JP6544800B2 - Ink composition, ink jet recording method using the same, and colored body - Google Patents

Description

  The present invention relates to an ink composition which is extremely excellent in ozone gas resistance, an ink jet recording method using the same, and a colored body.

The recording method using an ink jet printer, that is, the ink jet recording method is one of the representative methods among various color recording methods. In the ink jet recording method, droplets of ink are generated and attached to various recording materials (paper, film, fabric, etc.) to perform recording. In this method, since the recording head and the recording material are not in direct contact with each other, the generation of sound is small and quiet. In addition, since it is characterized by its ease of downsizing and speeding up, it has been rapidly spreading in recent years, and significant growth is expected in the future.
Conventionally, aqueous inks in which a water-soluble dye is dissolved in an aqueous medium have been used as fountain pens, felt pens, etc. and inks for inkjet recording. A water-soluble organic solvent is generally added to these aqueous inks in order to prevent clogging of the ink at the pen point and the ink discharge nozzle. In these inks, providing a recorded image of a sufficient density, preventing clogging of the pen tip and the nozzle, good drying property on the recording material, less bleeding, and storage stability Are required to be superior. In addition, the water-soluble dye to be used is required to be particularly high in water solubility and high in water-soluble organic solvent added to the ink. Furthermore, image fastness such as water fastness, light fastness, gas fastness and moisture fastness is required for the formed image.

  Among these, gas resistance refers to the resistance to the phenomenon that ozone gas or the like having an oxidation effect present in the air acts on the pigment on the recording material or in the recording material to discolor the recorded image. It is. Besides ozone gas, NOx, SOx, etc. may be mentioned as the oxidizing gas having this kind of action. However, among these oxidizing gases, ozone gas is considered to be the main cause of promoting the phenomenon of color change of ink jet recorded images, and in particular, ozone gas resistance is regarded as important. An ink receptive layer is provided on the surface of the ink jet paper which can obtain photographic image quality in order to accelerate the drying of the ink and to reduce the bleeding in the high image quality. As a material of the ink receiving layer, a material such as a porous white inorganic substance is often used. Discoloration due to ozone gas or the like is remarkably observed on such a recording sheet. Since the phenomenon of discoloration and fading due to the oxidizing gas is characteristic of ink jet recorded images, improvement of gas resistance, particularly ozone gas resistance, is one of the most important problems in ink jet recording.

  Also, the bronzing phenomenon may be a problem. The bronzing phenomenon is a phenomenon in which a pigment is brought on a metal piece on the surface of a non-recording material to cause glaring due to pigment association, ink absorption failure and the like. When this phenomenon occurs, the gloss, the print quality, and the print density are all inferior. In particular, when a metal phthalocyanine dye is used as a pigment, it often appears as a "red float phenomenon" in a portion where printing is performed at a high density, and the balance as the whole image becomes uneven, which reduces the quality. Dyes that do not cause the phenomenon are desired. Also, in recent years, glossy paper is often used as a recording medium having a texture close to that of a photo, but when a bronzing phenomenon occurs, the gloss on the surface of the recorded material varies, and the texture of the image is significantly impaired. Also from this point of view, dyes that do not cause the bronzing phenomenon are strongly desired. In addition, in this specification, the pigment | dye which does not produce this bronzing phenomenon is described as a pigment | dye which is excellent in bronzing property.

  In the future, in order to expand the field of use of ink jet recording, further improvement in light resistance, gas resistance, moisture resistance, water resistance, bronzing resistance and the like is strongly demanded for ink jet recorded images. In addition to this, as a black image, it is required to be excellent in color rendering. The phenomenon in which the hue appears to change depending on the type of light source is referred to as color rendering, but in general, this phenomenon tends to occur in black dyeings and recorded matter. In the field of dyeing processing, it is common to use a compound having absorption at a long wavelength as a method of improving color rendering, and such methods are disclosed in, for example, Patent Document 6 and Non-Patent Document 1.

  Although inks of various hues are prepared from various dyes, black ink is an important ink used for both mono-color and full-color images. Although many dyes have been proposed as dyes for these black inks, they have not yet been able to provide sufficiently satisfactory market requirements. Many of the proposed dyes are azo dyes, of which C.I. I. Disazo dyes such as Food Black 2 have problems such as poor water resistance and moisture resistance, insufficient light resistance and gas resistance, and high color rendering. Polyazo dyes having extended conjugated systems generally have problems such as low water solubility, a tendency to cause a bronzing phenomenon in which a recorded image partially has metallic gloss, and insufficient light resistance and gas resistance. Moreover, in the case of azo metal-containing pigments, which are also proposed in many cases, some have good light resistance, but because they contain metal ions, they are not preferable for the safety to organisms and environmental problems, and the gas resistance is extremely weak. There is a problem of

  As a black compound (black pigment) for ink jet recording improved about gas resistance which has become the most important subject in recent years, for example, a compound described in Patent Document 1 can be mentioned. Although the gas resistance of these compounds has been improved, they do not sufficiently meet the market requirements. Further, azo compounds having a benzimidazolopyridone skeleton, which is one of the features of the black pigment of the present invention, are disclosed in Patent Documents 3 to 5, and the like. Patent Documents 3 and 4 disclose that a trisazo compound and a water-soluble black compound are used for ink jet recording. Further, Patent Documents 5 and 8 disclose that a tetrakisazo compound and a water-soluble black compound are used for inkjet recording.

International Publication 2005/054374 WO 2004/050768 International Publication 2007/077931 International Publication 2009/069279 JP, 2008-169374, A Unexamined-Japanese-Patent No. 01-284562 JP 2004-75719 A International Publication 2012/081640 International Publication 2014/132926 Processing Technology Vol. 31 No. 9 1996 599-602

  The present invention is particularly excellent in ozone gas resistance when recorded on ink jet paper, and excellent in light resistance and moisture resistance, very high in print density, excellent in bronzing resistance and color rendering, and low in saturation. It is an object of the present invention to provide an ink composition having a high-quality black hue, in particular, an ink composition for inkjet recording.

  As a result of extensive research to solve the problems as described above, the present inventors have found that the azo compound having a specific skeleton has extremely high ozone resistance and solves the problems. The present invention has been completed.

２）
アゾ化合物（Ａ）の分子内におけるアゾ結合（−Ｎ＝Ｎ−）の数が４又は５である上記１）に記載のインク組成物、
３）
上記１）又は２）に記載のアゾ化合物（Ａ）が、下記式（４）で表されるアゾ化合物である上記１）又は２）に記載のインク組成物、

［式（４）中、
Ｒ¹は、（Ｃ１〜Ｃ４）アルキル基；カルボキシ基で置換された（Ｃ１〜Ｃ４）アルキル基；フェニル基；スルホ基で置換されたフェニル基；又は、カルボキシ基；を表し、
Ｒ²はシアノ基；カルバモイル基；又は、カルボキシ基；を表し、
Ｒ³及びＲ⁴は、それぞれ独立して、水素原子；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ハロゲン原子；又は、スルホ基；を表し、
Ｒ⁵は、（Ｃ１〜Ｃ４）アルキルチオ基；ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；又は下記式（５）で表される基を表し、
Ｒ⁶は、（Ｃ１〜Ｃ４）アルキルチオ基；ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；、又は下記式（２）で表される基を表し、
Ｒ⁷は、（Ｃ１〜Ｃ４）アルキルチオ基；ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；又は下記式（５）で表される基を表し、
Ｒ⁸〜Ｒ¹⁰は、それぞれ独立して、水素原子；カルボキシ基；スルホ基；（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；ハロゲン原子；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；、又は下記式（５）で表される基；を表し、
Ｒ¹¹〜Ｒ¹³及びＲ¹⁶は、それぞれ独立して、水素原子；カルボキシ基；スルホ基；ヒドロキシ基；アセチルアミノ基；ハロゲン原子；シアノ基；ニトロ基；スルファモイル基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；（Ｃ１〜Ｃ４）アルキルスルホニル基；、又はヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルスルホニル基；を表す。
ただし、Ｒ⁵〜Ｒ¹⁰のうち、少なくとも１つは下記式（５）で表される基である。
また、破線のベンゼン環は、存在しても、存在しなくても良い。

式（５）中、
Ｒ¹⁴は、少なくとも１つのスルホ基を置換基として有する、アニリノ基；またはナフチルアミノ基；であり、
該アニリノ基またはナフチルアミノ基は、さらにスルホ基；、カルボキシ基；、リン酸基；、スルファモイル基；、カルバモイル基；、ヒドロキシ基；、（Ｃ１〜Ｃ６）アルコキシ基；、アミノ基；、モノ−またはジ−（Ｃ１〜Ｃ６）アルキルアミノ基；、モノ−またはジ−アリールアミノ基；、アセチルアミノ基；、ウレイド基；、（Ｃ１〜Ｃ６）アルキル基；、シアノ基；、ハロゲン原子；、（Ｃ１〜Ｃ６）アルキルスルホニル基；及び（Ｃ１〜Ｃ６）アルキルチオ基から成る群から選択される１種または２種以上の置換基で置換されてもよく、
Ｒ¹⁵は、アニリノ基；、ナフチルアミノ基；、モノ−またはジ−（Ｃ１〜Ｃ６）アルキルアミノ基；、モノ−またはジ−アリールアミノ基；、アミノ基；、（Ｃ１〜６）アルキルチオ基；又はフェニルチオ基；、フェノキシ基；、（Ｃ１〜Ｃ６）アルコキシ基又はヒドロキシ基；であり、Ｒ¹⁵における上記置換基は、さらにスルホ基；、カルボキシ基；、リン酸基；、スルファモイル基；、カルバモイル基；、ヒドロキシ基；、アルコキシ基；、アミノ基；、モノ−またはジ−（Ｃ１〜Ｃ６）アルキルアミノ基；、モノ−またはジ−アリールアミノ基；、アセチルアミノ基；、ウレイド基；、（Ｃ１〜Ｃ６）アルキル基；、フェニル基；、フリル基；、ピリジル基；、シアノ基；、ハロゲン原子；、（Ｃ１〜Ｃ６）アルキルスルホニル基；及び（Ｃ１〜Ｃ６）アルキルチオ基；から成る群から選択される１種または２種以上の置換基で置換されてもよい。また、式（５）中＊は結合位置を表す。]
４）
上記式（４）において、
Ｒ¹は、（Ｃ１〜Ｃ４）アルキル基；又はカルボキシ基で置換された（Ｃ１〜Ｃ４）アルキル基；を表し、
Ｒ²はシアノ基；カルバモイル基；又は、カルボキシ基；を表し、
Ｒ³及びＲ⁴は、それぞれ独立して、水素原子；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ハロゲン原子；又は、スルホ基；を表し、
Ｒ⁵は、（Ｃ１〜Ｃ４）アルキルチオ基；ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ⁶は、ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ⁷は、（Ｃ１〜Ｃ４）アルキルチオ基；ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；を表し、
Ｒ⁸〜Ｒ¹⁰は、それぞれ独立して、水素原子；カルボキシ基；スルホ基；（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；ハロゲン原子；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；、又は前記式（５）で表される基；を表し、
Ｒ¹¹〜Ｒ¹³及びＲ¹⁶は、それぞれ独立して、水素原子；カルボキシ基；スルホ基；ヒドロキシ基；アセチルアミノ基；ハロゲン原子；シアノ基；ニトロ基；スルファモイル基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；（Ｃ１〜Ｃ４）アルキルスルホニル基；、又はヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルスルホニル基；を表す、上記３）に記載のインク組成物。ただし、Ｒ^８〜Ｒ¹⁰のうち、少なくとも１つは前記式（５）で表される基である。
５）
前記式（４）において、
Ｒ¹は、（Ｃ１〜Ｃ４）アルキル基；又はカルボキシ基で置換された（Ｃ１〜Ｃ４）アルキル基；を表し、
Ｒ²はシアノ基；を表し、
Ｒ³及びＲ⁴は、それぞれ独立して、水素原子；（Ｃ１〜Ｃ４）アルコキシ基；又は、スルホ基；を表し、
Ｒ⁵は、ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ⁶は、ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ⁷は、スルホ（Ｃ１〜Ｃ４）アルコキシ基；を表し、
Ｒ⁸及びＲ¹⁰は、それぞれ独立して、（Ｃ１〜Ｃ４）アルキル基；、又は（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；
Ｒ⁹は前記式（５）で表される基であり、
Ｒ¹¹〜Ｒ¹³及びＲ¹⁶は、水素原子；スルホ基；又はニトロ基；である上記３）乃至４）のいずれか一項に記載のインク組成物、
６）
前記式（４）において、
Ｒ¹は、（Ｃ１〜Ｃ４）アルキル基；又はカルボキシ基で置換された（Ｃ１〜Ｃ４）アルキル基；を表し、
Ｒ²はシアノ基；を表し、
Ｒ³及びＲ⁴は、それぞれ独立して、水素原子；（Ｃ１〜Ｃ４）アルコキシ基；又は、スルホ基；を表し、
Ｒ⁵は、ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ⁶は、ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ⁷は、スルホ（Ｃ１〜Ｃ４）アルコキシ基；を表し、
Ｒ⁸、Ｒ¹⁰は、それぞれ独立して、メチル基；又は（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；を表し、
Ｒ⁹は、前記式（５）で表される基；を表し、
Ｒ¹¹〜Ｒ¹³及びＲ¹⁶は、水素原子；スルホ基；又はニトロ基；を表し、
Ｒ¹¹〜Ｒ¹³及びＲ¹⁶のうち少なくとも１つがニトロ基；であり、
前記式（５）において、
Ｒ¹⁴は、少なくとも１つのスルホ基を置換基として有する、アニリノ基であり、
該アニリノ基は、さらにスルホ基；、カルボキシ基；、ヒドロキシ基；、アルコキシ基；、（Ｃ１〜Ｃ６）アルキル基；、シアノ基；、ハロゲン原子；、（Ｃ１〜Ｃ６）アルキルスルホニル基；及び（Ｃ１〜Ｃ６）アルキルチオ基；から成る群から選択される１種または２種以上の置換基で置換されてもよく、
Ｒ¹⁵は、モノまたはジ（Ｃ１〜Ｃ６）アルキルアミノ基；、またはヒドロキシ基；であり、
該（Ｃ１〜Ｃ６）アルキルアミノ基は、さらにスルホ基；、カルボキシ基；、リン酸基；、ヒドロキシ基；、（Ｃ１〜Ｃ６）アルコキシ基；、アセチルアミノ基；、ウレイド基；、（Ｃ１〜Ｃ６）アルキル基；、フェニル基；、シアノ基；、ハロゲン原子；、（Ｃ１〜Ｃ６）アルキルスルホニル基及び（Ｃ１〜Ｃ６）アルキルチオ基；から成る群から選択される１種または２種以上の置換基で置換されてもよい、上記３）乃至５）のいずれか一項に記載のインク組成物、
７）
前記式（４）において、
Ｒ¹がメチル基；、
Ｒ²がシアノ基；、
Ｒ³がメトキシ基；、
Ｒ⁴がスルホ基；、
Ｒ⁵がスルホ（Ｃ１〜Ｃ４）アルキルチオ基；、
Ｒ⁶がスルホ（Ｃ１〜Ｃ４）アルキルチオ基；、
Ｒ⁷がスルホ（Ｃ１〜Ｃ４）アルコキシ基；、
Ｒ⁸が（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；
Ｒ¹⁰がメチル基；
Ｒ^９が上記式（５）で表される基；
Ｒ¹¹乃至Ｒ¹³及びＲ¹⁶のうち、少なくとも１つがニトロ基；、それ以外の３つがそれぞれ独立にスルホ基；、又は水素原子；であり、
前記式（５）において、Ｒ¹⁴が少なくとも１つのスルホ基を置換基として有するアニリノ基；であり、
該アニリノ基は、さらにスルホ基；、カルボキシ基；、ヒドロキシ基；、アルコキシ基；、アルキル基；、シアノ基；、ハロゲン原子；、（Ｃ１〜Ｃ６）アルキルスルホニル基；及び（Ｃ１〜Ｃ６）アルキルチオ基から成る群から選択される１種または２種以上の置換基で置換されてもよく、
Ｒ¹⁵が（Ｃ１〜Ｃ６）アルキルアミノ基；であり、
該（Ｃ１〜Ｃ６）アルキルアミノ基は、さらにスルホ基；、カルボキシ基；、ヒドロキシ基；、（Ｃ１〜Ｃ６）アルコキシ基；、（Ｃ１〜Ｃ６）アルキル基；、フェニル基；、ハロゲン原子；、（Ｃ１〜Ｃ６）アルキルスルホニル基；及び（Ｃ１〜Ｃ６）アルキルチオ基から成る群から選択される１種または２種以上の置換基で置換されてもよい上記３）乃至６）のいずれか一項に記載のインク組成物、
８）
前記式（４）において、
Ｒ¹がメチル基；、
Ｒ²がシアノ基；、
Ｒ³がメトキシ基；、
Ｒ⁴がスルホ基；、
Ｒ⁵がスルホ（Ｃ１〜Ｃ４）アルキルチオ基；、
Ｒ⁶がスルホ（Ｃ１〜Ｃ４）アルキルチオ基；、
Ｒ⁷がスルホ（Ｃ１〜Ｃ４）アルコキシ基；、
Ｒ⁸が（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；
Ｒ¹⁰がメチル基；
Ｒ^９が上記式（５）で表される基；
Ｒ¹¹乃至Ｒ¹³及びＲ¹⁶がニトロ基；、スルホ基；、又は水素原子；であり、前記式（５）において、Ｒ¹⁴が少なくとも１つのスルホ基を置換基として有するアニリノ基；であり、
該アニリノ基は、さらにスルホ基；で置換されてもよく、
Ｒ¹⁵が（Ｃ１〜Ｃ２）アルキルアミノ基；であり、
該（Ｃ１〜Ｃ２）アルキルアミノ基は、さらにスルホ基；で置換されてもよい上記３）乃至７）のいずれか一項に記載のインク組成物、
９）
水溶性有機溶剤をさらに含有する上記１）乃至８）に記載のインク組成物、
１０）
上記１）乃至９）のいずれか一項に記載のインク組成物をインクとして用い、該インクのインク滴を記録信号に応じて吐出させて被記録材に記録を行うインクジェット記録方法、
１１）
被記録材が情報伝達用シートである上記１）０に記載のインクジェット記録方法、
１２）
情報伝達用シートが普通紙又は多孔性白色無機物を含有するインク受容層を有するシ−トである上記１１）に記載のインクジェット記録方法、
１３）
上記１０）又は１１）に記載のインクジェット記録方法により着色された着色体、
１４）
上記１）乃至８）のいずれか一項に記載のインク組成物を含む容器が装填されたインクジェットプリンタ、に関する。 That is, the present invention
1)
Ink composition containing an azo compound (A) having a structure represented by the following formula (1), a structure represented by the following formula (2), and a structure represented by the following formula (3) in one molecule ,

