JP5816576B2 - Colored composition, method for producing colored composition, ink for ink jet recording, and ink jet recording method - Google Patents

Description

  The present invention relates to a coloring composition comprising a compound having a specific xanthene skeleton and a specific heteryl azo compound, an ink for ink jet recording, and an ink jet 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. Conventionally, water-based inks are mainly used for these ink-jet inks from the viewpoint of safety such as odor and fire hazard. 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.

  Many of these performances are satisfied by using water or a water-based ink containing a mixture of water and a water-soluble organic solvent as a main solvent, but color tone, vividness, light resistance, ozone resistance, water resistance Moisture resistance depends largely on the colorant, and various dyes have been studied in the past.

  Conventionally, as a magenta dye for inkjet, an acid dye having good color development and high water solubility, such as C.I. I. Acid Red 52, 249, 289, etc. are known, but when these dyes are used alone, although they are highly water-soluble, nozzle clogging is less likely to occur, but ozone resistance and light resistance performance are very high. It was low.

  Patent Document 1 discloses C.I., a xanthene derivative. I. Acid Red 289 and C.I. I. A water-based ink for ink-jet recording containing a dye comprising a xanthene derivative having more sulfo groups than Acid Red 289 is described.

  In addition, azo dyes are also known as magenta dyes for ink jet. As an azo dye having a good hue, Patent Document 2 discloses a good hue by using a heteryl azo dye having a specific substituent. And a coloring composition having fastness to light and ozone.

British Patent No. 2134129 JP 2006-143989 A

However, dyes specifically described in Patent Document 1 are required to further improve ozone resistance and light resistance. Further, the dye described in Patent Document 2 has good fastness such as light resistance and ozone resistance, but has left room for further improvement in hue. That is, in any case, the fastness and the hue are not sufficiently compatible.
An object of the present invention is to provide a coloring composition capable of achieving both high image fastness such as ozone resistance and light resistance and a good hue and high moisture resistance. 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 jet recording ink.

  As a result of intensive investigations in view of the above-described circumstances, the present inventors have combined a multimer of a compound having a xanthene skeleton into which a specific number of sulfo groups have been introduced with a coloring composition containing a specific heteryl azo compound, to thereby prevent ozone resistance. The present invention has been completed by finding that the image fastness such as the light resistance and the light fastness and the performance relating to the hue are particularly excellent than expected.

（一般式（１）中、Ｌは、下記一般式（Ｖ１）、（Ｖ２）、（Ｖ３）又は（Ｖ４）で表される連結基を表す。
Ｄは、一般式（２）で表される化合物から水素原子を１個取り除いた残基を表す。
ｍは、１を表す。
ｎは、２を表す。但し、複数のＤは、それぞれ同一でも異なっていてもよい。
一般式（２）中、Ｒ^４〜Ｒ^２４はそれぞれ独立に、水素原子又は置換基を表す。
但し、少なくとも１個以上のイオン性親水性基を有する。）

（一般式（Ｖ１）中、Ｒ^１０１及びＲ^１０２はそれぞれ独立に水素原子又は置換基を表す。
一般式（Ｖ２）中、Ｒ^２０１及びＲ^２０２はそれぞれ独立に水素原子又は置換基を表し、Ｌ^２０１はオキシ基（−Ｏ−）、チオ基（−Ｓ−）、カルボニル基（−ＣＯ−）、スルホニル基（−ＳＯ _２ −）、イミノ基（−ＮＨ−）、メチレン基（−ＣＨ _２ −）、アリーレン基、シクロアルキレン基、及びこれらを組み合わせて形成される基より選択される２価の連結基を表す。Ｒ^２０１とＲ^２０２は互いに結合して環を形成してもよい。
一般式（Ｖ３）中、Ｒ^３０１、Ｒ^３０２及びＲ^３０３はそれぞれ独立に水素原子又は置換基を表し、Ｘは置換基を有していてもよい炭素数２〜２０のアルキレン基を表し、Ｌ^３０１は単結合又は２価の連結基を表す。
一般式（Ｖ４）中、Ｒ^４０１及びＲ^４０２はそれぞれ独立に水素原子又は置換基を表す。）

一般式（４）中、Ｚ^１は、ハメットの置換基定数σｐ値が０．２０以上の電子求引性基を表す。
Ｚ^２は、水素原子、脂肪族基、芳香族基、アシル基、又はヘテロ環基を表す。
Ｒ^２３及びＲ^２４は、それぞれ独立に、水素原子、脂肪族基、芳香族基、ヘテロ環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、またはスルファモイル基を表す。ただし、Ｒ^２３及びＲ^２４が共に水素原子であることはない。
Ｒ^２１及びＲ^２２は、それぞれ独立に、水素原子、ハロゲン原子、脂肪族基、芳香族基、ヘテロ環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、ヘテロ環オキシ基、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、アルキルアミノ基、アリールアミノ基、ヘテロ環アミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、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、アルキルもしくはアリールスルホニルアミノ基、アリールオキシカルボニルアミノ基、ニトロ基、アルキルもしくはアリールチオ基、アルキルもしくはアリールスルホニル基、アルキルもしくはアリールスルフィニル基、スルファモイル基、スルホ基、またはヘテロ環チオ基を表す。また、Ｒ^２１とＲ^２３、またはＲ^２３とＲ^２４が結合して５または６員環を形成してもよい。
Ｒ^２５及びＲ^２９は、それぞれ独立に、アルキル基、アルコキシ基またはハロゲン原子を表す。但し、Ｒ^２５及びＲ^２９が共にアルキル基である時は、そのアルキル基を構成する炭素数の合計が３以上であって、それらは更に置換されていてもよい。
Ｒ^２６、Ｒ^２７、及びＲ^２８は、それぞれ独立にＲ^２１及びＲ^２２と同義であり、Ｒ^２５とＲ^２６、又は、Ｒ^２８とＲ^２９で互いに縮環していてもよい。
Ｑは、水素原子、脂肪族基、芳香族基またはヘテロ環基を表す。
上記Ｚ^１、Ｚ^２、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＱの各基は、更に置換基を有していてもよい。
但し、一般式（４）は、少なくとも一つのイオン性親水性基を有する。
＜２＞
前記一般式（２）中、Ｒ^４、Ｒ^８、Ｒ^９及びＲ^１３はそれぞれ独立に、水素原子又はアルキル基を表す、＜１＞に記載の着色組成物。
＜３＞
前記一般式（２）中、Ｒ^５〜Ｒ^７、Ｒ^１０〜Ｒ^１２及びＲ^１４〜Ｒ^２３は水素原子を表す、＜１＞又は＜２＞に記載の着色組成物。
＜４＞
前記一般式（１）中、Ｄは一般式（２）で表される化合物のＲ^５〜Ｒ^７、Ｒ^１０〜Ｒ^１２及びＲ^２４としての水素原子から、水素原子を１個取り除いた残基を表す、＜１＞〜＜３＞のいずれか一項に記載の着色組成物。
＜５＞
下記一般式（Ｗ１１）で表される化合物、及び一般式（Ｗ１５）で表される化合物からなる群より選ばれる少なくとも一種と、
下記一般式（４）で表される化合物とを含む着色組成物の製造方法であって、
一般式（Ｗ１１）で表される化合物が、下記（Ａ）を含む合成方法により合成される化合物であり、
一般式（Ｗ１５）で表される化合物が、下記（Ｂ）を含む合成方法により合成される化合物である、
着色組成物の製造方法。
（Ａ）スルホ基を有する一般式（Ｗ８）で表されるキサンテン化合物のスルホ基をクロロスルホニル基に変換して得られた一般式（Ｗ９）で表される化合物と、一般式（Ｗ１０）で表されるジアミンとを反応させて得られる化合物の加水分解により得られる一般式（Ｗ１１）で表される化合物の合成方法

一般式（Ｗ８）中、Ｒ ^６０１ 、Ｒ ^６０２ 、Ｒ ^６０３ 及びＲ ^６０４ は水素原子又はアルキル基を表し、Ｒ ^６０５ 、Ｒ ^６０６ 、Ｒ ^６０７ 、Ｒ ^６０８ 及びＲ ^６０９ は置換基を表し、ｎ ^６０１ は０〜１の整数を表し、ｎ ^６０２ 〜ｎ ^６０６ は０を表す。
一般式（Ｗ９）中、Ｒ ^６０１ 、Ｒ ^６０２ 、Ｒ ^６０３ 、Ｒ ^６０４ 、Ｒ ^６０５ 、Ｒ ^６０６ 、Ｒ ^６０７ 、Ｒ ^６０８ 、Ｒ ^６０９ 、ｎ ^６０１ 、ｎ ^６０２ 、ｎ ^６０３ は、ｎ ^６０４ 、ｎ ^６０５ 及びｎ ^６０６ は、一般式（Ｗ８）のＲ ^６０１ 、Ｒ ^６０２ 、Ｒ ^６０３ 、Ｒ ^６０４ 、Ｒ ^６０５ 、Ｒ ^６０６ 、Ｒ ^６０７ 、Ｒ ^６０８ 、Ｒ ^６０９ 、ｎ ^６０１ 、ｎ ^６０２ 、ｎ ^６０３ は、ｎ ^６０４ 、ｎ ^６０５ 及びｎ ^６０６ と同義である。
一般式（Ｗ１０）中、Ｒ ^２５ 及びＲ ^２６ はそれぞれ独立に、水素原子を表す。
Ｌ ^１ は下記一般式（Ｖ１）、（Ｖ２）、（Ｖ３）又は（Ｖ４）で表される連結基を表す。

（一般式（Ｖ１）中、Ｒ ^１０１ 及びＲ ^１０２ はそれぞれ独立に水素原子、アルキル基又はアリール基を表し、Ｒ ^１０１ とＲ ^１０２ は互いに結合して環を形成してもよい。
一般式（Ｖ２）中、Ｒ ^２０１ 及びＲ ^２０２ はそれぞれ独立に水素原子、又はアルキル基を表し、Ｒ ^２０１ とＲ ^２０２ は互いに結合して環を形成してもよい。Ｌ ^２０１ はオキシ基（−Ｏ−）、チオ基（−Ｓ−）、カルボニル基（−ＣＯ−）、スルホニル基（−ＳＯ _２ −）、イミノ基（−ＮＨ−）、メチレン基（−ＣＨ _２ −）、アリーレン基、シクロアルキレン基、及びこれらを組み合わせて形成される基より選択される２価の連結基を表す。Ｒ ^２０１ とＲ ^２０２ は互いに結合して環を形成してもよい。
一般式（Ｖ３）中、Ｒ ^３０１ 、及びＲ ^３０２ はそれぞれ独立に水素原子、又はアルキル基を表し、Ｒ ^３０１ とＲ ^３０２ は互いに結合して環を形成してもよい。Ｒ ^３０３ は水素原子、アミノ基、モノ若しくはジアルキルアミノ基、アリールアミノ基、又はアルキルチオ基を表し、これらは更にスルホ基、若しくはカルボキシル基より選択されるイオン性親水性基により置換されていてもよい。Ｘは置換基としてメチル基を有していてもよい炭素数２〜２０のアルキレン基を表し、Ｌ ^３０１ は単結合を表す。
一般式（Ｖ４）中、Ｒ ^４０１ は水素原子又は炭素数１〜６のアルキル基を表し、Ｒ ^４０２ はそれぞれ独立に水素原子又はスルホ基、若しくはカルボキシル基より選択されるイオン性親水性基を表す。）
一般式（Ｗ１１）中、Ｒ ^６０１ 、Ｒ ^６０２ 、Ｒ ^６０３ 、Ｒ ^６０４ 、Ｒ ^６０５ 、Ｒ ^６０６ 、Ｒ ^６０７ 、Ｒ ^６０８ 、Ｒ ^６０９ 、ｎ ^６０１ 、ｎ ^６０２ 、ｎ ^６０３ 、ｎ ^６０４ 、ｎ ^６０５ 、ｎ ^６０６ 、Ｒ ^２５ 、Ｒ ^２６ 及びＬ ^１ は、一般式（Ｗ８）中のＲ ^６０１ 、Ｒ ^６０２ 、Ｒ ^６０３ 、Ｒ ^６０４ 、Ｒ ^６０５ 、Ｒ ^６０６ 、Ｒ ^６０７ 、Ｒ ^６０８ 、Ｒ ^６０９ 、ｎ ^６０１ 、ｎ ^６０２ 、ｎ ^６０３ 、ｎ ^６０４ 、ｎ ^６０５ 、ｎ ^６０６ 、並びに一般式（Ｗ１０）中のＲ ^２５ 、Ｒ ^２６ 及びＬ ^１ と同義である。
（Ｂ）一般式（Ｗ１２）で表されるキサンテン化合物を、クロロスルホニル化して得られた一般式（Ｗ１３）で表される化合物と、一般式（Ｗ１４）で表される多価アミン等とを反応させて得られる化合物の加水分解により得られる一般式（Ｗ１５）で表される化合物の合成方法

一般式（Ｗ１２）中、Ｒ ^７０１ 、Ｒ ^７０２ 、Ｒ ^７０３ 及びＲ ^７０４ はそれぞれ独立に水素原子を表し、Ｒ ^７０５ 、Ｒ ^７０６ 及びＲ ^７０７ は置換基を表し、ｎ ^７０１ 〜ｎ ^７０３ は０を表し、ｎ ^７０４ 及びｎ ^７０５ はそれぞれ独立に０〜１の整数を表す。
一般式（Ｗ１３）及び（Ｗ１５）中、Ｒ ^７０１ 、Ｒ ^７０２ 、Ｒ ^７０３ 、Ｒ ^７０４ 、Ｒ ^７０５ 、Ｒ ^７０６ 、Ｒ ^７０７ 、ｎ ^７０１ 、ｎ ^７０２ 及びｎ ^７０３ は、一般式（Ｗ１２）のＲ ^７０１ 、Ｒ ^７０２ 、Ｒ ^７０３ 、Ｒ ^７０４ 、Ｒ ^７０５ 、Ｒ ^７０６ 、Ｒ ^７０７ 、ｎ ^７０１ 、ｎ ^７０２ 及びｎ ^７０３ と同義である。
一般式（Ｗ１４）及び（Ｗ１５）中、Ｒ ^２５ 、Ｒ ^２６ 及びＬ ^１ は、一般式（Ｗ１０）のＲ ^２５ 、Ｒ ^２６ 及びＬ ^１ と同義である。

一般式（４）中、Ｚ ^１ は、ハメットの置換基定数σｐ値が０．２０以上の電子求引性基を表す。
Ｚ ^２ は、水素原子、脂肪族基、芳香族基、アシル基、又はヘテロ環基を表す。
Ｒ ^２３ 及びＲ ^２４ は、それぞれ独立に、水素原子、脂肪族基、芳香族基、ヘテロ環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、またはスルファモイル基を表す。ただし、Ｒ ^２３ 及びＲ ^２４ が共に水素原子であることはない。
Ｒ ^２１ 及びＲ ^２２ は、それぞれ独立に、水素原子、ハロゲン原子、脂肪族基、芳香族基、ヘテロ環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、ヘテロ環オキシ基、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、アルキルアミノ基、アリールアミノ基、ヘテロ環アミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、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、アルキルもしくはアリールスルホニルアミノ基、アリールオキシカルボニルアミノ基、ニトロ基、アルキルもしくはアリールチオ基、アルキルもしくはアリールスルホニル基、アルキルもしくはアリールスルフィニル基、スルファモイル基、スルホ基、またはヘテロ環チオ基を表す。また、Ｒ ^２１ とＲ ^２３ 、またはＲ ^２３ とＲ ^２４ が結合して５または６員環を形成してもよい。
Ｒ ^２５ 及びＲ ^２９ は、それぞれ独立に、アルキル基、アルコキシ基またはハロゲン原子を表す。但し、Ｒ ^２５ 及びＲ ^２９ が共にアルキル基である時は、そのアルキル基を構成する炭素数の合計が３以上であって、それらは更に置換されていてもよい。
Ｒ ^２６ 、Ｒ ^２７ 、及びＲ ^２８ は、それぞれ独立にＲ ^２１ 及びＲ ^２２ と同義であり、Ｒ ^２５ とＲ ^２６ 、又は、Ｒ ^２８ とＲ ^２９ で互いに縮環していてもよい。
Ｑは、水素原子、脂肪族基、芳香族基またはヘテロ環基を表す。
上記Ｚ ^１ 、Ｚ ^２ 、Ｒ ^２１ 、Ｒ ^２２ 、Ｒ ^２３ 、Ｒ ^２４ 及びＱの各基は、更に置換基を有していてもよい。
但し、一般式（４）は、少なくとも一つのイオン性親水性基を有する。
＜６＞
前記一般式（４）におけるイオン性親水性基が、スルホ基、カルボキシル基、ホスホノ基、及び４級アンモニウム基より選択された少なくとも１つの基である、＜１＞〜＜４＞のいずれか一項に記載の着色組成物。
＜７＞
前記一般式（４）中、Ｒ^２３及びＲ^２４がそれぞれ独立に、水素原子、芳香族基、又はヘテロ基を表す＜１＞〜＜４＞、＜６＞のいずれか一項に記載の着色組成物。
＜８＞
一般式（１）で表される化合物の含有率が０．１〜２０質量％である＜１＞〜＜４＞、＜６＞、＜７＞のいずれか一項に記載の着色組成物。
＜９＞
一般式（４）で表される化合物の含有率が１〜５質量％である＜１＞〜＜４＞、＜６＞〜＜８＞のいずれか一項に記載の着色組成物。
＜１０＞
一般式（１）で表される化合物の含有量と、一般式（４）で表される化合物の合計の含有量との質量比が９５／５〜２０／８０である＜１＞〜＜４＞、＜６＞〜＜９＞のいずれか一項に記載の着色組成物。
＜１１＞
＜１＞〜＜４＞、＜６＞〜＜１０＞のいずれか一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。
＜１２＞
＜１＞〜＜４＞、＜６＞〜＜１０＞のいずれか一項に記載の着色組成物、又は＜１１＞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、前記＜１＞〜＜１２＞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。
〔１〕
下記一般式（１）で表される化合物と、下記一般式（４）で表される化合物とを含む着色組成物。

