JP2013249333A - Aqueous black ink composition, inkjet recording method using the same, and colored material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous black ink composition excellent in color developability of recorded matter, light resistance, ozone gas resistance, moisture resistance, water resistance, color rendering properties and sensor responsive characteristics, when used as inkjet recording ink or writing utensils, and which has good storage stability as a recording liquid because of excellent solubility, and to provide an inkjet recording method using the composition, and a colored material.SOLUTION: An aqueous black ink composition includes, as a pigment component, (i) C.I. Acid Black 2 and (ii) a dye having ≥70% pigment residual ratio after 4 hours in the ozone gas resistance test under conditions of 40 ppm ozone concentration, 60% RH of humidity and 24°C temperature.

Description

  The present invention relates to an aqueous black 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.

  When an ink jet printer is used, the type of recording paper is not selected, but the hue reproducibility is required not to depend on the medium or the light source. In particular, in black ink, since the reproducibility of hue is likely to depend on the media and the light source, development of an ink excellent in color rendering is desired.

  Furthermore, as one of the performances required in the commercial printing field, there is a light absorptivity (reflection characteristic) particularly in the near infrared light region outside the visible light region. This is because it is necessary to cope with reading of various sensors such as a near infrared light sensor.

  In addition to the above, the performance required for the ink composition for printing on plain paper includes color reproducibility (color development, ie, saturation and brightness), storage stability, and ozone resistance (oxidizing gas). Resistance), moisture resistance, and the like, and ink compositions that are sufficiently satisfactory in any of them have not been proposed yet.

  Therefore, in the future, in order to expand the field of use of printing methods using ink, the ink composition used for inkjet recording and the colored body colored thereby will have light resistance, ozone gas resistance, water resistance, moisture resistance. There is a strong demand for further improvements in sensor reading compatibility.

  Various hues of ink are prepared from various dyes, of which black ink is an important ink used for both monocolor and full color images. However, there are many technical difficulties in developing pigments that have neutral hues, high color densities, and excellent fastness in both the dark and light gamuts. Few have good performance. Therefore, generally, a black ink is prepared by mixing a plurality of various pigments. However, when an ink is prepared by mixing multiple dyes, the hue differs depending on the media (recording material) compared to the case of preparing an ink with a single dye. Problems such as increased discoloration are likely to occur.

  Many of the pigments proposed as dyes for black ink are azo pigments. I. Azo dyes such as Direct Black 19 have problems such as low optical density of the image, insufficient water resistance, light resistance and gas resistance. Similarly, some azo metal-containing dyes that have been proposed have good light resistance, but they contain metal ions, which is undesirable for safety and the environment for living organisms, and extremely low ozone gas resistance. There are problems such as. Many of these have been proposed, but have not yet been able to provide products that fully satisfy market demands.

  As black inks in which a dye for color adjustment is further blended with a black dye, for example, those disclosed in Patent Documents 1 to 3 have been proposed, but have not yet been provided with a product that sufficiently satisfies market demands.

  The dye used in the present invention is described in Patent Document 4. However, it cannot be said that these effects are sufficient as compared with the color rendering properties in the present invention. Accordingly, the present invention is realized by having a sufficient characteristic (for example, color rendering property) even when compared with the compounds described in the above-mentioned documents.

  Examples of the black colorant suitable for the dye ink for inkjet recording include the above-described C.I. I. A compound of the formula (1) described in Direct Black 19 and Patent Document 4 is known.

Japanese Examined Patent Publication No. 7-122044 Patent No. 3178200 JP-A-9-255906 JP 2009-084346 A

  The present invention is stable even when stored in the form of a solution for a long time, exhibits neutral gray to black without color, and has optical density, fastness, light resistance, ozone gas resistance, and water resistance of the printed image. The object is to provide an aqueous black ink composition that gives an excellent black recorded image.

  As a result of intensive studies to solve the above-described problems, the present inventors have found that C.I. which is a specific dye as the dye component (component (I)) of the black ink. I. By using Acid Black 2 together with a certain ozone-resistant dye, the hue is improved, the color rendering is particularly high and the sensor compatibility in the near-infrared light region is improved. In addition, the present inventors have found that an excellent aqueous black ink composition can be obtained and have reached the present invention.

［式（１）中、
ｎは０または１であり、
Ｒ¹はカルボキシ基；（Ｃ１〜Ｃ８）アルコキシカルボニル基；（Ｃ１〜Ｃ８）アルコキシカルボニル基またはカルボキシ基で置換されていても良い（Ｃ１〜Ｃ４）アルキル基；またはヒドロキシ基、スルホ基またはカルボキシ基で置換されていても良いフェニル基を表し、
Ｒ²からＲ⁴はそれぞれ独立に水素原子；塩素原子；ヒドロキシ基；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；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、スルホ基またはカルボキシ基で置換されても良い（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、スルホ基またはカルボキシ基で置換されても良いモノまたはジ（Ｃ１〜Ｃ４）アルキルアミノ基；ヒドロキシ基またはカルボキシ基で置換されても良い（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；ヒドロキシ基、スルホ基またはカルボキシ基で置換されても良いＮ’−（Ｃ１〜Ｃ４）アルキルウレイド基；ベンゼン環が塩素原子、（Ｃ１〜Ｃ４）アルキル基、ニトロ基、スルホ基またはカルボキシ基で置換されても良いフェニルアミノ基；ベンゼン環が塩素原子、（Ｃ１〜Ｃ４）アルキル基、ニトロ基、スルホ基またはカルボキシ基で置換されても良いベンゾイルアミノ基；またはベンゼン環が塩素原子、（Ｃ１〜Ｃ４）アルキル基、ニトロ基、スルホ基またはカルボキシ基で置換されていても良いフェニルスルホニルアミノ基；をそれぞれ表し、
基Ａは下記式（２）または（３）で示される置換複素環基であり、

（式（２）中、Ｒ⁵はメルカプト基；またはヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、ヒドロキシ（Ｃ１〜Ｃ４）アルコキシ基、スルホ基またはカルボキシ基で置換されても良い（Ｃ１〜Ｃ４）アルキルチオ基を表す。）

（式（３）中、Ｒ⁶からＲ⁸はそれぞれ独立に水素原子；塩素原子；カルボキシ基；スルホ基；ニトロ基；ヒドロキシ基；カルバモイル基；スルファモイル基；（Ｃ１〜Ｃ４）アルキル基；ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基またはカルボキシ基で置換されても良い（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、スルホ基またはカルボキシ基で置換されても良い（Ｃ１〜Ｃ４）アルキルスルホニル基；またはベンゼン環が塩素原子、（Ｃ１〜Ｃ４）アルキル基、ニトロ基、スルホ基またはカルボキシ基で置換されても良いフェニルスルホニル基；をそれぞれ表す。）
基Ｂは置換基を有しても良いフェニル基またはナフチル基であり、
基Ｂが置換フェニル基の場合はヒドロキシ基；スルホ基；カルボキシ基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；アミノ基；モノまたはジ（Ｃ１〜Ｃ４）アルキルアミノ基；アセチルアミノ基；ベンゼン環が塩素原子、（Ｃ１〜Ｃ４）アルキル基、ニトロ基、スルホ基またはカルボキシ基で置換されても良いベンゾイルアミノ基；よりなる群から選択される置換基を有し、
基Ｂが置換ナフチル基の場合はヒドロキシ基；スルホ基；（Ｃ１〜Ｃ４）アルコキシ基；ベンゼン環がメチル基、ニトロ基または塩素原子で置換されても良いフェニルスルホニルオキシ基；よりなる群から選択される置換基を有する。］
５）
上記式（１）において、
基Ｂが置換されても良いフェニル基であり、置換基がヒドロキシ基、スルホ基またはカルボキシ基である上記４）に記載の水性黒色インク組成物、
６）
上記式（１）において、
基Ｂが置換されても良いナフチル基であり、置換基がヒドロキシ基またはスルホ基である上記４）に記載の水性黒色インク組成物、
７）
上記式（１）において、
Ｒ^１が無置換（Ｃ１〜Ｃ４）アルキル基またはカルボキシ基、
Ｒ^２がスルホ（Ｃ１〜Ｃ４）アルコキシ基、
Ｒ^３が水素原子、
Ｒ^４が水素原子、メチル基またはエチル基である、
上記４）に記載の水性黒色インク組成物、
８）
上記式（１）において、
基Ａが式（２）で表され、
Ｒ^１がメチル基またはカルボキシ基、
Ｒ^５がスルホ（Ｃ１〜Ｃ４）アルキルチオ基またはカルボキシ（Ｃ１〜Ｃ４）アルキルチオ基である上記４）に記載の水性黒色インク組成物、
９）
上記式（１）において、
基Ａが式（３）で表され、
Ｒ^１がメチル基またはカルボキシ基、
Ｒ^６乃至Ｒ^８がそれぞれ独立に水素原子、塩素原子、カルボキシ基、スルホ基、ニトロ基、（Ｃ１〜Ｃ４）アルキル基、（Ｃ１〜Ｃ４）アルコキシ基、（Ｃ１〜Ｃ４）アルキルスルホニル基である上記４）に記載の水性黒色インク組成物、
１０）
上記式（１）において、
ｎが１であり、
Ｒ^１がカルボキシ基、
Ｒ^２がスルホプロポキシ基、
Ｒ^３が水素原子、
Ｒ^４がメチル基、
Ｒ^６乃至Ｒ^８がそれぞれ独立に水素原子、塩素原子、カルボキシ基、スルホ基、ニトロ基、メチル基、メトキシ基、メチルスルホニル基であり、
かつ基Ｂがスルホ基またはカルボキシ基で置換されても良いフェニル基である上記４）に記載のトリスアゾ化合物またはその塩、
１１）
（Ｉ）色素成分総質量中、前記染料（ｉ）を１０〜９０質量％、上記染料（ｉｉ）を１０〜９０質量％含有する上記１）乃至１０）のいずれか一項に記載の水性黒色インク組成物、
１２）
更に（ＩＩ）水溶性有機溶剤を含有する上記１）乃至１１）のいずれか一項に記載の水性黒色インク組成物、
１３）
更に（ＩＩＩ）尿素を含有する上記１）乃至１２）のいずれか一項に記載の水性黒色インク組成物、
１４）
インクジェット記録に用いる上記１）乃至１３）のいずれか一項に記載の水性黒色インク組成物、
１５）
上記１）乃至１４）のいずれか一項に記載の水性黒色インク組成物を用いるインクジェット記録方法、
１６）
インクジェット記録方法における被記録材が情報伝達用シートである上記１５）に記載のインクジェット記録方法、
１７）
上記情報伝達用シートが多孔性白色無機物を含有するインク受容層を有するシートである上記１６）に記載のインクジェット記録方法、
１８）
上記１）乃至１３）のいずれか一項に記載の水性黒色インク組成物を含む容器を装填したインクジェットプリンタ、
１９）
上記１）乃至１３）のいずれか一項に記載の水性黒色インク組成物によって着色された着色体、
に関する。 That is, the present invention
1)
(I) As a pigment component, (i) C.I. I. Acid Black 2 and (ii) in a ozone gas resistance test under conditions of an ozone concentration of 40 ppm, a humidity of 60% RH, and a temperature of 24 ° C., and a dye having a dye residual ratio of 70% or more after 4 hours An aqueous black ink composition,
2)
The water-based black ink composition according to 1) above, wherein the first dye (ii) is a dye having a λmax (maximum absorption wavelength) measured in an aqueous solution of pH 7 of 600 nm or more and 640 nm or less,
3)
The water-based black ink composition according to 1) or 2), wherein the dye (ii) is a dye having three or more azo bonds (—N═N—) in the molecule;
4)
The water-based black ink composition according to any one of 1) to 3), wherein the dye (ii) is a black dye represented by the following formula (1) or a salt thereof:

