JP2013249331A - 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 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 ≥90% pigment residual ratio after 8 hours in the ozone gas resistance test under conditions of 40 ppm ozone concentration, 60% RH of humidity and 24°C temperature. An inkjet recording method and a colored material using the aqueous black ink composition are also disclosed.

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 and color reproducibility, and not only the image fastness is high but also the 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.

  Moreover, the dye similar to the dye used by this invention is described in patent documents 4-7. 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 6 is known.

Japanese Examined Patent Publication No. 7-122044 Patent No. 3178200 JP-A-9-255906 JP 2012-46559 A JP 2009-108219 A JP 2008-169374 A International Publication No. 2008/56626

  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 combining Acid Black 2 and a dye having a certain ozone gas resistance, the hue has been improved, and in particular, the sensor compatibility in the near-infrared region has been improved. The inventors have found that an aqueous black ink composition can be obtained and have reached the present invention.

［式（１）中、
Ｒ¹は、（Ｃ１〜Ｃ４）アルキル基；カルボキシ基で置換された（Ｃ１〜Ｃ４）アルキル基；フェニル基；スルホ基で置換されたフェニル基；又は、カルボキシ基；を表し、
Ｒ²はシアノ基；カルバモイル基；又は、カルボキシ基；を表し、
Ｒ³及びＲ⁴は、それぞれ独立して、水素原子；（Ｃ１〜Ｃ４）アルキル基；ハロゲン原子；（Ｃ１〜Ｃ４）アルコキシ基；又は、スルホ基；を表し、
Ｒ⁵は、（Ｃ１〜Ｃ４）アルキルチオ基；ヒドロキシ基、スルホ基およびカルボキシル基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ⁶は、（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；を表し、
Ｒ⁷は、（Ｃ１〜Ｃ４）アルキルチオ基；ヒドロキシ基、スルホ基およびカルボキシル基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；を表し、
Ｒ⁸は、（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；を表し、
Ｒ⁹及びＲ¹⁰は、それぞれ独立して、水素原子；カルボキシ基；スルホ基；アセチルアミノ基；塩素原子；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基およびカルボキシル基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；を表す。
Ｒ¹¹からＲ¹³は、それぞれ独立に、水素原子；カルボキシ基；スルホ基；ヒドロキシ基；アセチルアミノ基；塩素原子；シアノ基；ニトロ基；スルファモイル基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；ヒドロキシ基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルコキシ基；（Ｃ１〜Ｃ４）アルキルスルホニル基；ヒドロキシ基、スルホ基およびカルボキシ基よりなる群から選択される少なくとも１種類の基で置換された（Ｃ１〜Ｃ４）アルキルスルホニル基；を表す。］
４）
上記染料（ｉｉ）が、上記式（１）中、
Ｒ¹がメチル基；またはフェニル基；、
Ｒ²がシアノ基；またはカルバモイル基；、
Ｒ³が水素原子；、メチル基；またはメトキシ基；、
Ｒ⁴がスルホ基；、
Ｒ⁵がスルホ基またはカルボキシ基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；、
Ｒ⁶が（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；、
Ｒ⁷がスルホ基またはカルボキシ基で置換された（Ｃ１〜Ｃ４）アルキルチオ基；、
Ｒ⁸が（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；、
Ｒ⁹がスルホ（Ｃ１〜Ｃ４）アルコキシ基；、
Ｒ¹⁰が（Ｃ１〜Ｃ４）アルキル基；、またはアセチルアミノ基；、
Ｒ¹¹からＲ¹³が、それぞれ独立に、水素原子；カルボキシ基；スルホ基；塩素原子；ニトロ基；メチル基；メトキシ基；スルファモイル基；スルホ基またはカルボキシ基で置換された（Ｃ１〜Ｃ４）アルキルスルホニル基；である、上記３）に記載の水性黒色インク組成物、
５）
上記染料（ｉｉ）が、上記式（１）において、
Ｒ¹がメチル基；、
Ｒ²がシアノ基；またはカルバモイル基；、
Ｒ³が水素原子；、メチル基；またはメトキシ基；、
Ｒ⁴がスルホ基；、
Ｒ⁵がスルホ（Ｃ１〜Ｃ４）アルキルチオ基；、
Ｒ⁶が（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；、
Ｒ⁷がスルホ（Ｃ１〜Ｃ４）アルキルチオ基；、
Ｒ⁸が（Ｃ１〜Ｃ４）アルキルカルボニルアミノ基；、
Ｒ⁹がスルホ（Ｃ１〜Ｃ４）アルコキシ基；、
Ｒ¹⁰が（Ｃ１〜Ｃ４）アルキル基；、またはアセチルアミノ基；、
Ｒ¹¹からＲ¹³が、それぞれ独立に、水素原子；カルボキシ基；スルホ基；塩素原子；ニトロ基；メチル基；メトキシ基；スルファモイル基；である、上記３）に記載の水性黒色インク組成物、
６）
（Ｉ）色素成分総質量中、上記染料（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５）に記載の水性黒色インク組成物、
７）
更に（ＩＩ）水溶性有機溶剤を含有する上記１）乃至６）のいずれか一項に記載の水性黒色インク組成物、
８）
更に（ＩＩＩ）尿素を含有する上記１）乃至７）のいずれか一項に記載の水性黒色インク組成物、
９）
インクジェット記録に用いる上記１）乃至８）のいずれか一項に記載の水性黒色インク組成物、
１０）
上記１）乃至９）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、
１１）
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１０）に記載のインクジェット記録方法、
１２）
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１１）に記載のインクジェット記録方法、
１３）
上記１）乃至９）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、
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 the ozone gas resistance test under the conditions of ozone concentration 40 ppm, humidity 60% RH, temperature 24 ° C., it contains a dye having a dye residual ratio of 90% or more after 8 hours An aqueous black ink composition,
2)
The water-based black ink composition according to 1), wherein the dye (ii) is a dye having four or more azo bonds (-N = N-) in the molecule;
3)
The water-based black ink composition according to 1) or 2), wherein the dye (ii) is a black dye represented by the following formula (1) or a salt thereof:

