JP2005068416A - Aqueous black ink composition and colored material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an aqueous ink composition capable of being used for inkjet recording and writing goods, having such a black color as to be neutral in color tones and high in print density, excellent in resistance to ozone gas, light resistance, moisture resistance, and color rendering properties, and having good storage stability as a recording liquid. <P>SOLUTION: This aqueous ink composition contains a water-soluble black dye (A) having ozone resistance and a condensation compound (B) of 4,4'-dinitrostilbene-2,2'-disulfonic acid or its salt with aminobenzenes, and/or its reductnat (C). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an aqueous black ink composition for an ink jet printer and a colored body thereby.

A recording method using an ink jet printer, which is one of the representative methods among various color recording methods, generates ink droplets and attaches them to various recording materials (paper, film, fabric, etc.) for recording. Is what you do. This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material do not contact each other and is quiet with little sound generation, and is easy to downsize and speed up. Expected. Conventionally, water-based inks in which water-soluble dyes are dissolved in an aqueous medium have been used as inks such as fountain pens, felt-tip pens, and ink-jet recording inks. In order to prevent clogging of ink, a water-soluble organic solvent is generally added. Therefore, in these conventional inks, it is possible to provide a recording image having a sufficient density, no clogging of the pen tip and nozzles, good drying on the recording material, less bleeding, It is required to have excellent storage stability, and the bronzing phenomenon is unlikely to occur in a printed image. Therefore, water-soluble dyes have particularly high solubility in water, and solubility in water-soluble organic solvents added to ink. High is required. Further, the formed image is required to have image fastness such as water resistance, light resistance, ozone resistance and moisture resistance.

Here, the bronzing phenomenon refers to the ease of occurrence of a glare phenomenon in which the dye becomes a piece of metal on the surface of the glossy paper due to the association of the dyes or poor ink absorption, and is also referred to as a bronzing phenomenon. When the bronze phenomenon occurs, the gloss, print quality, and print density are all inferior to those without the bronze phenomenon.

Ozone resistance is also called oxidation-resistant gas resistance or simply gas resistance. This is because ozone gas with an oxidizing action that exists in the air reacts with dyes in the recording paper and prints the printed image. It is resistance to the phenomenon of fading. In addition to ozone gas, NOx, SOx, and the like can be cited as an oxidizing gas having this type of action. Among these oxidizing gases, ozone gas is considered to be a causative substance that further promotes the discoloration and discoloration phenomenon of inkjet recorded images. In addition, ozone gas is used in an accelerated test for knowing the degree of oxidation resistance gas resistance. Such discoloration and fading due to an oxidizing gas such as ozone gas is characteristic of ink-jet images, and so improvement of ozone resistance (oxidation gas resistance and gas resistance) has become a more important issue. . In particular, the ink receiving layer provided on the surface of photographic image quality inkjet paper uses a porous material such as a white inorganic pigment to speed up ink drying and reduce bleeding at high image quality. In many cases, discoloration due to ozone gas is noticeable on such recording paper.

Furthermore, moisture resistance refers to resistance to a phenomenon that a dye pigment in a recording material bleeds when the colored recording material is stored in a high humidity atmosphere. If there is a blur of the dye pigment, the image quality is remarkably deteriorated particularly in an image that requires a high-definition image quality such as a photographic tone. Therefore, it is important to reduce such a blur as much as possible. Therefore, moisture resistance is also an important issue required as an ink-jet pigment, as with the aforementioned ozone resistance.

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 bodies colored thereby will be further improved in water resistance, light resistance, moisture resistance and ozone gas resistance. There is a strong demand for improvement.

Ink of various hues is prepared from various dyes, and black ink among them is an important ink used not only for printing character information but also for color images. However, there are many technical difficulties in developing pigments that exhibit a good black color with a neutral hue and high color density in both the dark and light color gamuts, and a small hue dependency on the light source. However, there are few that still have sufficient performance. Therefore, generally, a plurality of various pigments are mixed to form a black ink. When ink is prepared by mixing multiple dyes, the hue differs depending on the medium (recording material) compared to the case where ink is prepared with a single dye, and the discoloration is particularly large due to the decomposition of the dye by light or ozone gas. Problems are likely to occur.

As black inks in which yellow to orange dyes are further blended with black dyes, for example, those disclosed in Patent Documents 1 to 5 have been proposed, but have not yet been provided with products that sufficiently satisfy market demands.
Non-Patent Documents 1 and 2 describe the condensation dyes of 4,4′-dinitrostilbene-2,2′-disulfonic acid and aminobenzenes used in the present invention and the dyes obtained by the reduction thereof. .

Japanese Examined Patent Publication No. 7-122044 Japanese Patent No. 3178200 JP-A-9-255906 JP 60-49069 A JP 58-213069 A Kenzo Konishi, Nobuhiko Kuroki “Chemistry of Synthetic Dyes” Tatsumi Shoten March 15, 1965 143-145, 187-188 Hosoda Yutaka "Theoretical Manufacturing Dye Chemistry" Gihodo Co., Ltd. October 1, 1963 190-193

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, has a high density of images subjected to printing, has no change in hue for each medium, and An object of the present invention is to provide a black ink composition that gives a black recorded image excellent in moisture resistance, light resistance, and ozone gas resistance.

（式（３）中、Ａ及びＢはそれぞれ独立に置換されていても良いフェニル基、ナフチル基を表し、且つ、Ａ及びＢはそれぞれ少なくとも１つ以上のスルホ基を有する。ａ及びｂはそれぞれ単結合を表し、結合ａの結合位置は２位又は３位であり、結合ｂの結合位置は６位又は７位である。Ｘ、Ｙの一方はヒドロキシル基を、他方はアミノ基を表し、ｌは１又は２を表し、ｍ及びｎはそれぞれ独立に０又は１を表す。式（３）で表される分子が有する分子内に含まれるスルホ基、カルボキシル基の対イオンは水素イオン、アルカリ金属イオン、有機アミンのカチオン又はアンモニウムイオンである。）
で表されるアゾ染料及び下記式（４）

（式（４）中、Ｒ₆からＲ₁₁は置換基を示し、ｃ及びｄはそれぞれ単結合を示し、結合ｃの位置は１０または１１位、ｄの位置は１４または１５位、ｏ及びｐは０または１であり、ｑは１または２である。式（４）で表される分子が有するスルホ基、カルボキシル基の対イオンは水素イオン、アルカリ金属イオン、有機アミンのカチオン又はアンモニウムイオンである。）
で表されるアゾ染料からなる群から選ばれる少なくとも１種を含む染料である、（１）から（４）のいずれか一項に記載の水性黒色インク組成物、
（６）一般式（３）において、Ａ及びＢの置換基が、ハロゲン原子；ヒドロキシル基；アミノ基；カルボキシル基；スルホ基；ニトロ基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基；アシル基；フェニル基；ウレイド基；ヒドロキシル基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基若しくはカルボキシル基で置換されている（Ｃ１〜Ｃ４）アルキル基；ヒドロキシル基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基若しくはカルボキシル基で置換されている（Ｃ１〜Ｃ４）アルコキシ基；フェニル基、（Ｃ１〜Ｃ４）アルキル基若しくはアシル基によって置換されているアミノ基（これらのアミノ基上の置換基は更にカルボキシル基又はスルホ基で置換されていても良い）であり、
式（４）において、Ｒ₆からＲ₈が水素原子；ハロゲン原子；シアノ基；ヒドロキシル基；アミノ基；カルボキシル基；スルホ基；（Ｃ１〜Ｃ４）アルキル基若しくはフェニル基で置換されても良いスルファモイル基；ホスホ基；ニトロ基；アシル基；フェニル基；ウレイド基；ヒドロキシル基若しくは（Ｃ１〜Ｃ４）アルコキシ基で置換されても良い（Ｃ１〜Ｃ４）アルキル基；ヒドロキシル基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基若しくはカルボキシル基で置換されても良い（Ｃ１〜Ｃ４）アルコキシ基；フェニル基によって置換されているアミノ基（フェニル基はカルボキシル基若しくはスルホ基で更に置換されていてもよい）；アルキル基若しくはアシル基によって置換されているアミノ基であり、Ｒ₉が水素原子；ヒドロキシル基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基若しくはカルボキシル基で置換されても良い（Ｃ１〜Ｃ４）アルキル基；アミノ基、アルキル基、アルコキシ基、カルボキシル基又はスルホ基で置換されていても良いフェニル基であり、Ｒ₁₀及びＲ₁₁が水素原子；スルホ基；アセチルアミノ基；ヒドロキシル基若しくは（Ｃ１〜Ｃ４）アルコキシ基で置換されても良い（Ｃ１〜Ｃ４）アルキル基；ヒドロキシル基、（Ｃ１〜Ｃ４）アルコキシ基、スルホ基若しくはカルボキシル基で置換されても良い（Ｃ１〜Ｃ４）アルコキシ基である（５）に記載の水性黒色インク組成物、
（７）水溶性黒色用染料（Ａ）として、（５）に記載の式（３）で表されるアゾ化合物と式（４）で表されるアゾ化合物を含有する（５）又は（６）に記載の水性黒色インク組成物、
（８）（５）に記載の式（３）で表されるアゾ化合物と式（４）で表されるアゾ化合物の使用割合が、両者の総量に対し、式（３）で表されるアゾ化合物１０−８０質量％、式（４）で表されるアゾ化合物２０−９０質量％である（５）から（７）のいずれか一項に記載の水性黒色インク組成物、
（９）４，４'−ジニトロスチルベン−２，２'−ジスルホン酸若しくはその塩とアミノベンゼン類との縮合化合物におけるアミノベンゼン類が、下記式（２）

（式（２）中、Ｒ₁からＲ₅はそれぞれ独立に水素原子；ハロゲン原子；ヒドロキシル基；スルホ基；カルボキシル基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基を示す）
で表されるアゾ化合物である（１）から（８）のいずれか一項に記載の水性黒色インク組成物、
（１０）（１）から（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（１０）に記載のインクジェット記録方法、
（１２）情報伝達用シートが白色無機顔料を含有するシートである（１１）に記載のインクジェット記録方法、
（１３）（１）から（９）のいずれか一項に記載の水性黒色インク組成物を使用したインクジェットプリンタ、
（１４）（１３）に記載のインクジェットプリンタによって着色された着色体、
（１５）染料成分として、水中で５５０ｎｍから７００ｎｍの範囲に最大吸収波長を有する水溶性染料（Ａ）の少なくとも１種類以上と、下記式（１）の４，４'−ジニトロスチルベン−２，２'−ジスルホン酸

（式（１）中、Ｍは水素原子、アルカリ金属原子を示す。）
と、下記式（２）

（式（２）中、Ｒ₁からＲ₅はそれぞれ独立に水素原子；ハロゲン原子；ヒドロキシル基；スルホ基；カルボキシル基；（Ｃ１〜Ｃ４）アルキル基；（Ｃ１〜Ｃ４）アルコキシ基を示す）
で表される化合物との縮合染料（Ｂ）、（Ｂ）の還元によって得られる染料（Ｃ）（ここで、縮合後又は還元後の染料の対イオンは水素イオン、アルカリ金属イオン、有機アミンのカチオン、アンモニウムイオンである。）の少なくとも１種類以上を含むことを特徴とする水性インク組成物、
に関する。 As a result of intensive studies to solve the problems as described above, the present inventors have reached the present invention. That is, the present invention
(1) A water-soluble black dye (A) having ozone resistance and a condensation compound (B) of 4,4′-dinitrostilbene-2,2′-disulfonic acid or a salt thereof and aminobenzenes and / or An aqueous black ink composition containing the reductant (C);
(2) Condensation compound (B) of water-soluble black dye (A), 4,4′-dinitrostilbene-2,2′-disulfonic acid or a salt thereof and aminobenzene or a reduced form thereof (C) The blending ratio is 50-99.9% by mass of the water-soluble black dye (A) based on the total amount of (A) and (B) or (C), and the condensed compound (B) or its reduced form ( The aqueous black ink composition according to (1), wherein C) is 0.1 to 50% by mass,
(3) The aqueous black ink composition according to (1) or (2), wherein the water-soluble black dye (A) has a maximum absorption wavelength in the range of 550 nm to 700 nm in water,
(4) The water-soluble black dye (A) is a dye containing at least one water-soluble azo dye having 5 or more sulfo groups and 4 or more azo groups in one molecule, from (1) The water-based black ink composition according to any one of (3),
(5) The water-soluble black dye (A) is represented by the following general formula (3)