[In Formula (1),
n is 0 or 1;
R ¹ is a carboxy group; (C1-C8) alkoxycarbonyl group; (C1-C8) an alkoxycarbonyl group or a (C1-C4) alkyl group optionally substituted with a carboxy group; or a hydroxy group, a sulfo group or a carboxy group Represents a phenyl group which may be substituted with
R ² to R ⁴ each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a (C1-C4) alkyl group; a hydroxy group, a (C1-C4) alkoxy group, a hydroxy group (C1-C4) alkoxy group, sulfo group or carboxy group which may be substituted (C1-C4) alkoxy group; mono- or di (C1-C4) alkyl group which may be substituted with hydroxy group, sulfo group or carboxy group An amino group; a (C1-C4) alkylcarbonylamino group optionally substituted with a hydroxy group or a carboxy group; an N ′-(C1-C4) alkylureido group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; The benzene ring is a chlorine atom, a (C1-C4) alkyl group, a nitro group, a sulfo group or a carbocycle. A phenylamino group which may be substituted with a group; a benzene ring having a chlorine atom, a benzoylamino group which may be substituted with a (C1-C4) alkyl group, a nitro group, a sulfo group or a carboxy group; or a benzene ring having a chlorine atom, (C1-C4) each represents a phenylsulfonylamino group optionally substituted with an alkyl group, a nitro group, a sulfo group or a carboxy group;
Group A is a substituted heterocyclic group represented by the following formula (2) or (3),

(In formula (2), R ⁵ may be a mercapto group; or a hydroxy group, a (C1-C4) alkoxy group, a hydroxy (C1-C4) alkoxy group, a sulfo group, or a carboxy group (C1-C4). Represents an alkylthio group.)

(In formula (3), R ⁶ to R ⁸ are each independently a hydrogen atom; chlorine atom; carboxy group; sulfo group; nitro group; hydroxy group; carbamoyl group; sulfamoyl group; (C1-C4) alkyl group; , (C1 to C4) alkoxy group, sulfo group or carboxy group which may be substituted (C1 to C4) alkoxy group; hydroxy group, sulfo group or carboxy group which may be substituted (C1 to C4) alkylsulfonyl group Or a phenylsulfonyl group in which the benzene ring may be substituted with a chlorine atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, or a carboxy group;
Group B is an optionally substituted phenyl group or naphthyl group,
When group B is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; an amino group; a mono- or di (C1-C4) alkylamino group; An amino group; a benzene ring in which the benzene ring may be substituted with a chlorine atom, a (C1-C4) alkyl group, a nitro group, a sulfo group or a carboxy group; and a substituent selected from the group consisting of:
When group B is a substituted naphthyl group; selected from the group consisting of hydroxy group; sulfo group; (C1-C4) alkoxy group; phenylsulfonyloxy group in which the benzene ring may be substituted with methyl group, nitro group or chlorine atom; Having a substituent. ]
5)
In the above formula (1),
The water-based black ink composition as described in 4) above, wherein the group B is a phenyl group which may be substituted, and the substituent is a hydroxy group, a sulfo group or a carboxy group;
6)
In the above formula (1),
The water-based black ink composition as described in 4) above, wherein the group B is a naphthyl group which may be substituted, and the substituent is a hydroxy group or a sulfo group;
7)
In the above formula (1),
R ¹ is an unsubstituted (C1-C4) alkyl group or a carboxy group,
R ² is a sulfo (C1-C4) alkoxy group,
R ³ is a hydrogen atom,
R ⁴ is a hydrogen atom, a methyl group or an ethyl group,
The water-based black ink composition as described in 4) above,
8)
In the above formula (1),
Group A is represented by Formula (2),
R ¹ is a methyl group or a carboxy group,
The water-based black ink composition as described in 4) above, wherein R ⁵ is a sulfo (C1-C4) alkylthio group or a carboxy (C1-C4) alkylthio group,
9)
In the above formula (1),
Group A is represented by Formula (3),
R ¹ is a methyl group or a carboxy group,
R ^{6 to} R ⁸ are each independently a hydrogen atom, chlorine atom, carboxy group, sulfo group, nitro group, (C1-C4) alkyl group, (C1-C4) alkoxy group, or (C1-C4) alkylsulfonyl group. The water-based black ink composition as described in 4) above,
10)
In the above formula (1),
n is 1,
R ¹ is a carboxy group,
R ² is a sulfopropoxy group,
R ³ is a hydrogen atom,
R ⁴ is a methyl group,
R ^{6 to} R ⁸ are each independently a hydrogen atom, chlorine atom, carboxy group, sulfo group, nitro group, methyl group, methoxy group, methylsulfonyl group,
And the trisazo compound or a salt thereof according to 4) above, wherein the group B is a phenyl group which may be substituted with a sulfo group or a carboxy group,
11)
(I) The aqueous black according to any one of 1) to 10) above, wherein 10 to 90% by mass of the dye (i) and 10 to 90% by mass of the dye (ii) are contained in the total mass of the pigment component. An ink composition,
12)
(II) The water-based black ink composition according to any one of 1) to 11) above, which contains a water-soluble organic solvent,
13)
(III) The aqueous black ink composition according to any one of 1) to 12) above, which contains urea;
14)
The water-based black ink composition according to any one of 1) to 13) used for inkjet recording,
15)
An inkjet recording method using the aqueous black ink composition according to any one of 1) to 14) above;
16)
The inkjet recording method according to 15) above, wherein the recording material in the inkjet recording method is an information transmission sheet,
17)
The ink jet recording method according to 16) above, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance,
18)
An inkjet printer loaded with a container containing the aqueous black ink composition according to any one of 1) to 13) above;
19)
A colored body colored with the water-based black ink composition according to any one of 1) to 13) above;
About.

The aqueous black 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. Further, the aqueous black ink composition of the present invention is used for ink jet recording, writing instruments, etc., and prepares an ink having a low dye concentration and a neutral hue of a recorded image when recorded on plain paper and ink jet dedicated paper. Even in this case, a printed matter with a black hue can be obtained. In addition, the print density is high, and it is excellent in light resistance, ozone gas resistance, moisture 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, 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 aqueous black ink composition of the present invention comprises (i) C.I. I. Contains Acid Black 2. By containing this compound, compared with the conventional black ink composition, the hue, sensor compatibility in the near-infrared light region, and particularly the color rendering can be significantly improved.

  C. I. Acid Black 2 can be obtained from Orient Chemical Co., Ltd. as WATER BLACK R-455, R-510.

In addition to the above (i), the water-based black ink composition of the present invention includes (ii) an ozone gas resistance test under conditions of an ozone concentration of 40 ppm, a humidity of 60% RH, and a temperature of 24 ° C. In this method, a dye having a dye residual ratio of 70% or more after 4 hours is contained. The dye (ii) is not particularly limited as long as it has the above characteristics. Further, the ozone gas resistance test result may be 70% or more, preferably 75% or more, and more preferably 80% or more. The ozone gas resistance test is performed using the following glossy paper.
Glossy paper 3 Product name manufactured by EPSON [Photographic paper crispia (high gloss)]
The dye having this property is of course excellent in ozone gas resistance, but the above (i) C.I. I. By using in combination with Acid Black 2, it is possible to realize an aqueous black ink composition that is very excellent in other various fastness properties. Therefore, this configuration is indispensable for solving the above problems.

  The dye (ii) is preferably a dye having a λmax (maximum absorption wavelength) measured in an aqueous solution of pH 7 of 600 nm or more and 640 nm or less. When a dye having λmax in this range is used, the harmony with the black color of the dye (i) is very good, and an excellent color rendering property can be realized.

  The dye (ii) is not particularly limited as long as the dye (ii) has the above-described characteristics, but a dye (ii) having three or more azo bonds (—N═N—) in the molecule is particularly preferable. When the dye is used, a black ink composition having excellent color developability, water resistance, light resistance and color rendering can be obtained.

  When the black dye represented by the above formula (1) or a salt thereof is used as the dye (ii), the effect of the present invention is more remarkable and preferable.

The black dye represented by the formula (1) has a tautomer, and examples of the tautomer include the following formulas (4) to (6) in addition to the compound represented by the formula (1). Conceivable. These compounds are also included in the present invention. In formulas (4) to (6), R ^{1 to} R ⁴ have the same meaning as in formula (1) above.

（式（４）中、基Ａ、基ＢおよびＲ^１乃至Ｒ^４は式（１）におけるものと同じ意味を有する。）

(In formula (4), group A, group B and R ^{1 to} R ⁴ have the same meaning as in formula (1).)

（式（５）中、基Ａ、基ＢおよびＲ^１乃至Ｒ^４は式（１）におけるものと同じ意味を有する。）

(In the formula (5), the group A, the group B and R ^{1 to} R ⁴ have the same meaning as in the formula (1).)

（式（６）中、基Ａ、基ＢおよびＲ^１乃至Ｒ^４は式（１）におけるものと同じ意味を有する。）

(In formula (6), group A, group B and R ^{1 to} R ⁴ have the same meaning as in formula (1).)

In the above formula (1), R ¹ is a carboxy group; (C1-C8) alkoxycarbonyl group; (C1-C8) an alkyl group optionally substituted with an alkoxycarbonyl group or a carboxy group (C1-C4); or hydroxy Represents a phenyl group which may be substituted with a group, a sulfo group or a carboxy group.