[In Formula (1),
R ¹ represents a (C1-C4) alkyl group; a (C1-C4) alkyl group substituted with a carboxy group; a phenyl group; a phenyl group substituted with a sulfo group; or a carboxy group;
R ² represents a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ each independently represent a hydrogen atom; a (C1-C4) alkyl group; a halogen atom; a (C1-C4) alkoxy group; or a sulfo group;
R ⁵ represents a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxyl group;
R ⁶ represents a (C1-C4) alkylcarbonylamino group;
R ⁷ represents a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxyl group;
R ⁸ represents a (C1-C4) alkylcarbonylamino group;
R ⁹ and R ¹⁰ are each independently a hydrogen atom; a carboxy group; a sulfo group; an acetylamino group; a chlorine atom; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group; (C4) represents a (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of an alkoxy group, a sulfo group and a carboxyl group.
R ¹¹ to R ¹³ each independently represent a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; an acetylamino group; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group; (C1-C4) alkyl group; (C4) alkoxy group; (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group and carboxy group; (C1-C4) An alkylsulfonyl group; a (C1-C4) alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group. ]
4)
In the formula (1), the dye (ii) is
R ¹ is a methyl group; or a phenyl group;
R ² is a cyano group; or a carbamoyl group;
R ³ is a hydrogen atom; a methyl group; or a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is substituted by a sulfo group or a carboxy group (C1 -C4) alkylthio groups;,
R ⁶ is a (C1-C4) alkylcarbonylamino group;
R ⁷ is substituted by a sulfo group or a carboxy group (C1 -C4) alkylthio groups;,
R ⁸ is a (C1-C4) alkylcarbonylamino group;
R ⁹ is a sulfo (C1-C4) alkoxy group;
R ¹⁰ is a (C1-C4) alkyl group; or an acetylamino group;
R ¹¹ to R ¹³ are each independently a hydrogen atom; a carboxy group; a sulfo group; a chlorine atom; a nitro group; a methyl group; a methoxy group; a sulfamoyl group; a (C1-C4) alkyl substituted with a sulfo group or a carboxy group A water-based black ink composition as described in 3) above, which is a sulfonyl group;
5)
In the formula (1), the dye (ii) is
R ¹ is a methyl group;
R ² is a cyano group; or a carbamoyl group;
R ³ is a hydrogen atom; a methyl group; or a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C1-C4) alkylthio group;
R ⁶ is a (C1-C4) alkylcarbonylamino group;
R ⁷ is a sulfo (C1-C4) alkylthio group;
R ⁸ is a (C1-C4) alkylcarbonylamino group;
R ⁹ is a sulfo (C1-C4) alkoxy group;
R ¹⁰ is a (C1-C4) alkyl group; or an acetylamino group;
The aqueous black ink composition according to 3) above, wherein R ¹¹ to R ¹³ are each independently a hydrogen atom; a carboxy group; a sulfo group; a chlorine atom; a nitro group; a methyl group; a methoxy group; a sulfamoyl group;
6)
(I) The aqueous black ink composition as described in 1) to 5) 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.
7)
Further, (II) the water-based black ink composition according to any one of 1) to 6) above containing a water-soluble organic solvent,
8)
Furthermore, (III) the aqueous black ink composition according to any one of 1) to 7) above containing urea,
9)
The water-based black ink composition according to any one of 1) to 8) used for inkjet recording,
10)
An inkjet recording method using the aqueous black ink composition according to any one of 1) to 9) above;
11)
The inkjet recording method according to 10) above, wherein the recording material in the inkjet recording method is an information transmission sheet,
12)
The inkjet recording method according to 11), wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance,
13)
An inkjet printer loaded with a container containing the aqueous black ink composition according to any one of 1) to 9) 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 the above, a dye having a dye residual ratio of 90% or more after 8 hours is contained. The dye (ii) is not particularly limited as long as it has the above characteristics. The ozone gas resistance test result may be 90% or more, preferably 95% or more, and more preferably 98% or more. The ozone gas resistance test is performed using the following glossy paper.
Glossy paper 1: Glossy paper manufactured by Canon, trade name Photo paper Glossy Pro [PT-101A420]
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.

  Although it does not specifically limit as long as it has the said characteristic as dye (ii), Especially the dye (ii) which has four or more azo bonds (-N = N-) in a molecule | numerator is 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 (2) and (3) in addition to the compound represented by the formula (1). Conceivable. These compounds are also included in the present invention. In formulas (2) and (3), R ^{1 to} R ¹³ have the same meaning as in formula (1) above.

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

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

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

Preferable R ¹ includes a (C1 to C4) alkyl group, a (C1 to C4) alkyl group substituted with a carboxy group, a phenyl group, or a phenyl group substituted with a sulfo group.
More preferably, it is a (C1-C4) alkyl group, a phenyl group, or a phenyl group substituted with a sulfo group. More preferably, it is a (C1-C4) alkyl group or a phenyl group. Particularly preferred is a (C1-C4) alkyl group, with a methyl group being most preferred.

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

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

For R ³ or R ^4, the halogen atom, fluorine atom, chlorine atom, bromine atom, or iodine atom and the like, a chlorine atom is preferable.

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

R ³ and R ⁴ are each independently preferably a hydrogen atom, a (C1-C4) alkyl group, a (C1-C4) alkoxy group, or a sulfo group. More preferably, one is a combination of hydrogen atoms and the other is a sulfo group.
The substitution position of R ³ and R ⁴ is not particularly limited. When either one is a hydrogen atom and the other is a sulfo group, the sulfo group is not adjacent to any nitrogen atom constituting the benzimidazolopyridone ring. It is preferable to substitute one of the two carbon atoms.

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

As a preferable combination of R ^{1 to} R ⁴ in the formula (1), R ¹ is a (C1-C4) alkyl group or a phenyl group (preferably a (C1-C4) alkyl group, more preferably a methyl group), and R ² is Examples include a combination of a cyano group or a carbamoyl group (preferably a cyano group), R ³ is a hydrogen atom, a methyl group, a methoxy group (preferably a methoxy group), and R ⁴ is a sulfo group.

In the above formula (1), examples of the (C1 to C4) alkylthio group in R ⁵ include those in which alkyl is linear or branched, and linear is preferable. Specific examples thereof include straight chain such as methylthio group, ethylthio group, n-propylthio group and n-butylthio group; branched chain such as isopropylthio group, isobutylthio group, sec-butylthio group and tert-butylthio group. Things;

As the substituent in R ^5, the (C1 to C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group is a (C1 to C4) alkylthio group. Those having these substituents at any carbon atom can be mentioned. The number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited, but is preferably substituted with a carbon atom other than the carbon atom to which the sulfur atom in the alkylthio group is bonded.
Specific examples thereof include, for example, 2-hydroxyethylthio group, 2-hydroxypropylthio group, 3-hydroxypropylthio group, hydroxy (C1-C4) alkylthio group; 2-sulfoethylthio group, 3-sulfopropylthio group. A sulfo (C1 to C4) alkylthio group; a 2-carboxyethylthio group, a 3-carboxypropylthio group, a 4-carboxybutylthio group, and the like; a carboxy (C1 to C4) alkylthio group;

Among the above, preferable R ⁵ includes a sulfo (C1 to C4) alkylthio group or a carboxy (C1 to C4) alkylthio group, a sulfo (C1 to C4) alkylthio group is more preferable, and a sulfopropylthio group is particularly preferable. .

