocarbonyloxy group, Nn-octylcarbamoyloxy group and the like.

  The alkoxycarbonyloxy group is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, such as a methoxycarbonyloxy group, an ethoxycarbonyloxy group, a t-butoxycarbonyloxy group, or an n-octylcarbonyloxy group. Etc.

  The aryloxycarbonyloxy group is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, such as phenoxycarbonyloxy group, p-methoxyphenoxycarbonyloxy group, pn-hexadecyloxy. Examples include phenoxycarbonyloxy group.

  The amino group includes an alkylamino group, an arylamino group, and a heterocyclic amino group, preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted group having 6 to 30 carbon atoms. Examples of the substituted anilino group include a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, and a triazinylamino group.

  The acylamino group is preferably a formylamino group, 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 an acetylamino group, Examples include pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, and the like.

  The aminocarbonylamino group is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms, such as a carbamoylamino group, N, N-dimethylaminocarbonylamino group, or N, N-diethylaminocarbonylamino group. And a morpholinocarbonylamino group.

  The alkoxycarbonylamino group is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, such as methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, n-octadecyloxycarbonylamino. Group, N-methyl-methoxycarbonylamino group and the like.

  The aryloxycarbonylamino group is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, such as phenoxycarbonylamino group, p-chlorophenoxycarbonylamino group, mn-octyloxyphenoxy. Examples thereof include a carbonylamino group.

  The sulfamoylamino group is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, such as a sulfamoylamino group, N, N-dimethylaminosulfonylamino group, Nn- Examples include octylaminosulfonylamino group.

The alkyl or arylsulfonylamino group is 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 a methylsulfonylamino group. Butylsulfonylamino group, phenylsulfonylamino group, 2,3,5-trichlorophenylsulfonylamino group, p-methylphenylsulfonylamino group, and the like.
Preferred examples of the alkylthio group include substituted or unsubstituted alkylthio groups having 1 to 30 carbon atoms, such as a methylthio group, an ethylthio group, and an n-hexadecylthio group.

  Preferred examples of the arylthio group include substituted or unsubstituted arylthio groups having 6 to 30 carbon atoms such as a phenylthio group, a p-chlorophenylthio group, and an m-methoxyphenylthio group.

  Preferred examples of the heterocyclic thio group include substituted or unsubstituted heterocyclic thio groups having 2 to 30 carbon atoms, such as a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group.

  The sulfamoyl group is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, such as N-ethylsulfamoyl group, N- (3-dodecyloxypropyl) sulfamoyl group, N, N-dimethylsulfuryl group. Examples include a famoyl group, an N-acetylsulfamoyl group, an N-benzoylsulfamoyl group, and an N- (N′-phenylcarbamoyl) sulfamoyl group.

  The alkyl or arylsulfinyl group is 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 a methylsulfinyl group or an ethylsulfinyl group. , Phenylsulfinyl group, p-methylphenylsulfinyl group and the like.

  The alkyl or arylsulfonyl group is 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 a methylsulfonyl group or an ethylsulfonyl group. , Phenylsulfonyl group, p-methylphenylsulfonyl group and the like.

  The acyl group is preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, a substituted or unsubstituted group having 2 to 30 carbon atoms. Heterocyclic carbonyl groups bonded to carbonyl groups at substituted carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridyl Examples thereof include a carbonyl group and a 2-furylcarbonyl group.

  The aryloxycarbonyl group is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, such as phenoxycarbonyl group, o-chlorophenoxycarbonyl group, m-nitrophenoxycarbonyl group, pt- A butylphenoxycarbonyl group etc. are mentioned.

  The alkoxycarbonyl group is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, and an n-octadecyloxycarbonyl group.

  The carbamoyl group is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms, such as a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, or an N, N-di-n-octyl group. Examples thereof include a carbamoyl group and an N- (methylsulfonyl) carbamoyl group.

  The aryl or heterocyclic azo group is 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, such as a phenylazo group or p-chlorophenylazo group. Group, 5-ethylthio-1,3,4-thiadiazol-2-ylazo group and the like.

  Preferred examples of the imide group include an N-succinimide group and an N-phthalimide group.

  The phosphino group is preferably a substituted or unsubstituted phosphino group having 0 to 30 carbon atoms, such as a dimethylphosphino group, a diphenylphosphino group, a methylphenoxyphosphino group, and the like.

  The phosphinyl group is preferably a substituted or unsubstituted phosphinyl group having 0 to 30 carbon atoms, such as a phosphinyl group, a dioctyloxyphosphinyl group, a diethoxyphosphinyl group, and the like.

  Preferred examples of the phosphinyloxy group include substituted or unsubstituted phosphinyloxy groups having 0 to 30 carbon atoms such as a diphenoxyphosphinyloxy group and a dioctyloxyphosphinyloxy group.

  The phosphinylamino group is preferably a substituted or unsubstituted phosphinylamino group having 0 to 30 carbon atoms, such as a dimethoxyphosphinylamino group or a dimethylaminophosphinylamino group.

  Preferred examples of the silyl group include substituted or unsubstituted silyl groups having 0 to 30 carbon atoms such as a trimethylsilyl group, a t-butyldimethylsilyl group, and a phenyldimethylsilyl group.

  Examples of the ionic hydrophilic group include a sulfo group, a carboxyl group, a thiocarboxyl group, a sulfino group, a phosphono group, a dihydroxyphosphino group, and a quaternary ammonium group. Particularly preferred are a sulfo group and a carboxyl group. The ionic hydrophilic group may contain a cation or an anion, and a state containing the cation or anion is called a salt state. The carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of counter cations that form salts include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions) and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) are included, lithium salts, sodium salts, potassium salts, and ammonium salts are preferable, and mixed salts containing sodium salts or sodium salts as main components are included. More preferred is the sodium salt.

  In the present invention, when the compound is a salt, the salt is dissociated into ions in the water-soluble ink.

  The present invention is represented by a compound represented by general formula (1), a compound represented by general formula (2), a compound having a repeating unit represented by general formula (3), and general formula (4). The present invention relates to a coloring composition containing any one of the compounds and a copper compound soluble in water.

[Xanthene compound]
The colored composition of the present invention includes a compound represented by the general formula (1), a compound represented by the general formula (2), a compound having a repeating unit represented by the general formula (3), and a general formula ( 4) The xanthene compound of at least any one of the compounds represented by 4) is included. The xanthene compound is preferably soluble in water. Here, “soluble in water” means to dissolve at a rate of 0.5% by mass or more with respect to water at 25 ° C.
(Compound represented by formula (1) or (2))

In the general formula (1) and the general formula ^{(2), R 1, R} 3, R 4, R 5, R 6, R 8, R 9, R 10, R 11, R 12, R 14, R 15, R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a substituent, and X ¹ , X ² , X ³ and X ⁴ each independently represent a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted group Or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylamino group, substituted or unsubstituted arylamino group, substituted or unsubstituted heterylamino group, substituted or unsubstituted carbonyl Amino group, substituted or unsubstituted acyloxy group, substituted or unsubstituted aminocarbonyloxy group, substituted or unsubstituted sulfonylamino group, substituted or unsubstituted An alkoxycarbonylamino group, a substituted or unsubstituted aryloxycarbonylamino group, a substituted or unsubstituted ureido group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, M represents a hydrogen atom or an alkali metal N1, n2, n3 and n4 each independently represents an integer of 0 or 1.

In the general formula (1) and the general formula ^{(2), R 1, R} 3, R 4, R 5, R 6, R 8, R 9, R 10, R 11, R 12, R 14, R 15, R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or a substituent. R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ are substituents. As the substituent in the case of representing, a substituent selected from the above substituent group A can be mentioned.

In the general formula (1) and the general formula (2), R ¹ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ are In view of availability of raw materials and ease of synthesis, each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy Preferably represents a group, a carboxyl group, or a halogen atom, more preferably a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, particularly preferably a substituted or unsubstituted group. It is an alkyl group. As an alkyl group, a C1-C6 alkyl group is preferable, a C1-C3 alkyl group is more preferable, and a methyl group is still more preferable. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case each group has a substituent.

In general formula (1), R ⁴ and R ⁹ are each independently a hydrogen atom, substituted or non-substituted from the viewpoints of availability of raw materials and ease of synthesis, light resistance, ozone resistance, print density, and saturation. Substituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted aryloxy group, substituted or unsubstituted amino group, substituted or unsubstituted acylamino group, substituted or unsubstituted Alkoxycarbonylamino group, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group, substituted or unsubstituted alkylureido group, substituted or unsubstituted arylureido group, sulfo group, carboxyl group, Or a halogen atom, preferably a substituted or unsubstituted acyl Mino group, substituted or unsubstituted alkoxycarbonylamino group, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group, substituted or unsubstituted alkylureido group, substituted or unsubstituted arylureido group Or a sulfo group, particularly preferably a sulfo group. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case each group has a substituent.

In general formula (1), R ³ and R ⁸ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted group, from the viewpoint of availability of raw materials and ease of synthesis. Or an unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted amino group, a substituted or unsubstituted acylamino group, a substituted or unsubstituted alkoxycarbonylamino group, a substituted or unsubstituted alkylsulfonylamino Preferably represents a group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted alkylureido group, a substituted or unsubstituted arylureido group, a sulfo group, a carboxyl group, or a halogen atom, more preferably a hydrogen atom. A substituted or unsubstituted alkyl group or a sulfo group, especially Mashiku is a substituted or unsubstituted alkyl group. As an alkyl group, a C1-C6 alkyl group is preferable, a C1-C3 alkyl group is more preferable, and a methyl group is still more preferable. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case each group has a substituent.