2)
The ink composition according to the above 1), wherein the number of azo bonds (—N = N—) in the molecule of the azo compound (A) is 4 or 5.
3)
The ink composition according to 1) or 2), wherein the azo compound (A) according to 1) or 2) is an azo compound represented by the following formula (4):

[In the formula (4),
R ¹ represents a (C1 to C4) alkyl group; a (C1 to C4) alkyl group substituted with a carboxy group; a phenyl group; a phenyl group substituted with a sulfo group; or a carboxy group;
R ² represents a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ each independently represent a hydrogen atom; (C 1 -C 4) alkyl group; (C 1 -C 4) alkoxy group; halogen atom; or sulfo group;
R ⁵ is, (C1 -C4) alkylthio group; a hydroxy group substituted with at least one group selected from the group consisting of sulfo and carboxy groups (C1 -C4) alkylthio group; (C1 -C4) alkoxy A group (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the following formula (5):
R ⁶ is a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; (C1-C4) alkoxy A group; a (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the following formula (2):
R ⁷ represents a (C 1 -C 4) alkylthio group; a (C 1 -C 4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; A group (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the following formula (5):
R ^{8 to} R ¹⁰ each independently represent a hydrogen atom; carboxy group; sulfo group; (C 1 -C 4) alkylcarbonylamino group; halogen atom; (C 1 -C 4) alkyl group; (C 1 -C 4) alkoxy group; A (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group and a carboxy group; or a compound represented by the following formula (5) Represents a group
R ^{11 to} R ¹³ and R ¹⁶ each independently represent a hydrogen atom, a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, a (C1 to C4) alkyl group (C1 to C4) alkoxy group; (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group and a carboxy group; Or a (C1 to C4) alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group.
However, at least one of R ^{5 to} R ¹⁰ is a group represented by the following formula (5).
Further, the benzene ring indicated by a broken line may or may not be present.

In formula (5),
R ¹⁴ is an anilino group having at least one sulfo group as a substituent; or a naphthylamino group;
The anilino group or the naphthylamino group is further a sulfo group, a carboxy group, a phosphoric acid group, a sulfamoyl group, a carbamoyl group, a hydroxy group, a (C1-C6) alkoxy group, an amino group, a mono- Or a mono- or di-arylamino group; an acetylamino group; a ureido group; a (C1-C6) alkyl group; a cyano group; a halogen atom; And may be substituted with one or more substituents selected from the group consisting of a C1-C6) alkylsulfonyl group; and a (C1-C6) alkylthio group,
R ¹⁵ is an anilino group;, naphthylamino group; mono - or di - (C1 -C6) alkylamino group; a mono - or di - arylamino group; an amino group;, (Cl to 6) alkylthio group; Or a phenylthio group; a phenoxy group; a (C1-C6) alkoxy group or a hydroxy group, and the above-mentioned substituent in R ¹⁵ is further a sulfo group; a carboxy group; a phosphoric acid group; a sulfamoyl group; A hydroxy group; an alkoxy group; an amino group; a mono- or di- (C1-C6) alkylamino group; a mono- or di-arylamino group; an acetylamino group; a ureido group; , A phenyl group, a furyl group, a pyridyl group, a cyano group, a halogen atom, a (C1 to C6) alkylsulfonyl group; It may be substituted by one or more substituents selected from the group consisting of; (C1 -C6) alkylthio group. Moreover, * in Formula (5) represents a coupling | bonding position. ]
4)
In the above equation (4),
R ¹ represents a (C1 to C4) alkyl group; or a (C1 to C4) alkyl group substituted with a carboxy group;
R ² represents a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ each independently represent a hydrogen atom; (C 1 -C 4) alkyl group; (C 1 -C 4) alkoxy group; halogen atom; or sulfo group;
R ⁵ represents a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁶ represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁷ represents a (C 1 -C 4) alkylthio group; a (C 1 -C 4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; A group; a (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ^{8 to} R ¹⁰ each independently represent a hydrogen atom; carboxy group; sulfo group; (C 1 -C 4) alkylcarbonylamino group; halogen atom; (C 1 -C 4) alkyl group; (C 1 -C 4) alkoxy group; A (C1 to C4) alkoxy group substituted by at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group and a carboxy group; or the above formula (5) Represents a group
R ^{11 to} R ¹³ and R ¹⁶ each independently represent a hydrogen atom, a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, a (C1 to C4) alkyl group (C1 to C4) alkoxy group; (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group and a carboxy group; C1 to C4) alkylsulfonyl group; or (C1 to C4) alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; The ink composition as described. However, at least one of R ^{8 to} R ¹⁰ is a group represented by the formula (5).
5)
In the formula (4),
R ¹ represents a (C1 to C4) alkyl group; or a (C1 to C4) alkyl group substituted with a carboxy group;
R ² represents a cyano group;
R ³ and R ⁴ each independently represent a hydrogen atom; (C 1 -C ⁴ ) alkoxy group; or sulfo group;
R ⁵ represents a (C1-C4) alkylthio group substituted by at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁶ represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁷ represents a sulfo (C 1 -C 4) alkoxy group;
R ⁸ and R ¹⁰ each independently represent a (C1-C4) alkyl group; or a (C1-C4) alkylcarbonylamino group;
R ⁹ is a group represented by the above formula (5),
The ink composition according to any one of the above 3) to 4), wherein R ^{11 to} R ¹³ and R ¹⁶ are a hydrogen atom; a sulfo group; or a nitro group;
6)
In the formula (4),
R ¹ represents a (C1 to C4) alkyl group; or a (C1 to C4) alkyl group substituted with a carboxy group;
R ² represents a cyano group;
R ³ and R ⁴ each independently represent a hydrogen atom; (C 1 -C ⁴ ) alkoxy group; or sulfo group;
R ⁵ represents a (C1-C4) alkylthio group substituted by at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁶ represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁷ represents a sulfo (C 1 -C 4) alkoxy group;
R ⁸ and R ¹⁰ each independently represent a methyl group; or (C ¹ -C 4) alkylcarbonylamino group;
R ⁹ represents a group represented by the above formula (5);
R ^{11 to} R ¹³ and R ^{16 each} represent a hydrogen atom; a sulfo group; or a nitro group;
At least one of R ^{11 to} R ¹³ and R ¹⁶ is a nitro group;
In the formula (5),
R ¹⁴ is an anilino group having at least one sulfo group as a substituent,
The anilino group is further a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an (C1-C6) alkyl group, a cyano group, a halogen atom, a (C1-C6) alkyl sulfonyl group; C 1 -C 6) alkylthio group; and may be substituted by one or more substituents selected from the group consisting of
R ¹⁵ is mono- or di (C1 -C6) alkylamino group; or a hydroxy group; a and,
The (C1-C6) alkylamino group is further a sulfo group; a carboxy group; a phosphoric acid group; a hydroxy group; a (C1-C6) alkoxy group; an acetylamino group; a ureido group; C6) alkyl group; phenyl group; cyano group; halogen atom; (C1 to C6) alkylsulfonyl group and (C1 to C6) alkylthio group; one or more substituents selected from the group consisting of The ink composition according to any one of the above 3) to 5), which may be substituted with a group
7)
In the formula (4),
R ¹ is a methyl group;
R ² is a cyano group;
R ³ is a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C 1 -C 4) alkylthio group;
R ⁶ is a sulfo (C ¹ -C 4) alkylthio group;
R ⁷ is a sulfo (C 1 -C 4) alkoxy group;
R ⁸ is a (C 1 -C 4) alkylcarbonylamino group;
R ¹⁰ is a methyl group;
A group wherein R ⁹ is represented by the above formula (5);
At least one of R ^{11 to} R ¹³ and R ¹⁶ is a nitro group, and the other three are each independently a sulfo group; or a hydrogen atom;
An anilino group wherein R ¹⁴ has at least one sulfo group as a substituent in the above formula (5);
The anilino group is further a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an alkyl group, a cyano group, a halogen atom, a (C1 to C6) alkylsulfonyl group, and a (C1 to C6) alkylthio group. It may be substituted by one or more substituents selected from the group consisting of
R ¹⁵ is (C1 -C6) alkylamino group; a,
The (C1-C6) alkylamino group is further a sulfo group; a carboxy group; a hydroxy group; a (C1-C6) alkoxy group; a (C1-C6) alkyl group; a phenyl group; Any one of the above 3) to 6) which may be substituted by one or two or more substituents selected from the group consisting of (C1 to C6) alkylsulfonyl group; and (C1 to C6) alkylthio group The ink composition as described in
8)
In the formula (4),
R ¹ is a methyl group;
R ² is a cyano group;
R ³ is a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C 1 -C 4) alkylthio group;
R ⁶ is a sulfo (C ¹ -C 4) alkylthio group;
R ⁷ is a sulfo (C 1 -C 4) alkoxy group;
R ⁸ is a (C 1 -C 4) alkylcarbonylamino group;
R ¹⁰ is a methyl group;
A group wherein R ⁹ is represented by the above formula (5);
R ^{11 to} R ¹³ and R ^{16 each} is a nitro group, a sulfo group, or a hydrogen atom; and in the formula (5), an anilino group wherein R ¹⁴ has at least one sulfo group as a substituent,
The anilino group may be further substituted with a sulfo group;
R ¹⁵ is (C1 -C2) alkylamino group; a,
The ink composition according to any one of the above 3) to 7), wherein the (C 1 -C 2) alkylamino group may be further substituted with a sulfo group;
9)
The ink composition according to any one of the above 1) to 8), further comprising a water-soluble organic solvent
10)
An inkjet recording method for recording on a recording material by using the ink composition according to any one of the above 1) to 9) as an ink and discharging ink droplets of the ink according to a recording signal,
11)
The inkjet recording method according to the above 1) 0, wherein the recording material is a sheet for information transmission,
12)
11. The ink jet recording method according to 11), wherein the information transmitting sheet is a sheet having a plain paper or an ink receiving layer containing a porous white inorganic substance,
13)
A colored body colored by the ink jet recording method according to the above 10) or 11);
14)
The present invention relates to an inkjet printer loaded with a container containing the ink composition according to any one of the above 1) to 8).

  The ink composition of the present invention has high storage stability, is suitably used as an ink for ink jet recording, and when recorded on paper exclusively for ink jet recording, the printing density is very high, and in particular it is resistant to (ozone) gas. Excellent. Therefore, the ink composition of the present invention is extremely useful as an ink jet recording ink.

Hereinafter, the present invention will be described in detail.
The ink composition of the present invention comprises an azo compound having a structure represented by the formula (1), a structure represented by the formula (2), and a structure represented by the formula (3) in one molecule A) is contained. Since this skeleton is a skeleton that is highly resistant to ozone gas, it is not easily decomposed, and because it is a highly colored skeleton, it provides high printing density. Therefore, the azo compound to be used in the ink composition of the present invention is not particularly limited as long as it has a skeleton represented by the above formulas (1) to (3) in the molecule, and (3) may be directly bonded or may be bonded via another group in between. In addition, since the above formulas (1) to (3) realize the ozone resistance and the color forming property by their basic skeleton, they may have other functional groups on these structures.

  The azo compound used in the ink composition of the present invention preferably has 4 or 5 azo bonds (-N = N-) in the molecule, and particularly preferably 4 azo bonds. This is because, in the case of black ink, which is important as an ink-jet ink, in order to realize a high printing density, it is necessary to extend conjugation. If it has a skeleton represented by the above (1) to (3) in the configuration of the conjugated black azo compound, the ozone gas resistance can also be improved.

As an azo compound which has a structure represented by Formula (1)-(3) in said one molecule, the case where it is an azo compound represented by said Formula (4) is preferable. Although this azo compound may exist in the form of a tautomer or salt, it is described as an azo compound represented by Formula (4) including all these.
Here, examples of tautomers include structures represented by the following formulas (6) and (7), and the like. In the formulas (6) and (7), R ^{1 to} R ¹³ and R ¹⁶ have the same meaning as in the above formula (4).

In the above formula (1), R ¹ represents a (C1 to C4) alkyl group; a (C1 to C4) alkyl group substituted by a carboxy group; a phenyl group; a phenyl group substituted by a sulfo group; Represent.

Examples of the (C1 to C4) alkyl group for R ¹ include linear or branched non-substituted ones, and linear ones are preferable. Specific examples thereof include linear ones such as methyl, ethyl, n-propyl and n-butyl; branched ones such as isopropyl, isobutyl, sec-butyl and tert-butyl And the like. Preferred specific examples include a methyl group and an n-propyl group, and a methyl group is more preferable.

As the (C1-C4) alkyl group substituted by a carboxy group in R ^{1, those} in which any carbon atom of the above-mentioned unsubstituted (C1-C4) alkyl group is substituted with a carboxy group can be mentioned. The position of substitution of the carboxy group is not particularly limited, but is preferably at the end of the alkyl group, and the number of substitution of the carboxy group is one or two, preferably one. Specific examples include carboxymethyl group, 2-carboxyethyl group and the like. Preferred specific examples include a carboxymethyl group.

As R ¹ , a (C1 to C4) alkyl group and a (C1 to C4) alkyl group substituted with a carboxy group are preferable, but a (C1 to C4) alkyl group is more preferable.
More preferably, it is a methyl group or an n-propyl group. Particularly preferred is a methyl group.

In the above formula (1), R ² represents a cyano group; a carbamoyl group; or a carboxy group.

In the above formula (1), R ³ and R ⁴ are each independently a hydrogen atom; (C1 -C4) alkyl; (C1 -C4) alkoxy group; a halogen atom; or a sulfo group; represents a.

In R ³ and R ^4, (C1 -C4) alkyl group, including preferable and (C1 -C4) alkyl group in R ¹ means the same thing.

As the (C1 to C4) alkoxy group in R ³ and R ⁴ , a linear or branched unsubstituted one may be mentioned, and a linear one is preferable. Specific examples thereof include linear ones such as methoxy, ethoxy, n-propoxy and n-butoxy; branched ones such as isopropoxy, isobutoxy, sec-butoxy and tert-butoxy; Etc. Of these, methoxy is more preferred.

Preferred examples of R ³ and R ⁴ include a hydrogen atom, a (C 1 -C ⁴ ) alkoxy group, and a sulfo group, and one of them is a methoxy group, the other is a sulfo group, or either one is a hydrogen atom, the other Is more preferably a combination of sulfo groups. More preferably, one is a combination of a methoxy group and the other is a sulfo group.
The substitution position of R ³ and R ⁴ is not particularly limited, but when any one is a hydrogen atom and the other is a sulfo group, the sulfo group is any of four carbon atoms which do not constitute an imidazole ring of benzimidazolopyridone ring It is preferable to substitute by 2 or more.

The compound represented by the above-mentioned formula (4) of the present invention may be used as a mixture containing at least two kinds of regioisomers at the substitution positions of R ³ and R ⁴ from the viewpoint of easiness of synthesis and low cost. good.

As a preferable combination of R ^{1 to} R ⁴ in the above formula (4), R ¹ is a (C1 to C4) alkyl group (preferably a methyl group or an n-propyl group, more preferably a methyl group) and R ² is a cyano group group, R ³ is a hydrogen atom or a methoxy group, (preferably methoxy), R ⁴ can be mentioned a combination of a sulfo group.

R ⁵ is, (C1 -C4) alkylthio group; a hydroxy group substituted with at least one group selected from the group consisting of sulfo and carboxy groups (C1 -C4) alkylthio group; (C1 -C4) alkoxy A group; a (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the above formula (5).

As R ^5, hydroxy group, a sulfo group and at least one substituted with group (C1 -C4) alkylthio group selected from the group consisting of carboxy groups, of any of (C1 -C4) alkylthio group having a carbon As the atom, those having these substituents can be mentioned. The number of the substituents is usually one or two, preferably one. The position of the substituent is not particularly limited, but it is preferable to substitute a carbon atom other than the carbon atom to which the sulfur atom in the alkylthio group is bonded.
Specific examples thereof include 2-hydroxyethylthio group, 2-hydroxypropylthio group, 3-hydroxypropylthio group, 2-sulfoethylthio group, 3-sulfopropylthio group, 2-carboxyethylthio group, 3 -Carboxypropyl thio group, 4-carboxy butyl thio group, etc. are mentioned.
Among the above, preferable R ⁵ includes sulfo (C 1 to C ⁴ ) alkylthio group or carboxy (C 1 to C ⁴ ) alkylthio group, more preferably sulfo (C 1 to C ⁴ ) alkylthio group, and 3-sulfopropylthio group. Particularly preferred.