When R ¹ in Formula (1) is a (C1-C8) alkoxycarbonyl group, the alkoxycarbonyl group may be any of linear, branched, and alkyl moieties having a cyclic structure, but linear and branched A chain alkoxycarbonyl group is preferred. Specific examples include, for example, methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, n-butoxycarbonyl group, n-pentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyl. Straight chain such as oxycarbonyl group; isopropoxycarbonyl group, isobutyloxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, 2,2-dimethylpropoxycarbonyl group, isopentyloxycarbonyl group, sec-pentyloxycarbonyl Group, branched chain such as 2-methylbutyloxycarbonyl group; cyclopropylmethyloxycarbonyl group, cyclobutylmethyloxycarbonyl group, cyclopentyloxycarbonyl group, cyclohexyloxycal The alkyl moiety of such alkenyl groups have cyclic structures; and the like.
More preferably, it is a straight chain (C1-C6), still more preferably a straight chain (C1-C4) alkoxycarbonyl group. Specific examples are the same as those described above.

R ¹ in Formula (1) is a (C1-C4) alkyl group which may be substituted with a (C1-C8) alkoxycarbonyl group or a carboxy group, and the (C1-C4) alkyl group is unsubstituted (C1-C4). ) In the case of an alkyl group, the alkyl group may be either a straight chain or a branched chain, but is preferably a straight chain. Specific examples of the (C1 to C4) alkyl group include, for example, a straight chain such as a methyl group, an ethyl group, an n-propyl group, and an n-butyl group; an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and the like. Of branched chain.
Also when this (C1-C4) alkyl group has a substituent, this alkyl group may be the same as the above including a preferable thing. When the substituent is a (C1-C8) alkoxycarbonyl group, the alkoxycarbonyl group may be the same as the case where R ¹ is a (C1-C8) alkoxycarbonyl group, including preferred ones.
When R ¹ is a (C1-C4) alkyl group substituted with a (C1-C8) alkoxycarbonyl group, preferred specific examples include methoxycarbonylmethyl group, ethoxycarbonylethyl group, n-butoxycarbonylmethyl group, n- An octyloxycarboxyethyl group etc. are mentioned.
When R ¹ is a (C1-C4) alkyl group optionally substituted with a carboxy group, preferred specific examples include a carboxymethyl group, a 2-carboxyethyl group, a 3-carboxypropyl group, and the like.

Specific examples in the case where R ¹ in formula (1) is a phenyl group optionally substituted with a hydroxy group, a sulfo group or a carboxy group include, for example, an unsubstituted phenyl group; a 2-hydroxyphenyl group, a 4-hydroxy group Hydroxy-substituted phenyl groups such as phenyl groups; sulfo-substituted phenyl groups such as 2-sulfophenyl groups, 4-sulfophenyl groups, 2,4-disulfophenyl groups, and 3,5-disulfophenyl groups; 2-carboxyphenyl groups; Carboxy-substituted phenyl such as 4-carboxyphenyl group and 3,5-dicarboxyphenyl group; and phenyl groups substituted with plural kinds of groups such as 2-hydroxy-5-sulfophenyl group; and the like.

R ¹ in the above formula (1) is a carboxy group; (C1-C4) alkoxycarbonyl group; unsubstituted (C1-C4) alkyl group; carboxy group-substituted (C1-C4) alkyl group; or unsubstituted phenyl Groups are more preferred.
Specific examples of preferable R ¹ in the formula (1) include a methyl group, an ethyl group, a tert-butyl group, a carboxymethyl group, a 3-carboxypropyl group, a methoxycarbonylmethyl group, a carboxy group, a methoxycarboxy group, and an ethoxycarboxy group. N-octyloxycarboxy group, phenyl group, 2-hydroxyphenyl group, 4-sulfophenylmethyl group, more preferably methyl group, carboxymethyl group, carboxy group, and phenyl group, still more preferably methyl group, It is a carboxy group.

In the formula (1), R ² to R ⁴ are each independently a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a (C1 to C4) alkyl group; a hydroxy group, (C1 -C4) alkoxy group, hydroxy (C1-C4) alkoxy group, optionally substituted by a sulfo group or a carboxy group (C1-C4) alkoxy group; mono or optionally substituted by a hydroxy group, a sulfo group or a carboxy group Di (C1-C4) alkylamino group; (C1-C4) alkylcarbonylamino group optionally substituted with hydroxy group or carboxy group; N ′-(C1 optionally substituted with hydroxy group, sulfo group or carboxy group -C4) alkylureido group; benzene ring is chlorine atom, (C1-C4) alkyl group, nitro group A phenylamino group which may be substituted with a sulfo group or a carboxy group; a benzene ring whose benzene ring may be substituted with a chlorine atom, a (C1-C4) alkyl group, a nitro group, a sulfo group or a carboxy group; or a benzene ring Represents a phenylsulfonylamino group which may be substituted with a chlorine atom, a (C1-C4) alkyl group, a nitro group, a sulfo group or a carboxy group.

When R ^{2 to} R ⁴ in the formula (1) are an unsubstituted (C 1 to C ⁴ ) alkoxy group, the alkoxy group is preferably either a straight chain or a branched chain. Specific examples include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group and the like.
When the alkoxy group is substituted with a hydroxy group, a (C1-C4) alkoxy group, a hydroxy (C1-C4) alkoxy group, a sulfo group or a carboxy group, specific examples thereof include, for example, a 2-hydroxyethoxy group, 2 -Hydroxy (C1-C4) alkoxy group such as hydroxypropoxy group and 3-hydroxypropoxy group; methoxyethoxy group, ethoxyethoxy group, n-propoxyethoxy group, isopropoxyethoxy group, n-butoxyethoxy group, methoxypropoxy group, (C1-C4) alkoxy (C1-C4) alkoxy groups such as ethoxypropoxy group, n-propoxypropoxy group, isopropoxybutoxy group, n-propoxybutoxy group; hydroxy (C1-C4) such as 2-hydroxyethoxyethoxy group Alkoxy (C1-C ) Alkoxy group; sulfo (C1-C4) alkoxy group such as 3-sulfopropoxy group, 4-sulfobutoxy group; carboxy (C1-C4) alkoxy such as carboxymethoxy group, 2-carboxyethoxy group, 3-carboxypropoxy group Group; etc. are mentioned.

When R ^{2 to} R ⁴ in the above formula (1) are an unsubstituted mono- or di (C1-C4) alkylamino group, the (C1-C4) alkyl moiety is preferably either a straight chain or a branched chain. Specific examples thereof include methylamino group, ethylamino group, n-propylamino group, isopropylamino group, n-butylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, di-n-butyl. Straight chain such as amino group; branched chain such as sec-butylamino group, tert-butylamino group, diisopropylamino group; and the like.
When the mono- or di (C1-C4) alkylamino group is substituted with a hydroxy group, a sulfo group or a carboxy group, specific examples thereof include, for example, a 2-hydroxyethylamino group, a 2-hydroxypropylamino group, Hydroxy-substituted mono- or di (C1-C4) alkylamino groups such as 2,2'-dihydroxydiethylamino group; 2-sulfoethylamino group, 3-sulfopropylamino group, 4-sulfobutylamino group, 3,3'- Sulfo-substituted mono- or di (C1-C4) alkylamino groups such as disulfodipropylamino group; carboxymethylamino group, 2-carboxyethylamino group, 3-carboxypropylamino group, 2,2′-dicarboxydiethylamino group Carboxy-substituted mono- or di (C1-C4) alkylamino groups such as; That.

When R ^{2 to} R ⁴ in the above formula (1) are an unsubstituted (C1 to C4) alkylcarbonylamino group, the (C1 to C4) alkyl moiety may be linear or branched, but Those that are chains are preferred. Specific examples include acetylamino group, propanoylamino group, butanoylamino group and the like.
When the (C1-C4) alkylcarbonylamino group is substituted with a hydroxy group or a carboxy group, specific examples of the (C1-C4) alkylcarbonylamino group include, for example, a hydroxyethanoylamino group, 2-hydroxy And hydroxy (C1-C4) alkylcarbonylamino groups such as propanoylamino group and 4-hydroxybutanoylamino group; carboxy (C1-C4) alkylcarbonylamino groups such as 3-carboxypropanoylamino group; and the like.

When R ^{2 to} R ⁴ in the above formula (1) are N ′-(C 1 to C ⁴ ) alkylureido groups, those having a substituent are preferable to being unsubstituted.
When the N ′-(C1 to C4) alkylureido group is substituted with a hydroxy group, a sulfo group or a carboxy group, specific examples thereof include, for example, an N′-2-hydroxyethylureido group, N′-3. -N'-hydroxy (C1-C4) alkylureido group such as hydroxyethylureido group; N'-sulfo (C1-C4) such as N'-2-sulfoethylureido group, N'-3-sulfopropylureido group An alkylureido group; N′-carboxy (C 1 -C) such as N′-carboxymethylureido group, N′-2-carboxyethylureido group, N′-3-carboxypropylureido group, N′-4-carboxybutylureido group; C4) alkylureido group; and the like.

Specific examples of the phenylamino group in which R ^{2 to} R ⁴ in the above formula (1) may be substituted with a benzene ring by a chlorine atom, a (C1 to C4) alkyl group, a nitro group, a sulfo group or a carboxy group include Unsubstituted phenylamino group; chlorine atom-substituted phenylamino group such as 2-chlorophenylamino group, 4-chlorophenylamino group, 2,4-dichlorophenylamino group; 2-methylphenylamino group, 4-methylphenylamino group, 4 (C1-C4) alkyl-substituted phenylamino groups such as tert-butylphenylamino group; nitro-substituted phenylamino groups such as 2-nitrophenylamino group and 4-nitrophenylamino group; 3-sulfophenylamino group, 4- Sulfophenylamino group, 2,4-disulfophenylamino group, 3,5-disulfophenyl group Sulfo-substituted phenylamino groups such as 2-carboxyphenyl groups; 2-carboxyphenylamino groups, 4-carboxyphenylamino groups, 2,5-dicarboxyphenylamino groups, carboxy-substituted phenylamino groups such as 3,5-dicarboxyphenylamino groups And the like.

R ^{2 to} R ⁴ in the above formula (1) are a phenylamino group, a benzoylamino group or a phenylsulfonylamino group having a substituent, and the substituent of the benzene ring contained in each group is a (C1 to C4) alkyl. When it is a group, the alkyl group may be linear, branched or cyclic, but is preferably linear or branched. Specific examples include, for example, straight chain such as methyl group, ethyl group, n-propyl group and n-butyl group; branched chain such as isopropyl group, isobutyl group, sec-butyl group and tert-butyl group. It is done.

