JP2012046559A - Azo compound, ink composition, recording method and colored material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment having a high grade black hue, excellent in gas(ozone) resistance and light resistance irrespective of pigment density in ink, and exhibiting extraordinarily high printing density, scarce color rendering properties and low chroma, when recorded on exclusive paper for inkjet; an ink composition containing the pigment, in particular, a black ink composition for inkjet recording.SOLUTION: The pigment is an azo compound expressed by formula (1) or a tautomer thereof or a salt thereof. In the formula, Ris alkyl or the like; Ris cyano or the like; Rand Rare sulfo or the like; Ris sulfo or the like; Ris phenyl or the like; Ris alkylthio substituted by sulfo, or the like; Ris alkylcarbonylamino or the like; Ris alkoxy substituted by sulfo, or the like; Ris alkyl or the like; and Rto Rare sulfo or the like.

Description

The present invention relates to a novel azo compound or a tautomer thereof, or a salt thereof, an ink composition containing these, and a colored product colored by them.

A recording method using an ink jet printer, that is, an ink jet recording method is one of representative methods among various color recording methods. The ink jet recording method performs recording by generating droplets of ink and attaching them to various recording materials (paper, film, fabric, etc.). This method is quiet because it does not generate sound because the recording head and the recording material are not in direct contact. In addition, due to the feature that it is easy to downsize and increase the speed, it has been spreading rapidly in recent years and is expected to grow greatly in the future. Conventionally, water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used as fountain pens, felt-tip pens, and inks for ink jet recording. In general, a water-soluble organic solvent is added to these water-based inks in order to prevent clogging of the ink at the pen tip or the ink discharge nozzle. With these inks, it is possible to provide a recording image with sufficient density, no clogging of the pen tip and nozzles, good drying on the recording material, less bleeding, and storage stability. It is required to be excellent. In addition, the water-soluble dye used is required to have a particularly high solubility in water and a high solubility in a water-soluble organic solvent added to the ink. Further, the formed image is required to have image fastness such as water resistance, light resistance, gas resistance and moisture resistance.

Among these, the gas resistance refers to the resistance to a phenomenon in which ozone gas having an oxidizing action existing in the air acts on the dye on the recording paper or in the recording paper to discolor the recorded image. . In addition to ozone gas, examples of the oxidizing gas having this kind of action include NOx and SOx. However, among these oxidizing gases, ozone gas is regarded as a main causative substance that promotes the discoloration phenomenon of ink jet recorded images, and particularly, ozone gas resistance is regarded as important. An ink receiving layer is provided on the surface of the exclusive inkjet paper capable of obtaining photographic image quality in order to expedite ink drying and to reduce bleeding at high image quality. In many cases, the ink receiving layer is made of a material such as a porous white inorganic material. On such a recording paper, the discoloration due to ozone gas or the like is noticeable. Since this discoloration phenomenon due to the oxidizing gas is characteristic of an ink jet recording image, improvement of gas resistance, particularly ozone gas resistance, is one of the most important issues in ink jet recording.

The light resistance required for the formed image is required to be independent of the dye concentration in the ink. That is, when used in light color inks such as light cyan, light magenta, light yellow, and gray, it is required that the color fading due to light does not significantly decrease. The light magenta, light cyan, light yellow, and gray light inks used here are used in combination with the conventionally used cyan, magenta, yellow, and black inks, so that the granularity of the recorded image and the light to dark areas are recorded. It is known that the gradation property when connecting gradations is improved.
In general, when a light color ink formed at a low density is used, the light resistance tends to be remarkably lowered, and the development of a color material which has improved these is one of the important problems in the inkjet ink.

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 and the like is strongly demanded for ink jet recorded images. In addition to this, a black image is required to have a low color rendering property. A phenomenon in which the hue appears to change depending on the type of the light source is referred to as color rendering, but generally this phenomenon is likely to occur in black dyed matter or recorded matter. In the field of dyeing and processing, it is common to use a compound having absorption at a long wavelength as a method for improving color rendering properties. For example, Patent Documents 7 and 8 and Non-Patent Document 1 disclose these methods.

Various hue inks are prepared from various pigments, of which black ink is an important ink used for both monocolor and full color images. Many pigments for these black inks have been proposed to date, but they have not yet provided a pigment that sufficiently satisfies the demands of the market. 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. A polyazo dye having an extended conjugated system generally has problems such as low water solubility, easily causing a bronzing phenomenon in which a recorded image has a partially metallic luster, and insufficient light resistance and gas resistance. Similarly, many azo metal-containing dyes that have been proposed have good light resistance, but they contain metal ions, which are undesirable for safety and environmental issues for living organisms, and have extremely high gas resistance. There are problems such as weakness.

As a black compound (black pigment) for ink jet recording improved with respect to gas resistance, which has become the most important issue in recent years, for example, the compounds described in Patent Document 1 can be mentioned. Although the gas resistance of these compounds has been improved, they do not fully meet market demands. Further, azo compounds having a benzimidazolopyridone skeleton, which is one of the characteristics of the black pigment of the present invention, are disclosed in Patent Documents 2 to 6 and the like. Patent Document 3 discloses trisazo compounds, but these trisazo compounds have a symmetrical structure in which two benzimidazolopyridone skeletons are further bonded to each end of a linking group containing an azo structure by an azo structure. Nothing similar to the asymmetric azo compound of the present invention is disclosed. Patent Documents 4 and 5 disclose that a trisazo compound and a water-soluble black compound are used for inkjet recording. Patent Document 6 discloses that a tetrakisazo compound and a water-soluble black compound are used for inkjet recording.

International Publication No. 2005/054374 Pamphlet International Publication No. 2004/050768 Pamphlet German Patent No. 2000004488 International Publication No. 2007/077931 Pamphlet International Publication No. 2009/069279 Pamphlet JP 2008-169374 A Japanese Patent Laid-Open No. 01-284562 Japanese Patent Publication No. 05-018955 JP 2009-132794 A International Publication No. 2008/056626 Pamphlet Processing Technology Vol. 31, No. 9, 1996, 599-602

The present invention, when recorded on ink jet dedicated paper, is excellent in (ozone) gas resistance and light resistance regardless of the pigment concentration in the ink, the printing density is very high, the color rendering property is low, and the saturation is low. It is an object of the present invention to provide a pigment having a high-quality black hue and an ink composition containing the pigment, particularly a black ink composition for inkjet recording.

［式（１）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；ハロゲン原子；（Ｃ１〜Ｃ４）アルコキシ基；又は、スルホ基；を表し、
Ｒ₅は、水素原子；カルボキシ基；スルホ基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；置換基として、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、及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、
Ｒ₆は、（Ｃ２〜Ｃ４）アルキル基；
置換基として、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、及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）アルキル基；
（Ｃ１〜Ｃ４）アルキルアミノ基；置換基として、ハロゲン原子、ニトロ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、フェニル基、及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）アルキルアミノ基；
（Ｃ１〜Ｃ４）ジアルキルアミノ基；置換基として、ハロゲン原子、ニトロ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、フェニル基、及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）ジアルキルアミノ基；
フェニル基；置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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フェニル基；
フェニルアミノ基；置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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フェニルアミノ基；
ジフェニルアミノ基；置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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ジフェニルアミノ基；
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ル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、
Ｒ₈は、（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基を表し、
Ｒ₉及びＲ₁₀は、それぞれ独立に水素原子；カルボキシ基；スルホ基；アセチルアミノ基；（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ル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）アルキルチオ基；ヒドロキシ基、スルホ基およびカルボキシル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、
Ｒ₁₁からＲ₁₃は、それぞれ独立に、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ル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；ヒドロキシ基、スルホ基およびカルボキシル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。］
２）下記式（２）で表されるアゾ化合物若しくはその互変異性体、又はそれらの塩。

［式（２）中、
Ｒ₁からＲ₁₃は、式（１）におけるものと同じ意味を表す。]
３）式（１）及び（２）において、Ｒ₁₁からＲ₁₃の少なくともひとつがスルホ基またはカルボキシ基であり、Ｒ_６からＲ₁₀の少なくともひとつがスルホ基またはスルホ（Ｃ１〜Ｃ４）アルコキシ基である１）又は２）のいずれか一項に記載のアゾ化合物若しくはその互変異性体、又はそれらの塩。
４）式（１）及び（２）において、
Ｒ₁は（Ｃ１〜Ｃ４）アルキル基；又はフェニル基を表し、
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のいずれか一方は、スルホ基であり、他方は、水素原子；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；又は、スルホ基；を表し、
Ｒ₅は水素原子；カルボキシ基；スルホ基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；置換基として、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、及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、
Ｒ₆は、（Ｃ２〜Ｃ４）アルキル基；
置換基として、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、及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）アルキル基；
（Ｃ１〜Ｃ４）アルキルアミノ基；置換基として、ハロゲン原子、ニトロ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、フェニル基、及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）アルキルアミノ基；
（Ｃ１〜Ｃ４）ジアルキルアミノ基；置換基として、ハロゲン原子、ニトロ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、フェニル基、及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）ジアルキルアミノ基；
フェニル基；置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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フェニル基；
フェニルアミノ基；置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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フェニルアミノ基；
ジフェニルアミノ基；置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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ジフェニルアミノ基；
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ル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、
Ｒ₈は、（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基を表し、
Ｒ₉及びＲ₁₀は、それぞれ独立に水素原子；カルボキシ基；（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ル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）アルキルチオ基；ヒドロキシ基、スルホ基およびカルボキシル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、
Ｒ₁₁からＲ₁₃は、それぞれ独立に、水素原子；カルボキシ基；スルホ基；ハロゲン原子；（Ｃ１〜Ｃ４）アルキル基；を表す１）又は２）のいずれか一項に記載のアゾ化合物若しくはその互変異性体、又はそれらの塩。
５）式（１）及び（２）において、
Ｒ₁は（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のいずれか一方は、スルホ基であり、他方は、水素原子；又は、（Ｃ１〜Ｃ４）アルキル基；を表し、
Ｒ₅は水素原子；又はスルホ基；を表し、
Ｒ₆は、（Ｃ２〜Ｃ４）アルキル基；
置換基として、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、及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）アルキル基；
（Ｃ１〜Ｃ４）アルキルアミノ基；置換基として、ハロゲン原子、ニトロ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、フェニル基、及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）アルキルアミノ基；
（Ｃ１〜Ｃ４）ジアルキルアミノ基；置換基として、ハロゲン原子、ニトロ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基、フェニル基、及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）ジアルキルアミノ基；
フェニル基；置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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フェニル基；
フェニルアミノ基；置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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フェニルアミノ基；
ジフェニルアミノ基；置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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ジフェニルアミノ基；
を表し、
Ｒ₇は、スルホ基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ₈は、（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基を表し、
Ｒ₉は、スルホ基で置換された（Ｃ１〜Ｃ４）アルコキシ基を表し、
Ｒ₁₀は、（Ｃ１〜Ｃ４）アルキル基を表し、
Ｒ₁₁からＲ₁₃のうちいずれか一つはスルホ基であり、他の二つはそれぞれ独立に、水素原子；カルボキシ基；スルホ基；ハロゲン原子；（Ｃ１〜Ｃ４）アルキル基；を表す１）又は２）のいずれか一項に記載のアゾ化合物若しくはその互変異性体、又はそれらの塩。
６）式（１）及び（２）において、
Ｒ₁は（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のいずれか一方は、スルホ基であり、他方は、水素原子；又は、（Ｃ１〜Ｃ４）アルキル基；を表し、
Ｒ₅は水素原子；又はスルホ基；を表し、
Ｒ₆は、フェニル基；又は置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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フェニル基；
Ｒ₇は、スルホ基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ₈は、（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基を表し、
Ｒ₉は、スルホ基で置換された（Ｃ１〜Ｃ４）アルコキシ基を表し、
Ｒ₁₀は、（Ｃ１〜Ｃ４）アルキル基を表し、
Ｒ₁₁からＲ₁₃のうちいずれか一つはスルホ基であり、他の二つはそれぞれ独立に、水素原子；カルボキシ基；スルホ基；ハロゲン原子；（Ｃ１〜Ｃ４）アルキル基；を表す１）又は２）のいずれか一項に記載のアゾ化合物若しくはその互変異性体、又はそれらの塩。
７）式（１）及び（２）において、
Ｒ₁は（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のいずれか一方は、スルホ基であり、他方は、水素原子；又は、メチル基；を表し、
Ｒ₅は水素原子；又はスルホ基；を表し、
Ｒ₆は、フェニル基；又は置換基として、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、ハロゲン原子、ニトロ基、スルホ基、ヒドロキシ基、（Ｃ１〜Ｃ４）アルキルチオ基、（Ｃ１〜Ｃ４）アルキルアミノ基、（Ｃ１〜Ｃ４）ジアルキルアミノ基、及びカルボキシル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フェニル基；
Ｒ₇は、スルホ基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ₈は、（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基を表し、
Ｒ₉は、スルホ基で置換された（Ｃ１〜Ｃ４）アルコキシ基を表し、
Ｒ₁₀は、（Ｃ１〜Ｃ４）アルキル基を表し、
Ｒ₁₁は、ハロゲン原子を表し、
Ｒ₁₂は、スルホ基を表し、
Ｒ₁₃は水素原子を表す１）又は２）のいずれか一項に記載のアゾ化合物若しくはその互変異性体、又はそれらの塩。
８）式（１）及び（２）において、
Ｒ₁₁の置換位置が４位であり、
Ｒ₁₂の置換位置が５位であり、
Ｒ₁₃の置換位置が６位である７）に記載のアゾ化合物若しくはその互変異性体、又はそれらの塩。
９）１）から８）のいずれか一項に記載のアゾ化合物若しくはその互変異性体、又はそれらの塩を、色素として少なくとも１種類含有する水性インク組成物。
１０）水溶性有機溶剤をさらに含有する請求項９に記載の水性インク組成物。
１１）９）又は１０）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。
１２）被記録材が情報伝達用シートである１１）に記載のインクジェット記録方法。
１３）情報伝達用シートが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１２）に記載のインクジェット記録方法。
１４）９）又は１０）に記載のインク組成物を含む容器を装填したインクジェットプリンタ。
１５）
ａ）１）乃至８）のいずれか一項に記載のアゾ化合物若しくはその互変異性体、又はそれらの塩、
ｂ）９）又は１０）に記載の水性インク組成物、又は、
ｃ）１１）に記載のインクジェット記録方法、の３者のいずれかによって着色された着色体。 As a result of intensive studies to solve the problems as described above, the present inventors have found that a specific azo compound can solve the problems, and have completed the present invention. That is, the present invention relates to the following description.
1) An azo compound represented by the following formula (1), a tautomer thereof, or a salt thereof.