In the above formula (1), examples of the (C1 to C4) alkylcarbonylamino group in R ⁶ include those in which alkyl is linear or branched, and linear is preferable. Specific examples thereof include straight chain such as acetylamino group (methylcarbonylamino group), propionylamino group (ethylcarbonylamino group), n-propylcarbonylamino group, n-butylcarbonylamino group; isopropylcarbonylamino And branched chain groups such as an isobutylcarbonylamino group, a sec-butylcarbonylamino group, and a pivaloylamino group (tert-butylcarbonylamino group). Of these, a straight chain is preferable, and an acetylamino group is particularly preferable.

A preferred combination of R ⁵ and R ^{6 is} a combination of R ⁵ is a sulfo (C1-C4) alkylthio group, R ⁶ is an acetylamino group, R ⁵ is a sulfopropylthio group, and R ⁸ is an acetylamino group. Particularly preferred.

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

As the substituent for R ^7, the (C1 to C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group includes a (C1 to C4) alkylthio group. Those having these substituents at any carbon atom can be mentioned. The number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited, but is preferably substituted with a carbon atom other than the carbon atom to which the sulfur atom in the alkylthio group is bonded.
Specific examples thereof include, for example, 2-hydroxyethylthio group, 2-hydroxypropylthio group, 3-hydroxypropylthio group, hydroxy (C1-C4) alkylthio group; 2-sulfoethylthio group, 3-sulfopropylthio group. A sulfo (C1 to C4) alkylthio group; a 2-carboxyethylthio group, a 3-carboxypropylthio group, a 4-carboxybutylthio group, and the like; a carboxy (C1 to C4) alkylthio group;

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

In the above formula (1), examples of the (C1 to C4) alkylcarbonylamino group in R ⁸ include those in which alkyl is linear or branched, and linear is preferable. Specific examples thereof include straight chain such as acetylamino group (methylcarbonylamino group), propionylamino group (ethylcarbonylamino group), n-propylcarbonylamino group, n-butylcarbonylamino group; isopropylcarbonylamino And branched chain groups such as an isobutylcarbonylamino group, a sec-butylcarbonylamino group, and a pivaloylamino group (tert-butylcarbonylamino group). Of these, a straight chain is preferable, and an acetylamino group is particularly preferable.

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

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

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

(C1-C4) alkoxy group substituted with at least one kind of group selected from the group consisting of a hydroxy group, a (C1-C4) alkoxy group, a sulfo group, and a carboxy group as a substituent in R ⁹ and R ¹⁰ Examples thereof include those having these substituents on any carbon atom in the (C1-C4) alkoxy group. The number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited, but is preferably substituted with a carbon atom other than the carbon atom to which the oxygen atom in the alkoxy group is bonded.
Specific examples thereof include, for example, 2-hydroxyethoxy group, 2-hydroxypropoxy group, 3-hydroxypropoxy group, hydroxy (C1-C4) alkoxy group; 2-sulfoethoxy group, 3-sulfopropoxy group, 4-sulfo And a sulfo (C1 to C4) alkoxy group such as a butoxy group; a carboxy (C1 to C4) alkoxy group such as a 2-carboxyethoxy group, a 3-carboxypropoxy group, and a 4-carboxybutoxy group.

Among the above, preferable R ⁹ and R ¹⁰ include a sulfo (C1 to C4) alkylthio group or a carboxy (C1 to C4) alkylthio group, more preferably a sulfo (C1 to C4) alkylthio group, and a sulfopropylthio group. Is particularly preferred.

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

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

A preferred combination of R ⁹ and R ^{10 is} a combination in which R ⁹ is a sulfo (C1-C4) alkoxy group, R ¹⁰ is a (C1-C4) alkyl group, and R ⁹ is a sulfopropoxy group (particularly a 3-sulfopropoxy group). R ¹⁰ is a methyl group, R ⁹ is a sulfobutoxy group (particularly a 4-sulfobutoxy group is particularly preferable), and R ¹⁰ is a methyl group.

In the above formula (1), examples of the (C1 to C4) alkyl group in R ¹¹ to R ¹³ include the same ones including the (C1 to C4) alkyl group in R ¹ and preferred ones.

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

As a substituent in R ¹¹ to R ¹³ , (C 1 -C 4) alkoxy substituted with at least one group selected from the group consisting of a hydroxy group, a (C 1 -C 4) alkoxy group, a sulfo group, and a carboxy group The group is substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxy group, a sulfo group, and a carboxy group as a substituent in the above R ⁵ and R ⁶ (C1 -C4) The same thing is included including an alkoxy group and a preferable thing.

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

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

Among the above, preferable R ¹¹ includes a hydrogen atom, a carboxy group, a sulfo group, a nitro group, a chlorine atom, a methyl group, a methoxy group, and a (C1 to C4) alkylsulfonyl group, and a hydrogen atom, a carboxy group, a sulfo group. Group, nitro group, methyl group, methoxy group and chlorine atom are more preferred, and hydrogen atom and chlorine atom are particularly preferred.

Among the above, preferable R ¹² is a hydrogen atom, a carboxy group, a sulfo group, a nitro group, a chlorine atom, a methyl group, a methoxy group, a sulfamoyl group, a (C1 to C4) alkylsulfonyl group, or a carboxy (C1 to C4) alkyl. Examples include a sulfonyl group and a sulfo (C1 to C4) alkylsulfonyl group, and a sulfo group, a nitro group, a methyl group, a methoxy group, a sulfamoyl group, a sulfopropylsulfonyl group, and a carboxyethylsulfonyl group are more preferable, and a sulfo group is particularly preferable.

Among the above, preferable R ¹³ includes a hydrogen atom, a carboxy group, a sulfo group, a methoxy group, a nitro group, a chlorine atom, and a (C1 to C4) alkylsulfonyl group, and a hydrogen atom, a sulfo group, and a methoxy group are more preferable. Preferably, a hydrogen atom is particularly preferable.