（一般式（１）中、Ｌは、２〜４価の連結基を表す。
Ｄは、一般式（２）で表される化合物から水素原子を１〜５個取り除いた残基を表す。
ｍは、１〜１０の整数を表す。但し、複数のＬは、それぞれ同一でも異なっていてもよい。
ｎは、２〜１０の整数を表す。但し、複数のＤは、それぞれ同一でも異なっていてもよい。
一般式（２）中、Ｒ^４〜Ｒ^２４はそれぞれ独立に、水素原子又は置換基を表す。
但し、少なくとも１個以上のイオン性親水性基を有する。）

一般式（４）中、Ｚ^１は、ハメットの置換基定数σｐ値が０．２０以上の電子求引性基を表す。
Ｚ^２は、水素原子、脂肪族基、芳香族基、アシル基、又はヘテロ環基を表す。
Ｒ^２３及びＲ^２４は、それぞれ独立に、水素原子、脂肪族基、芳香族基、ヘテロ環基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、カルバモイル基、アルキルスルホニル基、アリールスルホニル基、またはスルファモイル基を表す。ただし、Ｒ^２３及びＲ^２４が共に水素原子であることはない。
Ｒ^２１及びＲ^２２は、それぞれ独立に、水素原子、ハロゲン原子、脂肪族基、芳香族基、ヘテロ環基、シアノ基、カルボキシル基、カルバモイル基、アルコキシカルボニル基、アリールオキシカルボニル基、アシル基、ヒドロキシ基、アルコキシ基、アリールオキシ基、シリルオキシ基、アシルオキシ基、カルバモイルオキシ基、ヘテロ環オキシ基、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、アルキルアミノ基、アリールアミノ基、ヘテロ環アミノ基、アシルアミノ基、ウレイド基、スルファモイルアミノ基、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、アルキルもしくはアリールスルホニルアミノ基、アリールオキシカルボニルアミノ基、ニトロ基、アルキルもしくはアリールチオ基、アルキルもしくはアリールスルホニル基、アルキルもしくはアリールスルフィニル基、スルファモイル基、スルホ基、またはヘテロ環チオ基を表す。また、Ｒ^２１とＲ^２３、またはＲ^２３とＲ^２４が結合して５または６員環を形成してもよい。
Ｒ^２５及びＲ^２９は、それぞれ独立に、アルキル基、アルコキシ基またはハロゲン原子を表す。但し、Ｒ^２５及びＲ^２９が共にアルキル基である時は、そのアルキル基を構成する炭素数の合計が３以上であって、それらは更に置換されていてもよい。
Ｒ^２６、Ｒ^２７、及びＲ^２８は、それぞれ独立にＲ^２１及びＲ^２２と同義であり、Ｒ^２５とＲ^２６、又は、Ｒ^２８とＲ^２９で互いに縮環していてもよい。
Ｑは、水素原子、脂肪族基、芳香族基またはヘテロ環基を表す。
上記Ｚ^１、Ｚ^２、Ｒ^２１、Ｒ^２２、Ｒ^２３、Ｒ^２４及びＱの各基は、更に置換基を有していてもよい。
但し、一般式（４）は、少なくとも一つのイオン性親水性基を有する。
〔２〕
前記一般式（２）中、Ｒ^４、Ｒ^８、Ｒ^９及びＲ^１３はそれぞれ独立に、水素原子又はアルキル基を表す、〔１〕に記載の着色組成物。
〔３〕
前記一般式（２）中、Ｒ^５〜Ｒ^７、Ｒ^１０〜Ｒ^１２及びＲ^１４〜Ｒ^２３は水素原子を表す、〔１〕又は〔２〕に記載の着色組成物。
〔４〕
前記一般式（１）中、Ｄは一般式（２）で表される化合物のＲ^５〜Ｒ^７、Ｒ^１０〜Ｒ^１２及びＲ^２４としての水素原子から、水素原子を１個取り除いた残基を表す、〔１〕〜〔３〕のいずれか一項に記載の着色組成物。
〔５〕
前記一般式（１）で表される化合物が、
一般式（３）で表される化合物をクロロスルホニル化する工程、
一般式（ｄ）で表されるジアミン化合物と反応させる工程、
残存するクロロスルホニル基を加水分解する工程、を含む合成方法により合成される化合物である、〔１〕〜〔４〕のいずれか一項に記載の着色組成物。

（一般式（３）中、Ｒ^４〜Ｒ^２３はそれぞれ独立に、水素原子又は置換基を表す。一般式（ｄ）中、Ｒ^２５及びＲ^２６はそれぞれ独立に、水素原子又は置換基を表す。Ｌ^１は２価の連結基を表す。）
〔６〕
前記一般式（４）におけるイオン性親水性基が、スルホ基、カルボキシル基、ホスホノ基、及び４級アンモニウム基より選択された少なくとも１つの基である、〔１〕〜〔５〕のいずれか一項に記載の着色組成物。
〔７〕
前記一般式（４）中、Ｒ^２３及びＲ^２４がそれぞれ独立に、水素原子、芳香族基、又はヘテロ基を表す〔１〕〜〔６〕のいずれか一項に記載の着色組成物。
〔８〕
一般式（１）で表される化合物の含有率が０．１〜２０質量％である〔１〕〜〔７〕のいずれか一項に記載の着色組成物。
〔９〕
一般式（４）で表される化合物の含有率が１〜５質量％である〔１〕〜〔８〕のいずれか一項に記載の着色組成物。
〔１０〕
一般式（１）で表される化合物の含有量と、一般式（４）で表される化合物の含有量との質量比が９５／５〜２０／８０である〔１〕〜〔９〕のいずれか一項に記載の着色組成物。
〔１１〕
〔１〕〜〔１０〕のいずれか一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。
〔１２〕
〔１〕〜〔１０〕のいずれか一項に記載の着色組成物、又は〔１１〕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。 That is, the present invention is as follows.
<1>
A coloring composition comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (4).

(In general formula (1), L represents a linking group represented by the following general formula (V1), (V2), (V3) or (V4)).
D represents a residue obtained by removing one hydrogen atom from the compound represented by the general formula (2).
m represents 1 .
n represents 2 . However, the plurality of D may be the same or different.
In General Formula (2), R ^{4 to} R ²⁴ each independently represent a hydrogen atom or a substituent.
However, it has at least one ionic hydrophilic group. )

(In general formula (V1), R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or a substituent.
In General Formula (V2), R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom or a substituent, and L ²⁰¹ represents an oxy group (—O—), a thio group (—S—), or a carbonyl group (—CO—). , A sulfonyl group (—SO ₂ —), an imino group (—NH—), a methylene group (—CH ₂ —), an arylene group, a cycloalkylene group, and a divalent group selected from a combination thereof . Represents a linking group. R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
In general formula (V3), R ³⁰¹ , R ³⁰² and R ³⁰³ each independently represent a hydrogen atom or a substituent, X represents an alkylene group having 2 to 20 carbon atoms which may have a substituent, and L ³⁰¹ represents a single bond or a divalent linking group.
In general formula (V4), R ⁴⁰¹ and R ⁴⁰² each independently represent a hydrogen atom or a substituent. )

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. However, R ²³ and R ²⁴ are not both hydrogen atoms.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. R ²¹ and R ²³ , or R ²³ and R ²⁴ may be bonded to form a 5- or 6-membered ring.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
Each group of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ and Q may further have a substituent.
However, general formula (4) has at least one ionic hydrophilic group.
<2>
In the general formula ^(2), R ^4, the R 8, ^{R 9} and ^{R 13} each independently represent a hydrogen atom or an alkyl group, a colored composition according to <1>.
<3>
In formula ^{(2), R 5 ~R 7} , R 10 ~R 12 and ^R 14 ^{to R 23} represents a hydrogen atom, a colored composition according to <1> or <2>.
<4>
In the general formula (1), D is a residue obtained by removing one hydrogen atom from hydrogen atoms as R ^{5 to} R ⁷ , R ^{10 to} R ¹² and R ²⁴ of the compound represented by the general formula (2). The coloring composition as described in any one of <1>-<3> representing.
<5>
At least one selected from the group consisting of a compound represented by the following general formula (W11) and a compound represented by the general formula (W15);
It is a manufacturing method of the coloring composition containing the compound represented by following General formula (4),
The compound represented by the general formula (W11) is a compound synthesized by a synthesis method including the following (A),
The compound represented by the general formula (W15) is a compound synthesized by a synthesis method including the following (B).
A method for producing a colored composition .
(A) a compound represented by general formula (W9) obtained by converting a sulfo group of a xanthene compound represented by general formula (W8) having a sulfo group into a chlorosulfonyl group; and general formula (W10) Method for synthesizing compound represented by general formula (W11) obtained by hydrolysis of compound obtained by reaction with diamine represented

In the general formula ^{(W8), R 601, R} 602, R 603 and ^{R 604} represents a hydrogen atom or an alkyl ^{group, R 605, R 606, R} 607, R 608 and ^{R 609} represent a ^{substituent, n 601} is represents an integer of ^0~1, n 602 ^{~n 606} is 0.
In general formula (W9), R ⁶⁰¹ , R ⁶⁰² , R ⁶⁰³ , R ⁶⁰⁴ , R ⁶⁰⁵ , R ⁶⁰⁶ , R ⁶⁰⁷ , R ⁶⁰⁸ , R ⁶⁰⁹ , n ⁶⁰¹ , n ⁶⁰² , n ⁶⁰³ are n ⁶⁰⁴ , n ⁶⁰⁵ and n ⁶⁰⁶ is represented by R ⁶⁰¹ , R ⁶⁰² , R ⁶⁰³ , R ⁶⁰⁴ , R ⁶⁰⁵ , R ⁶⁰⁶ , R ⁶⁰⁷ , R ⁶⁰⁸ , R ⁶⁰⁹ , n ⁶⁰¹ , n ⁶⁰² , n ⁶⁰³ in the general formula (W8) , n ⁶⁰⁴ , the same meaning as n ⁶⁰⁵ and ^{n 606.}
In general formula (W10), R ²⁵ and R ²⁶ each independently represent a hydrogen atom.
L ¹ represents a linking group represented by the following general formula (V1), (V2), (V3) or (V4).

(In General Formula (V1), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ¹⁰¹ and R ¹⁰² may be bonded to each other to form a ring.
In General Formula (V2), R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom or an alkyl group, and R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. L ²⁰¹ represents an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), an imino group (—NH—), a methylene group (—CH ₂ ). -), An arylene group, a cycloalkylene group, and a divalent linking group selected from a group formed by a combination thereof. R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
In general formula (V3), R ³⁰¹ and R ³⁰² each independently represent a hydrogen atom or an alkyl group, and R ³⁰¹ and R ³⁰² may be bonded to each other to form a ring. R ³⁰³ is a hydrogen atom, an amino group, a mono- or dialkylamino group, an arylamino group, or alkylthio group, which may be substituted by further sulfo group, or an ionic hydrophilic group selected from a carboxyl group . X represents an alkylene group having 2 to 20 carbon atoms which may have a methyl group as a substituent, and L ³⁰¹ represents a single bond.
In general formula (V4), R ⁴⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴⁰² each independently represents an ionic hydrophilic group selected from a hydrogen atom, a sulfo group, or a carboxyl group. . )
In general formula (W11), ^R601 , ^R602 , ^R603 , ^R604 , ^R605 , ^R606 , ^R607 , ^R608 , ^R609 , ⁿ⁶⁰¹ , ⁿ⁶⁰² , ⁿ⁶⁰³ , ⁿ⁶⁰⁴ , ⁿ⁶⁰⁵ , n ⁶⁰⁶ , R ²⁵ , R ²⁶ and L ¹ are R ⁶⁰¹ , R ⁶⁰² , R ⁶⁰³ , R ⁶⁰⁴ , R ⁶⁰⁵ , R ⁶⁰⁶ , R ⁶⁰⁷ , R ⁶⁰⁸ , R ⁶⁰⁹ , n ⁶⁰¹ , n in the general formula (W8) ⁶⁰² , n ⁶⁰³ , n ⁶⁰⁴ , n ⁶⁰⁵ , n ⁶⁰⁶ , and R ²⁵ , R ^26, and L ^{1 in} general formula (W10) .
(B) A compound represented by general formula (W13) obtained by chlorosulfonylating a xanthene compound represented by general formula (W12), a polyvalent amine represented by general formula (W14), and the like. Method for synthesizing compound represented by general formula (W15) obtained by hydrolysis of compound obtained by reaction

In general formula (W12), R ⁷⁰¹ , R ⁷⁰² , R ⁷⁰³ and R ⁷⁰⁴ each independently represent a hydrogen atom, R ⁷⁰⁵ , R ⁷⁰⁶ and R ⁷⁰⁷ each represent a substituent, and n ^{701 to} n ⁷⁰³ represent 0. , N ⁷⁰⁴ and n ⁷⁰⁵ each independently represents an integer of 0 to 1.
In general formulas (W13) and (W15), R ⁷⁰¹ , R ⁷⁰² , R ⁷⁰³ , R ⁷⁰⁴ , R ⁷⁰⁵ , R ⁷⁰⁶ , R ⁷⁰⁷ , n ⁷⁰¹ , n ^702, and n ⁷⁰³ are the same as R ^{701 in} general formula (W12). , R ⁷⁰² , R ⁷⁰³ , R ⁷⁰⁴ , R ⁷⁰⁵ , R ⁷⁰⁶ , R ⁷⁰⁷ , n ⁷⁰¹ , n ⁷⁰² and n ⁷⁰³ .
In general formulas (W14) and (W15), R ²⁵ , R ²⁶ and L ¹ have the same meanings as R ²⁵ , R ²⁶ and L ¹ in general formula (W10) .

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. However, R ²³ and R ²⁴ are not both hydrogen atoms.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. R ²¹ and R ²³ , or R ²³ and R ²⁴ may be bonded to form a 5- or 6-membered ring.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
Each group of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ and Q may further have a substituent.
However, general formula (4) has at least one ionic hydrophilic group.
<6>
Any one of <1> to < 4 >, wherein the ionic hydrophilic group in the general formula (4) is at least one group selected from a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. The coloring composition according to item.
<7>
The coloring according to any one of <1> to <4>, <6>, in which R ²³ and R ²⁴ each independently represent a hydrogen atom, an aromatic group, or a hetero group in the general formula (4). Composition.
<8>
The coloring composition as described in any one of <1>- <4>, <6>, <7> whose content rate of the compound represented by General formula (1) is 0.1-20 mass%.
<9>
The coloring composition as described in any one of <1>- <4> and <6>- <8> whose content rate of the compound represented by General formula (4) is 1-5 mass%.
<10>
The mass ratio of the content of the compound represented by the general formula (1) and the total content of the compound represented by the general formula (4) is 95/5 to 20/80 <1> to <4 >, The coloring composition as described in any one of <6>- <9>.
<11>
<1>- <4>, <6>- <10> The inkjet recording ink containing the coloring composition as described in any one of <10>.
<12>
<1>- <4>, <6>- <10> The inkjet recording method of forming an image using the coloring composition as described in any one of <10>, or the inkjet recording ink as described in <11>.
The present invention is the invention according to the above <1> to <12>, but other matters are described below for reference.
[1]
A coloring composition comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (4).