Specific examples of R ^{2 to} R ⁴ in the above formula (1) are benzoylamino groups in which the benzene ring may be substituted with a chlorine atom, a (C1 to C4) alkyl group, a nitro group, a sulfo group, or a carboxy group. , Unsubstituted benzoylamino group; chlorine atom-substituted benzoylamino group such as 2-chlorobenzoylamino group, 4-chlorobenzoylamino group, 2,4-dichlorophenylamino group; 2-methylbenzoylamino group, 3-methylbenzoylamino group (C1-C4) alkyl-substituted benzoylamino groups such as 4-methylbenzoylamino group; nitro-substituted benzoylamino groups such as 2-nitrobenzoylamino group, 4-nitrobenzoylamino group and 3,5-dinitrobenzoylamino group; Such as 2-sulfobenzoylamino group, 4-sulfobenzoylamino group, etc. Substituted benzoylamino group; 2-carboxy benzoylamino group, 4-carboxyphenyl benzoylamino group, 3,5-carboxymethyl carboxy-substituted benzoylamino group such as benzoylamino group; and the like.

Specific examples of the phenylsulfonylamino group in which R ^{2 to} R ⁴ in the above formula (1) may be substituted with a benzene ring by a chlorine atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, or a carboxy group For example, unsubstituted phenylsulfonylamino group; chlorine atom-substituted phenylsulfonylamino group such as 2-chlorophenylsulfonylamino group, 4-chlorophenylsulfonylamino group; 2-methylphenylsulfonylamino group, 4-methylphenylsulfonylamino group, 4- (C1-C4) alkyl-substituted phenylsulfonylamino groups such as tert-butylphenylsulfonylamino group; nitro-substituted phenylsulfonyl groups such as 2-nitrophenylsulfonylamino group, 3-nitrophenylsulfonylamino group, 4-nitrophenylsulfonylamino group A A sulfo-substituted phenylsulfonylamino group such as a 3-sulfophenylsulfonylamino group or a 4-sulfophenylsulfonylamino group; a carboxy-substituted phenylsulfonylamino group such as a 3-carboxyphenylsulfonylamino group or a 4-carboxyphenylsulfonylamino group; And the like.

Specific examples of preferable R ² to R ⁴ in the above formula (1) include a hydrogen atom, a carboxy group, a sulfo group, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a 2-hydroxyethoxy group, a 2-sulfoethoxy group, 3-sulfopropoxy group, 4-sulfobutoxy group, carboxymethoxy group, 2-carboxyethoxy group, methylamino group, ethylamino group, 2-hydroxyethylamino group, 2-sulfoethylamino group, 3-sulfopropylamino group 2-carboxyethylamino group, dimethylamino group, diethylamino group, 2,2′-dihydroxydiethylamino group, 2,2′-dicarboxydiethylamino group, 3,3′-disulfodipropylamino group, acetylamino group, 3-carboxypropanoylamino group, 4-hydroxybutanoylamino group, N′-cal Xymethylureido group, N′-2-sulfoethylureido group, 4-sulfophenylamino group, 2,4-disulfophenylamino group, 2,5-dicarboxyphenylamino group, benzoylamino group, 3-sulfobenzoyl Amino group, 2-carboxybenzoylamino group, phenylsulfonylamino group, 4-methylphenylsulfonylamino group, 4-nitrophenylsulfonylamino group, 3-sulfophenylsulfonylamino group, 4-carboxyphenylsulfonylamino group, etc. More preferably, hydrogen atom, sulfo group, methyl group, methoxy group, 2-hydroxyethoxy group, 2-sulfoethoxy group, 3-sulfopropoxy group, 4-sulfobutoxy group, dimethylamino group, 3,3′-di Sulfodipropylamino group, acetylamino group, 3-carbo A xylpropanoylamino group, an N′-2-sulfoethylureido group, a 2,4-disulfophenylamino group, a benzoylamino group, and a 4-methylphenylsulfonylamino group, and more preferably a hydrogen atom, a sulfo group, A methyl group, a methoxy group, and a 3-sulfopropoxy group;

In a preferable combination of R ² to R ⁴ in the formula (1), R ² is a 3-sulfopropoxy group or 4-sulfobutoxy group, R ³ is a hydrogen atom, and R ⁴ is a methyl group.

In the above formula (2), R ⁵ may be substituted with a mercapto group; or a hydroxy group, a (C1-C4) alkoxy group, a hydroxy (C1-C4) alkoxy group, a sulfo group, or a carboxy group (C1-C4). Represents an alkylthio group.

When R ⁵ in the above formula (2) is a (C1-C4) alkylthio group, the (C1-C4) alkyl moiety is preferably a straight chain or branched chain, but more preferably a straight chain. Specific examples thereof include methylthio group, ethylthio group, n-propylthio group, isopropylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group and the like.
When R ⁵ is a (C1 to C4) alkylthio group having a substituent, the substituent is preferably a hydroxy group, a sulfo group or a carboxy group, more preferably a sulfo group or a carboxy group. Specific examples of the (C1-C4) alkylthio group having a substituent include, for example, hydroxy (C1-C4) alkylthio groups such as 2-hydroxyethylthio group, 2-hydroxypropylthio group, 3-hydroxypropoxythio group; Ethylthio group, ethoxyethylthio group, n-propoxyethylthio group, isopropoxyethylthio group, n-butoxyethylthio group, methoxypropylthio group, ethoxypropylthio group, n-propoxypropylthio group, isopropoxybutylthio group Groups, (C1-C4) alkoxy (C1-C4) alkylthio groups such as n-propoxypropylthio group; hydroxy (C1-C4) alkoxy (C1-C4) alkylthio groups such as 2-hydroxyethoxyethylthio group; Sulfopropylthio group, 4-sulfobutylthio group Sulfo (C1 -C4) alkylthio group; a carboxymethyl thio group, 2-carboxyethyl thio group, 3-carboxy-carboxy and propyl thio group (C1 -C4) alkylthio group; and the like.

Specific examples of preferable R ⁵ in the above formula (2) include a mercapto (—SH) group, a methylthio group, an ethylthio group, a 2-hydroxyethylthio group, a methoxyethylthio group, an ethoxyethylthio group, a 2-sulfoethylthio group, 3-sulfopropylthio group, 4-sulfobutylthio group, carboxymethylthio group, 2-carboxyethylthio group, 3-carboxypropylthio group and the like, more preferably methylthio group, 3-sulfopropylthio group, carboxy A methylthio group and a 2-carboxyethylthio group, more preferably a 3-sulfopropylthio group and a 2-carboxyethylthio group.

In the above formula (3), R ⁶ to R ⁸ are each independently a hydrogen atom; chlorine atom; carboxy group; sulfo group; nitro group; hydroxy group; carbamoyl group; sulfamoyl group; (C1-C4) alkyl group; , (C1 to C4) alkoxy group, sulfo group or carboxy group which may be substituted (C1 to C4) alkoxy group; hydroxy group, sulfo group or carboxy group which may be substituted (C1 to C4) alkylsulfonyl group Or a phenylsulfonyl group in which the benzene ring may be substituted with a chlorine atom, a (C1-C4) alkyl group, a nitro group, a sulfo group or a carboxy group.

When R ⁶ to R ⁸ in the above formula (3) are (C1 to C4) alkyl groups, the alkyl group may be linear, branched or cyclic, but is linear or branched. Preferably, a straight chain is more preferable. Specific examples include, for example, straight chain such as methyl group, ethyl group, n-propyl group and n-butyl group; branched chain such as isopropyl group, isobutyl group, sec-butyl group and tert-butyl group. It is done.

When R ⁶ to R ⁸ in the above formula (3) are (C1-C4) alkoxy groups which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group or a carboxy group, the substituent is It may be the same as the case where R ^{2 to} R ⁴ in the above formula (1) including a preferable one are a corresponding (C1 to C4) alkoxy group.

Specific examples of the (C1-C4) alkylsulfonyl group in which R ⁶ to R ⁸ in the above formula (3) may be substituted with a hydroxy group, a sulfo group or a carboxy group include, for example, a methylsulfonyl group, an ethylsulfonyl group, Linear or branched (C1-C4) alkylsulfonyl groups such as propylsulfonyl group, isopropylsulfonyl group, n-butylsulfonyl group, sec-butylsulfonyl group, tert-butylsulfonyl group; 2-hydroxyethylsulfonyl group, 3 -Hydroxy (C1-C4) alkylsulfonyl group such as hydroxypropylsulfonyl group; sulfo (C1-C4) alkylsulfonyl group such as 2-sulfoethylsulfonyl group, 3-sulfopropylsulfonyl group, 4-sulfobutylsulfonyl group; carboxy Methylsulfonyl group, 2- Carboxymethyl ethylsulfonyl group, 3-carboxy-carboxy (C1 -C4) such as propylsulfonyl alkylsulfonyl group; and the like.

Specific examples of the phenylsulfonyl group in which R ⁶ to R ⁸ in the above formula (3) may be substituted with a chlorine atom, a (C1 to C4) alkyl group, a nitro group, a sulfo group, or a carboxy group are as follows: An unsubstituted phenylsulfonyl group; a chlorine atom-substituted phenylsulfonyl group such as a 2-chlorophenylsulfonyl group and a 4-chlorophenylsulfonyl group; a 2-methylphenylsulfonyl group, a 4-methylphenylsulfonyl group, a 2,4-dimethylphenylsulfonyl group, (C1-C4) alkyl-substituted phenylsulfonyl groups such as 4-tert-butylphenylsulfonyl group; nitro-substituted phenylsulfonyl groups such as 2-nitrophenylsulfonyl group and 4-nitrophenylsulfonyl group; 3-sulfophenylsulfonyl group, 4 -Sulfophenylsulfonyl group Sulfo-substituted phenylsulfonyl groups such as 3,5-disulfophenylsulfonyl group; carboxy-substituted phenylsulfonyl groups such as 2-carboxyphenylsulfonyl group, 4-carboxyphenylsulfonyl group and 3,5-dicarboxyphenylsulfonyl group; Can be mentioned.

Specific examples of preferable R ⁶ to R ⁸ in the above formula (3) include a hydrogen atom, a chlorine atom, a carboxy group, a sulfo group, a nitro group, a methyl group, an ethyl group, a methoxy group, an ethoxy group, a 2-hydroxyethoxy group, 2-sulfoethoxy group, 3-sulfopropoxy group, 4-sulfobutoxy group, carboxymethoxy group, 2-carboxyethoxy group, methylsulfonyl group, ethylsulfonyl group, tert-butylsulfonyl group, 2-hydroxyethylsulfonyl group, 3 -Sulfopropylsulfonyl group, 2-carboxyethylsulfonyl group, phenylsulfonyl group, 4-chlorophenylsulfonyl group, 4-methylphenylsulfonyl group, 2,4-dimethylphenylsulfonyl group, 4-nitrophenylsulfonyl group, 4-sulfophenyl Sulfonyl group, 2-carboxy An sulfonylsulfonyl group, a 4-carboxyphenylsulfonyl group, and the like, more preferably a hydrogen atom, a chlorine atom, a carboxy group, a sulfo group, a nitro group, a methyl group, a methoxy group, a methylsulfonyl group, or a 2-carboxyphenylsulfonyl group. And more preferably a hydrogen atom, a sulfo group, or a methoxy group. Among R ⁶ to R ⁸ , at least one is preferably a hydrogen atom, and at least one is preferably a substituent other than a hydrogen atom.

