JP2015034208A - Ink composition, inkjet recording method using the same, and colored product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ink composition being stable even when stored in high concentration for a long period of time, allowing a very excellent hue of a printed image, and giving a recorded image of black color being excellent in various fastnesses, particularly in light fastness and ozone gas fastness, of a printed image.SOLUTION: An ink composition contains (A) a coloring matter represented by the formula (1) and (B) a coloring matter having a maximum absorption wavelength (λ max) of 340 to 440 nm in an aqueous solvent, a half value width of 150 nm or more, and a molecular weight of 1800 to 5000. [Rto Reach independently represent a hydrogen atom, a sulfo group or the like, and n represents 0 or 1, respectively.]

Description

  The present invention relates to an ink composition, an ink jet recording method using the same, and a colored body.

A recording method using an ink jet printer, which is one of representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) to perform recording. Is. This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material are not in direct contact, so there is little noise and quietness, and it is easy to reduce the size and speed. Expected.
Conventionally, water-based inks in which water-soluble pigments are dissolved in an aqueous medium have been used as inks for fountain pens, felt-tip pens and the like and inks for ink jet printing. In these water-based inks, a water-soluble organic solvent is generally added 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. Furthermore, the formed image is required to have image fastness such as water resistance and light fastness, color reproducibility and color rendering, and not only high image fastness but also balance of each color is important. .

  Due to the recent development of inkjet technology, the improvement in printing speed in inkjet printing is remarkable. For this reason, there is a movement to use an inkjet printer in the same manner as a laser printer using electronic toner for printing a document on plain paper, which is the main use in commercial printing and office environments. Ink jet printers have the advantage that the type of recording paper is not limited and the price of the machine is relatively low. In particular, ink jet printers are spreading in small to medium office environments such as SOHO. As described above, when an inkjet printer is used for printing on plain paper, color development and water resistance tend to be more important among qualities required for printed matter. In order to satisfy these performances, a method of using a pigment ink has been proposed. However, since the pigment ink is not a solution but a dispersion in which a solid pigment is dispersed, problems such as poor storage stability of the ink when the pigment ink is used, problems such as clogging of the nozzles of the printer head, etc. Is more likely to occur compared to dye inks. In addition, when pigment ink is used, it is often a problem that the printed image has low abrasion resistance. In the case of a dye ink, since the dye which is a pigment component is dissolved in the ink, problems caused by such a pigment ink are relatively unlikely to occur. However, since dye inks are generally significantly inferior to pigment inks in particular in terms of color developability, light resistance and water resistance, improvements are strongly desired.

By the way, in order to record image or character information on a color display of a computer in color by an ink jet printer, generally a subtraction method using four colors of ink of yellow (Y), magenta (M), cyan (C) and black (K). Mixed colors are used, whereby the recorded image is expressed in color. In order to reproduce an additive color mixture image of red (R), green (G), and blue (B) on a CRT (CRT) display etc. as faithfully as possible with a subtractive color mixture image, each dye used in the ink, particularly Y, Each of M and C is desired to have a hue close to a standard color and to be clear. The clearness mentioned here generally means having a high saturation. When the three primary colors Y, M, and C with low saturation are used, the color area that can be expressed in a single color or mixed color becomes narrow, and the range of the color area that is desired to be expressed may be insufficient. For this reason, development of highly saturated pigments and inks containing them is desired.
In addition, the ink performance is required to be stable for long-term storage, high in recorded image density, and excellent in fastness such as water resistance, moisture resistance, light resistance and gas resistance. It is done.
Here, the moisture resistance is a resistance to a phenomenon in which a dye that forms an image after recording is discolored due to excessive moisture mainly in the ambient environment contained in the atmosphere or oozes out of the image. In recent years, ink-jet recordings exhibited in various environments are regarded as important problems, but inks that sufficiently satisfy market demands have not yet been developed.
In addition, gas resistance refers to a gas that has an oxidizing action (also referred to as an oxidizing gas) existing in the air and reacts with a dye (dye) of a recorded image on or in a recording material. This is the resistance to the phenomenon of discoloration of images. Among oxidizing gases, ozone gas is considered to be a main causative substance that promotes the discoloration and fading phenomenon of ink jet recorded images. Since this discoloration phenomenon is characteristic of ink jet recorded images, improvement of ozone gas resistance is an important technical problem in this field.

  One method for obtaining a photographic image-recorded inkjet image is to provide an ink-receiving layer on the surface of a recording material. The ink receiving layer provided for such a purpose often contains a porous white inorganic substance in order to speed up drying of the ink and to reduce bleeding of the pigment with high image quality. However, particularly in such a recording material, the color fading due to the ozone gas is noticeable. With the recent spread of digital cameras and color printers, there are increasing opportunities to print images obtained with digital cameras and the like as photographic image quality at home, so the above-mentioned color change of recorded images due to oxidizing gas is regarded as a problem. .

  Among other ink compositions, black ink is an important ink used for both monocolor and full color images. However, it is technically difficult to develop a pigment that exhibits a good black color with a neutral hue between dark and light gamut, high print density, and low hue dependency on the light source. Although it is being developed, there are still few that have sufficient performance. Therefore, generally, a black ink is prepared by blending a plurality of various pigments. However, when an ink is prepared by mixing a plurality of dyes, the hue differs depending on the medium (recording material) as compared with the case where the ink is prepared with a single dye. 2) Decomposition of the dye by light or ozone gas. In particular, there is a problem that discoloration becomes large.

As a black ink composition for inkjet having various durability of printed matter, for example, one disclosed in Patent Document 1 has been proposed. This ink composition has a very good hue as a black color, and is an ink composition in which the image fastness of the printed matter has been greatly improved. We have not yet provided products that fully satisfy the requirements of

JP-A-11-70729 Japanese Patent No. 3346755 Japanese Patent No. 4100800 International Publication No. 2010/125903 International Publication No. 2006/051850 International Publication No. 2011/043184

  The present invention is stable even when stored for a long time, exhibits a neutral black to gray color with low saturation and no color in both dark and light color printing, and the printed image has a high density. Another object of the present invention is to provide a water-based black ink composition that gives a black recorded image that is excellent in light resistance and moisture resistance of a recorded image without any change in hue for each medium.

  As a result of intensive studies, the present inventors have found that an ink composition in which a specific dye (component (A)) represented by the following formula (1) and a dye having a specific property are combined is described above. The present invention has been completed by finding out that it solves the problem.

[ 式（１）中、
Ｒ^１、Ｒ^２、Ｒ^５、Ｒ^６及びＲ^７は、それぞれ独立に、水素原子；ハロゲン原子；シアノ基；ヒドロキシ基；スルホ基；カルボキシ基；スルファモイル基；ホスホ基；ニトロ基；ウレイド基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、若しくは（Ｃ１〜Ｃ４）アルコキシ基で置換された（Ｃ１〜Ｃ４）アルキル基；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；アシル基；Ｎ−アルキルアミノスルホニル基；Ｎ−フェニルアミノスルホニル基；スルホ基、カルボキシ基、及びヒドロキシ基よりなる群から選択される少なくとも１種類以上の基で置換されたＮ−アルキルアミノスルホニル基；アルキルスルホニル基；スルホ基、カルボキシ基、及びヒドロキシ基よりなる群から選択される少なくとも１種類以上の基で置換されたアルキルスルホニル基；アシルアミノ基；アルキルスルホニルアミノ基；フェニルスルホニルアミノ基；又はハロゲン原子、（Ｃ１〜Ｃ４）アルキル基、及びニトロ基からなる群より選択される少なくとも１種類以上の基で置換されたフェニルスルホニルアミノ基；を、
Ｒ^３及びＲ^４は、それぞれ独立に、水素原子；ハロゲン原子；シアノ基；カルボキシ基；スルホ基；ニトロ基；（Ｃ１〜Ｃ４）アルキル基；ヒドロキシ基、若しくは（Ｃ１〜Ｃ４）アルコキシ基で置換された（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、及びカルボキシ基よりなる群より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；スルホ基、若しくはカルボキシ基で置換され（Ｃ１〜Ｃ４）アルキルチオ基；アシルアミノ基；アルキルスルホニルアミノ基；フェニルスルホニルアミノ基；又はハロゲン原子、（Ｃ１〜Ｃ４）アルキル基、及びニトロ基よりなる群より選択される少なくとも１種類以上の基で置換されたフェニルスルホニルアミノ基；を、
ｎは０または１をそれぞれ表す。]
２）
式（１）において、
Ｒ^１乃至Ｒ^７のうち、少なくとも３以上はスルホ基、又はカルボキシ基である、上記１）に記載のインク組成物、
３）
式（１）において、
Ｒ^１、及びＲ^２が、それぞれ独立に、水素原子；スルホ基；カルボキシ基；又はヒドロキシ基；であり、
Ｒ^３、及びＲ^４が、それぞれ独立に、水素原子；ハロゲン原子；カルボキシ基；スルホ基；スルホ基、若しくはカルボキシ基で置換された（Ｃ１〜Ｃ４）アルコキシ基；又はスルホ基、若しくはカルボキシ基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；であり、
Ｒ^５乃至Ｒ^７が、それぞれ独立に、水素原子；ハロゲン原子；スルホ基；カルボキシ基；ヒドロキシ基；又は（Ｃ１〜Ｃ４）アルコキシ基；であり、
ｎが１である、上記１）又は２）に記載のインク組成物、
４）
上記式（１）において、
Ｒ^１がカルボキシ基、又はスルホ基であり、
Ｒ^２が水素原子であり、
Ｒ^３がスルホ基であり、
Ｒ^４が水素原子であり、
Ｒ^５が水素原子、カルボキシ基又はスルホ基であり、
Ｒ^６がカルボキシ基又はスルホ基であり、
Ｒ^７が水素原子であり、
ｎが１である、上記１）乃至３）のいずれか一項に記載のインク組成物、
５）
上記成分（Ｂ）が、下記式（２）で表される染料である、上記１）乃至４）のいずれか一項に記載のインク組成物、