A preferred combination of R ¹¹ to R ^{13 is} a combination of R ¹¹ as a hydrogen atom, R ¹² as a sulfo group, R ¹³ as a hydrogen atom, R ¹¹ as a hydrogen atom, R ¹² as a sulfamoyl group, and R ¹³ as a hydrogen atom, Or a combination of R ¹¹ is a hydrogen atom, R ¹² is a chlorine atom, R ¹³ is a sulfo group, R ¹¹ is a hydrogen atom, R ¹² is a chlorine atom, and R ¹³ is a sulfo group is particularly preferable.

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

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

Specific examples of preferable combinations in the formula (1) include the following combinations (i) to (iii). (Ii) is preferable to (i), and (iii) is most preferable.
(I)
R ¹ is a methyl group; or a phenyl group;
R ² is a cyano group; or a carbamoyl group;
R ³ is a hydrogen atom; a methyl group; or a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is substituted by a sulfo group or a carboxy group (C1 -C4) alkylthio groups;,
R ⁶ is a (C1-C4) alkylcarbonylamino group;
R ⁷ is substituted by a sulfo group or a carboxy group (C1 -C4) alkylthio groups;,
R ⁸ is a (C1-C4) alkylcarbonylamino group;
R ⁹ is a sulfo (C1-C4) alkoxy group;
R ¹⁰ is a (C1-C4) alkyl group; or an acetylamino group;
R ¹¹ to R ¹³ are each independently a hydrogen atom; a carboxy group; a sulfo group; a methyl group; a methoxy group; a chlorine atom; a nitro group; a sulfamoyl group; a (C1-C4) alkyl substituted with a sulfo group or a carboxy group A sulfonyl group;
(Ii)
R ¹ is a methyl group;
R ² is a cyano group; or a carbamoyl group;
R ³ is a hydrogen atom; a methyl group; or a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C1-C4) alkylthio group;
R ⁶ is a (C1-C4) alkylcarbonylamino group;
R ⁷ is a sulfo (C1-C4) alkylthio group;
R ⁸ is a (C1-C4) alkylcarbonylamino group;
R ⁹ is a sulfo (C1-C4) alkoxy group;
R ¹⁰ is a (C1-C4) alkyl group; or an acetylamino group;
A combination in which R ¹¹ to R ¹³ are each independently a hydrogen atom; a sulfo group; a methyl group; a methoxy group; a chlorine atom; a nitro group;
(Iii)
R ¹ is a methyl group;
R ² is a cyano group;
R ³ is a hydrogen atom; or a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C1-C4) alkylthio group;
R ⁶ is an acetylamino group;
R ⁷ is a sulfo (C1-C4) alkylthio group;
R ⁸ is an acetylamino group;
R ⁹ is a sulfopropoxy group; or a sulfobutoxy group;
R ¹⁰ is a (C1-C4) alkyl group;
R ¹¹ is a hydrogen atom; or a sulfo group;
R ¹² is a sulfo group; or a chlorine atom;
A combination in which R ¹³ is a hydrogen atom; or a sulfo group.

  Any of the black dyes represented by the above formulas (1) to (3) 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 (4). 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

The alkyl group of Z ¹ , Z ² , Z ³ and Z ^{4 in} the general formula (4) is preferably a (C1 to C4) alkyl group, 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 (4) 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 organic cation salts include halogen salts of quaternary ammonium ions represented by the above formula (4) 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 (5) to (12), R ^{1 to} R ¹³ represent the same meaning as in the above formula (1).

  A compound represented by the following formula (5) is diazotized by a conventional method, and the obtained diazo compound and a compound represented by the following formula (6) are subjected to a coupling reaction by a conventional method, and represented by the following formula (7). To obtain the compound.

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

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

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

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

Although it does not specifically limit as a suitable specific example of the azo compound of this invention represented by Formula (1), The compound shown by the structural formula given to the following Table 2 thru | or 17 is mentioned.
In each table, functional groups such as sulfo group and carboxy group are described in the form of free acid for convenience.

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

  The diazotization of the compound of the formula (7) is carried out in a manner known per se, for example nitrites, such as sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 40 ° C., preferably 5 to 30 ° C. It is carried out using an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of formula (7) with the compound of formula (8) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 40 ° C, preferably 10 to 30 ° C, and at an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. The same base as described above can be used. The compound of formula (7) and the compound of formula (8) are used in approximately stoichiometric amounts.

  The diazotization of the compound of the formula (9) is carried out in a manner known per se, for example nitrites, such as sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 50 ° C., preferably 5 to 40 ° C. It is carried out using an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of formula (9) with the compound of formula (10) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 50 [deg.] C, preferably 10 to 40 [deg.] C and an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. The same base as described above can be used. The compound of formula (9) and the compound of formula (10) are used in approximately stoichiometric amounts.

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

  The 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) 20 to 70% by mass of the above (i) and 5 to 50% by mass of (ii) with respect to 20 to 70% by mass are preferable in the total mass of the pigment component. Furthermore, it is particularly preferable to contain 30 to 60% by mass of the above (i) and 5 to 20% by mass of the above (ii) with respect to 30 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-C4 such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, and tertiary butanol. Carboxylic acid amides such as alkanol, N, N-dimethylformamide or N, N-dimethylacetamide, lactams such as 2-pyrrolidone and N-methylpyrrolidin-2-one, 1,3-dimethylimidazolidin-2-one or 1 , Cyclic ureas such as 3-dimethylhexahydropyrimido-2-one, ketones such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one, or cyclic ethers such as ketoalcohol, tetrahydrofuran, dioxane, Ethylene glycol, 1, -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 glycol, Monomers, oligomers or polyalkylene glycols or thioglycols having (C2-C6) alkylene units such as polypropylene glycol, thiodiglycol and dithiodiglycol, polyols such as glycerin, hexane-1,2,6-triol (triols), Ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether , Polyhydric alcohols (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.

The present invention will be described more specifically with reference to synthesis examples and 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)
41.8 parts of 4-chloro-3-nitroaniline was dissolved in 60.0 parts of N-methyl-2-pyrrolidone, and 35.2 parts of acetic anhydride was added dropwise thereto in about 15 minutes. After the dropwise addition, the reaction solution was added to 400 parts of water after reacting at 40-50 ° C. for 2 hours. After stirring at room temperature for 30 minutes, the precipitated solid was filtered, and the resulting solid was washed with 100 parts of funnel water, separated and dried to obtain 63.0 parts of a compound represented by the following formula (13). Obtained.