A preferable combination of R ⁶ to R ⁸ in the above formula (3) is a hydrogen atom, a methoxy group and a sulfo group, or one is a sulfo group and the other two are hydrogen atoms. In the case where one is a sulfo group and the other two are hydrogen atoms, the substitution position of sulfo is more preferably the 6-position of the benzothiazole ring.

  In the above formula (1), the group B is an optionally substituted phenyl group or naphthyl group, and when the group B is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a (C1-C4) alkyl group; C1-C4) alkoxy group; amino group; mono- or di (C1-C4) alkylamino group; acetylamino group; benzene ring substituted with chlorine atom, (C1-C4) alkyl group, nitro group, sulfo group or carboxy group A benzoylamino group that has a substituent selected from the group consisting of: a hydroxy group in the case of a substituted naphthyl group; a sulfo group; a (C1-C4) alkoxy group; a benzene ring that is a methyl group, a nitro group, or A phenylsulfonyloxy group which may be substituted with a chlorine atom; and a substituent selected from the group consisting of:

When the group B in the above formula (1) is a phenyl group or a naphthyl group having a substituent, and the substituent is a (C1 to C4) alkoxy group, the alkoxy group includes the preferable ones in the above formula (1 ) In R ^{2 to} R ⁴ may be the same as those in the case of an unsubstituted (C1 to C4) alkoxy group.

When the group B in the above formula (1) is a mono- or di (C1-C4) alkylamino group-substituted phenyl group, the mono- or di (C1-C4) alkylamino group includes those represented by the formula (1) In which R ^{2 to} R ⁴ are an unsubstituted mono- or di (C1-C4) alkylamino group.

  When the group B in the above formula (1) is a substituted naphthyl group and the substituent is a phenylsulfonyloxy group which may be substituted with a methyl group, a nitro group or a chlorine atom, specific examples thereof include, for example, unsubstituted Phenylsulfonyloxy group; methyl-substituted phenylsulfonyloxy group such as 4-methylphenylsulfonyloxy group and 2,4-dimethylphenylsulfonyloxy group; nitro-substituted phenyl such as 2-nitrophenylsulfonyloxy group and 4-nitrosulfonyloxy group A sulfonyloxy group; a chlorine atom-substituted phenylsulfonyloxy group such as a 4-chlorophenylsulfonyloxy group, a 2,4-dichlorophenylsulfonyloxy group, a 3,5-dichlorophenylsulfonyloxy group; and the like.

  In the above formula (1), n is preferably 1.

  Specific examples of preferred substituents when the group B in the above formula (1) is a substituted phenyl group include hydrogen atom, hydroxy group, sulfo group, carboxy group, methyl group, ethyl group, methoxy group, ethoxy group, dimethylamino group. Group, acetylamino group, benzoylamino group, 4-sulfobenzoylamino group, 4-carboxybenzoylamino group and the like, more preferably hydrogen atom, hydroxy group, sulfo group, carboxy group, methyl group, acetylamino group More preferably, they are a hydrogen atom, a sulfo group, and a carboxy group.

  Specific examples of preferred substituents when the group B in the above formula (1) is a substituted naphthyl group are hydrogen atom, hydroxy group, sulfo group, methoxy group, ethoxy group, phenylsulfonyloxy group, 4-methylphenylsulfonyloxy A hydrogen atom, a hydroxy group, a sulfo group, and a methoxy group, and more preferably a hydrogen atom and a sulfo group.

  Specific examples of preferable group B in the above formula (1) include phenyl group, 2-sulfophenyl group, 4-sulfophenyl group, 2,4-disulfophenyl group, 3,5-disulfophenyl group, 4-carboxy. Phenyl group, 3,5-carboxyphenyl group, 4-methylphenyl group, 3-methylphenyl group, 3-hydroxy-4-carboxyphenyl group, 5-sulfo-3-carboxy-2-hydroxyphenyl group, 4-methoxy Phenyl group, 4-acetylaminophenyl group, naphthyl group, naphth-2-yl group, 6-sulfonaphthyl group, 7-sulfonaphthyl group, 4,7-disulfonaphthyl group, 5,7-disulfonaphth-2-yl A group, 6,8-disulfonaphth-2-yl group, 4,8-disulfonaphth-2-yl group, 4,6,8-trisulfonaphth-2-yl group, etc. More preferably, a phenyl group, 4-sulfophenyl group, 2,4-disulfophenyl group, 4-carboxyphenyl group, 3,5-carboxyphenyl group, 5,7-disulfonaphth-2-yl group, 4,8 -A disulfonaphth-2-yl group, more preferably a phenyl group, a 4-sulfophenyl group, a 4-carboxyphenyl group, or a 3,5-carboxyphenyl group.

The compound which combined the preferable thing described about the substituent of the said Formula (1) to (6) is more preferable, and the compound which combined more preferable things is further more preferable. The same applies to preferable ones. As described above, in the formulas (4) to (6), the group A, the group B, and R ^{1 to} R ⁴ have the same meaning as in the formula (1).

  Any of the black dyes represented by the above formulas (1) and (4) to (6) can be used as a salt thereof.

  The salt of the compound represented by the formula (1) means an inorganic or organic cation salt independently. Among these, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred inorganic salts are lithium, sodium, potassium salts, and ammonium salts. Examples of organic cation salts include, but are not limited to, salts of compounds represented by the following general formula (7). In addition, the free acid of the azo compound of the present invention, its tautomer, and various salts thereof may be a mixture. For example, any combination such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, a mixture of lithium salt, sodium salt and ammonium salt may be used. The physical properties such as solubility may vary depending on the type of salt, and the physical properties that meet the purpose can be selected by selecting the type of salt as appropriate, or by changing the ratio when multiple salts are included. It is also possible to obtain a mixture having

As the alkyl group of Z ¹ , Z ² , Z ³ and Z ^{4 in} the general formula (7), a (C1-C4) alkyl group is preferable, and specific examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, Examples thereof include an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
Examples of hydroxyalkyl groups include hydroxy- (C1) such as hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group and 2-hydroxybutyl group. -C4) An alkyl group is mentioned.
Examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2 -Hydroxy (C1-C4) alkoxy- (C1-C4) alkyl groups, such as a hydroxy ethoxybutyl group, are mentioned, Among these, a hydroxy ethoxy- (C1-C4) alkyl group is preferable. Particularly preferred are hydrogen atom; methyl group; hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxybutyl group, etc. Hydroxy- (C1-C4) alkyl group; hydroxyethoxymethyl group, 2-hydroxyethoxyethyl group, 3-hydroxyethoxypropyl group, 2-hydroxyethoxypropyl group, 4-hydroxyethoxybutyl group, 3-hydroxyethoxybutyl group, Examples include hydroxyethoxy- (C1-C4) alkyl groups such as 2-hydroxyethoxybutyl group.

Specific examples of Z ¹ , Z ² , Z ³ and Z ^{4 in} the general formula (7) are shown in Table 1 below.

  Preferable examples of the organic cation salt include monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, and triisopropanolamine salt.

As a method for synthesizing a desired salt of the azo compound represented by the formula (1) of the present invention, after completion of the final step in the synthesis reaction of the compound represented by the formula (1), a desired inorganic salt or organic Obtained by adding a mineral acid such as hydrochloric acid to the reaction solution and isolating the azo compound from the reaction solution in the form of a free acid. The free acid is washed with water, acidic water or an aqueous organic medium as necessary to remove impurities such as attached inorganic salts, and again in an aqueous medium (preferably in water). And a method of forming a salt by adding an organic base corresponding to the desired inorganic base or the above-described quaternary ammonium salt. By such a method, the salt of the target azo compound can be obtained in the form of a solution or a precipitated solid. Here, acidic water refers to water obtained by dissolving a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid in water. The aqueous organic medium refers to an admixture of water and an organic substance and / or an organic solvent that are miscible with water.
Examples of the water-miscible organic substance and organic solvent include water-soluble organic solvents described later.

Examples of inorganic salts used when the azo compound represented by the above formula (1) is used as a desired salt include halogen salts of alkali metals such as lithium chloride, sodium chloride and potassium chloride; lithium carbonate, sodium carbonate, carbonate Alkali metal carbonates such as potassium; Alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide; Halogen salts of ammonium ions such as ammonium chloride and ammonium bromide; Ammonium hydroxide (ammonia water) And the like.
Examples of the organic cation salt include halogen salts of quaternary ammonium ions represented by the above formula (7) such as diethanolamine hydrochloride and triethanolamine hydrochloride.

  Of the above inorganic and organic cation salts, lithium and sodium salts are particularly preferred.

The tetrakisazo compound of the present invention represented by the formula (1) can be synthesized, for example, by the following method. Moreover, the structural formula of the compound in each process shall be represented with the form of a free acid.
In the following formulas (8) to (13), R ^{1 to} R ¹³ represent the same meaning as in the above formula (1).

  A compound represented by the following formula (8) is diazotized by a conventional method, and this and a compound represented by the following formula (9) are coupled by a conventional method to obtain a compound represented by the following formula (10).

（式（８）中、基Ａは式（２）および式（３）におけるのと同じ意味を有する。）

（式（９）中、Ｒ^２からＲ^４は式（１）におけるのと同じ意味を有する。）

（式（１０）中、Ｒ^２からＲ^４は式（１）におけるのと同じ意味を有する。）

(In formula (8), group A has the same meaning as in formula (2) and formula (3).)

(In formula (9), R ² to R ⁴ have the same meaning as in formula (1).)

(In formula (10), R ² to R ⁴ have the same meaning as in formula (1).)

  The obtained compound of formula (10) is diazotized by a conventional method, and then this and a compound represented by the following formula (11) are coupled by a conventional method to obtain a compound represented by the following formula (12). .

（式（１１）中、ｎは式（１）におけるのと同じ意味を有する。）

(In formula (11), n has the same meaning as in formula (1).)

（式（１２）中、ｎおよびＲ^２からＲ^４は式（１）におけるのと同じ意味を有する。）

(In formula (12), n and R ² to R ⁴ have the same meaning as in formula (1).)