[In Formula (1),
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 ₄ each independently represent a hydrogen atom; a (C1-C4) alkyl group; a halogen atom; a (C1-C4) alkoxy group; or a sulfo group;
R ₅ is a hydrogen atom; a carboxy group; a sulfo group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; as a substituent, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group. (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of:
R ₆ is a (C 2 -C 4) alkyl group;
As a substituent, a (C1-C4) alkyl 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) alkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) alkylamino group substituted with a group;
(C1-C4) dialkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) dialkylamino group substituted with a group;
Phenyl group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkylamino A phenyl group substituted with at least one group selected from the group consisting of a group, a (C1-C4) dialkylamino group, and a carboxyl group;
Phenylamino group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A phenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Diphenylamino group: As a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A diphenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Represents
R ₇ 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 carboxyl group;
R ₈ represents a (C1-C4) alkylcarbonylamino group,
R ₉ and R ₁₀ are each independently a hydrogen atom; a carboxy group; a sulfo group; an acetylamino group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group, a (C1-C4) alkoxy group, (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of sulfo group and carboxyl group; (C1-C4) alkylthio group; selected from the group consisting of hydroxy group, sulfo group and carboxyl group A (C1-C4) alkylthio group substituted with at least one group selected from
R ₁₁ to R ₁₃ are each independently 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; (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 carboxyl group; (C1-C4) An alkylsulfonyl group; 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 carboxyl group. ]
2) An azo compound represented by the following formula (2), a tautomer thereof, or a salt thereof.

[In Formula (2),
R ₁ to R ₁₃ represent the same meaning as in formula (1). ]
3) In the formulas (1) and (2), at least one of R ₁₁ to R ₁₃ is a sulfo group or a carboxy group, and at least one of R ₆ to R ₁₀ is a sulfo group or a sulfo (C1-C4) alkoxy group. The azo compound according to any one of 1) or 2), a tautomer thereof, or a salt thereof.
4) In the formulas (1) and (2),
R ₁ represents a (C1-C4) alkyl group; or a phenyl group,
R ₂ represents a cyano group; a carbamoyl group; or a carboxy group;
One of R ₃ and R ₄ is a sulfo group, and the other represents a hydrogen atom; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; or a sulfo group;
R ₅ is a hydrogen atom; a carboxy group; a sulfo group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; as a substituent, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group. (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of:
R ₆ is a (C 2 -C 4) alkyl group;
As a substituent, a (C1-C4) alkyl 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) alkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) alkylamino group substituted with a group;
(C1-C4) dialkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) dialkylamino group substituted with a group;
Phenyl group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkylamino A phenyl group substituted with at least one group selected from the group consisting of a group, a (C1-C4) dialkylamino group, and a carboxyl group;
Phenylamino group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A phenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Diphenylamino group: As a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A diphenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Represents
R ₇ 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 carboxyl group;
R ₈ represents a (C1-C4) alkylcarbonylamino group,
R ₉ and R ₁₀ are each independently a hydrogen atom; a carboxy group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxyl group. (C1-C4) alkoxy group substituted with at least one group selected from the group; (C1-C4) alkylthio group; at least one group selected from the group consisting of hydroxy group, sulfo group and carboxyl group (C1-C4) alkylthio group substituted with
R ₁₁ to R ₁₃ each independently represents a hydrogen atom; a carboxy group; a sulfo group; a halogen atom; (C1-C4) an alkyl group; 1) or 2) according to any one of 2) or a azo compound thereof Tautomers or salts thereof.
5) In the formulas (1) and (2),
R ₁ represents a (C1-C4) alkyl group,
R ₂ represents a cyano group; a carbamoyl group; or a carboxy group;
One of R ₃ and R ₄ represents a sulfo group, and the other represents a hydrogen atom; or a (C1-C4) alkyl group;
R ₅ represents a hydrogen atom; or a sulfo group;
R ₆ is a (C 2 -C 4) alkyl group;
As a substituent, a (C1-C4) alkyl 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) alkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) alkylamino group substituted with a group;
(C1-C4) dialkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) dialkylamino group substituted with a group;
Phenyl group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkylamino A phenyl group substituted with at least one group selected from the group consisting of a group, a (C1-C4) dialkylamino group, and a carboxyl group;
Phenylamino group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A phenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Diphenylamino group: As a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A diphenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Represents
R ₇ represents a (C1-C4) alkylthio group substituted with a sulfo group;
R ₈ represents a (C1-C4) alkylcarbonylamino group,
R ₉ represents a (C1-C4) alkoxy group substituted with a sulfo group,
R ₁₀ represents a (C1-C4) alkyl group,
Any one of R ₁₁ to R ₁₃ is a sulfo group, and the other two are each independently a hydrogen atom; a carboxy group; a sulfo group; a halogen atom; a (C1-C4) alkyl group; Or the azo compound according to any one of 2) or a tautomer thereof, or a salt thereof.
6) In equations (1) and (2),
R ₁ represents a (C1-C4) alkyl group,
R ₂ represents a cyano group; a carbamoyl group; or a carboxy group;
One of R ₃ and R ₄ represents a sulfo group, and the other represents a hydrogen atom; or a (C1-C4) alkyl group;
R ₅ represents a hydrogen atom; or a sulfo group;
R ₆ is a phenyl group; or (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, -C4) a phenyl group substituted with at least one group selected from the group consisting of an alkylamino group, a (C1-C4) dialkylamino group, and a carboxyl group;
R ₇ represents a (C1-C4) alkylthio group substituted with a sulfo group;
R ₈ represents a (C1-C4) alkylcarbonylamino group,
R ₉ represents a (C1-C4) alkoxy group substituted with a sulfo group,
R ₁₀ represents a (C1-C4) alkyl group,
Any one of R ₁₁ to R ₁₃ is a sulfo group, and the other two are each independently a hydrogen atom; a carboxy group; a sulfo group; a halogen atom; a (C1-C4) alkyl group; Or the azo compound according to any one of 2) or a tautomer thereof, or a salt thereof.
7) In the formulas (1) and (2),
R ₁ represents a (C1-C4) alkyl group,
R ₂ represents a cyano group; a carbamoyl group; or a carboxy group;
One of R ₃ and R ₄ is a sulfo group, and the other represents a hydrogen atom; or a methyl group;
R ₅ represents a hydrogen atom; or a sulfo group;
R ₆ is a phenyl group; or (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, -C4) a phenyl group substituted with at least one group selected from the group consisting of an alkylamino group, a (C1-C4) dialkylamino group, and a carboxyl group;
R ₇ represents a (C1-C4) alkylthio group substituted with a sulfo group;
R ₈ represents a (C1-C4) alkylcarbonylamino group,
R ₉ represents a (C1-C4) alkoxy group substituted with a sulfo group,
R ₁₀ represents a (C1-C4) alkyl group,
R ₁₁ represents a halogen atom,
R ₁₂ represents a sulfo group,
R ₁₃ is an azo compound or a tautomer thereof according to any one of 1) or 2) represents a hydrogen atom, or a salt thereof.
8) In the formulas (1) and (2),
The substitution position of R ₁₁ is position 4,
The substitution position of R ₁₂ is at position 5,
The azo compound according to 7), wherein the substitution position of R ₁₃ is position 6, or a tautomer thereof, or a salt thereof.
9) An aqueous ink composition comprising at least one azo compound or a tautomer thereof according to any one of 1) to 8) or a salt thereof as a dye.
10) The water-based ink composition according to claim 9, further comprising a water-soluble organic solvent.
11) An ink jet recording method in which the ink composition described in 9) or 10) is used as an ink, and ink droplets of the ink are ejected according to a recording signal to perform recording on a recording material.
12) The inkjet recording method according to 11), wherein the recording material is an information transmission sheet.
13) The ink jet recording method according to 12), wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance.
14) An ink jet printer loaded with a container containing the ink composition according to 9) or 10).
15)
a) The azo compound according to any one of 1) to 8) or a tautomer thereof, or a salt thereof,
b) The water-based ink composition according to 9) or 10), or
c) A colored body colored by any one of the three methods described in 11).

The azo compound of the present invention or a salt thereof, and an ink composition containing the azo compound are suitably used as an ink for ink jet recording, and when recorded on ink jet dedicated paper, the print density is very high and the color rendering property is low. In addition, the ink composition containing the azo compound of the present invention has a low chroma and a high-quality black hue, and is excellent in (ozone) gas resistance and light resistance even at high and low concentrations. It is extremely useful as a black ink for inkjet recording.

Hereinafter, the present invention will be described in detail.
For the sake of convenience, in the present specification, the “azo compound of the present invention”, including all of the “azo compound of the present invention or a tautomer thereof, or a salt thereof”, will be simply described below.
The azo compound of the present invention represented by the formula (1) has a tautomer, and the tautomer includes the following formulas (3) and (4) in addition to the compound represented by the formula (1). Etc. are considered. These compounds are also included in the present invention. In formulas (3) and (4), R _{1 to} R ₁₃ have the same meaning as in formula (1) above.

In the above formula (1),
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. Among these, (C1-C4) alkyl groups or phenyl groups are preferred, and (C1-C4) alkyl groups are more preferred.

In the above formula (1),
R ₂ represents a cyano group, a carbamoyl group or a carboxy group, and among them, a cyano group or a carbamoyl group is preferable, and a cyano group is most preferable.