(Process 2)
42.9 parts of the compound represented by the formula (13) obtained in Synthesis Example 1 (Step 1) was dissolved in 115.0 parts of N-methyl-2-pyrrolidone, and sodium 3-mercaptopropanesulfonate was dissolved therein. 40.9 parts and 29.0 parts of potassium carbonate were added. After the addition, the mixture was heated to 130 to 140 ° C. and reacted at the same temperature for 2 hours. After further adding 3.6 parts of sodium 3-mercaptopropanesulfonate, the mixture was reacted at 130 to 140 ° C. for 1 hour. After cooling to 60 ° C., the reaction solution was added to 700 parts of 2-propanol, and the solid obtained after cooling to room temperature was collected by filtration. The obtained wet cake was dissolved in 300 parts of water, adjusted to pH 3.0 to 4.0 by adding 35% hydrochloric acid, salted out with sodium chloride, and the precipitated solid was collected by filtration, and the following formula (14 ) Was obtained as a wet cake.

(Process 3)
In 150 parts of water, 102.6 parts of a wet cake of the compound represented by the formula (14) obtained in Synthesis Example 1 (Step 2), 1.6 parts of activated carbon and 0.4 parts of anhydrous iron chloride (III) After heating to 60 ° C., 15.9 parts of 80% hydrazine hydrate was added dropwise over about 30 minutes. After heating to 90 ° C., the reaction was carried out at the same temperature for 1.5 hours. After cooling to 40 ° C., insoluble matters were removed by filtration, and the filtrate was cooled to room temperature. The pH was adjusted to 1.0 to 1.5 by addition of 50% sulfuric acid, and the precipitated solid was collected by filtration to obtain 62.3 parts of a compound represented by the following formula (15) as a wet cake.

(Process 4)
After adding 12.6 parts of 5-amino-2-chlorobenzenesulfonic acid represented by the following formula (16) to 40 parts of water, an aqueous solution is obtained at pH 4.0 to 5.0 by adding a 25% aqueous sodium hydroxide solution. It was. After adding 25 parts of 35% hydrochloric acid, 12.6 parts of 40% aqueous sodium nitrite solution was added and reacted for about 30 minutes. 1.5 parts of sulfamic acid was added thereto and stirred for 5 minutes to obtain a diazo reaction liquid.
On the other hand, after adding 32.4 parts of a wet cake of the compound represented by the formula (15) obtained in Synthesis Example 1 (Step 3) to 200 parts of water, pH 4 was obtained by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0 to 5.0. This aqueous solution was added dropwise to the diazo reaction solution obtained above in about 5 minutes. After the dropwise addition, the reaction was continued for 3 hours while maintaining the pH at 2.0 to 2.5 by adding a 15% aqueous sodium carbonate solution, and then salted out by adding sodium chloride. The precipitated solid was collected by filtration to obtain 31.5 parts of a compound represented by the following formula (17) as a wet cake.

(Process 5)
After adding the total amount of the wet cake of the compound represented by the formula (17) obtained in Synthesis Example 1 (Step 4) to 40 parts of water, pH 6.0 to 7.0 is added by adding a 25% aqueous sodium hydroxide solution. As an aqueous solution was obtained. After adding 24.8 parts of 35% hydrochloric acid, 9.8 parts of 40% aqueous sodium nitrite solution was added and reacted for about 30 minutes. 2.0 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, after adding 30.8 parts of a wet cake of the compound represented by the formula (15) obtained in Synthesis Example 1 (Step 3) to 250 parts of water, pH 4 was obtained by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0 to 5.0. This aqueous solution was added dropwise to the diazo reaction solution obtained above in about 5 minutes. After the dropwise addition, the reaction was continued for 3 hours while maintaining the pH at 2.0 to 2.5 by adding a 15% aqueous sodium carbonate solution, and then salted out by adding sodium chloride. The precipitated solid was collected by filtration to obtain 90 parts of a compound represented by the following formula (18) as a wet cake.

(Step 6)
To 250 parts of water, 45 parts of a wet cake of the compound represented by the formula (18) obtained in Synthesis Example 1 (Step 5) was added and dissolved by stirring. After adding 16.5 parts of 35% hydrochloric acid, 4.7 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 2.0 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 5.5 parts of a compound of the following formula (19) obtained by the method described in JP-A-2004-083492 is added to 60 parts of water, and the pH is 4.5 to 5.5 by adding a 25% aqueous sodium hydroxide solution. As an aqueous solution was obtained. This aqueous solution was added dropwise to the diazo reaction solution obtained above in about 5 minutes. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 2.0 to 3.0 by adding a 15% aqueous sodium carbonate solution. After the pH was adjusted to 4.5 by adding a 15% aqueous sodium carbonate solution, 350 parts of methanol was added. The precipitated solid was collected by filtration to obtain 96.6 parts of a compound represented by the following formula (20) as a wet cake.

(Step 7)
To 170 parts of water, 32.2 parts of a wet cake of the compound represented by the formula (20) obtained in Synthesis Example 1 (Step 6) was added and dissolved by stirring. After adding 5.2 parts of 35% hydrochloric acid, 1.5 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 1.0 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 2.2 parts of a compound represented by the following formula (21) obtained by the method described in Patent Document 4 is added to 60 parts of water, and a 25% aqueous sodium hydroxide solution is added to adjust the pH to 7.5 to 8.5. To obtain an aqueous solution. The diazo reaction liquid obtained above was dropped into this aqueous solution at 15 to 30 ° C. for about 30 minutes. At this time, an aqueous sodium carbonate solution was added to maintain the pH of the reaction solution at 7.5 to 8.5, and the reaction was further continued for 2 hours while maintaining the same temperature and pH adjustment. Sodium chloride was added to the reaction solution for salting out, and the precipitated solid was separated by filtration to obtain 29.5 parts of a wet cake. The obtained wet cake was dissolved in 100 parts of water, the pH was adjusted to 7.0 to 7.5 with 35% hydrochloric acid, 80 parts of methanol was added, and the precipitated solid was collected by filtration. The obtained wet cake was dissolved again in 60 parts of water, and 90 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain 6.3 parts of a compound represented by the following formula (22) of the present invention as a sodium salt (λmax: 589 nm, ozone gas resistance test result glossy paper 1:95 %that's all).