  The present invention represented by the formula (1) is obtained by diazotizing the obtained compound of the formula (12) by a conventional method and then coupling it with a compound represented by the following formula (13) by a conventional method. The trisazo compound can be obtained.

（式（１３）中、Ｒ^１および基Ｂは式（１）におけるのと同じ意味を有する。）

(In formula (13), R ¹ and group B have the same meaning as in formula (1).)

  In addition, the compound represented by Formula (13) can purchase a commercial item as a product, or can be synthesize | combined by a well-known method.

Although it does not specifically limit as a suitable specific example of the compound of this invention shown to the said Formula (1), The compound shown by the structural formula given to the following Table 2-7 is mentioned.
In each table, functional groups such as sulfo groups and carboxy groups are described in the form of free acids for convenience.

  The diazotization of the compound of the above formula (8) is carried out by a method known per se. For example, using nitrosylsulfuric acid in sulfuric acid, acetic acid or phosphoric acid, for example at a temperature of -5 to 20 ° C, preferably 5 to 10 ° C. Coupling of the diazotized compound of the compound of formula (8) with the compound of formula (9) is also carried out under conditions known per se. It is carried out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 30 ° C. The compound of formula (8) and the compound of formula (9) are used in approximately stoichiometric amounts.

  The diazotization of the compound of the above formula (10) is also carried out by a method known per se. For example, nitrite in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent), for example, at a temperature of -5 to 40 ° C, preferably 5 to 30 ° C. For example, using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound of formula (10) and the compound of formula (11) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C., preferably 10 to 30 ° C. and at a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 6-10. Since the diazotization reaction solution is acidic and the reaction system is further acidified by the progress of the coupling reaction, it is preferable to adjust the pH value by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate, acetates such as sodium acetate, ammonia, and organic amines. . The compounds of formulas (10) and (11) are used in approximately stoichiometric amounts.

  The diazotization of the compound of the above formula (12) is also carried out by a method known per se. For example, nitrite in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid in water or an aqueous organic medium (such as a mixture of water and a water-soluble organic solvent), for example, at a temperature of -5 to 40 ° C, preferably 10 to 30 ° C. For example, using an alkali metal nitrite such as sodium nitrite. Coupling of the diazotized compound of the compound of formula (12) and the compound of formula (13) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 50 ° C., preferably 10 to 30 ° C. and at a weakly acidic to alkaline pH value. It is preferably carried out at a weakly acidic to weakly alkaline pH value, for example, pH 6 to 10, and the pH value is adjusted by adding a base. As the base, the same ones as described above can be used. The compounds of formulas (12) and (13) are used in approximately stoichiometric amounts.

  The black dye represented by the above formula (1) can be isolated in the form of a free acid by adding a mineral acid after the coupling reaction, and the inorganic salt can be removed therefrom by washing with water or acidified water. I can do it. Next, the acid type dye having a low salt content thus obtained can be neutralized with a desired inorganic or organic base in an aqueous medium to obtain a solution of the corresponding salt. Examples of inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate. Examples of the organic base include, but are not limited to, organic amines such as alkanolamines such as diethanolamine and triethanolamine.

  The aqueous black ink composition of the present invention comprises (i) C.I. I. Acid Black 2 is contained in an amount of 0.1 to 10% by mass, preferably 0.5 to 5% by mass, more preferably 1 to 4% by mass, and further dye (ii) 0.1 to 20% by mass, preferably Is an ink composition containing 1% by mass to 10% by mass with water as the main medium. Moreover, also when it contains the compound represented by the said Formula (1) as dye (ii), it is 0.1-20 mass% similarly, Preferably it is 1-10 mass%, More preferably, it is 2-8 mass%. contains.

  When the black ink composition of the present invention is used as an ink for an ink jet printer, C.I. I. As the compound represented by Acid Black 2 or the above formula (1), it is preferable to use a compound containing a small amount of an inorganic substance such as a chloride or sulfate of a metal cation. % Or less (against the chromogen). In order to produce the compound of the present invention with a small amount of inorganic substances, for example, a conventional method using a reverse osmosis membrane or a dried product or wet cake of the compound of the present invention is stirred in a mixed solvent of alcohol such as methanol and water, and filtered. Desalting treatment may be performed by a method such as drying.

  The aqueous black ink composition of the present invention may further contain a dye having another hue for the purpose of adjusting the color tone. The other dye is preferably a reactive dye, an acid dye, or a direct dye, and more preferably a direct dye, from the viewpoint of dyeing properties of the dye on the recording material.

  Specific examples of the reactive dye that may be contained in the aqueous black ink composition of the present invention include C.I. I. Yellow dyes such as Reactive Yellow 2, 3, 18, 81, 84, 85, 95, 99, 102; I. Orange dyes such as Reactive Orange 5, 9, 12, 13, 35, 45, 99; I. Brown dyes such as Reactive Brown 2, 8, 9, 17, 33; I. Red dyes such as Reactive Red 3, 3: 1, 4, 13, 24, 29, 31, 33, 125, 151, 206, 218, 226, 245; I. Violet dyes such as Reactive Violet 1, 24; I. Blue dyes such as Reactive Blue 2, 5, 10, 13, 14, 15, 15: 1, 49, 63, 71, 72, 75, 162, 176; I. Green dyes such as Reactive Green 5, 8, 19; I. And black dyes such as Reactive Black 1, 8, 23, 39, and the like.

  Specific examples of the acid dye that may be contained in the aqueous black ink composition of the present invention include C.I. I. Acid Yellow 1, 3, 11, 17, 18, 19, 23, 25, 36, 38, 40, 40: 1, 42, 44, 49, 59, 59: 1, 61, 65, 72, 73, 79, Yellow dyes such as 99, 104, 110, 159, 169, 176, 184, 193, 200, 204, 207, 215, 219, 219: 1, 220, 230, 232, 235, 241, 242, 246; C. I. Acid Orange 3, 7, 8, 10, 19, 24, 51, 56, 67, 74, 80, 86, 87, 88, 89, 94, 95, 107, 108, 116, 122, 127, 140, 142, Orange dyes such as 144, 149, 152, 156, 162, 166, 168; I. Acid Brown 2, 4, 13, 14, 19, 28, 44, 123, 224, 226, 227, 248, 282, 283, 289, 294, 297, 298, 301, 355, 357, 413, etc. A dye; I. Acid Red 1, 6, 8, 9, 13, 18, 27, 35, 37, 52, 54, 57, 73, 82, 88, 97, 97: 1, 106, 111, 114, 118, 119, 127, 131, 138, 143, 145, 151, 183, 195, 198, 211, 215, 217, 225, 226, 249, 251, 254, 256, 257, 260, 261, 264, 265, 266, 274, 276, Red dyes such as 277, 289, 296, 299, 315, 318, 336, 337, 357, 359, 361, 362, 364, 366, 399, 407, 415; I. Violet dyes such as Acid Violet 17, 19, 21, 42, 43, 47, 48, 49, 54, 66, 78, 90, 97, 102, 109, 126; I. Acid Blue 1, 7, 9, 15, 23, 25, 40, 61: 1, 62, 72, 74, 80, 83, 90, 92, 103, 104, 112, 113, 114, 120, 127, 127: 1, 128, 129, 138, 140, 142, 156, 158, 171, 182, 185, 193, 199, 201, 203, 204, 205, 207, 209, 220, 221, 224, 225, 229, 230, 239, 249, 258, 260, 264, 277: 1, 278, 279, 280, 284, 290, 296, 298, 300, 317, 324, 333, 335, 338, 342, 350, and other blue dyes; C. I. Acid Green 1, 9, 12, 16, 19, 20, 25, 27, 28, 40, 43, 56, 73, 81, 84, 104, 108, 109, etc .; I. Acid Black 1, 2, 3, 24, 24: 1, 26, 31, 50, 52, 52: 1, 58, 60, 63, 107, 109, 112, 119, 132, 140, 155, 172, 187, And black dyes such as 188, 194, 207, and 222.

  Specific examples of the direct dye that may be contained in the aqueous black ink composition of the present invention include C.I. I. Direct Yellow 8, 11, 12, 21, 28, 33, 39, 44, 49, 50, 85, 86, 87, 88, 89, 98, 100, 110, 132, 142, 144, 146, etc. A dye; I. Orange dyes such as Direct Orange 17, 26, 39, 102; I. Direct Red 2, 4, 6, 9, 17, 23, 26, 28, 31, 39, 54, 55, 57, 62, 63, 64, 65, 68, 72, 75, 76, 79, 80, 81, 83 83: 1, 84, 89, 92, 95, 99, 111, 141, 173, 180, 184, 207, 211, 212, 214, 218, 221, 223, 224, 225, 226, 227, 232, 233 Red dyes such as C., 240, 241, 242, 243, 247; I. Violet dyes such as Direct Violet 7, 9, 47, 48, 51, 66, 90, 93, 94, 95, 98, 100, 101; I. Direct Blue 1, 15, 22, 25, 41, 76, 77, 80, 86, 87, 90, 98, 106, 108, 120, 158, 163, 168, 199, 200, 201, 202, 226, etc. Dyes of the system; C. I. Brown dyes such as Direct Brown 106, 125, 195; I. Direct Black 17, 19, 22, 31, 32, 51, 62, 71, 74, 112, 113, 154, 168, 195 and the like; and the like.

  Among these toning dyes, C.I. I. Direct Yellow 86, 132, 142, C.I. I. Direct Orange 17, 39, C.I. I. Direct Red 80, 84, 227, C.I. I. Direct Brown 106, 125, 195, C.I. I. Direct Orange 95, C.I. I. When one or two or more dyes selected from Direct Red 249, 254 are contained, the black ink composition of the present invention is further preferred because the range of color reproducibility can be further expanded.

  When other dyes are contained, (I) 10 to 90% by mass of (i) and 5 to 50% by mass of (ii) with respect to 10 to 90% by mass are preferable in the total mass of the pigment component. Furthermore, it is particularly preferable to contain 20 to 60% by mass of the above (i) and 5 to 20% by mass of the above (ii) with respect to 20 to 60% by mass.

  The water-based black ink composition of the present invention is prepared using water as a medium. If necessary, the water-soluble organic solvent (organic solvent miscible with water) (component (II)) or the like can be used as long as the effects of the present invention are not impaired. You may contain an ink preparation agent suitably. The pH of the ink composition is preferably pH 6 to 10 and more preferably pH 7 to 10 in terms of improving storage stability. Moreover, as surface tension of a coloring composition, 25-70 mN / m is preferable and 25-60 mN / m is more preferable. Furthermore, the viscosity of the colored composition is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less.