In general formula (1) and general formula (2), X ¹ , X ² , X ³ and X ⁴ are each independently a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, substituted Or an unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heterylamino group, a substituted or unsubstituted carbonylamino group, a substituted or unsubstituted acyloxy Group, substituted or unsubstituted aminocarbonyloxy group, substituted or unsubstituted sulfonylamino group, substituted or unsubstituted alkoxycarbonylamino group, substituted or unsubstituted aryloxycarbonylamino group, substituted or unsubstituted ureido group, Substituted or unsubstituted alkylthio group, or substituted or unsubstituted An arylthio group of conversion.

As the alkoxy group when X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms is more preferable. . The alkoxy group may be linear, branched or cyclic. Specifically, the alkoxy group is preferably a methoxy group, an ethoxy group, a propyloxy group, an isopropyloxy group, a cyclohexyloxy group, or a 2-ethylhexyloxy group. In addition, examples of the substituent in the case where the alkoxy group has a substituent include a substituent selected from the above substituent group A, an ionic hydrophilic group is preferable, a carboxyl group or a sulfo group is more preferable, and a carboxyl group is further preferable.

The aryloxy group when X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted aryloxy group is preferably an aryloxy group having 6 to 14 carbon atoms, and an aryloxy group having 6 to 10 carbon atoms. Group is more preferable, and phenyloxy group is still more preferable. In addition, examples of the substituent in the case where the aryloxy group has a substituent include a substituent selected from the above-mentioned substituent group A, an ionic hydrophilic group is preferable, a carboxyl group or a sulfo group is more preferable, and a carboxyl group is Further preferred.

The heterocyclic group contained in the heterocyclic oxy group when X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted heterocyclic oxy group includes a triazine group, a thiazolyl group, a benzothiazolyl group, or a thiadiazolyl group. preferable. Further, the substituent in the case where the heterocyclic oxy group has a substituent includes a substituent selected from the above-mentioned substituent group A, and a substituted or unsubstituted amino group, a substituted or unsubstituted sulfamoyl group is preferable, Alternatively, an unsubstituted alkylamino group, a substituted or unsubstituted alkylsulfamoyl group is more preferable, and an ionic hydrophilic group (preferably a carboxyl group or a sulfo group, more preferably a carboxyl group) substituted with an alkylamino group or Alkylsulfamoyl groups are particularly preferred.

In the case where X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted alkylamino group, the alkylamino group may be a dialkylamino group or a monoalkylamino group. From the viewpoint of solubility in water, a monoalkylamino group is preferable. The alkyl group in the alkylamino group is preferably an alkyl group having 1 to 8 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case an alkylamino group has a substituent.

When X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted arylamino group, the arylamino group may be a diarylamino group or a monoarylamino group. From the viewpoint of solubility in water, a monoarylamino group is preferable. An arylamino group having 6 to 14 carbon atoms is preferred, an arylamino group having 6 to 10 carbon atoms is more preferred, and a phenylamino group is still more preferred. In addition, examples of the substituent in the case where the arylamino group has a substituent include a substituent selected from the above substituent group A.

The heterocyclic group contained in the heterylamino group when X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted heterylamino group is preferably a triazine group, a thiazolyl group, a benzothiazolyl group, or a thiadiazolyl group. In addition, examples of the substituent when the heterylamino group has a substituent include a substituent selected from the above substituent group A, and a substituted or unsubstituted amino group and a substituted or unsubstituted sulfamoyl group are preferable.

When X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted carbonylamino group, the substituted carbonylamino group includes a substituted or unsubstituted alkylcarbonylamino group, or a substituted or unsubstituted arylcarbonylamino group. Groups are preferred. When it represents an unsubstituted carbonylamino group, it is preferably —NHCO— and is preferably bonded to L ¹ of the general formula (3) or L ² of the general formula (4).

In the case where X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted alkylcarbonylamino group, the alkylcarbonylamino group is a monoalkylcarbonylamino group from the viewpoint of ease of synthesis and solubility in water. It is preferably a group. As the alkyl group in the alkylcarbonylamino group, an alkyl group having 1 to 8 carbon atoms is preferable, and an alkyl group having 1 to 3 carbon atoms is more preferable. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case an alkylcarbonylamino group has a substituent.

In the case where X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted arylcarbonylamino group, the arylcarbonylamino group may be monoarylcarbonyl from the viewpoint of ease of synthesis and solubility in water. An amino group is preferred. The aryl group in the arylcarbonylamino group is preferably an aryl group having 6 to 14 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Specifically, a phenyl group, a biphenyl group, and a naphthyl group are preferable, and a phenyl group is more preferable. In addition, examples of the substituent in the case where the arylcarbonylamino group has a substituent include a substituent selected from the above substituent group A, and include a carboxyl group, a hydroxyl group, a phosphono group, and an alkoxy group (preferably having 1 to 6 carbon atoms). And more preferably a cyclohexyloxy group.

As the acyloxy group when X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted acyloxy group, an acyloxy group having 1 to 18 carbon atoms is preferable, and an acyloxy group having 1 to 8 carbon atoms is more preferable. . Specific examples of the acyloxy group include an acetyloxy group and a benzoyloxy group, and an acetyloxy group is preferable. In addition, examples of the substituent in the case where the acyloxy group has a substituent include a substituent selected from the above substituent group A, an ionic hydrophilic group is preferable, a carboxyl group or a sulfo group is more preferable, and a carboxyl group is further preferable.

The aminocarbonyloxy group in which X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted aminocarbonyloxy group is preferably an aminocarbonyloxy group having 1 to 18 carbon atoms, and 1 to 8 carbon atoms. The aminocarbonyloxy group is more preferable. Specific examples of the aminocarbonyloxy group include an unsubstituted aminocarbonyloxy group, a dimethylaminocarbonyloxy group, and a phenylaminocarbonyloxy group, and an unsubstituted aminocarbonyloxy group and a dimethylaminocarbonyloxy group are preferable. In addition, the substituent in the case where the aminocarbonyloxy group has a substituent includes a substituent selected from the above substituent group A, an ionic hydrophilic group is preferable, a carboxyl group or a sulfo group is more preferable, and a carboxyl group Is more preferable.

When X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted sulfonylamino group, the substituted sulfonylamino group includes a substituted or unsubstituted alkylsulfonylamino group, or a substituted or unsubstituted arylsulfonylamino group. Groups are preferred. When an unsubstituted sulfonylamino group is represented, it is preferably —NHSO ₂ —, and preferably bonded to L ¹ of the general formula (3) or L ² of the general formula (4).

The alkylsulfonylamino group in the case where X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted alkylsulfonylamino group is preferably an alkylsulfonylamino group having 1 to 6 carbon atoms, and 1 to 3 carbon atoms. The alkylsulfonylamino group is more preferable, and the methylsulfonylamino group is more preferable. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case an alkylsulfonylamino group has a substituent.

The arylsulfonylamino group when X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted arylsulfonylamino group is preferably an arylsulfonylamino group having 6 to 14 carbon atoms, and 6 to 10 carbon atoms. Of the arylsulfonylamino group is more preferable, and a phenylsulfonylamino group is more preferable. In addition, examples of the substituent in the case where the arylsulfonylamino group has a substituent include substituents selected from the above substituent group A, and a carboxyl group is particularly preferable.

The alkoxy group in the alkoxycarbonylamino group when X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted alkoxycarbonylamino group is preferably an alkoxy group having 1 to 8 carbon atoms, An alkoxy group of ˜3 is more preferred. The alkoxycarbonylamino group may be linear, branched or cyclic. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case an alkoxycarbonylamino group has a substituent.

The aryloxy group in the aryloxycarbonylamino group when X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted aryloxycarbonylamino group is preferably an aryloxy group having 6 to 14 carbon atoms. An aryloxy group having 6 to 10 carbon atoms is more preferable. As the aryloxycarbonylamino group, a phenyloxycarbonylamino group is more preferable. In addition, examples of the substituent in the case where the aryloxycarbonylamino group has a substituent include a substituent selected from the above substituent group A.

When X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted ureido group, examples of the substituent that the substituted ureido group has include a substituent selected from the above substituent group A, a heterocyclic group, An alkyl group or an aryl group is preferable, and an alkyl group or an aryl group is more preferable. The substituted ureido group may be a di-substituted ureido group or a mono-substituted ureido group, but is preferably a mono-substituted ureido group from the viewpoint of ease of synthesis and solubility in water.

The alkylthio group in the case where X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted alkylthio group is preferably an alkylthio group having 1 to 18 carbon atoms, more preferably an alkylthio group having 1 to 8 carbon atoms. . Specific examples of the alkylthio group include a methylthio group, an ethylthio group, and a propylthio group. A methylthio group and an ethylthio group are preferable, and a methylthio group is more preferable. In addition, examples of the substituent in the case where the alkylthio group has a substituent include a substituent selected from the above substituent group A, an ionic hydrophilic group is preferable, a carboxyl group or a sulfo group is more preferable, and a carboxyl group is further preferable.

When X ¹ , X ² , X ³ and X ⁴ represent a substituted or unsubstituted arylthio group, the arylthio group is preferably an arylthio group having 6 to 14 carbon atoms, more preferably an arylthio group having 6 to 10 carbon atoms. More preferred is a phenylthio group. In addition, examples of the substituent in the case where the arylthio group has a substituent include a substituent selected from the above-mentioned substituent group A, an ionic hydrophilic group is preferable, a carboxyl group or a sulfo group is more preferable, and a carboxyl group is further preferable.

X ¹ , X ² , X ³ and X ⁴ are preferably a hydroxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted carbonylamino group, from the viewpoint of saturation, light resistance and ozone resistance, A substituted or unsubstituted acyloxy group, a substituted or unsubstituted sulfonylamino group, and a substituted or unsubstituted ureido group, more preferably a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, A substituted or unsubstituted heterylamino group, a substituted or unsubstituted carbonylamino group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, and a substituted or unsubstituted ureido group, substituted or unsubstituted Unsubstituted alkylcarbonylamino group, substituted or unsubstituted Lumpur carbonylamino group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, or represent a substituted or unsubstituted ureido group particularly preferred.