(In the general formula (1), L represents a divalent to tetravalent linking group.
D represents a residue obtained by removing 1 to 5 hydrogen atoms from the compound represented by the general formula (2).
m represents an integer of 1 to 10. However, the plurality of L may be the same or different.
n represents an integer of 2 to 10. However, the plurality of D may be the same or different.
In General Formula (2), R ^{4 to} R ²⁴ each independently represent a hydrogen atom or a substituent.
However, it has at least one ionic hydrophilic group. )

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. However, R ²³ and R ²⁴ are not both hydrogen atoms.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. R ²¹ and R ²³ , or R ²³ and R ²⁴ may be bonded to form a 5- or 6-membered ring.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
Each group of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ and Q may further have a substituent.
However, general formula (4) has at least one ionic hydrophilic group.
[2]
In said general formula (2), R < ⁴ >, R <^8> , R < ⁹ > and R < ¹³ > represent a hydrogen atom or an alkyl group each independently, The coloring composition as described in [1].
[3]
In said general formula (2), R < ⁵ > -R < ⁷ >, R < ¹⁰ > -R < ¹² > and R < ¹⁴ > -R < ²³ > represent a hydrogen atom, The coloring composition as described in [1] or [2].
[4]
In the general formula (1), D is a residue obtained by removing one hydrogen atom from hydrogen atoms as R ^{5 to} R ⁷ , R ^{10 to} R ¹² and R ²⁴ of the compound represented by the general formula (2). The coloring composition according to any one of [1] to [3],
[5]
The compound represented by the general formula (1) is
A step of chlorosulfonylating the compound represented by the general formula (3),
Reacting with the diamine compound represented by the general formula (d);
The coloring composition according to any one of [1] to [4], which is a compound synthesized by a synthesis method including a step of hydrolyzing a remaining chlorosulfonyl group.

(In General Formula (3), R ^{4 to} R ²³ each independently represents a hydrogen atom or a substituent. In General Formula (d), R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a substituent. L ¹ represents a divalent linking group.)
[6]
Any one of [1] to [5], wherein the ionic hydrophilic group in the general formula (4) is at least one group selected from a sulfo group, a carboxyl group, a phosphono group, and a quaternary ammonium group. The coloring composition according to item.
[7]
The colored composition according to any one of [1] to [6], wherein in the general formula (4), R ²³ and R ²⁴ each independently represents a hydrogen atom, an aromatic group, or a hetero group.
[8]
The coloring composition as described in any one of [1]-[7] whose content rate of the compound represented by General formula (1) is 0.1-20 mass%.
[9]
The coloring composition as described in any one of [1]-[8] whose content rate of the compound represented by General formula (4) is 1-5 mass%.
[10]
The mass ratio of the content of the compound represented by the general formula (1) and the content of the compound represented by the general formula (4) is 95/5 to 20/80. The coloring composition as described in any one.
[11]
Ink for inkjet recording containing the coloring composition as described in any one of [1]-[10].
[12]
An inkjet recording method for forming an image using the colored composition according to any one of [1] to [10] or the inkjet recording ink according to [11].

  According to the present invention, there is provided a coloring composition capable of achieving both high image fastness such as ozone resistance and light resistance and a good hue and high moisture resistance. Also provided are an ink jet recording ink containing the coloring composition and an ink jet recording method using the ink jet recording ink. The colored composition of the present invention is particularly useful as a magenta ink.

FIG. 1 is a graph showing an absorption spectrum of a compound (1-1), which is an example of a compound represented by the general formula (1) in the present invention, in a dilute aqueous solution.

Hereinafter, the present invention will be described in detail.
First, in the present invention, the substituent group A is defined.

(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.

  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 phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo 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 carboxyl group, phosphono group and sulfo group may be in the form of a salt. Examples of counter cations that form a salt include ammonium ion, alkali metal ion (eg, lithium ion, sodium ion, potassium ion) and organic. Cation (eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium) is included, lithium salt, sodium salt, potassium salt, ammonium salt is preferable, sodium salt or mixed salt containing sodium salt as main component Are more preferred, and the sodium salt is most preferred.

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

  The coloring composition of the present invention comprises a compound having a specific xanthene skeleton represented by the general formula (1) or a salt thereof, and a specific heteryl azo compound represented by the general formula (4).

[Compound represented by the general formula (1)]
The compound represented by the general formula (1) of the present invention includes a compound, a salt thereof, and a hydrate thereof.
Since the compound of the present invention contains a plurality of specific xanthene derivative structures, the action mechanism is unknown, but it is excellent in image fastness such as ozone resistance and light resistance. In addition, by increasing the amount through the linking group L, the molecular weight is increased, the molecular movement under high humidity conditions is suppressed, and the moisture resistance is excellent.

In general formula (1), L represents a divalent to tetravalent linking group.
D represents a residue obtained by removing 1 to 5 hydrogen atoms from the compound represented by the general formula (2).
m represents an integer of 1 to 10. However, the plurality of L may be the same or different.
n represents an integer of 2 to 10. However, the plurality of D may be the same or different.
In General Formula (2), R ^{4 to} R ²⁴ each independently represent a hydrogen atom or a substituent.
However, it has at least one ionic hydrophilic group.

  m represents an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 6, still more preferably 1 to 4, and particularly preferably 1 to 3. . By setting m within these ranges, the moisture resistance can be improved while maintaining solubility and suppressing clogging of the head in ink jet printing.

n represents an integer of 2 to 10, preferably an integer of 2 to 8, more preferably an integer of 2 to 6, and further preferably 2 to 4. By setting n within these ranges, solubility can be maintained, and moisture resistance can be improved while suppressing head clogging in ink jet printing.
In general formula (1), L represents a divalent to tetravalent linking group. Examples of the divalent to tetravalent linking group include an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), and an imino group (—NH—). , A methylene group (—CH ₂ —), an arylene group, a cycloalkylene group, a heteroarylene group, an ethylene-1,2-diyl group (—CH═CH—) and a group formed by combining these, and a sulfonyl group A group containing a group (—SO ₂ —), an imino group (—NH—), a methylene group (—CH ₂ —), an ethylene-1,2-diyl group (—CH═CH—), an arylene, and a heteroarylene group. More preferred.
L is more preferably a divalent linking group.
L may have a substituent, and examples of the substituent in the case of having a substituent include the substituent group A, and include an alkyl group, an aryl group, a heterocyclic group, an alkylamino group, an arylamino group. Group or an ionic hydrophilic group is preferable, and an arylamino group or an ionic hydrophilic group is more preferable. These may be further substituted with the substituent group A, and more preferably substituted with an ionic hydrophilic group.

  L is preferably a linking group represented by the following general formula (V1), (V2), (V3) or (V4).

(In general formula (V1), R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or a substituent.
In General Formula (V2), R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom or a substituent, and L ²⁰¹ represents a divalent linking group.
In general formula (V3), R ³⁰¹ , R ³⁰² and R ³⁰³ each independently represent a hydrogen atom or a substituent, X represents an alkylene group having 2 to 20 carbon atoms which may have a substituent, and L ³⁰¹ represents a single bond or a divalent linking group.
In general formula (V4), R ⁴⁰¹ and R ⁴⁰² each independently represent a hydrogen atom or a substituent. )

In general formula (V1),
R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or a substituent. Preferably, they are a hydrogen atom or the said group A of a substituent, More preferably, they are a hydrogen atom, an alkyl group, or an aryl group, Especially preferably, they are a hydrogen atom or an alkyl group. R ¹⁰¹ and R ¹⁰² may combine with each other to form a ring.

In general formula (V2),
R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom or a substituent. Preferably, they are a hydrogen atom or the said group A of a substituent, More preferably, they are a hydrogen atom, an alkyl group, or an aryl group, Especially preferably, they are a hydrogen atom or an alkyl group. R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
L ²⁰¹ represents a divalent linking group. Examples of the divalent linking group include an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), an imino group (—NH—), and methylene. Examples include a group (—CH ₂ —), an arylene group, a cycloalkylene group, and a group formed by combining these. Preferred is an alkylene group having 1 to 20 carbon atoms, a cyclohexylene group, a phenylene group or a xylylene group, and more preferred is an alkylene group having 1 to 16 carbon atoms, a cyclohexylene group, a phenylene group or a xylylene group. Particularly preferred is an alkylene group having 1 to 8 carbon atoms, a cyclohexylene group, an m-phenylene group or a xylylene group.

In general formula (V3),
R ³⁰¹ and ³⁰² each independently represent a hydrogen atom or a substituent, preferably a hydrogen atom or substituent group A, and preferably a hydrogen atom, an alkyl group, an aryl group, a heterocyclic group, an alkylamino group, or an arylamino group. Are preferable, and a hydrogen atom and an alkyl group are more preferable. R ³⁰¹ and R ³⁰² may be bonded to each other to form a ring.
R ³⁰³ represents a hydrogen atom or a substituent, preferably a hydrogen atom or the substituent group A, and more preferably an amino group, a mono- or dialkylamino group, an arylamino group, or an alkylthio group. These may be further substituted with the substituent group A, and more preferably substituted with an ionic hydrophilic group.

X represents an alkylene group having 2 to 20 carbon atoms which may have a substituent, or an arylene having 6 to 10 carbon atoms which may have a substituent. An alkylene group having 2 to 20 carbon atoms is preferable from the viewpoint of ease of synthesis.
Among the alkylene groups having 2 to 20 carbon atoms, an ethylene group and an n-propylene group are preferable, and an ethylene group is more preferable. A methyl group is mentioned as a substituent in the case of having a substituent.

L ³⁰¹ represents a single bond or a divalent linking group. Examples of the divalent linking group include an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), an imino group (—NH—), and methylene. A group (—CH ₂ —), an arylene group, a cycloalkylene group, and a group formed by a combination thereof, including a phenylene group, a cyclohexylene group, and a methylene group, and L ³⁰¹ is a single bond. More preferably.

In general formula (V4),
R ⁴⁰¹ each independently represents a hydrogen atom or a substituent. Preferably they are a hydrogen atom or the said group A of a substituent, More preferably, they are a hydrogen atom or a C1-C6 alkyl group, Especially preferably, it is a hydrogen atom.
R ⁴⁰² each independently represents a hydrogen atom or a substituent, preferably a hydrogen atom or the substituent group A, more preferably an ionic hydrophilic group, and particularly preferably a sulfo group.

  Specific examples of L in the general formula (1) are given below, but the present invention is not limited to these specific examples.

  D in the general formula (1) represents a residue obtained by removing one hydrogen atom from the compound represented by the general formula (2).

In General Formula (2), R ^{4 to} R ²³ each independently represents a hydrogen atom or a substituent. Examples of the substituent include the above-described substituent group A.
In general formula (2), it is preferable that R ⁴ , R ⁸ , R ⁹ and R ¹³ each independently represent a hydrogen atom or an alkyl group. The alkyl group may be unsubstituted or substituted, and is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms, and an alkyl group having 1 to 10 carbon atoms. Groups are more preferred. Examples thereof include a methyl group, an ethyl group, an ethynyl group, an isopropanyl group, and a 2-ethylhexyl group. R ⁴ , R ⁸ , R ⁹ and R ¹³ each independently preferably represent an alkyl group because of the hue.
In general formula (2), R ^{5 to} R ⁷ , R ^{10 to} R ^12, and R ^{14 to} R ²³ preferably represent a hydrogen atom for ease of synthesis. R ²⁴ is preferably a hydrogen atom or an ionic hydrophilic group, and more preferably a sulfo group.

In general formula (1), D represents 1 hydrogen atom from hydrogen atoms as R ^{5 to} R ⁷ , R ^{10 to} R ¹² , R ¹⁹ , R ²² or R ²⁴ of the compound represented by general formula (2). It is preferred for the ease of synthesis to represent ˜5 removed residues.

The compound of the present invention represented by the general formula (1)
A step of chlorosulfonylating the compound represented by the general formula (3),
Reacting with the diamine compound represented by the general formula (d);
A compound synthesized by a synthesis method including a step of hydrolyzing the remaining chlorosulfonyl group is preferable from the viewpoint of availability of raw materials and inexpensive production.

In General Formula (3), R ^{4 to} R ²³ each independently represents a hydrogen atom or a substituent.
In general formula (d), R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a substituent. L ₁ represents a divalent linking group.

In the general formula ^(3), R 4 ^{to R 23} have the same meanings as ^R 4 ^{to R 23} in the general formula (2), and preferred examples are also the same.
In general formula (d), R ²⁵ and R ²⁶ are each independently preferably a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. More preferably a hydrogen atom or a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom.
L ₁ is preferably a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cyclohexylene group, a substituted or unsubstituted phenylene group, a substituted or unsubstituted xylylene group, substituted or unsubstituted More preferably, it is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, an unsubstituted cyclohexylene group, an unsubstituted phenylene group, an unsubstituted xylylene group, or a substituted stilbene-4,4′-diyl group. Or an unsubstituted stilbene-4,4′-diyl group, and particularly preferably a stilbene-4,4′-diyl group substituted with a sulfo group.

  Specific examples of the compound represented by the general formula (3) are given below, but the present invention is not limited to these specific examples.

Specific examples of the compound represented by the general formula (d) are given below, but the present invention is not limited to these specific examples.

  Although the production method of the present invention will be described, the concept of the present invention can be obtained by multiplying the xanthene compound represented by the general formula (2) through a linking group. It is not limited.

(1) A method of linking from an anilino group portion of a xanthene compound via methylene

In general formula (W1), R ⁵⁰¹ represents a substituent, and n ⁵⁰¹ represents an integer of 0 to 4. When n ⁵⁰¹ is 2 or more, the plurality of R ^501s may be the same or different.

In General Formula (W2), R ⁵⁰² and R ⁵⁰³ represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. However, R ⁵⁰² and R ⁵⁰³ are not simultaneously hydrogen atoms.

In the formula ^{(W3), R 501, R} 502, R 503 and ^{n 501} each has the same meaning as ^{R 501, R 502, R 503} and ^{n 501} in the general formula (W1) and (W2).

In General Formula (W4), R ⁵⁰⁴ , R ^505, and R ⁵⁰⁶ represent substituents, n ⁵⁰² and n ⁵⁰³ represent an integer of 0 to 3, and n ⁵⁰⁴ represents an integer of 0 to 4. When n ⁵⁰² , n ⁵⁰³ and / or n ⁵⁰⁴ are each independently 2 or more, the plurality of R ⁵⁰⁴ , R ⁵⁰⁵ or / and R ⁵⁰⁶ may be the same or different.

In the general formula (W5), R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ , R ⁵⁰⁶ , n ⁵⁰¹ , n ⁵⁰² , n ⁵⁰³ and n ⁵⁰⁴ are represented by the general formulas (W1), (W2) and (W4). And R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ , R ⁵⁰⁶ , n ⁵⁰¹ , n ⁵⁰² , n ^503, and n ⁵⁰⁴ .

In General Formula (W6), R ⁵⁰⁷ represents a substituent, and n ⁵⁰⁵ represents an integer of 0 to 5. When n ⁵⁰⁵ is 2 or more, the plurality of R ⁵⁰⁷ may be the same or different.

In the general formula (W7), R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ , R ⁵⁰⁶ , R ⁵⁰⁷ , n ⁵⁰¹ , n ⁵⁰² , n ⁵⁰³ , n ⁵⁰⁴ and n ⁵⁰⁵ are represented by the general formula (W1), Same as R ⁵⁰¹ , R ⁵⁰² , R ⁵⁰³ , R ⁵⁰⁴ , R ⁵⁰⁵ , R ⁵⁰⁶ , R ⁵⁰⁷ , n ⁵⁰¹ , n ⁵⁰² , n ⁵⁰³ , n ⁵⁰⁴ and n ^{505 in} (W2), (W4) and (W6). is there.

A compound represented by the general formula (W3) is obtained by heating and stirring 2 mol of the compound represented by the general formula (W1) and 1 mol of the compound represented by the general formula (W2) in the presence of S strong acid. be able to.
Obtaining a compound represented by the general formula (W5) by heating and stirring 1 mol of the compound represented by the general formula (W3) and 1 mol of the compound represented by the general formula (W4) together with aluminum chloride. it can.
By heating and stirring 1 mol of the compound represented by the general formula (W5) and 2 mol or more of the compound represented by the general formula (W6) together with zinc chloride, the compound of the present invention represented by the general formula (W7) is obtained. A compound corresponding to the general formula (1) can be obtained.

The compound represented by (W1) can be obtained as a reagent (for example, catalog number D146005 manufactured by Aldrich).
The compound represented by (W2) can be obtained as a reagent (eg, Sigma / Aldrich, catalog number 227048).
The compound represented by (W4) can be synthesized by a method described in Journal of the American Chemical Society 46, 1899 (1924).
The compound represented by (W5) can be obtained as a reagent (for example, catalog number D146005 manufactured by Aldrich).

  In addition, in order to impart water solubility necessary for using the compound of the present invention as a water-based ink for inkjet applications, a post-reaction such as sulfonation of the compound represented by the general formula (W7) is performed. Is preferred. The details of this production method are illustrated in the examples.