[式（２）中、
Ａは式（３）で表される構造を表し、
Ｂは式（４）で表される構造を表し、
Ｘは、２価の架橋基（ただし、少なくとも２つ以上の窒素原子を有し、Ａ及びＢはそれぞれ異なる窒素原子に置換している。）を表し、
式（３）及び（４）中、
Ｒ^１０１からＲ^１０８はそれぞれ独立に、水素原子；ハロゲン原子；スルホ基；カルボキシ基；スルファモイル基；カルバモイル基；（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、ヒドロキシ（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；（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；カルボキシ基で置換された（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；ウレイド基；モノ（Ｃ１〜Ｃ４）アルキルウレイド基；ジ（Ｃ１〜Ｃ４）アルキルウレイド基；ヒドロキシ基、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モノ（Ｃ１〜Ｃ４）アルキルウレイド基；ヒドロキシ基、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ジ（Ｃ１〜Ｃ４）アルキルウレイド基；ベンゾイルアミノ基；ベンゼン環が、ハロゲン原子、（Ｃ１〜Ｃ４）アルキル基、ニトロ基、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ベンゾイルアミノ基；ベンゼンスルホニルアミノ基；又は、ベンゼン環が、ハロゲン原子、（Ｃ１〜Ｃ４）アルキル基、ニトロ基、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フェニルスルホニルアミノ基；を表し、
＊はＸとの置換位置を表す。］
６）
上記式（２）中、
Ｘが脂肪族ジアミン（Ａ及びＢはそれぞれ異なる窒素原子に置換している。）を表す上記５）に記載のインク組成物、
７）
上記式（２）中、
Ｘが、（Ｃ１〜Ｃ８）アルキレンジアミノ基；ヒドロキシ基若しくはカルボキシ基で置換された（Ｃ１〜Ｃ８）アルキレンジアミノ基；Ｎ−（Ｃ１〜Ｃ４）アルキル−（Ｃ１〜Ｃ６）アルキレンジアミノ基；アルキル部分がヒドロキシ基、若しくはカルボキシ基で置換されたＮ−（Ｃ１〜Ｃ４）アルキル−（Ｃ１〜Ｃ６）アルキレンジアミノ基；アミノ（Ｃ１〜Ｃ６）アルコキシ（Ｃ１〜Ｃ６）アルキルアミノ基；アミノ（Ｃ１〜Ｃ４）アルコキシ（Ｃ１〜Ｃ４）アルコキシ（Ｃ１〜Ｃ４）アルキルアミノ基；ピペラジン−１，４−ジイル基；又は、（Ｃ１〜Ｃ４）アルキル基若しくは（Ｃ１〜Ｃ４）アルコキシ基で置換されたピペラジン−１，４−ジイル基；を表す、上記５）に記載のインク組成物、
８）
上記式（３）及び（４）において、
Ｒ^１０１からＲ^１０８がそれぞれ独立に、水素原子；ハロゲン原子；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；スルホ基若しくはカルボキシ基で置換された（Ｃ１〜Ｃ４）アルコキシ基；
又は、（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；である上記５）乃至７）のいずれか一項に記載のインク組成物、
９）
更に（Ｃ）水溶性有機溶剤を含有する上記１）乃至８）のいずれか一項に記載のインク組成物、
１０）
上記成分（Ｃ）が、２−ピロリドン、グリセリン系溶剤及びグリコール系溶剤からなる群から選択される１又は２以上の水溶性有機溶剤である上記９）に記載のインク組成物、
１１）
インク組成物における色素分の総量中、上記成分（Ａ）の含有率が４０質量％以上である上記１）乃至９）のいずれか一項に記載のインク組成物、
１２）
インクジェット記録用である上記１）乃至１１）のいずれか一項に記載のインク組成物、
１３）
上記１）乃至１２）のいずれか一項に記載のインク組成物をインクとして用い、該インクのインク滴を記録信号に応じて吐出させて被記録材に付着させ、記録を行うインクジェット記録方法、
１４）
被記録材が情報伝達用シートである上記１３）に記載のインクジェット記録方法、
１５）
情報伝達用シートが普通紙又は多孔性白色無機物を含むインク受容層を有するシ−トである上記１４）に記載のインクジェット記録方法、
１６）
上記１３）乃至１５）のいずれか一項に記載のインクジェット記録方法により着色された着色体、
１７）
上記１）乃至１２）のいずれか一項に記載のインク組成物を含む容器が装填されたインクジェットプリンタ、
に関する。 That is, the present invention
1)
(A) a dye represented by the following formula (1), (B) a maximum absorption wavelength (λmax) in an aqueous solvent of 340 nm to less than 440 nm, a half width of 150 nm to less than 300 nm, and a molecular weight of 1800 or more An ink composition containing a pigment that is 5000 or less,

[In Formula (1),
R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom; a halogen atom; a cyano group; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a phospho group; a nitro group; (C1-C4) alkyl group; (C1-C4) alkoxy group; hydroxy group, or (C1-C4) alkyl group substituted with (C1-C4) alkoxy group; hydroxy group, (C1-C4) alkoxy group, (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a sulfo group and a carboxy group; an acyl group; an N-alkylaminosulfonyl group; an N-phenylaminosulfonyl group; a sulfo group; N-alkylaminosulfuryl substituted with at least one group selected from the group consisting of a carboxy group and a hydroxy group An alkylsulfonyl group; an alkylsulfonyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group; an acylamino group; an alkylsulfonylamino group; a phenylsulfonylamino group; Or a phenylsulfonylamino group substituted with at least one group selected from the group consisting of halogen atoms, (C1-C4) alkyl groups, and nitro groups;
R ³ and R ⁴ are each independently substituted with a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; a (C1-C4) alkyl group; a hydroxy group, or a (C1-C4) alkoxy group. (C1-C4) alkyl group; (C1-C4) alkoxy group; substituted with at least one group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group, and carboxy group (C1-C4) alkoxy group; (C1-C4) alkylthio group; substituted with sulfo group or carboxy group (C1-C4) alkylthio group; acylamino group; alkylsulfonylamino group; phenylsulfonylamino group; or halogen atom , (C1-C4) alkyl group and at least one selected from the group consisting of nitro groups And; phenylsulfonylamino group substituted with a group
n represents 0 or 1, respectively. ]
2)
In equation (1),
The ink composition according to 1), wherein at least three of R ^{1 to} R ⁷ are a sulfo group or a carboxy group,
3)
In equation (1),
R ¹ and R ² are each independently a hydrogen atom; a sulfo group; a carboxy group; or a hydroxy group;
R ³ and R ⁴ are each independently a hydrogen atom; a halogen atom; a carboxy group; a sulfo group; a (C1-C4) alkoxy group substituted with a sulfo group or a carboxy group; or a sulfo group or a carboxy group. A substituted (C1-C4) alkylthio group;
R ^{5 to} R ⁷ are each independently a hydrogen atom; a halogen atom; a sulfo group; a carboxy group; a hydroxy group; or a (C1-C4) alkoxy group;
the ink composition according to 1) or 2), wherein n is 1;
4)
In the above formula (1),
R ¹ is a carboxy group or a sulfo group,
R ² is a hydrogen atom,
R ³ is a sulfo group,
R ⁴ is a hydrogen atom,
R ⁵ is a hydrogen atom, a carboxy group or a sulfo group,
R ⁶ is a carboxy group or a sulfo group,
R ⁷ is a hydrogen atom,
The ink composition according to any one of 1) to 3) above, wherein n is 1.
5)
The ink composition according to any one of 1) to 4), wherein the component (B) is a dye represented by the following formula (2):

[In Formula (2),
A represents the structure represented by Formula (3),
B represents the structure represented by Formula (4);
X represents a divalent bridging group (provided that it has at least two nitrogen atoms, and A and B are each substituted with different nitrogen atoms);
In formulas (3) and (4),
R ¹⁰¹ to R ¹⁰⁸ each independently represents a hydrogen atom; a halogen atom; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; (C1) alkoxy group substituted with at least one group selected from the group consisting of C4) alkoxy group, hydroxy (C1 to C4) alkoxy group, sulfo group, and carboxy group; (C1 to C4) alkyl A (C1-C4) alkylcarbonylamino group substituted with a carboxy group; a ureido group; a mono (C1-C4) alkylureido group; a di (C1-C4) alkylureido group; a hydroxy group, a sulfo group, and Mono (C1) substituted with at least one group selected from the group consisting of carboxy groups C4) an alkylureido group; a di (C1-C4) alkylureido group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group; a benzoylamino group; A benzoylamino group substituted with at least one group selected from the group consisting of an atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, and a carboxy group; a benzenesulfonylamino group; or a benzene ring, A phenylsulfonylamino group substituted with at least one group selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, and a carboxy group;
* Represents a substitution position with X. ]
6)
In the above formula (2),
The ink composition according to 5) above, wherein X represents an aliphatic diamine (A and B are each substituted with a different nitrogen atom);
7)
In the above formula (2),
X is a (C1-C8) alkylene diamino group; a (C1-C8) alkylene diamino group substituted with a hydroxy group or a carboxy group; N- (C1-C4) alkyl- (C1-C6) alkylene diamino group; an alkyl moiety N- (C1-C4) alkyl- (C1-C6) alkylenediamino group substituted with hydroxy group or carboxy group; amino (C1-C6) alkoxy (C1-C6) alkylamino group; amino (C1-C4) Piperazine-1 substituted with (C1-C4) alkoxy (C1-C4) alkylamino group; piperazine-1,4-diyl group; or (C1-C4) alkyl group or (C1-C4) alkoxy group , 4-diyl group; the ink composition according to 5) above,
8)
In the above formulas (3) and (4),
R ¹⁰¹ to R ¹⁰⁸ are each independently a hydrogen atom; a halogen atom; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a (C1-C4) alkoxy group substituted with a sulfo group or a carboxy group;
Or (C1-C4) an alkylcarbonylamino group; the ink composition according to any one of 5) to 7) above,
9)
Furthermore, (C) the ink composition according to any one of 1) to 8) above, which contains a water-soluble organic solvent,
10)
The ink composition as described in 9) above, wherein the component (C) is one or two or more water-soluble organic solvents selected from the group consisting of 2-pyrrolidone, a glycerin solvent, and a glycol solvent.
11)
Ink composition as described in any one of said 1) thru | or 9) whose content rate of said component (A) is 40 mass% or more in the total amount of the coloring matter in an ink composition,
12)
The ink composition according to any one of 1) to 11) above, which is for inkjet recording;
13)
An ink jet recording method in which the ink composition according to any one of 1) to 12) above is used as ink, and ink droplets of the ink are ejected in accordance with a recording signal to adhere to a recording material, and recording is performed;
14)
The inkjet recording method according to 13) above, wherein the recording material is an information transmission sheet,
15)
14) The ink jet recording method according to the above 14), wherein the information transmission sheet is a sheet having an ink receiving layer containing plain paper or a porous white inorganic substance.
16)
A colored body colored by the inkjet recording method according to any one of 13) to 15) above,
17)
An inkjet printer loaded with a container containing the ink composition according to any one of 1) to 12) above;
About.

The ink composition of the present invention has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage. In addition, the ink composition of the present invention is used for inkjet recording, writing instruments, etc., and when the ink of a recorded image has a neutral hue and a low pigment concentration when recorded on plain paper and inkjet dedicated paper However, a printed matter with a black hue can be obtained. In addition, the print density is high, and it is excellent in light resistance, moisture resistance, ozone gas resistance, water resistance, and near infrared light sensor compatibility.
Further, when used together with magenta, cyan and yellow dyes, full color ink jet recording excellent in high color development, light resistance, moisture resistance, ozone gas resistance and water resistance is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet recording.

The present invention will be described in detail.
The ink composition of the present invention contains a dye represented by the above formula (1) as the component (A). By containing this compound, light resistance and moisture resistance can be remarkably improved as compared with the conventional ink composition. This compound can be obtained by the method described in International Publication No. 2006/051850.

In the above formula (1), R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom; a halogen atom; a cyano group; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; A nitro group; a ureido group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group, or a (C1-C4) alkyl group substituted with an alkoxy group; a hydroxy group; (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of an alkoxy group, a sulfo group, and a carboxy group; an acyl group; an N-alkylaminosulfonyl group; an N-phenyl group An aminosulfonyl group; substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group; An alkylsulfonyl group; an alkylsulfonyl group; an alkylsulfonyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group; an acylamino group; an alkylsulfonylamino group; An amino group; or a phenylsulfonylamino group substituted with at least one group selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, and a nitro group.

In the above formula (1), examples of the halogen atom in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. An atom is preferable and a fluorine atom and a chlorine atom are more preferable.

In the above formula (1), examples of the (C1-C4) alkyl group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ include a linear or branched unsubstituted group. Those are preferred. Specific examples thereof include, for example, a linear group such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group; a branched chain such as an isopropyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group; Is mentioned. Preferable specific examples include a methyl group and an n-propyl group, and a methyl group is more preferable.

In the above formula (1), examples of the (C1-C4) alkoxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ include those in which the alkyl moiety is a linear or branched unsubstituted group, A straight chain is preferred. Specific examples thereof include, for example, straight chain such as methoxy group, ethoxy group, n-propoxy group, and n-butoxy group; branched chain such as isopropoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group; Etc. Preferably, a methoxy group, an ethoxy group, and n-propoxy group are mentioned, A methoxy group is more preferable.