  M represents a hydrogen atom or an alkali metal. Examples of the alkali metal include lithium, sodium, and potassium. From the availability of raw materials, sodium and potassium are preferable, and sodium is more preferable.

From the viewpoint of solubility in water, in general formula (1), at least one of n1 and n2 in general formula (1) represents an integer of 1, or R ¹ in general formula (1), At least one of R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , X ¹ , and X ² , or n3 and n4 in general formula (2) in general formula (2) At least one of them represents an integer of 1, or R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁹ , R ²⁰ , X ³ , and X ^{4 in} the general formula (2) At least one preferably has an ionic hydrophilic group such as a carboxyl group, a sulfo group, or a phosphono group. It becomes a compound soluble in water by having an ionic hydrophilic group. Examples of counterions of these ionic hydrophilic groups include hydrogen atoms (protons), alkali metal cations (lithium ions, sodium ions, or potassium ions), ammonium ions, and the like.
The compound represented by the general formula (1) or the general formula (2) is preferably 1 to 70% by mass and more preferably 2 to 50% by mass with respect to water at 25 ° C. In the compound represented by the general formula (1) or the general formula (2), the number of ionic hydrophilic groups is preferably 1 to 9, and more preferably 1 to 5.

  The compound represented by the general formula (1) or the general formula (2) is represented by the following general formula (1-1) or general formula (2-1) from the viewpoint of saturation, light resistance and ozone resistance. It is preferable that it is a compound.

In the general formula (1-1) and the general formula ^{(2-1), R 1, R} 3, R 4, R 5, R 6, R 8, R 9, R 10, R 11, R 12, R 14, R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom or a substituent, and R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ each independently represent a substituted or unsubstituted alkyl group or substituted Or an unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted carbonyl group, a substituted or unsubstituted sulfonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group Carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted mono Represents a reelaminocarbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, or a substituted or unsubstituted alkylarylaminocarbonyl group, M represents a hydrogen atom or an alkali metal, and n1, n2, n3 and n4 each independently An integer of 0 or 1 is represented.

In the general formula (1-1) and the general formula ^{(2-1), R 1, R} 3, R 4, R 5, R 6, R 8, R 9, R 10, R 11, R 12, R 14, Specific examples and preferred ranges of R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁹ , R ²⁰ , M, n1, n2, n3, and n4 are R ¹ , R in general formula (1) and general formula (2). ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁹ , R ²⁰ , M, n1, n2, It is the same as n3 and n4.

The alkyl group in the case where R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. . Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case an alkyl group has a substituent.

The aryl group when R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted aryl group is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. A phenyl group is more preferable. In addition, examples of the substituent in the case where the aryl group has a substituent include a substituent selected from the above substituent group A.

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted heterocyclic group, the heterocyclic group is preferably a triazine group, a thiazolyl group, a benzothiazolyl group, or a thiadiazolyl group. In addition, examples of the substituent in the case where the heterocyclic group has a substituent include a substituent selected from the above substituent group A, and a substituted or unsubstituted amino group and a substituted or unsubstituted sulfamoyl group are preferable.

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted carbonyl group, the substituted carbonyl group is preferably a substituted or unsubstituted alkylcarbonyl group or a substituted or unsubstituted arylcarbonyl group. When an unsubstituted carbonyl group is represented, it is preferably —CO— and is preferably bonded to L ¹ of the general formula (3) or L ² of the general formula (4).

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted alkylcarbonyl group, the alkyl group in the alkylcarbonyl group is preferably an alkyl group having 1 to 8 carbon atoms, The alkyl group is more preferable. Moreover, the substituent selected from the said substituent group A is mentioned as a substituent in case an alkylcarbonyl group has a substituent.

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted arylcarbonyl group, the aryl group in the arylcarbonyl group is preferably an aryl group having 6 to 14 carbon atoms, preferably 6 to 10 carbon atoms. The aryl group is more preferable. Specifically, the arylcarbonyl group is preferably a phenylcarbonyl group, a biphenylcarbonyl group, or a naphthylcarbonyl group, and more preferably a phenylcarbonyl group. In addition, examples of the substituent in the case where the arylcarbonyl group has a substituent include a substituent selected from the above substituent group A, and include a carboxyl group, a hydroxyl group, a phosphono group, and an alkoxy group (preferably having 1 to 6 carbon atoms) An alkoxy group, more preferably a cyclohexyloxy group).

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted sulfonyl group, the substituted sulfonyl group is preferably a substituted or unsubstituted alkylsulfonyl group or a substituted or unsubstituted arylsulfonyl group. When an unsubstituted sulfonyl group is represented, it is preferably —SO ₂ — and is preferably bonded to L ¹ of the general formula (3) or L ² of the general formula (4).

The alkylsulfonyl group in the case where R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted alkylsulfonyl group is preferably an alkylsulfonyl group having 1 to 6 carbon atoms, and an alkylsulfonyl group having 1 to 3 carbon atoms. A group is more preferable, and a methylsulfonyl group is still more preferable. In addition, examples of the substituent when the alkylsulfonyl group has a substituent include a substituent selected from the above substituent group A.

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted arylsulfonyl group, the arylsulfonyl group is preferably an arylsulfonyl group having 6 to 14 carbon atoms, and an arylsulfonyl group having 6 to 10 carbon atoms. Group is more preferable, and phenylsulfonyl group is still more preferable. In addition, examples of the substituent in the case where the arylsulfonyl group has a substituent include a substituent selected from the above substituent group A, and a carboxyl group is particularly preferable.

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted alkoxycarbonyl group, the alkoxy group in the alkoxycarbonyl group is preferably an alkoxy group having 1 to 8 carbon atoms, and 1 to 3 carbon atoms. The alkoxy group is more preferable. In addition, examples of the substituent in the case where the alkoxycarbonyl group has a substituent include a substituent selected from the above substituent group A.

The aryloxy group in the aryloxycarbonyl group when R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted aryloxycarbonyl group is preferably an aryloxy group having 6 to 14 carbon atoms. An aryloxy group of several 6 to 10 is more preferable. As the aryloxycarbonyl group, a phenyloxycarbonyl group is more preferable. In addition, examples of the substituent in the case where the aryloxycarbonyl group has a substituent include a substituent selected from the above substituent group A, and a nitro group is particularly preferable.

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted monoalkylaminocarbonyl group, the monoalkylaminocarbonyl group is preferably represented by —CONHR ²⁰³ . Here, R ²⁰³ represents an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, an isopropyl group, a hexyl group. 2-ethylhexyl group, dodecyl group and cyclohexyl group are more preferable, and isopropyl group is particularly preferable. In addition, the substituent in the case where the monoalkylaminocarbonyl group has a substituent includes a substituent selected from the above substituent group A, and particularly a phenyl group, a carboxyl group, a substituted or unsubstituted amino group, and a hydroxyl group. preferable.

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted dialkylaminocarbonyl group, the dialkylaminocarbonyl group is preferably represented by —CONR ²⁰⁴ R ²⁰⁵ . Here, R ²⁰⁴ and R ²⁰⁵ each independently represent an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably a methyl group or an isopropyl group. In addition, examples of the substituent in the case where the dialkylaminocarbonyl group has a substituent include a substituent selected from the above-mentioned substituent group A, and include a carboxyl group and an alkyloxycarbonyl group (preferably an alkyloxycarbonyl having 2 to 6 carbon atoms). Group, more preferably an ethyloxycarbonyl group).

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted monoarylaminocarbonyl group, the monoarylaminocarbonyl group is preferably represented by —CONHR ²⁰⁶ . R ²⁰⁶ represents an aryl group having 6 to 14 carbon atoms, preferably an aryl group having 6 to 12 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Specifically, a phenyl group, a biphenyl group, and a naphthyl group are preferable, and a phenyl group is more preferable. In addition, examples of the substituent in the case where the monoarylaminocarbonyl group has a substituent include a substituent selected from the above substituent group A, and include a carboxyl group, a hydroxyl group, a phosphono group, and an alkoxy group (preferably having a carbon number of 1 to 6 alkoxy group, more preferably cyclohexyloxy group).

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted diarylaminocarbonyl group, the diarylaminocarbonyl group is preferably represented by —CONR ²⁰⁷ R ²⁰⁸ . Wherein ^{R 207} and ^{R 208} represents an aryl group having 6 to 14 carbon atoms each independently, preferably an aryl group having 6 to 10 carbon atoms, a phenyl group is more preferable. In addition, examples of the substituent in the case where the diarylaminocarbonyl group has a substituent include a substituent selected from the above substituent group A.

When R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ represent a substituted or unsubstituted alkylarylaminocarbonyl group, the alkylarylaminocarbonyl group is preferably represented by —CONR ²⁰⁹ R ²¹⁰ . Here, R ²⁰⁹ represents an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, a methyl group, an ethyl group, an isopropyl group, or a hexyl group. 2-ethylhexyl group, dodecyl group and cyclohexyl group are more preferable, and methyl group is particularly preferable. R ²¹⁰ represents an aryl group having 6 to 14 carbon atoms, preferably an aryl group having 6 to 12 carbon atoms, and more preferably an aryl group having 6 to 10 carbon atoms. Specifically, a phenyl group, a biphenyl group, and a naphthyl group are preferable, and a phenyl group is more preferable. In addition, examples of the substituent in the case where the alkylarylaminocarbonyl group has a substituent include substituents selected from the above substituent group A.

R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted sulfonyl group, substituted Or unsubstituted alkoxycarbonyl group, substituted or unsubstituted aryloxycarbonyl group, carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylamino It preferably represents a carbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, or a substituted or unsubstituted alkylarylaminocarbonyl group. A substituted or unsubstituted sulfonyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted Is an unsubstituted aryloxycarbonyl group, carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diaryl More preferably, it represents an aminocarbonyl group or a substituted or unsubstituted alkylarylaminocarbonyl group.