(In Formula (3), A and B each independently represent a phenyl group or a naphthyl group, and A and B each have at least one sulfo group. Represents a single bond, the bond position of bond a is 2-position or 3-position, the bond position of bond b is 6-position or 7-position, one of X and Y represents a hydroxyl group, the other represents an amino group, l represents 1 or 2, and m and n each independently represents 0 or 1. The sulfo group and carboxyl group counter ion contained in the molecule represented by the formula (3) are a hydrogen ion, an alkali Metal ions, organic amine cations or ammonium ions.)
An azo dye represented by the following formula (4)

(In the formula (4), R ₆ to R ₁₁ represent substituents, c and d each represent a single bond, the position of the bond c is the 10 or 11 position, the position of d is the 14 or 15 position, o and p Is 0 or 1, and q is 1 or 2. The counter ion of the sulfo group and carboxyl group of the molecule represented by formula (4) is a hydrogen ion, an alkali metal ion, a cation of an organic amine, or an ammonium ion. is there.)
The aqueous black ink composition according to any one of (1) to (4), which is a dye containing at least one selected from the group consisting of azo dyes represented by:
(6) In the general formula (3), the substituents of A and B are halogen atom; hydroxyl group; amino group; carboxyl group; sulfo group; nitro group; (C1-C4) alkyl group; Group; acyl group; phenyl group; ureido group; hydroxyl group, (C1-C4) alkoxy group, (C1-C4) alkyl group substituted by sulfo group or carboxyl group; hydroxyl group, (C1-C4) alkoxy group , (C1-C4) alkoxy groups substituted by sulfo groups or carboxyl groups; amino groups substituted by phenyl groups, (C1-C4) alkyl groups or acyl groups (substituents on these amino groups are further Which may be substituted with a carboxyl group or a sulfo group),
In formula (4), R ₆ to R ₈ are a hydrogen atom; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a sulfo group; and a (C1-C4) alkyl group or a phenyl group. Phospho group; nitro group; acyl group; phenyl group; ureido group; hydroxyl group or (C1-C4) alkyl group optionally substituted with (C1-C4) alkoxy group; hydroxyl group, (C1-C4) alkoxy An alkoxy group optionally substituted by a group, a sulfo group or a carboxyl group; an amino group substituted by a phenyl group (the phenyl group may be further substituted by a carboxyl group or a sulfo group); alkyl an amino group substituted by a group or an acyl group, R ₉ is a hydrogen atom; a hydroxyl , (C1-C4) alkoxy group, sulfo group or carboxyl group which may be substituted with (C1-C4) alkyl group; phenyl optionally substituted with amino group, alkyl group, alkoxy group, carboxyl group or sulfo group R ₁₀ and R ₁₁ are a hydrogen atom; a sulfo group; an acetylamino group; a hydroxyl group or a (C1-C4) alkyl group optionally substituted with a (C1-C4) alkoxy group; a hydroxyl group, (C1- C4) The aqueous black ink composition according to (5), which is an (C1-C4) alkoxy group which may be substituted with an alkoxy group, a sulfo group or a carboxyl group,
(7) The water-soluble dye for black (A) contains the azo compound represented by the formula (3) described in (5) and the azo compound represented by the formula (4) (5) or (6) An aqueous black ink composition as described in
(8) The ratio of the azo compound represented by formula (3) described in (5) and the azo compound represented by formula (4) is azo represented by formula (3) with respect to the total amount of both. The water-based black ink composition according to any one of (5) to (7), wherein the compound is 10-80% by mass and the azo compound represented by the formula (4) is 20-90% by mass,
(9) Aminobenzenes in a condensation compound of 4,4′-dinitrostilbene-2,2′-disulfonic acid or a salt thereof and aminobenzenes are represented by the following formula (2):

(In formula (2), R ₁ to R ₅ each independently represent a hydrogen atom; a halogen atom; a hydroxyl group; a sulfo group; a carboxyl group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group)
The water-based black ink composition according to any one of (1) to (8), which is an azo compound represented by:
(10) An inkjet recording method using the water-based black ink composition according to any one of (1) to (9),
(11) The inkjet recording method according to (10), 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 containing a white inorganic pigment,
(13) An inkjet printer using the aqueous black ink composition according to any one of (1) to (9),
(14) A colored body colored by the ink jet printer according to (13),
(15) As a dye component, at least one kind of water-soluble dye (A) having a maximum absorption wavelength in the range of 550 nm to 700 nm in water, and 4,4′-dinitrostilbene-2,2 of the following formula (1) '-Disulfonic acid

(In formula (1), M represents a hydrogen atom or an alkali metal atom.)
And the following formula (2)

(In formula (2), R ₁ to R ₅ each independently represent a hydrogen atom; a halogen atom; a hydroxyl group; a sulfo group; a carboxyl group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group)
The dye (C) obtained by the reduction of the condensation dye (B) and (B) with the compound represented by the formula (wherein the counterion of the dye after the condensation or reduction is a hydrogen ion, an alkali metal ion or an organic amine) An aqueous ink composition comprising at least one of cation and ammonium ion),
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. The water-based black ink composition of the present invention is used for ink jet recording and writing instruments. When recorded on plain paper and ink jet exclusive paper, the hue of the recorded image is neutral, the printing density is high, and ozone gas resistance Excellent in light resistance, light resistance, moisture resistance and color rendering. By using it together with magenta, cyan and yellow dyes, full-color ink jet recording excellent in light resistance and water resistance is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet recording.

Hereinafter, the present invention will be described in detail.
The ozone-resistant water-soluble black dye (A) used in the present invention is a recording image colored with an ink containing the same, the bronzing phenomenon does not occur, and gloss and print quality are good. This is a black dye having good ozone resistance of the recorded image. When the ozone resistance test of the recorded image was performed by the method shown in Examples below, the color difference after the test was less than 15, and the residual ratio of the dye. Is 80% or more. Furthermore, the water-soluble black dye (A) preferably has a maximum absorption wavelength in the range of 550 to 700 nm in the visible light region in water, preferably an azo dye represented by the general formula (3) and a general dye A dye containing at least one selected from the group consisting of azo dyes represented by formula (4) is used.

As aminobenzenes that can be used to obtain a condensed compound (B) of 4,4′-dinitrostilbene-2,2′-disulfonic acid or a salt thereof and aminobenzenes and / or a reduced form (C) thereof, For example, an azo compound represented by the general formula (2) can be given.
In R ₁ to R ₅ in the general formula (2), examples of the (C1-C4) alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. Can be mentioned. Examples of the (C1-C4) alkoxy group include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.

Examples of preferable R ₁ to R ₅ in the general formula (2) are hydrogen, hydroxyl, sulfo, carboxyl, methyl, ethyl, methoxy, ethoxy, more preferably hydrogen, hydroxyl, sulfo, carboxyl, methyl, methoxy. .

In the general formula (3), A and B each independently represent a phenyl group or a naphthyl group which may be substituted, and each component contains at least one sulfo group. These may be further substituted or unsubstituted. In the examples of the substituent for substituting A and B, examples of the (C1 to C4) alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl and the like. It is done.
Examples of (C1-C4) alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy and the like.
Examples of acyl groups include acetyl and benzoyl.

Examples of (C1-C4) alkyl groups substituted by hydroxyl, (C1-C4) alkoxy, sulfo or carboxyl groups include 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, methoxyethyl 2-ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, methoxypropyl, ethoxypropyl, n-propoxypropyl, isopropoxybutyl, n-propoxybutyl, sulfomethyl, sulfoethyl, 2-sulfopropyl, 3 -Sulfopropyl, sulfo-n-butyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxy-n-butyl and the like.

Examples of (C1-C4) alkoxy groups substituted with a hydroxyl group, a (C1-C4) alkoxy group, a sulfo group or a carboxyl group include 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy, 2- Methoxyethoxy, 2-ethoxyethoxy, 2-n-propoxyethoxy, 2-isopropoxyethoxy, 2-n-butoxyethoxy, 3-methoxypropoxy, 3-ethoxypropoxy, 3-n-propoxypropoxy, 4-isopropoxybutoxy 4-n-propoxybutoxy, sulfomethoxy, 2-sulfoethoxy, 2-sulfopropoxy, 3-sulfopropoxy, 4-sulfo-n-butoxy, carboxymethoxy, 2-carboxyethoxy, 3-carboxypropoxy, 4-carboxy -N-but Shea, and the like.

Examples of the amino group substituted by a phenyl group, a (C1-C4) alkyl group, or an acyl group, which may be further substituted with a carboxy group or a sulfo group, include phenylamino, carboxyphenylamino, dicarboxylphenyl Amino, sulfophenylamino, disulfophenylamino, carboxyethylamino, carboxypropylamino, carboxy-n-butylamino, sulfoethylamino, 2-sulfopropylamino, 3-sulfopropylamino, sulfo-n-butylamino, acetyl Examples include amino and benzoylamino groups.

Preferred substituents for A and B in the general formula (3) are sulfo; carboxyl; (C1-C4) acylamino such as acetylamino; hydroxyl; nitro; halogen atom such as chlorine; (C1-C4) alkyl such as methyl; (C1-C4) alkoxy such as methoxy; sulfo (C1-C4) alkoxy such as 3-sulfopropoxy; phenylamino; sulfophenylamino; mono- or dicarboxyphenylamino. More preferred are sulfo, carboxyl, methyl, methoxy, 3-sulfopropoxy, hydroxyl and acetylamino.

Preferred A in the general formula (3) is phenyl having at least one sulfonic acid group directly or as a sulfo (C1-C4) alkoxy group at the ortho position or the meta position, more preferably at the ortho position with respect to the azo group. A naphthyl group having 1 to 3 groups or sulfonic acid groups, and more preferably the phenyl group. In the case of the phenyl group, it may further have 1 to 2 groups, more preferably 1 group, as preferred substituents for A and B. When the phenyl group has two substituents including a sulfonic acid group, 2-position and 4-position, 2-position and 5-position, or 3-position and 4-position on the phenyl group are preferable.
As preferable B of General formula (3), the same group as said preferable A can be mentioned independently of A.

Preferred compounds of general formula (3) have the preferred A and B above, m and n are each independently 0 or 1, l is 1 or 2, more preferably 2, and bond a is in position 2. Alternatively, a compound in which the 3-position, the bond b is in the 6-position or the 7-position, and one of X and Y is a hydroxyl group and the other is an amino group can be exemplified.

Examples of the substituent represented by R ₆ to R ₁₁ in the general formula (4) include the following groups.
R ₆ to R ₈ are each independently a hydrogen atom; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a sulfo group; a (C1-C4) alkyl group or a sulfamoyl group that may be substituted with a phenyl group. Phospho group; nitro group; acyl group; phenyl group; ureido group; hydroxyl group or (C1-C4) alkyl group optionally substituted with (C1-C4) alkoxy group; hydroxyl group, (C1-C4) alkoxy group An alkoxy group which may be substituted with a sulfo group or a carboxyl group (C1-C4); a phenyl-substituted amino group (the phenyl group may be substituted with a carboxyl group or a sulfo group); an alkyl group or an acyl group An amino group that is present.
R ₉ is a hydrogen atom; a hydroxyl group, a (C 1 -C 4) alkoxy group, a sulfo group or a carboxyl group (C 1 -C 4) alkyl group; an amino group, an alkyl group, an alkoxy group, a carboxyl group or a sulfo group And a phenyl group which may be substituted with a group.
R ₁₀ and R ₁₁ are each a hydrogen atom; a sulfo group; an acetylamino group; a hydroxyl group or a (C1-C4) alkyl group optionally substituted with a (C1-C4) alkoxy group; a hydroxyl group, (C1-C4) alkoxy (C1-C4) alkoxy group which may be substituted with a group, a sulfo group or a carboxyl group.