In the above formula (1),
R ₃ and R ₄ each independently represent a hydrogen atom, a (C1-C4) alkyl group, a halogen atom, a (C1-C4) alkoxy group, or a sulfo group.
Among these, a hydrogen atom, a (C1-C4) alkyl group, a (C1-C4) alkoxy group, or a sulfo group is preferable. More preferably, any one is a sulfo group, and the other is a hydrogen atom, a (C1-C4) alkyl group, a (C1-C4) alkoxy group, or a sulfo group.
More preferably, either one is a sulfo group and the other is a hydrogen atom or a methyl group.
The substitution position of R ₃ and R ₄ is not particularly limited, but when either one is a hydrogen atom and the other is a sulfo group, the sulfo group is not adjacent to any nitrogen atom constituting the benzimidazolopyridone ring. It is preferable to substitute one of the two carbon atoms.

The compound represented by the above formula (1) of the present invention may be used as a mixture containing at least two kinds of positional isomers at the substitution positions of RR ₃ and R ₄ from the viewpoint of ease of synthesis and low cost. good.

In the above formula (1),
R ₅ is a hydrogen atom; a carboxy group; a sulfo group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; as a substituent, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group. (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of: Of these, a hydrogen atom; or a sulfo group;

In the above formula (1),
R ₆ is a (C 2 -C 4) alkyl group;
As a substituent, a (C1-C4) alkyl 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) alkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) alkylamino group substituted with a group;
(C1-C4) dialkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) dialkylamino group substituted with a group;
Phenyl group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkylamino A phenyl group substituted with at least one group selected from the group consisting of a group, a (C1-C4) dialkylamino group, and a carboxyl group;
Phenylamino group; as a substituent, a hydrogen atom, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1- A phenylamino group substituted with at least one group selected from the group consisting of C4) alkylamino group, (C1-C4) dialkylamino group, and carboxyl group;
Diphenylamino group: As a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A diphenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Represents.
In the present invention, in order to realize the effect particularly remarkably, among the above substituents, a phenyl group; or (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group as the substituent , Sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkylamino group, (C1-C4) dialkylamino group, and at least one group selected from the group consisting of carboxyl groups Particularly preferred are phenyl groups. More preferably, it is a phenyl group, a (C1-C4) alkyl group, a (C1-C4) alkoxy group, a phenyl group substituted with a chlorine atom, a sulfo group, or a carboxyl group.

In the above formula (1),
R ₇ represents a (C1 to C4) alkylthio group; a (C1 to C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxyl group as a substituent. . Among these, (C1-C4) alkylthio groups substituted with a sulfo group are preferable.

In the above formula (1),
R ₈ represents a (C1-C4) alkylcarbonylamino group.

In the above formula (1),
R ₉ and R ₁₀ are each independently a hydrogen atom; a carboxy group; a sulfo group; an acetylamino group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group as a substituent, and (C1-C4). (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of alkoxy groups, sulfo groups and carboxyl groups; (C1-C4) alkylthio groups; consisting of hydroxy groups, sulfo groups and carboxyl groups (C1-C4) alkylthio group substituted with at least one group selected from the group.
Of these, a hydrogen atom; a carboxy group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxyl group are preferably selected. (C1-C4) alkoxy group substituted with at least one group; (C1-C4) alkylthio group; substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxyl group ( C1-C4) alkylthio group; and (C1-C4) alkoxy group substituted with a sulfo group and (C1-C4) alkyl group. As a particularly preferred combination, R ₉ is a (C1-C4) alkoxy group substituted with a sulfo group, and R ₁₀ is a (C1-C4) alkyl group.

In the above formula (1),
R ₁₁ to R ₁₃ are each independently 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; (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 carboxyl group; (C1-C4) An alkylsulfonyl group; 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 carboxyl group. Among these, preferred substituents are hydrogen atom; carboxy group; sulfo group; halogen atom; (C1-C4) alkyl group. In addition, any one of R ₁₁ to R ₁₃ is a sulfo group, and the other two are each independently a hydrogen atom; a carboxy group; a sulfo group; a halogen atom; or a (C1-C4) alkyl group. A particularly preferred and more preferred combination is when R ₁₁ represents a halogen atom, R ₁₂ represents a sulfo group, and R ₁₃ represents a hydrogen atom. Further, as these substitution positions, it is most preferable that the substitution position of R ₁₁ is the 4-position, the substitution position of R ₁₂ is the 5-position, and the substitution position of R ₁₃ is the 6-position.

R ₁ to R ₁₃ in the above formula (1) will be described below with specific examples.
Examples of the (C1 to C4) alkyl group for R ₁ include a linear or branched unsubstituted group, and a linear group is preferable. Specific examples thereof include straight chain such as methyl, ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, sec-butyl and tert-butyl; Preferable specific examples include methyl and n-propyl, and methyl is particularly preferable.

Examples of the (C1 to C4) alkyl group substituted with a carboxy group in R ₁ include those in which any carbon atom of the unsubstituted (C1 to C4) alkyl group is substituted with a carboxy group. The substitution position of the carboxy group is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitutions of carboxy is 1 or 2, preferably 1. Specific examples include carboxymethyl and 2-carboxyethyl. Preferred examples include carboxymethyl.

Examples of the phenyl group substituted with a sulfo group in R ₁ include a phenyl group having 1 to 3, preferably 1 or 2 substituted sulfo groups, and the substitution position of the sulfo group is not particularly limited. Specific examples include 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5-disulfophenyl, and the like. A preferred specific example is 4-sulfophenyl.

Particularly preferable R ₁ is a (C1-C4) alkyl group as described above, and methyl is most preferable among them.

In the above formula (1), R ₂ represents a cyano group; a carbamoyl group; or a carboxy group. A cyano group or a carbamoyl group is preferable, and a cyano group is more preferable.

In the above formula (1), examples of the (C1 to C4) alkyl group in R ₃ and R ₄ include the same as the (C1 to C4) alkyl group in R ₁ and preferable ones.

In R ₃ and R _4, the halogen atom, fluorine atom, chlorine atom, bromine atom, or iodine atom and the like, a chlorine atom is preferable.

Examples of the (C1 to C4) alkoxy group in R ₃ and R ₄ include a linear or branched unsubstituted group, and a linear group is preferable. Specific examples include straight chain such as methoxy, ethoxy, n-propoxy and n-butoxy; branched chain such as isopropoxy, isobutoxy, sec-butoxy and tert-butoxy; Of these, methoxy is particularly preferred.

As described above, a particularly preferred combination of R ₃ and R ₄ is one of which is a sulfo group and the other is a hydrogen atom or a methyl group.

In the above formula (1), examples of the (C1-C4) alkyl group in R ₅ include the same as the (C1-C4) alkyl group in R ₁ and preferred ones.

Examples of the (C1 to C4) alkoxy group in R ₅ include the same groups as the (C1 to C4) alkoxy group in R ₃ and R ₄ , including preferable ones.

In R ₅ , the substituent is substituted with at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a hydroxy (C1-C4) alkoxy group, a sulfo group, and a carboxy group. Examples of the (C1-C4) alkoxy group include those having any of these substituents on any carbon atom in the (C1-C4) alkoxy group. The number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited, but is preferably substituted with a carbon atom other than the carbon atom to which the oxygen atom in the alkoxy group is bonded.
Specific examples include hydroxy (C1-C4) alkoxy groups such as 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy; methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, isopropoxyethoxy, n-butoxyethoxy, (C1-C4) alkoxy (C1-C4) alkoxy groups such as methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy; hydroxy (C1-C4) alkoxy such as 2-hydroxyethoxyethoxy ( C1-C4) alkoxy group; carboxy (C1-C4) alkoxy group such as carboxymethoxy, 2-carboxyethoxy, 3-carboxypropoxy; 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobu Sulfo (C1 -C4) alkoxy group such as alkoxy; and the like.

Among the above, R ₅ is particularly preferably a hydrogen atom or a sulfo group.

Examples of the (C2 to C4) alkyl group for R ₆ include a linear or branched unsubstituted group, and a linear group is preferable. Specific examples thereof include straight chain such as ethyl, n-propyl and n-butyl; branched chain such as isopropyl, isobutyl, sec-butyl and tert-butyl; Preferable specific examples include ethyl and n-propyl, and ethyl is particularly preferable.

Examples of the (C1-C4) alkyl group substituted with a hydroxy group in R ₆ include those in which any carbon atom of the unsubstituted (C1-C4) alkyl group is substituted with a hydroxy group. The substitution position of the hydroxy group is not particularly limited, but it is preferably substituted at the terminal of the alkyl group, and the hydroxy substitution number is 1 or 2, preferably 1. Specific examples include hydroxymethyl and hydroxyethyl. A preferred specific example is hydroxymethyl.

Examples of the (C1-C4) alkyl group substituted with a sulfo group in R ₆ include those in which a sulfo group is substituted on any carbon atom of the unsubstituted (C1-C4) alkyl group. The substitution position of the sulfo group is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitution of sulfo is 1 or 2, preferably 1. Specific examples include sulfomethyl and sulfoethyl. A preferred specific example is sulfomethyl.

Examples of the (C1 to C4) alkyl group substituted with a carboxy group in R ₆ include those in which any carbon atom of the unsubstituted (C1 to C4) alkyl group is substituted with a carboxy group. The substitution position of the carboxy group is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitutions of carboxy is 1 or 2, preferably 1. Specific examples include carboxymethyl and 2-carboxyethyl. Preferred examples include carboxymethyl.

As the (C1-C4) alkyl group substituted with the (C1-C4) alkoxy group in R _6, a (C1-C4) alkoxy group is substituted on any carbon atom of the unsubstituted (C1-C4) alkyl group. The thing which was done is mentioned. Although the substitution position of the (C1-C4) alkoxy group is not particularly limited, it is preferably substituted at the end of the alkyl group, and the substitution number of the (C1-C4) alkoxy group is 1 or 2, preferably 1. Specific examples include methoxymethyl, 2-methoxyethyl, 2-methoxy-n-propyl, 3-methoxy-n-propyl, 2-methoxy-n-butyl, 3-methoxy-n-butyl, 4-methoxy-n. -Butyl, ethoxymethyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 4-ethoxy-n-butyl, isopropoxymethyl, n-propoxyethyl and the like.

Examples of the (C1 to C4) alkylamino group for R ₆ include a linear or branched unsubstituted group, and a linear one is preferable. Specific examples thereof include, for example, linear ones such as methylamino, ethylamino, n-propylamino, and n-butylamino; branched ones such as isopropylamino, isobutylamino, sec-butylamino, and tert-butylamino; Is mentioned. Preferable specific examples include methylamino, ethylamino, and n-propylamino, and methylamino or ethylamino is particularly preferable.

The substituent in R ₆ was substituted with at least one group selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group ( Examples of the C1-C4) alkylamino group include those having these substituents on any carbon atom in the (C1-C4) alkylamino group. The number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited.
For example,
Chloromethylamino, 2-chloroethylamino, 2-chloropropylamino, 3-chloropropylamino, 2-bromoethylamino, 3-iodoethylamino, halogeno (C1-C4) alkylamino groups;
Nitro (C1-C4) alkylamino groups such as nitromethylamino, 2-nitroethylamino;
2-hydroxyethylamino, 3-hydroxypropylamino and the like, hydroxy (C1-C4) alkylamino groups;
Methoxyethylamino, ethoxypropylamino, etc., (C1-C4) alkoxy (C1-C4) alkylamino groups;
2-sulfoethylamino, 3-sulfopropylamino and the like, sulfo (C1-C4) alkylamino groups;
2-carboxyethylamino, 3-carboxypropylamino and the like, carboxy (C1-C4) alkylamino groups;
Phenyl (C1-C4) alkylamino groups such as phenylmethylamino, 2-phenylethylamino;
In addition, when it is a phenyl group as a substituent of the (C1-C4) alkylamino group, it is at least one group selected from the group consisting of a hydrogen atom, a halogen atom, a nitro group, a hydroxy group, a sulfo group and a carboxy group. It may be replaced. The number of the substituents is usually 1 or 2, preferably 1. Of these, a hydrogen atom, a sulfo group, a chlorine atom and a carboxy group are preferable, and a hydrogen atom, a sulfo group and a carboxy group are particularly preferable.