In the above formula (1), the (C1-C4) alkyl group substituted with a hydroxy group or a (C1-C4) alkoxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ includes the above ( A C1-C4) alkyl group in which any one or both of a hydroxy group and a (C1-C4) alkoxy group are substituted is mentioned. The substitution position of the hydroxy group or the (C1 to C4) alkoxy group is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitutions is 1 or 2, preferably 1. In the said (C1-C4) alkoxy group, the same thing is mentioned including the said (C1-C4) alkoxy group, a specific example, a preferable thing, and a more preferable thing. Specific examples of the hydroxy group or the (C1-C4) alkyl group substituted with a (C1-C4) alkoxy group include a hydroxymethyl group, a 2-hydroxyethyl group, a 3-hydroxy-n-propyl group, a 4-hydroxy group. -N-butyl group, methoxymethyl group, 2-methoxyethyl group, 3-methoxy-n-propyl group, 4-methoxy-n-butyl group, ethoxymethyl group, 2-ethoxyethyl group, 3-ethoxy-n- Propyl group, 4-ethoxy-n-butyl group, n-propoxymethyl group, 2- (n-propoxy) ethyl group, 3- (n-propoxy) -n-propyl group, 4- (n-propoxy) -n -Butyl group, (n-butoxy) methyl group, 2- (n-butoxy) ethyl group, 3- (n-butoxy) -n-propyl group, 4- (n-butoxy) -n-butyl group And the like.

In the above formula (1), at least one selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ . The (C1 to C4) alkoxy group substituted with the group is selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group, and a carboxy group on the carbon atom of the (C1 to C4) alkoxy group. And at least one kind of group substituted. The substitution position of the hydroxy group, (C1-C4) alkoxy group, sulfo group, or carboxy group is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitutions is 1 or 2, preferably 1. Examples of the (C1 to C4) alkoxy group as a substituent include the above (C1 to C4) alkoxy groups and specific examples, preferable ones, and more preferable ones. Specific examples of the (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group include a hydroxymethoxy group, a hydroxy group Substituted with a hydroxy group such as ethoxy group, hydroxy-n-propoxy group, hydroxy-n-butoxy group; methoxymethoxy group, methoxyethoxy group, methoxy-n-propoxy group, methoxy-n-butoxy group, ethoxymethoxy Group, ethoxyethoxy group, ethoxy-n-propoxy group, ethoxy-n-butoxy group, (n-propoxy) methoxy group, (n-propoxy) ethoxy group, (n-propoxy) -n-propoxy group, (n- Propoxy) -n-butoxy group, (n-butoxy) methoxy group, (n-butoxy) Toxi group, (n-butoxy) -n-propoxy group, (n-butoxy) -n-butoxy group, isopropoxymethoxy group, isopropoxyethoxy group, isopropoxy-n-propoxy group, isopropoxy-n-butoxy group , (Tert-butoxy) methoxy group, (tert-butoxy) ethoxy group, (tert-butoxy) -n-propoxy group, (tert-butoxy) -n-butoxy group and the like (C1-C4) alkoxy groups. Substituted with a sulfo group such as sulfomethoxy group, sulfoethoxy group, sulfo-n-propoxy group, sulfo-n-butoxy group; carboxymethoxy group, carboxyethoxy group, carboxy-n-propoxy group, carboxy Substituted with a carboxy group such as -n-butoxy group; and sulfo-n Propoxy group, a sulfo -n- butoxy group, a carboxy -n- propoxy group, a carboxy -n- butoxy group are preferable, sulfo -n- propoxy group, a sulfo -n- butoxy group are more preferable.

In the above formula (1), examples of the acyl group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ include an alkylcarbonyl group, a phenylcarbonyl group (benzoyl group), an aldehyde group, or an amide group. . Examples of the alkylcarbonyl group include those in which the alkyl moiety is linear or branched, and linear is preferable. Specific examples thereof include, for example, linear groups such as an acetyl group (methylcarbonyl group), propionyl group (ethylcarbonyl group), n-propylcarbonyl group, n-butylcarbonyl group; isopropylcarbonyl group, isobutylcarbonyl group, sec -Branched ones such as a butylcarbonyl group and a pivaloyl group (tert-butylcarbonyl group); a straight-chain one is preferable and an acetylamino group is more preferable. As the acyl group, an alkylcarbonyl group and a benzoyl group are preferable, and an acetyl group is more preferable.

In the above formula (1), as the N-alkylaminosulfonyl group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , the alkyl moiety is a (C1 to C8) alkyl group, preferably (C1 to C6). ) An alkyl group, more preferably a (C1-C4) alkyl group, and the same as the above (C1-C4) alkyl group and specific examples, preferable ones, and more preferable ones. Specific examples of the N-alkylaminosulfonyl group include N-methylaminosulfonyl group, N-ethylaminosulfonyl group, N- (n-propyl) aminosulfonyl group, N- (n-butyl) aminosulfonyl group, N- And isopropylaminosulfonyl group, N- (tert-butyl) aminosulfonyl group, and the like. N-methylaminosulfonyl group, N-ethylaminosulfonyl group, N- (n-propyl) aminosulfonyl group, N- (n- (Butyl) aminosulfonyl group is preferable, and N-methylaminosulfonyl group and N-ethylaminosulfonyl group are more preferable.

In the above formula (1), N substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ Examples of the -alkylaminosulfonyl group include those in which at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group is substituted on the carbon atom of the alkyl part of the N-alkylaminosulfonyl group. It is done. The substitution position is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitution is usually 1 to 3, preferably 1. Specific examples of the N-alkylaminosulfonyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group include an N-sulfomethylaminosulfonyl group, N- (2 Substituted with a sulfo group such as -sulfoethyl) aminosulfonyl group, N- (3-sulfo-n-propyl) aminosulfonyl group, N- (4-sulfo-n-butyl) aminosulfonyl group; N-carboxymethyl A carboxy group such as an aminosulfonyl group, N- (2-carboxyethyl) aminosulfonyl group, N- (3-carboxy-n-propyl) aminosulfonyl group, N- (4-carboxy-n-butyl) aminosulfonyl group; Substituted: N-hydroxymethylaminosulfonyl group, N- (2-hydroxyethyl) aminosulfur Substituted with a hydroxy group such as a nyl group, an N- (3-hydroxy-n-propyl) aminosulfonyl group, an N- (4-hydroxy-n-butyl) aminosulfonyl group, a sulfo group, or Those substituted with a carboxy group are preferred, and an N- (2-sulfoethyl) aminosulfonyl group and an N- (2-carboxyethyl) aminosulfonyl group are more preferred.

In the above formula (1), as the alkylsulfonyl group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , the alkyl part is a (C1-C8) alkyl group, preferably a (C1-C6) alkyl group. More preferably, it is a (C1-C4) alkyl group, and the same as the above (C1-C4) alkyl group and specific examples, preferable ones, and more preferable ones. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, an n-propylsulfonyl group, and an n-butylsulfonyl group.

In the above formula (1), alkyl substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ Examples of the sulfonyl group include those in which at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group is substituted on the carbon atom of the alkyl portion of the alkylsulfonyl group. Although the substitution position is not particularly limited, it is preferably substituted at the end of the alkyl group, and the number of substitution is usually 1 to 3, preferably 1 or 2. Specific examples of the alkylsulfonyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group include a sulfomethylsulfonyl group, a 2-sulfoethylsulfonyl group, and a 3-sulfo group. Substituted with a sulfo group such as -n-propylsulfonyl group, 4-sulfo-n-butylsulfonyl group; carboxymethylsulfonyl group, 2-carboxyethylsulfonyl group, 3-carboxy-n-propylsulfonyl group, 4- Substituted with a carboxy group such as carboxy-n-butylsulfonyl group; such as hydroxymethylsulfonyl group, 2-hydroxyethylsulfonyl group, 3-hydroxy-n-propylsulfonyl group, 4-carboxy-n-butylsulfonyl group, etc. Substituted with a hydroxy group; E group preferably substituted with a carboxy group, 2-sulfoethyl sulfonyl group, 2-carboxyethyl sulfonyl group is more preferable.

In the above formula (1), examples of the acylamino group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ include those in which the acyl group is substituted on the amino group, and include an alkylcarbonylamino group, phenylcarbonylamino Group (benzoylamino group) and the like. Specific examples of the alkylcarbonylamino group include linear ones such as acetylamino group (methylcarbonylamino group), propionylamino group (ethylcarbonylamino group), n-propylcarbonylamino group, and n-butylcarbonylamino group. Branched chain groups such as isopropylcarbonylamino group, isobutylcarbonylamino group, sec-butylcarbonylamino group, pivaloylamino group (tert-butylcarbonylamino group), and the like. More preferred. As the acylamino group, an alkylcarbonylamino group and a benzoylamino group are preferable, and an acetylamino group and a benzoylamino group are more preferable.

In the above formula (1), as the alkylsulfonylamino group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , the alkyl part is a (C1-C8) alkyl group, preferably (C1-C6) alkyl. Groups, more preferably those which are (C1-C4) alkyl groups, and the same as the above (C1-C4) alkyl groups and specific examples, preferred ones and more preferred ones. Specific examples of the alkylsulfonylamino group include methylsulfonylamino group, ethylsulfonylamino group, n-propylsulfonylamino group, n-butylsulfonylamino group, isopropylsulfonylamino group, tert-butylsulfonylamino group, and the like. A methylsulfonylamino group, an ethylsulfonylamino group, an n-propylsulfonylamino group, and an n-butylsulfonylamino group are preferable, and a methylsulfonylamino group and an ethylsulfonylamino group are more preferable.

In the above formula (1), at least one group selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, and a nitro group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ Examples of the substituted phenylsulfonylamino group include those in which at least one group selected from the group consisting of a halogen atom, a (C1 to C4) alkyl group, and a nitro group is substituted on the carbon atom of the phenylsulfonylamino group. It is done. Although it does not restrict | limit especially as a substitution position of at least 1 type of group selected from the group which consists of a halogen atom, a (C1-C4) alkyl group, and a nitro group, It substitutes by carbon atoms other than the carbon atom couple | bonded with the sulfur atom. And the number of substitution is usually 1 to 3, preferably 1 or 2, and more preferably 1. Examples of the halogen atom include the above-mentioned halogen atoms and specific examples, preferable ones, and more preferable ones, and (C1-C4) alkyl groups include the above-mentioned (C1-C4) alkyl groups and specific examples, preferably. And the like, including the more preferable ones. Specific examples of the phenylsulfonylamino group substituted with at least one group selected from the group consisting of a halogen atom, a (C1 to C4) alkyl group, and a nitro group include a 2-chlorophenylsulfonylamino group, 3- Substituted with halogen atoms such as chlorophenylsulfonylamino group, 4-chlorophenylsulfonylamino group, 2-bromophenylsulfonylamino group, 4-fluorophenylsulfonylamino group; 2-methylphenylsulfonylamino group, 3-methylphenylsulfonyl (C1-C4) alkyl such as amino group, 4-methylphenylsulfonylamino group, 2-ethylphenylsulfonylamino group, 3- (n-propyl) phenylsulfonylamino group, 4- (n-butyl) phenylsulfonylamino group Substituted with groups Substituted with a nitro group such as a 2-nitrophenylsulfonylamino group, a 3-nitrophenylsulfonylamino group, a 4-nitrophenylsulfonylamino group; Are preferable, and 4-methylphenylsulfonylamino group is more preferable.

In Formula (1), R ³ and R ⁴ each independently represent a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; a (C1-C4) alkyl group; a hydroxy group, or (C1- C4) (C1-C4) alkyl group substituted with an alkoxy group; (C1-C4) alkoxy group; at least one selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group, and carboxy group (C1-C4) alkoxy group substituted with various groups; (C1-C4) alkylthio group; (C1-C4) alkylthio group substituted with sulfo group or carboxy group; acylamino group; alkylsulfonylamino group; phenyl A sulfonylamino group; or selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, and a nitro group Without even phenylsulfonyl amino group substituted with one or more groups; represents a.

In the formula (1), the halogen atom in R ³ and R ⁴ is the same as the halogen atom in the above R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , including specific examples, preferred ones, and more preferred ones. Things.

In the formula (1), as the (C1-C4) alkyl group in R ³ and R ^4, the (C1-C4) alkyl group in the above R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , specific examples, The same thing is mentioned including a preferable thing and a more preferable thing.