(Compound having a repeating unit represented by the general formula (3))
General formula (3):

In General Formula (3), L ¹ represents a divalent linking group, and D ¹ represents a partial structure in which two hydrogen atoms are removed from the compound represented by General Formula (1) or General Formula (2). n ¹ represents 2 to 100.

In General Formula (3), L ¹ represents a divalent linking group, and is a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, or two or more selected from these It is preferable that it is a bivalent coupling group which combines.

  The alkylene group may be linear, branched or cyclic. The number of carbon atoms of the alkylene group is preferably 1-18, more preferably 2-16, and still more preferably 4-8. Preferable specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a cyclohexylene group (preferably 1,3-cyclohexylene group or 1,4-cyclohexylene group). Examples of the substituent in the case where the alkylene group has a substituent include a substituent selected from the above substituent group A, and a 1,4-cyclohexylene group is preferable.

  The arylene group is preferably an arylene group having 6 to 14 carbon atoms, more preferably an arylene group having 6 to 10 carbon atoms, a phenylene group (preferably a 1,3-phenylene group or a 1,4-phenylene group) or a naphthylene group. (Preferably 1,5-naphthylene group) is more preferable. In addition, examples of the substituent in the case where the aryloxy group has a substituent include a substituent selected from the above substituent group A, an ionic hydrophilic group is preferable, a carboxyl group or a sulfo group is more preferable, and a sulfo group is Further preferred.

  The alkenylene group is preferably an alkenylene group having 2 to 18 carbon atoms, more preferably an alkenylene group having 2 to 12 carbon atoms, and still more preferably an alkenylene group having 2 to 8 carbon atoms. Preferred specific examples of the alkenylene group are preferably a vinylene group and a 2-butenylene group. Examples of the substituent when the alkenylene group has a substituent include a substituent selected from the above substituent group A, and an alkyl group is preferable.

L ¹ is a divalent linking group formed by combining two or more selected from the above-mentioned substituted or unsubstituted alkylene group, substituted or unsubstituted arylene group, and substituted or unsubstituted alkenylene group. Also good.
Specific examples of the divalent linking group include the following linking groups. In the following linking groups, * represents a bonding position.

In General Formula (3), D ¹ represents a partial structure in which two hydrogen atoms are removed from the compound represented by General Formula (1) or General Formula (2). General formula (1) and general formula (2) are as above-mentioned.
From the viewpoint of solubility, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ^{8 in} the partial structure in which two hydrogen atoms are removed from the compound represented by the general formula (1) represented by D ¹ , R ^9, R ¹⁰ , and R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R in the partial structure in which two hydrogen atoms are removed from the compound represented by the general formula (2) ^At least one of ¹⁷ , R ¹⁹ and R ²⁰ preferably has an ionic hydrophilic group such as a carboxyl group, a sulfo group, or a phosphono group, more preferably at least two are ionic hydrophilic groups, Among the hydrophilic groups, it is preferable to represent a sulfo group. Examples of the counter cation of these ionic hydrophilic groups include a hydrogen atom (proton), an alkali metal cation (lithium ion, sodium ion, or potassium ion), an ammonium ion, and the like, but easy synthesis (as dye powder) From the viewpoint of ease of handling, it is preferably an alkali metal cation.
From the viewpoint of solubility, at least one of n1 and n2 of the compound represented by the general formula (1) is 1, and at least one of n3 and n4 of the compound represented by the general formula (2) is 1 is also a preferred form. As a more preferable embodiment, both n1 and n2 of the compound represented by the general formula (1) are 1, and both n3 and n4 of the compound represented by the general formula (2) are 1. Is a more preferred form.

In the general formula (3), ^{n 1} represents 2 to 100, preferably 2 to 50 from the viewpoint of solubility and moisture resistance, and more preferably from 2 to 30, more preferably 2 to 15. n ¹ need not be an integer, if a fractional represents the average value of the mixture can be calculated from the molecular weight measurement by GPC measurement. In the present specification, unless otherwise specified, GPC uses HLC-8020GPC (manufactured by Tosoh Corporation), and the column is measured with TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ200 (manufactured by Tosoh Corporation), and the number average molecular weight. Was calculated by polystyrene conversion. The carrier may be selected as appropriate, but tetrahydrofuran is used as long as it can be dissolved.
Moreover, the structure of the terminal of the compound which has a repeating unit represented by General formula (3) is not specifically limited, It is based on the compound etc. which are used for a synthesis | combination.

  Moreover, the structure of the terminal of the compound which has a repeating unit represented by General formula (3) is not specifically limited, It is based on the compound etc. which are used for a synthesis | combination.

General formula (3) is a compound having a repeating unit represented by any one of the following general formulas (3-1) to (3-4) from the viewpoints of saturation, light resistance, and ozone resistance. preferable.
General formula (3-1):

In General Formula (3-1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ³⁰¹ , R ³⁰² , R ³⁰³ and ³⁰⁴ are each independently a hydrogen atom or Represents a substituent, L ¹⁰¹ represents a divalent linking group, M represents a hydrogen atom or an alkali metal, n1 and n2 represent 0 to 1, and n101 represents 2 to 100.

In the general formula (3-1), n101 is the same meaning as ^{n 1} in the general formula (3), and preferred ranges are also the same.

In General Formula (3-1), L ¹⁰¹ has the same meaning as L ¹ in General Formula (3), and specific examples and preferred ranges thereof are also the same.

In General Formula (3-1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , M, n1 and n2 are R ¹ , R in General Formula (1). ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , M, n1 and n2, and specific examples and preferred ranges are also the same.

From the viewpoint of solubility, at least one of R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ and R ^{10 in} the general formula (3-1) is a carboxyl group, It is preferable to have an ionic hydrophilic group such as a sulfo group or a phosphono group, more preferably at least two are ionic hydrophilic groups, and it is preferable to represent a sulfo group among the ionic hydrophilic groups. Examples of the counter cation of these ionic hydrophilic groups include a hydrogen atom (proton), an alkali metal cation (lithium ion, sodium ion, or potassium ion), an ammonium ion, and the like, but easy synthesis (as dye powder) From the viewpoint of ease of handling, it is preferably an alkali metal cation.
From the viewpoint of solubility, it is also a preferred embodiment that at least one of n1 and n2 of the compound represented by the general formula (3-1) is 1. It is a more preferable embodiment that both n1 and n2 of the compound represented by the general formula (3-1) are 1.

In general formula (3-1), R ³⁰¹ , R ³⁰² , R ³⁰³ and ³⁰⁴ each independently represent a hydrogen atom or a substituent, and from the viewpoint of availability of raw materials, a hydrogen atom, a substituted or unsubstituted alkyl group, and a substituent Alternatively, an unsubstituted aryl group is preferable, a hydrogen atom or a substituted or unsubstituted alkyl group is more preferable, a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is further preferable, and a hydrogen atom is most preferable.

  Formula (3-2):

In General Formula (3-2), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent a hydrogen atom or a substituent, and L ¹⁰² is divalent. M represents a hydrogen atom or an alkali metal, n1 and n2 each independently represents an integer of 0 or 1, and n102 represents 2 to 100.

In General Formula (3-2), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , L ¹⁰² , M, n1, n2 and n102 are represented by General Formula (3- It is synonymous with R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , L ¹⁰¹ , M, n1, n2 and n101 in 1), and the preferred range is also the same.

  General formula (3-3):

In General Formula (3-3), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , and R ¹⁰ each independently represent a hydrogen atom or a substituent, and L ¹⁰³ is divalent. M represents a hydrogen atom or an alkali metal, n1 and n2 each independently represents an integer of 0 or 1, and n103 represents 2 to 100.

In general formula (3-3), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , L ¹⁰³ , M, n1, n2 and n103 are represented by general formula (3- It is synonymous with R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , L ¹⁰¹ , M, n1, n2 and n101 in 1), and the preferred range is also the same.

  General formula (3-4):

In general formula (3-4), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , R ³⁰⁵ and R ³⁰⁶ each independently represent a hydrogen atom or a substituent, L ¹⁰⁴ represents a divalent linking group, M represents a hydrogen atom or an alkali metal, n1 and n2 each independently represents an integer of 0 or 1, and n401 represents 2 to 100.

In general formula (3-4), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , L ¹⁰⁴ , M, n1, n2 and n401 are represented by general formula (3- It is synonymous with R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , L ¹⁰¹ , M, n1, n2 and n101 in 1), and the preferred range is also the same.
In General Formula (3-4), R ³⁰⁵ and R ³⁰⁶ have the same meanings as R ³⁰² and R ^{303 in} General Formula (3-1), respectively, and the preferred ranges are also the same.

(Compound represented by the general formula (4))
General formula (4):

In the general formula (4), L ² represents a n ² divalent linking group, D ² is the one removed portion structure a hydrogen atom from a compound represented by the above general formula (1) or general formula (2) Represent. n ² represents an integer of 2 to 6.

In the general formula (4), L ² represents a n ² divalent linking group, a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, an ether group, a triazine group, cyanuric It is preferably a divalent to hexavalent linking group formed by combining a group, an amino group, a pentaerythritol derivative, a dipentaerythritol derivative, or two or more selected from these.
Specific examples and preferred ranges when L ² in the general formula (4) is an alkylene group, an arylene group or an alkenylene group are the same as the alkylene group, arylene group or alkenylene group of L ¹ in the general formula (3).
Specific examples of the linking group represented by L ² include the following linking groups. In the following linking groups, * represents a bonding position.