(2) A method of reacting a xanthene compound having a sulfo group with a polyvalent amine after converting the sulfo group to a chlorosulfonyl group

In the general formula ^{(W8), R 601, R} 602, R 603 and ^{R 604} represent a hydrogen atom or a ^{substituent, R 605, R 606, R} 607, R 608 and ^{R 609} represent a ^{substituent, n 601} is It represents an integer of 0 to ^{1, n 602} and ^{n 603} represents an integer of 0 to ^{3, n 604} and ^{n 605} represents an integer of 0 to ^{3, n 606} represents an integer of 0-4. When n ⁶⁰² , n ⁶⁰³ , n ⁶⁰⁴ and / or n ⁶⁰⁵ is 2 or more, a plurality of R ⁶⁰⁵ , R ⁶⁰⁶ , R ⁶⁰⁷ , R ⁶⁰⁸ and / or R ⁶⁰⁹ may be the same or different.

In general formula (W9), R ⁶⁰¹ , R ⁶⁰² , R ⁶⁰³ , R ⁶⁰⁴ , R ⁶⁰⁵ , R ⁶⁰⁶ , R ⁶⁰⁷ , R ⁶⁰⁸ , R ⁶⁰⁹ , n ⁶⁰¹ , n ⁶⁰² , n ⁶⁰³ are n ⁶⁰⁴ , n ⁶⁰⁵ and n ⁶⁰⁶ is represented by R ⁶⁰¹ , R ⁶⁰² , R ⁶⁰³ , R ⁶⁰⁴ , R ⁶⁰⁵ , R ⁶⁰⁶ , R ⁶⁰⁷ , R ⁶⁰⁸ , R ⁶⁰⁹ , n ⁶⁰¹ , n ⁶⁰² , n ⁶⁰³ in the general formula (W8), n ⁶⁰⁴ , the same meaning as n ⁶⁰⁵ and ^{n 606.}

In the general formula ^{(W10), R 25, R} 26 and ^{L 1} have the same meaning as ^{R 25, R 26} and _{L 1} in the general formula (d).

In general formula (W11), ^R601 , ^R602 , ^R603 , ^R604 , ^R605 , ^R606 , ^R607 , ^R608 , ^R609 , ⁿ⁶⁰¹ , ⁿ⁶⁰² , ⁿ⁶⁰³ are ⁿ⁶⁰⁴ , ⁿ⁶⁰⁵ , n ⁶⁰⁶ , R ²⁵ , R ²⁶ and L ¹ are R ⁶⁰¹ , R ⁶⁰² , R ⁶⁰³ , R ⁶⁰⁴ , R ⁶⁰⁵ , R ⁶⁰⁶ , R ⁶⁰⁷ , R ⁶⁰⁸ , R in general formula (W8) and general formula (d). ^{609, n 601, n 602,} n 603 ^is the ^{n 604, n 605, n 606} , R 25, the same meaning as ^{R 26} and _{L 1.}

The compound represented by the general formula (W8) can be obtained as a reagent (eg, Chugai Kasei Co., Ltd., trade name CHUGAI AMINOL FAST PINKR, etc.).
The compound represented by the general formula (W10) can be obtained as a reagent (for example, catalog number D25206, manufactured by Aldrich).

By converting the compound represented by the general formula (W8) into an acid chloride using a chlorinating agent such as phosphorus oxychloride or thionyl chloride, the general formula (W9) can be obtained.
Reacting the compound represented by the general formula (W9) and the compound represented by the general formula (W10) at an arbitrary ratio (preferably a molar ratio of 2: 1), and hydrolyzing the unreacted sulfonyl chloride with an alkali. Thus, the compound represented by the general formula (1) of the present invention can be obtained as a mixture having a representative structure represented by the general formula (W11).

The representative structure represented by the general formula (W11) will be described. The binding site between the xanthene skeleton and the linking group is the sulfonic acid or sulfonate site of the xanthene compound used as the general formula (W8), and there is no selectivity of the reaction.
As a form which can be contained in the mixture obtained by hydrolysis of the compound obtained by reacting the compound represented by the general formula (W9) and the compound represented by the general formula (W10), not only the dimer but also 3 Examples include oligomers such as a monomer and a tetramer. Such multimers (oligomers) can take the form of straight lines, branched shapes, cyclic shapes, and combinations thereof.
In addition, in this specification, although these are shown using the typical structure represented by general formula (W11), it has shown that such a mixture is included.

(3) A method of reacting a xanthene compound with a polyvalent amine after direct chlorosulfonylation

In General Formula (W12), R ⁷⁰¹ , R ⁷⁰² , R ⁷⁰³ and R ⁷⁰⁴ each independently represent a hydrogen atom or a substituent, R ⁷⁰⁵ , R ⁷⁰⁶ and R ⁷⁰⁷ each represent a substituent, and n ⁷⁰¹ is 0 to 4 N ⁷⁰² and n ⁷⁰³ each independently represents an integer of 0 to 2, and n ⁷⁰⁴ and n ⁷⁰⁵ each independently represents an integer of 0 to 1. When n ⁷⁰¹ , n ⁷⁰² and / or n ⁷⁰³ are each independently 2 or more, a plurality of R ⁷⁰⁵ , R ⁷⁰⁶ and / or R ⁷⁰⁷ may be the same or different.

In general formula (W13), R ⁷⁰¹ , R ⁷⁰² , R ⁷⁰³ , R ⁷⁰⁴ , R ⁷⁰⁵ , R ⁷⁰⁶ , R ⁷⁰⁷ and n ⁷⁰¹ , n ⁷⁰² and n ⁷⁰³ are represented by R ⁷⁰¹ , R ⁷⁰² , It is synonymous with R ⁷⁰³ , R ⁷⁰⁴ , R ⁷⁰⁵ , R ⁷⁰⁶ , R ⁷⁰⁷ , n ⁷⁰¹ , n ⁷⁰² and n ⁷⁰³ .

In the general formula ^{(W14), R 25, R} 26 and ^{L 1} have the same meaning as ^{R 25, R 26} and _{L 1} in the general formula (d).

In general formula (W15), R ⁷⁰¹ , R ⁷⁰² , R ⁷⁰³ , R ⁷⁰⁴ , R ⁷⁰⁵ , R ⁷⁰⁶ , R ⁷⁰⁷ and n ⁷⁰¹ , n ⁷⁰² , n ⁷⁰³ , R ²⁵ , R ²⁶ and L ¹ are represented by the general formula ( W12) and R ⁷⁰¹ , R ⁷⁰² , R ⁷⁰³ , R ⁷⁰⁴ , R ⁷⁰⁵ , R ⁷⁰⁶ , R ⁷⁰⁷ , n ⁷⁰¹ , n ⁷⁰² , n ⁷⁰³ , R ²⁵ , R ²⁶ and L _{1 in} general formula (d) is there.

The compound represented by the general formula (W12) can be obtained as a reagent (eg, Chugai Kasei Co., Ltd., trade name CHUGAI AMINOL FAST PINKR, etc.).
The compound represented by the general formula (W14) can be obtained as a reagent (for example, catalog number D25206 manufactured by Aldrich).

The compound represented by the general formula (W13) can be obtained by chlorosulfonylating the compound represented by the general formula (W12) using chlorosulfonic acid.
Reacting the compound represented by the general formula (W13) and the compound represented by the general formula (W14) at an arbitrary ratio (preferably a molar ratio of 2: 1), and hydrolyzing the unreacted sulfonyl chloride with an alkali. Thus, the compound represented by the general formula (1) of the present invention can be obtained as a mixture having a representative structure represented by the general formula (W15).

The representative structure represented by the general formula (W15) will be described. The bonding site between the xanthene skeleton and the linking group is the sulfonyl chloride site of the xanthene compound of general formula (W13), and there is no reaction selectivity.
As a form that can be contained in a mixture obtained by hydrolysis of a compound obtained by reacting a compound represented by the general formula (W13) and a compound represented by the general formula (W14), not only a dimer but also 3 Examples include oligomers such as a monomer and a tetramer. Such multimers (oligomers) can take the form of straight lines, branched shapes, cyclic shapes, and combinations thereof.
In addition, in this specification, although these are shown using the typical structure represented by general formula (W15), it has shown that such a mixture is included.

  Specific examples (representative structures) of the compound of the present invention represented by the general formula (1) are listed below, but the present invention is not limited to these specific examples.

Exemplified Compound 1-1: After reacting Compound A (2 mol) with 4,4′-diaminostilbene-2,2′-disulfonic acid (1 mol), unreacted sulfonyl chloride was hydroxylated. A reaction mixture containing the following structure, which can be hydrolyzed with sodium

Compound A:

Illustrative compound 1-2: A reaction mixture containing the following structure, obtained by reacting compound A (2 mol) with ethylenediamine (1 mol) and then hydrolyzing unreacted sulfonyl chloride with sodium hydroxide.

Exemplified Compound 1-3: A reaction mixture containing the following structure, obtained by reacting Compound A (2 mol) with piperazine (1 mol) in a ratio and then hydrolyzing unreacted sulfonyl chloride with sodium hydroxide.

Illustrative compound 1-4: After reacting compound A (2 mol) with 2,5-dimethylpiperazine (1 mol), unreacted sulfonyl chloride can be hydrolyzed with sodium hydroxide. Reaction mixture containing structure

Exemplary Compound 1-5: After reacting compound A (2 mol) with 1- (2-aminoethyl) piperazine (1 mol), unreacted sulfonyl chloride can be hydrolyzed with sodium hydroxide. A reaction mixture comprising the following structure:

Exemplary Compound 1-6: After reacting compound A (2 mol) with 1,4-bis (3-aminopropyl) piperazine) (1 mol), unreacted sulfonyl chloride was treated with sodium hydroxide. A reaction mixture comprising the following structure, which can be hydrolyzed

Illustrative compound 1-7: After reacting compound A (2 mol) and 1,2-cyclohexanediamine (1 mol) in proportion, unreacted sulfonyl chloride can be hydrolyzed with sodium hydroxide, Reaction mixture containing structure

Exemplified Compound 1-8: After reacting at a ratio of Compound A (2 mol) and 1,3-cyclohexanediamine (1 mol), unreacted sulfonyl chloride can be hydrolyzed with sodium hydroxide. Reaction mixture containing structure

Illustrative compound 1-9: After reacting compound A (2 mol) and 1,4-cyclohexanediamine (1 mol) in proportion, unreacted sulfonyl chloride can be hydrolyzed with sodium hydroxide, Reaction mixture containing structure

Exemplified Compound 1-10: After reacting at a ratio of Compound A (2 mol) and m-phenylenediamine (1 mol), the following structure can be obtained by hydrolyzing unreacted sulfonyl chloride with sodium hydroxide. Containing reaction mixture

Exemplified Compound 1-11: The following structure, which can be obtained by reacting Compound A (2 mol) with p-xylylenediamine (1 mol) and then hydrolyzing unreacted sulfonyl chloride with sodium hydroxide. Containing reaction mixture

Exemplary Compound 1-12: Compound A (2 mol) and disodium 4,6-di (2-aminoethylamino) -1,3,5-triazin-2-ylaminobenzene-2,5-disulfonate (1 The reaction mixture containing the following structure, which can be obtained by hydrolyzing unreacted sulfonyl chloride with sodium hydroxide

Illustrative compound 1-13: In a ratio of compound A (2 mol) to disodium 4,6-di (2-aminoethylamino) -1,3,5-triazin-2-ylaminoisophthalate (1 mol) After reacting, a reaction mixture containing the following structure, which can be obtained by hydrolyzing unreacted sulfonyl chloride with sodium hydroxide

Exemplified Compound 1-14: After reacting Compound A (2 mol) with 4,6-di (2-aminoethylamino) -2-hydroxy-1,3,5-triazine (1 mol), A reaction mixture comprising the following structure, obtained by hydrolyzing unreacted sulfonyl chloride with sodium hydroxide

Exemplary Compound 1-15:

Exemplary Compound 1-16:

Exemplary Compound 1-17: After reacting Compound B (2 mol) with 4,4′-diaminostilbene-2,2′-disulfonic acid (1 mol), unreacted sulfonyl chloride was hydroxylated. A reaction mixture containing the following structure, which can be hydrolyzed with sodium

Compound B

Exemplary Compound 1-18: After reacting Compound C (2 mol) with 4,4′-diaminostilbene-2,2′-disulfonic acid (1 mol), unreacted sulfonyl chloride was hydroxylated. A reaction mixture containing the following structure, which can be hydrolyzed with sodium

Compound C

Exemplary Compound 1-19: After reacting compound D (2 mol) with 4,4′-diaminostilbene-2,2′-disulfonic acid (1 mol), unreacted sulfonyl chloride was hydroxylated. A reaction mixture containing the following structure, which can be hydrolyzed with sodium

Compound D

Exemplary Compound 1-20: After reacting Compound A (1 mol), Compound B (1 mol), and 4,4′-diaminostilbene-2,2′-disulfonic acid (1 mol), A reaction mixture comprising the following structure, obtained by hydrolyzing unreacted sulfonyl chloride with sodium hydroxide

Exemplary Compound 1-21: After reacting Compound A (2 mol) with 4,4′-diaminostilbene-2,2′-disulfonic acid (1 mol), unreacted sulfonyl chloride was hydroxylated. Reaction mixture containing the following structure, which can be hydrolyzed with lithium

Exemplary Compound 1-22: After reacting compound A (2 mol) with 4,4′-diaminostilbene-2,2′-disulfonic acid (1 mol), unreacted sulfonyl chloride was hydroxylated A reaction mixture comprising the following structure, which can be hydrolyzed with potassium

Exemplary Compound 1-23: After reacting Compound A (2 mol) with 4,4′-diaminostilbene-2,2′-disulfonic acid (1 mol), unreacted sulfonyl chloride was hydroxylated. A reaction mixture containing the following structure, obtained by hydrolysis with sodium and conversion to an ammonium salt using an ion exchange resin

Exemplified compound 1-24: After reacting compound E (2 mol) with 4,4′-diaminostilbene-2,2′-disulfonic acid (1 mol), unreacted sulfonyl chloride was hydroxylated A reaction mixture containing the following structure, which can be hydrolyzed with sodium

Compound E: about 1: 1 mixture of compounds E1 and E2

Exemplified Compound 1-25: In a ratio of Compound E (2 mol) to 4,6-di (2-aminoethylamino) -1,3,5-triazin-2-ylaminoisophthalate disodium (1 mol) After reacting, a reaction mixture containing the following structure, which can be obtained by hydrolyzing unreacted sulfonyl chloride with sodium hydroxide

[Compound represented by formula (4)]

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. However, R ²³ and R ²⁴ are not both hydrogen atoms.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. R ²¹ and R ²³ , or R ²³ and R ²⁴ may be bonded to form a 5- or 6-membered ring.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
Each group of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ and Q may further have a substituent.
However, general formula (4) has at least one ionic hydrophilic group.

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.

(Hammett's substituent constant σp value)
Hammett's substituent constant σp value used in this specification will be described. Hammett's rule is a method described in 1935 by L. E. in order to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to a substituent having a known value that can be found in the above-mentioned book. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule.

The electron-withdrawing group of Z ^{1 is} an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less.

  Specific examples of the electron withdrawing group having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphono group, diaryl Phosphono group, diarylphosphinyl group, alkylsulfinyl, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, halogenated alkoxy Group, halogenated aryloxy group, halogenated alkylamino group, halogenated alkylthio group, heterocyclic group, halogen atom, azo group, selenocyanate group, and other electron withdrawing groups with a σp value of 0.20 or more The aryl group I can get lost.

Z ¹ is preferably a cyano group, a nitro group, or a halogen atom from the viewpoint of hue and fastness, more preferably a halogen atom or a cyano group, and most preferably a cyano group.

In General Formula (4), Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
Examples of the aliphatic group include an alkyl group and a cycloalkyl group.
Examples of the aromatic group include an aryl group.
Moreover, an aralkyl group is mentioned as a group applicable to an aromatic group and an aliphatic group.

The alkyl group is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples include a methyl group, an ethyl group, a butyl group, an isopropyl group, t -A butyl group etc. are mentioned.
The alkyl group may have a substituent, and examples of the substituent include the above-mentioned substituent group A, and are preferably a hydroxyl group, an alkoxy group, a cyano group, a halogen atom, and an ionic hydrophilic group. .
Examples of the alkyl group having a substituent include a hydroxyethyl group, a methoxyethyl group, a cyanoethyl group, a trifluoromethyl group, a 3-sulfopropyl group, and a 4-sulfobutyl group.

The cycloalkyl group is preferably a cycloalkyl group having 5 to 12 carbon atoms, and examples thereof include a cyclohexyl group.
The cycloalkyl group may have a substituent, and examples of the substituent include the substituent group A described above, and an ionic hydrophilic group is preferable.

As the aralkyl group, an aralkyl group having 7 to 12 carbon atoms is preferable, and examples thereof include a benzyl group and a 2-phenethyl group.
The aralkyl group may have a substituent, and examples of the substituent include the aforementioned substituent group A, and an ionic hydrophilic group is preferable.