In the formula (1), as the hydroxy group in R ³ and R ⁴ or the (C1-C4) alkyl group substituted with the (C1-C4) alkoxy group, the above R ¹ , R ² , R ⁵ , R ⁶ and The hydroxy group in R ⁷ or the (C1-C4) alkyl group substituted with a (C1-C4) alkoxy group, and specific examples, preferable ones, and more preferable ones are exemplified.

In formula (1), as the (C1 to C4) alkoxy group in R ³ and R ^4, the (C1 to C4) alkoxy group in the above R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , specific examples, The same thing is mentioned including a preferable thing and a more preferable thing.

In formula (1), substituted with at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, or a carboxy group in R ³ and R ⁴ (C1-C4) The alkoxy group is 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 in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ . (C1-C4) alkoxy groups substituted with and specific examples, preferred ones, and more preferred ones.

In formula (1), examples of the (C1 to C4) alkylthio group in R ³ and R ⁴ include those in which the alkyl part is linear or branched, and linear is preferable. Specific examples include straight chain groups such as methylthio group, ethylthio group, n-propylthio group, and n-butylthio group; branched chain groups such as isopropylthio group, isobutylthio group, sec-propylthio group, and tert-butylthio group; A straight chain is preferable, and a methylthio group is more preferable.

In formula (1), as the (C1-C4) alkylthio group substituted with a sulfo group or a carboxy group in R ³ and R ⁴ , any carbon atom in the (C1-C4) alkylthio group may be substituted with these carbon atoms. What has a substituent is 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 sulfur atom in the alkylthio group is bonded. Specific examples thereof include those substituted with a sulfo group such as 2-sulfoethylthio, 3-sulfo-n-propylthio, 4-sulfo-n-butylthio group, etc .; 2-carboxyethylthio, 3-carboxy- those substituted with a carboxy group such as n-propylthio, 4-carboxy-n-butylthio and the like, and those substituted with a sulfo group are preferred, and a 3-sulfopropylthio group is particularly preferred.

In the formula (1), the acylamino group in R ³ and R ⁴ is the same as the acylamino group in the above R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , including specific examples, preferred ones and more preferred ones. Things.

In formula (1), as the alkylsulfonylamino group in R ³ and R ^4, the alkylsulfonylamino group in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , specific examples, preferable ones, and more preferable ones. The same thing is mentioned including.

In the formula (1), as the phenylsulfonylamino substituted with at least one group selected from the group consisting of a halogen atom in R ³ and R ⁴ , a (C1-C4) alkyl group, and a nitro group, Phenylsulfonylamino substituted with at least one group selected from the group consisting of a halogen atom in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ , a (C1-C4) alkyl group, and a nitro group; Specific examples, preferable ones, and more preferable ones are also included.

In formula (1), preferred as R ¹ and R ² is a case where one of them is a hydrogen atom or a sulfo group, and the other is a carboxy group, a sulfo group or a (C1-C4) alkoxy group, and more preferred. Is the case where either one is a hydrogen atom and the other is a carboxyl group or a sulfo group.
Preferred as R ³ and R ⁴ is the case where one is a sulfo group, a carboxy group, or a sulfo (C1-C4) alkoxy group, and the other is a hydrogen atom, a sulfo group, or a (C1-C4) alkyl group, More preferably, one is a sulfo group and the other is a hydrogen atom.
Any one of R ⁵ , R ⁶ and R ⁷ is preferably a sulfo group, a carboxy group, a (C1-C4) alkoxy group, or a halogen atom, and a sulfo group is more preferable.
n may be 0 or 1, but 1 is more preferable.

Of the above R ¹ to R ⁷ , compounds in which preferable ones are combined are more preferable, and compounds in which more preferable ones are combined are more preferable. The same applies to combinations of preferable and more preferable ones.

Specific examples of the dye represented by the above formula (1) are shown in Tables 1 to 3 below. However, it is not limited to these.
Of these, the dye of Compound No. 1 is particularly preferred.

  In the ink composition of the present invention, as the component (B), the maximum absorption wavelength (λmax) in the aqueous medium is 340 nm or more and less than 440 nm, the half width is 150 nm or more and less than 300 nm, and the molecular weight is 1800 or more and less than 5000. Containing a dye.

The maximum absorption wavelength (λmax) in an aqueous medium represents an absorption wavelength at which the molar extinction coefficient measured in an aqueous solution having a pH of 7 to 8 is maximized.
When the maximum absorption wavelength (λmax) is less than 340 nm, the saturation of the ink composition is little decreased, and the same is true when the wavelength is 440 nm or more.

  The half-value width is a value representing the width of the horizontal axis where the value of the vertical axis is half the maximum when the absorption wavelength is plotted with the horizontal axis representing the wavelength and the vertical axis representing the absorbance. This is a value that indicates whether the is sharp or wide. A dye having a large half-value width tends to have low saturation, and is useful when adjusting black ink.

  The molecular weight of component (B) affects the solubility of the dye. Therefore, when the molecular weight is less than 1800, the moisture resistance tends to be slightly inferior, and when it exceeds 5000, the storage stability of the dye solution tends to decrease.

  As a component (B), the pigment | dye represented by the said Formula (2) is preferable. The pigment | dye represented by Formula (2) can be obtained by the method as described in international publication 2011/043184, for example.

  In the above formula (2), A represents the structure represented by the formula (3), B represents the structure represented by the formula (4), and X represents a divalent bridging group (however, at least two or more). And A and B are each substituted with a different nitrogen atom).

  In the above formula (2), specific examples of X include (C1-C8) alkylene diamino group; (C1-C8) alkylene diamino group substituted with a hydroxy group or a carboxy group; N- (C1-C4) alkyl- (C1-C6) alkylene diamino group; N- (C1-C4) alkyl- (C1-C6) alkylene diamino group in which the alkyl moiety is substituted with a hydroxy group or a carboxy group; amino (C1-C6) alkoxy (C1- C6) alkylamino group; amino (C1-C4) alkoxy (C1-C4) alkoxy (C1-C4) alkylamino group; xylylenediamine group; piperazine-1,4-diyl group; (C1-C4) alkyl group or (C1-C4) piperazine-1,4-diyl group substituted by alkoxy group; or phenylenediamino group Etc. The.

In the above formula (2), it is preferable that X is an aliphatic diamine. However, A and B are each substituted with a different nitrogen atom.
The aliphatic diamine may be linear, branched or cyclic, and may be either saturated or unsaturated. Making X an aliphatic diamine is more advantageous from the viewpoint of ease of synthesis than using an aromatic diamine.
That is, as X in Formula (2), (C1-C8) alkylene diamino group; (C1-C8) alkylene diamino group substituted by a hydroxy group or a carboxy group; N- (C1-C4) alkyl- (C1 -C6) alkylene diamino group; N- (C1-C4) alkyl- (C1-C6) alkylene diamino group in which the alkyl moiety is substituted with a hydroxy group or a carboxy group; amino (C1-C6) alkoxy (C1-C6) Alkylamino group; amino (C1-C4) alkoxy (C1-C4) alkoxy (C1-C4) alkylamino group; piperazine-1,4-diyl group; (C1-C4) alkyl group or (C1-C4) alkoxy group A piperazine-1,4-diyl group substituted with is preferred, and a piperazine-1,4-diyl group is particularly preferred. There.

  In X, the (C1 to C8) alkylenediamino group includes a straight chain or branched chain group, and a straight chain group is preferable. The range of carbon number is usually (C1 to C8), preferably (C2 to C8), more preferably (C2 to C6), and still more preferably (C2 to C4). Specific examples include ethylenediamino, 1,3-propylenediamino, 1,4-butylenediamino, 1,5-pentylenediamino, 1,6-hexylenediamino, 1,7-heptylenediamino, 1,8. -Straight chain such as octylene diamino; Branched chain such as 2-methyl-1,3-propylene diamino, 3-methyl-1,4-butylene diamino, 4-methyl-1,6-hexylene diamino Etc.

  Examples of the (C1 to C8) alkylenediamino group substituted with a hydroxy group or a carboxy group in X include those having these substituents on any carbon atom in the (C1 to C8) alkylenediamino group. The number of the substituent is not particularly limited, but is preferably 1 or 2. Moreover, when it has two or more substituents, the kind may be same or different, but the same thing is preferable. Specific examples include hydroxy-substituted (C1-C8) alkylenediamino groups such as 2-hydroxy-1,3-propylenediamino, 2-hydroxy-1,4-butylenediamino, 3-hydroxy-1,6-hexylenediamino, and the like. 1-carboxyethylenediamino, 1-carboxy-1,3-propylenediamino, 1-carboxy-1,4-butylenediamino, 1-carboxy-1,5-pentylenediamino, 1,5-dicarboxy-1, Carboxy substituted (C1-C8) alkylenediamino groups such as 5-pentylenediamino and the like can be mentioned.

  In X, the N- (C1-C4) alkyl- (C1-C6) alkylenediamino group is one in which one nitrogen atom of the (C1-C6) alkylenediamino group is substituted with a (C1-C4) alkyl group. Means. In the present specification, a nitrogen atom substituted with a (C1-C4) alkyl group in a diamino group is represented as “N”, and the other nitrogen atom is represented as “N ′” as necessary. The range of the carbon number of the alkylene moiety is usually (C1-C6), preferably C2-C4, particularly preferably C2 or C3. As this (C1-C4) alkyl group, a linear or branched thing is mentioned, A linear thing is preferable. Specific examples include N-linear (C1-C4) alkyl- (C1-C6) alkylene such as N-methylethylenediamino group, N-ethylethylenediamino group, N-propylethylenediamino group, N-butylethylenediamino group. Diamino group; N-branched (C1-C4) alkyl- (C1-C4) such as N-isopropylethylenediamino group, N-isobutylethylenediamino group, N-sec-butylethylenediamino group, Nt-butylethylenediamino group C6) alkylene diamino group; and the like.

  In X, the N- (C1-C4) alkyl- (C1-C6) alkylenediamino group in which the alkyl moiety is substituted with a hydroxy group or a carboxy group is the N- (C1-C4) alkyl- (C1-C6). What has a hydroxyl group or a carboxy group in the arbitrary carbon atoms of the alkyl part of the N- (C1-C4) alkyl group in an alkylene diamino group is mentioned. The position of the substituent is not particularly limited, but it is preferable that the nitrogen atom and the hydroxy group are not substituted with the same carbon atom. Examples of the range of the carbon number of the alkylene moiety include the same range as in the N- (C1-C4) alkyl- (C1-C6) alkylenediamino group including preferable ones. Further, the range of the carbon number of the alkyl moiety is usually (C1 to C4), preferably (C2 to C4), more preferably (C2 to C3). The number of the substituents is usually 1 or 2, preferably 1. Moreover, when it has two or more substituents, the kind may be same or different, but the same thing is preferable. Specific examples include N- (2-hydroxyethyl) ethylenediamino group, N- (3-hydroxypropyl) ethylenediamino group, N- (2-hydroxypropyl) ethylenediamino group, N- (4-hydroxybutyl) ethylene. N-hydroxy substituted (C1-C4) alkyl- (C1-C6) alkylenediamino group such as diamino group; N- (carboxymethyl) ethylenediamino group, N- (2-carboxyethyl) ethylenediamino group, N- (3 -Carboxypropyl) ethylenediamino group, N-carboxy substituted (C1-C4) alkyl- (C1-C6) alkylenediamino group such as N- (4-carboxybutyl) ethylenediamino group; and the like.

  In X, the amino (C1 to C6) alkoxy (C1 to C6) alkylamino group includes a linear or branched one, and a linear one is preferred. The range of carbon number is usually an amino (C1-C6) alkoxy (C1-C6) alkylamino group, preferably an amino (C2-C4) alkoxy (C2-C4) alkylamino group, particularly preferably an amino group. (C2 to C3) alkoxy (C2 to C3) alkylamino groups may be mentioned. Specific examples include aminoethoxyethylamino, aminoethoxypropylamino, aminopropoxypropylamino, aminoethoxypentylamino and the like.