As R ^5, hydroxy group, a sulfo group and at least one substituted with group (C1 -C4) alkoxy group is selected from the group consisting of carboxy groups, of any of (C1 -C4) alkoxy group having a carbon As the atom, those having these substituents can be mentioned. The number of the substituents is usually one or two, preferably one. The position of the substituent is not particularly limited, but it is preferable to substitute a carbon atom other than the carbon atom to which the sulfur atom in the alkylthio group is bonded.
Specific examples thereof include 2-hydroxyethoxy group, 2-hydroxypropoxy group, 3-hydroxypropoxy group, 2-sulfoethoxy group, 3-sulfopropoxy group, 2-carboxyethoxy group, 3-carboxypropoxy group, 4 -Carboxybutoxy groups etc. may be mentioned.

The group represented by the above-mentioned formula (5) as R ⁵ is anilino group having at least one sulfo group as a substituent as R ¹⁴ ; or naphthylamino group; as R ¹⁵ anilino group ;, naphthylamino group Mono- or di- (C1-C6) alkylamino group; mono- or di-arylamino group; amino group; (C1-6) alkylthio group; or phenylthio group; phenoxy group; To C6) an alkoxy group or a hydroxy group as a substituent.

Anilino group having at least one sulfo group as a substituent and a naphthylamino group having at least one sulfo group as a substituent as R ¹⁴ are a sulfo group; a carboxy group; a phosphoric acid group; a sulfamoyl group; Carbamoyl group; hydroxy group; (C1-C6) alkoxy group; amino group; mono- or di- (C1-C6) alkylamino group; mono- or di-arylamino group; acetylamino group Ureido group; (C1-C6) alkyl group; cyano group; halogen atom; (C1-C6) alkylsulfonyl group; and (C1-C6) alkylthio group; one or more selected from the group consisting of It may be substituted by two or more types of substituents.

As the (C1 to C6) alkoxy group in the substituent which the anilino group and the naphthylamino group of R ¹⁴ may have, a linear, branched or cyclic C1 to C6, preferably C1 to C4, preferably C1. -C3 alkoxy group is mentioned. Among these, linear or branched ones are preferable, and linear ones are more preferable. Specific examples thereof include linear ones such as methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexyloxy group; isopropoxy group, isobutoxy group, t-butoxy group, isopentoxy group And branched ones such as isohexyloxy group; cyclic ones such as cyclopropoxy group, cyclopentoxy group and cyclohexyloxy group; and the like.

As the mono- (C1 to C6) alkylamino group in the substituent which the anilino group and the naphthylamino group of R ¹⁴ may have, linear or branched mono C1 to C6, preferably mono C1 to C4, Preferably, a C1-C3 alkylamino group is mentioned. Specific examples thereof include linear ones such as methylamino, ethylamino, n-propylamino and n-butylamino; branched ones such as isopropylamino, isobutylamino and t-butylamino; and the like.
Di in R ¹⁴ - The (C1 -C6) alkylamino group, the alkyl mentioned in the monoalkylamino group, dialkylamino groups having two independently. Specific examples include dimethylamino, diethylamino, methylethylamino and the like.

The mono-arylamino group in the substituent which the anilino group and the naphthylamino group of R ¹⁴ may have is a mono (C6 to C10) aromatic amino group, preferably a phenylamino group or a naphthylamino group, more preferably A phenylamino group is mentioned.
As a di-arylamino group in R < ¹⁴ >, the diarylamino group which has independently two aryl mentioned by the said monoaryl amino group is mentioned. Preferably, those having the same aryl, more preferably two phenyl groups are mentioned, and a specific example is a diphenylamino group.

As the (C1 to C6) alkyl group in the substituent which the anilino group and the naphthylamino group of R ¹⁴ may have, a linear, branched or cyclic (C1 to C6), preferably (C1 to C4), Preferably a (C1-C3) alkyl group is mentioned. A linear or branched one is preferable, and a linear one is more preferable. Specific examples thereof include linear ones such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group; isopropyl group, isobutyl group, isopentyl group, isohexyl group and the like And branched ones; cyclic ones such as cyclopropyl, cyclopentyl and cyclohexyl; and the like.

A fluorine atom, a chlorine atom and a bromine atom are mentioned as a halogen atom in the substituent which the anilino group and the naphthylamino group of R ¹⁴ may have, a fluorine atom or a chlorine atom is preferable, and a chlorine atom is more preferable.

The alkylsulfonyl group in the substituent which the anilino group and the naphthylamino group of R ¹⁴ may have is a linear or branched (C1 to C6), preferably (C1 to C4), more preferably (C1 to C4). C3) an alkylsulfonyl group is mentioned. Linear is preferred. Specific examples thereof include linear ones such as methanesulfonyl, ethanesulfonyl and propanesulfonyl; branched ones such as isopropyl sulfonyl; and the like.

The alkylthio group in the substituent which the anilino group and the naphthylamino group of R ¹⁴ may have includes a linear or branched C1-C6, preferably C1-C4, more preferably a C1-C3 alkylthio group. . Linear is preferred. Specific examples thereof include linear ones such as methylthio, ethylthio, propylthio and butylthio; branched ones such as isopropylthio; and the like.

The substituent which the anilino group and the naphthylamino group of R ¹⁴ may have is preferably a sulfo group, a carboxy group, a phosphoric acid group, a hydroxy group, an alkoxy group, an acetylamino group, a ureido group, a nitro group and a chlorine atom. A sulfo group, a carboxy group, a hydroxy group, an alkoxy group, a nitro group and a chlorine atom are more preferable, a sulfo group, a carboxy group, a hydroxy group, a methoxy group, a nitro group and a chlorine atom are more preferable, and a sulfo group is particularly preferable.

R ¹⁵ is an anilino group;, naphthylamino group; mono - or di - (C1 -C6) alkylamino group; a mono - or di - arylamino group; an amino group;, (Cl to 6) alkylthio group; Or a phenylthio group; a phenoxy group; a (C1-C6) alkoxy group; or a hydroxy group.

Mono at R ¹⁵ - or di - (C1 -C6) alkylamino ^group, mono-in substituent that may be possessed by an anilino group and a naphthylamino group ^{R 14} - the same meaning as (C1 -C6) alkylamino group Represent.
(Cl to 6) alkylthio group in R ^{15 represent} the same meaning as (Cl to 6) alkylthio group in the substituent that may be possessed by an anilino group and a naphthylamino group ^{R 14.}
(C1 -C6) alkoxy group in R ^{15 represent} the same meaning as (C1 -C6) alkoxy group in the substituent that may be possessed by an anilino group and a naphthylamino group ^{R 14.}

The above substituent in R ¹⁵ is further a sulfo group, a carboxy group, a phosphate group, a sulfamoyl group, a carbamoyl group, a hydroxy group, a (C1-C6) alkoxy group, an amino group, mono- or Mono- or di-arylamino group; acetylamino group; ureido group; (C1-C6) alkyl group; phenyl group; furyl group; pyridyl group A cyano group; a halogen atom; a (C1-C6) alkylsulfonyl group; and a (C1-C6) alkylthio group; optionally substituted with one or more substituents selected from the group consisting of .

The (C1-C6) alkoxy group which the above-mentioned substituent in R ¹⁵ may have is a linear, branched or cyclic (C1-C6), preferably (C1-C4), more preferably (C1-C6). C3) an alkoxy group is mentioned. A linear or branched one is preferable, and a linear one is more preferable. Specific examples thereof include linear ones such as methoxy group, ethoxy group, n-propoxy group, n-butoxy group, n-pentoxy group, n-hexyloxy group; isopropoxy group, isobutoxy group, t-butoxy group, isopentoxy group And branched ones such as isohexyloxy group; cyclic ones such as cyclopropoxy group, cyclopentoxy group and cyclohexyloxy group; and the like.

As the mono (C1 to C6) alkylamino group which the above-mentioned substituent in R ¹⁵ may have, linear or branched mono C1 to C6, preferably mono C1 to C4, more preferably C1 to C3 alkyl An amino group is mentioned. Specific examples thereof include linear ones such as methylamino, ethylamino, n-propylamino and n-butylamino; branched ones such as isopropylamino, isobutylamino and t-butylamino; and the like.
The substituent may have di in R ¹⁵ - The (C1 -C6) alkylamino group, the alkyl mentioned in the monoalkylamino group, dialkylamino groups having two independently. Specific examples include dimethylamino, diethylamino, methylethylamino and the like.

As a mono-arylamino group which the said substituent in R ¹⁵ may have, a mono (C6-C10) aromatic amino group, Preferably a phenylamino group or a naphthylamino group, More preferably, a phenylamino group is mentioned .
Examples of the di-arylamino group which may be possessed by a mono- or di- (C 1 -C 6) alkylamino group or a mono- or di-arylamino group in R ¹⁵ include the aryls mentioned for the monoarylamino group, The diarylamino group which has two independently is mentioned. Preferred are those having the same aryl, more preferably two phenyl, and specific examples are diphenylamino.

As the (C1 to C6) alkyl group which the above substituent in R ¹⁵ may have, a linear, branched or cyclic (C1 to C6), preferably (C1 to C4), more preferably (C1 to C3) ) Alkyl groups. A linear or branched one is preferable, and a linear one is more preferable. Specific examples thereof include linear ones such as methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group and n-hexyl group; isopropyl group, isobutyl group, isopentyl group, isohexyl group and the like And branched ones; cyclic ones such as cyclopropyl, cyclopentyl and cyclohexyl; and the like.

The halogen atom with which the substituent has the R ^15, a fluorine atom, a chlorine atom and a bromine atom, preferably a fluorine atom or a chlorine atom, a chlorine atom is more preferable.

As the (C1 to C6) alkylsulfonyl group which the above substituent in R ¹⁵ may have, a linear or branched (C1 to C6), preferably (C1 to C4), more preferably (C1 to C3) ) Alkylsulfonyl group is mentioned. Linear is preferred. Specific examples thereof include linear ones such as methanesulfonyl group, ethanesulfonyl group, propanesulfonyl group and the like; branched ones such as isopropylsulfonyl group; and the like.

As the (C1 to C6) alkylthio group which the above substituent in R ¹⁵ may have, a linear or branched (C1 to C6), preferably (C1 to C6), more preferably (C1 to C6) An alkylthio group is mentioned. Linear is preferred. Specific examples thereof include linear ones such as methylthio, ethylthio, propylthio and butylthio; branched ones such as isopropylthio; and the like.

The substituent which the above-mentioned substituent in R ¹⁵ may have is preferably a sulfo group, a carboxy group, a phosphoric acid group, a hydroxy group, an alkoxy group, an acetylamino group, a ureido group, a nitro group and a chlorine atom, and a sulfo group A carboxy group, a hydroxy group, an alkoxy group, a nitro group and a chlorine atom are more preferable, a sulfo group, a carboxy group, a hydroxy group, a methoxy group, a nitro group and a chlorine atom are more preferable, and a sulfo group is particularly preferable.

R ⁶ is a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; (C1-C4) alkoxy A group; a (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the above formula (5).

As R ⁶ , a (C 1 -C 4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group is a hydroxy group, a sulfo group, and a carboxy group in R ⁵ It means the same thing including a preferable thing as a (C1-C4) alkylthio group substituted by at least one kind of group selected from the group consisting of.
The (C1-C4) alkoxy group substituted by at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group as R ⁶ is a hydroxy group, a sulfo group and a carboxy group in R ⁵ It means the same thing including a preferable thing and the (C1-C4) alkoxy group substituted by at least one kind of group selected from the group consisting of.

R ⁷ represents a (C 1 -C 4) alkylthio group; a (C 1 -C 4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; A group; a (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the above formula (5).

(C1-C4) alkylthio group substituted with at least one group selected from the group consisting of hydroxy group, sulfo group and carboxy group in R ⁷ is a group consisting of hydroxy group, sulfo group and carboxy group in R ⁵ And the same as the (C1-C4) alkylthio group substituted with at least one type of group selected from A group (C1-C4) alkoxy substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group in R ⁷ is a group consisting of a hydroxy group, a sulfo group and a carboxy group in R ⁵ And the same as the (C1-C4) alkoxy group substituted with at least one type of group selected from and preferable ones.
The group represented by the above-mentioned formula (5) in R ⁷ has the same meaning as the group represented by the formula (5) in R ⁵ , including preferable ones.
Preferred as R ⁷ is a (C 1 -C 4) alkoxy group substituted by at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group, more preferably a sulfo group (C1 to C4) alkoxy group, particularly preferably 3-sulfopropoxy group.

R ^{8 to} R ¹⁰ each independently represent a hydrogen atom; carboxy group; sulfo group; (C 1 -C 4) alkylcarbonylamino group; halogen atom; (C 1 -C 4) alkyl group; (C 1 -C 4) alkoxy group; A (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group and a carboxy group; or the above formula (5) Represents a group

As the (C1 to C4) alkylcarbonylamino group for R ^{8 to} R ¹⁰ , a linear or branched non-substituted alkyl group is mentioned, and a linear one is preferable. Specific examples thereof include linear ones such as acetylamino (methylcarbonylamino), propionylamino (ethylcarbonylamino), n-propylcarbonylamino, n-butylcarbonylamino and the like; isopropylcarbonylamino, isobutylcarbonylamino, sec And branched ones such as -butylcarbonylamino, pivaloylamino (tert-butylcarbonylamino) and the like. Among these, linear ones are preferable, and acetylamino group is particularly preferable.
As the (C1 to C4) alkoxy group substituted by at least one kind of group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group and a carboxy group in R ^{8 to} R ¹⁰ , And those having any of these substituents at any carbon atom in the C4 alkoxy group can be mentioned. The number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited, but it is preferable to substitute a carbon atom other than the carbon atom to which the oxygen atom in the alkoxy group is bonded. Specific examples thereof include 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy and the like, hydroxy (C1 to C4) alkoxy group; 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy and the like, sulfo ( C1-C4) alkoxy group; 2-carboxyethoxy, 3-carboxypropoxy, 4-carboxybutoxy and the like, carboxy (C1-C4) alkoxy group;
The group represented by the said Formula (5) in R < ⁸ > -R < ¹⁰ > represents the same meaning as the group represented by Formula (5) in R < ⁵ > including a preferable thing.

In R ^{5 to} R ¹⁰ , any one is a group necessarily represented by the above formula (5), preferably a group where any one of R ^{8 to} R ¹⁰ is represented by the above formula (5) More preferably, R ⁹ is a group represented by the above formula (2).

R ^{11 to} R ¹³ each independently represent a hydrogen atom; carboxy group; sulfo group; hydroxy group; acetylamino group; halogen atom; cyano group; nitro group; sulfamoyl group; (C 1 to C 4) alkyl group; -C4) alkoxy group; (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group and a carboxy group; (C1-C4) Or an alkylsulfonyl group; or a (C1-C4) alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group.

The (C1 to C4) alkoxy group substituted by at least one kind of group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group, and a carboxy group in R ^{11 to} R ¹³ is the above R (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group, and a carboxy group in ^{8 to} R ¹⁰ , and preferred The same ones can be mentioned, including
The (C1 -C4) alkylsulfonyl group in R ¹¹ to R ^13, can be mentioned a straight or branched chain, a straight chain is preferred. Specific examples thereof include linear ones such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl and n-butylsulfonyl; branched ones such as isopropylsulfonyl and isobutylsulfonyl; and the like.
Among the above, methylsulfonyl, ethylsulfonyl and isopropylsulfonyl are preferred, and methylsulfonyl is particularly preferred.
As the (C1 to C4) alkylsulfonyl group substituted by at least one type of group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group as a substituent in R ¹¹ to R ¹³ , the above (C 1 to C 4) can be mentioned. Examples of C4) an alkylsulfonyl group include those obtained by substituting the above-mentioned group at any carbon atom, and the number of the substituents is generally 1 or 2, preferably 1. The position of the substituent is not particularly limited. Specific examples thereof include hydroxy-substituted ones such as hydroxyethylsulfonyl and 2-hydroxypropylsulfonyl; sulfo-substituted ones such as 2-sulfoethylsulfonyl and 3-sulfopropylsulfonyl; 2-carboxyethyl sulfonyl and 3-carboxypropyl sulfonyl And the like, such as those substituted with carboxy;

Among the above, preferred examples of R ¹¹ include a hydrogen atom, a carboxy group, a sulfo group, a nitro group, a chlorine atom, a methyl group, a methoxy group and a (C1-C4) alkylsulfonyl group. More preferred are a carboxy group, a sulfo group, a nitro group, a chlorine atom, a (C1-C4) alkylsulfonyl group, or a methyl group and a methoxy group, and a hydrogen atom and a sulfo group are particularly preferred.

Among the above, preferable R ¹² is a hydrogen atom, a carboxy group, a sulfo group, a nitro group, a chlorine atom, a methyl group, a methoxy group, a sulfamoyl group, a (C1 to C4) alkylsulfonyl group, a carboxy (C1 to C4) alkyl And sulfonyl group, sulfo (C 1 -C 4) alkylsulfonyl group, hydrogen atom or carboxy group which is electron withdrawing group, sulfo group, nitro group, chlorine atom, sulfamoyl group, (C 1 -C 4) alkylsulfonyl group, A carboxy (C1 to C4) alkylsulfonyl group, a sulfo (C1 to C4) alkylsulfonyl group, a methyl group or a methoxy group is more preferable, and a sulfo group, a nitro group, a methyl group, a methoxy group, a sulfamoyl group, a sulfopropylsulfonyl group, The carboxyethylsulfonyl group is more preferable, and the nitro group is particularly preferable. Preferred.