Examples of the sulfamoyl group which may be substituted with an alkyl group or a phenyl group in R ₆ to R ₈ include sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N- (n-butyl) sulfamoyl, N, N-dimethylsulfamoyl, N, N-di (n-propyl) sulfamoyl, N-phenylsulfamoyl and the like are preferable, and sulfamoyl is preferable.

Examples of the (C1-C4) alkyl group which may be substituted with a hydroxyl group or a (C1-C4) alkoxy group in R ₆ to R ₈ , R ₁₀ and R ₁₁ in the general formula (4) include methyl, ethyl , N-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n- Examples include propoxyethyl, 2-isopropoxyethyl, 2-n-butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n-propoxypropyl, 4-isopropoxybutyl, 4-n-propoxybutyl and the like.

Examples of (C1 to C4) alkoxy group which may be substituted with a hydroxyl group, (C1 to C4) alkoxy group, sulfo group or carboxyl group in R ₆ to R ₈ , R ₁₀ and R ₁₁ in formula (4) As methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy, 2-methoxyethoxy, 2-ethoxyethoxy 2-n-propoxyethoxy, 2-isopropoxyethoxy, 2-n-butoxyethoxy, 3-methoxypropoxy, 3-ethoxypropoxy, 3-n-propoxypropoxy, 4-isopropoxybutoxy, 4-n-propoxybutoxy , 2- (2-hydroxyethoxy) ethoxy Carboxymethoxy, 2-carboxyethoxy, 3-carboxypropoxy, 3-sulfopropoxy, 4-sulfobutoxy and the like.

Examples of the (C1-C4) alkyl group which may be substituted with a hydroxyl group, a (C1-C4) alkoxy group, a sulfo group or a carboxyl group in R ₉ in the general formula (4) include methyl, ethyl, n- Propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 2-n-propoxyethyl, 2-isopropoxyethyl, 2-n-butoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-n-propoxypropyl, 4-isopropoxybutyl, 4-n-propoxybutyl, 2- (2-hydroxyethoxy ) Ethyl, carboxymethyl, 2-carboxyethyl, 3-carboxy Propyl, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl and the like.
Examples of the phenyl group which may be substituted with an amino group, an alkyl group, an alkoxy group, a carboxyl group or a sulfo group in R ₉ include phenyl, methylphenyl, methoxyphenyl, aminophenyl, sulfophenyl, sulfamoylphenyl. , Methylsulfonylphenyl, methoxysulfonylphenyl, bissulfophenyl, carboxyphenyl, biscarboxyphenyl and the like.

Examples of the amino group substituted with a phenyl group in R ₆ to R ₈ in the general formula (4) (the phenyl group may be further substituted with a carboxyl group or a sulfo group) include phenylamino, sulfophenyl Amino, bissulfophenylamino, carboxyphenylamino, biscarboxyphenylamino and the like can be mentioned. Examples of amino groups substituted by alkyl groups or acyl groups include methylamino, ethylamino, n-propylamino, isopropylamino, n-butylamino, isobutylamino, N, N-dimethylamino, N, N- Examples include diethylamino, N, N-di (n-propyl) amino, N, N-di (isopropyl) amino, N-ethyl-N-methylamino, acetylamino, propionylamino, butyrylamino, benzoylamino and the like.

Preferred R ₆ to R ₈ in the general formula (4) are hydrogen, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 2-ethoxyethoxy, 3-sulfopropoxy, 4- Sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, chlorine, bromine, cyano, nitro, acetyl, benzoyl, carboxy, sulfo, sulfamoyl, N-ethylsulfamoyl, phospho, hydroxy, amino, carboxymethylamino, carboxypropylamino, Bis-carboxymethylamino, acetylamino, benzoylamino, ureido, phenylamino, sulfophenylamino, carboxyphenylamino, dicarboxyphenylamino and the like, more preferably hydrogen, methyl, methoxy, Ethoxy, 2-hydroxyethoxy, 3-sulfopropoxy, nitro, carboxy, sulfo, phospho, acetylamino. More preferably, R ₆ to R ₈ are a group selected from the group consisting of a phenyl-substituted amino group in which at least one of these is a sulfo group, a carboxyl group, and a carboxy group or a sulfo group as a substituent, and the remaining groups May be any, but preferably the remaining two groups are each independently selected from the group consisting of hydrogen, (C1-C4) alkylamino, (C1-C4) alkyl, halogen, preferably chloro, hydroxy and sulfamoyl. This is the case when the group is selected. More preferably, R ₆ to R ₈ are one in which one is a sulfo group and the other two are hydrogen.

Preferred R ₉ in the general formula (4) is hydrogen; (C1-C4) alkyl group such as methyl, ethyl or propyl; (C1-C4) alkyl group having any of hydroxy, methoxy or sulfo as a substituent, such as 2 -Hydroxyethyl, 2-methoxyethyl; a phenyl group which may have 1 or 2 groups selected from the group consisting of an amino group, a sulfo group, a (C1-C4) alkoxy group and a carboxyl group as a substituent; For example, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl or carboxymethyl, phenyl, aminosulfophenyl, methoxysulfophenyl, carboxyphenyl, and more preferably hydrogen, methyl, 2-hydroxyethyl, 3-sulfopropyl, Of these, phenyl is particularly preferred. There.

Preferred R ₁₀ and R ₁₁ in the general formula (4) are hydrogen; an unsubstituted (C1-C4) alkyl group or an unsubstituted or substituted group having any of hydroxy, methoxy, sulfo or carboxy (C1-C4). Alkoxy groups such as methyl, methoxy, ethyl, ethoxy, propyl, propoxy, 2-hydroxyethoxy, 2-methoxyethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, sulfo, acetylamino and the like More preferably methyl, methoxy, ethoxy, 2-hydroxyethoxy, 3-sulfopropoxy. Moreover, it is preferable that at least one of R ₁₀ and R ₁₁ is an unsubstituted or (C1-C4) alkoxy group having any of hydroxy, methoxy, sulfo or carboxy as a substituent, and in that case, the other is independently (C1-C4) alkoxy groups having any of hydroxy, methoxy, sulfo or carboxy as substituents, such as 3-sulfopropoxy or 2-hydroxyethoxy, or unsubstituted (C1-C4) alkyl such as methyl groups.

Preferred combinations of the substituents from R ₆ represented by R ₁₁ is, in each section above, a case of combining a group described as the preferred, by combining more preferable for each term, from R ₆ This is a more preferable combination of substituents represented by R ₁₁ .

The counter ion of the condensation dye of the general formula (1) and aminobenzenes and the dye obtained by the reduction thereof is a cation of an organic amine in addition to a hydrogen ion, an alkali metal ion or the like after the condensation or after the subsequent reduction. Alternatively, ammonium ions can be substituted. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the organic amine include methylamine, ethylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.

Examples of the water-soluble black dye (A) having ozone resistance and having a maximum absorption wavelength in the range of 550 nm to 700 nm in water include dyes represented by general formula (3) and general formula (4). .
The counter ions of the dyes represented by the general formulas (3) and (4) are each independently a hydrogen ion, an alkali metal ion, a cation of an organic amine, or an ammonium ion. Examples of the alkali metal include sodium, potassium, lithium and the like. Examples of the organic amine include methylamine, ethylamine, monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.

Preferred counter ions of the dyes represented by the general formulas (3) and (4) are alkali metal ions such as hydrogen ion, sodium ion, potassium ion and lithium ion, ammonium ion, monoethanolamine ion, diethanolamine ion, and triethanol. Examples thereof include alkanolamine ions such as amine ion, monoisopropanolamine ion, diisopropanolamine ion, and triisopropanolamine ion.

The dye compounds represented by the general formula (3) and the general formula (4) having a maximum absorption wavelength in the range of 550 nm to 700 nm in water are both suitable for black dyes. Presents a good black color. However, when the printing density is low, the general formula (3) is slightly bluish and the general formula (4) is slightly purple. To the dye of the general formula (3) and / or the general formula (4) and the dye, the condensed dye (B) of the general formula (1) and the general formula (2) and / or the dye (C) obtained by the reduction thereof. By blending, the hue can be adjusted from neutral gray to black, and the image fastness such as water resistance, light resistance, ozone gas resistance, moisture resistance, etc. possessed by the dyes of general formula (3) and general formula (4) The aqueous black ink composition of the present invention can be obtained which is not impaired and does not lower the printing density.

There are two types of dyes: one type of water-soluble black dye (A) and a condensation dye of 4,4′-dinitrostilbene-2,2′-disulfonic acid and aminobenzenes and / or a dye obtained by reduction thereof. Ink consisting of only a dye exhibits a good black color, but in order to obtain a more neutral black, a neutral gray to black color even when the printing density is low, and a better black color rendering property, it is water soluble. It is preferable to use the general formula (3) and the general formula (4) in combination as the dye (A).

Examples of aminobenzenes used in the present invention include compounds represented by the general formula (2), and preferred examples of the compounds represented by the general formula (2) are not particularly limited. The following structures are mentioned. (In the formulas in the table, sulfo group and carboxyl group are shown in free acid form)

  A condensed dye of 4,4′-dinitrostilbene-2,2′-disulfonic acid and a compound of the general formula (2) and a dye obtained by reduction thereof can be obtained, for example, by the methods described in Non-Patent Document 1 and Non-Patent Document 2. Can be synthesized.

  The condensate (B) of 4,4′-dinitrostilbene-2,2′-disulfonic acid and the compound of the general formula (2) is used with respect to 1 mol of 4,4′-dinitrostilbene-2,2′-disulfonic acid. The compound of the general formula (2) is usually 1 to 2.5 mol, preferably 1.3 to 1.8 mol, usually caustic, preferably sodium hydroxide, usually 85 to 100 ° C., usually 3 Obtained by reacting for ~ 15 hours. Although it is known that the resulting condensate is not a single product, the following structure is considered to be the main component. (Non-patent documents 1 and 2)

As the reducing agent used for the reduction reaction of the condensate (B), sodium sulfide and glucose are preferably used, and 4,4′-dinitrostilbene-2,2′-disulfonic acid 1 used to synthesize the condensate is used. It is usually obtained by reacting at 0.1 to 0.4 mol with respect to mol and usually reacting at 80 to 95 ° C. for 0.5 to 2 hours. Although it is known that the compound (C) obtained by the reduction of (B) is not a single substance, the following structure is considered to be the main component. (Non-patent documents 1 and 2)

The 4,4′-dinitrostilbene-2,2′-disulfonic acid used in the present invention and the condensed dye (B) of the general formula (2) and / or the dye (C) obtained by the reduction thereof are usually subjected to the above reaction. The resulting reaction product is used as a mixture, but the main component may be purified and used. In the ink composition of the present invention, the compound (B) can be used, but usually the reduced form (C) of the condensation compound (B) is more preferable.

Although it does not specifically limit as a suitable example of the azo dye represented by General formula (3) used by this invention, The azo compound shown to the following Tables 3-6 is mentioned. (In the formulas in the table, sulfo group and carboxyl group are shown in free acid form)

Although it does not specifically limit as a suitable example of the azo dye represented by General formula (4) of this invention, The azo dye shown to the following Tables 7-9 is mentioned. (In the formulas in the table, sulfo group and carboxyl group are shown in free acid form)

The azo dye represented by the general formula (3) used in the present invention can be synthesized, for example, by the following method. (Here, the structural formula of the compound in each step is expressed in the form of a free acid)
That is, the general formula (7)

(In formula (7), n has the same meaning as n in formula (3).)
The compound represented by general formula (8) is diazotized by a conventional method.