  Examples of the water-soluble organic solvent (component (II)) used in the preparation of the aqueous black ink composition include (C1 to C1) such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, and tertiary butanol. C4) Alkanol, carboxylic acid amides such as N, N-dimethylformamide or N, N-dimethylacetamide, lactams such as 2-pyrrolidone and N-methylpyrrolidin-2-one, 1,3-dimethylimidazolidin-2-one Or cyclic ureas such as 1,3-dimethylhexahydropyrimido-2-one, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one or cyclic such as keto alcohol, tetrahydrofuran, dioxane, etc. Ether, ethylene glycol, , 2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene Monomers, oligomers or polyalkylene glycols such as glycols, polypropylene glycols, thiodiglycols, dithiodiglycols, etc., oligomers or polyalkylene glycols or thioglycols, glycerols, polyols such as hexane-1,2,6-triols (triols) ), Ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether Ether, polyhydric alcohol (C1 -C4) alkyl ethers such as diethylene glycol monobutyl ether (butyl carbitol) or triethylene glycol monomethyl ether or triethylene glycol monoethyl ether, gamma-butyrolactone or dimethyl sulfoxide and the like. Among these water-soluble organic solvents, 2-pyrrolidone, isopropyl alcohol, glycerin, diglycerin, butyl carbitol, ethylene glycol, diethylene glycol, and propylene glycol are preferable, and 2-pyrrolidone, isopropyl alcohol, glycerin, Butyl carbitol. These organic solvents may be used alone or in combination of two or more.

  The preferable content rate of the water-soluble solvent is 0 to 50% by mass, and more preferably 25 to 50% by mass with respect to the total amount of the aqueous black ink composition of the present invention.

  Examples of the ink preparation used in the preparation of the aqueous black ink composition include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventives, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, and oxidation agents. Examples thereof include an inhibitor and a surfactant.

  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 (component (III)) 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.

  These ink preparation agents are used alone or in combination.

  In the production of the aqueous black 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 the preparation of the black 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 water-based black ink composition of the present invention can be used in various fields, and is suitable for a water-based ink for writing, a water-based printing ink, an information recording ink, and the like, and an ink-jet ink containing the ink composition. It is particularly preferably used as the ink jet recording method of the present invention, which will be described later.

  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 black ink composition of the present invention as an inkjet ink. In the ink jet recording method of the present invention, recording is performed on the image receiving material using the aqueous black ink composition of the present invention, but there are no particular restrictions on the ink nozzles used at that time, and they are appropriately selected according to the purpose. Known methods, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element, and an electrical signal to an acoustic beam. Use an acoustic ink jet system that irradiates the changed ink and ejects the ink using the radiation pressure, a thermal ink jet (bubble jet (registered trademark)) system that uses the pressure generated by heating the ink to form bubbles. be able to. 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 body of the present invention is colored with the aqueous black ink composition of the present invention, and more preferably is colored with an ink jet printer using the aqueous black 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 material on the surface is greatly discolored by ozone gas, but the aqueous black ink composition of the present invention is resistant to ozone gas. Therefore, 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 black 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 black ink composition of the present invention is very clear on a recording material such as plain paper and an information transmission sheet having an ink receiving layer, has a high saturation and printing density, and has a black recorded image with an ideal hue. give. Therefore, it is also possible to faithfully reproduce a photographic color image on paper. In addition, the aqueous black ink composition of the present invention has very good storage stability without solid precipitation, physical property change, hue change and the like after long-term storage.
The aqueous black 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 near the nozzle is very unlikely to occur. ) Is not blocked. In addition, the aqueous black ink composition of the present invention uses a continuous ink jet printer, and when the ink is recirculated at a relatively long time interval or used intermittently by an on-demand ink jet printer, Does not cause changes in physical properties.
Furthermore, the image recorded on the information transmission sheet having the ink receiving layer by the aqueous black ink composition of the present invention has various fastness properties such as water resistance, moisture resistance, ozone gas resistance, abrasion resistance, and light resistance. In particular, 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 black ink composition of the present invention is extremely useful for various recording ink applications, particularly ink jet recording ink applications.

EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. Unless otherwise specified, “part” and “%” in the text are based on mass, and the reaction temperature is the internal temperature. Moreover, in each structural formula of the compound obtained in the Example, acidic functional groups, such as a carboxy group and a sulfo group, were described in the form of a free acid. Synthesis Examples 1 to 3 are synthesis examples of the compound represented by Formula (1).
[(A) Synthesis of black dye]
[Synthesis Example 1]
(Process 1)
5.0 parts of 2-amino-6-methoxybenzothiazole was slowly added at 15-25 ° C. in 16.0 parts of 15% fuming sulfuric acid. After the addition, the mixture was stirred at the same temperature for 2 hours, and then added dropwise to 60.0 parts of ice water in about 10 minutes. The precipitated crystals were collected by filtration and dried to obtain 6.4 parts of a compound of the following formula (14).

(Process 2)
In 20 parts of 50% sulfuric acid, 3.2 parts of the compound of the formula (14) obtained in Synthesis Example 2 (Step 1) was suspended in 20.0 parts of 50% sulfuric acid and stirred at 5 to 10 ° C. at 40 ° C. A diazo suspension was obtained by dripping 4.7 parts of% nitrosylsulfuric acid in about 10 minutes.
On the other hand, an aqueous solution was obtained by adding 2.9 parts of the compound of the following formula (15), 0.4 part of sulfamic acid, and then sodium hydroxide to 30 parts of water to adjust the pH to 5.0 to 5.5.
The above diazo suspension was added dropwise to the obtained aqueous solution at a reaction temperature of 20 to 30 ° C. for about 10 minutes.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, sodium hydroxide was added to adjust the pH to 0.7 to 1.2, and the precipitated solid was collected by filtration to obtain a wet cake containing a compound of the following formula (16). It was. In addition, the compound of following formula (15) was obtained by the method of Unexamined-Japanese-Patent No. 2004-083492.

(Process 3)
An aqueous solution was obtained by adding 3.0 parts of the compound of the following formula (17) to 30.0 parts of water and then adding sodium hydroxide to adjust the pH to 7.5 to 8.0.
On the other hand, with stirring, the wet cake containing the compound of formula (16) obtained in Synthesis Example 1 (Step 2) was suspended in 110.0 parts of water, and sodium hydroxide was added to adjust the pH to 6.0 to 6.5. As a result, an aqueous solution was obtained.
To the obtained aqueous solution, 3.6 parts of 35% hydrochloric acid and then 2.2 parts of 40% aqueous sodium nitrite solution were added dropwise at a reaction temperature of 15 to 20 ° C. over about 5 minutes to obtain a diazo suspension.
The obtained diazo suspension was added dropwise to the previously obtained aqueous solution containing the compound of the formula (17) at a reaction temperature of 20 to 30 ° C. for 20 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 8.0.
After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours, salted out by addition of sodium chloride, and the precipitated solid was collected by filtration to obtain a wet cake containing a compound of the following formula (18).

(Process 4)
An aqueous solution was obtained by adding 3.3 parts of the compound of the following formula (19) to 30.0 parts of water and then adding sodium hydroxide to adjust the pH to 7.5 to 8.0.
On the other hand, with stirring, the wet cake containing the compound of the formula (18) obtained in Synthesis Example 1 (Step 3) was dissolved in 150.0 parts of water, 3.3 parts of 35% hydrochloric acid, and then the reaction temperature of 20-25. A diazo liquid was obtained by dropwise addition of 2.0 parts of a 40% aqueous sodium nitrite solution at about 5 minutes in about 5 minutes.
The obtained diazo liquid was added dropwise to the aqueous solution containing the compound of the formula (19) obtained previously at a reaction temperature of 20 to 30 ° C. for 30 minutes. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 7.0 to 8.0.
After completion of dropping, the mixture was stirred at the same temperature for 2 hours, sodium chloride was added for salting out, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved in 180.0 parts of water, 250.0 parts of methanol was added for crystallization, and the precipitated solid was collected by filtration to obtain a wet cake. The obtained wet cake was dissolved again in 150 parts of water, and 400.0 parts of methanol was added for crystallization, and the precipitated solid was collected by filtration and dried to obtain No. 1 in the above Table 4 of the present invention. 14 and No. 1 in Table 5. A 11.3 part mixture of 22 compounds was obtained as a sodium salt (λmax: 604.0 nm, ozone gas resistance test result 84% or more).

[Synthesis Example 2]
In Synthesis Example 1 (Step 2), the same as in Synthesis Example 1 except that 3.2 parts of the compound of Formula (14) is 3.5 parts of 2-aminobenzothiazole-6-sulfonic acid. 12.9 parts of the compound of the formula (20) (No. 24 compound in Table 5) was obtained as a sodium salt (λmax: 604.5 nm, ozone gas resistance test result 80% or more).

[(A) Preparation of Black Ink Composition]
[Examples 1 to 3]
The black ink composition of the present invention was prepared by mixing each component at the composition ratio shown in Table 8 below and stirring for about 1 hour until the solid content was dissolved. Then, a 0.45 μm membrane filter (trade name, cellulose acetate filter paper) The black ink composition for a test was prepared by filtering with Advantech). As a dye, it prepared by the combination as described in the following Examples 1-3.
In Table 8, “Surfinol 104PG50” is a trade name, which is an acetylene glycol nonionic surfactant manufactured by Nissin Chemical.

[Example 1]
C. I. Acid Black 2 (X = 0.7 part)
Compound synthesized in Synthesis Example 1 (X = 2.8 parts)
Total X = 3.5 parts

[Example 2]
C. I. Acid Black 2 (X = 1.4 parts)
Compound synthesized in Synthesis Example 1 (X = 2.1 parts)
Total X = 3.5 parts

[Example 3]
C. I. Acid Black 2 (X = 2.1 copies)
Compound synthesized in Synthesis Example 1 (X = 1.4 parts)
Total X = 3.5 parts

  These aqueous black ink compositions did not cause precipitation separation during storage and did not change their physical properties even after long-term storage.

  As Comparative Example 1, the dyes for Comparative Examples were mixed at the composition ratios shown in Table 8 in the same manner as in Examples 1 to 3, and a black ink composition for Comparative Examples was prepared in the same manner.