Among the above, preferable R ¹³ includes a hydrogen atom, a carboxy group, a sulfo group, a methoxy group, a nitro group, a chlorine atom, and a (C1 to C4) alkylsulfonyl group, and is a hydrogen atom or an electron-withdrawing substituent A carboxy group, a sulfo group, a nitro group, a chlorine atom, a (C1-C4) alkylsulfonyl group or a methoxy group is more preferable, and a hydrogen atom is particularly preferable.

In addition, the dashed benzene ring to which R ¹¹ to R ¹³ are bonded may or may not be present.

Specific examples of preferred combinations in the above formulas (1) and (2) include the following combinations (i) to (v). (Ii) or (iii) is more preferable, and (iv) or (v) is more preferable.
(I)
R ¹ is a methyl group;
R ² is a cyano group;
R ³ is a hydrogen atom; or a methoxy group;
R ⁴ is a sulfo group;
(C1-C4) alkylthio group wherein R ⁵ is substituted with a sulfo group or a carboxy group;
(C1-C4) alkylthio group wherein R ⁶ is substituted with a sulfo group or a carboxy group;
R ⁷ is a sulfo (C 1 -C 4) alkoxy group;
R ⁸ is a (C 1 -C 4) alkylcarbonylamino group;
Group R ⁹ is represented by the following formula (8);,
R ¹⁰ is a methyl group;
R ¹¹ to R ¹³ each independently represent a hydrogen atom; sulfo group; nitro group;
(Ii)
R ¹ is a methyl group;
R ² is a cyano group;
R ³ is a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C 1 -C 4) alkylthio group;
R ⁶ is a sulfo (C ¹ -C 4) alkylthio group;
R ⁷ is a sulfo (C 1 -C 4) alkoxy group;
R ⁸ is a (C 1 -C 4) alkylcarbonylamino group;
Group R ⁹ is represented by the following formula (8);,
R ¹⁰ is a methyl group,
R ¹¹ is a nitro group,
R ¹² is a sulfo group,
R ¹³ is a hydrogen atom (iii)
R ¹ is a methyl group;
R ² is a cyano group;
R ³ is a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C 1 -C 4) alkylthio group;
R ⁶ is a sulfo (C ¹ -C 4) alkylthio group;
R ⁷ is a sulfo (C 1 -C 4) alkoxy group;
R ⁸ is a (C 1 -C 4) alkylcarbonylamino group;
Group R ⁹ is represented by the following formula (8);,
R ¹⁰ is a methyl group,
R ¹¹ is a sulfo group,
R ¹² is a nitro group,
R ¹³ is a hydrogen atom (iv)
R ¹ is a methyl group;
R ² is a cyano group;
R ³ is a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C 1 -C 4) alkylthio group;
R ⁶ is a sulfo (C ¹ -C 4) alkylthio group;
R ⁷ is a sulfopropoxy group; or a sulfobutoxy group;
R ⁸ is an acetylamino group;
Group R ⁹ is represented by the following formula (8);,
R ¹⁰ is a methyl group,
R ¹¹ is a nitro group,
R ¹² is a sulfo group,
R ¹³ is a hydrogen atom (v)
R ¹ is a methyl group;
R ² is a cyano group;
R ³ is a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C 1 -C 4) alkylthio group;
R ⁶ is a sulfo (C ¹ -C 4) alkylthio group;
R ⁷ is a sulfopropoxy group; or a sulfobutoxy group;
R ⁸ is an acetylamino group;
Group R ⁹ is represented by the following formula (8);,
R ¹⁰ is a methyl group,
R ¹¹ is a sulfo group,
R ¹² is a nitro group,
A combination wherein R ¹³ is a hydrogen atom.

  The compound which combined the preferable things described about the various substituent in the said Formula (1), its combination, its substitution position etc. is more preferable, and what combined more preferable things is still more preferable. The same applies to more preferable ones and combinations of preferable ones and more preferable ones.

The tetrakisazo compound of the present invention represented by the above formula (1) can be synthesized, for example, by the following method. In addition, structural formulas of compounds in each step are represented in the form of free acid.
In the following formulas (9) to (16), R ^{1 to} R ¹⁵ have the same meaning as in the above formula (4).
The compound represented by the following formula (9) is diazotized by an ordinary method, and the obtained diazo compound and the compound represented by the following formula (10) are subjected to a coupling reaction by an ordinary method, and the table by the following formula (11) To obtain the compound

  After diazotizing the obtained compound represented by the said Formula (11) by a conventional method, coupling reaction of the obtained diazo compound and the compound represented by following formula (12) is carried out by a conventional method, The compound represented by (13) is obtained.

  After diazotizing the obtained compound represented by the said Formula (13) by a conventional method, coupling reaction of the obtained diazo compound and the compound represented by following formula (14) is carried out by a conventional method, The compound represented by (15) is obtained.

  After diazotizing the obtained compound represented by the said Formula (15) by a conventional method, coupling reaction of the obtained diazo compound and the compound represented by following formula (16) by a conventional method is carried out. The azo compound of the present invention represented by the above formula (4) can be obtained.

  In addition, the compound represented by the said Formula (16) can be synthesize | combined according to the method of the said patent document 3. FIG.

Although it does not specifically limit as a suitable specific example of the azo compound used for this invention, The compound etc. shown by the structural formula listed to following Table 1 thru | or 13 are mentioned.
In each table, functional groups such as sulfo group and carboxy group are conveniently described in the form of free acid. Ac in the following formula represents an acetyl group.

The diazotization of the compounds of the above formula (9) is carried out in a manner known per se, for example nitrites in an inorganic acid medium, for example at a temperature of -5 to 30 ° C, preferably 0 to 15 ° C. It is carried out using alkali metal nitrites such as sodium nitrite.
The coupling of the diazo compound of the compound represented by the formula (9) with the compound represented by the formula (10) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 0 to 25 ° C, and at an acidic to neutral pH value, for example at pH 1 to 6. Since the diazotization reaction solution is acidic and the reaction system is further acidified as the coupling reaction proceeds, the pH value of the reaction solution is adjusted to a preferable pH condition by addition of a base. As a base, for example, alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia, organic amines and the like can be used. .
The compound represented by the above formula (9) and the compound represented by the above formula (10) are used in substantially stoichiometric amounts.

The diazotization of the compounds of the above formula (11) is carried out in a manner known per se, for example nitrites in an inorganic acid medium, for example at a temperature of -5 to 40 ° C, preferably 5 to 30 ° C. It is carried out using alkali metal nitrites such as sodium nitrite.
The coupling of the diazo compound of the compound represented by the formula (11) with the compound represented by the formula (12) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 40 ° C, preferably 10 to 30 ° C, and at an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction solution is acidic and the reaction system is further acidified as the coupling reaction proceeds, the pH value of the reaction solution is adjusted to a preferable pH condition by addition of a base. As the base, the same one as described above can be used.
The compound represented by the formula (11) and the compound represented by the above formula (12) are used in approximately stoichiometric amounts.

The diazotization of the compounds of the above formula (13) is carried out in a manner known per se, for example nitrites in an inorganic acid medium, for example at a temperature of -5 to 50 ° C, preferably 5 to 40 ° C. It is carried out using an alkali metal nitrite such as sodium nitrate.
The coupling of the diazo compound of the compound represented by the formula (13) with the compound represented by the formula (14) is also carried out under conditions known per se. It is advantageously carried out in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 40 ° C, and at an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction solution is acidic and the reaction system is further acidified as the coupling reaction proceeds, the pH value of the reaction solution is adjusted to a preferable pH condition by addition of a base. As the base, the same one as described above can be used.
The compound represented by the above formula (13) and the compound represented by the above formula (14) are used in substantially stoichiometric amounts.

The diazotization of the compounds of the above formula (15) is also carried out in a manner known per se, for example nitrites in mineral acid medium, for example at temperatures of -5 to 50 ° C, preferably 10 to 40 ° C, eg nitrites It is carried out using an alkali metal nitrite such as sodium.
The coupling of the diazo compound of the compound represented by the formula (15) with the compound represented by the formula (16) is also carried out under conditions known per se. It is advantageous to work in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 40 ° C, and at a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example pH 5 to 10, and the adjustment of the pH value is carried out by addition of a base. As the base, the same one as described above can be used.
The compound represented by the above formula (15) and the compound represented by the above formula (16) are used in substantially stoichiometric amounts.

The salt of the azo compound represented by the above formula (4) is a salt with an inorganic or organic cation. Among them, salts with inorganic cations include alkali metal salts, alkaline earth metal salts and ammonium salts, and preferred inorganic salts are salts of lithium, sodium and potassium, and ammonium salts. Moreover, as a salt with an organic cation, although the salt with the quaternary ammonium ion represented, for example by following formula (17) is mentioned, it is not limited to these.
In addition, the free acid of the azo compound of the present invention, its tautomer, and various salts thereof may be a mixture. For example, any combination may be used, such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt, and ammonium salt. Physical properties such as solubility may differ depending on the kind of salt, and it is possible to meet the purpose by selecting the kind of salt as appropriate, or changing the ratio of multiple salts if they are included. A mixture having physical properties can also be obtained.

In the above formula (17), Z ¹ , Z ² , Z ³ and Z ⁴ are each independently selected from the group consisting of a hydrogen atom, an unsubstituted alkyl group, a hydroxyalkyl group and a hydroxyalkoxyalkyl group And at least one is a group other than a hydrogen atom.
Specific examples of the alkyl group of Z ^{1 to} Z ⁴ in the above formula (17) are methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group And the like, and specific examples of the hydroxyalkyl group include a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, and a 2-hydroxy group. And hydroxy (C1 to C4) alkyl groups such as butyl group. Specific examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl and 2-hydroxyethoxypropyl. Group, 4-hydroxyethoxybutyl group, 3-hydroxye group Examples include hydroxy (C1 to C4) alkoxy (C1 to C4) alkyl groups such as a methoxybutyl group and 2-hydroxyethoxybutyl group. Among these, a hydroxyethoxy (C1-C4) alkyl group is preferable. Particularly preferred are a hydrogen atom; methyl group; hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxybutyl group And hydroxy (C1 to C4) alkyl groups such as; hydroxyethoxymethyl group, 2-hydroxyethoxyethyl group, 3-hydroxyethoxypropyl group, 2-hydroxyethoxypropyl group, 4-hydroxyethoxybutyl group, 3-hydroxyethoxybutyl group And hydroxyethoxy (C1-C4) alkyl groups such as 2-hydroxyethoxybutyl group; and the like.

Specific examples of the combination of Z ¹ , Z ² , Z ³ and Z ^{4 in} the preferred compounds represented by the above formula (17) are shown in Table 14 below.

As a method of synthesizing a desired salt of an azo compound (for example, an azo compound represented by the above formula (4)) used in the ink composition of the present invention, a synthesis reaction of a compound represented by the above formula (4) Method of salting out by adding desired inorganic salt or organic quaternary ammonium salt to the reaction solution after completion of the final step; adding mineral acid such as hydrochloric acid to the reaction solution to release the azo compound from the reaction solution After isolation in the form of acid, the obtained free acid is washed with water, acidic water, aqueous organic medium, etc. as necessary to remove impurities such as attached inorganic salts, and again aqueous A method of forming a salt by adding a desired inorganic base or an organic base corresponding to the above quaternary ammonium salt to the free acid in a medium (preferably in water); and the like. By such a method, the salt of the target azo compound can be obtained in the form of a solution or a precipitated solid. Here, acidic water refers to, for example, a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid dissolved in water to make it acidic. In addition, the aqueous organic medium refers to a mixture of water with an organic substance and / or an organic solvent or the like which is all miscible with water.
Examples of the water-miscible organic substance and organic solvent include water-soluble organic solvents described later.
Examples of the inorganic salt used when making the azo compound represented by the above formula (4) into a desired salt include: halogen salts of alkali metals such as lithium chloride, sodium chloride and potassium chloride; lithium carbonate, sodium carbonate, carbonate Carbonates of alkali metals such as potassium; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; halogen salts of ammonium ions such as ammonium chloride and ammonium bromide; ammonium hydroxide (ammonia water) And hydroxides of ammonium ions such as
Moreover, as an example of the salt of an organic cation, the halogen salt of quaternary ammonium ion etc. which are represented by said Formula (17), such as a diethanolamine hydrochloride and a triethanolamine hydrochloride, etc. are mentioned, for example.

  The ink composition of the present invention can dye a material made of cellulose by using an aqueous composition. Further, it is also possible to dye a material having a carbonamide bond, and can be widely used for dyeing of leather, textiles, paper, etc. On the other hand, as a typical usage of the compound of the present invention, an ink composition obtained by dissolving in a liquid medium is mentioned, and it is preferable to use as an ink composition for inkjet recording.

  The reaction liquid containing the compound having the above structures (1) to (3), for example, the reaction liquid after the final step in the synthesis reaction of the compound represented by the above formula (4) is directly used for the production of the ink composition. It can be used. However, the method of drying the reaction solution, for example, spray drying; salting out by adding an inorganic salt such as sodium chloride, potassium chloride, calcium chloride or sodium sulfate to the reaction solution; hydrochloric acid, sulfuric acid to the reaction solution A method of acid precipitation by adding a mineral acid such as nitric acid; or a method of acid precipitation which combines the above-mentioned salting-out and acid precipitation; or the like, and the compound is isolated by a method such as Compositions can also be prepared. The azo compound of the present invention is preferably used after being isolated.

  The ink composition of the present invention is usually 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass, using the azo compound having the above structures (1) to (3) as a pigment. It is an aqueous ink composition containing. The ink composition of the present invention is prepared using water as a medium, and may contain a water-soluble organic solvent or an ink preparation agent, as needed, within the range that does not impair the effects of the present invention. The water-soluble organic solvent may have a function as a dye solubilizer, an anti-drying agent (wetting agent), a viscosity modifier, a penetration accelerator, a surface tension regulator, an antifoamer, etc., and the ink composition of the present invention It is preferable to contain it. Examples of the ink preparation agent include known preservatives, mildewproofing agents, pH adjusters, chelating agents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, antioxidants, surfactants, etc. And additives. The ink composition of the present invention contains 0 to 30% by mass, preferably 5 to 30% by mass, of the water-soluble organic solvent, and 0 to 15% by mass, preferably 0 to 7% by mass of the ink preparation agent based on the total mass. You may contain each%. The remainder other than the above is water. The pH of the ink composition is preferably 5 to 11 and more preferably 7 to 10 from the viewpoint of improving storage stability. The surface tension of the ink composition is preferably 25 to 70 mN / m, and more preferably 25 to 60 mN / m. Furthermore, the viscosity of the ink composition is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less.

The ink composition of the present invention may appropriately contain, for example, other coloring dyes and the like in addition to the azo compound of the present invention, for the purpose of adjusting the subtle shade of black or the like. Even in such a case, the total mass of the dye contained in the ink composition of the present invention may be in the above range with respect to the total mass of the ink composition.
As dyes for color adjustment, yellow (for example, CI Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 161, etc. ), Orange (for example, CI Direct Orange 17, CI Direct Orange 26, CI Direct Orange 29, CI Direct Orange 39, CI Direct Orange 49, etc.), Brown, Scarlet (Eg, CI Direct Red 89, etc.), Red (eg, CI Direct Red 62, CI Direct Red 75, CI Direct Red 79, CI Direct Red 80, CI Direct Red 84, CI Direct Red 225, CI Direct 226, etc.), magenta (eg, CI Direct Red 227), violet, blue, navy, cyan (eg, CI Direct Blue 199, CI Acid Blue 249, etc.), green (eg, Acid Green 1) Other dyes having various hues such as C.I.), black (eg, C. I. Acid Black 2), etc.
The ink composition of the present invention can be used by blending one or more types of these coloring dyes, as long as the effects obtained by the azo compound of the present invention are not impaired. Even in this case, the total amount of dyes contained in the ink composition may be in the above range. Further, the compounding ratio of the azo compound of the present invention to the above-mentioned color-adjusting dye depends on the hue of the color-adjusting dye etc., but it is about 20: 1 to 1: 2, preferably 10: 1 to 1: 1. It is.
When the ink composition of the present invention is used as an ink for ink jet recording, it is preferable to use one having a low content of inorganic impurities such as chlorides and sulfates of metal cations in the azo compound of the present invention. The standard of the content of the inorganic impurities is about 1% by mass or less with respect to the total mass of the dye. The lower limit may be below the detection limit of the analytical instrument, ie 0%. In order to produce the azo compound of the present invention containing a small amount of inorganic impurities, for example, a method using a reverse osmosis membrane; a dried product of the azo compound of the present invention or a wet cake is an alcohol such as methanol, preferably (C1 to C4) alcohol and The suspension purification may be carried out by stirring in a mixed solvent of water, and the precipitate may be desalted by a known method such as a method of filtering and separating and drying the precipitate.

Specific examples of the water-soluble organic solvent that can be used to prepare the ink composition of the present invention include, for example, (C1 to C4) such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol and the like. Alcohols; Carboxylic acid amides such as N, N-dimethylformamide, N, N-dimethylacetamide and the like; 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone, N-methylpyrrolidin-2-one and the like Lactams; Cyclic ureas such as 1,3-dimethylimidazolidin-2-one and 1,3-dimethylhexahydropyrimid-2-one; acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one Such as ketones or keto alcohols; tetrahydrofuran, dioxane, etc. Ethers; ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene Mono-, oligo-, or polyalkylene glycols or thioglycols having C2-C6 alkylene units such as glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, dithiodiglycol; trimethylolpropane, glycerin, hexane-1, Polyols such as 2,6-triol (preferably triol); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol (C1-C4) alkyl ethers of polyhydric alcohols such as monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol) triethylene glycol monomethyl ether, triethylene glycol monoethyl ether; γ-butyrolactone; dimethyl sulfoxide; etc Can be mentioned. These organic solvents may be used alone or in combination of two or more.
Although the above water-soluble organic solvents include substances which are solid at normal temperature, such as trimethylolpropane and the like, they are water-soluble even if they are solid, and when they are dissolved in water As it can be used for the same purpose as the water-soluble organic solvent, it is conveniently described in the category of the water-soluble organic solvent in the present specification.