Examples of the (C1 to C4) dialkylamino group for R ₆ include a linear or branched unsubstituted group, and a linear one is preferred. Specific examples thereof include straight chain such as dimethylamino, diethylamino, di-n-propylamino and di-n-butylamino; branched chain such as diisopropylamino, diisobutylamino, disec-butylamino and ditert-butylamino. Those having different alkyl chain lengths such as methylethylamino, methylpropylamino, and ethylpropylamino. Preferable specific examples include dimethylamino, diethylamino, and methylethylamino, and dimethylamino or diethylamino is particularly preferable.

The substituent in R ₆ was substituted with at least one group selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group ( Examples of the C1-C4) dialkylamino group include those having these substituents at any carbon atom in each (C1-C4) alkyl chain of the (C1-C4) dialkylamino group. The number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited.
For example,
Bis (chloromethyl) amino, chloromethylmethylamino, bis (2-chloroethyl) amino, ethylchloroethylamino, bis (2-chloropropyl) amino, bis (3-chloropropyl) amino, 2-bromoethylethylamino, Halogeno (C1-C4) dialkylamino groups such as 3-iodoethylethylamino;
Nitromethylethylamino, bis (2-nitroethyl) amino, ethyl (2-nitroethylamino, etc., nitro (C1-C4) dialkylamino groups;
Bis (2-hydroxyethyl) amino, 2-hydroxyethylmethylamino, 3-hydroxypropylmethylamino, etc., hydroxy (C1-C4) dialkylamino groups;
Methoxyethylmethylamino, diethoxypropylamino and the like, (C1-C4) alkoxy (C1-C4) dialkylamino groups;
Di (2-sulfoethyl) amino, 3-sulfopropylethylamino and the like, sulfo (C1-C4) dialkylamino groups;
Carboxy (C1-C4) dialkylamino groups such as ethyl 2-carboxyethylamino, di (3-carboxypropyl) amino;
Di (phenylmethyl) amino, di (2-phenylethyl) amino and the like, phenyl (C1-C4) alkylamino groups;
In addition, when it is a phenyl group as a substituent of the (C1-C4) alkylamino group, it is substituted with at least one group selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a sulfo group, and a carboxy group. May be. The number of the substituents is usually 1 or 2, preferably 1.

(C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkylamino group as substituents for R ₆ , A (C1-C4) dialkylamino group, and a phenyl group substituted with at least one group selected from the group consisting of carboxyl groups, those having any of these substituents on any carbon atom in the phenyl group Is mentioned. The number of the substituents is usually 1 to 5, preferably 1 to 3, and more preferably 1 or 2. Substituents are preferably substituted at the 3 or 4 position, with the carbon attached to the carbonyl group being taken as 1.
For example,
2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl 2,3,4-trimethylphenyl 2,3,5-trimethylphenyl, 2,3,6-trimethylphenyl, 2,4,5-trimethylphenyl, 2,4,6-trimethylphenyl,
2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,4-diethylphenyl, 2,5-diethylphenyl, 3,4-diethylphenyl, 3,5-diethylphenyl, etc. (C1-C4) alkyl A phenyl group;
2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2,5-dimethoxyphenyl, 3,4-dimethoxyphenyl, 3,5-dimethoxyphenyl 2,3,4-trimethoxy Phenyl, 2,3,5-trimethoxyphenyl, 2,3,6-trimethoxyphenyl, 2,4,5-trimethoxyphenyl, 2,4,6-trimethoxyphenyl,
2-ethoxyphenyl, 3-ethoxyphenyl, 4-ethoxyphenyl, 2,4-diethoxyphenyl, 2,5-diethoxyphenyl, 3,4-diethoxyphenyl, 3,5-diethoxyphenyl,
2-methoxy-4-ethoxyphenyl, 2-ethoxy-3-methoxyphenyl, and the like (C1-C4) alkoxyphenyl groups;
2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3,4-trifluorophenyl, 2,3,5-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl,
2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,3,4-trichlorophenyl 2,3,5-trichlorophenyl, 2,3,6-trichlorophenyl, 2,4,5-trichlorophenyl, 2,4,6-trichlorophenyl,
2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,3-dibromophenyl, 2,4-dibromophenyl, 2,5-dibromophenyl, 3,4-dibromophenyl, 3,5-dibromophenyl, Halogenophenyl groups such as 2,3,4-tribromophenyl, 2,3,5-tribromophenyl;
2-nitrophenyl, 3-nitrophenyl, 4-nitrophenyl and the like, nitrophenyl groups;
2-sulfophenyl, 3-sulfophenyl, 4-sulfophenyl, 2,3-disulfophenyl, 2,4-disulfophenyl, 2,5-disulfophenyl, 3,4-disulfophenyl, 3, 5-disulfophenyl, 2,3,4-trisulfophenyl, 2,3,5-trisulfophenyl, 2,3,6-trisulfophenyl, 2,4,5-trisulfophenyl, 2,4, A sulfophenyl group such as 6-trisulfophenyl;
2-hydroxyphenyl, 3-hydroxyphenyl, 4-hydroxyphenyl, 2,3-dihydroxyphenyl, 2,4-hydroxyphenyl, 2,5-dihydroxyphenyl, 3,4-dihydroxyphenyl, 3,5-dihydroxyphenyl, etc. A hydroxyphenyl group;
2-methylthiophenyl, 3-methylthiophenyl, 4-methylthiophenyl, 2,4-dimethylthiophenyl, 2,5-dimethylthiophenyl, 3,4-dimethylthiophenyl, 3,5-dimethylthiophenyl,
2-ethylthiophenyl, 3-ethylthiophenyl, 4-ethylthiophenyl, 2,4-diethylthiophenyl, 2,5-diethylthiophenyl, 3,4-diethylthiophenyl, 3,5-diethylthiophenyl,
(C1-C4) alkylthiophenyl groups such as 2-methylthio-4-ethylthiophenyl;
2-methylaminophenyl, 3-methylaminophenyl, 4-methylaminophenyl, 2,4-di (methylamino) phenyl, 2,5-di (methylamino) phenyl, 3,4-di (methylamino) phenyl 3,5-di (methylamino) phenyl,
2-ethylaminophenyl, 3-ethylaminophenyl, 4-ethylaminophenyl, 2,4-di (ethylamino) phenyl, 2,5-di (ethylamino) phenyl, 3,4-di (ethylamino) phenyl 3,5-di (ethylamino) phenyl,
(C1-C4) alkylaminophenyl groups such as 2-methylamino-4-ethylaminophenyl;
2-dimethylaminophenyl, 3-dimethylaminophenyl, 4-dimethylaminophenyl, 2-ethylmethylaminophenyl, 3-ethylmethylaminophenyl, 4-ethylmethylaminophenyl, 2,4-dimethylaminophenyl, 2,5 -Dimethylaminophenyl, 3,4-dimethylaminophenyl, 3,5-dimethylaminophenyl,
2-diethylaminophenyl, 3-diethylaminophenyl, 4-diethylaminophenyl, 2,4-bis (diethylamino) phenyl, 2,5-bis (diethylamino) phenyl, 3,4-bis (diethylamino) phenyl, 3,5-bis (Diethylamino) phenyl,
2-dimethylamino-4-diethylaminophenyl, etc. (C1-C4) dialkylaminophenyl groups 2-carboxyphenyl, 3-carboxyphenyl, 4-carboxyphenyl, 2,3-dicarboxyphenyl, 2,4-dicarboxy Phenyl, 2,5-dicarboxyphenyl, 3,4-dicarboxyphenyl, 3,5-dicarboxyphenyl, 2,3,4-tricarboxyphenyl, 2,3,5-tricarboxyphenyl, 2,3, Examples include 6-tricarboxyphenyl, 2,4,5-tricarboxyphenyl, 2,4,6-tricarboxyphenyl, and the like.

Among the above, particularly preferable R ₆ is a phenyl group, a (C1-C4) alkyl group, a (C1-C4) alkoxy group, a halogen atom, a nitro group, a sulfo group, a hydroxy group, (C1-C4) as a substituent. And a phenyl group substituted with at least one group selected from the group consisting of an alkylthio group, a (C1-C4) alkylamino group, a (C1-C4) dialkylamino group, and a carboxyl group, specifically Phenyl group, 4-methylphenyl group, 3-methylphenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-methoxyphenyl group, 2-carboxyphenyl group, 3-carboxyphenyl group, 4-carboxyphenyl group, 2-sulfophenyl group, 3-sulfophenyl group, 4-sulfophenyl group, etc. Preferred.

In the above formula (1), examples of the (C1 to C4) alkylthio group for R ₇ include a linear or branched unsubstituted alkyl group, and a linear one is preferred. Specific examples thereof include, for example, a linear chain such as a methylthio group, an ethylthio group, an n-propylthio group, and an n-butylthio group; a branched chain such as an isopropylthio group, an isobutylthio group, a sec-butylthio group, and a tert-butylthio group. Can be mentioned.

As the substituent for R _7, the (C1 to 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 includes a (C1 to C4) alkylthio group. Those having these substituents at any carbon atom 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 is preferably substituted with a carbon atom other than the carbon atom to which the oxygen atom in the alkylthio group is bonded.
Specific examples thereof include, for example, 2-hydroxyethylthio group, 2-hydroxypropylthio group, 3-hydroxypropylthio group, hydroxy (C1-C4) alkylthio group; 2-sulfoethylthio group, 3-sulfopropylthio group. A sulfo (C1 to C4) alkylthio group; a 2-carboxyethylthio group, a 3-carboxypropylthio group, a 4-carboxybutylthio group, and the like; a carboxy (C1 to C4) alkylthio group;

Among the above, preferable R ₇ includes a sulfo (C1 to C4) alkylthio group or a carboxy (C1 to C4) alkylthio group, a sulfo (C1 to C4) alkylthio group is more preferable, and a sulfopropylthio group is particularly preferable. .

Examples of the (C1 to C4) alkylcarbonylamino group for R ₈ include straight chain or branched chain unsubstituted alkyl groups, and straight chain groups are preferred. Specific examples thereof include straight chain such as acetylamino (methylcarbonylamino), propionylamino (ethylcarbonylamino), n-propylcarbonylamino, n-butylcarbonylamino; isopropylcarbonylamino, isobutylcarbonylamino, sec -Branched ones such as butylcarbonylamino and pivaloylamino (tert-butylcarbonylamino); Of these, a straight chain is preferable, and an acetylamino group is particularly preferable.

A preferred combination of R ₇ and R _{8 is} a combination of R ₇ is a sulfo (C1-C4) alkylthio group, R ₈ is an acetylamino group, R ₇ is a sulfopropylthio group, and R ₈ is an acetylamino group. Particularly preferred.

In the above formula (1), examples of the (C1 to C4) alkyl group in R ₉ and R ₁₀ include the same as the (C1 to C4) alkyl group in R ₁ and preferable ones.

Examples of the (C1 to C4) alkoxy group in R ₉ and R ₁₀ include the same groups as the (C1 to C4) alkoxy group in R ₃ and R ₄ , including preferable ones.

As a substituent in R ₉ and R ₁₀ , substituted with at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a hydroxy (C1-C4) alkoxy group, a sulfo group, and a carboxy group As the (C1-C4) alkoxy group, as a substituent in the above R ₅ and R ₆ , from a hydroxy group, a (C1-C4) alkoxy group, a hydroxy (C1-C4) alkoxy group, a sulfo group, and a carboxy group (C1-C4) alkoxy groups substituted with at least one group selected from the group consisting of the same groups, including preferred groups, and the like.

Examples of the (C1-C4) alkylthio group in R ₉ and R ₁₀ include the same groups as those described above including the (C1-C4) alkylthio group in R ₇ and preferred ones.

As the substituent in R ₉ and R _10, the (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 includes the hydroxy group in R ₇ described above. (C1-C4) alkylthio groups substituted with at least one group selected from the group consisting of a group, a sulfo group, and a carboxy group, and the same ones including preferred ones.

Among the above, preferable R ₉ includes a sulfo (C1 to C4) alkoxy group and a carboxy (C1 to C4) alkoxy group, a sulfo (C1 to C4) alkoxy group is more preferable, and a sulfopropoxy group is particularly preferable.