[Synthesis Example 2]
A sodium salt of 6.3 parts of the compound represented by the formula (22) obtained in Synthesis Example 1 and 14 parts of lithium chloride were added to 140 parts of water and stirred to obtain an aqueous solution. 400 parts of 2-propanol was added and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake and 12.5 parts of lithium chloride were again added to 150 parts of water and stirred to obtain an aqueous solution. 350 parts of 2-propanol was added and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake was dissolved in 80 parts of water, 150 parts of 2-propanol was added, and the precipitated solid was separated by filtration to obtain a wet cake. The wet cake obtained again was dissolved in 40 parts of water, 100 parts of 2-propanol was added, the precipitated solid was separated by filtration, and dried to obtain compound 4.5 represented by the above formula (22) of the present invention. Part was obtained as a mixed salt of sodium and lithium (λmax: 586 nm, ozone gas resistance test result glossy paper: 99% or more).

[Synthesis Example 3]
(Process 1)
15.2 parts of 2-methyl-6-nitroaniline were dissolved in 300 parts of methanol. The resulting solution was transferred into an autoclave, 2.0 parts of 5% Pd / carbon was added, and the reaction was carried out at 20 ° C. to 30 ° C. under a hydrogen pressure of 0.2 MPa-0.5 MPa until there was no hydrogen absorption. The reaction was further continued at the same temperature for 30 minutes. The catalyst (5% Pd / carbon) was separated by filtration to obtain a solution (filtrate) containing a compound represented by the following formula (23).

(Process 2)
To 200 parts of the solution containing the compound represented by the formula (23) obtained in Synthesis Example 3 (Step 1), 13.0 parts of methyl cyanoacetate was added and refluxed for 30 minutes. 100 parts, then sodium carbonate was added to adjust the pH to 7.0 to 7.5, and the precipitated solid was separated by filtration and dried to obtain 8.3 parts of a compound represented by the following formula (24).

(Process 3)
8.3 parts of the compound represented by the formula (24), 12.0 parts of 28% sodium methoxide, and 7.2 parts of methyl acetoacetate were added to 100 parts of ethanol, and the mixture was refluxed for 30 minutes. 100 parts of water and then 35% hydrochloric acid were added to adjust the pH to 7.0 to 7.5, and the precipitated solid was separated by filtration and dried to obtain 11.1 parts of a compound represented by the following formula (25). It was. The obtained compound represented by the following formula (25) was a mixture of compounds in which a methoxy group was substituted with b or c.

(Process 4)
After slowly adding 5.6 parts of the compound represented by the above formula (25) at 5 to 10 ° C. in 77 parts of 8% fuming sulfuric acid, the mixture was reacted at the same temperature for 1.5 hours. The reaction solution was dropped into 150 parts of ice water in about 10 minutes, stirred at 65 to 70 ° C. for 30 minutes, and then the precipitated solid was filtered and separated to obtain a wet compound of the following formula (26). 24.4 parts of cake were obtained. In the compound represented by the following formula (26), the methoxy group is at the position b and the substitution position of the sulfo group is a, c or d, or the methoxy group is at the position c, It was a mixture of compounds in which the substitution position was a, b or d.

(Process 5)
In the synthesis example 1 (step 7), instead of using 2.2 parts of the compound represented by the formula (21), the wetness of the compound represented by the formula (26) obtained in the synthesis example 3 (step 4). 6.3 parts of the compound represented by the following formula (27) of the present invention was obtained as a sodium salt in the same manner as in Synthesis Example 1 (Step 7) except that 7.2 parts of the cake was used. In the obtained dye, the methoxy group in the following formula (27) is at the position b, the substitution position of the sulfo group is a, c or d, or the methoxy group is at the position c, It was a mixed dye composed of 2 to 6 compounds whose substitution positions were a, b or d.

[Synthesis Example 4]
In the synthesis example 2, instead of using 6.3 parts of the sodium salt of the compound represented by the formula (22), sodium of the compound represented by the formula (27) obtained in the synthesis example 3 (step 5). Except for using 8.8 parts of the salt, 4.5 parts of the compound represented by the above formula (27) of the present invention was obtained as a mixed salt of sodium and lithium (λmax: 592 nm, ozone gas resistance test) Result Glossy paper 1: 95% or more).

[Synthesis Example 5]
(Process 1)
15.2 parts of 2-methyl-6-nitroaniline were dissolved in 300 parts of methanol. The obtained solution was transferred into an autoclave, 2.0 parts of 5% Pd / carbon was added, and under stirring, under hydrogen pressure of 0.2 MPa-0.5 MPa at 20 ° C. to 30 ° C. until no hydrogen was absorbed. After the reaction, the reaction was further continued at the same temperature for 30 minutes. The catalyst (5% Pd / carbon) was separated by filtration to obtain a solution (filtrate) containing a compound represented by the following formula (28).

(Process 2)
After adding 13.0 parts of the compound represented by the following formula (29) to 200 parts of the solution containing the compound represented by the above formula (28) and refluxing with stirring for 30 minutes, the reaction liquid was concentrated under reduced pressure, and water 150 Parts, then sodium carbonate was added to pH 7.0-7.5. The precipitated solid was separated by filtration and dried to obtain 8.4 parts of a compound represented by the following formula (30).
The compound represented by the following formula (29) was obtained by the method described in Patent Document 11.

(Process 3)
8.4 parts of the compound represented by the formula (30), 12.3 parts of 28% sodium methoxide, and 7.4 parts of methyl acetoacetate were added to 100 parts of ethanol, and the mixture was refluxed for 30 minutes. 150 parts of water and then 35% hydrochloric acid were added to adjust the pH to 7.0 to 7.5, and the precipitated solid was separated by filtration and dried to obtain 10.0 parts of a compound represented by the following formula (31). It was. The compound represented by the following formula (31) was a compound in which a methyl group was substituted at the position a or d.

(Process 4)
After slowly adding 5.0 parts of the compound represented by the above formula (31) at 5 to 10 ° C. in 102 parts of 3% fuming sulfuric acid, the mixture was stirred at the same temperature for 1 hour. The reaction solution was dropped into 240 parts of ice water in about 10 minutes, and the precipitated solid was separated by filtration to obtain 14.7 parts of a wet cake containing a compound represented by the following formula (32). In the compound represented by the following formula (32), the methyl group is at position a and the sulfo group substitution position is c, or the methyl group is at d position and the sulfo group substitution position is b. It was one of the compounds.

(Process 5)
In the synthesis example 1 (step 7), instead of using 2.2 parts of the compound represented by the formula (21), the wetness of the compound represented by the formula (32) obtained in the synthesis example 5 (step 4) Except for using 6.0 parts of cake, 6.0 parts of the compound represented by the following formula (33) of the present invention was obtained as a sodium salt. In the obtained dye, the methyl group in the following formula (33) is at the position b, and the substitution position of the sulfo group is a, c, or d, or the methyl group is at the position c, It was a mixed dye composed of 2 to 6 compounds whose substitution positions were a, b or d.