  Hereinafter, about antiseptic and mildew proofing agents, pH adjusters, chelating agents, rust inhibitors, water soluble ultraviolet absorbers, water soluble polymer compounds, dye solubilizers, antioxidants, and surfactants which can be used as ink preparation agents Describe.

  As the mildew proofing agent, sodium dehydroacetate, sodium benzoate, sodium pyridinethion-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof and the like can be mentioned. It is preferable to use 0.02 to 1.00 mass% of these in the ink composition.

As the preservative, for example, organic sulfur type, organic nitrogen sulfur type, organic halogen type, haloallyl sulfone type, iodopropargyl type, N-haloalkylthio type, nitrile type, pyridine type, 8-oxyquinoline type, benzothiazole Systems, isothiazolines, dithiols, pyridine oxides, nitropropanes, organotins, phenols, quaternary ammonium salts, triazines, thiazines, anilides, anilides, adamantanes, dithiocarbamates, brominated indanones, Compounds such as benzyl bromide acetate type, inorganic salt type and the like can be mentioned.
Specific examples of organic halogen compounds include, for example, pentachlorophenol sodium, specific examples of pyridine oxide compounds include, for example, 2-pyridinethiol-1-oxide sodium, and specific examples of isothiazoline compounds For example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2 -Methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride and the like. Specific examples of other preservatives and fungicides include anhydrous sodium acetate, sodium sorbate and sodium benzoate.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink in the range of approximately 5 to 11 without adversely affecting the prepared ink. Specific examples thereof include: alkanolamines such as diethanolamine, triethanolamine, N-methyldiethanolamine, etc .; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide etc .; ammonium hydroxide (ammonia water) Carbonates of alkali metals such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate and potassium carbonate; alkali metal salts of organic acids such as potassium acetate; and inorganic bases such as sodium silicate and disodium phosphate.

  Specific examples of the chelating agent include, for example, sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracildiacetate and the like.

  Examples of the rust inhibitor include acid sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropyl ammonium nitrite, pentaerythritol tetranitrate, dicyclohexyl ammonium nitrite and the like.

  Examples of the water-soluble UV absorber include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds and triazine compounds.

  Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.

  Examples of the dye solubilizer include ε-caprolactam, ethylene carbonate, urea and the like.

  As the antioxidant, for example, various organic and metal complex antifading agents can be used. Examples of the organic antifading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, amines, chromans, alkoxyanilines, heterocycles, etc. .

Examples of the surfactant include known surfactants such as anionic, cationic and nonionic surfactants.
As an anionic surfactant, alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurine salts, alkyl sulfates Polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfuric acid ester salt, lauryl alcohol sulfuric acid ester salt, alkylphenol type phosphoric acid ester, alkyl type phosphoric acid ester, alkyl aryl sulfonic acid salt, Diethylsulfosuccinate, diethylhexylsulfosuccinate, dioctylsulfoborate and the like can be mentioned.

  As a cationic surfactant, a 2-vinylpyridine derivative, a poly 4-vinylpyridine derivative, etc. are mentioned.

  Amphoteric surfactants such as lauryl dimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, coconut oil fatty acid amidopropyl dimethylaminoacetic acid betaine, polyoctyl polyaminoethyl glycine, imidazoline derivatives, etc. Can be mentioned.

As nonionic surfactants, ethers such as polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, etc .; Esters such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate and the like; 2,4,7,9-Tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octin-3,6-diol, 3,5-dimeth Acetylene glycol (alcohol) type such as l-1-hexyn-3-ol; Nifrin Chemical Co., Ltd., trade name Surfynol 104, 105, 82, 465, orphine STG etc; polyglycol ether type (eg SIGMA-ALDRICH) Tergitol 15-S-7 etc .; and the like.
The above-mentioned ink preparation agents are used alone or in combination.

  The ink composition of the present invention can be obtained by mixing and stirring the above components in any order. The obtained ink composition may optionally be subjected to precision filtration with a membrane filter or the like in order to remove impurities, and when used for ink jet recording, it is preferable to carry out the filtration. The pore size of the filter for microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

  The ink composition of the present invention can be used in various fields, but is suitable for aqueous ink for writing, aqueous printing ink, information recording ink, etc., and it is particularly preferable to use as an ink for inkjet recording, which will be described later. It is suitably used in the ink jet recording method of the present invention.

The ink jet recording method of the present invention is a method of recording by using the ink composition of the present invention as an ink and discharging ink droplets of the ink according to a recording signal to adhere to a recording material. In the inkjet recording method of the present invention, the ink head, the ink nozzle and the like used for recording are not particularly limited, and can be appropriately selected according to the purpose.
This recording method is a known method, for example, a charge control method in which ink is ejected using electrostatic attraction; a drop-on-demand method (pressure pulse method) using an oscillating pressure of a piezo element; an acoustic beam for an electric signal Acoustic ink jet method of irradiating the ink and discharging the ink by utilizing the radiation pressure; thermal ink which heats the ink to form air bubbles and utilizes the generated pressure, so-called bubble jet (registered trademark) method Etc. can be used.

The recording material used in the ink jet recording method of the present invention is not particularly limited, but, for example, a sheet for information transmission such as paper, film, etc., fiber or cloth (cellulose, nylon, wool, etc.), leather, substrate for color filter And the like, and among them, a sheet for information transmission is preferable.
As this information transmission sheet, a sheet subjected to surface treatment, specifically, a sheet provided with an ink receiving layer on a substrate such as paper, synthetic paper, film and the like is preferable. The ink receptive layer may be, for example, impregnating or coating the above-mentioned base material with a cationic polymer; porous white inorganic substances capable of absorbing a pigment in the ink, such as porous silica, alumina sol, special ceramics, etc .; It coats with the hydrophilic polymers, such as pyrrolidone, on the above-mentioned substrate surface;
A sheet for information transmission provided with such an ink receiving layer is usually called an ink jet paper (film), glossy paper (film) or the like. Specific examples thereof include Canon Inc., trade name Professional photo paper, super photo paper or matte photo paper; Seiko Epson Corporation, trade name Photo paper (gloss), PM matte paper, Crispe; Nippon Hewlett-Packard Co., Ltd. Commercially available product names: Advanced Photo Paper, Premium Plus Photo Paper, Premium Glossy Film or Photo Paper; and the like, and they are commercially available. Of course, plain paper can also be used.

  Among the above-mentioned information transmitting sheets, it is known that an image recorded on a sheet coated with a porous white inorganic substance on the surface is particularly discolored and discolored by ozone gas. However, since the ink composition of the present invention is excellent in ozone gas resistance, it exerts a great effect even when ink jet recording is performed on such a recording material.

In order to perform recording on a recording material by the ink jet recording method of the present invention, for example, a container containing the above-described ink composition may be loaded at a predetermined position of an ink jet printer, and recording may be performed on the recording material by the above method.
The ink jet recording method of the present invention comprises the black ink composition of the present invention and, for example, known magenta, cyan, yellow, and optionally green, blue (or violet), red (or orange), etc. as described above. The ink composition of each color may be used in combination.
The ink composition of each color is injected into each container, and each container is loaded at a predetermined position of the ink jet printer and used for ink jet recording, similarly to the container containing the black ink composition of the present invention.

  The colored body of the present invention means a substance colored by the ink composition of the present invention or the recording system. The substance to be colored is not particularly limited, but preferred examples include the recording material used in the above-mentioned ink jet recording method.

The ink composition of the present invention is a water-based black ink composition, is free from solid precipitation, physical property change, color change and the like after storage for a long period of time, and has good storage stability.
The image recorded with the ink composition of the present invention is particularly excellent in ozone gas resistance, high in print density, excellent in bronzing property, low in color rendering property, low in chroma, high quality black hue Have. It is also excellent in various fastness properties such as light resistance, moisture resistance, water resistance and the like. Furthermore, by using the ink composition containing each of the magenta, cyan and yellow dyes in combination, it is possible to perform full color ink jet recording excellent in various fastnesses and excellent in storage stability.
As described above, the ink composition containing the azo compound of the present invention can be used as an ink for ink jet recording, a writing tool, etc., and is excellent in discharge stability, and particularly as an ink for ink jet recording It is suitable.

Hereinafter, the present invention will be specifically described by the synthesis examples, but the present invention is not limited at all by the following synthesis examples.
In the text, "part" and "%" are based on mass unless otherwise specified.
All operations such as synthesis reactions and crystallization were performed under stirring unless otherwise noted. In each of the following formulas, acidic functional groups such as sulfo and carboxy are represented in the form of free acid. The pH value and the reaction temperature in the synthesis reaction were both measured in the reaction system.
In addition, the maximum absorption wavelength (λmax) of the synthesized compound was measured in an aqueous solution at pH 7 to 8, and the measured value was described in the synthesis example for the measured compound.
The azo compounds of the present invention synthesized in the following synthesis examples all showed a solubility of 100 g / liter or more in water.

[(A) Synthesis of dye]
"Composition example 1"
(Step 1)

  In 200 parts of ice water, 18.4 parts of cyanuric chloride and trade name Reokol TD-50 (0.1 part) were added and stirred at 10 ° C. or less for 30 minutes. Next, 31.7 parts of 2,5-disulfoaniline (use a commercially available product with a purity of 88.4%) is added, and adjusted to pH 2.8 to 3.0 with a 10% aqueous sodium hydroxide solution at 0 to 10 ° C. for 2 hours The reaction was performed at 25 to 30 ° C. for 1 hour while adjusting the pH to 2.8 to 3.0. 16.9 parts of 4-chloro- 3-nitro aniline was added to this reaction liquid, and reaction was performed at 40-45 degreeC for 2 hours, setting pH 5.0-5.5 with 10% sodium hydroxide aqueous solution. 18.8 parts of 2-amino ethane sulfonic acid was added to this reaction liquid, and reaction was performed at 70-80 degreeC for 3 hours, setting pH 7.0-7.5 with 10% sodium hydroxide aqueous solution. At this time, the liquid volume was 600 parts. After 120 parts of sodium chloride was added to this solution and stirred for 30 minutes, the precipitated solid was filtered to obtain 193 parts of a wet cake containing a compound represented by the following formula (18).

（工程２）

(Step 2)

  193 parts of the wet cake containing the above formula (18) obtained in step 1 is dissolved in 90 parts of N-methyl-2-pyrrolidone, and 19.1 parts of sodium 3-mercaptopropanesulfonate and potassium carbonate 15. 2 parts were added. After the addition, the mixture was heated to 100 to 110 ° C. and reacted at the same temperature for 2 hours. After cooling to 60 ° C., 150 parts of water was added to the reaction liquid, and the pH was adjusted to 1.0 to 1.5 by the addition of 35% hydrochloric acid. At this time, the liquid volume was 550 parts. After 110 parts of sodium chloride was added to this solution and stirred for 30 minutes, the precipitated solid was separated by filtration to obtain 204 parts of a wet cake containing a compound represented by the following formula (19).

(Step 3)
To 150 parts of water were added 204 parts of a wet cake of the compound represented by the formula (19) obtained in Synthesis Example 1 (Step 2), 5 parts of activated carbon, and 0.6 parts of anhydrous iron (III) chloride After heating to 60 ° C., 11.3 parts of 80% hydrazine hydrate was added dropwise over about 30 minutes. After heating to 90 ° C., the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., insolubles were removed by filtration and the filtrate was cooled to room temperature. The pH was adjusted to 1.0 to 1.5 by the addition of 50% sulfuric acid. At this time, the liquid volume was 625 parts. After 125 parts of sodium chloride was added to this solution and stirred for 30 minutes, the precipitated solid was separated by filtration to obtain 98 parts of a wet cake containing a compound represented by the following formula (20).

(Step 4)
After adding 12.2 parts of sodium 2-amino-5-nitrobenzenesulfonate represented by the following formula (21) to 50 parts of water, the aqueous solution is adjusted to pH 4.0 to 5.0 by the addition of a 25% aqueous sodium hydroxide solution. Obtained. After adding 18.3 parts of 35% hydrochloric acid, 10.5 parts of a 40% aqueous sodium nitrite solution were added, and the reaction was allowed to proceed for about 30 minutes. To this was added 1.5 parts of sulfamic acid, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, 11.0 parts of a compound of the following formula (22) obtained by the method described in WO 2012/081640 is added to 100 parts of water, and the pH is adjusted to 4.0 to 5 by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After dripping, sodium chloride was added after making it react for 3 hours, hold | maintaining pH to 4.0-6.0 by addition of 15% sodium carbonate aqueous solution. The precipitated solid was separated by filtration to obtain 103.8 parts of a wet cake containing a compound represented by the following formula (23).

(Step 5)
After adding the entire amount of the wet cake of the compound represented by the formula (23) obtained in the above Synthesis Example 1 (step 4) to 80 parts of water, adding a 25% aqueous solution of sodium hydroxide to pH 6.0 to 7.0 As an aqueous solution. After 16.5 parts of 35% hydrochloric acid was added, 10.6 parts of 40% aqueous sodium nitrite solution was added, and the reaction was allowed to proceed for about 30 minutes. To this was added 7.5 parts of sulfamic acid, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, after adding 64.7 parts of a wet cake of the compound represented by the formula (20) obtained in the above-mentioned Synthesis Example 1 (step 3) to 100 parts of water, the pH 4. The aqueous solution was obtained as 0-5.0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 3.5 by the addition of a 15% aqueous sodium carbonate solution. Sodium chloride was added to this solution, and the precipitated solid was separated by filtration to obtain 104 parts of a wet cake containing a compound represented by the following formula (24).

(Step 6)
52 parts of wet cakes of the compound represented by Formula (24) obtained by the said synthesis example 1 (process 5) were added to 100 parts of water, and it stirred and melt | dissolved. After the addition of 7.8 parts of 35% hydrochloric acid, 2.8 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. Thereto, 0.8 part of sulfamic acid was added and stirred for 5 minutes to obtain a diazo reaction liquid.
On the other hand, 3.7 parts of a compound of the following formula (25) obtained by the method described in JP-A-2004-083492 is added to 80 parts of water, and a 25% aqueous solution of sodium hydroxide is added to pH 6.0-7. An aqueous solution was obtained as 0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 4.5 by the addition of a 15% aqueous sodium carbonate solution. After the pH was adjusted to 7.0 to 7.5 by the addition of 25% aqueous sodium hydroxide solution, sodium chloride was added. The precipitated solid was separated by filtration to obtain 29.5 parts of a wet cake containing a compound represented by the following formula (26).

(Step 7)
To 80 parts of water, 29.5 parts of a wet cake of the compound represented by the formula (26) obtained in the above-mentioned Synthesis Example 1 (step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.4 parts of a compound of the following formula (27) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 21.5 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain a 12.1 part sodium salt of a compound represented by the following formula (28) of the present invention as a black powder.
λmax: 597 nm.

Synthesis Example 2
(Step 7)
To 80 parts of water, 29.5 parts of a wet cake of the compound represented by the formula (26) obtained in the above-mentioned Synthesis Example 1 (step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.0 parts of a compound of the following formula (29) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 21.5 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain a compound represented by the following formula (30) of the present invention as a black powder as 10.6 parts sodium salt.
λmax: 597 nm.

Synthesis Example 3
(Step 1)
In 200 parts of ice water, 18.4 parts of cyanuric chloride and trade name Reokol TD-50 (0.1 part) were added and stirred at 10 ° C. or less for 30 minutes. Next, 31.7 parts of 2,5-disulfoaniline (use a commercially available product with a purity of 88.4%) is added, and adjusted to pH 2.8 to 3.0 with a 10% aqueous sodium hydroxide solution at 0 to 10 ° C. for 2 hours The reaction was performed at 25 to 30 ° C. for 1 hour while adjusting the pH to 2.8 to 3.0. 16.9 parts of 4-chloro- 3-nitro aniline was added to this reaction liquid, and reaction was performed at 40-45 degreeC for 2 hours, setting pH 5.0-5.5 with 10% sodium hydroxide aqueous solution. 19.6 parts of 3-mercapto propane sulfonic acid was added to this reaction liquid, and reaction was performed at 70-80 degreeC for 3 hours, setting pH 7.0-7.5 with 10% sodium hydroxide aqueous solution. At this time, the liquid volume was 600 parts. After 120 parts of sodium chloride was added to this solution and stirred for 30 minutes, the precipitated solid was filtered to obtain 181 parts of a wet cake containing a compound represented by the following formula (31).

(Step 2)
In 90 parts of N-methyl-2-pyrrolidone, 181 parts of the wet cake containing the above formula (31) obtained in step 1 is dissolved, and 19.1 parts of sodium 3-mercaptopropanesulfonate and potassium carbonate 15. 2 parts were added. After the addition, the mixture was heated to 100 to 110 ° C. and reacted at the same temperature for 2 hours. After cooling to 60 ° C., 150 parts of water was added to the reaction liquid, and the pH was adjusted to 1.0 to 1.5 by the addition of 35% hydrochloric acid. At this time, the liquid volume was 525 parts. After adding 105 parts of sodium chloride to this solution and stirring for 30 minutes, the precipitated solid was separated by filtration to obtain 218 parts of a wet cake containing a compound represented by the following formula (32).