Among the above, preferable R ₁₀ includes (C1 to C4) alkyl group, (C1 to C4) alkoxy group, sulfo (C1 to C4) alkoxy group and carboxy (C1 to C4) alkoxy group. C4) An alkyl group is more preferable, and a methyl group is particularly preferable.

A preferred combination of R ₉ and R _{10 is} a combination of R ₉ is a sulfo (C1-C4) alkoxy group, R ₁₀ is a (C1-C4) alkyl group, R ₉ is a sulfopropoxy group, and R ₁₀ is a methyl group. Combinations are particularly preferred.

Examples of the (C1-C4) alkyl group in R ₁₁ to R ₁₃ include the same groups as those described above including the (C1-C4) alkyl group in R ₁ and preferred ones.

Examples of the (C1 to C4) alkoxy group in R ₁₁ to R ₁₃ include the same groups as the (C1 to C4) alkoxy group in R ₃ and R ₄ , including preferable ones.

In R ₁₁ to R ₁₃ , the substituent is at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a hydroxy (C1-C4) alkoxy group, a sulfo group, and a carboxy group. As the substituted (C1 to C4) alkoxy group, as a substituent in the above R ₅ and R ₆ , a hydroxy group, a (C1 to C4) alkoxy group, a hydroxy (C1 to C4) alkoxy group, a sulfo group, and a carboxy group (C1-C4) alkoxy groups substituted with at least one group selected from the group consisting of the same groups, including preferable groups, and the like.

Examples of the (C1 to C4) alkylsulfonyl group in R ₁₁ to R ₁₃ include linear or branched ones, and linear ones are preferred. Specific examples thereof include linear ones such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl and n-butylsulfonyl; branched ones such as isopropylsulfonyl and isobutylsulfonyl;
Of the above, methylsulfonyl, ethylsulfonyl, and isopropylsulfonyl are preferable, and methylsulfonyl is particularly preferable.

As the substituent in R ₁₁ to R ₁₃ , the (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 includes the above (C1 to C1). C4) The above-mentioned groups are substituted on any carbon atom in the alkylsulfonyl group, and the number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited.
Specific examples include hydroxy-substituted compounds such as hydroxyethylsulfonyl and 2-hydroxypropylsulfonyl; sulfo-substituted compounds such as 2-sulfoethylsulfonyl and 3-sulfopropylsulfonyl; 2-carboxyethylsulfonyl and 3-carboxypropylsulfonyl. Carboxy-substituted ones such as;

Among the above, preferable R ₁₁ includes a hydrogen atom, a carboxy group, a sulfo group, a nitro group, a halogen atom, a methyl group, a methoxy group, and a (C1-C4) alkylsulfonyl group, and a hydrogen atom, a carboxy group, a sulfo group. Group, nitro group, methyl group, methoxy group and chlorine atom are more preferred, and chlorine atom is 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, or a carboxy (C1 to C4) alkyl. Examples include a sulfonyl group and a sulfo (C1 to C4) alkylsulfonyl group, and a sulfo group, a nitro group, a methyl group, a methoxy group, a sulfamoyl group, a sulfopropylsulfonyl group, and a carboxyethylsulfonyl group are more preferable, and a sulfo group is particularly preferable.

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 a hydrogen atom, a sulfo group, and a methoxy group are more preferable. A hydrogen atom and a sulfo group are particularly preferable.

A preferred combination of R ₁₁ to R _{13 is} a combination in which R ₁₁ is a chlorine atom, and one of R ₁₂ and R ₁₃ is a sulfo group, R ₁₁ is a chlorine atom, R ₁₂ is a sulfo group, and R ₁₃ is A combination of hydrogen atoms is particularly preferred.

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

A more preferred compound of the above formula (1) is a compound represented by the following formula (2).

In the above formula (2), from R ₁ R ₁₀ have the same meanings as in the above formula (1), combinations of the preferred groups and preferred groups are also the same as in the formula (1), the above R ₇ ~ R ₁₀ is more preferably substituted at the position of formula (2).

R ₁₃ from R ₁₁ in the formula (2) represents the same meaning as R ₁₃ from R ₁₁ in the formula (1), combinations of the preferred groups and preferred groups are also the same as in the formula (1). As the substitution, the substitution position of R ₁₁ is 4-position, the substitution position of R ₁₂ is 5-position, and the substitution position of R ₁₃ is most preferably 6-position.

Specific examples of preferable combinations in the formulas (1) and (2) include the following combinations (i) to (iv). (Ii) is preferable to (i), more preferably (iii), and (iv) is most preferable.
(I)
In formulas (1) and (2),
R ₁ is a methyl group,
R ₂ is a cyano group or a carbamoyl group,
R ₃ is a hydrogen atom, a methyl group or a methoxy group,
R ₄ is a sulfo group,
R ₅ is a hydrogen atom, or a sulfo group R ₆ is a (C2-C4) alkyl group;
As a substituent, a (C1-C4) alkyl 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) alkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) alkylamino group substituted with a group;
(C1-C4) dialkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) dialkylamino group substituted with a group;
(C1-C4) dialkylamino group;
Phenyl group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkylamino A phenyl group substituted with at least one group selected from the group consisting of a group, a (C1-C4) dialkylamino group, and a carboxyl group;
Phenylamino group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A phenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Diphenylamino group: As a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A diphenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
R ₇ is a sulfo (C1-C4) alkylthio group,
R ₈ is an acetylamino group,
R ₉ is a sulfopropoxy group,
R ₁₀ is a (C1 to C4) alkyl group R ₁₁ to R ₁₃ are each independently a hydrogen atom; a carboxy group; a sulfo group; a halogen atom; a methyl group; a methoxy group; a sulfamoyl group;
(Ii)
In formulas (1) and (2),
R ₁ is a methyl group,
R ₂ is a cyano group or a carbamoyl group,
R ₃ is a hydrogen atom or a methyl group,
R ₄ is a sulfo group,
R ₅ is a hydrogen atom, or a sulfo group R ₆ is a (C2-C4) alkyl group;
Phenyl group; substituted with at least one group selected from the group consisting of (C1-C4) alkyl group, (C1-C4) alkoxy group, chlorine atom, sulfo group, hydroxy group, and carboxyl group A phenyl group,
R ₇ is a sulfo group (C1-C4) alkylthio group,
R ₈ is an acetylamino group,
R ₉ is a sulfopropoxy group,
R ₁₀ is a (C1-C4) alkyl group R ₁₁ to R ₁₃ are each independently a hydrogen atom; a carboxy group; a sulfo group; a chlorine atom; a methyl group; a methoxy group; a sulfamoyl group;
In formulas (1) and (2),
R ₁ is a methyl group,
R ₂ is a cyano group,
R ₃ is a hydrogen atom,
R ₄ is a sulfo group,
R ₅ is a hydrogen atom, or a sulfo group R ₆ is a phenyl group; the substituent is selected from the group consisting of a C1-C2 alkyl group, a C1-C2 alkoxy group, a chlorine atom, a sulfo group, a hydroxy group, and a carboxyl group A phenyl group substituted with at least one group;
R ₇ is a sulfo (C1-C4) alkylthio group,
R ₈ is an acetylamino group,
R ₉ is a sulfopropoxy group,
R ₁₀ is a (C1-C4) alkyl group R ₁₁ to R ₁₃ are each independently a hydrogen atom; a carboxy group; a sulfo group; a chlorine atom; a methyl group; a methoxy group;
(Iv)
In formulas (1) and (2),
R ₁ is a methyl group,
R ₂ is a cyano group,
R ₃ is a hydrogen atom,
R ₄ is a sulfo group,
R ₅ is a hydrogen atom, or a sulfo group R ₆ is a phenyl group; the substituent is selected from the group consisting of a C1-C2 alkyl group, a C1-C2 alkoxy group, a chlorine atom, a sulfo group, a hydroxy group, and a carboxyl group A phenyl group substituted with at least one group;
R ₇ is a sulfopropylthio group,
R ₈ is an acetylamino group,
R ₉ is a sulfopropoxy group,
R ₁₀ is a (C1-C4) alkyl group R ₁₁ is a chlorine atom,
R ₁₂ is a sulfo group,
R ₁₃ is a hydrogen atom or a sulfo group;

The trisazo compound of the present invention represented by the formula (1) can be synthesized, for example, by the following method. Moreover, the structural formula of the compound in each process shall be represented with the form of a free acid.
In the following formulas (5) to (12), R ₁ to R ₁₃ represent the same meaning as in the above formula (1).
A compound represented by the following formula (5) is diazotized by a conventional method, and the obtained diazo compound and a compound represented by the following formula (6) are subjected to a coupling reaction by a conventional method, and represented by the following formula (7). To obtain the compound.

The obtained compound of the above formula (7) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (8) are subjected to a coupling reaction by a conventional method to obtain the following formula (9) To obtain a compound represented by:

The obtained compound of the above formula (9) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (10) are subjected to a coupling reaction by a conventional method to obtain the following formula (11) To obtain a compound represented by:

The obtained compound of the above formula (11) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (12) are subjected to a coupling reaction by a conventional method, whereby the above formula ( The azo compound of the present invention represented by 1) can be obtained.

The compound represented by the above formula (12) can be synthesized according to the method described in Patent Document 3.

Although it does not specifically limit as a suitable specific example of the azo compound of this invention represented by Formula (1), The compound shown by the structural formula given to the following Table 1 thru | or 20 is mentioned.
In each table, functional groups such as sulfo group and carboxy group are described in the form of free acid for convenience.

The diazotization of the compound of formula (5) is carried out in a manner known per se, for example nitrites, such as sodium nitrite, 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 an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of formula (5) with the compound of formula (6) 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 pH 1-6. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. Examples of the base that can be used include 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 and organic amines. . The compound of formula (5) and the compound of formula (6) are used in approximately stoichiometric amounts.

The diazotization of the compound of the formula (7) is carried out in a manner known per se, for example nitrites, such as sodium nitrite, 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 an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of formula (7) with the compound of formula (8) 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 liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. The same base as described above can be used. The compound of formula (7) and the compound of formula (8) are used in approximately stoichiometric amounts.

The diazotization of the compound of the formula (9) is carried out in a manner known per se, for example nitrites, such as sodium nitrite, 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 salt. Coupling of the diazotized compound of the compound of formula (9) with the compound of 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 50 [deg.] C, preferably 10 to 40 [deg.] C and an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. The same base as described above can be used. The compound of formula (9) and the compound of formula (10) are used in approximately stoichiometric amounts.

The diazotization of the compound of formula (11) is also carried out in a manner known per se, for example a subnitrite such as nitrite, for example sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 40 ° C. It is carried out using an alkali metal nitrate. Coupling of the diazotized compound of the compound of formula (11) and the compound of formula (12) is also carried out under conditions known per se. It is advantageous to carry out the reaction in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C, preferably 10 to 40 ° C, and 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 pH value is adjusted by adding a base. The same base as described above can be used. The compounds of formulas (11) and (12) are used in approximately stoichiometric amounts.

The salt of the azo compound represented by the formula (1) is a salt with an inorganic or organic cation. Among these, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred inorganic salts are lithium, sodium, potassium, and ammonium salts. Examples of the organic cation salt include, but are not limited to, salts with quaternary ammonium ions represented by the following formula (13). 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 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 may be used. The physical properties such as solubility may vary depending on the type of salt, and the physical properties that meet the purpose can be selected by selecting the type of salt as appropriate, or by changing the ratio when multiple salts are included. It is also possible to obtain a mixture having

In the above formula (13), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a group selected from the group consisting of a hydrogen atom, an unsubstituted alkyl group, a hydroxyalkyl group and a hydroxyalkoxyalkyl group, At least one is a group other than a hydrogen atom.
Specific examples of the alkyl group represented by Z ^{1 to} Z ⁴ in the formula (13) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Specific examples include hydroxy (C1-C4) alkyl groups such as hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, and the like. Examples of alkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl and the like. Ci (C1-C4) alkoxy (C1-C4) alkyl groups may be mentioned, and among these, hydroxyethoxy (C1-C4) alkyl is preferred. Particularly preferred are hydrogen atoms; hydroxy (C1-C4) alkyl groups such as methyl, hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, etc. Hydroxyethoxy (C1-C4) alkyl such as hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl Groups.