(In formula (8), l, X, and Y have the same meaning as l, X, and Y in general formula (3).)
And the following general formula (9)

(In the formula (9), l, n, X and Y represent the same meaning as l, n, X and Y in the general formula (3).)
To obtain a compound represented by: In addition to this, a compound represented by the following general formula (10) or (11)

(In Formula (10) and Formula (11), the phenyl group and naphthyl group have the same substituent as A or B in Formula (3).)
Was diazotized, which was converted into the following general formula (12)

(In the formula (12), m has the same meaning as m in the general formula (3).)
By a coupling reaction with a compound represented by the following general formula (13) or (14):

(In the formulas (13) and (14), m has the same meaning as m in the general formula (3).)
To obtain a compound represented by: This compound is further diazotized and subjected to a coupling reaction with the compound represented by the general formula (9) to produce the following general formula (15) or (16)

(In the formulas (15) and (16), m, l, n, X, and Y have the same meaning as in the general formula (3).)
The compound represented by general formula (17) or (18) produced by alkali treatment

(In the formulas (17) and (18), m, l, n, X, and Y have the same meaning as in the general formula (3).)
To obtain a compound represented by: By coupling a diazotized compound of the compound represented by the general formula (10) or (11) to this, the following general formulas (19) and (20) which are tetraazo compounds represented by the general formula (3) ), (21) or (22)

(In the formulas (19) to (22), m, l, and n have the same meaning as in the general formula (3), and the phenyl group or naphthyl group present at both ends is the A in the general formula (3). And have the same substituent as B)
Are obtained respectively. In addition, the compound represented by the general formula (13) or (14) is diazotized and subjected to a coupling reaction with the compound represented by the general formula (8), whereby the general formula (23) or (24)

(In formulas (23) and (24), l, n, X, and Y have the same meaning as in general formula (3).)
Is obtained by coupling a diazotized compound represented by the general formula (13) or (14) to the azo dye represented by the general formula (3). (19), (20), (21) or (22) can be obtained.

The diazotization of the compound represented by the general formula (7) is carried out by a method known per se, for example, a nitrite such as nitrous acid in an inorganic acid medium, for example, at a temperature of -5 to 30 ° C, preferably 0 to 10 ° C. It is carried out using an alkali metal nitrite such as sodium nitrate. Coupling of the diazotized compound of the compound of the general formula (7) and the compound of the general formula (8) is also carried out under conditions known per se. It is advantageous to carry out in an aqueous or aqueous organic medium, for example at a temperature of -5 to 30 ° C., preferably 10 to 25 ° C. and a pH value of weakly acidic to weakly alkaline. Preferably, it is carried out at a weakly acidic to neutral pH value, for example, pH 2-7. The neutralization of the acid generated by the progress of the reaction and the adjustment of the pH value are carried out by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia and organic amines. . The compounds of general formulas (7) and (8) are used in approximately stoichiometric amounts.

The diazotization of the compounds of the general formulas (10), (11) is also carried out in a manner known per se, for example nitrites such as nitrous acid at a temperature of eg -5 to 30 ° C., preferably 0 to 20 ° C. in an inorganic acid medium. It is carried out using an alkali metal nitrite such as sodium nitrate. Coupling of the diazotized compound of the compounds of general formulas (10) and (11) with the compound of general formula (12) is also carried out under conditions known per se. It is advantageous to carry out the reaction in an aqueous or aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 25 ° C and a weakly acidic to alkaline pH value. Preferably, it is carried out at a neutral to alkaline pH value, for example, pH 7-11. The pH value is adjusted by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia and organic amines. . The compounds of general formulas (10), (11) and (12) are used in approximately stoichiometric amounts.

Production of the compound of general formula (17) or (18) by hydrolysis of the compound of general formula (15) or (16) is also carried out by a method known per se. The heating is preferably carried out in an aqueous alkaline medium. For example, sodium hydroxide or potassium hydroxide is added to the reaction solution containing the compound of the general formula (15) or (16) to adjust the pH to 9.5 or more. For example, by heating to a temperature of 20 to 150 ° C., preferably 30 to 100 ° C. At this time, the pH value of the reaction solution is preferably maintained at 9.5 to 11.5. The pH value is adjusted by adding a base. As the base, those described above can be used.

Coupling of the diazotized compounds of the compounds of the general formulas (10) and (11) and the compounds of the general formulas (17) and (18) is also carried out under conditions known per se. It is advantageous to carry out in an aqueous or aqueous organic medium, for example at a temperature of -5 to 30 [deg.] C, preferably 0 to 10 [deg.] C and a pH of weakly acidic to weakly alkaline. Preferably, it is carried out at a weakly acidic to neutral pH value, for example, pH 3-7. The neutralization of the acid generated by the progress of the reaction and the adjustment of the pH value are carried out by adding a base. Examples of bases 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, and ammonia or organic amines. it can. The compounds of general formulas (10), (11) and (17), (18) are used in approximately stoichiometric amounts.

The pentaazo compound represented by the general formula (4) can be synthesized, for example, by the following method. (The description about the substitution position of each substituent is omitted, and the structural formula of the compound in each step is expressed in the form of a free acid.) That is, the following general formula (25)

(In formula (25), p has the same meaning as p in formula (4).)
The compound represented by formula (1) is diazotized by a conventional method and the following compound (26)

(In the formula (26), R ₉ has the same meaning as R ₉ in the general formula (4).)
A general formula (27) produced by a coupling reaction with a compound represented by the formula:

(In the formula (27), p, R ₉ represents the general formula in (4) p, the same meanings as R _9.)
To obtain a compound represented by: Apart from this, the general formula (28)

(Formula (28) in, R _6, R ₇ and R ₈ are as defined R _6, R ₇ and R ₈ in the general formula (4).)
A compound obtained by diazotizing a compound represented by the following general formula (29)

(In formula (29), o has the same meaning as o in general formula (4).)
A coupling reaction with the compound represented by formula (30):

(In the formula (30), o, R ₆ , R ₇ and R ₈ have the same meaning as in the general formula (4).)
To obtain a compound represented by: This was diazotized by a conventional method and the compound represented by the above general formula (27) was coupled to give a general formula (31)

(In the formula (31), o, p, R ₆ , R ₇ , R ₈ and R ₉ have the same meaning as in the general formula (4).)
To obtain a compound represented by: This is hydrolyzed to give the general formula (32)

(In the formula (32), o, p, R ₆ , R ₇ , R ₈ and R ₉ have the same meaning as in the general formula (4).)
To obtain a compound represented by: Apart from this, the general formula (33)

(In formula (33), q has the same meaning as q in formula (4).)
A compound obtained by diazotizing a compound represented by the following general formula (34):

(In formula (34), R ₁₀ and R ₁₁ have the same meaning as R ₁₀ and R ₁₁ in formula (4).)
And a compound represented by the general formula (35):

(In the formula (35), q, R ₁₀ and R ₁₁ have the same meaning as in the general formula (4).)
To obtain a compound represented by: This was diazotized by a conventional method and subjected to a coupling reaction with the compound represented by the general formula (32) to give a general formula (36)

(In the formula (36), o, p, q, R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ and R ₁₁ have the same meaning as in the general formula (4).)
To obtain a compound represented by: By hydrolyzing this, the compound represented by the general formula (4) can be obtained. A compound obtained by diazotizing a compound of the general formula (35) by a conventional method is represented by the following general formula (37).

(In formula (37), p has the same meaning as p in formula (4).)
By coupling to a compound represented by the general formula (38)

(In the formula (38), p, q, R ₁₀ and R ₁₁ have the same meaning as in the general formula (4).)
To obtain a compound represented by: This is hydrolyzed to give the general formula (39)

(In the formula (39), p, q, R ₁₀ and R ₁₁ have the same meaning as in the general formula (4).)
To obtain a compound represented by: This was diazotized by a conventional method and coupled to a compound represented by the following general formula (26) to give a general formula (40)

(In the formula (40), p, q, R ₉ , R ₁₀ and R ₁₁ have the same meaning as in the general formula (4).)
To obtain a compound represented by: The compound represented by the general formula (4) can also be obtained by coupling a compound obtained by diazotizing the compound represented by the general formula (30) by a conventional method.

 The diazotization of the compound of general formula (25) is carried out in a manner known per se, for example of nitrite, for example sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 30 ° C, preferably 5 to 15 ° C. It is carried out using alkali metal nitrite. Coupling of the diazotized product of the compound of general formula (25) and the compound of general formula (26) is also carried out under conditions known per se. It is advantageous to carry out in an aqueous or aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 5 to 20 ° C and an acidic to neutral pH value. Preferably, it is carried out at a weakly acidic to neutral pH value, for example, pH 2-6. The neutralization of the acid generated by the progress of the reaction and the adjustment of the pH value are carried out by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia and organic amines. . The compounds of general formulas (25) and (26) are used in approximately stoichiometric amounts.

The diazotization of the compound of the general formula (28) is also carried out in a manner known per se, for example nitrites such as sodium nitrite at a temperature of eg -5 to 30 ° C., preferably 0 to 15 ° C. in an inorganic acid medium. It is carried out using an alkali metal nitrite salt. Coupling of the diazotized product of the compound of general formula (28) and the compound of general formula (29) is also carried out under conditions known per se. It is advantageous to carry out the reaction in an aqueous or aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 25 ° 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. Examples of bases 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, and ammonia or organic amines. it can. The compounds of general formulas (28) and (29) are used in approximately stoichiometric amounts.

The diazotization of the compound of general formula (30) is also carried out in a manner known per se, for example nitrites such as sodium nitrite in inorganic acid media at temperatures of, for example, -5 to 30 ° C, preferably 5 to 20 ° C. It is carried out using an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of the general formula (30) and the compound of the general formula (27) is also carried out under conditions known per se. It is advantageous to carry out the reaction in an aqueous or aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 25 ° 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 5-10. The neutralization of the acid generated by the progress of the reaction and the adjustment of the pH value are carried out by adding a base. Examples of bases 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, and ammonia or organic amines. it can. The compounds of general formulas (30) and (27) are used in approximately stoichiometric amounts.

Production of the compound of general formula (32) by hydrolysis of the compound of general formula (31) is also carried out by a method known per se. The method is preferably a method of heating in an aqueous alkaline medium. For example, after adding sodium hydroxide or potassium hydroxide to a reaction solution containing the compound of the general formula (31) to adjust the pH to 9.5 or higher, for example, 20 to It is carried out by heating to a temperature of 150 ° C., preferably 30 to 100 ° C. At this time, the pH value of the reaction solution is preferably maintained at 9.5 to 11.5. The pH value is adjusted by adding a base. As the base, those described above can be used.

The diazotization of the compound of the general formula (33) is also carried out in a manner known per se, for example nitrites such as sodium nitrite at a temperature of eg -5 to 30 ° C., preferably 0 to 15 ° C. in an inorganic acid medium. It is carried out using an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of the general formula (33) and the compound of the general formula (34) is also carried out under conditions known per se. It is advantageous to carry out in an aqueous or aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 5 to 20 ° C and an acidic to weakly alkaline pH value. It is preferably carried out at an acidic to neutral pH value, for example, pH 2-6. The neutralization of the acid generated by the progress of the reaction and the adjustment of the pH value are carried out by adding a base. Examples of bases 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, and ammonia or organic amines. it can. The compounds of general formulas (33) and (34) are used in approximately stoichiometric amounts.

The diazotization of the compound of general formula (35) is also 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 5 to 20 ° C. It is carried out using an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of the general formula (35) and the compound of the general formula (32) is also carried out under conditions known per se. It is advantageous to carry out the reaction in an aqueous or aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 10 to 25 ° 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. Examples of bases 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, and ammonia or organic amines. it can. The compounds of general formulas (35) and (32) are used in approximately stoichiometric amounts.

Production of the compound of general formula (4) by hydrolysis of the compound of general formula (36) is also carried out by a method known per se. The method is preferably a method of heating in an aqueous alkaline medium. For example, after adding sodium hydroxide or potassium hydroxide to a reaction solution containing the compound of the general formula (36) to adjust the pH to 9.5 or more, for example, 20 to It is carried out by heating to a temperature of 150 ° C., preferably 30 to 100 ° C. At this time, the pH value of the reaction solution is preferably maintained at 9.5 to 11.5. The pH value is adjusted by adding a base. As the base, those described above can be used.