As the aryl group, an aryl group having 6 to 12 carbon atoms is preferable, and examples thereof include a phenyl group and a naphthyl group.
The aryl group may have a substituent, and examples of the substituent include the substituent group A described above, an amide group, a sulfonamide group, an ester group, and the like. An alkyl group, an alkoxy group, a halogen atom, and an alkylamino group. It is preferably a group, an amide group, a carbamoyl group, a sulfamoyl group, a sulfonamide group, a hydroxy group, an ester group, or an ionic hydrophilic group.
Examples of the aryl group having a substituent include a p-tolyl group, a p-methoxyphenyl group, o-chlorophenyl, and m- (3-sulfopropylamino) phenyl group.

The heterocyclic group (heterocyclic group) is preferably a 5-membered or 6-membered heterocyclic group. Examples thereof include a 2-pyridyl group, 2-thienyl group, 2-thiazolyl group, 2-benzothiazolyl group, 2- Examples thereof include a benzoxazolyl group and a 2-furyl group.
The heterocyclic group may have a substituent, and examples of the substituent include the above-described substituent group A, amide group, sulfonamido group, ester group, and the like. Amido group, carbamoyl group, sulfamoyl group, sulfone An amide group, a hydroxy group, an ester group and an ionic hydrophilic group are preferred.

As the acyl group, an acyl group having 1 to 12 carbon atoms is preferable, and examples thereof include an acetyl group and a benzoyl group.
The acyl group may have a substituent, and examples of the substituent include the aforementioned substituent group A, and an ionic hydrophilic group is preferable.

Z ² is preferably an alkyl group or an aryl group, and is an alkyl group having 3 to 4 carbon atoms (preferably an isopropyl group or a t-butyl group), a phenyl group, or the 2-position, 4-position or the pyrazole mother nucleus side. More preferred is a phenyl group having a further substituent at any of the 6-positions, and even more preferred is a t-butyl group.

In general formula (4), R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl. Represents a group, an arylsulfonyl group, or a sulfamoyl group.
Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
Examples of the aromatic group include an aryl group.
Moreover, an aralkyl group is mentioned as a group applicable to an aromatic group and an aliphatic group.
However, R ²³ and R ²⁴ are not both hydrogen atoms.

Examples of the alkyl group, cycloalkyl group, aralkyl group, aryl group, heterocyclic group, and acyl group include the groups described for Z ² above.
Each group may further have a substituent, and examples of the substituent are the same as the examples described for Z ² above.

As the alkenyl group, an alkenyl group having 5 to 12 carbon atoms is preferable, and examples thereof include a vinyl group and an allyl group.
The alkenyl group may have a substituent, and examples of the substituent include the aforementioned substituent group A, and an ionic hydrophilic group is preferable.

Examples of the alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, and alkynyl group include the groups described in Substituent Group A described above.
Each group may further have a substituent, and examples of the substituent include the substituent group A described above.

R ²³ and R ²⁴ are each independently a hydrogen atom, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aromatic group, heterocyclic group, sulfonyl group, acyl group, or carbamoyl group from the viewpoint of hue. And more preferably a hydrogen atom, an alkyl group, an aralkyl group, an aromatic group, a heterocyclic group, a sulfonyl group, or an acyl group, and a hydrogen atom, an aromatic group, or a heterocyclic group. Is more preferable.
It is particularly preferable that R ²³ is a hydrogen atom or a heterocyclic group, and R ²⁴ is an aromatic group.
As the heterocyclic group, a benzoxazolyl group or a benzothiazolyl group is particularly preferable, and more specifically, a benzothiazolyl group substituted with an unsubstituted or sulfo group (including a salt state) is preferable.
The aromatic group is preferably an aryl group substituted with at least one group selected from an alkyl group and a sulfo group (including a salt state), and at least one group selected from an alkyl group and a sulfo group is substituted. A phenyl group is particularly preferred.
Specific examples and preferred ranges of the counter cation when the sulfo group is in a salt state are the same as the specific examples and preferred ranges when the compound represented by the general formula (1) is a salt.

In the general formula (4), R ²¹ and R ²² are each independently a hydrogen atom, a halogen atom, an aliphatic group, an aromatic group, a heterocyclic group, a cyano group, a carboxyl group, a carbamoyl group, an alkoxycarbonyl group, an aryl Oxycarbonyl group, acyl group, hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group , Heterocyclic amino group, acylamino group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl Represents an arylthio group, an alkyl- or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group, or a heterocyclic thio group. R ²¹ and R ²³ , or R ²³ and R ²⁴ may be bonded to form a 5- or 6-membered ring.
Examples of the aliphatic group include an alkyl group, a cycloalkyl group, an alkenyl group, and an alkynyl group.
Examples of the aromatic group include an aryl group.
Moreover, an aralkyl group is mentioned as a group applicable to an aromatic group and an aliphatic group.

Specific examples of the groups represented by R ²¹ and R ²² include the groups described in the substituent group A described above.
Each group may further have a substituent, and examples of the substituent include the substituent group A described above.

R ²¹ and R ²² are preferably a hydrogen atom, an alkyl group, a carbamoyl group, or a cyano group from the viewpoint of ease of synthesis, light resistance, and ozone resistance. More preferably, it is an alkyl group, a carbamoyl group, or a cyano group. In particular, it is preferable that R ²¹ is a hydrogen atom and R ²² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (most preferably a methyl group).

In General Formula (4), R ²⁵ and R ²⁹ each independently represent an alkyl group, an alkoxy group, or a halogen atom. When R ²⁵ and R ²⁹ are both alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.

Specific examples of the alkyl group, alkoxy group, and halogen atom include the groups described in Substituent Group A described above.
The alkyl group and alkoxy group may further have a substituent, and examples of the substituent include the substituent group A described above.

R ²⁵ and R ²⁹ are preferably alkyl groups from the viewpoint of light resistance and ozone resistance, and each is an alkyl group having 1 to 3 carbon atoms (preferably a methyl group, an ethyl group, or an isopropyl group). Is preferred. However, the total number of carbon atoms constituting the alkyl group of R ²⁵ and R ²⁹ is 3 or more, and the total number of carbon atoms is preferably an alkyl group which may be substituted and has 3 to 5 carbon atoms. The total is more preferably an unsubstituted alkyl group having 4 to 5 carbon atoms.

In the general formula (4), R ²⁶ , R ²⁷ , and R ²⁸ are each independently synonymous with R ²¹ and R ^22, and are mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ^29. May be.
Specific examples of R ²⁶ , R ²⁷ , and R ²⁸ are the same as the specific examples of R ²¹ and R ²² , and the preferred ranges are also the same, but as R ²⁶ , R ²⁷ , and R ²⁸ , a hydrogen atom, an alkyl group Or a sulfo group (including a salt state) is preferable, and a hydrogen atom, an alkyl group having 1 to 4 carbon atoms (most preferably a methyl group), or a sulfo group is more preferable.
Specific examples and preferred ranges of the counter cation when the sulfo group is in a salt state are the same as the specific examples and preferred ranges when the compound represented by the general formula (1) is a salt.

In general formula (4), Q represents a hydrogen atom, an aliphatic group, an aromatic group, or a heterocyclic group.
Examples of the aliphatic group include an alkyl group, a cycloalkyl group, and an alkenyl group.
Examples of the aromatic group include an aryl group.
Moreover, an aralkyl group is mentioned as a group applicable to an aromatic group and an aliphatic group.

Specific examples of the alkyl group, cycloalkyl group, aralkyl group, alkenyl group, aryl group, and heterocyclic group include the groups described in R ²³ and R ²⁴ described above.
Each group may further have a substituent, and examples of the substituent are the same as the examples described in the above R ²³ and R ²⁴ .

Q is preferably an aryl group or a heterocyclic group substituted with an electron-withdrawing group or a sulfo group (including a salt state). Specific examples and preferred ranges of the counter cation when the sulfo group is in a salt state are the same as the specific examples and preferred ranges when the compound represented by the general formula (1) is a salt.
The electron withdrawing group is an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, preferably 0.30 or more. The upper limit of the σp value is preferably 1.0 or less.
Specific examples of the electron-withdrawing group having a σp value of 0.20 or more include the electron-withdrawing group described in Z ¹ above, preferably a cyano group, a nitro group, or a halogen atom.

The compound represented by the general formula (4) has at least one ionic hydrophilic group.
The ionic hydrophilic group is preferably at least one group selected from a sulfo group, a carboxyl group, a phosphono group and a quaternary ammonium group from the viewpoint of water solubility.
As the ionic hydrophilic group, at least one group selected from a sulfo group, a carboxyl group, and a phosphono group is preferable, and among them, a carboxyl group and a sulfo group are preferable. In particular, at least one is most preferably a sulfo group. The carboxyl group, phosphono group, and sulfo group may be in the form of a salt. Examples of counter ions that form a salt include ammonium ions, alkali metal ions (eg, lithium ions, sodium ions, potassium ions), and organic cations. (Eg, tetramethylammonium ion, tetramethylguanidinium ion, tetramethylphosphonium). Among the counter ions, alkali metal salts are preferable. Among alkali metal salts, potassium ion, sodium ion, and lithium ion are preferable, lithium ion and sodium ion are more preferable, and sodium ion is most preferable.

  The compound represented by the general formula (4) preferably has 3 or more and 6 or less ionic hydrophilic groups in its molecule from the viewpoint of water solubility, and has 3 or more and 6 or less sulfo groups. More preferably, it has 3 or more and 5 or less sulfo groups.

  The compound represented by the general formula (4) is preferably a compound represented by the following general formula (4 ').

In General Formula (4 ′), Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , and R ₄₃ are each independently a hydrogen atom, aliphatic Represents a group, an aromatic group, a heterocyclic group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfamoyl group, or an ionic hydrophilic group.
M ₁ and M ₂ each independently represents an oxygen atom or a sulfur atom.
Each group of Z ² , R ²¹ and R ²² may further have a substituent.
However, the general formula (4 ′) has at least one ionic hydrophilic group.

In general formula (4 ′), Z ² , R ²¹ , R ²² , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ are respectively Z ² , R ²¹ , R ^{22 in} general formula (4). ^{R 25, R 26, R 27} , R 28, and has the same meaning as ^{R 29,} it is the same specific examples and preferred ranges.

In general formula (4 ′), R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , and R ₄₃ are respectively Independently, hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, or ionic hydrophilic group Represents. Specific examples of these groups are the same as those described for R ²³ and R ²⁴ in the general formula (4). The ionic hydrophilic group is as described above.
R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₃₅ , R ₃₆ , R ₃₇ , R ₃₈ , R ₃₉ , R ₄₀ , R ₄₁ , R ₄₂ , and R ₄₃ are a hydrogen atom, an alkyl group, or a sulfo group It is preferable that

In General Formula (4 ′), M ₁ and M ₂ each independently represent an oxygen atom or a sulfur atom, and preferably a sulfur atom.

  A method for synthesizing the compound represented by the general formula (4) will be described. Here, the manufacturing method of the compound represented by the following general formula (4-R1) or (4-R2) among the compounds represented by the general formula (4) will be described.

In the general formula (4-R1), Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ are each represented by the general formula ( It is synonymous with Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ in 4). Q ₁ represents an aliphatic group, an aromatic group or a heterocyclic group.
In the general formula (4-R2), Z ¹ , Z ² , R ²¹ , R ²² , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ²⁹ are each represented by the general formula (4). ^{Z 1, Z 2, R 21} , R 22, R 24, R 25, R 26, R 27, R 28, and the same meaning as ^{R 29.} Q ₁ and Q ₂ each independently represents an aliphatic group, an aromatic group, or a heterocyclic group.

The compound of the general formula (4-R1) can be obtained by any of the following methods, <1> and / or <2>.
Method <1> includes (a) a step of reacting an aminopyrazole represented by the following general formula (4-1) with a diazotizing agent to form a diazonium salt, (b) formed in step (a) above. Reacting the prepared diazonium salt with a coupling agent represented by the following general formula (4-2) to form a compound represented by the following general formula (4-H1), and (c) presence of a base A method comprising a step of reacting the compound formed in the step (b) with an alkylating agent, an arylating agent or a heterylating agent to form a compound represented by the general formula (4-R1). is there.

In the general formulas (4-1), (4-2), and (4-H1), Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are each represented by Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ^{29 in the} general formula (4). It is synonymous.

  Method <2> is a method including a step of introducing a water-soluble group into the compound represented by the general formula (4-R1) by electrophilic reaction. Furthermore, the method described in detail below is preferable for the electrophilic reaction.

  In the method <1>, it is preferable to use a dilute hydrochloric acid aqueous solution of sodium nitrite as the diazotizing agent used in step (a). In addition, isopentyl nitrite and nitrosylsulfuric acid can also be used as diazotizing agents.

In method <1>, the coupling agent used in step (b) is most preferably a nitrogen-containing 6-membered heterocyclic coupler represented by the general formula (4). Preferred examples of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , and R ^{29 in} the general formula (4) are those of the general formula (4). Same as the case.

  In the method <1>, the alkylating agent, arylating agent, or heterylating agent used in the step (c) is represented by the following general formulas (5), (6), and (7).

In the general formula (5), R represents an optionally substituted alkyl group, and X represents a halogen atom or OSO ₂ R ′. R ′ represents an alkyl group or an aryl group such as a phenyl group.
In the general formula (6), Ar represents a phenyl group substituted with an electron withdrawing group, and is preferably substituted with a substituent having a total Hammett σp value of 0.2 or more. X represents a halogen atom or OSO ₂ R ′. R ′ represents an alkyl group or an aryl group such as a phenyl group.
In the general formula (7), Het represents a heterocyclic ring, and a 2-pyridyl group, a 2-thienyl group, a 2-thiazolyl group, a 2-benzothiazolyl group, a triazyl group, and a 2-furyl group are preferable. X represents a halogen atom or OSO ₂ R ′. R ′ represents an alkyl group or an aryl group such as a phenyl group.
As the base used in the step (c), an organic base such as diisopropylethylamine and an inorganic base such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium hydroxide, potassium hydroxide can be used. .

The electrophilic reaction in the above method <2> includes sulfonation, Mannich reaction, and Friedel-Crafts reaction. Of these, sulfonation is preferred.
As a method of sulfonating the general formula (4-R1), sulfonation is performed using a sulfonating agent such as concentrated sulfuric acid, 10% to 60% fuming sulfuric acid, chlorosulfonic acid, sulfur trioxide, amidosulfuric acid and the like. Can do. A solvent may be used, and as the solvent, acetic acid, acetic anhydride, sulfolane, ethyl acetate, ether, carbon tetrachloride, acetonitrile, or the like may be used.
In formula ^{_{(4-R1), Q 1}} , R 23, R 24, R 26 (R 28), it is preferred ^{that R 27} is _{^{sulfonation, Q 1, R 23, R}} 24, R 26 (R 28 ), When the substituent of R ²⁷ has a plurality of reactive sites capable of being sulfonated, sulfonated dyes having different substitution positions may be mixed.
In this case, a sulfonated dye having a different substitution position in the range of 0.1% to 50% by HPLC area% may be mixed with the main sulfonated dye. The reaction temperature (Celsius) is desirably from -5 degrees to 80 degrees, and more desirably from 10 degrees to 70 degrees. The reaction time is preferably between 30 minutes and 10 hours, more preferably between 1 hour and 6 hours.

  In the production method of the general formula (4-R1) or the general formula (4-R2), the deoxygenation condition is preferably produced by filling the reaction system with an inert gas such as nitrogen or argon, It is preferable to bubble the reaction solution with these inert gases.

  Aminopyrazole represented by general formula (4-1), which is a starting material used in step (a) of method <1>, is disclosed in U.S. Pat. No. 3,336,285 and Heterocycles, 20,519 (1983) and Japanese Patent Publication No. 6-19036.

  Pyridine couplers (coupling agents represented by general formula (4-2)) used in step (b) of method <1> are disclosed in JP-A-51-83931, JP-A-49-74718, It can be synthesized by the method described in Japanese Patent Publication No. 52-46230.

  The azo dye represented by the general formula (4) can be synthesized by the production method of the present invention described above. Specific examples of the azo dye of the present invention are shown below, but are not limited to the following examples. In the following specific examples, the sulfo group may be in a salt state.

(Coloring composition)
The coloring composition of the present invention contains at least one compound represented by the above general formula (1) of the present invention and at least one compound represented by the above general formula (4) of the present invention. The synergistic effect of the compound represented by the general formula (1) and the compound represented by the general formula (4) makes it possible to achieve both good fastness and good hue.
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 content of the compound of the present invention contained in the colored composition is the kind of substituents in the general formula (1) and general formula (4) used, and the solvent used for producing the colored composition. The content of the compound represented by the general formula (1) in the colored composition is preferably 0.1 to 20% by mass with respect to the total mass of the colored composition, although it is determined depending on the type of component. , 0.4 to 10% by mass, more preferably 0.75 to 6% by mass.