Specific examples of combinations of Z ¹ , Z ² , Z ³ , and Z ⁴ of the preferred compound as the formula (13) are shown in Table 21 below.

As a method for synthesizing a desired salt of the azo compound represented by the formula (1) of the present invention, after completion of the final step in the synthesis reaction of the compound represented by the formula (1), a desired inorganic salt or organic Obtained by adding a mineral acid such as hydrochloric acid to the reaction solution and isolating the azo compound from the reaction solution in the form of a free acid. The free acid is washed with water, acidic water or an aqueous organic medium as necessary to remove impurities such as attached inorganic salts, and again in an aqueous medium (preferably in water). And a method of forming a salt by adding an organic base corresponding to the desired inorganic base or the above-described quaternary ammonium salt. 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 water obtained by dissolving a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid in water. The aqueous organic medium refers to an admixture of water and an organic substance and / or an organic solvent that are miscible with water.
Examples of the water-miscible organic substance and organic solvent include water-soluble organic solvents described later.
Examples of inorganic salts used when the azo compound represented by the formula (1) is used as a desired salt include alkali metal halogen salts such as lithium chloride, sodium chloride and potassium chloride; lithium carbonate, sodium carbonate and potassium carbonate Alkali metal carbonates such as lithium hydroxide, sodium hydroxide, potassium hydroxide and other alkali metal hydroxides; ammonium ion halogen salts such as ammonium chloride and ammonium bromide; ammonium hydroxide (ammonia water), etc. And ammonium ion hydroxides.
Examples of the organic cation salt include, for example, halogen salts of quaternary ammonium ions represented by the above formula (13) such as diethanolamine hydrochloride and triethanolamine hydrochloride.

The ink composition of the present invention will be described. The azo compound represented by the formula (1) of the present invention can dye a material made of cellulose by forming an aqueous composition containing the compound. In addition, materials having a carbonamide bond can be dyed, and can be widely used for dyeing leather, fabrics, paper, and the like. On the other hand, a typical use of the compound of the present invention is an ink composition dissolved in a liquid medium, and is preferably used as an ink composition for inkjet recording.

A reaction liquid containing the compound represented by the formula (1), for example, a reaction liquid after completion of the final step in the synthesis reaction of the compound represented by the formula (1) is directly used for the production of the ink composition. I can do things. However, the reaction solution is dried, for example, spray-dried; the reaction solution is salted out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate; the reaction solution is treated with hydrochloric acid, sulfuric acid The compound is isolated by a method of acid precipitation by adding a mineral acid such as nitric acid, or the like; A product 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 1 to 8% by mass, using the azo compound represented by the formula (1) of the present invention as a pigment. It is a water-based 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 and an ink preparation agent as necessary within a range that does not impair the effects of the present invention. The water-soluble organic solvent may have a function as a dye-dissolving agent, a drying inhibitor (wetting agent), a viscosity modifier, a penetration accelerator, a surface tension modifier, an antifoaming agent, etc., and the ink composition of the present invention It is preferable to contain them. Examples of the ink preparation agent include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventives, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, antioxidants, and surfactants. These additives may be mentioned. In the ink composition of the present invention, the water-soluble organic solvent is 0 to 30% by mass, preferably 5 to 30% by mass, and the ink preparation agent is 0 to 15% by mass, preferably 0 to 7% by mass, based on the total mass. % May be contained respectively. The remainder other than the above is water. The pH of the ink composition is preferably pH 5 to 11 and more preferably pH 7 to 10 in terms of improving storage stability. Further, 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.

In addition to the azo compound of the present invention, the ink composition of the present invention may appropriately contain other toning pigments and the like for the purpose of adjusting the subtle hue of black. Even in such a case, the total mass of the pigment 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.
Examples of toning dyes include yellow (for example, CI Acid Yellow 17, CI Acid Yellow 23, CI Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 142, CI Direct Yellow 161, etc.), orange (eg, CI Direct Orange 17, CI Direct Orange 26, CI Direct 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, etc.) Direct Red 75, CI Direct Red 79, CI Direct Red 80, CI Direct Red 84, CI Direct Red 225, CI Direct Red 226, etc.), magenta (for example, CI Direct Red 227, etc.), violet, blue, navy, cyan ( For example, CI direct blue 199, CI acid blue 249, etc.), green, black, and other dyes having various hues.
The ink composition of the present invention can be used by blending one or more of these toning 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 the coloring matter contained in the ink composition may be in the above range. The mixing ratio of the azo compound of the present invention to the toning dye is approximately 20: 1 to 1: 2, preferably 10: 1 to 1: 1, depending on the hue of the toning dye and the like. It is.
When the ink composition of the present invention is used as an ink for ink-jet recording, it is preferable to use an ink containing a small amount of inorganic impurities such as metal cation chloride and sulfate 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 pigment. The lower limit may be less than the detection limit of the analytical instrument, that is, 0%. In order to produce the azo compound of the present invention with a small amount of inorganic impurities, for example, a method using a reverse osmosis membrane; or a dried product or wet cake of the azo compound of the present invention with an alcohol such as methanol, preferably (C1-C4) alcohol In addition, the mixture may be suspended and purified in a mixed solvent of water and water, and the precipitate may be desalted by a known method such as a method of separating and drying the precipitate by filtration.

Specific examples of water-soluble organic solvents that can be used in preparing the ink composition of the present invention include (C1-C4) alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol or tert-butanol. A carboxylic acid amide such as N, N-dimethylformamide or N, N-dimethylacetamide; a lactam such as 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone or N-methylpyrrolidin-2-one Cyclic cyclic ureas such as 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2-one; acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one, etc. Ketones or ketoalcohols; tetrahydrofuran, dioxa Cyclic ethers such as 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, Mono-, oligo- or polyalkylene glycols or thioglycols having C2-C6 alkylene units such as tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol or dithiodiglycol; trimethylolpropane, glycerin or hexane-1 , 2,6-triol and other polyols (preferably triol); ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol (C1-C4) alkyl ethers of polyhydric alcohols such as dimethyl monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol) triethylene glycol monomethyl ether or triethylene glycol monoethyl ether; γ-butyrolactone; or dimethyl Sulfoxide; and the like. These organic solvents may be used alone or in combination of two or more.
The water-soluble organic solvent mentioned above contains substances that are solid at room temperature, such as trimethylolpropane, but these are water-soluble even when they are solid, and when dissolved in water Since it can be used for the same purpose as the water-soluble organic solvent, it is described in the category of the water-soluble organic solvent for the sake of convenience.

Hereinafter, antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventives, water-soluble UV absorbers, water-soluble polymer compounds, dye dissolving agents, antioxidants, and surfactants that can be used as ink preparation agents Describe.

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

Examples of preservatives include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, and benzothiazole. , Isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, benzyl Examples thereof include bromoacetate-based or inorganic salt-based compounds. Specific examples of organic halogen compounds include sodium pentachlorophenol, specific examples of pyridine oxide compounds include, for example, sodium 2-pyridinethiol-1-oxide, and isothiazoline compounds include, 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 -Isothiazoline-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 antiseptic / antifungal agents include anhydrous sodium acetate, sodium sorbate, sodium benzoate, and the like.

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

Specific examples of the chelating reagent include, for example, disodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate or sodium uracil diacetate.

Examples of the rust preventive agent include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, dicyclohexylammonium nitrite, and the like.

Examples of the water-soluble ultraviolet 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 dissolving agent 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 anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines or heterocyclic rings. .

Examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants.
Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate poly Oxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethyl Examples include sulfosuccinate, diethylhexylsylsulfosuccinate, and dioctylsulfosuccinate.

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.

Examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, or imidazoline derivatives. Is mentioned.

Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, and other ethers; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl Acetylene glycol (alcohol) series such as lu-1-hexyn-3-ol; trade name Surfynol 104, 105, 82, 465, Olphine STG, etc. manufactured by Nissin Chemical; Polyglycol ether series (for example, SIGMA-ALDRICH) Manufactured by Tergitol 15-S-7, etc.).
The above 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 an arbitrary order. If desired, the obtained ink composition may be subjected to microfiltration with a membrane filter or the like to remove impurities, and when used for ink jet recording, it is preferable to perform the filtration. The pore diameter of the filter for performing 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 a water-based ink for writing, a water-based printing ink, an information recording ink, and the like, and is particularly preferably used as an ink for ink-jet recording. 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 performing recording by using the ink composition of the present invention as an ink, and ejecting ink droplets of the ink in accordance with a recording signal to adhere to a recording material. In the ink jet recording method of the present invention, there are no particular limitations on the ink head, ink nozzles, and the like used for recording, and they can be appropriately selected according to the purpose.
This recording method is a known method, for example, a charge control method that ejects ink using electrostatic attraction force; a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element; An acoustic ink jet method that irradiates the ink instead of the ink and discharges the ink using the radiation pressure; a thermal ink jet that heats the ink to form bubbles and uses the generated pressure, a 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. For example, information transmission sheets such as paper and film, fibers and cloths (cellulose, nylon, wool, etc.), leather, and color filter base materials. Among them, an information transmission sheet is preferable.
The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet, a synthetic paper, a film or other base material provided with an ink receiving layer. The ink receiving layer is formed by, for example, impregnating or coating the above-mentioned base material with a cationic polymer; or a porous white inorganic substance capable of absorbing a pigment in the ink, such as porous silica, alumina sol, or special ceramics. And a hydrophilic polymer such as polyvinyl pyrrolidone, and the like.
The information transmission sheet provided with such an ink receiving layer is usually called ink jet dedicated paper (film), glossy paper (film) or the like. Specific examples include Canon Inc., trade name: Professional Photo Paper, Super Photo Paper, or Matt Photo Paper; Seiko Epson Corporation, trade name: Photo Paper (Glossy), PM Matt Paper, Crispia; Japan Hewlett-Packard Co. Made by company, product name Advanced Photo Paper, Premium Plus Photo Paper, Premium Glossy Film or Photo Paper, etc., and are available as commercial products. Of course, plain paper can also be used.

  Among the information transmission sheets described above, it is known that an image recorded on a sheet coated with a porous white inorganic substance has a particularly large discoloration due to ozone gas. However, since the ink composition of the present invention is excellent in ozone gas resistance, a great effect is exhibited even when ink jet recording is performed on such a recording material.

In order to record on a recording material by the ink jet recording method of the present invention, for example, a container containing the above ink composition may be loaded at a predetermined position of an ink jet printer and recorded on the recording material by the above method.
The inkjet recording method of the present invention comprises the black ink composition of the present invention and, for example, the known magenta, cyan, yellow, and green, blue (or violet), red (or orange), etc. as necessary. These ink compositions of the respective colors can also be used in combination.
The ink composition of each color is injected into each container, and each container is loaded into a predetermined position of the ink jet printer and used for ink jet recording in the same manner as the container containing the black ink composition of the present invention.

The colored body of the present invention is
a) The azo compound according to any one of 1) to 8) or a tautomer thereof, or a salt thereof,
b) The water-based ink composition as described in 9) or 10) above, or
c) A substance colored by any one of the three methods of the ink jet recording method described in 11) above [the three of a) to c)].
Although there is no restriction | limiting in particular about the substance to be colored, The recording material etc. which are used for said inkjet recording method are mentioned preferably.

The azo compound of the present invention is a black pigment. This compound is easy to synthesize and inexpensive, and has a feature of low saturation, and therefore exhibits a more preferable hue as black. Moreover, since it is excellent in water solubility, the filterability with a membrane filter in the process of producing an ink composition is good.
Further, the ink composition of the present invention containing the azo compound is an aqueous black ink composition, and has good storage stability without solid precipitation, physical property change, color change, etc. after long-term storage.
An image recorded with the ink composition of the present invention has an excellent ozone resistance, a very high printing density, a low color rendering, a low chroma, and a high-quality black hue. Excellent fastness such as light resistance, moisture resistance and water resistance. Further, when used in combination with ink compositions containing magenta, cyan and yellow pigments, full-color ink jet recording with excellent fastness and storage stability is possible.
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 instrument, and the like, and has excellent ejection stability. Is preferred.

EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not limited at all by the following example.
In the text, “parts” and “%” are based on mass unless otherwise specified.
Operations such as each synthesis reaction and crystallization were performed under stirring unless otherwise specified.
In 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 are both measured values in the reaction system.
Moreover, the maximum absorption wavelength (λmax) of the synthesized compound was measured in an aqueous solution having a pH of 7 to 8, and the measured value of the measured compound was described in Examples.
The azo compounds of the present invention synthesized in the following examples all showed a solubility of 100 g / liter or more in water.

Example 1
(Process 1)
After adding 29.3 parts of metamic acid to 500 parts of water, an aqueous solution was obtained by adding a 25% aqueous sodium hydroxide solution to a pH of 5.0 to 6.0. 24.9 parts of benzoyl chloride was added dropwise. After the dropwise addition, the mixture was reacted for 2 hours while maintaining the pH at 5.0 to 6.0 with a 25% aqueous sodium hydroxide solution. The reaction solution was salted out by adding sodium chloride. The precipitated solid was collected by filtration to obtain 85.8 parts of a compound represented by the following formula (14) as a wet cake.

(Process 2)
After adding 33.8 parts of 4-chloroaniline-3-sulfonic acid to 120 parts of water, an aqueous solution was obtained by adding a 25% aqueous sodium hydroxide solution to pH 9.0 to 10.0. 32.5 parts of 40% sodium nitrite aqueous solution was added and stirred for about 30 minutes to obtain a reaction solution. The reaction solution was poured into a mixed solution of 35 parts of 35% hydrochloric acid in 100 parts of ice water, stirred for 1 hour, further added with 0.2 parts of sulfamic acid and stirred for 5 minutes to obtain a diazo reaction solution.
On the other hand, after adding 85.8 parts of a wet cake of the compound represented by the formula (14) obtained in Example 1 (Step 1) to 240 parts of water, a pH of 6. was obtained by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0 to 7.0. This aqueous solution was added dropwise to the diazo reaction solution obtained above in about 20 minutes. After the dropwise addition, the mixture was reacted for 16 hours while maintaining the pH at 1.2 to 1.5 by adding a 15% aqueous sodium carbonate solution. The pH was adjusted to 0.5 to 1.5 by adding 35% hydrochloric acid, and after stirring for 1 hour, salting out was performed by adding sodium chloride. The precipitated solid was collected by filtration to obtain 155.9 parts of a compound represented by the following formula (15) as a wet cake.

(Process 3)
41.8 parts of 4-chloro-3-nitroaniline was dissolved in 60.0 parts of N-methyl-2-pyrrolidone, and 35.2 parts of acetic anhydride was added dropwise thereto in about 15 minutes. After the dropwise addition, the reaction solution was added to 400 parts of water after reacting at 40-50 ° C. for 2 hours. After stirring at room temperature for 30 minutes, the precipitated solid was filtered, and the obtained solid was washed with 100 parts of funnel water, separated and dried to obtain 63.0 parts of a compound represented by the following formula (16). Obtained.

(Process 4)
42.9 parts of the compound represented by the formula (16) obtained in Example 1 (Step 3) was dissolved in 115.0 parts of N-methyl-2-pyrrolidone, and sodium 3-mercaptopropanesulfonate was dissolved therein. 40.9 parts and 29.0 parts of potassium carbonate were added. After the addition, the mixture was heated to 130 to 140 ° C. and reacted at the same temperature for 2 hours. After further adding 3.6 parts of sodium 3-mercaptopropanesulfonate, the mixture was reacted at 130 to 140 ° C. for 1 hour. After cooling to 60 ° C., the reaction solution was added to 700 parts of 2-propanol, and the solid obtained after cooling to room temperature was collected by filtration. The obtained wet cake was dissolved in 300 parts of water, adjusted to pH 3.0 to 4.0 by adding 35% hydrochloric acid, salted out with sodium chloride, and the precipitated solid was collected by filtration, and the following formula (17 ) Was obtained as a wet cake.

(Process 5)
In 150 parts of water, 102.6 parts of a wet cake of the compound represented by the formula (17) obtained in Example 1 (Step 4), 1.6 parts of activated carbon and 0.4 parts of anhydrous iron (III) chloride. After heating to 60 ° C., 15.9 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 1.5 hours. After cooling to 40 ° C., insoluble matters were removed by filtration, and the filtrate was cooled to room temperature. The pH was adjusted to 1.0 to 1.5 by addition of 50% sulfuric acid, and the precipitated solid was collected by filtration to obtain 62.3 parts of a compound represented by the following formula (18) as a wet cake.

(Step 6)
After adding 12.0 parts of a wet cake of the compound represented by the formula (15) obtained in Example 1 (Step 2) to 100 parts of water, 3.5 parts of 35% hydrochloric acid and 40% sodium nitrite 1.7 parts of an aqueous solution was added and reacted for about 30 minutes. 0.2 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, after adding 5.4 parts of a wet cake of the compound represented by the formula (18) obtained in Example 1 (Step 5) to 40 parts of water, pH 3. An aqueous solution was obtained as 0 to 4.0. This aqueous solution was added dropwise to the diazo reaction solution obtained above in about 5 minutes. After dripping, it reacted for 3 hours, maintaining pH at 1.0-2.0 by addition of 15% sodium carbonate aqueous solution. The pH was adjusted to 0.5 to 1.5 by adding 35% hydrochloric acid, and after stirring for 20 hours, salting out was performed by adding sodium chloride. The precipitated solid was collected by filtration to obtain 14.5 parts of a compound represented by the following formula (19) as a wet cake.

(Step 7)
14.5 parts of a wet cake of the compound represented by the formula (19) obtained in Example 1 (Step 6) above was added to 50 parts of water and dissolved by stirring. After adding 8.0 parts of 35% hydrochloric acid, 1.6 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 0.1 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 2.2 parts of a compound of the following formula (20) obtained by the method described in JP-A-2004-083492 is added to 30 parts of water, and pH is 4.5 to 5.5 by adding a 25% aqueous sodium hydroxide solution. As an aqueous solution was obtained. This aqueous solution was added dropwise to the diazo reaction solution obtained above in about 5 minutes. After dripping, it reacted for 12 hours, maintaining pH at 2.0-3.0 by addition of 15% sodium carbonate aqueous solution. After stirring for 12 hours, salting out was performed by adding sodium chloride. The precipitated solid was collected by filtration to obtain 29.3 parts of a compound represented by the following formula (21) as a wet cake.

(Process 8)
To 100 parts of water, 29.3 parts of a wet cake of the compound represented by the formula (21) obtained in Example 1 (Step 7) was added and dissolved by stirring. After adding 10 parts of 35% hydrochloric acid, 0.7 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 0.1 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 2.8 parts of a compound represented by the following formula (22) obtained by the method described in Patent Document 4 is added to 35 parts of water, and a 25% aqueous sodium hydroxide solution is added to adjust the pH to 7.5 to 8.5. To obtain an aqueous solution. The diazo reaction liquid obtained above was dropped into this aqueous solution at 15 to 30 ° C. for about 30 minutes. At this time, an aqueous sodium carbonate solution was added to maintain the pH of the reaction solution at 7.0 to 8.0, and the reaction was further continued for 2 hours while maintaining the same temperature and pH adjustment. 300 parts of isopropyl alcohol was added to the reaction solution, and the precipitated solid was separated by filtration to obtain 66.7 parts of a wet cake. The obtained wet cake was dissolved in 100 parts of water, the pH was adjusted to 7.0 to 7.5 with 35% hydrochloric acid, 300 parts of methanol was added, and the precipitated solid was collected by filtration. The obtained wet cake was again dissolved in 100 parts of water, and then 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain 5.3 parts of a compound represented by the following formula (23) of the present invention as a sodium salt. In addition, this compound is a compound of the compound number 1 or 2 of Table 1.
λmax: 585 nm.

Example 2
(A) Preparation of high-concentration ink After obtaining the black ink composition of the present invention by mixing the components shown in Table 22 below, it was obtained by filtering out impurities with a 0.45 μm membrane filter. Ink was used as Example 2. The obtained ink composition is hereinafter referred to as “ink”.
The water used was ion exchange water. At the time of ink preparation, the pH of the ink was adjusted to pH 7-9 with sodium hydroxide, and then ion exchange water was added to make a total amount of 100 parts. In addition, Nissin Chemical Co., Ltd. product name Surfinol 104PG50 was used as the surfactant in Table 6 below.

Comparative Example 1
A comparative ink was prepared in the same manner as in Example 2 except that the pigment of the following formula (24) was used as the black pigment for comparison. The following various tests conducted using this ink are referred to as Comparative Example 1. In addition, the compound of the following formula (24) is the compound of Example 8 in Patent Document 9, and was obtained by following the method described in the document.

Comparative Example 2
A comparative ink was prepared in the same manner as in Example 2 except that the pigment of the following formula (25) was used as the black pigment for comparison. The following various tests conducted using this ink are referred to as Comparative Example 2. In addition, the compound of the following formula (25) is the compound of Example 1 in Patent Document 10, and was obtained by trying the method described in the document.

(B) Inkjet recording Using the ink obtained above, Canon inkjet printer, trade name PIXUS
Using iP4500, inkjet recording was performed on glossy paper manufactured by Canon, trade name Photo Paper Glossy Pro [Platinum Grade].
When printing, create an image pattern so that six levels of gradations of 100%, 80%, 60%, 40%, 20%, 10% density can be obtained. The following evaluation test was carried out using this as a test piece.

(C) Evaluation of recorded image
Each recorded image obtained using the ink of Example 2 and Comparative Examples 1 and 2 was evaluated by measuring the density change of the image before and after the test.
The density change of the recorded image is measured by measuring the gradation portion where the reflection density D value of the recorded image before the test is closest to 1.0, using a colorimeter manufactured by X-rite, the product name SpectroEye. did. In the color measurement, all were performed under the conditions of DIN, viewing angle 2 °, and light source D65 based on the density standard. In this test, in all the test pieces, the 60% density gradation portion was a portion where the reflection density D value was close to 1.0.
The specific test method is as follows.

(D) Ozone test Each recorded image obtained using the inks of Example 2 and Comparative Examples 1 and 2 was naturally dried for 24 hours after printing, and the product name Ozone Weather manufactured by Suga Test Instruments Co., Ltd. Each test piece was allowed to stand for 24 hours under the conditions of an ozone concentration of 30 ppm, a humidity of 50% RH, and a temperature of 23 ° C. using an ohmmeter.
After the test, the colorimetry was performed using the above-described colorimeter, and the dye residual ratio was determined by (reflected density after test / reflected density before test) × 100 (%) and evaluated according to the following criteria. The results are shown in Table 23 below.
◎ Residual rate: 80% or more ○ Residual rate: 70% or more and less than 80% △ Residual rate: 60% or more and less than 70% x Residual rate: Less than 60%

(E) Light resistance test Suga Test Instruments Co., Ltd., product name Low-temperature cycle xenon weatherometer XL75 Each test piece is installed, irradiance is 100,000 Lux, humidity is 60% RH, temperature is 24 ° C. Under irradiation for 48 hours. The recorded images of each test piece before and after exposure to xenon light were measured using the above colorimeter, and the residual dye ratio (reflected density after test / reflected density before test) × 100 (% ) And evaluated according to the following criteria. The results are shown in Table 23 below.
◎ Residual rate: 90% or more ○ Residual rate: 85% or more and less than 90% △ Residual rate: 80% or more and less than 85% × Residual rate: less than 80%

Example 3
(F) Preparation of Low Concentration Ink The ink of Example 3 was obtained as a low dye concentration ink by mixing the components shown in Table 24 below. The ink of Example 3 was obtained in the same manner as the ink of Example 2 except that the pigment concentration was different.

Comparative Examples 3 and 4
A comparative low pigment concentration ink was prepared in the same manner as in Example 3 except that the pigments of the above formulas (24) and (25) were used as the black pigments to be compared. The ink using the above formula (24) was set as Comparative Example 3, and the ink using the above formula (25) was set as Comparative Example 4.