For example, in the case of a sodium salt, a dye or a salt thereof used in the aqueous black ink composition of the present invention or a salt thereof (hereinafter simply referred to as a compound unless otherwise specified) is obtained by adding sodium chloride to the reaction solution, Sodium salt is obtained by salting out and filtering. Further, a sodium salt is dissolved in water, and an acid is added to precipitate crystals in an acidic manner, followed by filtration to obtain a dye cake in the form of a free acid. Subsequently, the dye compound in the form of the free acid is dissolved or suspended in water, and a base corresponding to the target salt, such as an amine or an alkali metal compound other than sodium, is added and dissolved to obtain a solution of each salt. It is done. From this solution, a salt other than the sodium salt can be obtained by precipitating, filtering, and drying each salt by a conventional method.

Water-soluble black dye (A) (hereinafter also simply referred to as water-soluble dye (A)), 4,4′-dinitrostilbene-2,2′-disulfonic acid or a salt thereof (hereinafter also referred to as DNST), and aminobenzenes The compounding ratio of the condensation compound (B) and / or its reduced form (C) with respect to the total amount of (A) and (B) or (C) is usually from 50% to 99. 9%, preferably 60% to 95%, and the condensation compound (B) and / or its reduced form (C) is usually 0.1-50% by mass, preferably 5% to 40% by mass. .
As the water-soluble dye (A), an azo dye represented by the general formula (3) and / or an azo dye represented by the general formula (4) is preferably used. Either of the ink compositions may be used, but it is usually preferable to use both in combination. When used in combination, the content (mass) of the azo dye represented by the general formula (3) is preferably in the range of 10% to 80% with respect to the total amount (mass) of the water-soluble dye (A). More preferably, it is in the range of% to 70%. The content (mass) of the azo dye represented by the general formula (4) is preferably in the range of 20% to 90% with respect to the total amount (mass) of the water-soluble dye (A), preferably 30% to 80%. It is more preferable that it is in the range. In addition, the ratio of these dye compounds is a ratio in the powder conversion after a desalting process.
Further, the aqueous ink composition may be mixed with other pigments for fine adjustment of the hue.

In the aqueous black ink composition of the present invention, the total amount of these dye compounds is usually from 0.1 to 20% by mass, preferably from 1 to 10% by mass, more preferably from 2 to 8% by mass, based on the entire ink composition. It is a composition containing water as a main solvent. The aqueous black ink composition of the present invention may further contain, for example, 0 to 30% by mass of a water-soluble organic solvent and 0 to 5% by mass of an ink preparation agent, for example. The remainder other than the above is water. The pH of the aqueous black ink composition is preferably pH 5 to 11 and more preferably pH 7 to 10 in terms of improving storage stability. The surface tension of the aqueous black ink composition is preferably 25 to 70 mN / m, and more preferably 25 to 60 mN / m. Furthermore, the viscosity of the aqueous black ink composition is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less.

When the aqueous black ink composition of the present invention is used as an ink for an ink jet printer, it is preferable to prepare an ink composition having a low content of inorganic substances such as metal cation chlorides and sulfates. Therefore, the thing with little content of the inorganic substance in the dye to be used is preferable, and the content is about 0.1 mass% or less (with respect to the whole dye), for example. In order to produce a dye compound with a small amount of inorganic substances, for example, a conventional method using a reverse osmosis membrane or a method of stirring a dried product of a dye compound or a wet cake in a mixed solvent of alcohol such as methanol and water, filtering and drying. Can be desalted with

Examples of water-soluble organic solvents that can be used in the preparation of the aqueous black ink composition of the present invention include C1-C4 alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and tert-butanol, N, Carboxylic acid amides such as N-dimethylformamide or N, N-dimethylacetamide, lactams such as 2-pyrrolidone and N-methylpyrrolidin-2-one, 1,3-dimethylimidazolidin-2-one or 1,3-dimethyl Cyclic ureas such as hexahydropyrimido-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 , 2-Propylene Recall, 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, polypropylene glycol , Monomers having (C2-C6) alkylene units such as thiodiglycol and dithiodiglycol, oligomers or polyalkylene glycols or thioglycols, polyols such as glycerin, hexane-1,2,6-triol (triols), ethylene glycol Monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether or trie Polyhydric alcohol (C1 -C4) alkyl ethers such as glycol monomethyl ether or triethylene glycol monoethyl ether, gamma-butyrolactone or dimethyl sulfoxide and the like. These organic solvents may be used alone or in combination of two or more.

Examples of the ink preparation agent used as necessary in the preparation of the aqueous black ink composition include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust preventive agents, water-soluble ultraviolet absorbers, water-soluble polymer compounds, and dye-dissolving agents. , Antioxidants, surfactants and the like.

Examples of the antiseptic / antifungal agent include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8- Oxyquinoline, benzothiazole, isothiazoline, dithiol, pyridine oxydide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, Examples thereof include brominated indanone compounds, benzyl bromoacetate compounds, and inorganic salt compounds. 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, sodium dehydroacetate, sodium pyridinethione-1-oxide, ethyl p-hydroxybenzoate, and the like. These are preferably used in an aqueous black ink composition in an amount of 0.02 to 1.00% by mass.

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.

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 the anionic surfactant include alkyl sulfonic acid, alkyl carboxylate, α-olefin sulfonate, polyoxyethylene alkyl ether acetate, N-acyl amino acid and its salt, N-acyl methyl taurate, alkyl sulfate polyoxy Alkyl 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, alkylallylsulfone hydrochloride, diethylsulfone Acid salts, dioctyl sulfosuccinate diethyl hexylsilsulfosuccinate 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 Acetylene glycols such as 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol (for example, Surfhinol 104, 105 manufactured by Nisshin Chemical Co., Ltd.) 82, 465, Olfin STG, etc.). These ink preparation agents are used alone or in combination.

The aqueous black ink composition of the present invention can be obtained by mixing and stirring the above components in an arbitrary order. The obtained ink composition may be filtered with a membrane filter or the like in order to remove impurities.

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 preferable to use as Therefore, the inkjet ink of the present invention is preferably used in the inkjet recording method of the present invention 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 an inkjet ink containing the aqueous black ink composition. In the ink jet recording method of the present invention, recording is performed on a recording material using an ink jet ink containing the water-based black ink composition, but there is no particular limitation on the ink nozzles used at that time, It can be appropriately selected according to the purpose.

There is no restriction | limiting in particular as said recording material, For example, a well-known recording material, for example, plain paper, resin coated paper, inkjet exclusive paper, a film, electrophotographic co-paper, cloth, glass, a metal, ceramics etc. are mentioned.

In the inkjet recording method of the present invention, among the recording materials, the following recording papers and recording films called, for example, inkjet exclusive paper, inkjet glossy paper, inkjet exclusive film and the like are particularly preferable.

The recording paper and the recording film are formed by laminating a support and an image receiving layer and, if necessary, laminating other layers such as a back coat layer. Each layer including the image receiving layer may be one layer or two or more layers.

The support is composed of chemical pulp such as LBKP and NBKP, mechanical pulp such as GP, PGW, RMP, TMP, CTMP, CMP, and CGP, and waste paper pulp such as DIP. , Binders, sizing agents, fixing agents, cationic agents, paper strength enhancers, etc., which are added and mixed, and manufactured with various devices such as long net paper machines and circular net paper machines can be used. In addition, synthetic paper, plastic film sheets, and the like may be used.

The thickness of the support is about 10 to 250 μm, and the basis weight is preferably 10 to 250 g / m ² .

The support may be provided with the image receiving layer, may further be provided with the back coat layer, and after providing a size press or anchor coat layer with starch, polyvinyl alcohol or the like, the image receiving layer and The back coat layer may be provided. The support may be flattened by a calendar device such as a machine calendar, a TG calendar, or a soft calendar.

Among the above-mentioned supports, papers laminated on both sides with polyolefin (for example, polyethylene, polystyrene, polyethylene terephthalate, polybutene, and copolymers thereof) and plastic films are preferably used.

The image-receiving layer may contain a pigment, an aqueous binder, a mordant, a water resistance agent, a light resistance improver, a surfactant, and other additives.

The pigment is preferably a white pigment, and examples of the white pigment include calcium carbonate, kaolin, talc, clay, diatomaceous earth, synthetic amorphous silica, aluminum silicate, magnesium silicate, calcium silicate, aluminum hydroxide, alumina, Preferable examples include inorganic white pigments such as lithopone, zeolite, barium sulfate, calcium sulfate, titanium dioxide, zinc sulfide and zinc carbonate, and organic pigments such as styrene pigment, acrylic pigment, urea resin and melamine resin. Among these white pigments, porous inorganic pigments are preferable.

Examples of the aqueous binder include water-soluble polymers such as polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, polyvinylpyrrolidone, polyalkylene oxide, and polyalkylene oxide derivatives. And water dispersible polymers such as styrene butadiene latex and acrylic emulsion. These aqueous binders may be used alone or in combination of two or more.

A polymer mordant is preferably used as the mordant.

The water-proofing agent is effective for making the image water-resistant, and a cationic resin is preferable. Examples of the cationic resin include polyamide polyamine epichlorohydrin, polyethyleneimine, polyamine sulfone, dimethyldiallylammonium chloride polymer, cationic polyacrylamide, colloidal silica, and the like.

Examples of the light resistance improver include zinc sulfate, zinc oxide, hindered amine-based antioxidants, benzophenone-based and benzotriazole-based ultraviolet absorbers, and the like.

The surfactant functions as a coating aid, a peelability improver, a slippage improver or an antistatic agent. An organic fluoro compound may be used in place of the surfactant. Examples of the organic fluoro compound include a fluorine surfactant, an oily fluorine compound (for example, fluorine oil) and a solid fluorine compound resin (for example, tetrafluoroethylene resin).

Examples of the other additives include pigment dispersants, thickeners, antifoaming agents, dyes, fluorescent whitening agents, preservatives, pH adjusting agents, matting agents, and hardening agents.

The back coat layer may contain a white pigment, an aqueous binder, and other components.

Examples of the white pigment include light calcium carbonate, heavy calcium carbonate, kaolin, talc, calcium sulfate, barium sulfate, titanium dioxide, zinc oxide, zinc sulfide, zinc carbonate, satin white, aluminum silicate, diatomaceous earth, calcium silicate. , Magnesium silicate, synthetic amorphous silica, colloidal silica, colloidal alumina, pseudoboehmite, aluminum hydroxide, alumina, lithopone, zeolite, hydrous halloysite, magnesium carbonate, magnesium hydroxide, white inorganic pigments, styrene plastic pigment, acrylic Organic pigments such as plastic pigments, polyethylene, microcapsules, urea resins, melamine resins, and the like.

Examples of the aqueous binder include styrene / maleate copolymer, styrene / acrylate copolymer, polyvinyl alcohol, silanol-modified polyvinyl alcohol, starch, cationized starch, casein, gelatin, carboxymethylcellulose, hydroxyethylcellulose, and polyvinylpyrrolidone. And water-dispersible polymers such as styrene butadiene latex and acrylic emulsion.

Examples of the other components include an antifoaming agent, an antifoaming agent, a dye, a fluorescent brightening agent, a preservative, and a water-proofing agent.

A polymer latex may be added to the constituent layers (including the backcoat layer) in the recording paper and recording film. The polymer latex is used for the purpose of improving film physical properties such as dimensional stabilization, curling prevention, adhesion prevention, and film cracking prevention. When a polymer latex having a low glass transition temperature (40 ° C. or lower) is added to the layer containing the mordant, cracking and curling of the layer can be prevented. Further, curling can be prevented by adding a polymer latex having a high glass transition temperature to the back coat layer.