  By making the content of the compound represented by the general formula (1) contained in the coloring composition 0.75% by mass or more, the color development of the ink on the recording medium when printed can be improved, and Necessary image density can be secured. Moreover, when the total amount of the compounds represented by the general formula (1) contained in the colored composition is 20% by mass or less, the dischargeability of the colored composition can be improved when used in the ink jet recording method. In addition, it is possible to obtain an effect such that the inkjet nozzle is not easily clogged.

  From the viewpoint of hue, the content of the compound represented by the general formula (4) in the coloring composition is preferably 0.1 to 18% by mass with respect to the total mass of the coloring composition, and 0.15 More preferably, it is contained in an amount of 10 to 10% by mass.

  In the colored composition, the mass ratio of the compound represented by the general formula (1) and the compound represented by the general formula (4) is preferably 95/5 to 5/95, and 95/5 to 10 / More preferably, it is 90, and it is still more preferable that it is 95/5-20/80. By setting the mass ratio within the above range, it is preferable from the viewpoint of light resistance, ozone resistance, and hue balance.

  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 present invention also relates to an inkjet recording ink containing the coloring composition of the present invention.
The ink for inkjet recording can be prepared by dissolving and / or dispersing the compound (mixture) of the present invention in an oleophilic medium or an aqueous medium. Preferably, the ink uses an aqueous medium.
If necessary, other additives can be contained 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.

  The anti-drying agent is preferably used for the purpose of preventing clogging due to drying of the ink for ink jet recording at the ink ejection port of the nozzle used in the ink jet recording method.

  As the drying inhibitor, a water-soluble organic solvent having a vapor pressure lower than that of water is preferable. Specific examples include ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin. Polyhydric alcohols typified by trimethylolpropane, etc., lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic rings such as N-ethylmorpholine, sulfolane, dimethyl sulfoxide, 3 Sulfur-containing compounds such as sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives. Of these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. Moreover, said anti-drying agent may be used independently and may be used together 2 or more types. These drying inhibitors are preferably contained in the ink in an amount of 10 to 50% by mass.

  The penetration accelerator is preferably used for the purpose of allowing the ink for ink jet recording to penetrate better into paper. As the penetration enhancer, alcohols such as ethanol, isopropanol, butanol, di (tri) ethylene glycol monobutyl ether, 1,2-hexanediol, sodium lauryl sulfate, sodium oleate, nonionic surfactants and the like can be used. . If these are contained in the ink in an amount of 5 to 30% by mass, they usually have a sufficient effect, and it is preferable to use them in a range of addition amounts that do not cause printing bleeding and paper loss (print through).

  The ultraviolet absorber is used for the purpose of improving image storability. Examples of the ultraviolet absorber include benzotriazoles described in JP-A Nos. 58-185677, 61-190537, JP-A-2-782, JP-A-5-97075, JP-A-9-34057, and the like. Compounds, benzophenone compounds described in JP-A No. 46-2784, JP-A No. 5-194433, U.S. Pat. No. 3,214,463, etc., JP-B Nos. 48-30492, 56-21114, Cinnamic acid compounds described in JP-A-10-88106, JP-A-4-298503, JP-A-8-53427, JP-A-8-239368, JP-A-10-182621, JP-A-8 No. -502911, etc., triazine compounds, Research Disclosure No. Compounds described in No. 24239, compounds that emit fluorescence by absorbing ultraviolet rays typified by stilbene-based and benzoxazole-based compounds, so-called fluorescent brighteners, can also be used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the anti-fading agent, various organic and metal complex anti-fading agents can be used. Organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc. Complex, zinc complex and the like. More specifically, Research Disclosure No. No. 17643, No. VII, I to J, ibid. 15162, ibid. No. 18716, page 650, left column, ibid. No. 36544, page 527, ibid. No. 307105, page 872, ibid. The compounds described in the patent cited in No. 15162 and the compounds included in the general formulas and compound examples of the representative compounds described in pages 127 to 137 of JP-A-62-215272 can be used.

  Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof. These are preferably used in the ink in an amount of 0.02 to 1.00% by mass.

  As the pH adjuster, the neutralizing agent (organic base, inorganic alkali) can be used. For the purpose of improving the storage stability of the ink for ink jet recording, the pH adjusting agent is preferably added so that the ink for ink jet recording has a pH of 6 to 10, and more preferably added to have a pH of 7 to 10. preferable.

  Examples of the surface tension adjusting agent include nonionic, cationic and anionic surfactants. The surface tension of the ink for ink jet recording of the present invention is preferably 25 to 70 mN / m. Furthermore, 25-60 mN / m is preferable. Further, the viscosity of the ink for ink jet recording of the present invention is preferably 30 mPa · s or less. Furthermore, it is more preferable to adjust to 20 mPa · s or less. Examples of surfactants include fatty acid salts, alkyl sulfate esters, alkyl benzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalene sulfonate formalin condensates, polyoxyethylene alkyl sulfates. Anionic surfactants such as ester salts, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, polyoxyethylene fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkylamine, glycerin fatty acid ester Nonionic surfactants such as oxyethyleneoxypropylene block copolymers are preferred. Further, SURFYNOLS (Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant, is also preferably used. An amine oxide type amphoteric surfactant such as N, N-dimethyl-N-alkylamine oxide is also preferred. Further, pages (37) to (38) of JP-A-59-157,636, Research Disclosure No. The surfactants described in 308119 (1989) can also be used.

  As the antifoaming agent, fluorine-based, silicone-based compounds, chelating agents represented by EDTA, and the like can be used as necessary.

  When the compound of the present invention is dispersed in an aqueous medium, as described in JP-A Nos. 11-286637, 2000-78491, 2000-80259, 2000-62370, and the like, Colored fine particles containing a compound and an oil-soluble polymer are dispersed in an aqueous medium, or as described in Japanese Patent Application Nos. 2000-78454, 2000-78491, 2000-203856, and 2000-203857. It is preferable that the compound of the present invention dissolved in a high boiling point organic solvent is dispersed in an aqueous medium. The specific method for dispersing the compound of the present invention in an aqueous medium, the oil-soluble polymer to be used, the high-boiling organic solvent, the additive, and the amount used thereof are preferably those described in the above-mentioned patent publications. be able to. Alternatively, the compound of the present invention may be dispersed in a fine particle state as a solid. At the time of dispersion, a dispersant or a surfactant can be used. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, attritor, roll mill, agitator mill, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer) Specific examples of commercially available devices include gorin homogenizers, microfluidizers, DeBEE2000, and the like. In addition to the above-mentioned patents, the ink jet recording ink preparation method described above is disclosed in JP-A Nos. 5-148436, 5-295212, 7-97541, 7-82515, and 7-118584. Details are described in Japanese Laid-Open Patent Publication No. 11-286637 and Japanese Patent Application No. 2000-87539, and can also be used to prepare the ink for inkjet recording of the present invention.

  As the aqueous medium, a mixture containing water as a main component and optionally adding a water-miscible organic solvent can be used. Examples of the water-miscible organic solvent include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyvalent Alcohols (eg, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol), glycol derivatives (eg , Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl Ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether , Triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amine (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine) , Triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl- 2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, the said water miscible organic solvent may use 2 or more types together.

  In 100 parts by mass of the inkjet recording ink of the present invention, the compound of the present invention is preferably contained in an amount of 0.2 parts by mass or more and 10 parts by mass or less, and more preferably 1 part by mass or more and 6 parts by mass or less. In addition, in the ink for inkjet recording of the present invention, other dyes may be used in combination with the compound of the present invention. When two or more kinds of dyes are used in combination, the total content of the dyes is preferably within the above 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 inkjet recording of the present invention 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 yellow dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, heterocycles such as pyrazolone and pyridone, open-chain active methylene compounds, etc. as coupling components (hereinafter referred to as coupler components); for example, coupler components Azomethine dyes having open-chain active methylene compounds as examples; methine dyes such as benzylidene dyes and monomethine oxonol dyes; quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dyes Examples of the species include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes.

  Any applicable magenta dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, azomethine dyes having pyrazolones, pyrazolotriazoles, etc. as coupler components; for example arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, Methine dyes such as oxonol dyes; Carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc., quinone dyes such as naphthoquinone, anthraquinone, anthrapyridone, etc., condensed polycycles such as dioxazine dyes, etc. And dyes.

  Any applicable cyan dye can be used. For example, aryl or heteryl azo dyes having phenols, naphthols, anilines and the like as coupler components; for example, azomethine dyes having phenols, naphthols, heterocyclic rings such as pyrrolotriazole as coupler components; cyanine dyes, oxonol dyes, Examples include polymethine dyes such as merocyanine dyes; carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

Each of the above dyes may exhibit yellow, magenta, and cyan colors only after a part of the chromophore is dissociated. In this case, the counter cation is an alkali metal or an inorganic cation such as ammonium. Alternatively, it may be an organic cation such as pyridinium or a quaternary ammonium salt, and may further be a polymer cation having these in a partial structure.
Applicable black materials include disazo, trisazo, tetraazo dyes, and carbon black dispersions.

  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, energy is supplied to the ink for ink jet recording, and a known image receiving material, that is, plain paper, resin-coated paper, such as JP-A-8-169172, JP-A-8-27693, JP-A-2-276670, JP-A-7-276789, JP-A-9-323475, JP-A-62-238783, JP-A-10-153989, JP-A-10-217473, JP-A-10-235995 10-337947, 10-217597, 10-337947, etc. Form images on inkjet paper, film, electrophotographic paper, cloth, glass, metal, ceramics, etc. To do.

  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.

Hereinafter, a recording paper and a recording film used for ink jet printing using the ink of the present invention will be described.
The support in recording paper and recording film is made of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMPMP, CGP, and waste paper pulp such as DIP. Additives such as known pigments, binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc. can be mixed and manufactured using various devices such as long net paper machines and circular net paper machines. is there. In addition to these supports, either synthetic paper or plastic film sheets may be used. The thickness of the support is preferably 10 to 250 μm and the basis weight is preferably 10 to 250 g / m 2.
The support may be provided with an ink receiving layer and a backcoat layer as they are, or after a size press or anchor coat layer is provided with starch, polyvinyl alcohol or the like, an ink receiving layer and a backcoat layer may be provided. Further, the support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar. In the present invention, paper and plastic films laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene and copolymers thereof) are more preferably used as the support.
It is preferable to add a white pigment (for example, titanium oxide or zinc oxide) or a tinting dye (for example, cobalt blue, ultramarine blue, or neodymium oxide) to the polyolefin.

  The ink receiving layer provided on the support contains a pigment and an aqueous binder. As the pigment, a white pigment is preferable, and as the white pigment, calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, lithopone, zeolite, Examples thereof include white inorganic pigments such as barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigments, acrylic pigments, urea resins and melamine resins. As the white pigment contained in the ink receiving layer, porous inorganic pigments are preferable, and synthetic amorphous silica having a large pore area is particularly preferable. As the synthetic amorphous silica, either anhydrous silicic acid obtained by a dry production method or hydrous silicic acid obtained by a wet production method can be used, but it is particularly desirable to use hydrous silicic acid.

Examples of the aqueous binder contained in the ink receiving layer include polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. Water-dispersible polymers such as water-soluble polymers, styrene butadiene latexes, and acrylic emulsions. These aqueous binders can be used alone or in combination of two or more. In the present invention, among these, polyvinyl alcohol and silanol-modified polyvinyl alcohol are particularly preferable in terms of adhesion to the pigment and resistance to peeling of the ink receiving layer.
The ink receiving layer can contain a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives in addition to the pigment and the aqueous binder.

The mordant added to the ink receiving layer is preferably immobilized. For that purpose, a polymer mordant is preferably used.
For the polymer mordant, JP-A-48-28325, 54-74430, 54-124726, 55-22766, 55-142339, 60-23850, 60-23835, 60-23852, 60-23853, 60-57836, 60-60643, 60-118834, 60-122940, 60-122941, 60-122942, 60- No. 235134, JP-A-1-161236, U.S. Pat.Nos. 2,484,430, 2,548,564, 3,148,061, 3,309,690, 4,115,124, 4,124,386, 4,193,800, 4,2,387,305, It is described in each specification of the same No. 4450224. An image receiving material containing a polymer mordant described in JP-A-1-161236, pages 212 to 215 is particularly preferred. When the polymer mordant described in the publication is used, an image with excellent image quality is obtained and the light resistance of the image is improved.

  The water-proofing agent is effective for making the image water-resistant. As these water-proofing agents, cationic resins are particularly desirable. Examples of such cationic resins include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, etc. Among these cationic resins, polyamide polyamine epichlorohydrin is particularly preferable. is there. The content of these cationic resins is preferably 1 to 15% by mass, particularly 3 to 10% by mass, based on the total solid content of the ink receiving layer.

  Examples of the light fastness improver include zinc sulfate, zinc oxide, hindered amine antioxidants, and benzotriazole ultraviolet absorbers such as benzophenone. Of these, zinc sulfate is particularly preferred.

  The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. The surfactant is described in JP-A Nos. 62-173463 and 62-183457. An organic fluoro compound may be used in place of the surfactant. The organic fluoro compound is preferably hydrophobic. Examples of the organic fluoro compound include a fluorine-based surfactant, an oily fluorine-based compound (for example, fluorine oil), and a solid fluorine compound resin (for example, tetrafluoroethylene resin). The organic fluoro compounds are described in JP-B-57-9053 (columns 8 to 17), JP-A-61-20994, and 62-135826. Examples of other additives added to the ink receiving layer include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusters, matting agents, and hardening agents. . The ink receiving layer may be one layer or two layers.

  The recording paper and the recording film can be provided with a back coat layer, and examples of components that can be added to this layer include a white pigment, an aqueous binder, and other components. Examples of white pigments contained in the backcoat layer include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, and aluminum silicate. White inorganic pigments such as diatomaceous earth, calcium silicate, magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide And organic pigments such as styrene plastic pigment, acrylic plastic pigment, polyethylene, microcapsule, urea resin and melamine resin.

  As the aqueous binder contained in the backcoat layer, styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose Water-soluble polymers such as hydroxyethyl cellulose and polyvinyl pyrrolidone, and water-dispersible polymers such as styrene butadiene latex and acrylic emulsion. Examples of other components contained in the backcoat layer include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-resistant agent.

  Polymer latex may be added to the constituent layers (including the backcoat layer) of the ink jet recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. The polymer latex is described in JP-A Nos. 62-245258, 62-136648, and 62-110066. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to a layer containing a mordant, cracking and curling of the layer can be prevented. Also, curling can be prevented by adding a polymer latex having a high glass transition temperature to the backcoat layer.

  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)
[Synthesis of Exemplified Compound 1-1]
To a 500 mL three-necked flask, add 120 g of chlorosulfonic acid and 12.4 g of phosphorus oxychloride, carefully add 19 g of Acid Red 289 (manufactured by Chugai Kasei Co., Ltd., 71% content) while stirring, and then at 70 ° C. for 1 hour. Reacted. After cooling the reaction solution to room temperature, the reaction solution was carefully poured into a 2 L beaker where 600 g of ice was being stirred to precipitate a solid. The precipitated solid was separated by filtration and washed with a saturated saline solution at 10 ° C. or lower to obtain 80.4 g of a compound A wet cake.
In a 1 L three-necked flask, 80.4 g of wet cake was added with 450 g of ice water and dispersed at 5 ° C. or lower, and 3.9 g of 4,4′-diaminostilbene-2,2′-disulfonic acid (95%) manufactured by Acros was added. A solution adjusted to pH 9.0 with 2N aqueous sodium hydroxide solution in 60 mL of water and dissolved was added and heated to 50 ° C. The mixture was stirred at 50 ° C. until the pH change disappeared, and further stirred at 50 ° C. for 1 hour while maintaining the pH at 9 with a 2N aqueous sodium hydroxide solution.
The reaction solution was passed through a GF / F filter (manufactured by Whatman) to remove insoluble matters, sodium chloride corresponding to 25% by weight of the total weight of the obtained filtrate was added, and concentrated hydrochloric acid was used while stirring at room temperature. The pH was adjusted to 4 to precipitate a solid. The precipitated solid was separated by filtration, and the obtained solid was dispersed in 600 mL of water, dissolved in 2N sodium hydroxide with pH adjusted to 9, and then electric conductivity of 10 μS or less using a dialysis tube. The mixture was desalted until it became, and again passed through a GF / F filter for dust removal, and the obtained filtrate was concentrated and dried at 60 ° C. to obtain 17.4 g of green glossy crystals of Exemplified Compound 1-1.
As a result of measurement of MS spectrum, 706.3 (100 corresponding to [(M−3) / 3] ⁻ of a dimer (m = 1, n = 2 in the general formula (1)) which is a typical structure of the compound. %), 529.5 corresponding to [(M-4) / 4] ⁻ was observed. In addition, 823.7 corresponding to [(M−3) / 3] ⁻ of different dimers (m = 2 and n = 2 in the general formula (1)), and [(M−4) / 4 ] 617.5 corresponding to ⁻ was observed, and 836.5 corresponding to [(M−4) / 4] ⁻ of the trimer (m = 2 in the general formula (1), n = 3) was observed. It was. The absorption spectrum of the compound in an aqueous solution was 531 nm.