[Comparative Example 1]
Compound synthesized in Example 1 (X = 3.5 parts)
Total X = 3.5 parts

[(B) Inkjet print]
Using the respective ink compositions obtained in Examples 1 to 3 and Comparative Example 1, inkjet recording was performed on the following glossy papers 1, 2 and 3 using an inkjet printer (trade name: Canon IP4100).
Glossy paper 1: Glossy paper manufactured by Canon, trade name Photo paper Glossy Pro [PT-101A420]
Glossy paper 2: Glossy paper manufactured by Canon, trade name Photo paper Glossy gold [GL-101A420]
Glossy paper 3 Product name manufactured by EPSON [Photographic paper crispia (high gloss)]
At the time of printing, an image pattern is created so as to obtain six gradations of reflection densities of 100%, 80%, 60%, 40%, 20%, and 10%, and dark black to light black gradation recording is performed. A product was obtained, and this was used as a test piece to conduct the following evaluation test. Since the gray scale mode is used at the time of printing, yellow, cyan and magenta recording liquids other than the black recording liquid are not used together.

[(C) Evaluation of color rendering properties]
With respect to 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, and the reflection density Dk value of the recorded image before the test was 1.0. The measurement was performed by measuring the nearest gradation part. In the color measurement, all were performed under the conditions of DIN and a viewing angle of 2 ° on the basis of density.
[1] Light source color rendering evaluation
The test piece of glossy paper 1 was subjected to color measurement using the following light sources 1 to 5, and a comparative evaluation was made between the measured values of the light source 1 and the measured values of the light sources 2 to 5.
Light source 1: D50
Light source 2: D65
Light source 3: F2
Light source 4: F3
Light source 5: F4
In the evaluation, Lab was measured, and the difference was defined as a color difference ΔE. ΔE was calculated by the following formula.
ΔE = {(L ₁ −L ₂ ) ² × (a ₁ −a ₂ ) ² × (b ₁ −b ₂ ) ² } ^1/2
The results and criteria are shown below.

×：ΔＥ＞２．０
△：２．０≧ΔＥ＞１．０
○：ΔＥ≦１．０

×: ΔE> 2.0
Δ: 2.0 ≧ ΔE> 1.0
○: ΔE ≦ 1.0

×：ΔＥ＞９０．０
△：９０．０≧ΔＥ＞７０．０
○：ΔＥ≦７０．０

×: ΔE> 90.0
Δ: 90.0 ≧ ΔE> 70.0
○: ΔE ≦ 70.0

×：ΔＥ＞２００．０
△：２００．０≧ΔＥ＞１２０．０
○：ΔＥ≦１２０．０

×: ΔE> 200.0
Δ: 200.0 ≧ ΔE> 120.0
○: ΔE ≦ 120.0

×：ΔＥ＞３３０．０
△：３３０．０≧ΔＥ＞２３０．０
○：ΔＥ≦２３０．０

［２）メディア演色性評価］
上記光源１を用い、上記光沢紙１乃至３の試験片について測色を行い、光沢紙１での測定値と光沢紙２及び３での測定値との比較評価を行った。
評価については、上記評価１）と同様にΔＥを算出し比較した。
以下に結果と判断基準を示す。

×: ΔE> 330.0
Δ: 330.0 ≧ ΔE> 230.0
○: ΔE ≦ 230.0

[2] Media color rendering evaluation
Using the light source 1, color measurement was performed on the test pieces of the glossy papers 1 to 3, and the measured values of the glossy paper 1 and the measured values of the glossy papers 2 and 3 were compared and evaluated.
About evaluation, (DELTA) E was computed similarly to said evaluation 1), and compared.
The results and criteria are shown below.

×：ΔＥ＞２．０
△：２．０≧ΔＥ＞１．２
○：ΔＥ≦１．２

×: ΔE> 2.0
Δ: 2.0 ≧ ΔE> 1.2
○: ΔE ≦ 1.2

×：ΔＥ＞２０．０
△：２０．０≧ΔＥ＞１０．０
○：ΔＥ≦１０．０

×: ΔE> 20.0
Δ: 20.0 ≧ ΔE> 10.0
○: ΔE ≦ 10.0

  From Table 9 thru | or 14, it turns out that the water-based black ink composition of this invention is excellent in light source color rendering property and media color rendering property compared with the conventional black ink (comparative example).

The aqueous black ink composition of the present invention is excellent in light source color rendering properties and media color rendering properties. Therefore, it is suitably used as a black ink liquid for ink jet recording and writing instruments.

Claims (19)

(I) As a pigment component, (i) C.I. I. Acid Black 2 and (ii) in a ozone gas resistance test under conditions of an ozone concentration of 40 ppm, a humidity of 60% RH, and a temperature of 24 ° C., and a dye having a dye residual ratio of 70% or more after 4 hours An aqueous black ink composition. The aqueous black ink composition according to claim 1, wherein the dye (ii) is a dye having a λmax (maximum absorption wavelength) measured in an aqueous solution of pH 7 of 600 nm or more and 640 nm or less. The aqueous black ink composition according to claim 1 or 2, wherein the dye (ii) is a dye having three or more azo bonds (-N = N-) in the molecule. The water-based black ink composition according to any one of claims 1 to 3, wherein the dye (ii) is a black dye represented by the following formula (1) or a salt thereof.

[In Formula (1),
n is 0 or 1;
R ¹ is a carboxy group; (C1-C8) alkoxycarbonyl group; (C1-C8) an alkoxycarbonyl group or a (C1-C4) alkyl group optionally substituted with a carboxy group; or a hydroxy group, a sulfo group or a carboxy group Represents a phenyl group which may be substituted with
R ² to R ⁴ each independently represent a hydrogen atom; a chlorine atom; a hydroxy group; a sulfo group; a carboxy group; a sulfamoyl group; a carbamoyl group; a (C1-C4) alkyl group; a hydroxy group, a (C1-C4) alkoxy group, a hydroxy group (C1-C4) alkoxy group, sulfo group or carboxy group which may be substituted (C1-C4) alkoxy group; mono- or di (C1-C4) alkyl group which may be substituted with hydroxy group, sulfo group or carboxy group An amino group; a (C1-C4) alkylcarbonylamino group optionally substituted with a hydroxy group or a carboxy group; an N ′-(C1-C4) alkylureido group optionally substituted with a hydroxy group, a sulfo group or a carboxy group; The benzene ring is a chlorine atom, a (C1-C4) alkyl group, a nitro group, a sulfo group or a carbocycle. A phenylamino group which may be substituted with a group; a benzene ring having a chlorine atom, a benzoylamino group which may be substituted with a (C1-C4) alkyl group, a nitro group, a sulfo group or a carboxy group; or a benzene ring having a chlorine atom, (C1-C4) each represents a phenylsulfonylamino group optionally substituted with an alkyl group, a nitro group, a sulfo group or a carboxy group;
Group A is a substituted heterocyclic group represented by the following formula (2) or (3),

(In formula (2), R ⁵ may be a mercapto group; or a hydroxy group, a (C1-C4) alkoxy group, a hydroxy (C1-C4) alkoxy group, a sulfo group, or a carboxy group (C1-C4). Represents an alkylthio group.)

(In formula (3), R ⁶ to R ⁸ are each independently a hydrogen atom; chlorine atom; carboxy group; sulfo group; nitro group; hydroxy group; carbamoyl group; sulfamoyl group; (C1-C4) alkyl group; , (C1 to C4) alkoxy group, sulfo group or carboxy group which may be substituted (C1 to C4) alkoxy group; hydroxy group, sulfo group or carboxy group which may be substituted (C1 to C4) alkylsulfonyl group Or a phenylsulfonyl group in which the benzene ring may be substituted with a chlorine atom, a (C1-C4) alkyl group, a nitro group, a sulfo group, or a carboxy group;
Group B is an optionally substituted phenyl group or naphthyl group,
When group B is a substituted phenyl group, a hydroxy group; a sulfo group; a carboxy group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; an amino group; a mono- or di (C1-C4) alkylamino group; An amino group; a benzene ring in which the benzene ring may be substituted with a chlorine atom, a (C1-C4) alkyl group, a nitro group, a sulfo group or a carboxy group; and a substituent selected from the group consisting of:
When group B is a substituted naphthyl group; selected from the group consisting of hydroxy group; sulfo group; (C1-C4) alkoxy group; phenylsulfonyloxy group in which the benzene ring may be substituted with methyl group, nitro group or chlorine atom; Having a substituent. ]. In the formula (1),
The water-based black ink composition according to claim 4, wherein the group B is a phenyl group which may be substituted, and the substituent is a hydroxy group, a sulfo group or a carboxy group. In the formula (1),
The aqueous black ink composition according to claim 4, wherein the group B is a naphthyl group which may be substituted, and the substituent is a hydroxy group or a sulfo group. In the formula (1),
R ¹ is an unsubstituted (C1-C4) alkyl group or a carboxy group,
R ² is a sulfo (C1-C4) alkoxy group,
R ³ is a hydrogen atom,
R ⁴ is a hydrogen atom, a methyl group or an ethyl group,
The water-based black ink composition according to claim 4. In the formula (1),
Group A is represented by Formula (2),
R ¹ is a methyl group or a carboxy group,
The water-based black ink composition according to claim 4, wherein R ⁵ is a sulfo (C1-C4) alkylthio group or a carboxy (C1-C4) alkylthio group. In the formula (1),
Group A is represented by Formula (3),
R ¹ is a methyl group or a carboxy group,
R ^{6 to} R ⁸ are each independently a hydrogen atom, chlorine atom, carboxy group, sulfo group, nitro group, (C1-C4) alkyl group, (C1-C4) alkoxy group, or (C1-C4) alkylsulfonyl group. The water-based black ink composition according to claim 4. In the formula (1),
n is 1,
R ¹ is a carboxy group,
R ² is a sulfopropoxy group,
R ³ is a hydrogen atom,
R ⁴ is a methyl group,
R ^{6 to} R ⁸ are each independently a hydrogen atom, chlorine atom, carboxy group, sulfo group, nitro group, methyl group, methoxy group, methylsulfonyl group,
The trisazo compound or a salt thereof according to claim 4, wherein the group B is a phenyl group which may be substituted with a sulfo group or a carboxy group. 11. The aqueous black ink according to claim 1, wherein the dye (i) is contained in an amount of 10 to 90% by mass and the dye (ii) is contained in an amount of 10 to 90% by mass in a total mass of the pigment component. Composition. The water-based black ink composition according to any one of claims 1 to 11, further comprising (II) a water-soluble organic solvent. The aqueous black ink composition according to any one of claims 1 to 12, further comprising (III) urea. The aqueous black ink composition according to any one of claims 1 to 13, which is used for inkjet recording. An ink jet recording method using the water-based black ink composition according to any one of claims 1 to 14. The inkjet recording method according to claim 15, wherein the recording material in the inkjet recording method is an information transmission sheet. The ink jet recording method according to claim 16, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance. An inkjet printer loaded with a container containing the aqueous black ink composition according to claim 1. A colored body colored with the aqueous black ink composition according to any one of claims 1 to 13.