In General Formula (4), D ² represents a partial structure in which one hydrogen atom is removed from the compound represented by General Formula (1) or General Formula (2). General formula (1) or general formula (2) is as described above.
From the viewpoint of solubility, R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ^{8 in} the partial structure in which one hydrogen atom is removed from the compound represented by the general formula (1) represented by D ² , R ^9, R ¹⁰ , and R ¹¹ , R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁶ , R in the partial structure in which two hydrogen atoms are removed from the compound represented by the general formula (2) ^At least one of ¹⁷ , R ¹⁹ and R ²⁰ preferably has an ionic hydrophilic group such as a carboxyl group, a sulfo group, or a phosphono group, more preferably at least two are ionic hydrophilic groups, Among the hydrophilic groups, it is preferable to represent a sulfo group. Examples of the counter cation of these ionic hydrophilic groups include a hydrogen atom (proton), an alkali metal cation (lithium ion, sodium ion, or potassium ion), an ammonium ion, and the like, but easy synthesis (as dye powder) From the viewpoint of ease of handling, it is preferably an alkali metal cation.
From the viewpoint of solubility, at least one of n1 and n2 of the compound represented by the general formula (1) is 1, and at least one of n3 and n4 of the compound represented by the general formula (2). One is also a preferred form. Furthermore, it is more that both n1 and n2 of the compound represented by the general formula (1) are 1, and that both n3 and n4 of the compound represented by the general formula (2) are 1. This is a preferred form.

In the general formula (4), n ² represents an integer of 2 to 6, the raw material availability, ease of synthesis, is 2 or 3 from the viewpoint of solubility in water, and most preferably 2.

The compound represented by the general formula (4) is a compound represented by any one of the general formulas (4-1) to (4-4) from the viewpoints of saturation, light resistance, and ozone resistance. preferable.
Formula (4-1):

In General Formula (4-1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and X ^1a represents a substituted or Unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted carbonyl group, substituted or unsubstituted sulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted aryloxycarbonyl group, carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylamino Represents a carbonyl group or a substituted or unsubstituted alkylarylaminocarbonyl group. , M represents a hydrogen atom or an alkali metal, n1 and n2 each independently represent 0 or 1, n201 represents an integer of 2-6.
In General Formula (4-1), L ²⁰¹ represents an n201-valent linking group.

In General Formula (4-1), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , M, n1, and n2 are R ¹ , R in General Formula (1), respectively. ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , M, n1, and n2 have the same meaning, and specific examples and preferred ranges are also the same.

In General Formula (4-1), X ^1a has the same meaning as R ¹⁰¹ in General Formula (1-1), and specific examples and preferred ranges thereof are also the same.

In General Formula (4-1), L ²⁰¹ has the same meaning as L ² in General Formula (4), and specific examples and preferred ranges thereof are also the same.

In the general formula (4-1), n201 is the same meaning as ^{n 2} in the general formula (4), and preferred ranges are also the same.

  Formula (4-2):

In general formula (4-2), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and X ^1a is substituted or Unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted carbonyl group, substituted or unsubstituted sulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted aryloxycarbonyl group, carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylamino Represents a carbonyl group or a substituted or unsubstituted alkylarylaminocarbonyl group. . M represents a hydrogen atom or an alkali metal, n1 and n2 each independently represents an integer of 0 or 1, and n202 represents an integer of 2 to 6.
In General Formula (4-2), L ²⁰² represents an n202-valent linking group.

In general formula (4-2), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , X ^1a , L ²⁰² , M, n1, n2 and n202 are represented by the general formula ( 4-1) are the same as R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , X ^1a , L ²⁰¹ , M, n1, n2 and n ²⁰¹ , and specific examples The preferred range is also the same.

  Formula (4-3):

In General Formula (4-3), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and X ^1a represents a substituted or Unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted carbonyl group, substituted or unsubstituted sulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted aryloxycarbonyl group, carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylamino Represents a carbonyl group or a substituted or unsubstituted alkylarylaminocarbonyl group. . M represents a hydrogen atom or an alkali metal, n1 and n2 each independently represents an integer of 0 or 1, and n203 represents an integer of 2 to 6.
In General Formula (4-3), L ²⁰³ represents an n203-valent linking group.

In general formula (4-3), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , X ^1a , L ²⁰³ , M, n1, n2 and n203 are represented by the general formula ( 4-1) are the same as R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , X ^1a , L ²⁰¹ , M, n1, n2 and n ²⁰¹ , and specific examples The preferred range is also the same.

  Formula (4-4):

In General Formula (4-4), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a substituent, and X ^1a is a substituted or Unsubstituted alkyl group, substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted carbonyl group, substituted or unsubstituted sulfonyl group, substituted or unsubstituted alkoxycarbonyl group, substituted or Unsubstituted aryloxycarbonyl group, carbamoyl group, substituted or unsubstituted monoalkylaminocarbonyl group, substituted or unsubstituted dialkylaminocarbonyl group, substituted or unsubstituted monoarylaminocarbonyl group, substituted or unsubstituted diarylamino Represents a carbonyl group or a substituted or unsubstituted alkylarylaminocarbonyl group. . M represents a hydrogen atom or an alkali metal, n1 and n2 each independently represents an integer of 0 or 1, and n204 represents an integer of 2 to 6.
In General Formula (4-4), L ²⁰⁴ represents an n204-valent linking group.

In general formula (4-4), R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , X ^1a , L ²⁰⁴ , M, n1, n2 and n204 are represented by the general formula ( 4-1) are the same as R ¹ , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁰ , X ^1a , L ²⁰¹ , M, n1, n2 and n ²⁰¹ , and specific examples The preferred range is also the same.

  A compound represented by the following general formula (1), a compound represented by the general formula (2), a compound having a repeating unit represented by the general formula (3), and a compound represented by the general formula (4) Although the specific example is given, it is not necessarily limited to these. In the structural formulas of the following specific compounds, Me represents a methyl group, Et represents an ethyl group, i-Pr represents an isopropyl group, and Ph represents a phenyl group.

[Copper compound soluble in water]
The coloring composition of the present invention contains a water-soluble copper compound. Here, “soluble in water” means to dissolve at a rate of 0.5% by mass or more with respect to water at 25 ° C.

  The copper compound used in the present invention is preferably copper (II) chlorate, copper (II) chloride, copper (II) salicylate, copper (II) gluconate, copper (II) formate, disodium copper ethylenediaminetetraacetate And at least one selected from the group consisting of (II) and copper (II) acetate, and more preferably, from the viewpoint of solubility in ink, copper (II) chloride, copper (II) chlorate, glucone Examples include at least one selected from the group consisting of acid copper (II), copper formate (II), and ethylenediaminetetraacetic acid disodium copper (II). More preferably, from the viewpoint of safety, copper (II) gluconate and / or disodium copper (II) ethylenediaminetetraacetate can be mentioned, and copper (II) gluconate is most preferred. By including this compound in the colored composition of the present invention, a recorded image having good light resistance can be realized without impairing the hue of the coloring material.

(Coloring composition)
The colored composition of the present invention includes a compound represented by the general formula (1), a compound represented by the general formula (2), a compound having a repeating unit represented by the general formula (3), and the general formula (4). The xanthene compound soluble in water and the copper compound soluble in water are contained.
By combining the specific xanthene compound used in the present invention with a copper compound, a colored composition excellent in light resistance, ozone resistance and hue was obtained.
The coloring composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The coloring composition of the present invention can be prepared by dissolving and / or dispersing the compound of the present invention in a lipophilic medium or an aqueous medium as a medium. Preferably, an aqueous medium is used. The coloring composition of the present invention includes an ink composition excluding a medium.

  In the present invention, the compound represented by the general formula (1), the compound represented by the general formula (2), the compound having a repeating unit represented by the general formula (3), and the general The content of the water-soluble xanthene compound selected from the compounds represented by formula (4) is determined by the type of xanthene compound used and the type of solvent component used to produce the colored composition. However, the content of the xanthene compound in the colored composition is preferably 1 to 20% by mass, more preferably 1 to 10% by mass, and more preferably 2 to 6% by mass with respect to the total mass of the colored composition. % Is more preferable.

  By making the content of the water-soluble xanthene compound contained in the coloring composition 1% by mass or more, the color development property of the ink on the recording medium when printed can be improved, and the required image The concentration can be secured. Moreover, when the total amount of the xanthene compound soluble in water contained in the coloring composition is 20% by mass or less, the discharging property of the coloring composition can be improved when used in the ink jet recording method, and the ink jet ink is used. The effect that the nozzle is not easily clogged is obtained.

  In the present invention, the content of the copper compound contained in the colored composition is preferably 0.05 to 5% by mass, more preferably 0.1 to 4% by mass, More preferably, it is contained in an amount of 1.5% by mass. By setting it in this range, a recorded image having good light resistance can be realized without impairing the hue of the color material.

  The compound represented by the general formula (1), the compound represented by the general formula (2), the compound having a repeating unit represented by the general formula (3), and the general formula (4) contained in the coloring composition. Is preferably 350/1 to 7/3, and preferably 35/1 to 7/3, as the mass ratio of the content of any of the compounds represented by More preferably, it is more preferably 14/1 to 7/3. By setting it within the range of 350/1 to 7/3, a recorded image having good light resistance can be realized without impairing the hue, and the storage stability with ink liquid and the reliability of clogging in ink jet printing, etc. Excellent in properties.

  The coloring composition of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention. Examples of other additives include additives that can be used in ink jet recording inks described later.

[Ink for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described.
The ink for inkjet recording of the present invention includes a compound represented by the general formula (1) of the present invention, a compound represented by the general formula (2), a compound having a repeating unit represented by the general formula (3), and A water-soluble xanthene compound of any one of the compounds represented by the general formula (4) and a water-soluble copper compound are contained.
The ink for inkjet recording can be prepared by dissolving and / or dispersing the compound of the present invention in an oleophilic medium or an aqueous medium. The ink for inkjet recording is preferably an ink using an aqueous medium.
The ink for ink jet recording can contain other additives as required within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Well-known additives, such as a foaming agent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive agent, a chelating agent, are mentioned. These various additives are directly added to the ink liquid in the case of water-soluble ink. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the preparation of the dye dispersion, but it may be added to the oil phase or the aqueous phase at the time of preparation.