  In X, the amino (C1-C4) alkoxy (C1-C4) alkoxy (C1-C4) alkylamino group includes a linear or branched one, and a linear one is preferred. The range of carbon number is usually amino (C1-C4) alkoxy (C1-C4) alkoxy (C1-C4) alkylamino group, preferably amino (C2-C4) alkoxy (C2-C4) alkoxy (C2-C4). ) Alkylamino group, particularly preferably an amino (C2-C3) alkoxy (C2-C3) alkoxy (C2-C3) alkylamino group. Specific examples include straight chain such as aminoethoxyethoxyethylamino, aminoethoxypropoxyethylamino, aminoethoxybutoxyethylamino; aminoethoxy (2-methylethoxy) ethylamino, aminoethoxy (2-methylpropoxy) ethylamino Branched chain such as; and the like.

  In X, examples of the xylylenediamino group include o-, m-, and p-xylylenediamino groups, and an m- or p-xylylenediamino group is preferable.

  In X, the piperazine-1,4-diyl group substituted with a (C1-C4) alkyl group or a (C1-C4) alkoxy group includes any of these substituents on any carbon atom of the ring-constituting atom of the piperazine ring. The thing which has is mentioned. The number of the substituents is usually 1 or 2, preferably 1. Moreover, when it has two or more substituents, the kind may be same or different, but the same thing is preferable. Specific examples include 2-methylpiperazine-1,4-diyl group, 2-ethylpiperazine-1,4-diyl group, 2,5-dimethylpiperazine-1,4-diyl group, 2,6-dimethylpiperazine- 1,4-diyl group, 2,5-diethylpiperazine-1,4-diyl group, 2-methyl-5-ethylpiperazine-1,4-diyl group; and the like.

  In X, examples of the phenylenediamino group include o-, m-, and p-phenylenediamino groups, and m- or p-phenylenediamino groups are preferred.

  Among the above, X is (C1-C8) alkylenediamino group; (C1-C8) alkylenediamino group substituted with a carboxy group; N- (C1-C4) alkyl- (alkyl moiety substituted with hydroxy) Preferred examples include C1-C6) alkylenediamino group; amino (C1-C4) alkoxy (C1-C4) alkoxy (C1-C4) alkylamino group; xylylenediamino group; or piperazine-1,4-diyl group. . More preferably, (C2-C4) alkylenediamino group; (C2-C6) alkylenediamino group substituted with a carboxy group; N- (C2-C3) alkyl- (C2-C3) wherein the alkyl moiety is substituted with a hydroxy group ) Alkylenediamino group; amino (C2-C3) alkoxy (C2-C3) alkoxy (C2-C3) alkylamino group; m- or p-xylylenediamine group; or piperazine-1,4-diyl group; It is done. More preferably, (C1-C8) alkylene diamino group; xylylenediamine group; or piperazine-1,4-diyl group; Among these, preferred specific examples include 1,2-ethylenediamino; 1,3-propylenediamino; 1,4-butylenediamino; 1-carboxypentylene-1,5-diamino; N-2-hydroxyethyl- And ethylenediamino; aminoethoxyethoxyethylamino; m-xylylenediamine; or piperazine-1,4-diyl.

In the above formulas (3) and (4), R ¹⁰¹ to R ¹⁰⁸ are each independently hydrogen atom; halogen atom; sulfo group; carboxy group; sulfamoyl group; carbamoyl group; (C1-C4) alkyl group; C4) alkoxy group; substituted with at least one group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, hydroxy (C1-C4) alkoxy group, sulfo group, and carboxy group (C1-C4) (C1-C4) alkylcarbonylamino group; (C1-C4) alkylcarbonylamino group substituted with a carboxy group; ureido group; mono (C1-C4) alkylureido group; di (C1-C4) An alkylureido group; at least selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group Mono (C1-C4) alkylureido group substituted with a kind of group; di (C1-C4) alkylureido substituted with at least one kind of group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group A benzoylamino group; a benzoylamino group in which the benzene ring is substituted with at least one group selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, and a carboxy group; A benzenesulfonylamino group; or a phenylsulfonylamino in which the benzene ring is substituted with at least one group selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, and a carboxy group Represents a group;

In the above formulas (3) and (4), examples of the halogen atom in R ¹⁰¹ to R ¹⁰⁸ include halogen atoms in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ in the above formula (1) and specific examples. The same thing is mentioned including a preferable thing and a more preferable thing.

In the above formulas (3) and (4), as the (C1-C4) alkyl group in R ¹⁰¹ to R ^108, in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ in the above formula (1) (C1-C4) alkyl groups and specific examples, preferable ones, and more preferable ones are included.

In the above formulas (3) and (4), as the (C1-C4) alkoxy group in R ¹⁰¹ to R ^108, in R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ in the above formula (1) (C1-C4) alkoxy groups and specific examples, preferred ones, and more preferred ones are included.

In the above formulas (3) and (4), R ¹⁰¹ to R ¹⁰⁸ are 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. The (C1-C4) alkoxy group substituted with at least one kind of group includes a hydroxy group, a (C1-C4) alkoxy group, a hydroxy (C1-C4) alkoxy on the carbon atom of the (C1-C4) alkoxy group. Examples include those substituted with at least one group selected from the group consisting of a group, a sulfo group, and a carboxy group. The substitution position of the hydroxy group, (C1-C4) alkoxy group, hydroxy (C1-C4) alkoxy group, sulfo group, or carboxy group is not particularly limited, but it is preferably substituted at the end of the alkyl group, and the number of substitutions is 1. Or 2, preferably 1. Examples of the (C1 to C4) alkoxy group as a substituent include the above (C1 to C4) alkoxy groups and specific examples, preferable ones, and more preferable ones. Specific examples of the (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group include a hydroxymethoxy group, a hydroxy group Substituted with a hydroxy group such as ethoxy group, hydroxy-n-propoxy group, hydroxy-n-butoxy group; methoxymethoxy group, methoxyethoxy group, methoxy-n-propoxy group, methoxy-n-butoxy group, ethoxymethoxy Group, ethoxyethoxy group, ethoxy-n-propoxy group, ethoxy-n-butoxy group, (n-propoxy) methoxy group, (n-propoxy) ethoxy group, (n-propoxy) -n-propoxy group, (n- Propoxy) -n-butoxy group, (n-butoxy) methoxy group, (n-butoxy) Toxi group, (n-butoxy) -n-propoxy group, (n-butoxy) -n-butoxy group, isopropoxymethoxy group, isopropoxyethoxy group, isopropoxy-n-propoxy group, isopropoxy-n-butoxy group , (Tert-butoxy) methoxy group, (tert-butoxy) ethoxy group, (tert-butoxy) -n-propoxy group, (tert-butoxy) -n-butoxy group and the like (C1-C4) alkoxy groups. Hydroxymethoxymethoxy group, 2-hydroxymethoxyethoxy group, 3- (hydroxy-n-propoxy) methoxy group, (4-hydroxy-n-butoxy) methoxy group, 4- (4-hydroxy-n-butoxy) -Substituted by hydroxy (C1-C4) alkoxy group such as n-butoxy group; sulfo Substituted with a sulfo group such as a toxi group, sulfoethoxy group, sulfo-n-propoxy group, sulfo-n-butoxy group; carboxymethoxy group, carboxyethoxy group, carboxy-n-propoxy group, carboxy-n-butoxy And a sulfo-n-propoxy group, a sulfo-n-butoxy group, a carboxy-n-propoxy group, a carboxy-n-butoxy group, and a sulfo-n-propoxy group. And a sulfo-n-butoxy group is more preferable.

In the above formulas (3) and (4), examples of the (C1-C4) alkylcarbonylamino group in R ¹⁰¹ to R ¹⁰⁸ include those in which the alkyl moiety is linear or branched, and linear Are preferred. Specific examples thereof include straight chain such as acetylamino group (methylcarbonylamino group), propionylamino group (ethylcarbonylamino group), n-propylcarbonylamino group, n-butylcarbonylamino group; isopropylcarbonylamino A branched chain group such as a group, an isobutylcarbonylamino group, a sec-butylcarbonylamino group, a pivaloylamino group (tert-butylcarbonylamino group), etc., and a straight chain group is preferable, and an acetylamino group is more preferable.

In the above formulas (3) and (4), examples of the (C1-C4) alkylcarbonylamino group substituted with a carboxy group in R ¹⁰¹ to R ¹⁰⁸ include those in which the alkyl part is linear or branched. A straight chain is preferable. Specific examples thereof include, for example, a straight chain such as carboxymethylcarbonylamino group, 2-carboxyethylcarbonylamino group, 3-carboxy-n-propylcarbonylamino group, 4-carboxy-n-butylcarbonylamino group; Branched chain such as isopropylcarbonylamino group, carboxyisobutylcarbonylamino group, carboxy-sec-butylcarbonylamino group, carboxy-tert-butylcarbonylamino group, etc. Is more preferable.

In the above formula (3) and ^(4), in the ^{R 101 R 108,} as mono (C1 -C4) alkylureido group, the alkyl moieties are a straight chain or branched chain. The substitution position of the (C1 to C4) alkyl is not particularly limited, but is preferably substituted with “N ′”. In the present specification, “mono (C1-C4) alkylureido group” means “(C1-C4) alkylNH—CO—NH—” group or “H ₂ N—CO—N ((C1-C4) alkyl”. )-”Group, and in the benzene ring to which R ¹⁰¹ and R ¹⁰⁸ are bonded, the nitrogen atom directly bonded to the benzene ring is“ N ”, and the nitrogen atom bonded to this nitrogen atom via a carbonyl (CO) group Is described as “N ′”. Therefore, the substitution position of the (C1-C4) alkyl is “N ′” for the former and “N” for the latter. Specific examples include straight chain such as N′-ethylureido, N′-propylureido, N′-butylureido; N′-isopropylureido, N′-isobutylureido, N′-t-butylureido, etc. Branched chain; and the like.

In the above formulas (3) and (4), the di (C1-C4) alkylureido group in R ¹⁰¹ to R ¹⁰⁸ includes a linear or branched one. The substitution position of the (C1 to C4) alkyl is not particularly limited, and one in each of “N” and “N ′” according to the substitution position in the “mono (C1 to C4) alkylureido group”, or “N """Includes two substitutions, the latter being preferred. The two (C1-C4) alkyls may be the same or different, but the same is preferable. Specific examples include N ′, N′-dimethylureido, N ′, N′-diethylureido, N ′, N′-dipropylureido, N ′, N′-dibutylureido and the like; N ′ , N′-diisopropylureido, N ′, N′-diisobutylureido and the like; and the like.

In the above formula (3) and ^(4), in the ^{R 101 R 108,} hydroxy group, sulfo group, and at least one mono (C1 -C4) alkyl optionally substituted with a group selected from the group consisting of a carboxy group As a ureido group, what has these substituents in the arbitrary carbon atoms in the said mono (C1-C4) alkylureido group is mentioned. The number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited, but preferably the same carbon atom is not substituted with a nitrogen atom and a hydroxy group. Specific examples include N′-mono (hydroxy (C1-C4) alkyl) ureido groups such as N′-2-hydroxyethylureido and N′-3-hydroxypropylureido; N′-2-sulfoethylureido, N ′ N′-mono (sulfo (C1-C4) alkyl) ureido group such as “-3-sulfopropylureido; N′-carboxymethylureido, N′-2-carboxyethylureido, N′-3-carboxypropylureido, N′-mono (carboxy (C1-C4) alkyl) ureido groups such as N′-4-carboxybutylureido; and the like.