(Step 3)
To 150 parts of water were added 218 parts of a wet cake of the compound represented by the formula (32) obtained in the above Synthesis Example 1 (step 2), 5 parts of activated carbon, and 0.6 parts of anhydrous iron (III) chloride After heating to 60 ° C., 11.3 parts of 80% hydrazine hydrate was added dropwise over about 30 minutes. After heating to 90 ° C., the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., insolubles were removed by filtration and the filtrate was cooled to room temperature. The pH was adjusted to 1.0 to 1.5 by the addition of 50% sulfuric acid. At this time, the liquid volume was 625 parts. After 125 parts of sodium chloride was added to this solution and stirred for 30 minutes, the precipitated solid was separated by filtration to obtain 112 parts of a wet cake containing a compound represented by the following formula (33).

(Step 5)
After adding the entire amount of the wet cake of the compound represented by the formula (23) obtained in the above Synthesis Example 1 (step 4) to 80 parts of water, adding a 25% aqueous solution of sodium hydroxide to pH 6.0 to 7.0 As an aqueous solution. After 16.5 parts of 35% hydrochloric acid was added, 10.6 parts of 40% aqueous sodium nitrite solution was added, and the reaction was allowed to proceed for about 30 minutes. To this was added 7.5 parts of sulfamic acid, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, 73.9 parts of a wet cake of the compound represented by the formula (33) obtained in the above-mentioned Synthesis Example 3 (step 3) was added to 100 parts of water, and then a 25% aqueous sodium hydroxide solution was added to adjust pH4. The aqueous solution was obtained as 0-5.0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 3.5 by the addition of a 15% aqueous sodium carbonate solution. Sodium chloride was added to this solution, and the precipitated solid was separated by filtration to obtain 99 parts of a wet cake containing a compound represented by the following formula (34).

(Step 6)
To 100 parts of water, 49.5 parts of a wet cake of the compound represented by the formula (34) obtained in the above-mentioned Synthesis Example 3 (Step 5) was added, stirred and dissolved. After the addition of 7.8 parts of 35% hydrochloric acid, 2.8 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. Thereto, 0.8 part of sulfamic acid was added and stirred for 5 minutes to obtain a diazo reaction liquid.
On the other hand, 3.7 parts of the compound of the above formula (25) obtained by the method described in JP-A No. 2004-083492 is added to 80 parts of water, and a pH of 6.0 to 7 is added by the addition of a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 4.5 by the addition of a 15% aqueous sodium carbonate solution. After the pH was adjusted to 7.0 to 7.5 by the addition of 25% aqueous sodium hydroxide solution, sodium chloride was added. The precipitated solid was separated by filtration to obtain 31.2 parts of a wet cake containing a compound represented by the following formula (35).

(Step 7)
To 80 parts of water, 31.2 parts of a wet cake of the compound represented by the formula (35) obtained in the above-mentioned Synthesis Example 3 (Step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.0 parts of the compound of the above formula (29) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 20.3 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain 11.2 parts of a compound represented by the following formula (36) of the present invention as a black powder as a sodium salt.
λmax: 590 nm.

Synthesis Example 4
(Step 7)
To 80 parts of water, 31.2 parts of a wet cake of the compound represented by the formula (35) obtained in the above-mentioned Synthesis Example 3 (Step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.4 parts of the compound of the above formula (29) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 20.3 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain a compound represented by the following formula (37) of the present invention as a black powder as 9.5 parts of a sodium salt.
λmax: 597 nm.

Synthesis Example 5

(Step 4)
After adding 12.2 parts of sodium 2-amino-5-nitrobenzenesulfonate represented by the above formula (21) to 50 parts of water, the aqueous solution is adjusted to pH 4.0 to 5.0 by the addition of a 25% aqueous sodium hydroxide solution. Obtained. After adding 18.3 parts of 35% hydrochloric acid, 10.5 parts of a 40% aqueous sodium nitrite solution were added, and the reaction was allowed to proceed for about 30 minutes. To this was added 1.5 parts of sulfamic acid, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, 64.7 parts of a wet cake of the compound represented by the formula (20) obtained in the above-mentioned Synthesis Example 1 (step 3) is added to 100 parts of water, and the pH 4. The aqueous solution was obtained as 0-5.0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After dripping, sodium chloride was added after making it react for 3 hours, hold | maintaining pH to 4.0-6.0 by addition of 15% sodium carbonate aqueous solution. The precipitated solid was separated by filtration to obtain 141.2 parts of a wet cake containing a compound represented by the following formula (38).

(Step 5)
After adding the whole amount of the wet cake of the compound represented by the formula (38) obtained in the above Synthesis Example 5 (step 4) to 80 parts of water, pH 6.0 to 7.0 by addition of a 25% aqueous solution of sodium hydroxide As an aqueous solution. After 16.5 parts of 35% hydrochloric acid was added, 10.6 parts of 40% aqueous sodium nitrite solution was added, and the reaction was allowed to proceed for about 30 minutes. To this was added 7.5 parts of sulfamic acid, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, 11.0 parts of the compound of the above formula (22) obtained by the method described in WO 2012/081640 is added to 100 parts of water, and the pH is adjusted to 4.0 to 5 by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 3.5 by the addition of a 15% aqueous sodium carbonate solution. Sodium chloride was added to this solution, and the precipitated solid was separated by filtration to obtain 110 parts of a wet cake containing a compound represented by the following formula (39).

(Step 6)
To 100 parts of water, 55 parts of a wet cake of the compound represented by the formula (39) obtained in the above-mentioned Synthesis Example 1 (Step 5) was added, stirred and dissolved. After the addition of 7.8 parts of 35% hydrochloric acid, 2.8 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. Thereto, 0.8 part of sulfamic acid was added and stirred for 5 minutes to obtain a diazo reaction liquid.
On the other hand, 7.7 parts of the compound of the above formula (25) obtained by the method described in JP-A No. 2004-083492 is added to 80 parts of water, and the pH is adjusted to 6.0 to 7 by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 4.5 by the addition of a 15% aqueous sodium carbonate solution. After the pH was adjusted to 7.0 to 7.5 by the addition of 25% aqueous sodium hydroxide solution, sodium chloride was added. The precipitated solid was separated by filtration to obtain 65 parts of a wet cake containing a compound represented by the following formula (40).

(Step 7)
32.5 parts of wet cakes of the compound represented by Formula (40) obtained by the said synthesis example 1 (process 6) were added to 80 parts of water, and it stirred and melt | dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.4 parts of the compound of the above formula (27) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 21.5 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain a compound represented by the following formula (41) of the present invention as a black powder as 12.5 parts of a sodium salt.
λmax: 602 nm.

Synthesis Example 6
(Step 7)
To 80 parts of water, 32.5 parts of a wet cake of the compound represented by the formula (41) obtained in the above-mentioned Synthesis Example 6 (step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.0 parts of the compound of the above formula (27) obtained by the method described in International Publication 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 21.5 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain a compound represented by the following formula (42) of the present invention as a black powder as a 12.5 part sodium salt.
λmax: 591 nm.

Synthesis Example 7
(Step A)
18.6 parts of 4-amino-2-nitrophenol was added to 80 parts of acetone and dissolved. Next, 11.5 parts of acetic anhydride were added, and reaction was performed at 50 to 55 ° C. for 2 hours. After adding 200 parts of water to this reaction liquid and stirring for 30 minutes, the precipitated solid was filtered to obtain 32.1 parts of a wet cake containing a compound represented by the following formula (43).

(Step B)
32.1 parts of a wet cake containing the above formula (43) obtained in step A is dissolved in 50 parts of N-methyl-2-pyrrolidone, and 19.3 parts of propane sultone and 21.8 parts of potassium carbonate are dissolved therein. Added. After the addition, the mixture was heated to 100 to 110 ° C. and reacted at the same temperature for 2 hours. After cooling to 60 ° C., 44 parts of water and 44 parts of 35% hydrochloric acid were added to the reaction solution. After the addition, the temperature was raised to 100 ° C., and the reaction was carried out at the same temperature for 3 hours. After the reaction, the reaction solution was cooled to 5 ° C., and the precipitated solid was filtered and dried to obtain 34.3 parts of a compound represented by the following formula (44).

(Step 1)
In 200 parts of ice water, 18.4 parts of cyanuric chloride and trade name Reokol TD-50 (0.1 part) were added and stirred at 10 ° C. or less for 30 minutes. Next, 32.1 parts of 2,5-disulfoaniline (use a commercial product having a purity of 88.4%) are added, and the pH is adjusted to 2.8 to 3.0 with a 10% aqueous sodium hydroxide solution at 0 to 10 ° C for 2 hours The reaction was performed at 25 to 30 ° C. for 1 hour while adjusting the pH to 2.8 to 3.0. To this reaction solution is added 30.4 parts of the above formula (44) obtained in Synthesis Example 7 (Step B), and adjusted to pH 5.0 to 5.5 with a 10% aqueous sodium hydroxide solution at 40 to 45 ° C. for 2 hours The reaction was done. To this reaction solution was added 20.6 parts of 2-aminoethanesulfonic acid, and the reaction was allowed to proceed at 70-80 ° C. for 3 hours while adjusting to pH 7.0-7.5 with a 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 600 parts. After 120 parts of sodium chloride was added to this solution and stirred for 30 minutes, the precipitated solid was filtered to obtain 78.1 parts of a wet cake containing a compound represented by the following formula (45).

(Step 2)
In 150 parts of water, 78.1 parts of a wet cake of the compound represented by the formula (45) obtained in the above Synthesis Example 7 (Step 1), 5 parts of activated carbon, and 0.6 parts of anhydrous iron (III) chloride After addition and heating to 60 ° C., 12.6 parts of 80% hydrazine hydrate was added dropwise over about 30 minutes. After heating to 90 ° C., the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., insolubles were removed by filtration and the filtrate was cooled to room temperature. The pH was adjusted to 1.0 to 1.5 by the addition of 50% sulfuric acid. At this time, the liquid volume was 625 parts. After adding 200 parts of methanol to this solution and stirring for 30 minutes, the precipitated solid was filtered and dried to obtain 43 parts of a compound represented by the following formula (46).

(Step 5)
After adding the entire amount of the wet cake of the compound represented by the formula (23) obtained in the above Synthesis Example 1 (step 4) to 80 parts of water, adding a 25% aqueous solution of sodium hydroxide to pH 6.0 to 7.0 As an aqueous solution. After 16.5 parts of 35% hydrochloric acid was added, 10.6 parts of 40% aqueous sodium nitrite solution was added, and the reaction was allowed to proceed for about 30 minutes. To this was added 7.5 parts of sulfamic acid, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, 11.0 parts of the compound of the above formula (22) obtained by the method described in WO 2012/081640 is added to 100 parts of water, and then a 25% aqueous solution of sodium hydroxide is added to 100 parts of water. The aqueous solution was obtained as pH 4.0-5.0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 3.5 by the addition of a 15% aqueous sodium carbonate solution. Sodium chloride was added to this solution, and the precipitated solid was separated by filtration to obtain 95 parts of a wet cake containing a compound represented by the following formula (47).

(Step 6)
To 100 parts of water, 47.5 parts of a wet cake of the compound represented by the formula (47) obtained in the above Synthesis Example 7 (Step 5) was added, stirred and dissolved. After the addition of 7.8 parts of 35% hydrochloric acid, 2.8 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. Thereto, 0.8 part of sulfamic acid was added and stirred for 5 minutes to obtain a diazo reaction liquid.
On the other hand, 20.2 parts of the compound of the formula (46) obtained in the above Synthesis Example 7 (step 2) is added to 80 parts of water, and the pH is adjusted to 6.0 to 7.0 by the addition of a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 4.5 by the addition of a 15% aqueous sodium carbonate solution. After the pH was adjusted to 7.0 to 7.5 by the addition of 25% aqueous sodium hydroxide solution, sodium chloride was added. The precipitated solid was separated by filtration to obtain 30.3 parts of a wet cake containing a compound represented by the following formula (48).

(Step 7)
To 80 parts of water, 15.1 parts of a wet cake of the compound represented by the formula (48) obtained in the above-mentioned Synthesis Example 7 (Step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.4 parts of the compound of the above formula (22) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 29 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain 6.2 parts of a compound represented by the following formula (49) of the present invention as a black powder as a sodium salt.
λmax: 638 nm.

Synthesis Example 8
(Step 7)
To 80 parts of water, 15.1 parts of a wet cake of the compound represented by the formula (49) obtained in the above-mentioned Synthesis Example 7 (Step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.0 parts of a compound of the following formula (22) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 21.5 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain a compound represented by the following formula (50) of the present invention as a black powder as 4.2 parts of a sodium salt.
λmax: 630 nm.

Synthesis Example 9
(Step 1)
In 200 parts of ice water, 18.4 parts of cyanuric chloride and trade name Reokol TD-50 (0.1 part) were added and stirred at 10 ° C. or less for 30 minutes. Next, 31.7 parts of 2,5-disulfoaniline (use a commercially available product with a purity of 88.4%) is added, and adjusted to pH 2.8 to 3.0 with a 10% aqueous sodium hydroxide solution at 0 to 10 ° C. for 2 hours The reaction was performed at 25 to 30 ° C. for 1 hour while adjusting the pH to 2.8 to 3.0. 16.9 parts of 4-chloro- 3-nitro aniline was added to this reaction liquid, and reaction was performed at 40-45 degreeC for 2 hours, setting pH 5.0-5.5 with 10% sodium hydroxide aqueous solution. 123 parts of nicotinic acid were added to this reaction liquid, and reaction was performed at 90 to 95 ° C. for 5 hours while adjusting to pH 9.0 to 9.2 with 10% aqueous sodium hydroxide solution. At this time, the liquid volume was 600 parts. After adding 120 parts of sodium chloride to this solution and stirring for 90 minutes, the pH is adjusted to 2.0 to 2.5 with 35% hydrochloric acid, and the precipitated solid is filtered to obtain a compound represented by the following formula (51) There were obtained 181 parts of a wet cake.

（工程２）

(Step 2)

  A wet cake containing 181 parts of the above formula (51) obtained in step 1 is dissolved in 90 parts of N-methyl-2-pyrrolidone, and 19.1 parts of sodium 3-mercaptopropanesulfonate and potassium carbonate 15. 2 parts were added. After the addition, the mixture was heated to 100 to 110 ° C. and reacted at the same temperature for 2 hours. After cooling to 60 ° C., 150 parts of water was added to the reaction liquid, and the pH was adjusted to 1.0 to 1.5 by the addition of 35% hydrochloric acid. At this time, the liquid volume was 525 parts. After adding 105 parts of sodium chloride to this solution and stirring for 30 minutes, the precipitated solid was separated by filtration to obtain 205 parts of a wet cake containing a compound represented by the following formula (52).

(Step 3)
To 150 parts of water, add 218 parts of a wet cake of the compound represented by the formula (52) obtained in Step 2, 5 parts of activated carbon, and 0.6 parts of anhydrous iron (III) chloride, and after heating to 60 ° C. 11.3 parts of 80% hydrazine hydrate was added dropwise over about 30 minutes. After heating to 90 ° C., the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., insolubles were removed by filtration and the filtrate was cooled to room temperature. The pH was adjusted to 1.0 to 1.5 by the addition of 50% sulfuric acid. At this time, the liquid volume was 625 parts. After 125 parts of sodium chloride was added to this solution and stirred for 30 minutes, the precipitated solid was separated by filtration to obtain 98 parts of a wet cake containing a compound represented by the following formula (53).

(Step 5)
After adding the entire amount of the wet cake of the compound represented by the formula (23) obtained in the above Synthesis Example 1 (step 4) to 80 parts of water, adding a 25% aqueous solution of sodium hydroxide to pH 6.0 to 7.0 As an aqueous solution. After 16.5 parts of 35% hydrochloric acid was added, 10.6 parts of 40% aqueous sodium nitrite solution was added, and the reaction was allowed to proceed for about 30 minutes. To this was added 7.5 parts of sulfamic acid, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, after adding 64.7 parts of a wet cake of the compound represented by the formula (53) obtained in the above Synthesis Example 9 (Step 3) to 100 parts of water, pH 25 was obtained by the addition of a 25% aqueous sodium hydroxide solution. The aqueous solution was obtained as 0-5.0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 3.5 by the addition of a 15% aqueous sodium carbonate solution. Sodium chloride was added to this solution, and the precipitated solid was separated by filtration to obtain 92 parts of a wet cake containing a compound represented by the following formula (54).

(Step 6)
To 100 parts of water, 46 parts of a wet cake of a compound represented by the formula (54) obtained in the above-mentioned Synthesis Example 9 (Step 5) was added, stirred and dissolved. After the addition of 7.8 parts of 35% hydrochloric acid, 2.8 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. Thereto, 0.8 part of sulfamic acid was added and stirred for 5 minutes to obtain a diazo reaction liquid.
On the other hand, 3.7 parts of the compound of the above formula (25) obtained by the method described in JP-A No. 2004-083492 is added to 80 parts of water, and a pH of 6.0 to 7 is added by the addition of a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 4.5 by the addition of a 15% aqueous sodium carbonate solution. After the pH was adjusted to 7.0 to 7.5 by the addition of 25% aqueous sodium hydroxide solution, sodium chloride was added. The precipitated solid was separated by filtration to obtain 35.2 parts of a wet cake containing a compound represented by the following formula (55).