[Synthesis of Exemplified Compound 1-2]
To a 250 mL three-necked flask, add 60 g of chlorosulfonic acid and 6.2 g of phosphorus oxychloride, carefully add 9.54 g of Acid Red 289 (manufactured by Chugai Kasei Co., Ltd., 71% content) while stirring, and then add 70 mL at 70 ° C. The reaction was carried out for 1 hour. After the reaction solution was cooled to room temperature, the reaction solution was carefully poured into a 1 L beaker where 300 g of ice was being stirred to precipitate a solid. The precipitated solid was separated by filtration and washed with a saturated saline solution at 10 ° C. or lower to obtain a wet cake of Compound A.
Disperse the entire amount of Compound A wet cake in 150 mL of ice water in a 1 L beaker, add 0.30 g of ethylenediamine, and react at 50 ° C. for 3 hours while maintaining the pH of the reaction solution at 9 using a 2N aqueous sodium hydroxide solution. I let you. The reaction solution is cooled to room temperature, insoluble matter is removed using a Whatman GF / F filter, pH is adjusted to 8.5 using dilute hydrochloric acid, and electric conductivity is 10 μS or less using a dialysis tube. The salt was desalted until the concentration became 4.2 to give 4.2 g of green glossy crystals of Exemplary Compound 1-2.
As a result of measurement of MS spectrum, 905.5 corresponding to [(M-2) / 2] ⁻ of the dimer (m = 1, n = 2 in the general formula (1)) which is a representative structure of the compound, [ (M-3) / 3] - it corresponds to 603 (100%), [( M-4) / 4] - corresponding to 452 was observed at. The absorption spectrum of the compound in an aqueous solution was 530 nm.

[Synthesis of Exemplified Compound 1-3]
4.3 g of green glossy crystals of Exemplified Compound 1-3 was obtained in the same manner except that ethylenediamine in the synthesis of Exemplified Compound 1-2 was changed to 4.3 g of piperazine. As a result of measurement of MS spectrum, 918 corresponding to [(M−2) / 2] ⁻ of a dimer (m = 1, n = 2 in the general formula (1)) which is a representative structure of the compound, [(M -3) / 3] ^- , 611 (100%), and [(M-4) / 4] ^- , corresponding to 458, were observed. The absorption spectrum of the compound in an aqueous solution was 529 nm.

[Synthesis of Exemplified Compound 1-4]
Except that ethylenediamine in the synthesis of the exemplary compound 1-2 was changed to 0.57 g of 2,5-dimethylpiperazine, 4.1 g of green glossy crystals of the exemplary compound 1-4 was obtained. As a result of measurement of MS spectrum, 932 corresponding to [(M−2) / 2] ⁻ of the dimer (m = 1, n = 2 in the general formula (1)) which is a representative structure of the compound, [(M -3) / 3] ^- , 621 (100%), and [(M-4) / 4] ^- , 465.5, were observed. The absorption spectrum of the compound in an aqueous solution was 529 nm.

[Synthesis of Exemplified Compound 1-5]
4.4 g of green glossy crystals of Exemplified Compound 1-5 was obtained in the same manner except that ethylenediamine in the synthesis of Exemplified Compound 1-2 was changed to 0.65 g of 1- (2-aminoethyl) piperazine. As a result of measurement of MS spectrum, 944.5 corresponding to [(M−2) / 2] ⁻ of a dimer (m = 1, n = 2 in the general formula (1)) which is a representative structure of the compound, [ (M-3) / 3] - it corresponds to 629 (100%), [( M-4) / 4] - was observed 471.7 corresponding to. The absorption spectrum of the compound in an aqueous solution was 529 nm.

[Synthesis of Exemplified Compound 1-6]
4.9 g of green glossy crystals of Exemplified Compound 1-6 was obtained in the same manner except that ethylenediamine in the synthesis of Exemplified Compound 1-2 was changed to 1.00 g of 1,4-bis (3-aminopropyl) piperazine). It was. As a result of measurement of MS spectrum, 975.1 corresponding to [(M-2) / 2] ⁻ of the dimer (m = 1, n = 2 in the general formula (1)) which is a representative structure of the compound, [ (M-3) / 3] - corresponds to 649.7 (100%), [( M-4) / 4] - corresponding to ^- corresponding to 487.1 and [(M-5) / 5 ] 389.4 was observed. The absorption spectrum of the compound in an aqueous solution was 529 nm.

[Synthesis of Exemplified Compound 1-7]
Except that ethylenediamine in the synthesis of Exemplified Compound 1-2 was changed to 0.57 g of 1,2-cyclohexanediamine, 4.0 g of green glossy crystals of Exemplified Compound 1-7 was obtained. As a result of measurement of MS spectrum, 932.1 corresponding to [(M−2) / 2] ⁻ of a dimer (m = 1, n = 2 in the general formula (1)) which is a representative structure of the compound, [ 621 (100%) corresponding to (M-3) / 3] ^- , 465.5 corresponding to [(M-4) / 4] ^- , and 372 corresponding to [(M-5) / 5] ^- . 2 was observed. The absorption spectrum of the compound in an aqueous solution was 530 nm.

[Synthesis of Exemplified Compound 1-8]
Except changing ethylenediamine in the synthesis | combination of the said exemplary compound 1-2 to 0.53 g of 1, 3- cyclohexanediamine, 4.1g of green glossy crystals of the exemplary compound 1-8 were obtained similarly. As a result of measurement of MS spectrum, 932.1 corresponding to [(M−2) / 2] ⁻ of a dimer (m = 1, n = 2 in the general formula (1)) which is a representative structure of the compound, [ 621 (100%) corresponding to (M-3) / 3] ^- , 465.5 corresponding to [(M-4) / 4] ^- , and 372 corresponding to [(M-5) / 5] ^- . 2 was observed. The absorption spectrum of the compound in an aqueous solution was 530 nm.

[Synthesis of Exemplified Compound 1-9]
Except that ethylenediamine in the synthesis of the exemplary compound 1-2 was changed to 0.57 g of 1,4-cyclohexanediamine, 4.1 g of green glossy crystals of the exemplary compound 1-9 was obtained. As a result of measurement of MS spectrum, 932.1 corresponding to [(M−2) / 2] ⁻ of a dimer (m = 1, n = 2 in the general formula (1)) which is a representative structure of the compound, [ 621 corresponding to (M-3) / 3] ^- , 465.5 (100%) corresponding to [(M-4) / 4] ^- , and 372 corresponding to [(M-5) / 5] ^- . 2 was observed. The absorption spectrum of the compound in an aqueous solution was 530 nm.

[Synthesis of Exemplified Compound 1-10]
4.0 g of green glossy crystals of Exemplified Compound 1-10 was obtained in the same manner except that ethylenediamine in the synthesis of Exemplified Compound 1-2 was changed to 0.54 g of m-phenylenediamine. As a result of measurement of MS spectrum, 929 corresponding to [(M−2) / 2] ⁻ of a dimer (m = 1, n = 2 in the general formula (1)) which is a representative structure of the compound, [(M -3) / 3] ^- , 619 (100%), [(M-4) / 4] ^- , 464 and [(M-5) / 5] ^- , 371 were observed. The absorption spectrum of the compound in an aqueous solution was 530 nm.

[Synthesis of Exemplified Compound 1-12]
<Synthesis of Intermediate B>

Intermediate B

In a 2 L beaker, 18.6 g of cyanuric chloride, 100 g of ice water, and 4 drops of calsolene oil were added and stirred at an internal temperature of 5 ° C. or lower. To this, 20.4 g of N-acetylethylenediamine was added at once at an internal temperature of 5 ° C. or less. After stirring at an internal temperature of 5 ° C. for 2 hours and at room temperature overnight, the mixture was further stirred at an internal temperature of 30 ° C. for 1 hour, at an internal temperature of 40 ° C. for 1 hour, and at an internal temperature of 50 ° C. for 4 hours. The precipitated solid was filtered off while hot, and the obtained white solid was dispersed in 500 mL of acetone and stirred at room temperature for 15 minutes. The solid was filtered off and washed with 200 mL of acetone. The obtained white solid was dispersed in 800 mL of water at room temperature, 28.9 g of 2,5-disulfoaniline monosodium salt was added thereto, and then the pH was adjusted to 9 using 2N aqueous sodium hydroxide solution. After the internal temperature was raised to 80 ° C. and reacted for 2 hours, 250 g of sodium chloride was added and cooled to room temperature. The pH was adjusted to 1 or less using concentrated hydrochloric acid, the precipitated solid was filtered off, and the obtained wet cake was dispersed in 500 mL of acetone and stirred at room temperature for 15 minutes. The solid was filtered off and washed thoroughly with acetone, and the resulting crystals were vacuum dried at 40 ° C. to obtain 40.2 g of a white solid. As a result of measurement of MS spectrum, 531 corresponding to [M-1] ⁻ of Intermediate B was observed.

<Synthesis of Intermediate C>
Intermediate C

To a 500 mL three-necked flask, 25 g of Intermediate B, 180 mL of water, and 20 mL of concentrated hydrochloric acid were added and reacted at 95 ° C. for 6 hours. The reaction solution was cooled to 50 ° C., 56 g of sodium chloride was added, and further cooled to room temperature, and the precipitated solid was filtered off. The obtained solid was dispersed in 100 mL of water, dissolved while neutralizing with 2N sodium hydroxide, and 150 mL of acetone was added dropwise to the resulting solution. The precipitated crystals were separated by filtration, washed with 200 mL of acetone, and then air-dried at 60 ° C. to obtain 19 g of intermediate C white crystals. As a result of measurement of MS spectrum, 531 corresponding to [M-1] ⁻ of Intermediate C was observed. The crystal content obtained from the results of elemental analysis was estimated to be 82%.

<Synthesis of Exemplified Compound 1-12>
4.7 g of green glossy crystals of Exemplified Compound 1-12 was obtained in the same manner except that ethylenediamine in the synthesis of Exemplified Compound 1-2 was changed to 2.73 g of Intermediate C (82% content). Measurement results of the MS spectrum, the (m = 1, n = 2 in the general formula (1)) representative structure in which dimer of the compound [(M-3) / 3 ] - corresponding to 732.4 [( M-4) / 4] ^- corresponding to 549 (100%) and the [(M-5) / 5 ] - corresponding to 439 was observed at. The absorption spectrum of the compound in an aqueous solution was 530 nm.

[Synthesis of Exemplified Compound 1-13]
<Synthesis of Intermediate D>
Intermediate D

In a 2 L beaker, 18.6 g of cyanuric chloride, 100 g of ice water, and 4 drops of calsolene oil were added and stirred at an internal temperature of 5 ° C. or lower. To this, 20.4 g of N-acetylethylenediamine was added at once at an internal temperature of 5 ° C. or less. After stirring at an internal temperature of 5 ° C. for 2 hours and at room temperature overnight, the mixture was further stirred at an internal temperature of 30 ° C. for 1 hour, at an internal temperature of 40 ° C. for 1 hour, and at an internal temperature of 50 ° C. for 4 hours. The precipitated solid was filtered off while hot, and the obtained white solid was dispersed in 500 mL of acetone and stirred at room temperature for 15 minutes. The solid was filtered off and washed with 200 mL of acetone. The obtained white solid was dispersed in 800 mL of water at room temperature, 19 g of 5-aminoisophthalic acid was added thereto, and then the pH was adjusted to 9 using 2N aqueous sodium hydroxide solution. The internal temperature was raised to 80 ° C. and reacted for 2 hours, and then cooled to room temperature. The precipitated solid was filtered off and sufficiently washed with water, and then the obtained wet cake was dispersed in 500 mL of acetone and stirred at room temperature for 15 minutes. The solid was filtered off and washed thoroughly with acetone, and the resulting crystals were vacuum dried at 40 ° C. to obtain 28.6 g of a white solid. As a result of measurement of MS spectrum, 461 corresponding to [M + 1] ⁺ of Intermediate D was observed.

<Synthesis of Intermediate E>
Intermediate E

Into a 500 mL three-necked flask, 25 g of Intermediate D, 180 mL of water, and 20 mL of concentrated hydrochloric acid were added and reacted at 95 ° C. for 6 hours. The reaction solution was cooled to 50 ° C., 56 g of sodium chloride was added, and further cooled to room temperature, and the precipitated solid was filtered off. The obtained solid was dispersed in 100 mL of water, dissolved while neutralizing with 2N sodium hydroxide, and 150 mL of acetone was added dropwise to the resulting solution. The precipitated crystals were separated by filtration, washed with 200 mL of acetone, and then air-dried at 60 ° C. to obtain 18 g of white crystals of Intermediate E. As a result of measurement of MS spectrum, 375 corresponding to [M-1] ⁻ of Intermediate E was observed. The crystal content obtained from the results of elemental analysis was estimated to be 88%.
<Synthesis of Exemplified Compound 1-13>
Except having changed ethylenediamine in the synthesis | combination of the said exemplary compound 1-2 to the intermediate E (content rate 88%) 2.13g, it carried out similarly and obtained 4.5g of green glossy crystals of the exemplary compound 1-13. Measurement results of the MS spectrum, the (m = 1, n = 2 in the general formula (1)) representative structure in which dimer of the compound [(M-3) / 3 ] - corresponding to 708.6 [( 534.2 (100%) corresponding to M-4) / 4] ⁻ and 424.8 corresponding to [(M-5) / 5] ⁻ were observed. The absorption spectrum of the compound in an aqueous solution was 529 nm.

[Synthesis of Exemplified Compound 1-15]
<Synthesis of Intermediate F>
Intermediate F

To a 1 L three-necked flask, 122.4 g of 2,6-dimethylaniline and 47.2 g of cyclohexanone were added. After carefully adding 120 mL of concentrated hydrochloric acid, the mixture was refluxed for 2 days. Cool the reaction solution to room temperature, add 500 mL of water, adjust the pH to 8 or higher using concentrated aqueous sodium hydroxide, extract with dichloromethane, dry the organic layer with sodium sulfate, and use a rotary evaporator. Concentrate, add hexane to the concentrate to precipitate a solid, filter the solid, wash the filtered solid thoroughly with hexane and dry at 60 ° C. to obtain 77 g of intermediate F pink white solid It was. From the measurement results of the MS spectrum, 323 corresponding to [M + 1] ⁺ of the intermediate F was observed.

<Synthesis of Intermediate G>
Intermediate G

To a 1 L three-necked flask, 100 g of 2-sulfobenzoic acid cyclic anhydride and 150 g of resorcinol were added and carefully heated to 140 ° C. (dissolved at about 80 ° C. and completely dissolved at about 120 ° C. Exothermic at around 140 ° C. And began to rise to around 150 ° C.). The reaction liquid solidified when reacted at 140 ° C. for about 30 minutes. The internal temperature was cooled to 100 ° C., 600 mL of water was carefully added dropwise to allow stirring, and this reaction solution was poured into a stirring place of 1000 mL of warm water in a separately prepared 2 L beaker, and crystals precipitated Was filtered off, washed thoroughly with 5000 mL of warm water, and dried in a vacuum dryer at 60 ° C. to obtain 119 g of brown crystals of Intermediate G. From the result of MS spectrum, 368 corresponding to [M] ⁺ of the intermediate G was observed.

<Synthesis of Intermediate H>
Intermediate H

119 g of intermediate G and 250 g of phosphorus oxychloride were added to a 1 L three-necked flask, heated to 90 ° C., and reacted for 2 hours. The reaction solution was cooled to room temperature, this reaction solution was poured into a large amount of ice, and the precipitated crystals were separated by filtration and washed thoroughly with water. The obtained brown crystals were stirred in 2500 mL of dichloromethane, insoluble matters were filtered off, the filtrate was dried over anhydrous sodium sulfate, concentrated and solidified using a rotary evaporator, and an intermediate H yellow powder 53. 4 g was obtained. From the results of MS spectrum, 406 corresponding to [M + 1] ⁺ of intermediate H was observed.

<Synthesis of Intermediate I>
Intermediate I

To a 250 mL three-necked flask, 20.25 g of intermediate H and 80 mL of sulfolane were added, and 27 g of aluminum chloride was carefully added while stirring at room temperature (the internal temperature rose to about 60 ° C.). While stirring at an internal temperature of 60 ° C., 8.06 g of intermediate F was added, followed by dropwise addition of 10.6 g of triethylamine, and then reacted at an internal temperature of 90 ° C. for 2 hours. The reaction solution was cooled to room temperature, poured into 1 L of water, and the precipitated crystals were collected by filtration, washed thoroughly with water, and air-dried at 60 ° C. to obtain 25.7 g of Intermediate I orange brown. As a result of MS spectrum, 1059 corresponding to [M + 1] ⁺ of Intermediate I was observed.