[Synthesis Example 6]
In the synthesis example 2, instead of using 6.3 parts of the sodium salt of the compound represented by the formula (22), sodium of the compound represented by the formula (33) obtained in the synthesis example 5 (step 5). Except for using 8.8 parts of the salt, 4.0 parts of the compound represented by the above formula (33) of the present invention was obtained as a mixed salt of sodium and lithium (λmax: 590 nm, ozone gas resistance test) Result Glossy paper 1: 99% or more).

[Synthesis Example 7]
(Process 1)
To 250 parts of water, 45 parts of a wet cake of the compound represented by the formula (16) obtained in Synthesis Example 1 (Step 4) was added and dissolved by stirring. After adding 16.5 parts of 35% hydrochloric acid, 4.7 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 2.0 parts of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 5.8 parts of the compound of the following formula (34) obtained by the method described in JP-A-2004-083492 is added to 60 parts of water, and the pH is 4.5 to 5.5 by adding a 25% aqueous sodium hydroxide solution. As an aqueous solution was obtained. This aqueous solution was added dropwise to the diazo reaction solution obtained above in about 5 minutes. After the dropwise addition, the mixture was reacted for 3 hours while maintaining the pH at 2.0 to 3.0 by adding a 15% aqueous sodium carbonate solution. After the pH was adjusted to 4.5 by adding a 15% aqueous sodium carbonate solution, 350 parts of methanol was added. The precipitated solid was collected by filtration to obtain 94.0 parts of a compound represented by the following formula (35) as a wet cake.

(Process 2)
To 170 parts of water, 31.3 parts of a wet cake of a compound represented by the formula (35) obtained in Synthesis Example 7 (Step 1) was added and dissolved by stirring. After adding 5.2 parts of 35% hydrochloric acid, 1.5 parts of 40% aqueous sodium nitrite solution was added and stirred for about 30 minutes. 1.0 part of sulfamic acid was added here, and it stirred for 5 minutes, and obtained the diazo reaction liquid.
On the other hand, 2.2 parts of the compound represented by the formula (21) obtained by the method described in Patent Document 4 is added to 60 parts of water, and 25% aqueous sodium hydroxide solution is added to adjust the pH to 7.5 to 8.5. To obtain an aqueous solution. The diazo reaction liquid obtained above was dropped into this aqueous solution at 15 to 30 ° C. for about 30 minutes. At this time, an aqueous sodium carbonate solution was added to maintain the pH of the reaction solution at 7.5 to 8.5, and the reaction was further continued for 2 hours while maintaining the same temperature and pH adjustment. Sodium chloride was added to the reaction solution for salting out, and the precipitated solid was separated by filtration to obtain 30.0 parts of a wet cake. The obtained wet cake was dissolved in 100 parts of water, the pH was adjusted to 7.0 to 7.5 with 35% hydrochloric acid, 80 parts of methanol was added, and the precipitated solid was collected by filtration. The obtained wet cake was dissolved again in 60 parts of water, and 90 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain 6.0 parts of a compound represented by the following formula (36) of the present invention as a sodium salt.

[Synthesis Example 8]
A sodium salt of 6.0 parts of the compound represented by the formula (36) obtained in Synthesis Example 7 and 14 parts of lithium chloride were added to 140 parts of water and stirred to obtain an aqueous solution. 400 parts of 2-propanol was added and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake and 12.5 parts of lithium chloride were again added to 150 parts of water and stirred to obtain an aqueous solution. 350 parts of 2-propanol was added and the precipitated solid was separated by filtration to obtain a wet cake. The obtained wet cake was dissolved in 80 parts of water, 150 parts of 2-propanol was added, and the precipitated solid was separated by filtration to obtain a wet cake. The wet cake obtained again was dissolved in 40 parts of water, 100 parts of 2-propanol was added, the precipitated solid was separated by filtration, and dried to obtain compound 4.3 represented by the above formula (36) of the present invention. Part was obtained as a mixed salt of sodium and lithium (λmax: 590 nm, ozone gas resistance test result glossy paper: 99% or more).

[Synthesis Example 9]
In the synthesis example 1 (step 7), instead of using 2.2 parts of the compound represented by the formula (21), the wetness of the compound represented by the formula (26) obtained in the synthesis example 3 (step 4). 5.6 parts of a compound represented by the following formula (37) of the present invention was obtained as a sodium salt in the same manner except that 7.2 parts of cake was used. In the obtained dye, the methoxy group in the following formula (37) is at the position b, the substitution position of the sulfo group is a, c or d, or the methoxy group is at the position c, It was a mixed dye composed of 2 to 6 compounds whose substitution positions were a, b or d.

[Synthesis Example 10]
In the synthesis example 7, instead of using 6.0 parts of the sodium salt of the compound represented by the formula (36), the sodium salt 5.6 of the compound represented by the formula (37) obtained in the synthesis example 9 is used. 4.0 parts of the compound represented by the above formula (37) of the present invention were obtained as a mixed salt of sodium and lithium in the same manner except that parts were used. (Λmax: 597 nm ozone gas resistance test result glossy paper 1: 99% or more).

[(B) Preparation of Black Ink Composition]
[Examples 1 to 3]
The black ink composition of the present invention was mixed with the components shown in Table 18 below and stirred for about 1 hour until the solid content was dissolved, and 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 was prepared in the combination described in Examples 11 to 14 below.
In Table 18, “Surfinol 104PG50” is a trade name, and 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 4 (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 4 (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 4 (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, as in Examples 1 to 3, dyes for comparative examples were mixed at the composition ratios shown in Table 18, and black ink compositions for comparative examples were prepared in the same manner.

[Comparative Example 1]
Compound synthesized in Synthesis Example 4 (X = 3.5 parts)
Total X = 3.5 parts

[(C) 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, 4 and 5 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: Glossy paper made by EPSON, product name High gloss crispier When printing, 6 levels of gradation with reflection density of 100%, 80%, 60%, 40%, 20%, 10% can be obtained. An image pattern was prepared to obtain a dark black to light black gradation recorded matter, and this was used as a test piece to carry out 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. Among the test methods described below, in the print density evaluation, which is an item to be evaluated using a colorimeter, when measuring the print density (reflection density D value) of a printed material, the portion with the highest D value is used. It was. Similarly, when the reflectance in the near-infrared region was evaluated using a spectrophotometer, the measurement was performed using the gradation portion having the highest D value of the printed matter.

[(D) 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.