  As additives that can be used in the present invention, the additives described in JP-A-2013-133394, [0091] to [0101] can be used. About a usage form, a usage method, etc., the content described in the said patent document can be used preferably.

  The water-soluble xanthene compound is preferably contained in an amount of 0.2% by mass or more and 10% by mass or less, more preferably 1% by mass or more and 6% by mass or less, in 100 parts by mass of the inkjet recording ink of the present invention. . In addition, in the ink for ink jet recording of the present invention, other dyes may be used in combination with the xanthene compound soluble in water. When using 2 or more types of pigment | dyes together, it is preferable that the sum total of content of a pigment | dye is the said range.

  The ink for inkjet recording of the present invention preferably has a viscosity of 30 mPa · s or less. The surface tension is preferably 25 mN / m or more and 70 mN / m or less. Viscosity and surface tension are various additives such as viscosity modifiers, surface tension modifiers, specific resistance modifiers, film modifiers, UV absorbers, antioxidants, antifading agents, antifungal agents, and rust inhibitors. It can be adjusted by adding a dispersant and a surfactant.

  The ink for ink jet recording of the present invention can be used in various color tones, but is preferably used in a magenta color ink. Further, it can be used not only for forming a single color image but also for forming a full color image. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Any applicable dye can be used. Examples thereof include the dyes described in JP 2013-133394 A [0105] to [0108].

  The ink composition of the present invention can be used in recording methods such as printing, copying, marking, writing, drawing, stamping, and the like, and is particularly suitable for use in an inkjet recording method.

[Inkjet recording method]
The present invention also relates to an inkjet recording method for forming an image using the colored composition or the inkjet recording ink of the present invention.
In the ink jet recording method of the present invention, a known image receiving material, that is, plain paper, resin-coated paper, for example, JP-A-8-169172, JP-A-8-27693, and JP-A-2 JP-A-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153789, JP-A-10-217473, JP-A-10-235995, Form images on inkjet paper, film, electrophotographic co-paper, fabric, glass, metal, ceramics, etc. described in JP-A-10-337947, JP-A-10-217597, and JP-A-10-337947 .

  When forming an image, a polymer fine particle dispersion (also referred to as polymer latex) may be used in combination for the purpose of imparting glossiness or water resistance or improving weather resistance. The timing of applying the polymer latex to the image receiving material may be before, after, or simultaneously with the application of the colorant, and therefore the addition place may be in the image receiving paper. It may be in ink or may be used as a liquid material of polymer latex alone. Specifically, Japanese Patent Application Nos. 2000-363090, 2000-315231, 2000-354380, 2000-343944, 2000-268952, 2000-299465, 2000-297365, etc. The method described in the specification can be preferably used.

[Inkjet printer cartridge and inkjet recording]
The ink cartridge for ink jet recording of the present invention is filled with the ink for ink jet recording of the present invention described above. Further, the ink-jet recorded matter of the present invention is obtained by forming a colored image on a recording material using the above-described ink for ink-jet recording of the present invention.

  As the recording paper and recording film used for ink jet printing using the ink of the present invention, for example, those described in JP-A No. 2013-133394 [0112] to [0121] can be applied.

  The ink of the present invention is not limited to an ink jet recording system, and is a known system, for example, a charge control system that discharges ink using electrostatic attraction, a drop-on-demand system (pressure) that uses the vibration pressure of a piezo element. Pulse method), acoustic ink jet method that converts electrical signal into acoustic beam and irradiates ink and uses ink to discharge ink, and thermal ink jet that heats ink to form bubbles and uses generated pressure Used for systems. Inkjet recording methods use a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent inks. The method is included.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited to these Examples at all. Unless otherwise specified, “%” and “parts” in the examples are% by mass and parts by mass.

(Synthesis example 1) Synthesis | combination of exemplary compound (1-2) It can synthesize | combine according to the method of the synthesis example 2 of Unexamined-Japanese-Patent No. 2011-148773.

(Synthesis example 2) Synthesis | combination of exemplary compound (1-3) Exemplary compound (1-3) is compoundable according to the following scheme, for example.

(Synthesis of Intermediate (B))
3 ′, 6′-dichlorospiro [3H-2,1-benzooxathiol-3,9 ′-[9H] xanthene] -1,1-dioxide (manufactured by Chugai Kasei Co., Ltd., DCSF (trade name)) 20 g, 2, 46 g of 4-diaminomesitylene-6-sulfonic acid, 30 g of diazabicycloundecene (DBU) and 6.7 g of zinc chloride were added to 250 g of ethylene glycol and reacted at 150 ° C. for 6 hours. The obtained reaction solution was cooled to room temperature, poured into 1 L of acetonitrile, and the obtained crystals were purified by column chromatography (filler: Sephadex LH-20 (Pharmacia), developing solvent: water / methanol) A body (C) was obtained. Yield 7.7 g, 19% yield, MS (m / z) = 836 ([M-1] ⁻ , 100%).

(Synthesis of Exemplary Compound (1-3))
20 g of intermediate (B) was dissolved in 120 mL of N, N-dimethylacetamide (DMAc), and the internal temperature was cooled to 0 ° C. Here, 10 mL of phenyl chloroformate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while keeping the internal temperature at 5 ° C. or lower, and then reacted at 0 to 5 ° C. for 90 minutes. The obtained reaction solution was poured into 1500 mL of ethyl acetate, the precipitated crystals were filtered off, dissolved in 200 mL of water, the pH was adjusted to 7 with dilute aqueous sodium hydroxide solution, and the resulting aqueous solution was subjected to column chromatography (filler : Sephadex LH-20 (Pharmacia), developing solvent: water / methanol). After concentrating with a rotary evaporator, it is dissolved again in water, and after passing through a strongly acidic ion exchange resin (Amberlite IR124-H (trade name), manufactured by Oregano Co., Ltd.), pH is adjusted using a dilute aqueous sodium hydroxide solution. Was adjusted to 7 and subjected to dust filtration using a membrane filter, and then concentrated to dryness using a rotary evaporator to obtain a green glossy solid of the exemplary compound (1-5). Yield 24 g, 93% yield. MS (m / z) = 1054 ([M-Na] ^- , 100%). The absorption maximum wavelength of the absorption spectrum of the exemplified compound (1-3) in a dilute aqueous solution was 531 nm.

(Synthesis example 3) Synthesis | combination of exemplary compound (1-1) Exemplary compound (1-1) is compoundable according to the following scheme.

4 g of the intermediate (B) obtained as a synthetic intermediate of the aforementioned exemplary compound (1-3) was dissolved in 56 mL of N, N-dimethylacetamide (DMAc), and the internal temperature was cooled to 0 ° C. 4.8 mL of phenyl chloroformate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while keeping the internal temperature at 5 ° C. or lower, and then reacted at room temperature for 90 minutes. The internal temperature was again cooled to 0 ° C., and 4.0 mL of isopropylamine (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at an internal temperature of 10 ° C. or lower, followed by stirring at room temperature for 30 minutes. The resulting reaction solution was poured into a large excess of ethyl acetate, and the precipitated solid was filtered off. The obtained solid was dissolved in water, pH was adjusted to 7 with dilute sodium hydroxide aqueous solution, and the obtained aqueous solution was subjected to column chromatography (filler: Sephadex LH-20 (Pharmacia), developing solvent: water / methanol). ). After concentrating with a rotary evaporator, it is dissolved again in water, and after passing through a strongly acidic ion exchange resin (Amberlite IR120-H (trade name), manufactured by Oregano), pH is adjusted using a dilute aqueous sodium hydroxide solution. Was adjusted to 7 and subjected to dust filtration using a membrane filter, and then concentrated to dryness using a rotary evaporator to obtain a green glossy solid of the exemplary compound (1-1). Yield 3.1 g, 67% yield. MS (m / z) = 962 ([M-1] ^- , 100%). The absorption maximum wavelength of the absorption spectrum of Exemplified Compound (1-1) in a dilute aqueous solution was 531 nm, and the molar extinction coefficient was 65000.

(Synthesis example 4) Synthesis | combination of exemplary compound (3-2) 3.0 g of above-mentioned exemplary compound (1-3) was dissolved in 30 mL of N, N- dimethylacetamide (DMAc), and internal temperature was cooled to 0 degreeC. A solution prepared by dissolving 0.32 g of 1,3-cyclohexanediamine in 10 mL of N, N-dimethylacetamide (DMAc) was added dropwise over 30 minutes, and then reacted at room temperature for 24 hours. The reaction solution was poured into 300 mL of isopropyl alcohol, and the precipitated crystals were separated by filtration and redissolved in 100 mL of water. After passing through a strongly acidic ion exchange resin (Amberlite IR-124H (trade name), manufactured by Organo), the pH was adjusted to 7.0 using a dilute aqueous sodium hydroxide solution. After removing the inorganic salt from the aqueous solution using a dialysis membrane (fractionated molecular weight 3500, Spectra / Por3 Dialysis Membrane (trade name, Spectrum = Laboratory)), the solution was concentrated to dryness and the metal of the exemplified compound (3-2) 2.5 g of glossy crystals were obtained. The repeating unit was estimated to be 10.9 from the molecular weight in terms of polystyrene by GPC measurement. Moreover, the absorption maximum wavelength of the UV-Vis spectrum of the dilute aqueous solution of exemplary compound (3-2) was 532 nm.

Synthesis Example 5 Synthesis of Exemplary Compound (4-2) Exemplary compound (4-2) can be synthesized, for example, according to the following scheme.