<Synthesis of Intermediate J>
Intermediate J

To a 250 mL three-necked flask, 11.4 g of 2,4,6-trimethylaniline, 19.4 g of intermediate I, 4.1 g of zinc chloride and 80 mL of sulfolane were added and reacted at 200 ° C. for 3 hours. The reaction solution is cooled to room temperature, 150 mL of ethyl acetate is added, and 300 mL of ethyl acetate is stirred in a separately prepared beaker, and the reaction solution is poured, and the precipitated crystals are separated by filtration. Then, it was thoroughly washed with water and further with acetone. The obtained crystals are dispersed in 500 mL of dichloromethane, and the crystals are filtered off. Further, the obtained crystals are dispersed in 500 mL of methanol, and the crystals are filtered off and dried by blowing at 60 ° C. 16.2 g of purple powder was obtained. From the results of MS spectrum, 1251 corresponding to [M-1] ⁻ of Intermediate J and 625 corresponding to [(M−2) / 2] ⁻ were observed.

<Synthesis of Exemplified Compound 1-15>
To a 250 mL three-necked flask, 60 g of chlorosulfonic acid and 6.2 g of phosphorus oxychloride were added, and 12.5 g of intermediate J was added in portions. After the internal temperature was raised to 70 ° C. and reacted for 1 hour, the reaction solution was cooled to room temperature, this reaction solution was poured into 300 g of ice water, the precipitated crystals were filtered off, and saturated brine was used. Washed. The obtained crystals were dispersed in 300 mL of water and reacted at an internal temperature of 50 ° C. for 6 hours while maintaining the pH at 9.0 with 2N sodium hydroxide. The insoluble matter was removed by filtration, the pH was adjusted to 8.5 using dilute hydrochloric acid, the electrical conductivity was desalted to 10 μS or less using a dialysis tube, and the mixture was concentrated and solidified to complete the concentration of exemplary compound 1-15. 8.9 g was obtained. As a result of MS spectrum, 867.1 corresponding to [(M-2) / 2] ⁻ of Exemplified compound 1-15, 577.7 corresponding to [(M-3) / 3] ⁻ and [(M− 4) / 4] ^- corresponding to 433.1 was observed in. The absorption spectrum of the compound in an aqueous solution was 529 nm.

[Compound (2-1)]

[Compound (2-2)]

[Compound (2-3)]

[Compound (2-4)]

[Compound (2-5)]

[Comparative Compound (AR289): CI Acid Red 289]

  However, (AR289) is a mixture of (AR289-1) and (AR289-2).

  The absorption maximum wavelength in a dilute aqueous solution of the compound (1-1) was 529 nm. The absorption spectrum is shown in FIG.

[Example 1]
Deionized water was added to the following components to make 100 g, and the mixture was stirred for 1 hour while heating 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.

2.0 g of compound of general formula (1) (the compound (1-1))
1.5 g of the compound of the general formula (4) (the compound (2-1))
Diethylene glycol 10.65g
Glycerin 14.70g
Diethylene glycol monobutyl ether 12.70g
Triethanolamine 0.65g
Olfin E1010 (Nissin Chemical Industry Co., Ltd.) 0.9g

[Examples 2-42 and Comparative Examples 1-3]
The ink liquids of Examples 2 to 42 and Comparative Examples 1 to 3 were prepared in the same manner as the ink liquids of Example 1 except that the dyes and dye addition amounts were changed as shown in Tables 1 and 2 below. did. As a comparative dye, C.I. I. Acid Red 289 (AR289) was used.

(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 Tables 1-2.
In Tables 1 and 2, ozone resistance and light resistance are determined by using each ink jet recording ink with a photo glossy paper (manufactured by EPSON Co., Ltd .; PM-700C) and photo glossy paper (manufactured by EPSON Co., Ltd., PM photo paper <gloss). > (KA420PSK, EPSON)) and then evaluated after recording the image.

<Ozone resistance>
While passing dry air through a double glass tube of a Siemens type ozonizer, an AC voltage of 5 kV was applied, and using this, the image was placed in a box set at an ozone gas concentration of 5 ± 0.1 ppm, room temperature, in a dark place. The formed photo glossy paper was allowed to stand for 7 days, and the image density before and after being left under ozone gas was measured using a reflection densitometer (X-Rite 310TR) and evaluated as a dye residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS.
The evaluation was made in three stages, with A being a dye residual ratio of 70% or more at any concentration, A being 1 or 2 points being less than 70% B, and C being less than 70% at all concentrations.

<Light resistance>
After measuring the image density Ci immediately after recording, the image was irradiated with xenon light (85,000 lux) for 7 days using a weather meter (Atlas C.165), and the image density Cf was measured again. The dye residual ratio ({(Ci−Cf) / Ci} × 100%) was calculated and evaluated from the difference in image density before and after the xenon light irradiation. The image density was measured using a reflection densitometer (X-Rite 310TR).
The dye residual ratio was measured at three points with reflection densities of 1, 1.5 and 2.0. At any concentration, the evaluation was made in three stages: A when the dye residual ratio was 80% or more, B as 1 or 1 or 2 points less than 80%, and C as less than 80% at all concentrations.

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

<Moisture resistance>
During ink-jet recording, a check pattern (a pattern in which squares having a 1.5 mm square with a density of 100% and 0% were alternately combined) was created to obtain a magenta-white check pattern print with high contrast. . After printing, the printed matter with the check pattern dried for 24 hours is allowed to stand for 3 days under the condition of 80 ° C. and 70% RH, and the degree of bleeding from the colored portion to the white portion is visually evaluated. Evaluation was made in three stages, where B was slightly blurred and C was clearly blurred.

  As is clear from the results of Tables 1 and 2, the inks of the examples using the colored composition of the present invention are extremely high in ozone resistance, light resistance, hue, and moisture resistance as compared with the inks of the comparative examples. It turns out that it has performance.

Claims (12)

A coloring composition comprising a compound represented by the following general formula (1) and a compound represented by the following general formula (4).

(In general formula (1), L represents a linking group represented by the following general formula (V1), (V2), (V3) or (V4)).
D represents a residue obtained by removing one hydrogen atom from the compound represented by the general formula (2).
m represents 1 .
n represents 2 . However, the plurality of D may be the same or different.
In General Formula (2), R ^{4 to} R ²⁴ each independently represent a hydrogen atom or a substituent.
However, it has at least one ionic hydrophilic group. )

(In general formula (V1), R ¹⁰¹ and R ¹⁰² each independently represents a hydrogen atom or a substituent.
In General Formula (V2), R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom or a substituent, and L ²⁰¹ represents an oxy group (—O—), a thio group (—S—), or a carbonyl group (—CO—). , A sulfonyl group (—SO ₂ —), an imino group (—NH—), a methylene group (—CH ₂ —), an arylene group, a cycloalkylene group, and a divalent group selected from a combination thereof . Represents a linking group. R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
In general formula (V3), R ³⁰¹ , R ³⁰² and R ³⁰³ each independently represent a hydrogen atom or a substituent, X represents an alkylene group having 2 to 20 carbon atoms which may have a substituent, and L ³⁰¹ represents a single bond or a divalent linking group.
In general formula (V4), R ⁴⁰¹ and R ⁴⁰² each independently represent a hydrogen atom or a substituent. )

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. However, R ²³ and R ²⁴ are not both hydrogen atoms.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. R ²¹ and R ²³ , or R ²³ and R ²⁴ may be bonded to form a 5- or 6-membered ring.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
Each group of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ and Q may further have a substituent.
However, general formula (4) has at least one ionic hydrophilic group. The coloring composition according to claim 1, wherein, in the general formula (2), R ⁴ , R ⁸ , R ⁹ and R ¹³ each independently represent a hydrogen atom or an alkyl group. The coloring composition of Claim 1 or 2 in which R < ⁵ > -R < ⁷ >, R < ¹⁰ > -R < ¹² > and R < ¹⁴ > -R < ²³ > represent a hydrogen atom in the said General formula (2). In the general formula (1), D is a residue obtained by removing one hydrogen atom from hydrogen atoms as R ^{5 to} R ⁷ , R ^{10 to} R ¹² and R ²⁴ of the compound represented by the general formula (2). The coloring composition as described in any one of Claims 1-3 which represents. At least one selected from the group consisting of a compound represented by the following general formula (W11) and a compound represented by the general formula (W15);
It is a manufacturing method of the coloring composition containing the compound represented by following General formula (4),
The compound represented by the general formula (W11) is a compound synthesized by a synthesis method including the following (A),
The compound represented by the general formula (W15) is a compound synthesized by a synthesis method including the following (B).
A method for producing a colored composition .
(A) a compound represented by general formula (W9) obtained by converting a sulfo group of a xanthene compound represented by general formula (W8) having a sulfo group into a chlorosulfonyl group; and general formula (W10) Method for synthesizing compound represented by general formula (W11) obtained by hydrolysis of compound obtained by reaction with diamine represented

In the general formula ^{(W8), R 601, R} 602, R 603 and ^{R 604} represents a hydrogen atom or an alkyl ^{group, R 605, R 606, R} 607, R 608 and ^{R 609} represent a ^{substituent, n 601} is represents an integer of ^0~1, n 602 ^{~n 606} is 0.
In general formula (W9), R ⁶⁰¹ , R ⁶⁰² , R ⁶⁰³ , R ⁶⁰⁴ , R ⁶⁰⁵ , R ⁶⁰⁶ , R ⁶⁰⁷ , R ⁶⁰⁸ , R ⁶⁰⁹ , n ⁶⁰¹ , n ⁶⁰² , n ⁶⁰³ are n ⁶⁰⁴ , n ⁶⁰⁵ and n ⁶⁰⁶ is represented by R ⁶⁰¹ , R ⁶⁰² , R ⁶⁰³ , R ⁶⁰⁴ , R ⁶⁰⁵ , R ⁶⁰⁶ , R ⁶⁰⁷ , R ⁶⁰⁸ , R ⁶⁰⁹ , n ⁶⁰¹ , n ⁶⁰² , n ⁶⁰³ in the general formula (W8) , n ⁶⁰⁴ , the same meaning as n ⁶⁰⁵ and ^{n 606.}
In general formula (W10), R ²⁵ and R ²⁶ each independently represent a hydrogen atom.
L ¹ represents a linking group represented by the following general formula (V1), (V2), (V3) or (V4).

(In General Formula (V1), R ¹⁰¹ and R ¹⁰² each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ¹⁰¹ and R ¹⁰² may be bonded to each other to form a ring.
In General Formula (V2), R ²⁰¹ and R ²⁰² each independently represent a hydrogen atom or an alkyl group, and R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring. L ²⁰¹ represents an oxy group (—O—), a thio group (—S—), a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), an imino group (—NH—), a methylene group (—CH ₂ ). -), An arylene group, a cycloalkylene group, and a divalent linking group selected from a group formed by a combination thereof. R ²⁰¹ and R ²⁰² may combine with each other to form a ring.
In general formula (V3), R ³⁰¹ and R ³⁰² each independently represent a hydrogen atom or an alkyl group, and R ³⁰¹ and R ³⁰² may be bonded to each other to form a ring. R ³⁰³ is a hydrogen atom, an amino group, a mono- or dialkylamino group, an arylamino group, or alkylthio group, which may be substituted by further sulfo group, or an ionic hydrophilic group selected from a carboxyl group . X represents an alkylene group having 2 to 20 carbon atoms which may have a methyl group as a substituent, and L ³⁰¹ represents a single bond.
In general formula (V4), R ⁴⁰¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ⁴⁰² each independently represents an ionic hydrophilic group selected from a hydrogen atom, a sulfo group, or a carboxyl group. . )
In general formula (W11), ^R601 , ^R602 , ^R603 , ^R604 , ^R605 , ^R606 , ^R607 , ^R608 , ^R609 , ⁿ⁶⁰¹ , ⁿ⁶⁰² , ⁿ⁶⁰³ , ⁿ⁶⁰⁴ , ⁿ⁶⁰⁵ , n ⁶⁰⁶ , R ²⁵ , R ²⁶ and L ¹ are R ⁶⁰¹ , R ⁶⁰² , R ⁶⁰³ , R ⁶⁰⁴ , R ⁶⁰⁵ , R ⁶⁰⁶ , R ⁶⁰⁷ , R ⁶⁰⁸ , R ⁶⁰⁹ , n ⁶⁰¹ , n in the general formula (W8) ⁶⁰² , n ⁶⁰³ , n ⁶⁰⁴ , n ⁶⁰⁵ , n ⁶⁰⁶ , and R ²⁵ , R ^26, and L ^{1 in} general formula (W10) .
(B) A compound represented by general formula (W13) obtained by chlorosulfonylating a xanthene compound represented by general formula (W12), a polyvalent amine represented by general formula (W14), and the like. Method for synthesizing compound represented by general formula (W15) obtained by hydrolysis of compound obtained by reaction

In general formula (W12), R ⁷⁰¹ , R ⁷⁰² , R ⁷⁰³ and R ⁷⁰⁴ each independently represent a hydrogen atom, R ⁷⁰⁵ , R ⁷⁰⁶ and R ⁷⁰⁷ each represent a substituent, and n ^{701 to} n ⁷⁰³ represent 0. , N ⁷⁰⁴ and n ⁷⁰⁵ each independently represents an integer of 0 to 1.
In general formulas (W13) and (W15), R ⁷⁰¹ , R ⁷⁰² , R ⁷⁰³ , R ⁷⁰⁴ , R ⁷⁰⁵ , R ⁷⁰⁶ , R ⁷⁰⁷ , n ⁷⁰¹ , n ^702, and n ⁷⁰³ are the same as R ^{701 in} general formula (W12). , R ⁷⁰² , R ⁷⁰³ , R ⁷⁰⁴ , R ⁷⁰⁵ , R ⁷⁰⁶ , R ⁷⁰⁷ , n ⁷⁰¹ , n ⁷⁰² and n ⁷⁰³ .
In general formulas (W14) and (W15), R ²⁵ , R ²⁶ and L ¹ have the same meanings as R ²⁵ , R ²⁶ and L ¹ in general formula (W10) .

In the general formula (4), Z ¹ represents an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more.
Z ² represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, or a heterocyclic group.
R ²³ and R ²⁴ are each independently a hydrogen atom, aliphatic group, aromatic group, heterocyclic group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, or Represents a sulfamoyl group. However, R ²³ and R ²⁴ are not both hydrogen atoms.
R ²¹ and R ²² are each independently a hydrogen atom, halogen atom, aliphatic group, aromatic group, heterocyclic group, cyano group, carboxyl group, carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, Hydroxy group, alkoxy group, aryloxy group, silyloxy group, acyloxy group, carbamoyloxy group, heterocyclic oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, alkylamino group, arylamino group, heterocyclic amino group, acylamino Group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkyl or arylsulfonylamino group, aryloxycarbonylamino group, nitro group, alkyl or arylthio Represents alkyl or arylsulfonyl group, an alkyl- or arylsulfinyl group, a sulfamoyl group, a sulfo group or a heterocyclic thio group,. R ²¹ and R ²³ , or R ²³ and R ²⁴ may be bonded to form a 5- or 6-membered ring.
R ²⁵ and R ²⁹ each independently represents an alkyl group, an alkoxy group or a halogen atom. However, when both R ²⁵ and R ²⁹ are alkyl groups, the total number of carbon atoms constituting the alkyl group is 3 or more, and they may be further substituted.
R ²⁶ , R ²⁷ , and R ²⁸ are independently synonymous with R ²¹ and R ^22, and may be mutually condensed at R ²⁵ and R ²⁶ , or R ²⁸ and R ²⁹ .
Q represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.
Each group of Z ¹ , Z ² , R ²¹ , R ²² , R ²³ , R ²⁴ and Q may further have a substituent.
However, general formula (4) has at least one ionic hydrophilic group. Ionic hydrophilic group in the general formula (4) is a sulfo group, a carboxyl group, a phosphono group, and at least one group selected from quaternary ammonium groups, any one of claim 1 to 4 The coloring composition as described. In the general formula (4), independently R ²³ and R ²⁴ are each a hydrogen atom, an aromatic group, or a coloring composition according to any one of claims 1 to 4, 6 represents a hetero group. The coloring composition according to any one of claims 1 to 4 , 6 , and 7 , wherein the content of the compound represented by the general formula (1) is 0.1 to 20% by mass. The colored composition according to any one of claims 1 to 4 and 6 to 8, wherein the content of the compound represented by the general formula (4) is 1 to 5% by mass. The mass ratio of the content of the compound represented by the general formula (1) and the total content of the compound represented by the general formula (4) is 95/5 to 20/80 . The coloring composition as described in any one of 6-9 . Ink for inkjet recording containing the coloring composition as described in any one of Claims 1-4 and 6-10 . An inkjet recording method for forming an image using the colored composition according to any one of claims 1 to 4 and 6 to 10, or the inkjet recording ink according to claim 11.

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