×：△Ｅ＞０．４
△：０．４≧△Ｅ＞０．３
○：△Ｅ≦０．３

×: ΔE> 0.4
Δ: 0.4 ≧ ΔE> 0.3
○: ΔE ≦ 0.3

×：△Ｅ＞６．０
△：６．０≧△Ｅ＞４．０
○：△Ｅ≦４．０

×: ΔE> 6.0
Δ: 6.0 ≧ ΔE> 4.0
○: ΔE ≦ 4.0

×：△Ｅ＞９．０
△：９．０≧△Ｅ＞５．０
○：△Ｅ≦５．０

×: ΔE> 9.0
Δ: 9.0 ≧ ΔE> 5.0
○: ΔE ≦ 5.0

×：△Ｅ＞１３．０
△：１３．０≧△Ｅ＞１０．０
○：△Ｅ≦１０．０
［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△Ｅを算出し比較した。
以下に結果と判断基準を示す。

×: ΔE> 13.0
Δ: 13.0 ≧ ΔE> 10.0
○: ΔE ≦ 10.0
[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 and compared similarly to said evaluation 1).
The results and criteria are shown below.

×：△Ｅ＞１２．０
△：１２．０≧△Ｅ＞９．０
○：△Ｅ≦９．０

×: ΔE> 12.0
Δ: 12.0 ≧ ΔE> 9.0
○: ΔE ≦ 9.0

×：△Ｅ＞８０．０
△：８０．０≧△Ｅ＞５５．０
○：△Ｅ≦５５．０

×: ΔE> 80.0
Δ: 80.0 ≧ ΔE> 55.0
○: ΔE ≦ 55.0

  From Tables 19 to 24, it can be seen that the water-based black ink composition of the present invention is superior in light source color rendering and media color rendering as 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 (13)

(I) As a pigment component, (i) C.I. I. Acid Black 2 and (ii) In the ozone gas resistance test under the conditions of ozone concentration 40 ppm, humidity 60% RH, temperature 24 ° C., it contains a dye having a dye residual ratio of 90% or more after 8 hours An aqueous black ink composition. The aqueous black ink composition according to claim 1, wherein the dye (ii) is a dye having four or more azo bonds (-N = N-) in the molecule. The aqueous black ink composition according to claim 1 or 2, wherein the dye (ii) is a black dye represented by the following formula (1) or a salt thereof.

[In Formula (1),
R ¹ represents a (C1-C4) alkyl group; a (C1-C4) alkyl group substituted with a carboxy group; a phenyl group; a phenyl group substituted with a sulfo group; or a carboxy group;
R ² represents a cyano group; a carbamoyl group; or a carboxy group;
R ³ and R ⁴ each independently represent a hydrogen atom; a (C1-C4) alkyl group; a halogen atom; a (C1-C4) alkoxy group; or a sulfo group;
R ⁵ represents a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxyl group;
R ⁶ represents a (C1-C4) alkylcarbonylamino group;
R ⁷ represents a (C1-C4) alkylthio group; a (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxyl group;
R ⁸ represents a (C1-C4) alkylcarbonylamino group;
R ⁹ and R ¹⁰ are each independently a hydrogen atom; a carboxy group; a sulfo group; an acetylamino group; a chlorine atom; a (C1-C4) alkyl group; a (C1-C4) alkoxy group; a hydroxy group; (C4) represents a (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of an alkoxy group, a sulfo group and a carboxyl group.
R ¹¹ to R ¹³ each independently represent a hydrogen atom; a carboxy group; a sulfo group; a hydroxy group; an acetylamino group; a chlorine atom; a cyano group; a nitro group; a sulfamoyl group; (C1-C4) alkyl group; (C4) alkoxy group; (C1-C4) alkoxy group substituted with at least one group selected from the group consisting of hydroxy group, (C1-C4) alkoxy group, sulfo group and carboxy group; (C1-C4) An alkylsulfonyl group; a (C1-C4) alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group. ]. The dye (ii) is in the above formula (1),
R ¹ is a methyl group; or a phenyl group;
R ² is a cyano group; or a carbamoyl group;
R ³ is a hydrogen atom; a methyl group; or a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is substituted by a sulfo group or a carboxy group (C1 -C4) alkylthio groups;,
R ⁶ is a (C1-C4) alkylcarbonylamino group;
R ⁷ is substituted by a sulfo group or a carboxy group (C1 -C4) alkylthio groups;,
R ⁸ is a (C1-C4) alkylcarbonylamino group;
R ⁹ is a sulfo (C1-C4) alkoxy group;
R ¹⁰ is a (C1-C4) alkyl group; or an acetylamino group;
R ¹¹ to R ¹³ are each independently a hydrogen atom; a carboxy group; a sulfo group; a chlorine atom; a nitro group; a methyl group; a methoxy group; a sulfamoyl group; a (C1-C4) alkyl substituted with a sulfo group or a carboxy group The water-based black ink composition according to claim 3, which is a sulfonyl group. In the formula (1), the dye (ii) is
R ¹ is a methyl group;
R ² is a cyano group; or a carbamoyl group;
R ³ is a hydrogen atom; a methyl group; or a methoxy group;
R ⁴ is a sulfo group;
R ⁵ is a sulfo (C1-C4) alkylthio group;
R ⁶ is a (C1-C4) alkylcarbonylamino group;
R ⁷ is a sulfo (C1-C4) alkylthio group;
R ⁸ is a (C1-C4) alkylcarbonylamino group;
R ⁹ is a sulfo (C1-C4) alkoxy group;
R ¹⁰ is a (C1-C4) alkyl group; or an acetylamino group;
The aqueous black ink composition according to claim 3, wherein R ¹¹ to R ¹³ are each independently a hydrogen atom; a carboxy group; a sulfo group; a chlorine atom; a nitro group; a methyl group; a methoxy group; (I) The aqueous black ink composition according to any one of claims 1 to 5, comprising 10 to 90% by mass of the dye (i) and 10 to 90% by mass of the dye (ii) in the total mass of the pigment component. The aqueous black ink composition according to any one of claims 1 to 6, further comprising (II) a water-soluble organic solvent. The aqueous black ink composition according to any one of claims 1 to 7, further comprising (III) urea. The aqueous black ink composition according to any one of claims 1 to 8, which is used for ink jet recording. An ink jet recording method using the water-based black ink composition according to claim 1. The inkjet recording method according to claim 10, wherein the recording material in the inkjet recording method is an information transmission sheet. The inkjet recording method according to claim 11, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance. An ink jet printer loaded with a container containing the aqueous black ink composition according to claim 1.