The ink jet recording method of the present invention is not particularly limited, and is a known method, for example, a charge control method in which ink is ejected using electrostatic attraction force, or a drop-on-demand method (pressure) using vibration pressure of a piezo element. Pulse system), acoustic ink jet system that changes electrical signal into acoustic beam, irradiates ink and uses ink to discharge ink, thermal ink jet that heats ink to form bubbles and uses generated pressure (bubble) Any of a jet (registered trademark) system may be used. 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 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. The water-based black ink composition of the present invention is used for ink jet recording and writing instruments. When recorded on plain paper and ink jet exclusive paper, the hue of the recorded image is neutral, the printing density is high, and ozone gas resistance Excellent in light resistance, light resistance, moisture resistance and color rendering. By using it together with magenta, cyan and yellow dyes, full-color ink jet recording excellent in light resistance and water resistance is possible. Thus, the ink composition of the present invention is extremely useful as a black ink for inkjet recording.

Hereinafter, the present invention will be described more specifically with reference to examples. In the text, “parts” and “%” are based on mass unless otherwise specified. The sulfo group is expressed in the form of a free acid.

Synthesis example 1
In 675 parts of water, 115 parts of the compound of the formula (41), 98 parts of the compound of the formula (42), 61 parts of 48% aqueous sodium hydroxide solution and 11 parts of ethylene glycol were added and stirred at 98 ° C. for 10 hours to conduct the condensation reaction. Completed.

280 parts of water was added to the obtained reaction liquid, the liquid temperature was adjusted to 85 to 88 ° C., 12 parts of glucose was added, and the mixture was stirred for 2 hours to complete the reduction reaction. Next, the pH was adjusted to 9.0 to 9.5 using hydrochloric acid, salted out using sodium chloride, and filtered. The total amount of the cake obtained was dissolved in 2000 parts of water and crystallized by adding 2000 parts of methanol, and the crystals were desalted by filtration and separation. Next, the obtained crystal was dried to obtain 192 parts of an orange dye compound. The maximum absorption wavelength (λmax) of this compound in water was 413 nm, and the solubility in water was 100 g / l or more.

Synthesis example 2
Instead of the compound of formula (42), 230 parts of an orange compound was obtained in the same manner as in Example 1, except that 132 parts of the compound of formula (43) were used.
The maximum absorption wavelength (λmax) of this compound in water was 437 nm, and the solubility in water was 100 g / l or more.

Synthesis Example 3 (Synthesis of CI Direct Orange 62)
In 675 parts of water, 115 parts of the compound of the above formula (41), 172 parts of the compound of the following formula (44), 61 parts of 48% aqueous sodium hydroxide and 11 parts of ethylene glycol were added, and stirred at 98 ° C. for 7 hours. The condensation reaction was completed.

The obtained reaction solution was adjusted to pH 9.0 to 9.5 using hydrochloric acid, salted out using sodium chloride, and filtered. The total amount of the cake obtained was dissolved in 2000 parts of water and crystallized by adding 2000 parts of methanol, and the crystals were desalted by filtration and separation. Next, the obtained crystals were dried to obtain 214 parts of an orange dye compound (CI Direct Orange 62). The maximum absorption wavelength (λmax) of this compound in water was 494 nm, and the solubility in water was about 100 g / l.

Synthesis example 4
In 1800 parts of water, 107.5 parts of the compound of the following formula (45) was adjusted to pH 5.5-8.0 with sodium hydroxide, and after adding 60.3 parts of 40% aqueous sodium nitrite solution, 1200 parts of water, The mixture was dropped into 52.2 parts of 35% hydrochloric acid at 5 to 10 ° C. and diazotized.

Next, 110 parts of 8-amino-1-hydroxynaphthalene-3,6-disulfonic acid was added to the obtained diazo suspension. After the addition, the obtained liquid was stirred overnight at 15 to 30 ° C. while maintaining the pH value at 2.0 to 3.0 with sodium carbonate to obtain a reaction liquid containing the compound of the formula (46).

Next, 135.9 parts of the compound of formula (47) was dissolved while adjusting the pH to 5.5 to 8.0 with sodium hydroxide, and then 128.9 parts of 35% hydrochloric acid and 56.92 parts of 40% aqueous sodium nitrite solution. Was added to diazotize. This diazo suspension was added dropwise to the reaction solution containing the compound of formula (46) at 15 to 30 ° C. During this addition, the pH value of the solution was maintained at 8.5 to 9.5 with sodium carbonate. After completion of the dropwise addition, the pH was kept at 8.5 to 9.5, and the mixture was further stirred at 15 to 30 ° C. for 3 hours to complete the coupling reaction to obtain a reaction solution containing the compound of formula (48). .

Next, this reaction solution was stirred with sodium hydroxide at pH 7.0 to 11.0, at a temperature of 60 ° C. for 3 hours, and hydrolyzed to obtain a compound of formula (49). Sodium chloride was added to the reaction solution for salting out, followed by isolation by filtration.

The total cake of the compound of formula (49) thus obtained was completely dissolved in 3000 parts of water by adjusting the pH to 8.5 to 9.5 with sodium hydroxide. 51.2 parts of 1-amino-2-benzenesulfonic acid was diazotized by a conventional method, and this suspension was added dropwise. It was dripped at 15-30 degreeC to the alkaline aqueous solution of the compound of Formula (49) previously melt | dissolved in this diazo suspension. During the dropwise addition, the pH value of the solution was maintained at 8.5 to 9.5 with sodium carbonate. After completion of the dropping, the mixture was further stirred at 15 to 30 ° C. for 3 hours at pH 8.5 to 9.5 to complete the coupling reaction, thereby obtaining a reaction solution containing the compound of the formula (50). After adjusting the pH value to 2.0 to 5.0 with 35% hydrochloric acid, the insoluble matter was removed by filtration, and salting out was performed by adding sodium chloride, followed by filtration. The total amount of the cake obtained was dissolved in 1000 parts of water, crystallized by adding 1000 parts of methanol, and desalted by filtration, then dried and used as a water-soluble black dye (A) (following formula 100.4 parts of a tetrakisazo compound represented by (50) was obtained. The maximum absorption wavelength (λmax) of this dye in water was 649 nm, and the solubility in water was 100 g / l or more.

Synthesis example 5
Instead of 107.5 parts of the compound of formula (45) in synthesis example 4 142.1 parts of the compound of formula (51), instead of 135.9 parts of compound of formula (47) 113. 7 parts were prepared in the same manner as in Synthesis Example 4 except that 66.9 parts of 1-amino-4-methoxy-2-benzenesulfonic acid was used instead of 51.2 parts of 1-amino-2-benzenesulfonic acid. 90.2 parts of water-soluble black dye (A) (tetrakisazo compound represented by the following formula (53)) used in the invention were obtained. The maximum absorption wavelength of this dye in water was 657 nm, and the solubility in water was 100 g / l or more.

Synthesis Example 6
28.4 parts of the compound of formula (51) are dissolved in 300 parts of water while adjusting the pH to 6.0 to 8.0 with sodium carbonate, and after addition of 18.7 parts of 35% hydrochloric acid, the temperature is adjusted to 0 to 5 ° C. Diazotization was performed by adding 10.7 parts of 40% aqueous sodium nitrite solution. A solution obtained by suspending 18.1 parts of 6-phenylamino-1-hydroxynaphthalene-3-sulfonic acid in 200 parts of water was added to the diazo suspension, and then the pH value of the solution was adjusted to 10 to 20 ° C. with sodium carbonate. The mixture was stirred for 12 hours while maintaining at 2.0 to 2.7. After stirring, the pH value was dissolved with sodium carbonate as 7.0 to 8.5 to obtain a solution containing the monoazo compound of the formula (54).

In 50 parts of water, 10.4 parts of 2-aminobenzenesulfonic acid are dissolved while adjusting the pH to 3.5 to 5.5 with sodium hydroxide, and at 0 to 10 ° C., 17.0 parts of 35% hydrochloric acid and 40% Diazotization was performed by adding 10.5 parts of an aqueous sodium nitrite solution. Next, 14.3 parts of 6-amino-1-hydroxynaphthalene-3-sulfonic acid is dissolved in 70 parts of water while adjusting the pH to 6.5 to 7.5 with sodium hydroxide, and anhydrous at 25 to 35 ° C. Acetylated by addition of 6.2 parts of acetic acid. The diazo suspension was added dropwise thereto while maintaining the pH value of the solution at 6.5 to 7.5 with sodium carbonate. After completion of the dropwise addition, the mixture was stirred at 15 to 30 ° C. for 2 hours at pH 7.0 to 8.0 to complete the coupling reaction, thereby obtaining a reaction solution containing the compound of the formula (55).

The reaction solution containing the compound of the formula (55) obtained above was heated to 90 ° C. After heating, sodium hydroxide was added to 2%, and the temperature was maintained at 90 to 95 ° C. for about 1 hour. After cooling to room temperature, the pH was adjusted to 3.5 to 5.0 with 35% hydrochloric acid, sodium chloride was added for salting out, filtered, and dried to obtain 23.0 parts of the compound of formula (52). 23.0 parts of the compound of the formula (52) obtained by the above reaction were dissolved in 200 parts of water while adjusting the pH to 6.0 to 7.5 with sodium hydroxide, and 35% hydrochloric acid 19 was added thereto at 15 to 25 ° C. After adding 9.9 parts, 9.9 parts of 40% aqueous sodium nitrite solution was added for diazotization. This diazo suspension was added to the aqueous solution containing the compound of the formula (54) obtained by the above reaction at 15 to 25 ° C., and the pH value of the solution was maintained at 7.5 to 8.5 with sodium carbonate over 30 minutes. And dripped. After completion of dropping, the mixture was stirred at 15 to 30 ° C. for 3 hours at pH 8.0 to 9.0 to complete the coupling reaction to obtain a solution containing the compound of formula (56).

The reaction solution was heated to 75 ° C. and reacted for 1 hour while maintaining the pH at 10.8 to 11.0 with sodium hydroxide. After the reaction, the pH was adjusted to 6.0-7.5 with 35% hydrochloric acid, sodium chloride was added, salted out, and filtered to obtain 46.5 parts of the compound of formula (57).

To 100 parts of N, N-dimethylformamide, 51.0 parts of 2-nitro-4-cresol, 50.0 parts of toluene and 19.5 parts of potassium hydroxide are added, and this is heated to 120 to 125 ° C. for 1 hour. The water produced by azeotropic distillation with toluene was distilled off. After raising the temperature to 130 to 135 ° C., 44.8 parts of propane sultone diluted with 50 parts of N, N-dimethylformamide was added dropwise over about 30 minutes. After reacting at the same temperature for 1 hour, the mixture was cooled to room temperature, 150 parts of water was added, and the pH was adjusted to 7.5 to 8.5 with an aqueous sodium hydroxide solution. This solution was concentrated by a rotary evaporator, transferred to an autoclave, and 1.0 part of 50% water-containing 5% palladium carbon was added. After enclosing hydrogen gas, the mixture was reacted at 55 to 65 ° C. for 2 hours to obtain a solution containing 56.8 parts of the compound of formula (58).

In 900 parts of water, 74.3 parts of the compound of the formula (59) were dissolved while adjusting the pH to 1.0 to 3.0 with hydrochloric acid, adjusted to 5 to 10 ° C., 53.2 parts of 35% hydrochloric acid, 40% Diazotization was performed by adding 27.0 parts of an aqueous sodium nitrate solution.

Next, a solution containing 36.8 parts of the compound of the formula (58) obtained by the above reaction was slowly added dropwise to the diazo suspension of the compound of the formula (59) obtained at a temperature of 0 to 10 ° C. After completion of the dropwise addition, the pH value is adjusted to 3.0 to 4.0 by adding an aqueous sodium hydroxide solution, and then 5 to 10 ° C. for 1 hour, 15 to 25 ° C. for 2 hours, and pH 3.0 to 4. The mixture was stirred at 0, an aqueous sodium hydroxide solution was added to adjust the pH value to 7.0 to 8.0, and the coupling reaction was completed to obtain a reaction solution containing the compound of formula (60).