[Synthesis of Intermediate (C)]
20 g of intermediate (B) was dissolved in 120 mL of N, N-dimethylacetamide (DMAc), and the internal temperature was cooled to zero. Here, 10 mL of isobutyryl chloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise while keeping the internal temperature at 5 or lower, and then reacted at 0 to 5 for 90 minutes. The obtained reaction solution was poured into 1500 mL of ethyl acetate, the precipitated crystals were filtered off, dissolved in 200 mL of water, the pH was adjusted to 7 with dilute aqueous sodium hydroxide solution, and the resulting aqueous solution was subjected to column chromatography (filler : Sephadex LH-20 (Pharmacia), developing solvent: water / methanol). After concentrating with a rotary evaporator, it is dissolved again in water, and after passing through a strongly acidic ion exchange resin (Amberlite IR124-H (trade name), manufactured by Oregano Co., Ltd.), pH is adjusted using a dilute aqueous sodium hydroxide solution. Was subjected to dust removal filtration using a membrane filter and then concentrated to dryness using a rotary evaporator to obtain an intermediate (C) green glossy solid. Yield 22 g, MS (m / z) = 884.2 ([M-Na] ^- , 100%).

[Synthesis of Intermediate (D)]
Intermediate (C) 22 g was dissolved in 120 mL of N, N-dimethylacetamide (DMAc), and the internal temperature was cooled to zero. Here, 5 mL of phenyl chloroformate (manufactured by Tokyo Chemical Industry Co., Ltd.) was dropped while keeping the internal temperature at 5 or lower, and then reacted at 0 to 5 for 90 minutes. The obtained reaction solution was poured into 1500 mL of ethyl acetate, the precipitated crystals were filtered off, dissolved in 200 mL of water, the pH was adjusted to 7 with dilute aqueous sodium hydroxide solution, and the resulting aqueous solution was subjected to column chromatography (filler : Sephadex LH-20 (Pharmacia), developing solvent: water / methanol). After concentrating with a rotary evaporator, it is dissolved again in water, and after passing through a strongly acidic ion exchange resin (Amberlite IR124-H (trade name), manufactured by Oregano Co., Ltd.), pH is adjusted using a dilute aqueous sodium hydroxide solution. Was adjusted to 7 and subjected to dust filtration using a membrane filter, and then concentrated to dryness using a rotary evaporator to obtain an intermediate (D) green glossy solid. Yield 20 g, MS (m / z) = 1004 ([M-Na] ^- , 100%).

[Synthesis of Exemplary Compound (4-2)]
Intermediate (D) (3.0 g) was dissolved in N, N-dimethylacetamide (DMAc) (30 mL), and the internal temperature was cooled to zero. A solution prepared by dissolving 0.2 g of ethylenediamine in 10 mL of N, N-dimethylacetamide (DMAc) was added dropwise over 30 minutes, and then reacted at room temperature for 24 hours. The reaction solution was poured into 300 mL of isopropyl alcohol, and the precipitated crystals were separated by filtration and redissolved in 100 mL of water. After passing through a strongly acidic ion exchange resin (Amberlite IR-124H (trade name), manufactured by Organo), the pH was adjusted to 7.0 using a dilute aqueous sodium hydroxide solution. After removing the inorganic salt from the aqueous solution using a dialysis membrane (fractionated molecular weight 3500, Spectra / Por3 Dialysis Membrane (trade name, Spectrum = Laboratory)), it was concentrated to dryness and the metal of the exemplary compound (4-2) 2.5 g of glossy crystals were obtained. The absorption maximum wavelength of the UV-Vis spectrum of the dilute aqueous solution of exemplary compound (4-2) was 532 nm.

  Other exemplary compounds can also be synthesized according to the above method.

[Examples 1 to 26, Comparative Examples 1 to 4]
<Preparation of ink composition>
An ink composition having the following composition was stirred for 1 hour while being heated at 30 to 40 ° C. Thereafter, the pH was adjusted to 9 with KOH 10 mol / L, and the mixture was filtered under reduced pressure through a microfilter having an average pore size of 0.25 μm to prepare a magenta ink liquid.
In addition, the numerical value in following Table 1 represents the mass ratio of each component.

Ink composition Dye compounds listed in Table 1 Addition amounts listed in Table 1 Copper compounds listed in Table 1 Addition amounts listed in Table 1 Triethylene glycol monobutyl ether 10% by mass
Glycerin 10% by mass
Triethylene glycol 5% by mass
Olphine E1010 (acetylene glycol surfactant, manufactured by Nissin Chemical Industry)
2% by mass
Water remaining

(Image recording and evaluation)
The following evaluation was performed on the inks for ink jet recording of the above Examples and Comparative Examples. The results are shown in Table 1.
In Table 1, the hue, ozone resistance, and light resistance of each ink jet recording ink are photo glossy paper (manufactured by EPSON Co., Ltd .; PM-700C) and photo glossy paper (manufactured by EPSON PM photo paper <gloss). > (KA420PSK, EPSON)) and then evaluated after recording the image.

<Light resistance>
The applied duty is adjusted so that OD (Optical Density) falls within the range of 0.9 to 1.1, magenta solid printing is performed, and the obtained printed matter is printed on a xenon light resistance tester XL-75s (trade name). : Manufactured by Suga Test Instruments Co., Ltd.), exposure was performed for 30 days under conditions of 23 ° C. relative humidity 50% and illuminance 75000 lux.
After the exposure, the OD value of the printed material was measured using a reflection densitometer (“Spectrilino” (trade name: manufactured by Gretag), the optical density residual ratio (ROD) was determined from the following formula, and evaluated according to the following criteria.
ROD (%) = (D / D0) × 100
D: OD after exposure test
D0: OD before exposure test
(Measurement conditions Light source: D50, viewing angle: 2 °, DIN-NB)
S: When ROD is 95% or more A: When ROD is 90% or more and less than 95% B: When ROD is 80% or more and less than 90% C: When ROD is 70% or more and less than 80% D: ROD is 60 %: Less than 70% E: ROD is less than 60%

<Light resistance improvement degree>
Compared to “ink without addition of copper compound”, “ink with addition of copper compound” has an image light fastness rank of 2 ranks or higher, A is 1 rank higher, B is the same rank, C is The case where the rank was lowered was defined as D. Separately, an ink not added with a copper compound was similarly prepared, light resistance was measured, and ranks were compared.

<Hue>
The hue was visually evaluated in three stages: best, good and poor. In Table 1 above, A indicates that the hue is the best, B indicates that the hue is good, and C indicates that the hue is poor.

<Ozone resistance>
A box in which a 5kV AC voltage is applied while passing dry air through a double glass tube of a Siemens type ozonizer, and the ozone gas concentration is set to 0.5 ± 0.1ppm, room temperature (24 ° C), and dark place. Inside, the photo glossy paper on which the image is formed is left for 7 days, and the image density before and after being left under ozone gas is measured using a reflection densitometer (X-Rite 310TR, manufactured by Xrite), and the optical density residual ratio (ROD) As described above, the light resistance ROD was evaluated in the same manner. The reflection density was measured at one point. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
S: When ROD is 95% or more A: When ROD is 90% or more and less than 95% B: When ROD is 80% or more and less than 90% C: When ROD is 70% or more and less than 80% D: ROD is 60 %: Less than 70% E: ROD is less than 60%

  In addition to the compounds exemplified in the present application, compounds used in Comparative Examples are shown below.

  As can be seen from the results, the compound represented by the general formula (1), the compound represented by the general formula (2), the compound having a repeating unit represented by the general formula (3), and the general formula (4) The ink of the example using the coloring composition of the present invention containing any one of the represented compounds and a copper compound soluble in water has improved light resistance and ozone resistance compared to the ink of the comparative example. , And the hue was also found to be excellent.

  The coloring composition of the present invention can obtain excellent light resistance, ozone resistance and hue.

Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on a Japanese patent application filed on September 30, 2014 (Japanese Patent Application No. 2014-202536), the contents of which are incorporated herein by reference.

Claims (10)

Compound represented by general formula (1 A ), compound represented by general formula (2 A ), compound having a repeating unit represented by general formula (3), and compound represented by general formula (4) A coloring composition comprising any of the above and a water-soluble copper compound.

In the general formula (1 A) and the general formula ^{(2 A), R 1,} R 5, R 6, R 10, R 11, R 15, R 1 6 及 beauty ^{R 20} each independently represent a substituted or unsubstituted alkyl represents a group, R ³ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or represents a sulfo group, R ⁴ and R ⁹ each independently represent a hydrogen atom, a substituted or unsubstituted acylamino group, Substituted or unsubstituted alkoxycarbonylamino group, substituted or unsubstituted alkylsulfonylamino group, substituted or unsubstituted arylsulfonylamino group, substituted or unsubstituted alkylureido group, substituted or unsubstituted arylureido group, or sulfo It represents a ^{group, R 12, R 14, R} 17 and ^{R 19} each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted It represents an aryl group, or a substituted or unsubstituted alkoxy ^{group, X 1, X 2, X} 3 and X ⁴ each independently substitution or unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted Heteriruamino group, substitution or unsubstituted acyloxy group, a substituted or unsubstituted aminocarbonyl group, substituted arylsulfonylamino group with a carboxyl group, a substituted or unsubstituted A substituted alkoxycarbonylamino group, a substituted or unsubstituted aryloxycarbonylamino group, a substituted or unsubstituted ureido group, a substituted or unsubstituted alkylthio group, or a substituted or unsubstituted arylthio group, and M is a hydrogen atom or Represents an alkali metal, n1, n2, n3 and n4 Each independently an integer of 0 or 1.
General formula (3):

In general formula (3), L ¹ is a divalent linkage formed by combining a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, or a combination of two or more thereof. represents a group, D ¹ represents a removing two partial structures of the hydrogen atom from the compound represented by the following general formula (1) or general formula (2). n ¹ represents 2 to 100.
General formula (4):

In General Formula (4), L ² represents a substituted or unsubstituted alkylene group, a substituted or unsubstituted arylene group, a substituted or unsubstituted alkenylene group, a triazine group, a cyanuric group, an amino group, or two or more selected from these represents a divalent to hexavalent linking group formed by combining, D ² represents a removing one partial structures a hydrogen atom from a compound represented by the following general formula (1) or general formula (2). n ² represents an integer of 2 to 6.