In the above formulas (3) and (4), di (C1-C4) alkyl substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group in R ¹⁰¹ to R ¹⁰⁸ Examples of the ureido group include those having these substituents on any carbon atom in the di (C1-C4) alkylureido group. The number of the substituents is usually 1 or 2, preferably 2. The position of the substituent is not particularly limited, but preferably the same carbon atom is not substituted with a nitrogen atom and a hydroxy group. Moreover, when it has two or more substituents, the kind may be same or different, but the same thing is preferable. Specific examples include N ′, N′-di (2-hydroxyethyl) ureido, N ′, N′-di (2-hydroxypropyl) ureido, N ′, N′-di (3-hydroxypropyl) ureido and the like. N ′, N′-di (hydroxy (C1-C4) alkyl) ureido group; N ′, N′-di (sulfo (C1-C4) such as N ′, N′-di (3-sulfopropyl) ureido Alkyl) ureido group; N ′, N′-di (carboxy (C1-C4) alkyl) ureido group such as N ′, N′-di (carboxymethyl) ureido; and the like.

In the above formulas (3) and (4), at least the benzene ring in R ¹⁰¹ to R ¹⁰⁸ is selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, and a carboxy group. As the benzoylamino group substituted with one kind of group, the carbon atom on the benzene ring of the benzoylamino group is selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, and a carboxy group And those substituted with at least one kind of group.

In the above formulas (3) and (4), at least the benzene ring in R ¹⁰¹ to R ¹⁰⁸ is selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, and a carboxy group. The phenylsulfonylamino group substituted with one kind of group is a group in which the carbon atom on the benzene ring of the phenylsulfonylamino group is a halogen atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, and a carboxy group. And those substituted with at least one group selected from the group consisting of: Examples of the halogen atom include the above-mentioned halogen atoms and specific examples, preferable ones, including particularly preferable ones, and (C1-C4) alkyl groups include the (C1-C4) alkyl groups and specific examples, preferable ones, The same thing is mentioned including a more preferable thing. The number of substitution is usually 1 to 3, preferably 1. Specific examples include 2-chlorophenylsulfonylamino group, 3-chlorophenylsulfonylamino group, 4-chlorophenylsulfonylamino group, 2,4-dichlorophenylsulfonylamino group, 2-fluorophenylsulfonylamino group, 3-fluorophenylsulfonylamino group. 4-fluorophenylsulfonylamino group, 2-bromophenylsulfonylamino group, 3-bromophenylsulfonylamino group, 4-bromophenylsulfonylamino group, 2-iodophenylsulfonylamino group, 3-iodophenylsulfonylamino group, 4 -Substituted with a halogen atom such as iodophenylsulfonylamino group; 2-methylphenylsulfonylamino group, 3-methylphenylsulfonylamino group, 4-methylphenylsulfonylamino group 2-ethylphenylsulfonylamino group, 3-ethylphenylsulfonylamino group, 4-ethylphenylsulfonylamino group, 2- (n-propyl) phenylsulfonylamino group, 3- (n-propyl) phenylsulfonylamino group, 4- (C1-C) such as (n-propyl) phenylsulfonylamino group, 2- (n-butyl) phenylsulfonylamino group, 3- (n-butyl) phenylsulfonylamino group, 4- (n-butyl) phenylsulfonylamino group, etc. C4) substituted by alkyl group; substituted by nitro group such as 2-nitrophenylsulfonylamino group, 3-nitrophenylsulfonylamino group, 4-nitrophenylsulfonylamino group, 3,5-dinitrophenylsulfonyl group 2-sulfophenylsulfonylamino group, 3-sulfur Substituted with a sulfo group such as phenylsulfonylamino group, 4-sulfophenylsulfonylamino group, 2,4-disulfophenylsulfonylamino group; 2-carboxyphenylsulfonylamino group, 3-carboxyphenylsulfonylamino group, 4 -Substituted with a carboxy group such as carboxyphenylsulfonylamino group and 3,5-dicarboxyphenylsulfonylamino group; preferred are those substituted with a sulfo group and a carboxy group, and substituted with a sulfo group. Is more preferable.

In the above formulas (3) and (4), R ¹⁰¹ to R ¹⁰⁸ are preferably (C1-C4) alkoxy groups in which at least one is substituted with a sulfo group. R ¹⁰¹ to R ¹⁰⁴ are each independently a hydrogen atom, a (C 1 -C 4) alkyl group, or a (C 1 -C 4) alkoxy group substituted with a sulfo group, and at least one of R ¹⁰¹ to R ¹⁰⁴ is More preferred is a (C1-C4) alkoxy group substituted with a sulfo group, and R ¹⁰⁵ to R ¹⁰⁸ are each independently a hydrogen atom or a (C1-C4) alkyl group. Also, at least one of R ¹⁰¹ and R ¹⁰² is a sulfopropoxy group, at least one of R ¹⁰³ and R ¹⁰⁴ is a sulfopropoxy group, and R ¹⁰⁵ to R ¹⁰⁸ are (C1-C4) alkyl groups. preferable.
One of R ¹⁰¹ and R ¹⁰² is a sulfopropoxy group, the other is a hydrogen atom or a sulfopropoxy group, one of R ¹⁰³ and R ¹⁰⁴ is a sulfopropoxy group, the other is a hydrogen atom or a sulfopropoxy group, and R ¹⁰⁵ To R ¹⁰⁸ is particularly preferably a methyl group.

Is not substituted position particularly limited in R ¹⁰¹ to R ^108, in each of the benzene rings to which they are substituted, position 1 the substitution position of the nitrogen atom attached to the triazine ring, a 4-position to the substitution position of the azo group, R ¹⁰¹ To R ¹⁰⁴ are preferably substituted at the 2-position, and R ¹⁰⁵ to R ¹⁰⁸ are preferably substituted at the 5-position.

  In the above formulas (3) and (4), the substitution positions of four sulfo groups whose substitution positions are not specified are not particularly limited. The sulfo group substituted on the benzene ring having one azo bond is preferably substituted at the 2-position, 3-position, or 4-position, preferably 4-position, with the substitution position of the azo bond as the 1-position.

Specific examples of the dye represented by the above formula (2) are shown in Tables 4 to 25 below. However, it is not limited to these.
Of these, the dye of Compound No. 59 is particularly preferred.

The dyes represented by the above formulas (1) and (2) can also be used as a free acid or a salt thereof. Examples of salts of the compounds represented by the above formulas (1) and (2) include salts with inorganic or organic cations. Specific examples of the inorganic cation salt include alkali metal salts such as lithium salts, sodium salts, potassium salts and the like; and ammonium salts (NH ₄ ⁺ ). Examples of the organic cation include, but are not limited to, quaternary ammonium represented by the following formula (5).

In the above formula (5), Z ^{1 to} Z ⁴ are each independently a hydrogen atom, a (C1 to C4) alkyl group, a hydroxy (C1 to C4) alkyl group, or a hydroxy (C1 to C4) alkoxy (C1 to C4) alkyl. Represents a group, and at least one of Z ^{1 to} Z ⁴ is a group other than a hydrogen atom.

Here, examples of the (C1-C4) alkyl group in Z ^{1 to} Z ⁴ include methyl, ethyl and the like. Similarly, examples of the hydroxy (C1-C4) alkyl group include hydroxymethyl, hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. It is done. Similarly, examples of the hydroxy (C1-C4) alkoxy (C1-C4) alkyl group include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3- (hydroxyethoxy) propyl, 3- (hydroxyethoxy) butyl, 2 -(Hydroxyethoxy) butyl etc. are mentioned.

  Among the above salts, preferred are alkali metal salts such as sodium, potassium and lithium; organic quaternary ammonium salts such as monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine salts; Ammonium salt; and the like. Of these, lithium salts, sodium salts, and ammonium salts are more preferable.

As will be apparent to those skilled in the art, the salt or free acid of the compounds represented by the above formulas (1) and (2) can be easily obtained by the following method or the like.
For example, in the synthesis reaction of the compound of formula (1), the reaction solution after completion of the final step, or an aqueous solution containing a salt of the compound of formula (1) or the like is dissolved in a water-soluble organic material such as acetone or (C1-C4) alcohol. The sodium salt of the compound of the above formula (1) can be obtained as a wet cake by separating the solid precipitated by a method of adding a solvent; a method of salting out by adding sodium chloride;
Further, after dissolving the obtained sodium salt wet cake in water, an acid such as hydrochloric acid is added to adjust the pH appropriately, and the precipitated solid is separated by filtration, whereby the free acid of the compound of the above formula (1) is obtained. Or a mixture of a free acid and a sodium salt in which a part of the compound of the formula (1) is a sodium salt.
Also, after dissolving the obtained sodium salt wet cake or its dry solid in water, an ammonium salt such as ammonium chloride is added, and an acid such as hydrochloric acid is added to adjust the pH appropriately, for example, to pH 1 to 3, By separating the precipitated solid by filtration, an ammonium salt of the compound of the above formula (1) can be obtained. A mixture of an ammonium salt of the compound of formula (1) and a sodium salt of the compound of formula (1) by appropriately adjusting the amount or / and pH of ammonium chloride to be added; or the free acid of the compound of formula (1) And a mixture of ammonium salts;
Further, as described later, a free acid solid can be directly obtained by adding a mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) to the reaction solution after completion of the above reaction. In this case, the wet cake of the free acid of the compound of formula (1) is added to water and stirred, for example, potassium hydroxide; lithium hydroxide; ammonia water; or water of organic quaternary ammonium of formula (5) By adding an oxide; etc. to form a salt, a potassium salt, a lithium salt, an ammonium salt, or a quaternary ammonium salt according to each added compound can be obtained. By limiting the number of moles of the above-mentioned hydroxide to be added with respect to the number of moles of free acid, for example, a mixed salt of lithium salt and sodium salt, etc .; and a mixture of lithium salt, sodium salt, and ammonium salt Salts and the like can also be prepared. The salt of the compound of the above formula (1) may change the physical properties such as solubility or the ink performance when used as an ink depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the intended ink performance.

  After completion of the reaction, the compound represented by the above formula (1) can be isolated as a solid free acid by adding a mineral acid such as hydrochloric acid, and the resulting free acid solid is water or, for example, hydrochloric acid water or the like. By washing with acidic water, inorganic salts (inorganic impurities) contained as impurities, such as sodium chloride and sodium sulfate, can be removed. As described above, the free acid of the compound of the present invention obtained as described above is obtained by treating the obtained wet cake or its dried solid with a desired inorganic or organic base in water to give a salt of the corresponding compound. Solution. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; and ammonium hydroxide (ammonia water). And the like. Examples of the organic base include, but are not limited to, organic amines corresponding to the quaternary ammonium represented by the above formula (5), for example, alkanolamines such as diethanolamine and triethanolamine.

  The method for producing a salt of the compound represented by the above formula (1) can also be applied to the compound represented by the above formula (2).

  The ink composition of the present invention contains 0.5 to 15% by mass, preferably 1 to 6% by mass, of the azo compound represented by the above formula (1) in the total amount. However, a higher concentration can be achieved from a combination of the high solubility of the compound represented by the above formula (1) and the dye represented by the above formula (2). Therefore, in order to obtain an ink composition with higher color development, the amount is more preferably 3% by mass or more.

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 Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 161, etc. ), Orange (for example, CI Direct Orange 17, CI Direct Orange 26, CI Direct Orange 29, CI Direct Orange 39, CI Direct Orange 49, etc.), Brown, Scarlet (E.g., CI Direct Red 89), red (e.g., CI Direct Red 62, CI Direct Red 75, CI Direct Red 79, CI Direct Red 80, CI Direct Red 84, CI Direct Red 225, CI Direct Red 226), magenta (for example, CI Direct Red 227), violet, blue, navy, cyan (for example, CI Direct Blue 199, CI Acid Blue 249, etc.), green (for example, Acid Green 1) ), Black (for example, CI Acid Black 2), and other dyes having various hues.

  In addition, the case where the content rate of the said component (A) is 40 mass% or more in the total amount of the pigment | dye content of this invention is preferable.