(Step 7)
To 80 parts of water, 35.2 parts of a wet cake of the compound represented by the formula (55) obtained in the above Synthesis Example 9 (Step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.4 parts of the compound of the above formula (27) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 20.9 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain 10.2 parts of a compound represented by the following formula (56) of the present invention as a black powder as a sodium salt.
λmax: 590 nm.

Synthesis Example 10
(Step 1)
In 200 parts of ice water, 18.4 parts of cyanuric chloride and trade name Reokol TD-50 (0.1 part) were added and stirred at 10 ° C. or less for 30 minutes. Next, 31.7 parts of 2,5-disulfoaniline (use a commercially available product with a purity of 88.4%) is added, and adjusted to pH 2.8 to 3.0 with a 10% aqueous sodium hydroxide solution at 0 to 10 ° C. for 2 hours The reaction was performed at 25 to 30 ° C. for 1 hour while adjusting the pH to 2.8 to 3.0. 16.9 parts of 4-chloro- 3-nitro aniline was added to this reaction liquid, and reaction was performed at 40-45 degreeC for 2 hours, setting pH 5.0-5.5 with 10% sodium hydroxide aqueous solution. 16.1 parts of benzylamines were added to this reaction liquid, and reaction was performed at 90-95 degreeC for 5 hours, setting pH 9.0-9.2 in 10% sodium hydroxide aqueous solution. At this time, the liquid volume was 600 parts. After adding 120 parts of sodium chloride to this solution and stirring for 90 minutes, the pH is adjusted to 2.0 to 2.5 with 35% hydrochloric acid, and the precipitated solid is filtered to obtain a compound represented by the following formula (57) 121 parts of wet cakes were obtained.

（工程２）

(Step 2)

  121 parts of the wet cake containing the above formula (57) obtained in step 1 is dissolved in 90 parts of N-methyl-2-pyrrolidone, and 19.1 parts of sodium 3-mercaptopropanesulfonate and potassium carbonate 15. 2 parts were added. After the addition, the mixture was heated to 100 to 110 ° C. and reacted at the same temperature for 2 hours. After cooling to 60 ° C., 150 parts of water was added to the reaction liquid, and the pH was adjusted to 1.0 to 1.5 by the addition of 35% hydrochloric acid. At this time, the liquid volume was 525 parts. After adding 105 parts of sodium chloride to this solution and stirring for 30 minutes, the precipitated solid was separated by filtration to obtain 153 parts of a wet cake containing a compound represented by the following formula (58).

(Step 3)
Add 153 parts of a wet cake of the compound represented by the formula (58) obtained in step 2, 5 parts of activated carbon, and 0.6 parts of anhydrous iron (III) chloride to 150 parts of water, and heat to 60 ° C. 11.3 parts of 80% hydrazine hydrate was added dropwise over about 30 minutes. After heating to 90 ° C., the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., insolubles were removed by filtration and the filtrate was cooled to room temperature. The pH was adjusted to 1.0 to 1.5 by the addition of 50% sulfuric acid. At this time, the liquid volume was 625 parts. After 125 parts of sodium chloride was added to this solution and stirred for 30 minutes, the precipitated solid was separated by filtration to obtain 121 parts of a wet cake containing a compound represented by the following formula (59).

(Step 4)
After adding the entire amount of the wet cake of the compound represented by the formula (23) obtained in the above Synthesis Example 1 (step 4) to 80 parts of water, adding a 25% aqueous solution of sodium hydroxide to pH 6.0 to 7.0 As an aqueous solution. After 16.5 parts of 35% hydrochloric acid was added, 10.6 parts of 40% aqueous sodium nitrite solution was added, and the reaction was allowed to proceed for about 30 minutes. To this was added 7.5 parts of sulfamic acid, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, 79.9 parts of a wet cake of the compound represented by the formula (59) obtained in the above-mentioned Synthesis Example 10 (step 3) is added to 100 parts of water, and then a 25% aqueous solution of sodium hydroxide is added to pH4. The aqueous solution was obtained as 0-5.0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 3.5 by the addition of a 15% aqueous sodium carbonate solution. Sodium chloride was added to this solution, and the precipitated solid was separated by filtration to obtain 84 parts of a wet cake containing a compound represented by the following formula (60).

(Step 5)
To 100 parts of water, 42 parts of a wet cake of a compound represented by the formula (60) obtained in the above Synthesis Example 10 (Step 5) was added, stirred and dissolved. After the addition of 7.8 parts of 35% hydrochloric acid, 2.8 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. Thereto, 0.8 part of sulfamic acid was added and stirred for 5 minutes to obtain a diazo reaction liquid.
On the other hand, 3.7 parts of the compound of the above formula (25) obtained by the method described in JP-A No. 2004-083492 is added to 80 parts of water, and a pH of 6.0 to 7 is added by the addition of a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 4.5 by the addition of a 15% aqueous sodium carbonate solution. After the pH was adjusted to 7.0 to 7.5 by the addition of 25% aqueous sodium hydroxide solution, sodium chloride was added. The precipitated solid was separated by filtration to obtain 39 parts of a wet cake containing a compound represented by the following formula (61).

(Step 7)
To 80 parts of water, 39 parts of a wet cake of the compound represented by the formula (61) obtained in the above-mentioned Synthesis Example 10 (Step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.4 parts of the compound of the above formula (27) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 20.9 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain a compound represented by the following formula (62) of the present invention as a black powder as a 8.5 part sodium salt.
λmax: 590 nm.

[合成例１１]
（工程１）

Synthesis Example 11
(Step 1)

  In 200 parts of ice water, 18.4 parts of cyanuric chloride and trade name Reokol TD-50 (0.1 part) were added and stirred at 10 ° C. or less for 30 minutes. Next, 31.7 parts of 2,5-disulfoaniline (use a commercially available product with a purity of 88.4%) is added, and adjusted to pH 2.8 to 3.0 with a 10% aqueous sodium hydroxide solution at 0 to 10 ° C. for 2 hours The reaction was performed at 25 to 30 ° C. for 1 hour while adjusting the pH to 2.8 to 3.0. 16.9 parts of 4-chloro- 3-nitro aniline was added to this reaction liquid, and reaction was performed at 40-45 degreeC for 2 hours, setting pH 5.0-5.5 with 10% sodium hydroxide aqueous solution. 37.2 parts of N-methyl taurine (65% of purity) was added to this reaction liquid, and reaction was performed at 90-95 degreeC for 5 hours, setting pH 9.0-9.2 with 10% sodium hydroxide aqueous solution. At this time, the liquid volume was 600 parts. After 120 parts of sodium chloride is added to this solution and stirred for 90 minutes, the pH is adjusted to 2.0 to 2.5 with 35% hydrochloric acid, and the precipitated solid is filtered to obtain a compound represented by the following formula (63) 132 parts of wet cakes were obtained.

（工程２）

(Step 2)

  121 parts of the wet cake containing the above formula (63) obtained in Step 1 is dissolved in 90 parts of N-methyl-2-pyrrolidone, and 19.1 parts of sodium 3-mercaptopropanesulfonate and potassium carbonate 15. 2 parts were added. After the addition, the mixture was heated to 100 to 110 ° C. and reacted at the same temperature for 2 hours. After cooling to 60 ° C., 150 parts of water was added to the reaction liquid, and the pH was adjusted to 1.0 to 1.5 by the addition of 35% hydrochloric acid. At this time, the liquid volume was 525 parts. After adding 105 parts of sodium chloride to this solution and stirring for 30 minutes, the precipitated solid was separated by filtration to obtain 123 parts of a wet cake containing a compound represented by the following formula (64).

(Step 3)
To 150 parts of water is added 123 parts of a wet cake of the compound represented by the formula (64) obtained in step 2, 5 parts of activated carbon, and 0.6 parts of anhydrous iron (III) chloride, and after heating to 60 ° C 11.3 parts of 80% hydrazine hydrate was added dropwise over about 30 minutes. After heating to 90 ° C., the reaction was carried out at the same temperature for 2 hours. After cooling to 40 ° C., insolubles were removed by filtration and the filtrate was cooled to room temperature. The pH was adjusted to 1.0 to 1.5 by the addition of 50% sulfuric acid. At this time, the liquid volume was 625 parts. After 125 parts of sodium chloride was added to this solution and stirred for 30 minutes, the precipitated solid was separated by filtration to obtain 111 parts of a wet cake containing a compound represented by the following formula (65).

(Step 5)
After adding the whole amount of the wet cake of the compound represented by the formula (22) obtained in the above Synthesis Example 1 (step 4) to 80 parts of water, pH 6.0 to 7.0 by addition of a 25% aqueous solution of sodium hydroxide As an aqueous solution. After 16.5 parts of 35% hydrochloric acid was added, 10.6 parts of 40% aqueous sodium nitrite solution was added, and the reaction was allowed to proceed for about 30 minutes. To this was added 7.5 parts of sulfamic acid, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, 73.3 parts of a wet cake of the compound represented by the formula (65) obtained in the above Synthesis Example 10 (Step 3) was added to 100 parts of water, and then a pH 4 by adding a 25% aqueous sodium hydroxide solution. The aqueous solution was obtained as 0-5.0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 3.5 by the addition of a 15% aqueous sodium carbonate solution. Sodium chloride was added to this solution, and the precipitated solid was separated by filtration to obtain 74 parts of a wet cake containing a compound represented by the following formula (66).

(Step 6)
To 100 parts of water, 37 parts of a wet cake of a compound represented by the formula (66) obtained in the above-mentioned Synthesis Example 10 (Step 5) was added, stirred and dissolved. After the addition of 7.8 parts of 35% hydrochloric acid, 2.8 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. Thereto, 0.8 part of sulfamic acid was added and stirred for 5 minutes to obtain a diazo reaction liquid.
On the other hand, 3.7 parts of the compound of the above formula (25) obtained by the method described in JP-A No. 2004-083492 is added to 80 parts of water, and a pH of 6.0 to 7 is added by the addition of a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0. This aqueous solution was added dropwise over about 5 minutes to the diazo reaction solution obtained above. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 3.0 to 4.5 by the addition of a 15% aqueous sodium carbonate solution. After the pH was adjusted to 7.0 to 7.5 by the addition of 25% aqueous sodium hydroxide solution, sodium chloride was added. The precipitated solid was separated by filtration to obtain 35 parts of a wet cake containing a compound represented by the following formula (67).

(Step 7)
To 80 parts of water, 35 parts of a wet cake of a compound represented by the formula (67) obtained in the above-mentioned Synthesis Example 10 (Step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.4 parts of the compound of the above formula (27) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 20.9 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain a compound represented by the following formula (68) of the present invention as a black powder as 9.5 parts of a sodium salt.
λmax: 590 nm.

[合成例１２]

Synthesis Example 12

(Step 7)
To 80 parts of water, 35 parts of a wet cake of the compound represented by the formula (67) obtained in the above-mentioned Synthesis Example 11 (Step 6) was added, stirred and dissolved. After the addition of 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous solution of sodium nitrite was added and stirred for about 30 minutes. 0.5 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 4.0 parts of the compound of the above formula (29) obtained by the method described in WO 2012/081640 is added to 80 parts of water, and a pH of 6.0 to 7 is obtained by the addition of a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as .0. The diazo reaction solution obtained above was added dropwise to this aqueous solution over about 30 minutes at 15 to 30 ° C. Under the present circumstances, 15% sodium carbonate aqueous solution was added, pH of the reaction liquid was hold | maintained at 6.5-7.5, and it reacted for 2 hours, maintaining adjustment of the same temperature and pH. Sodium chloride was added to the reaction solution to salt out, and the precipitated solid was separated by filtration to obtain 21.5 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, and after adjusting the pH to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was separated by filtration. The obtained wet cake was again dissolved in 40 parts of water, and 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain the compound represented by the above formula (69) of the present invention as a black powder as 8.7 parts sodium salt.
λmax: 630 nm.

[(B) Ink adjustment]
The ink composition of the present invention was obtained by using the azo compound of the present invention [Formula (28)] obtained in Synthesis Example 1 as a dye and mixing the compositions shown in Table 15 below to form a solution. . The resulting ink composition was filtered through a 0.45 μm membrane filter to remove impurities, and a test ink was prepared. The pH of this test ink was in the range of 8.0 to 9.5. In addition, in Table 3 below, "surfactant", was used trade name Surfynol ^RTM 104PG50 of manufactured by Nissin Chemical Industry Co., Ltd.. Preparation of an ink using the compound obtained in Synthesis Example 1 is referred to as Example 1.
Also, in the same manner as in Example 1 except that the dyes obtained in Synthesis Examples 2 to 4 and Synthesis Example 6 and Synthesis Examples 9 to 12 are used instead of the dye obtained in Synthesis Example 1, an ink for test is used. I adjusted each. This ink is referred to as Examples 2 to 9.

Comparative Example 1
A comparative ink was prepared in the same manner as Example 1, except that the dye described in WO 2012/081640 was used instead of the compound of the present invention obtained in Synthesis Example 1. Preparation of this ink is referred to as Comparative Example 1. The structural formula of the compound used in Comparative Example 1 is shown in the following Formula (70).

[(C) inkjet recording]
The inks prepared in Examples 1 to 9 and Comparative Example 1 were subjected to inkjet recording on the following two types of glossy paper using an inkjet printer (trade name: PIXUS ^RTM ip 7230 manufactured by Canon Inc.) . At the time of recording, an image pattern was formed so as to obtain six gradations of 100%, 85%, 70%, 55%, 40%, and 25% density, and a halftone recorded matter was obtained. The following test was performed using the obtained recorded matter as a test piece.

Glossy paper 1: Canon Inc. product name: Canon photo paper / Platinum grade (PT-201)
Glossy Paper 2: Seiko Epson Corporation, Product Name: Photo Paper Crispia (High Gloss)

[(D) Colorimetry of recorded image]
Various tests and their evaluation were performed by measuring the color of the test piece using a colorimeter manufactured by X-rite Co., Ltd., trade name SpectroEye. Colorimetry was performed under the conditions of ANSI A as a density standard, a viewing angle of 2 degrees, and a light source D50.
The test method of the recorded image and the evaluation method of the test result are described below.

[(E) Ozone resistance test]
Each test piece was left at an ozone concentration of 10 ppm, a tank temperature of 23 ° C., and a humidity of 50% RH for 24 hours using an ozone weather meter (manufactured by Suga Test Instruments Co., Ltd., type OMS-H). After the test, using the color measurement system, the hue (L * a * b *) before and after the test was measured to obtain the color difference. The color difference is better for smaller numbers. The results are shown in Table 8 below. The color difference was calculated by the following equation. In the following formula, ΔL ^* , Δa ^* and Δb ^* mean the difference between L ^* , a ^* and b ^* before and after exposure, respectively. At the time of the ozone resistance test, the hue (L * a * b *) of the recorded matter before the test was measured, and the color difference at the gradation portion of 100% was determined. Evaluation criteria are as follows. The results of each test are shown in Table 16.

Color difference is less than 11.5 ········
Color difference is more than 11.5 and less than 12.0 .......... △
Color difference is more than 12.0 ........... ×

Color difference (ΔE) = (ΔL ^* + Δa ^* + Δb ^* ) ^1/2

  As shown in Table 15, in the ozone resistance test of the printed matter, Examples 1 to 9 of the glossy paper show results superior to those of Comparative Example 1.

  From the above, it can be seen that the ink composition of the present invention of the present invention has high ozone resistance of printed matter as compared with the conventional dye.

The ink composition of the present invention is suitably used as a black ink for various recordings such as a writing instrument, particularly for ink jet recording.

Claims (22)

Ink composition containing an azo compound (A) having a structure represented by the following formula (1), a structure represented by the following formula (2), and a structure represented by the following formula (3) in one molecule .

The ink composition according to claim 1, wherein the number of azo bonds (-N = N-) in the molecule of the azo compound (A) is 4 or 5. The ink composition according to claim 1 or 2, wherein the azo compound (A) according to claim 1 or 2 is an azo compound represented by the following formula (4).

[In the formula (4),
R ¹ represents a (C1 to C4) alkyl group; a (C1 to C4) alkyl group substituted with a carboxy group; a phenyl group; a phenyl group substituted with a sulfo group; or a carboxy group;
R ² represents a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ each independently represent a hydrogen atom; (C 1 -C 4) alkyl group; (C 1 -C 4) alkoxy group; halogen atom; or sulfo group;
R ⁵ is, (C1 -C4) alkylthio group; a hydroxy group substituted with at least one group selected from the group consisting of sulfo and carboxy groups (C1 -C4) alkylthio group; (C1 -C4) alkoxy A group (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the following formula (5):
R ⁶ is a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; (C1-C4) alkoxy A group; a (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the following formula (2):
R ⁷ represents a (C 1 -C 4) alkylthio group; a (C 1 -C 4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; An alkoxy group; a (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the following formula (5):
R ^{8 to} R ¹⁰ each independently represent a hydrogen atom; carboxy group; sulfo group; (C 1 -C 4) alkylcarbonylamino group; halogen atom; (C 1 -C 4) alkyl group; (C 1 -C 4) alkoxy group; A (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group and a carboxy group; or a compound represented by the following formula (5) Represents a group
R ^{11 to} R ¹³ and R ¹⁶ each independently represent a hydrogen atom, a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, a (C1 to C4) alkyl group (C1 to C4) alkoxy group; (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group and a carboxy group; Or a (C1 to C4) alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group.
However, at least one of R ^{5 to} R ¹⁰ is a group represented by the following formula (5).
Further, the benzene ring indicated by a broken line may or may not be present.