A 1/6 amount of the obtained reaction solution containing the compound of the formula (60) was taken, and after addition of 16.5 parts of 35% hydrochloric acid, 8.7 parts of 40% aqueous sodium nitrite solution was added thereto for diazotization. This diazo solution was dissolved in a solution obtained by dissolving 46.5 parts of the compound of the formula (57) in 1000 parts of water at 15 to 30 ° C., while maintaining the pH value of the solution at 8.5 to 9.5 with sodium carbonate. It was added dropwise over a period of minutes. After completion of dropping, the mixture was stirred at 15 to 30 ° C. for 3 hours at pH 8.5 to 9.5 to complete the coupling reaction, thereby obtaining a reaction solution containing the compound of the formula (61).

The reaction solution was heated to 75 ° C. and reacted for 1 hour while maintaining the pH at 10.8 to 11.0 with sodium hydroxide. After the reaction, the pH was adjusted to 6.0-7.5 with 35% hydrochloric acid, sodium chloride was added, salted out, and filtered. The total amount of the cake obtained was dissolved in 500 parts of water, crystallized by adding 500 parts of methanol, desalted by filtration, then dried and used as a water-soluble black dye (A) (following formula 55.1 parts of the compound represented by (62) was obtained. The maximum absorption wavelength (λmax) of this compound in water was 570 nm, and the solubility in water was 100 g / l or more.

Synthesis example 7
A water-soluble black dye (A) used in the present invention in the same manner as in Synthesis Example 6 except that 28.4 parts of the compound of Formula (51) in Synthesis Example 6 is changed to 23.6 parts of the compound of Formula (45). 50.2 parts of (a compound represented by the following formula (63)) were obtained. The maximum absorption wavelength of this compound in water was 578 nm, and the solubility in water was 100 g / l or more.

(A) Preparation of ink In the following, all the dye components were desalted.

Example 1
The aqueous black ink composition of the present invention was prepared by mixing the components shown in Table 10 below. Subsequently, it filtered with a 0.45 micrometer membrane filter, and obtained the water-based black ink composition except the narrow thing.

Table 10
Compound obtained in Synthesis Example 1 1.4 parts Compound obtained in Synthesis Example 4 1.8 parts Compound obtained in Synthesis Example 7 1.8 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl- 2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surfinol 105 manufactured by Nisshin Chemical Co., Ltd.)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Example 2
The aqueous black ink composition of the present invention was prepared by mixing the components shown in Table 11 below. Subsequently, it filtered with a 0.45 micrometer membrane filter, and obtained the water-based black ink composition except the narrow thing.

Table 11
Compound obtained in Synthesis Example 1 1.4 parts Compound obtained in Synthesis Example 5 1.2 parts Compound obtained in Synthesis Example 6 2.4 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl- 2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surfinol 105 manufactured by Nisshin Chemical Co., Ltd.)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Example 3
The aqueous black ink composition of the present invention was prepared by mixing the components shown in Table 12 below. Subsequently, it filtered with a 0.45 micrometer membrane filter, and obtained the water-based black ink composition except the narrow thing.

Table 12
Compound obtained in Synthesis Example 1 1.4 parts Compound obtained in Synthesis Example 4 1.8 parts Compound obtained in Synthesis Example 6 1.8 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl- 2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surfinol 105 manufactured by Nisshin Chemical Co., Ltd.)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Example 4
The aqueous black ink composition of the present invention was prepared by mixing the components shown in Table 13 below. Subsequently, it filtered with a 0.45 micrometer membrane filter, and obtained the water-based black ink composition except the narrow thing.

Table 13
Compound obtained in Synthesis Example 1 1.5 parts Compound obtained in Synthesis Example 6 3.5 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 Parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surfinol 105 manufactured by Nissin Chemical)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Example 5
The aqueous black ink composition of the present invention was prepared by mixing the components shown in Table 14 below. Subsequently, it filtered with a 0.45 micrometer membrane filter, and obtained the water-based black ink composition except the narrow thing.

Table 14
Compound obtained in Synthesis Example 2 1.5 parts Compound obtained in Synthesis Example 5 2.3 parts Compound obtained in Synthesis Example 6 1.2 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl- 2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surfinol 105 manufactured by Nisshin Chemical Co., Ltd.)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Example 6
The aqueous black ink composition of the present invention was prepared by mixing the components shown in Table 15 below. Subsequently, it filtered with a 0.45 micrometer membrane filter, and obtained the water-based black ink composition except the narrow thing.

Table 15
1.5 parts of the compound obtained in Synthesis Example 3 (CI Direct Orange 62)
Compound obtained in Synthesis Example 5 2.0 parts Compound obtained in Synthesis Example 6 1.4 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 Parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surfinol 105 manufactured by Nissin Chemical)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

(B) Inkjet printing Using each of the aqueous black ink compositions of the present invention obtained as described above, by using an inkjet printer (trade name Canon BJ-S630), plain paper (Canon TLB5A4), exclusive glossy paper A (Canon) Inkjet recording was carried out on three types of paper, Professional Photo Paper PR-101) and exclusive glossy paper B (Canon Super Photo Paper SP-101). At the time of printing, an image pattern was prepared so that gradations with several levels of reflection density were obtained, and a half-tone black print was obtained. 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 in this light color portion. Among the test methods described below, in the hue evaluation measurement, which is an item to be evaluated using a colorimeter, when the a ^* value and b ^* value of the printed material are measured, the reflection density D value of the printed material is The highest part was used. Similarly, in the light resistance test and the ozone gas resistance test using the colorimeter, the measurement was performed using the gradation portion where the reflection density D value of the printed material before the test was closest to 1.0. Hue evaluation, bronze evaluation, humidity resistance test evaluation, and color rendering test evaluation were performed by visually observing the entire printed matter.

(C) Evaluation of recorded image
For the recorded image by the aqueous ink composition of the present invention, 7 points of hue, printing density, bronze property, color rendering, hue change after light resistance test, hue change after ozone gas resistance test, and degree of bleeding by humidity resistance test Was evaluated. The bronze property test, the ozone resistance test, and the moisture resistance test were performed only on the dedicated glossy papers A and B. The results are shown in Table 24. The test method is shown below.
(1) Hue Evaluation For the hue evaluation (numerical data) of the recorded image, visual evaluation and evaluation by a colorimeter were used in combination. In the evaluation by the colorimeter, the a ^* value and the b ^* value were measured using Gretag Macbeth SpectroEye (manufactured by GRETAG), and the C ^* value was calculated. The formula for calculating the C ^* value is C ^* = {(a ^* ) ² + (b ^* ) ² } ^1/2 . Judgment criteria are shown below.
○ It is a good black with no color by visual observation, and when measured, C ^* <5.0.
Δ: Good black with no color by visual observation, but 5.0 ≦ C ^* ≦ 10 when measured.
X Although it is visually colored or black with no color, it is 10 <C ^* when measured.
(2) Print density evaluation The hue density D value was measured using Gretag Macbeth SpectroEye (manufactured by GRETAG). Judgment criteria are shown below.
○ Plain paper: 1.2 ≦ D Glossy paper: 2.0 ≦ D
Δ Plain paper: 1.0 ≦ D <1.2 Glossy paper: 1.9 ≦ D <2.0
× Plain paper: D <1.0 Glossy paper: D <1.9
(3) Bronze property Bronze property on glossy paper was judged by visual observation. Judgment criteria are shown below.
○ Bronze phenomenon does not appear in all parts printed with several gradation levels.
△ There are both parts where bronze phenomenon appears and parts where it doesn't appear.
X Bronze phenomenon appears in all parts printed with several gradation levels.
(4) Color Rendering Test The degree of color change when viewed under tungsten light was visually determined based on the hue under a standard light source.
○ Hue change is small.
△ Hue change is slightly large.
× Hue change is large.
(5) Light resistance test A xenon weatherometer Ci4000 (manufactured by ATLAS) was used to irradiate a print sample with an illuminance of 0.36 W / square meter for 50 hours. After the test, the color was measured in the same manner as described above, and the color difference (ΔE) before and after the test and the residual ratio of density were determined. The determination was made according to the following criteria.
○ ΔE: Less than 10 and remaining rate: 80% or more Δ ΔE or remaining rate does not satisfy the condition of ○ × ΔE: 10 or more and remaining rate: less than 80% Bronze phenomenon When it appears, the light resistance cannot be determined. Therefore, when the result of the bronze test of (3) is x, the determination of light resistance is indicated as-in Table 24.
(6) Ozone resistance test Using an ozone weather meter (manufactured by Suga Test Instruments Co., Ltd.), the print sample was allowed to stand for 1 hour at an ozone gas concentration of 12 ppm, a humidity of 60% RH, and a temperature of 24 ° C. After the test, the color was measured in the same manner as described above, and the color difference (ΔE) before and after the test and the residual ratio of density were determined. The determination was made according to the following criteria.
○ ΔE: Less than 15 and remaining rate: 80% or more Δ ΔE or remaining rate does not satisfy the condition of ○ × ΔE: 15 or more and remaining rate: less than 80% Bronze phenomenon When it appears, the ozone resistance cannot be determined. Therefore, when the bronze test result of (3) is x, the determination of ozone resistance is indicated as-in Table 24.
(7) Humidity resistance test The printed sample was left at 50 ° C. and 90% RH for 3 days using a thermo-hygrostat (manufactured by Applied Giken Sangyo Co., Ltd.), and the bleeding of the dye before and after the test was judged visually.
○ Dye bleeding is hardly seen. △ Dye bleeding is slightly seen. × Dye bleeding is considerably seen.
When the bronze phenomenon appears, the determination of moisture resistance cannot be made. Therefore, when the result of the bronze test in (3) is x, the determination of moisture resistance is indicated as-in Table 24.

Comparative Example 1
Instead of the compounds obtained in Synthesis Examples 1 to 3 for comparison, C.I. I. An ink composition was prepared using the direct yellow 132 and the ink compositions shown in Table 16 below. (B) Inkjet print, and (C) Hue evaluation, hue density evaluation, light resistance evaluation, ozone gas resistance evaluation, humidity resistance evaluation, color rendering property evaluation and bronze of the recorded image obtained in the same manner as the evaluation of the recorded image The sex results are shown in Table 24.

Table 16
C. I. Direct Yellow 132 1.2 parts Compound obtained in Synthesis Example 5 1.3 parts Compound obtained in Synthesis Example 6 2.5 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surfinol 105 manufactured by Nisshin Chemical Co., Ltd.)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Comparative Example 2
Instead of the compounds obtained in Synthesis Examples 1 to 3 for comparison, C.I. I. Using Acid Yellow 17, ink compositions were prepared with the ink compositions shown in Table 17 below. (B) Inkjet print, and (C) Hue evaluation, hue density evaluation, light resistance evaluation, ozone gas resistance evaluation, humidity resistance evaluation, color rendering property evaluation and bronze of the recorded image obtained in the same manner as the evaluation of the recorded image The sex results are shown in Table 24.

Table 17
C. I. Acid Yellow 17 1.4 parts Compound obtained in Synthesis Example 4 1.8 parts Compound obtained in Synthesis Example 7 1.8 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4. 0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surfinol 105 manufactured by Nisshin Chemical Co., Ltd.)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Comparative Example 3
As a comparison object, an ink composition having the ink composition shown in Table 18 below was prepared using only the compound obtained in Synthesis Example 5 as a coloring matter. (B) Inkjet print, and (C) Hue evaluation, hue density evaluation, light resistance evaluation, ozone gas resistance evaluation, humidity resistance evaluation, color rendering property evaluation and bronze of the recorded image obtained in the same manner as the evaluation of the recorded image The sex results are shown in Table 24.