(G) Inkjet recording Using the ink obtained above, Canon inkjet printer, product name PIXUS
Using iP4500, inkjet recording was performed on glossy paper manufactured by Canon, trade name Photo Paper Glossy Pro [Platinum Grade].
When printing, create an image pattern so that six levels of gradations of 100%, 80%, 60%, 40%, 20%, 10% density can be obtained. The following evaluation test was carried out using this as a test piece.

(H) Evaluation of recorded image
Each recorded image obtained using the ink of Example 3 and Comparative Examples 3 and 4 was evaluated by measuring the density change of the image before and after the test.
The density change of the recorded image is measured by measuring the gradation portion where the reflection density D value of the recorded image before the test is closest to 1.0, using a colorimeter manufactured by X-rite, the product name SpectroEye. did. In the color measurement, all were performed under the conditions of DIN, viewing angle 2 °, and light source D65 based on the density standard. In this test, in all the test pieces, the 80% density gradation portion was a portion where the reflection density D value was close to 1.0.
The specific test method is as follows.

(I) Ozonity Test Each recorded image obtained using the inks of Example 3 and Comparative Examples 3 and 4 was naturally dried for 24 hours after printing, and was manufactured by Suga Test Instruments Co., Ltd. Each test piece was allowed to stand for 24 hours under the conditions of an ozone concentration of 30 ppm, a humidity of 50% RH, and a temperature of 23 ° C. using an ohmmeter.
After the test, the colorimetry was performed using the above-described colorimeter, and the dye residual ratio was determined by (reflected density after test / reflected density before test) × 100 (%) and evaluated according to the following criteria. The results are shown in Table 25 below.
◎ Residual rate: 80% or more ○ Residual rate: 70% or more and less than 80% △ Residual rate: 60% or more and less than 70% x Residual rate: Less than 60%

(J) Light Resistance Test Each recorded image obtained using the inks of Example 3 and Comparative Examples 3 and 4 was naturally dried for 24 hours after printing, and was manufactured by Suga Test Instruments Co., Ltd. Each test piece was installed in a xenon weatherometer XL75, and irradiation was performed for 48 hours under conditions of an irradiance of 100,000 Lux, a humidity of 60% RH, and a temperature of 24 ° C. The recorded images of each test piece before and after exposure to xenon light were measured using the above colorimeter, and the residual dye ratio (reflected density after test / reflected density before test) × 100 (% ) And evaluated according to the following criteria. The results are shown in Table 25 below.
◎ Residual rate: 90% or more ○ Residual rate: 85% or more and less than 90% △ Residual rate: 80% or more and less than 85% × Residual rate: less than 80%

As is apparent from the results in Table 23, the recorded image of Example 2 and the images obtained from Comparative Examples 1 and 2 have clear differences in ozone resistance and light resistance, and the ink of the present invention is excellent. Is clear. That is, it is clear that the residual ratio of the Dk concentration after the ozone resistance / light resistance test is high, and the fading to ozone and light is improved.
Further, as is clear from the results in Table 25, it is clear that the color fading with respect to ozone is also improved when the low density ink is adjusted. Furthermore, it was also revealed that the light resistance was improved as compared with the ink of Comparative Example 3.

The ink composition containing the azo compound of the present invention is suitably used as a black ink liquid for various recordings, particularly for inkjet recording.

Claims (15)

An azo compound represented by the following formula (1), a tautomer thereof, or a salt thereof.

[In Formula (1),
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 ₄ each independently represent a hydrogen atom; a (C1-C4) alkyl group; a halogen atom; a (C1-C4) alkoxy group; or a sulfo group;
R ₅ is a hydrogen atom; a carboxy group; a sulfo group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; as a substituent, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group. (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of:
R ₆ is a (C 2 -C 4) alkyl group;
As a substituent, a (C1-C4) alkyl 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) alkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) alkylamino group substituted with a group;
(C1-C4) dialkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) dialkylamino group substituted with a group;
Phenyl group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkylamino A phenyl group substituted with at least one group selected from the group consisting of a group, a (C1-C4) dialkylamino group, and a carboxyl group;
Phenylamino group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A phenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Diphenylamino group: As a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A diphenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Represents
R ₇ represents a (C1 to C4) alkylthio group; a (C1 to C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxyl group as a substituent;
R ₈ represents a (C1-C4) alkylcarbonylamino group,
R ₉ and R ₁₀ are each independently a hydrogen atom; a carboxy group; a sulfo group; an acetylamino group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group as a substituent, and (C1-C4). (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of alkoxy groups, sulfo groups and carboxyl groups; (C1-C4) alkylthio groups; consisting of hydroxy groups, sulfo groups and carboxyl groups (C1-C4) alkylthio group substituted with at least one group selected from the group;
R ₁₁ to R ₁₃ are each independently 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; (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 carboxyl group; (C1-C4) An alkylsulfonyl group; 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 carboxyl group. ] An azo compound represented by the following formula (2), a tautomer thereof, or a salt thereof.

[In Formula (2),
R ₁ to R ₁₃ represent the same meaning as in formula (1). ] In formulas (1) and (2), at least one of R ₁₁ to R ₁₃ is a sulfo group or a carboxy group, and at least one of R ₆ to R ₁₀ is a sulfo group or a sulfo (C1-C4) alkoxy group. Item 3. The azo compound according to any one of Items 1 and 2, or a tautomer thereof, or a salt thereof. In formulas (1) and (2),
R ₁ represents a (C1-C4) alkyl group; or a phenyl group,
R ₂ represents a cyano group; a carbamoyl group; or a carboxy group;
One of R ₃ and R ₄ is a sulfo group, and the other represents a hydrogen atom; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; or a sulfo group;
R ₅ is a hydrogen atom; a carboxy group; a sulfo group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; as a substituent, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group. (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of:
R ₆ is a (C 2 -C 4) alkyl group;
As a substituent, a (C1-C4) alkyl 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) alkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) alkylamino group substituted with a group;
(C1-C4) dialkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group (C1-C4) dialkylamino group substituted with a group; phenyl group; (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, ( A phenyl group substituted with at least one group selected from the group consisting of C1-C4) alkylthio groups, (C1-C4) alkylamino groups, (C1-C4) dialkylamino groups, and carboxyl groups;
Phenylamino group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A phenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Diphenylamino group: As a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A diphenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Represents
R ₇ 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 carboxyl group;
R ₈ represents a (C1-C4) alkylcarbonylamino group,
R ₉ and R ₁₀ are each independently a hydrogen atom; a carboxy group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxyl group. (C1-C4) alkoxy group substituted with at least one group selected from the group; (C1-C4) alkylthio group; at least one group selected from the group consisting of hydroxy group, sulfo group and carboxyl group (C1-C4) alkylthio group substituted with
R ₁₁ to R ₁₃ each independently represent a hydrogen atom; a carboxy group; a sulfo group; a halogen atom; a (C1-C4) alkyl group; or the azo compound according to claim 1 or 2, Tautomers or salts thereof. In formulas (1) and (2),
R ₁ represents a (C1-C4) alkyl group,
R ₂ represents a cyano group; a carbamoyl group; or a carboxy group;
One of R ₃ and R ₄ represents a sulfo group, and the other represents a hydrogen atom; or a (C1-C4) alkyl group;
R ₅ represents a hydrogen atom; or a sulfo group;
R ₆ is a (C 2 -C 4) alkyl group;
As a substituent, a (C1-C4) alkyl 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) alkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) alkylamino group substituted with a group;
(C1-C4) dialkylamino group; as a substituent, at least one kind selected from the group consisting of a halogen atom, a nitro group, a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, a phenyl group, and a carboxy group A (C1-C4) dialkylamino group substituted with a group;
(C1-C4) dialkylamino group;
Phenyl group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkylamino A phenyl group substituted with at least one group selected from the group consisting of a group, a (C1-C4) dialkylamino group, and a carboxyl group;
Phenylamino group; as a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A phenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Diphenylamino group: As a substituent, (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, (C1-C4) alkyl A diphenylamino group substituted with at least one group selected from the group consisting of an amino group, a (C1-C4) dialkylamino group, and a carboxyl group;
Represents
R ₇ represents a (C1-C4) alkylthio group substituted with a sulfo group;
R ₈ represents a (C1-C4) alkylcarbonylamino group,
R ₉ represents a (C1-C4) alkoxy group substituted with a sulfo group,
R ₁₀ represents a (C1-C4) alkyl group,
Any one of R ₁₁ to R ₁₃ is a sulfo group, and the other two independently represent a hydrogen atom; a carboxy group; a sulfo group; a halogen atom; a (C1-C4) alkyl group. 3. The azo compound according to any one of 1 or 2, or a tautomer thereof, or a salt thereof. In formulas (1) and (2),
R ₁ represents a (C1-C4) alkyl group,
R ₂ represents a cyano group; a carbamoyl group; or a carboxy group;
One of R ₃ and R ₄ represents a sulfo group, and the other represents a hydrogen atom; or a (C1-C4) alkyl group;
R ₅ represents a hydrogen atom; or a sulfo group;
R ₆ is a phenyl group; or (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, -C4) a phenyl group substituted with at least one group selected from the group consisting of an alkylamino group, a (C1-C4) dialkylamino group, and a carboxyl group;
R ₇ represents a (C1-C4) alkylthio group substituted with a sulfo group;
R ₈ represents a (C1-C4) alkylcarbonylamino group,
R ₉ represents a (C1-C4) alkoxy group substituted with a sulfo group,
R ₁₀ represents a (C1-C4) alkyl group,
Any one of R ₁₁ to R ₁₃ is a sulfo group, and the other two independently represent a hydrogen atom; a carboxy group; a sulfo group; a halogen atom; a (C1-C4) alkyl group. 3. The azo compound according to any one of 1 or 2, or a tautomer thereof, or a salt thereof. In formulas (1) and (2),
R ₁ represents a (C1-C4) alkyl group,
R ₂ represents a cyano group; a carbamoyl group; or a carboxy group;
One of R ₃ and R ₄ is a sulfo group, and the other represents a hydrogen atom; or a methyl group;
R ₅ represents a hydrogen atom; or a sulfo group;
R ₆ is a phenyl group; or (C1-C4) alkyl group, (C1-C4) alkoxy group, halogen atom, nitro group, sulfo group, hydroxy group, (C1-C4) alkylthio group, -C4) a phenyl group substituted with at least one group selected from the group consisting of an alkylamino group, a (C1-C4) dialkylamino group, and a carboxyl group;
R ₇ represents a (C1-C4) alkylthio group substituted with a sulfo group;
R ₈ represents a (C1-C4) alkylcarbonylamino group,
R ₉ represents a (C1-C4) alkoxy group substituted with a sulfo group,
R ₁₀ represents a (C1-C4) alkyl group,
R ₁₁ represents a halogen atom,
R ₁₂ represents a sulfo group,
R ₁₃ is an azo compound or a tautomer thereof according to any one of claims 1 or 2 represents a hydrogen atom, or a salt thereof. In formulas (1) and (2),
The substitution position of R ₁₁ is position 4,
The substitution position of R ₁₂ is at position 5,
The azo compound or a tautomer thereof or a salt thereof according to claim 7, wherein the substitution position of R ₁₃ is the 6-position. A water-based ink composition comprising at least one kind of the azo compound according to any one of claims 1 to 8, a tautomer thereof, or a salt thereof as a dye. The water-based ink composition according to claim 9, further comprising a water-soluble organic solvent. An ink jet recording method for performing recording on a recording material by using the ink composition according to claim 9 or 10 as ink and discharging ink droplets of the ink in accordance with a recording signal. The inkjet recording method according to claim 11, wherein the recording material is an information transmission sheet. 13. The ink jet recording method according to claim 12, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance. An ink jet printer loaded with a container containing the ink composition according to claim 9. a) The azo compound according to any one of claims 1 to 8, or a tautomer thereof, or a salt thereof,
b) The aqueous ink composition according to claim 9 or 10, or
c) A colored body colored by any one of the three methods of the ink jet recording method according to claim 11.