In formula (5),
R ¹⁴ is an anilino group having at least one sulfo group as a substituent; or a naphthylamino group;
The anilino group or the naphthylamino group is further a sulfo group, a carboxy group, a phosphoric acid group, a sulfamoyl group, a carbamoyl group, a hydroxy group, a (C1-C6) alkoxy group, an amino group, a mono- Or a mono- or di-arylamino group; an acetylamino group; a ureido group; a (C1-C6) alkyl group; a cyano group; a halogen atom; And may be substituted with one or more substituents selected from the group consisting of a C1-C6) alkylsulfonyl group; and a (C1-C6) alkylthio group,
R ¹⁵ is an anilino group;, naphthylamino group; mono - or di - (C1 -C6) alkylamino group; a mono - or di - arylamino group; an amino group;, (Cl to 6) alkylthio group; Or a phenylthio group; a phenoxy group; a (C1-C6) alkoxy group or a hydroxy group, and the above-mentioned substituent in R ¹⁵ is further a sulfo group; a carboxy group; a phosphoric acid group; a sulfamoyl group; A hydroxy group; an alkoxy group; an amino group; a mono- or di- (C1-C6) alkylamino group; a mono- or di-arylamino group; an acetylamino group; a ureido group; , A phenyl group, a furyl group, a pyridyl group, a cyano group, a halogen atom, a (C1 to C6) alkylsulfonyl group; It may be substituted by one or more substituents selected from the group consisting of; (C1 -C6) alkylthio group. Moreover, * in Formula (5) represents a coupling | bonding position. ] In the formula (4),
R ¹ represents a (C1 to C4) alkyl group; or a (C1 to C4) alkyl group substituted with a carboxy group;
R ² represents a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ each independently represent a hydrogen atom; (C 1 -C 4) alkyl group; (C 1 -C 4) alkoxy group; halogen atom; or sulfo group;
R ⁵ represents a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁶ represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁷ represents a (C 1 -C 4) alkylthio group; a (C 1 -C 4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; An alkoxy group; a (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ^{8 to} R ¹⁰ each independently represent a hydrogen atom; carboxy group; sulfo group; (C 1 -C 4) alkylcarbonylamino group; halogen atom; (C 1 -C 4) alkyl group; (C 1 -C 4) alkoxy group; A (C1 to C4) alkoxy group substituted by at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group and a carboxy group; or the above formula (5) Represents a group
R ^{11 to} R ¹³ and R ¹⁶ each independently represent a hydrogen atom, a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, a (C1 to C4) alkyl group (C1 to C4) alkoxy group; (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group and a carboxy group; 4. A C1-C4) alkylsulfonyl group; or a (C1-C4) alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; The ink composition as described. However, at least one of R ^{8 to} R ¹⁰ is a group represented by the formula (5). In the formula (4),
R ¹ represents a (C1 to C4) alkyl group; or a (C1 to C4) alkyl group substituted with a carboxy group;
R ² represents a cyano group;
R ³ and R ⁴ each independently represent a hydrogen atom; (C 1 -C ⁴ ) alkoxy group; or sulfo group;
R ⁵ represents a (C1-C4) alkylthio group substituted by at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁶ represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁷ represents a sulfo (C 1 -C 4) alkoxy group;
R ⁸ and R ¹⁰ each independently represent a (C1-C4) alkyl group; or a (C1-C4) alkylcarbonylamino group;
R ⁹ is a group represented by the above formula (5),
R ¹¹ to R ¹³ and R ¹⁶ are a hydrogen atom; a sulfo group; or a nitro group; a is claim 3 or ink composition according to 4. In the formula (4),
R ¹ represents a (C1 to C4) alkyl group; or a (C1 to C4) alkyl group substituted with a carboxy group;
R ² represents a cyano group;
R ³ and R ⁴ each independently represent a hydrogen atom; (C 1 -C ⁴ ) alkoxy group; or sulfo group;
R ⁵ represents a (C1-C4) alkylthio group substituted by at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁶ represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁷ represents a sulfo (C 1 -C 4) alkoxy group;
R ⁸ and R ¹⁰ each independently represent a methyl group; or (C ¹ -C 4) alkylcarbonylamino group;
R ⁹ represents a group represented by the above formula (5);
R ^{11 to} R ¹³ and R ^{16 each} represent a hydrogen atom; a sulfo group; or a nitro group;
At least one of R ^{11 to} R ¹³ and R ¹⁶ is a nitro group;
In the formula (5),
R ¹⁴ is an anilino group having at least one sulfo group as a substituent,
The anilino group is further a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an (C1-C6) alkyl group, a cyano group, a halogen atom, a (C1-C6) alkyl sulfonyl group; C 1 -C 6) alkylthio group; and may be substituted by one or more substituents selected from the group consisting of
R ¹⁵ is mono- or di (C1 -C6) alkylamino group; or a hydroxy group; a and,
The (C1-C6) alkylamino group is further a sulfo group; a carboxy group; a phosphoric acid group; a hydroxy group; a (C1-C6) alkoxy group; an acetylamino group; a ureido group; C6) alkyl group; phenyl group; cyano group; halogen atom; (C1 to C6) alkylsulfonyl group and (C1 to C6) alkylthio group; one or more substituents selected from the group consisting of The ink composition according to any one of claims 3 to 5, which may be substituted with a group. In the formula (4),
R ¹ is a methyl group;
R ² is a cyano group;
R ³ is a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C 1 -C 4) alkylthio group;
R ⁶ is a sulfo (C ¹ -C 4) alkylthio group;
R ⁷ is a sulfo (C 1 -C 4) alkoxy group;
R ⁸ is a (C 1 -C 4) alkylcarbonylamino group;
R ¹⁰ is a methyl group;
A group wherein R ⁹ is represented by the above formula (5);
At least one of R ^{11 to} R ¹³ and R ¹⁶ is a nitro group, and the other three are each independently a sulfo group; or a hydrogen atom;
An anilino group wherein R ¹⁴ has at least one sulfo group as a substituent in the above formula (5);
The anilino group is further a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an alkyl group, a cyano group, a halogen atom, a (C1 to C6) alkylsulfonyl group, and a (C1 to C6) alkylthio group. It may be substituted by one or more substituents selected from the group consisting of
R ¹⁵ is (C1 -C6) alkylamino group; a,
The (C1-C6) alkylamino group is further a sulfo group; a carboxy group; a hydroxy group; a (C1-C6) alkoxy group; a (C1-C6) alkyl group; a phenyl group; The compound according to any one of claims 3 to 6, which may be substituted by one or two or more substituents selected from the group consisting of (C1-C6) alkylsulfonyl group; and (C1-C6) alkylthio group. The ink composition as described. In the formula (4),
R ¹ is a methyl group;
R ² is a cyano group;
R ³ is a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C 1 -C 4) alkylthio group;
R ⁶ is a sulfo (C ¹ -C 4) alkylthio group;
R ⁷ is a sulfo (C 1 -C 4) alkoxy group;
R ⁸ is a (C 1 -C 4) alkylcarbonylamino group;
R ¹⁰ is a methyl group;
A group wherein R ⁹ is represented by the above formula (5);
R ^{11 to} R ¹³ and R ^{16 each} is a nitro group, a sulfo group, or a hydrogen atom; and in the formula (5), an anilino group wherein R ¹⁴ has at least one sulfo group as a substituent,
The anilino group may be further substituted with a sulfo group;
R ¹⁵ is (C1 -C2) alkylamino group; a,
The ink composition according to any one of claims 3 to 7, wherein the (C1-C2) alkylamino group may be further substituted with a sulfo group. The ink composition according to any one of claims 1 to 8, further comprising a water-soluble organic solvent. An ink jet recording method of recording on a recording material by using the ink composition according to any one of claims 1 to 9 as an ink and discharging ink droplets of the ink according to a recording signal. The ink jet recording method according to claim 10, wherein the recording material is a sheet for information transmission. The ink jet recording method according to claim 11, wherein the information transmitting sheet is a sheet having a plain paper or an ink receiving layer containing a porous white inorganic substance. A colored body colored by the inkjet recording method according to claim 10 or 11. An ink jet printer loaded with a container comprising the ink composition according to any one of claims 1 to 8. An azo compound having a structure represented by the following formula (1), a structure represented by the following formula (2), and a structure represented by the following formula (3) in one molecule.

The azo compound according to claim 15, wherein the number of azo bonds (-N = N-) in the molecule of the azo compound is 4 or 5. The azo compound according to claim 15 or 16, which is represented by the following formula (4).

[In the formula (4),
R ¹ Represents a (C1-C4) alkyl group; a (C1-C4) alkyl group substituted with a carboxy group; a phenyl group; a phenyl group substituted with a sulfo group; or a carboxy group;
R ² Represents a cyano group; a carbamoyl group; or a carboxy group;
R ³ And R ^Four Each independently represents a hydrogen atom; (C1 to C4) alkyl group; (C1 to C4) alkoxy group; halogen atom; or sulfo group;
R ^Five Is a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; a (C1-C4) alkoxy group; (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the following formula (5):
R ⁶ Is a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; a (C1-C4) alkoxy group; (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the following formula (2):
R ⁷ Is a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; a (C1-C4) alkoxy group A (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; or a group represented by the following formula (5):
R ⁸ ~ R ^Ten Each independently represents a hydrogen atom; a carboxy group; a sulfo group; a (C1 to C4) alkylcarbonylamino group; a halogen atom; a (C1 to C4) alkyl group; a (C1 to C4) alkoxy group; -C4) a (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of an alkoxy group, a sulfo group and a carboxy group; or a group represented by the following formula (5) ,
R ¹¹ ~ R ¹³ And R ¹⁶ Each independently represents a hydrogen atom, a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, a (C1 to C4) alkyl group, a (C1 to C4) alkoxy group (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group and carboxy group; (C1-C4) alkyl sulfonyl group; Or a (C1-C4) alkylsulfonyl group substituted by at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group.
However, R ^Five ~ R ^Ten Among them, at least one is a group represented by the following formula (5).
Further, the benzene ring indicated by a broken line may or may not be present.

In formula (5),
R ¹⁴ Or anilino group having at least one sulfo group as a substituent; or a naphthylamino group;
The anilino group or the naphthylamino group is further a sulfo group, a carboxy group, a phosphoric acid group, a sulfamoyl group, a carbamoyl group, a hydroxy group, a (C1-C6) alkoxy group, an amino group, a mono- Or a mono- or di-arylamino group; an acetylamino group; a ureido group; a (C1-C6) alkyl group; a cyano group; a halogen atom; And may be substituted with one or more substituents selected from the group consisting of a C1-C6) alkylsulfonyl group; and a (C1-C6) alkylthio group,
R ¹⁵ Is an anilino group; a naphthylamino group; a mono- or di- (C1-C6) alkylamino group; a mono- or di-arylamino group; an amino group; a (C1-6) alkylthio group; A phenoxy group; a (C 1 -C 6) alkoxy group or a hydroxy group; ¹⁵ The above substituent in the group is further a sulfo group, a carboxy group, a phosphate group, a sulfamoyl group, a carbamoyl group, a hydroxy group, an alkoxy group, an amino group, mono- or di- (C1-C6) Alkylamino group; mono- or di-arylamino group; acetylamino group; ureido group; (C1-C6) alkyl group; phenyl group; furyl group; pyridyl group; cyano group; The substituent may be substituted with one or more substituents selected from the group consisting of atoms; (C1-C6) alkylsulfonyl groups; and (C1-C6) alkylthio groups. Moreover, * in Formula (5) represents a coupling | bonding position. ] In the formula (4),
R ¹ Or represents a (C1-C4) alkyl group; or a (C1-C4) alkyl group substituted with a carboxy group;
R ² Represents a cyano group; a carbamoyl group; or a carboxy group;
R ³ And R ^Four Each independently represents a hydrogen atom; (C1 to C4) alkyl group; (C1 to C4) alkoxy group; halogen atom; or sulfo group;
R ^Five Represents a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁶ And represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁷ Is a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group; a (C1-C4) alkoxy group A (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁸ ~ R ^Ten Each independently represents a hydrogen atom; a carboxy group; a sulfo group; a (C1 to C4) alkylcarbonylamino group; a halogen atom; a (C1 to C4) alkyl group; a (C1 to C4) alkoxy group; -C4) a (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of an alkoxy group, a sulfo group and a carboxy group; or a group represented by the above formula (5) ,
R ¹¹ ~ R ¹³ And R ¹⁶ Each independently represents a hydrogen atom, a carboxy group, a sulfo group, a hydroxy group, an acetylamino group, a halogen atom, a cyano group, a nitro group, a sulfamoyl group, a (C1 to C4) alkyl group, a (C1 to C4) alkoxy group (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group and carboxy group; (C1-C4) alkyl sulfonyl group; The azo compound according to claim 17, which represents or (C1-C4) alkylsulfonyl group substituted with at least one group selected from the group consisting of hydroxy group, sulfo group and carboxy group. However, R ⁸ ~ R ^Ten And at least one of them is a group represented by the above formula (5). In the formula (4),
R ¹ Or represents a (C1-C4) alkyl group; or a (C1-C4) alkyl group substituted with a carboxy group;
R ² Represents a cyano group;
R ³ And R ^Four Each independently represents a hydrogen atom; (C 1 -C 4) alkoxy group; or sulfo group;
R ^Five And represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁶ And represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁷ Represents a sulfo (C1 to C4) alkoxy group;
R ⁸ And R ^Ten Each independently represents a (C1-C4) alkyl group; or a (C1-C4) alkylcarbonylamino group;
R ⁹ Is a group represented by the above formula (5),
R ¹¹ ~ R ¹³ And R ¹⁶ The azo compound according to claim 17 or 18, which is a hydrogen atom; a sulfo group; or a nitro group. In the formula (4),
R ¹ Or represents a (C1-C4) alkyl group; or a (C1-C4) alkyl group substituted with a carboxy group;
R ² Represents a cyano group;
R ³ And R ^Four Each independently represents a hydrogen atom; (C 1 -C 4) alkoxy group; or sulfo group;
R ^Five And represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁶ And represents a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group;
R ⁷ Represents a sulfo (C1 to C4) alkoxy group;
R ⁸ , R ^Ten Each independently represents a methyl group; or a (C1-C4) alkylcarbonylamino group;
R ⁹ Represents a group represented by the formula (5);
R ¹¹ ~ R ¹³ And R ¹⁶ Represents a hydrogen atom; a sulfo group; or a nitro group;
R ¹¹ ~ R ¹³ And R ¹⁶ At least one of which is a nitro group;
In the formula (5),
R ¹⁴ Is an anilino group having at least one sulfo group as a substituent,
The anilino group is further a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an (C1-C6) alkyl group, a cyano group, a halogen atom, a (C1-C6) alkyl sulfonyl group; C 1 -C 6) alkylthio group; and may be substituted by one or more substituents selected from the group consisting of
R ¹⁵ Is a mono or di (C1-C6) alkylamino group; or a hydroxy group;
The (C1-C6) alkylamino group is further a sulfo group; a carboxy group; a phosphoric acid group; a hydroxy group; a (C1-C6) alkoxy group; an acetylamino group; a ureido group; C6) alkyl group; phenyl group; cyano group; halogen atom; (C1 to C6) alkylsulfonyl group and (C1 to C6) alkylthio group; one or more substituents selected from the group consisting of The azo compound according to any one of claims 17 to 19, which may be substituted by a group. In the formula (4),
R ¹ Is a methyl group;
R ² Is a cyano group;
R ³ Is a methoxy group;
R ^Four Is a sulfo group;
R ^Five Is a sulfo (C1 to C4) alkylthio group;
R ⁶ Is a sulfo (C1 to C4) alkylthio group;
R ⁷ Is a sulfo (C1-C4) alkoxy group;
R ⁸ Is a (C1-C4) alkylcarbonylamino group;
R ^Ten Is a methyl group;
R ⁹ A group represented by the above formula (5);
R ¹¹ To R ¹³ And R ¹⁶ And at least one of them is a nitro group; and the other three are each independently a sulfo group; or a hydrogen atom;
In the above formula (5), R ¹⁴ Is anilino having at least one sulfo group as a substituent;
The anilino group is further a sulfo group, a carboxy group, a hydroxy group, an alkoxy group, an alkyl group, a cyano group, a halogen atom, a (C1 to C6) alkylsulfonyl group, and a (C1 to C6) alkylthio group. It may be substituted by one or more substituents selected from the group consisting of
R ¹⁵ Is a (C1-C6) alkylamino group;
The (C1-C6) alkylamino group is further a sulfo group; a carboxy group; a hydroxy group; a (C1-C6) alkoxy group; a (C1-C6) alkyl group; a phenyl group; 21. The compound according to any one of claims 17 to 20, which may be substituted by one or more substituents selected from the group consisting of (C1-C6) alkylsulfonyl group; and (C1-C6) alkylthio group. Azo compound described. In the formula (4),
R ¹ Is a methyl group;
R ² Is a cyano group;
R ³ Is a methoxy group;
R ^Four Is a sulfo group;
R ^Five Is a sulfo (C1 to C4) alkylthio group;
R ⁶ Is a sulfo (C1 to C4) alkylthio group;
R ⁷ Is a sulfo (C1-C4) alkoxy group;
R ⁸ Is a (C1-C4) alkylcarbonylamino group;
R ^Ten Is a methyl group;
R ⁹ A group represented by the above formula (5);
R ¹¹ To R ¹³ And R ¹⁶ Is a nitro group; a sulfo group; or a hydrogen atom; and in the above formula (5), R ¹⁴ Is anilino having at least one sulfo group as a substituent;
The anilino group may be further substituted with a sulfo group;
R ¹⁵ Is a (C1-C2) alkylamino group;
The azo compound according to any one of claims 17 to 21, wherein the (C1-C2) alkylamino group may be further substituted with a sulfo group.