The ink composition of the present invention is prepared using water as a medium, and may contain a water-soluble organic solvent (an organic solvent miscible with water) (component (C)) as long as the effects of the present invention are not impaired. . This water-soluble organic solvent dissolves the dye; prevents the composition from drying (maintains a wet state); adjusts the viscosity of the composition; promotes penetration of the dye into the recording material; adjusts the surface tension of the composition; An effect such as defoaming of the composition can be expected, and the ink composition of the present invention is preferably contained.
The water-soluble organic solvent (component (C)) used in the preparation of the water-based ink composition is not particularly limited. For example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, second butanol (C1-C4) alkanols such as tributanol, carboxylic acid amides such as N, N-dimethylformamide or N, N-dimethylacetamide, lactams such as 2-pyrrolidone and N-methylpyrrolidin-2-one, 1,3- Cyclic ureas such as dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido-2-one, ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one , Cyclic ethers such as tetrahydrofuran and dioxane Ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, pentamethylene glycol, 1,6-hexylene glycol, 1,2-hexylene glycol , Monomers having (C2-C6) alkylene units such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, dithiodiglycol, oligomers or polyalkylene glycols or thioglycols, Polyol (triol) such as glycerin, hexane-1,2,6-triol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether (C1-C4) alkyl ethers of polyhydric alcohols such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol) or triethylene glycol monomethyl ether or triethylene glycol monoethyl ether, γ-butyrolactone or dimethyl sulfoxide Etc. can be used.
The water-soluble organic solvent is preferably one or two or more water-soluble organic solvents selected from the group consisting of 2-pyrrolidone, glycerin solvents, and glycol solvents.
The glycerin-based solvent is an aliphatic hydrocarbon or ether in which a hydroxyl group is substituted on three carbon atoms. Among the above examples, polyols (triols) such as glycerin and hexane-1,2,6-triol. ) Etc. correspond to this.
Glycol solvents are aliphatic hydrocarbons or ethers in which two carbon atoms are substituted with hydroxy groups. Among the above examples, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol 1,2-butylene glycol, 1,4-butylene glycol, pentamethylene glycol, 1,6-hexylene glycol, 1,2-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene Monomers, oligomers or polyalkylene glycols or thioglycols having (C2 to C6) alkylene units such as glycol, polypropylene glycol, thiodiglycol, dithiodiglycol, glycerin, hexane-1,2,6 Polyols such as triols (triol), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene glycol monomethyl ether, or triethylene glycol monoethyl ether (C1 to C4) alkyl ethers of the polyhydric alcohols fall under this category.
Of these, 2-pyrrolidone, glycerin, ethylene glycol, pentamethylene glycol, and 1,2-hexylene glycol are more preferable.
These organic solvents may be used alone or in combination of two or more.

  The water-soluble organic solvent includes a substance that is solid at room temperature, such as trimethylolpropane. However, even if the substance or the like is solid, it shows water solubility, and an aqueous solution containing the substance or the like shows the same properties as the water-soluble organic solvent and can be used with the expectation of the same effect. Therefore, in this specification, for the sake of convenience, such a solid substance is included in the category of a water-soluble organic solvent as long as it can be used in expectation of the same effect as described above.

  The preferable content of the water-soluble solvent is 0 to 50% by mass, more preferably 25 to 50% by mass, based on the total amount of the water-based ink composition of the invention.

 The ink composition of the present invention may further contain an ink adjusting agent for the purpose of improving the storage stability of the ink composition. Examples of the ink adjusting agent include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventing agents, water-soluble UV absorbers, water-soluble polymer compounds, dye dissolving agents, antioxidants, surfactants, antifoaming agents. Agents and the like.

  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 coloring 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 oxyd, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone, benzyl bromide Acetate-based and inorganic salt-based compounds are exemplified. Examples of the organic halogen compound include sodium pentachlorophenol, examples of the pyridine oxido compound include sodium 2-pyridinethiol-1-oxide, and examples of the inorganic salt compound include anhydrous sodium acetate. Examples of the isothiazoline-based compound include 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, and 5 -Chloro-2-methyl-4-isothiazolin-3-one magnesium chloride, 5-chloro-2-methyl-4-isothiazolin-3-one calcium chloride, 2-methyl-4-isothiazolin-3-one calcium chloride, etc. Can be mentioned. Other antiseptic / antifungal agents include 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, for example, 5 to 11 without adversely affecting the prepared ink. Examples include alkanolamines such as diethanolamine, triethanolamine, N-methyldiethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, ammonium hydroxide (ammonia), or lithium carbonate. And alkali metal carbonates such as sodium carbonate, sodium hydrogen carbonate and potassium carbonate, and inorganic bases such as potassium acetate, sodium silicate and disodium phosphate.

  Examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetate, sodium hydroxyethylethylenediaminetriacetate, sodium diethylenetriaminepentaacetate, sodium uracil diacetate and the like.

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

  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 solubilizer include ε-caprolactam, ethylene carbonate, urea and the like. In particular, when urea is contained, it is one of the preferred embodiments of the present invention.

  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, heterocycles, and the like.

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 their salts, N-acyl methyl taurates, alkyl sulfate polys. 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, alkyl allyl sulfone hydrochloride, diethyl sulfo Examples thereof include oxalate, diethylhexylsilsulfosuccinate, dioctylsulfosuccinate and the like. Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives. Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazoline derivatives. is there. Nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether, polyoxyallylalkyl. Ethers such as alkyl ethers, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate Esters, polyoxyethylene stearate, 2,4,7,9-tetramethyl-5-decyne-4,7-di Lumpur, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3 acetylene glycol such as ol (e.g., manufactured by Nissin Chemical Industry Co., Ltd. Surfynol ^RTM 104 and 105 , 82, 420, 440, 465, Olfine ^RTM STG, etc.). Of these, Surfynol ^RTM 420, 440 and 465 are preferably used, and Surfynol ^RTM 440 is particularly preferably used. In the present specification, the superscript “RTM” means a registered trademark.

  Examples of antifoaming agents include highly oxidized oils, glycerin fatty acid esters, fluorines, and silicone compounds.

  These ink preparation agents are used alone or in combination. The surface tension of the ink composition of the present invention is usually 25 to 70 mN / m, preferably 25 to 60 mN / m, and the viscosity is preferably 30 mPa · s or less, more preferably 20 mPa · s or less.

  In the production of the aqueous ink composition of the present invention, there is no particular limitation on the order of dissolving each agent such as an additive. The water used for preparing the ink composition is preferably water with few impurities such as ion exchange water and distilled water. Further, if necessary, after the ink composition is prepared, fine filtration may be performed using a membrane filter or the like to remove impurities in the ink composition. In particular, when the ink composition of the present invention is used as an ink for ink jet recording, it is preferable to perform microfiltration. The pore size of the filter used for microfiltration is usually 1 to 0.1 μm, preferably 0.8 to 0.1 μm.

  The ink composition containing the compound of the present invention is suitable for use in printing, copying, marking, writing, drawing, stamping, or recording (printing), particularly in inkjet recording. In addition, the ink composition of the present invention is less likely to precipitate solids even when dried in the vicinity of the nozzles of the recording head of an ink jet printer, and for this reason, the recording head is also less likely to block.

  Next, the ink jet recording method of the present invention will be described. The inkjet recording method of the present invention is characterized in that recording is performed using the aqueous ink composition of the present invention as an inkjet ink. In the ink jet recording method of the present invention, recording is performed on an image receiving material using the aqueous ink composition of the present invention, but there are no particular limitations on the ink nozzles and the like used at that time, and they may be appropriately selected according to the purpose. Known methods, for example, a charge control system that ejects ink using electrostatic attraction, a drop-on-demand system (pressure pulse system) that uses the vibration pressure of a piezo element, and an electrical signal is converted into an acoustic beam. Use an acoustic ink jet system that irradiates ink and ejects ink using radiation pressure, a thermal ink jet (bubble jet (registered trademark)) system that uses ink to form bubbles by heating the ink, and the like. Can do. The inkjet recording method includes a method of ejecting a large number of low-density inks called photo inks in a small volume, a method of improving image quality using a plurality of inks having substantially the same hue and different concentrations, and colorless and transparent. A method using ink is included.

  The colored product of the present invention is colored with the above-described aqueous ink composition of the present invention, and more preferably is colored with an ink jet printer using the aqueous ink composition of the present invention. Examples of materials that can be colored include information transmission sheets such as paper and film, fibers and cloth (cellulose, nylon, wool, etc.), leather, and base materials for color filters. The information transmission sheet is preferably a surface-treated sheet, specifically, a sheet such as paper, synthetic paper, or film provided with an ink receiving layer. For the ink-receiving layer, for example, a porous white inorganic substance capable of absorbing the pigment in the ink such as porous silica, alumina sol, and special ceramics by impregnating or coating the above-mentioned base material with a cationic polymer is used. It is provided by coating the surface of the substrate together with a hydrophilic polymer such as polyvinylpyrrolidone. A paper provided with such an ink receiving layer is usually called ink jet dedicated paper (film), glossy paper (film), etc., for example, as a typical commercial product, Pictorico (manufactured by Asahi Glass Co., Ltd.), professional photo paper, Super photo paper, matte photo paper, glossy gold, platinum grade (all manufactured by Canon Inc.), photo paper (gloss), photo matte paper, photo paper Crispia (high gloss) (all manufactured by Seiko Epson Corp.) , Premium Plus Photo Paper, Premium Glossy Film, Photo Paper, Advanced Photo Paper (all manufactured by Hewlett-Packard Japan), Photo-like QP (manufactured by Konica Corporation), Painting Photo Finishing Pro (Fuji Film Co., Ltd.) ))). Of course, plain paper, high-quality paper, and coated paper can also be used.

  Among these, it is known that an image recorded on a recording material coated with a porous white inorganic substance on the surface is particularly prone to discoloration by ozone gas, but the aqueous ink composition of the present invention is also resistant to ozone gas. Since it is excellent, it is also effective when recording on such a recording material.

  In order to record on the recording material by the ink jet recording method of the present invention, for example, a container containing the above ink composition may be set at a predetermined position of the ink jet printer and recorded on the recording material by a normal method. . In the ink jet recording method of the present invention, a black ink composition of the present invention, a publicly known magenta ink composition, a cyan ink composition, a yellow ink composition, and a green ink composition, blue (or violet) as necessary. Used in combination with an ink composition and a red (or orange) ink composition. The ink composition of each color is poured into each container, and the container is used by being loaded into a predetermined position of the ink jet printer in the same manner as the container containing the aqueous ink composition for ink jet recording of the present invention. Examples of the ink jet printer include a piezo printer using mechanical vibration and a bubble jet (registered trademark) printer using bubbles generated by heating.

The water-based ink composition of the present invention is a black recorded image of an ideal hue that is very clear on a recording material such as plain paper and an information transmission sheet having an ink receiving layer, has high print density, and low saturation. give. Therefore, it is also possible to faithfully reproduce a photographic color image on paper. In addition, the aqueous ink composition of the present invention has very good storage stability without solid precipitation, physical property change, hue change, etc. after long-term storage.
The water-based ink composition of the present invention is used for inkjet recording and writing instruments, and even when used as an inkjet ink, solid precipitation due to drying of the ink composition in the vicinity of the nozzle is very unlikely to occur, and an ejector (recording head). There is no blockage. In addition, the aqueous ink composition of the present invention uses a continuous ink jet printer, and is used in a case where the ink is recirculated at a relatively long time interval or used intermittently by an on-demand ink jet printer. It does not cause changes in the physical properties.
Furthermore, the image recorded on the information transmission sheet having the ink receiving layer by the water-based ink composition of the present invention has various fastness properties such as water resistance, moisture resistance, ozone gas resistance, abrasion resistance, and light resistance, particularly The water resistance and ozone gas resistance are good, and for this reason, the long-term storage stability of photographic images is also excellent. Compared to conventional inks, it also has excellent color development properties such as saturation, brightness, and print density on plain paper, color rendering properties, especially sensor compatibility in the near-infrared light region, and high color development properties. Yes.
Thus, the water-based ink composition of the present invention is extremely useful for various recording ink applications, particularly for ink jet recording ink applications.