Table 18
Compound obtained in Synthesis Example 5 5.0 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0 .1 part (Surfinol 105 manufactured by Nissin Chemical)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Comparative Example 4
As a comparison object, an ink composition having the ink composition shown in Table 19 below was prepared using only the compound obtained in Synthesis Example 6 as a coloring matter. (B) Inkjet print, and (C) Hue evaluation, hue density evaluation, light resistance evaluation, ozone gas resistance evaluation, humidity resistance evaluation, color rendering property evaluation and bronze of the recorded image obtained in the same manner as the evaluation of the recorded image The sex results are shown in Table 24.

Table 19
Compound obtained in Synthesis Example 6 5.0 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0 .1 part (Surfinol 105 manufactured by Nissin Chemical)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Comparative Example 5
As a comparison object, an orange ink composition having the ink composition shown in Table 20 below was prepared using only the compound obtained in Synthesis Example 1 as a coloring matter. Table 24 shows the results obtained in the same manner as in the evaluation of (B) inkjet print and (C) recorded image. Since the hue is not black, the results of only light resistance evaluation, ozone gas resistance evaluation, moisture resistance evaluation and bronze resistance are shown in Table 24.

Table 20
Compound obtained in Synthesis Example 1 5.0 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0 .1 part (Surfinol 105 manufactured by Nissin Chemical)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Comparative Example 6
As a comparison object, C.I. described in Example 1 of Patent Document 4 as a pigment component. I. Direct Blue 248 and C.I. I. An ink composition was prepared with the ink compositions shown in Table 21 below using Direct Orange 62 at 1: 1. (B) Inkjet print, and (C) Hue evaluation, hue density evaluation, light resistance evaluation, ozone gas resistance evaluation, humidity resistance evaluation, color rendering property evaluation and bronze of the recorded image obtained in the same manner as the evaluation of the recorded image The sex results are shown in Table 24.

Table 21
C. I. Direct Blue 248 2.5 parts C.I. I. Direct Orange 62 2.5 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surphy Nord 105 manufactured by Nissin Chemical)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Comparative Example 7
As a comparison object, C.I. described in Example 4 of Patent Document 4 as a pigment component. I. Direct Blue 202 and C.I. I. An ink composition was prepared with the ink composition shown in Table 22 below using Direct Orange 62 at 4: 5. When this was mounted on a printer in the same manner as in the above (B) inkjet printing, printing was attempted. However, it was not possible to evaluate the printed matter.

Table 22
C. I. Direct Blue 202 2.2 parts C.I. I. Direct Orange 62 2.8 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surphy Nord 105 manufactured by Nissin Chemical)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Comparative Example 8-1
Patent Document 5 describes C.I. as a black dye blended with an orange direct dye. I. An ink composition having the ink composition shown in Table 21 below was prepared using Direct Black 19. (B) Inkjet print, and (C) Hue evaluation, hue density evaluation, light resistance evaluation, ozone gas resistance evaluation, humidity resistance evaluation, color rendering property evaluation and bronze of the recorded image obtained in the same manner as the evaluation of the recorded image The sex results are shown in Table 24.

Table 21
C. I. Direct black 19 5.0 parts Glycerin 5.0 parts Urea 5.0 parts N-methyl-2-pyrrolidone 4.0 parts Isopropyl alcohol 3.0 parts Butyl carbitol 2.0 parts Surfactant 0.1 parts (Surphy Nord 105 manufactured by Nissin Chemical)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

Comparative Example 8-2
As a comparison object, C.I. described in Example 1 of Patent Document 5 as a pigment component. I. Direct Black 19 and C.I. I. Ink compositions were prepared with the ink compositions shown in Table 22 below using Direct Orange 62 at 1: 1. (B) Inkjet print, and (C) Hue evaluation, hue density evaluation, light resistance evaluation, ozone gas resistance evaluation, humidity resistance evaluation, color rendering property evaluation and bronze of the recorded image obtained in the same manner as the evaluation of the recorded image The sex results are shown in Table 24.

Table 22
C. I. Direct Black 19 4.5 parts C.I. I. Direct Orange 62 0.5 part Glycerin 5.0 part Urea 5.0 part N-methyl-2-pyrrolidone 4.0 part Isopropyl alcohol 3.0 part Butyl carbitol 2.0 part Surfactant 0.1 part (Surphy Nord 105 manufactured by Nissin Chemical)
Water + aqueous lithium hydroxide 75.9 parts Total 100.0 parts

From Table 24, Comparative Example 3 and Comparative Example 4 which are tests with ink compositions using only the water-soluble black dye (A) used in the present invention obtained in Synthesis Example 5 and Synthesis Example 6 show hues. Slightly inferior, good in density, bronze property, color rendering property, light resistance, ozone resistance and moisture resistance, and an orange ink composition using only the dye obtained in Synthesis Example 1 (Comparative Example 5) ) Shows that the light resistance and ozone gas resistance are low. Surprisingly, however, the water-based black ink composition of the present invention in which the dye obtained in Synthesis Example 1 is blended with the water-soluble black dye (A) obtained in Synthesis Example 5 and Synthesis Example 6 has a C ^* value. Gives a neutral black print close to 0, the hue of the print is very high, and the print has excellent durability such as light resistance, ozone resistance, moisture resistance, etc. I understand.
Furthermore, in Comparative Example 6 using a blue dye as described in Patent Document 4, from Table 24, bronze property is inferior, and light resistance, ozone resistance, and moisture resistance cannot be evaluated. It is understood that the printed matter cannot be evaluated due to poor ejection properties with an inkjet printer, and is not suitable as an aqueous black ink for inkjet.
Further, Comparative Example 8-1 is inferior in bronze property in the special glossy paper B, and cannot be evaluated for light resistance, ozone resistance, and moisture resistance. In the special glossy paper A, the bronze property does not occur and the light resistance, Evaluation of ozone and moisture resistance was possible. Therefore, by adopting data of a recording material that can be evaluated, it can be seen that the black dye used in Comparative Example 8-1 has poor properties such as ozone resistance. Further, Comparative Example 8-2 has the same result as Comparative Example 8-1, and it can be seen that various properties such as ozone resistance are poor.

Claims (15)

Ozone-resistant water-soluble black dye (A) and condensed compound (B) of 4,4′-dinitrostilbene-2,2′-disulfonic acid or a salt thereof and aminobenzene and / or a reduced form thereof Aqueous black ink composition containing (C) The blending ratio of the water-soluble dye for black (A) and the condensed compound (B) of 4,4′-dinitrostilbene-2,2′-disulfonic acid or its salt and aminobenzene or its reduced form (C) is The water-soluble black dye (A) is 50-99.9% by mass based on the total amount of (A) and (B) or (C), and the condensed compound (B) or its reduced form (C) is The water-based black ink composition according to claim 1, which is 0.1 to 50% by mass. The aqueous black ink composition according to claim 1 or 2, wherein the water-soluble black dye (A) has a maximum absorption wavelength in the range of 550 nm to 700 nm in water. The water-soluble black dye (A) is a dye containing at least one kind of water-soluble azo dye having 5 or more sulfo groups and 4 or more azo groups in one molecule. The water-based black ink composition according to claim 1 The water-soluble black dye (A) is represented by the following general formula (3)

(In Formula (3), A and B each independently represent a phenyl group or a naphthyl group, and A and B each have at least one sulfo group. Represents a single bond, the bond position of bond a is 2-position or 3-position, the bond position of bond b is 6-position or 7-position, one of X and Y represents a hydroxyl group, the other represents an amino group, l represents 1 or 2, and m and n each independently represents 0 or 1. The sulfo group and carboxyl group counter ion contained in the molecule represented by the formula (3) are a hydrogen ion, an alkali Metal ions, organic amine cations or ammonium ions.)
An azo dye represented by the following formula (4)

(In the formula (4), R ₆ to R ₁₁ represent substituents, c and d each represent a single bond, the position of the bond c is the 10 or 11 position, the position of d is the 14 or 15 position, o and p Is 0 or 1, and q is 1 or 2. The counter ion of the sulfo group and carboxyl group of the molecule represented by formula (4) is a hydrogen ion, an alkali metal ion, a cation of an organic amine, or an ammonium ion. is there.)
5. The aqueous black ink composition according to claim 1, wherein the aqueous black ink composition comprises at least one selected from the group consisting of azo dyes represented by formula (1): In the general formula (3), the substituents A and B are a halogen atom; a hydroxyl group; an amino group; a carboxyl group; a sulfo group; a nitro group; a (C1-C4) alkyl group; Group; phenyl group; ureido group; hydroxyl group, (C1 to C4) alkoxy group, (C1 to C4) alkyl group substituted by sulfo group or carboxyl group; hydroxyl group, (C1 to C4) alkoxy group, sulfo group Or a (C1-C4) alkoxy group substituted by a carboxyl group; an amino group substituted by a phenyl group, a (C1-C4) alkyl group or an acyl group (substituents on these amino groups are further carboxyl groups or And may be substituted with a sulfo group)
In formula (4), R ₆ to R ₈ are a hydrogen atom; a halogen atom; a cyano group; a hydroxyl group; an amino group; a carboxyl group; a sulfo group; and a (C1-C4) alkyl group or a phenyl group. Phospho group; nitro group; acyl group; phenyl group; ureido group; hydroxyl group or (C1-C4) alkyl group optionally substituted with (C1-C4) alkoxy group; hydroxyl group, (C1-C4) alkoxy An alkoxy group optionally substituted by a group, a sulfo group or a carboxyl group; an amino group substituted by a phenyl group (the phenyl group may be further substituted by a carboxyl group or a sulfo group); alkyl an amino group substituted by a group or an acyl group, R ₉ is a hydrogen atom; a hydroxyl , (C1-C4) alkoxy group, sulfo group or carboxyl group which may be substituted with (C1-C4) alkyl group; phenyl optionally substituted with amino group, alkyl group, alkoxy group, carboxyl group or sulfo group R ₁₀ and R ₁₁ are a hydrogen atom; a sulfo group; an acetylamino group; a hydroxyl group or a (C1-C4) alkyl group optionally substituted with a (C1-C4) alkoxy group; a hydroxyl group, (C1- 6. The aqueous black ink composition according to claim 5, which is a (C1-C4) alkoxy group which may be substituted with C4) an alkoxy group, a sulfo group or a carboxyl group. The aqueous black according to claim 5 or 6, comprising an azo compound represented by formula (3) according to claim 5 and an azo compound represented by formula (4) as the water-soluble black dye (A). Ink composition The use ratio of the azo compound represented by the formula (3) and the azo compound represented by the formula (4) according to claim 5 is the azo compound 10- represented by the formula (3) with respect to the total amount of both. The water-based black ink composition according to any one of claims 5 to 7, which is 80% by mass and 20-90% by mass of the azo compound represented by the formula (4). Aminobenzenes in a condensation compound of 4,4′-dinitrostilbene-2,2′-disulfonic acid or a salt thereof and aminobenzenes are represented by the following formula (2):

(In formula (2), R ₁ to R ₅ each independently represent a hydrogen atom; a halogen atom; a hydroxyl group; a sulfo group; a carboxyl group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group)
The water-based black ink composition according to claim 1, which is an azo compound represented by the formula: An ink jet recording method using the water-based black ink composition according to any one of claims 1 to 9. 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 containing a white inorganic pigment. An inkjet printer using the aqueous black ink composition according to any one of claims 1 to 9. A colored body colored by the ink jet printer according to claim 13. As a dye component, at least one water-soluble dye (A) having a maximum absorption wavelength in the range of 550 nm to 700 nm in water, and 4,4′-dinitrostilbene-2,2′-disulfone represented by the following formula (1): acid

(In formula (1), M represents a hydrogen atom or an alkali metal atom.)
And the following formula (2)

(In formula (2), R ₁ to R ₅ each independently represent a hydrogen atom; a halogen atom; a hydroxyl group; a sulfo group; a carboxyl group; a (C1-C4) alkyl group; a (C1-C4) alkoxy group)
The dye (C) obtained by the reduction of the condensation dye (B) and (B) with the compound represented by the formula (wherein the counterion of the dye after the condensation or reduction is a hydrogen ion, an alkali metal ion or an organic amine) A water-based ink composition comprising at least one of cation and ammonium ion).