In general formula (1) and general formula (2), R ¹ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ and R ²⁰ each independently represents a substituted or unsubstituted alkyl group, R ³ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or a sulfo group, and R ⁴ and R ⁹ each independently represent a hydrogen atom, a substituted or unsubstituted acylamino group, substituted or unsubstituted An alkoxycarbonylamino group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted alkylureido group, a substituted or unsubstituted arylureido group, or a sulfo group, ^{R 12,} R 14, R ¹⁷ and ^{R 19} each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl Group, or a substituted or unsubstituted alkoxy group, a X ^{1, X 2,} X ³ and X ⁴ are each independently a hydroxyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted Or an unsubstituted heterocyclic oxy group, a substituted or unsubstituted alkylamino group, a substituted or unsubstituted arylamino group, a substituted or unsubstituted heterylamino group, a substituted or unsubstituted carbonylamino group, a substituted or unsubstituted acyloxy Group, substituted or unsubstituted aminocarbonyloxy group, substituted or unsubstituted sulfonylamino group, substituted or unsubstituted alkoxycarbonylamino group, substituted or unsubstituted aryloxycarbonylamino group, substituted or unsubstituted ureido group, A substituted or unsubstituted alkylthio group, Represents a substituted or unsubstituted arylthio group, M represents a hydrogen atom or an alkali metal, n1, n2, n3 and n4 each independently represent an integer of 0 or 1.
Compound represented by general formula (1A), compound represented by general formula (2A), compound having a repeating unit represented by general formula (3), compound represented by general formula (4), general When each group in the compound represented by the formula (1) and the compound represented by the general formula (2) has a substituent, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, Heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino Group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfur Moylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group , A carbamoyl group, an aryl or heterocyclic azo group, an imide group, a phosphino group, a phosphinyl group, a phosphinyloxy group, a phosphinylamino group, a silyl group, a sulfo group, and a carboxyl group. The compound represented by the general formula (1A), general formula (2A), general formula (1), or general formula (2) is represented by the following general formula (1-1) or general formula (2-1). The coloring composition according to claim 1 which is a compound.

Formula (1-1) and the general formula ^{(2-1), R 1, R} 5, R 6, R 10, R 11, R 15, R 1 6 及 beauty ^{R 20} are each independently substituted or unsubstituted of an alkyl group, R ³ and R ⁸ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, or represents a sulfo group, R ⁴ and R ⁹ each independently represent a hydrogen atom, a substituted or unsubstituted acylamino A group, a substituted or unsubstituted alkoxycarbonylamino group, a substituted or unsubstituted alkylsulfonylamino group, a substituted or unsubstituted arylsulfonylamino group, a substituted or unsubstituted alkylureido group, a substituted or unsubstituted arylureido group, or represents a sulfo ^{group, R 12, R 14, R} 17 and ^{R 19} each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or Mu置Represents an aryl group, or a substituted or unsubstituted alkoxy ^{group, R 101, R 102, R} 103 and ^{R 104} each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted A heterocyclic group , an arylsulfonyl group substituted with a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted aryloxycarbonyl group, a carbamoyl group, a substituted or unsubstituted monoalkylaminocarbonyl group, substituted or Represents an unsubstituted dialkylaminocarbonyl group, a substituted or unsubstituted monoarylaminocarbonyl group, a substituted or unsubstituted diarylaminocarbonyl group, or a substituted or unsubstituted alkylarylaminocarbonyl group, and M represents a hydrogen atom or an alkali metal Represents, n1, n2, n3 and n4 each independently represent an integer of 0 or 1.
When each group in the compound represented by the general formula (1-1) and the compound represented by the general formula (2-1) has a substituent, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, an alkynyl Group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group Amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, Sulfamoyl group, Alkyl or arylsulfinyl group, alkyl or arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl or heterocyclic azo group, imide group, phosphino group, phosphinyl group, phosphinyloxy group, phosphine group It has a substituent selected from a finylamino group, a silyl group, a sulfo group and a carboxyl group.   The compound represented by the general formula (1A), the compound represented by the general formula (2A), the compound having a repeating unit represented by the general formula (3-1), and the general formula (4-1). A coloring composition comprising any one of the above compounds and a water-soluble copper compound.

  In general formula (1A) and general formula (2A), R ¹ , R ⁵ , R ⁶ , R ¹⁰ , R ¹¹ , R ¹⁵ , R ¹⁶ And R ²⁰ Each independently represents an unsubstituted alkyl group, R ³ And R ⁸ Each independently represents a hydrogen atom, an unsubstituted alkyl group, or a sulfo group; ⁴ And R ⁹ Each independently represents a hydrogen atom or a sulfo group, R ¹² , R ¹⁴ , R ¹⁷ And R ¹⁹ Each independently represents a hydrogen atom or an unsubstituted alkyl group; ¹ , X ² , X ³ And X ⁴ Are each independently substituted with at least one substituent selected from the following substituent group A ′ or substituted with at least one substituent selected from the following substituent group A ′, or An unsubstituted arylamino group, an arylsulfonylamino group substituted with a carboxyl group, an unsubstituted or substituted alkoxycarbonylamino group substituted with at least one substituent selected from the following substituent group A ′, and the following substituent group A An aryloxycarbonylamino group substituted or unsubstituted with at least one substituent selected from ', an alkyl group substituted with at least one substituent selected from the following substituent group A' or an unsubstituted alkyl group Substituted with a substituted ureido group or at least one substituent selected from the following substituent group A ′ Represents an aryl group or unsubstituted substituted ureido group with an aryl group, M represents a hydrogen atom or an alkali metal, n1, n2, n3 and n4 each independently represent 0 or 1.
  Substituent group A ′: hydroxyl group, carboxyl group, sulfo group
  In the general formula (1A), at least one of n1 and n2 represents 1, or R in the general formula (1A) ³ , R ⁴ , R ⁸ , R ⁹ , X ¹ And X ² At least one of them has a carboxyl group or a sulfo group.
  At least one of n3 and n4 in the general formula (2A) represents 1, or X in the general formula (2A) ³ And X ⁴ At least one of them has a carboxyl group or a sulfo group.
  General formula (3-1):

  In general formula (3-1), R ¹ , R ⁵ , R ⁶ And R ¹⁰ Each independently represents an unsubstituted alkyl group, R ³ And R ⁸ Each independently represents a hydrogen atom, an unsubstituted alkyl group, or a sulfo group; ⁴ And R ⁹ Each independently represents a hydrogen atom or a sulfo group, R ³⁰¹ , R ³⁰² , R ³⁰³ as well as ³⁰⁴ Represents a hydrogen atom, L ¹⁰¹ Represents a divalent linking group selected from the following linking group group L, M represents a hydrogen atom or an alkali metal, n1 and n2 represent 0 or 1, and n101 represents 2 to 15.
  Linking group L:

  At least one of n1 and n2 in the general formula (3-1) represents 1, or R in the general formula (3-1) ³ , R ⁴ , R ⁸ And R ⁹ At least one of represents a sulfo group.
  Formula (4-1):

  In general formula (4-1), R ¹ , R ⁵ , R ⁶ And R ¹⁰ Each independently represents an unsubstituted alkyl group, R ³ And R ⁸ Each independently represents a hydrogen atom, an unsubstituted alkyl group, or a sulfo group; ⁴ And R ⁹ Each independently represents a hydrogen atom or a sulfo group; ^1a Represents an unsubstituted alkylcarbonyl group or an unsubstituted arylcarbonyl group, M represents a hydrogen atom or an alkali metal, n1 and n2 each independently represent 0 or 1, n201 represents 2, L ²⁰¹ Represents a divalent linking group selected from the above linking group group L.
  In formula (4-1), at least one of n1 and n2 represents 1, or R in formula (4-1) ³ , R ⁴ , R ⁸ And R ⁹ At least one of represents a sulfo group. General formula (1A), general formula (2A), general formula (1), general formula (2), general formula (1-1) , general formula (2-1) , general formula (3-1) or general formula R < ¹ > , R < ⁵ >, R < ⁶ >, R < ¹⁰ >, R < ¹¹ >, R <^15> , R <^16> and R < ²⁰ > in formula (4-1) each independently represents an unsubstituted alkyl group having 1 to 6 carbon atoms. The coloring composition of any one of 1-3. R ⁴ and R ^{9 in the} general formula (1A), general formula (1) , general formula (1-1) , general formula (3-1), or general formula (4-1) each independently represent a sulfo group. The coloring composition of any one of Claims 1-4 represented.   The copper compound is copper (II) chlorate, copper (II) chloride, copper (II) salicylate, copper (II) gluconate, copper (II) formate, disodium copper (II) ethylenediaminetetraacetate, and copper acetate The coloring composition according to any one of claims 1 to 5, which is at least one selected from the group consisting of (II). The compound represented by the general formula (1 A ), the compound represented by the general formula (2 A ), the compound having a repeating unit represented by the general formula (3), the compound represented by the general formula (4) Any one of the compound which has a repeating unit represented by general formula (3-1), and the compound represented by general formula (4-1) is 1-20 mass%. 2. A coloring composition according to item 1. The compound represented by the general formula (1 A ), the compound represented by the general formula (2 A ), the compound having a repeating unit represented by the general formula (3), the compound represented by the general formula (4) The content of any of the compound represented by formula (3-1) and the compound represented by formula (4-1) and the content of the water-soluble copper compound The coloring composition according to any one of claims 1 to 7, wherein the mass ratio of the pigment is 350/1 to 7/3.   The ink for inkjet recording containing the coloring composition of any one of Claims 1-8. The inkjet recording method of forming an image using the coloring composition of any one of Claims 1-8, or the inkjet recording ink of Claim 9.