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.
In each of the following formulas, the sulfo group is represented in the form of a free acid.
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]
Using (A) a compound of the following formula (6) and (B) a compound of the following formula (7), mixing each component at the composition ratio shown in Table 26 below, and approximately 1 hour until the solid content is dissolved After stirring, a black ink composition for test was prepared by filtering through a 0.45 μm membrane filter (trade name, cellulose acetate filter paper, manufactured by Advantech). The compound of the following formula (6) is the compound (21) described in International Publication No. 2006/051850, and the compound of the following formula (7) is the compound (31) described in International Publication No. 2011/043184, respectively. Obtained by following the described method.

[Comparative Example 1]
As a comparative black ink composition, a comparative ink was prepared in the same manner as in Example 1 except that the dye of formula (7) was not used and sodium hydroxide + ion exchanged water was increased. The following various tests conducted using this ink are referred to as Comparative Example 1.

[Comparative Example 2]
As a black ink composition to be compared, C.I. I. A comparative ink was prepared in the same manner as in Example 1 except that Acid Yellow 23 was used. The following various tests conducted using this ink are referred to as Comparative Example 2. In addition, C.I. I. A commercially available Acid Yellow 23 was used.

[Comparative Example 3]
A comparative ink was prepared in the same manner as in Example 1 except that a compound represented by the following formula (8) was used instead of the component (A) as a black ink composition to be compared. The following various tests conducted using this ink are referred to as Comparative Example 3. The compound of the following formula (8) is the compound (41) described in JP-A-2009-84346, and each was obtained by following the methods described in the literature.

[(B) Inkjet recording]
Using the ink compositions obtained in Example 1 and Comparative Examples 1 to 3, inkjet recording was performed on the following printing paper using an inkjet printer (trade name: EPSON PX-105).
Glossy paper 1: Product name manufactured by EPSON Co., Ltd. When printing, as a test piece for hue evaluation, the reflection density is 100%, 90%, 80%, 70%, 60%, 50%, 40%, 30%, 20 An image pattern was prepared so that 10 gradation levels of 10% and 10% were obtained, and a dark black to light black gradation recorded matter was obtained, and this was used as a test piece, and the following evaluation test was performed. In addition, as a test piece for evaluating moisture resistance, a lattice-like image pattern having a reflection density of 100% and 0% is prepared, black and white lattice-like recorded matter is obtained, and the following evaluation test is performed using this as a test piece. Carried out. Since the gray scale mode is used in any printing, yellow, cyan and magenta recording liquids other than the black recording liquid are not used in combination.

[(C) Evaluation]
Regarding the recorded image by the aqueous ink composition of the present invention, the density change of the recorded image was measured using a colorimeter manufactured by GRETAG-MACBETH, trade name: SpectroEye. When measuring colors, all were performed under the conditions of D65 as the light source, DIN NB as the density reference, and a viewing angle of 2 °.

○：ΔＥ≦９
△：９＜ΔＥ≦１１
×：１１＜ΔＥ [Light resistance evaluation]
Each recorded image obtained using the inks of Example 1 and Comparative Examples 1 to 3 was naturally dried for 24 hours after printing, and light intensity was measured using a Xenon Weather Meter XL75 manufactured by Suga Test Instruments Co., Ltd. Each test piece was left for 168 hours under the conditions of 100 klux, humidity 60% RH, and temperature 24 ° C.
After the test, the colorimetry is performed using the above colorimeter, and the color difference (ΔE) is calculated as ((L * after test−L * before test) ² + (a * after test−a * before test)). ² + - were evaluated in ^{2) 1/2} asked the following criteria (after the test ^b * b * before the ^test). As the evaluation obtained, a small value indicates that the color change after fading is small and is excellent.
The results are shown in Table 27 below.

○: ΔE ≦ 9
Δ: 9 <ΔE ≦ 11
×: 11 <ΔE

○：滲みなし
△：有色格子の周辺に若干の滲みが見える
×：明らかな滲みが見える [Moisture resistance evaluation]
Each recorded image obtained using the ink of Example 1 and Comparative Examples 1 to 3 was naturally dried for 24 hours after printing, and 30 ° C. and 90% RH using a Humidic Chamber IG400 manufactured by Yamato Scientific Co., Ltd. Each test piece was allowed to stand for 168 hours under the conditions described above. After completion of the test, the above test piece was visually confirmed and evaluated according to the following criteria. As an evaluation obtained, a sample with less bleeding shows excellent moisture resistance and is excellent.
The results are shown in Table 28 below.

○: No bleeding Δ: Slight bleeding is seen around the colored grid ×: Clear bleeding is visible

  From the results of Tables 27 and 28, it was confirmed that Example 1 was superior in light resistance and moisture resistance to Comparative Examples 1 to 3.

The azo compound of the present invention or a salt thereof and an ink composition containing the same have a very high printing density, low saturation, a high-quality black hue, and particularly excellent light resistance and moisture resistance. Therefore, it is suitably used for black ink for various recordings such as writing utensils, especially for ink jet recording.

Claims (17)

(A) a dye represented by the following formula (1), (B) a maximum absorption wavelength (λmax) in an aqueous solvent is 340 nm or more and less than 440 nm, a half width is 150 nm or more and less than 300 nm, and a molecular weight is 1800 or more. An ink composition containing a pigment that is 5000 or less.

[In Formula (1),
R ¹ , R ² , R ⁵ , R ⁶ and R ⁷ are each independently a hydrogen atom; a halogen atom; a cyano group; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a phospho group; a nitro group; (C1-C4) alkyl group; (C1-C4) alkoxy group; hydroxy group, or (C1-C4) alkyl group substituted with (C1-C4) alkoxy group; hydroxy group, (C1-C4) alkoxy group, (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of a sulfo group and a carboxy group; an acyl group; an N-alkylaminosulfonyl group; an N-phenylaminosulfonyl group; a sulfo group; N-alkylaminosulfuryl substituted with at least one group selected from the group consisting of a carboxy group and a hydroxy group An alkylsulfonyl group; an alkylsulfonyl group substituted with at least one group selected from the group consisting of a sulfo group, a carboxy group, and a hydroxy group; an acylamino group; an alkylsulfonylamino group; a phenylsulfonylamino group; Or a phenylsulfonylamino group substituted with at least one group selected from the group consisting of halogen atoms, (C1-C4) alkyl groups, and nitro groups;
R ³ and R ⁴ are each independently substituted with a hydrogen atom; a halogen atom; a cyano group; a carboxy group; a sulfo group; a nitro group; a (C1-C4) alkyl group; a hydroxy group, or a (C1-C4) alkoxy group. (C1-C4) alkyl group; (C1-C4) alkoxy group; substituted with at least one group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group, and carboxy group (C1-C4) alkoxy group; (C1-C4) alkylthio group; (C1-C4) alkylthio group substituted by sulfo group or carboxy group; acylamino group; alkylsulfonylamino group; phenylsulfonylamino group; At least one selected from the group consisting of an atom, a (C1-C4) alkyl group, and a nitro group; And; in substituted phenylsulfonylamino group
n represents 0 or 1, respectively. ] In equation (1),
2. The ink composition according to claim 1, wherein at least three of R ^{1 to} R ⁷ are a sulfo group or a carboxy group. In equation (1),
R ¹ and R ² are each independently a hydrogen atom; a sulfo group; a carboxy group; or a hydroxy group;
R ³ and R ⁴ are each independently a hydrogen atom; a halogen atom; a carboxy group; a sulfo group; a (C1-C4) alkoxy group substituted with a sulfo group or a carboxy group; or a sulfo group or a carboxy group. A substituted (C1-C4) alkylthio group;
R ^{5 to} R ⁷ are each independently a hydrogen atom; a halogen atom; a sulfo group; a carboxy group; a hydroxy group; or a (C1-C4) alkoxy group;
n is 1,
The ink composition according to claim 1 or 2. In the formula (1),
R ¹ is a carboxy group or a sulfo group,
R ² is a hydrogen atom,
R ³ is a sulfo group,
R ⁴ is a hydrogen atom,
R ⁵ is a hydrogen atom, a carboxy group or a sulfo group,
R ⁶ is a carboxy group or a sulfo group,
R ⁷ is a hydrogen atom,
The ink composition according to any one of claims 1 to 3, wherein n is 1. The ink composition according to any one of claims 1 to 4, wherein the component (B) is a dye represented by the following formula (2).

[In Formula (2),
A represents the structure represented by Formula (3),
B represents the structure represented by Formula (4);
X represents a divalent bridging group (provided that it has at least two nitrogen atoms, and A and B are each substituted with different nitrogen atoms);
In formulas (3) and (4),
R ¹⁰¹ to R ¹⁰⁸ each independently represent a hydrogen atom; a halogen atom; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group, (C1- C4) substituted with at least one group selected from the group consisting of an alkoxy group, a hydroxy (C1-C4) alkoxy group, a sulfo group, and a carboxy group (C1-C4)
(C1-C4) alkylcarbonylamino group; (C1-C4) alkylcarbonylamino group substituted with a carboxy group; ureido group; mono (C1-C4) alkylureido group; di (C1-C4) alkylureido A mono (C1-C4) alkylureido group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group; from a group consisting of a hydroxy group, a sulfo group, and a carboxy group Di (C1-C4) alkylureido group substituted with at least one selected group; benzoylamino group; benzene ring is a halogen atom, (C1-C4) alkyl group, nitro group, sulfo group, and carboxy group A benzoylamino group substituted with at least one group selected from the group consisting of: Or at least one selected from the group consisting of a halogen atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, and a carboxy group.
A phenylsulfonylamino group substituted with a kind of group;
* Represents a substitution position with X. ] In the formula (2),
The ink composition according to claim 5, wherein X represents an aliphatic diamine (A and B are each substituted with different nitrogen atoms). In the formula (2),
X is a (C1-C8) alkylene diamino group; a (C1-C8) alkylene diamino group substituted with a hydroxy group or a carboxy group; N- (C1-C4) alkyl- (C1-C6) alkylene diamino group; an alkyl moiety N- (C1-C4) alkyl- (C1-C6) alkylenediamino group substituted with hydroxy group or carboxy group; amino (C1-C6) alkoxy (C1-C6) alkylamino group; amino (C1-C4) Piperazine-1 substituted with (C1-C4) alkoxy (C1-C4) alkylamino group; piperazine-1,4-diyl group; or (C1-C4) alkyl group or (C1-C4) alkoxy group The ink composition according to claim 5, which represents a 1,4-diyl group. In the above formulas (3) and (4),
R ¹⁰¹ to R ¹⁰⁸ are each independently a hydrogen atom; a halogen atom; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a (C1-C4) alkoxy group substituted with a sulfo group or a carboxy group;
Or the ink composition according to any one of claims 5 to 7, which is a (C1-C4) alkylcarbonylamino group; The ink composition according to any one of claims 1 to 8, further comprising (C) a water-soluble organic solvent. The ink composition according to claim 9, wherein the component (C) is one or two or more water-soluble organic solvents selected from the group consisting of 2-pyrrolidone, a glycerin solvent, and a glycol solvent. The ink composition according to any one of claims 1 to 9, wherein the content of the component (A) is 40% by mass or more in the total amount of the coloring matter in the ink composition. The ink composition according to any one of claims 1 to 11, which is for inkjet recording. An ink jet recording method using the ink composition according to any one of claims 1 to 12 as ink, ejecting ink droplets of the ink in accordance with a recording signal, and depositing the ink on a recording material. The inkjet recording method according to claim 13, wherein the recording material is an information transmission sheet. 15. The ink jet recording method according to claim 14, wherein the information transmission sheet is a sheet having an ink receiving layer containing plain paper or a porous white inorganic substance. A colored body colored by the ink jet recording method according to any one of claims 13 to 15. An ink jet printer loaded with a container containing the ink composition according to claim 1.