JP6592443B2 - Water-soluble azo compound or salt thereof, ink composition and colored body - Google Patents

Description

  The present invention relates to a water-soluble azo compound or a salt thereof, an ink composition containing the same, and a colored body colored with these.

Among various color recording methods, various ink ejection methods have been developed as recording methods using an ink jet printer, which is one of the representative methods. These all generate ink droplets and attach them to various recording materials (paper, film, fabric, etc.) for recording. In this method, since the recording head and the recording material are not in direct contact with each other, no noise is generated and the method is quiet. In addition, since it has the characteristics that it is easy to downsize, speed up, and colorize, it has been rapidly spreading in recent years and is expected to grow greatly in the future.
Conventionally, inks such as fountain pens and felt pens, and inks for ink-jet recording have been used in which water-soluble pigments (dyes) are dissolved in an aqueous medium. In general, a water-soluble organic solvent is added to these water-based inks in order to prevent clogging of ink at a pen tip or an ink discharge nozzle. These inks give a recorded image of sufficient density, do not cause clogging of the pen tip and nozzles, have good drying properties on the recording material, have little bleeding, and have excellent storage stability. Such performance is required.

  Ink jet nozzle clogging occurs when the water in the ink evaporates in the vicinity of the nozzle before other solvents and additives, and the pigment solidifies and precipitates when the composition state is low in water and high in solvents and additives. There are many things that come from doing. Accordingly, one of the very important required performances is that solids are not easily deposited even when the moisture content in the ink is low. For this reason, high solubility in solvents and additives is one of the properties required for pigments. As a method for eliminating nozzle clogging, a method using a dye having a high printing density is known. By using a pigment having a high printing density, the pigment content in the ink can be reduced while maintaining the conventional printing density. This not only makes it difficult to precipitate the dye, but is also advantageous in terms of cost, and development of a dye having a high printing density is desired.

By the way, in order to record image or character information on a color display of a computer in color by an ink jet printer, generally a subtraction method using four colors of ink of yellow (Y), magenta (M), cyan (C), and black (K). Mixed colors are used, whereby the recorded image is expressed in color. In order to reproduce an additive color mixture image of red (R), green (G), and blue (B) on a CRT (CRT) display etc. as faithfully as possible with a subtractive color mixture image, each dye used in the ink, particularly Y, Each of M and C is desired to have a hue close to a standard color and to be clear. The clearness here means generally having high saturation. When the three primary colors Y, M, and C with low saturation are used, the color area that can be expressed in a single color or mixed color becomes narrow, and the range of the color area that is desired to be expressed may be insufficient. For this reason, development of highly saturated pigments and inks containing them is desired.
In addition, the ink performance is required to be stable for long-term storage, high in recorded image density, and excellent in fastness such as water resistance, moisture resistance, light resistance and gas resistance. It is done.
Here, the gas resistance means that a gas having an oxidizing action (also referred to as an oxidizing gas) existing in the air reacts with a dye (dye) of a recorded image on the recording material or in the recording material to record. This is the resistance to the phenomenon of discoloration of images. Among oxidizing gases, ozone gas is considered to be a main causative substance that promotes the discoloration and fading phenomenon of ink jet recorded images. Since this discoloration phenomenon is characteristic of ink jet recorded images, improvement of ozone gas resistance is an important technical problem in this field.

With the recent development of inkjet technology, the speed of inkjet recording (printing) has been remarkably improved. For this reason, similar to laser printers using electronic toner, there is a market trend to use inkjet printers for printing documents on plain paper, which is the main application in office environments. Inkjet printers have the advantage that the type of recording paper is not limited and the price of the printer itself is low, and it is becoming increasingly popular especially in small to medium-sized office environments such as small offices and home offices (SOHO). As described above, when an inkjet printer is used for printing on plain paper, hue, coloring (printing) density, and moisture resistance tend to be more important among the qualities required for printed matter.
In order to satisfy these performances, a method using a pigment ink has been proposed. However, since pigment ink does not dissolve in water-based ink, it does not enter a solution state, but is a dispersed ink. Therefore, when this is used for ink jet recording, there are problems with the stability of the ink itself and the nozzles of the recording head. Problems such as clogging occur. In addition, when pigment ink is used, there is often a problem in abrasion resistance. In the case of a dye ink, such a problem is considered to be relatively difficult to occur. However, in particular, the moisture resistance is extremely inferior to that of a pigment ink, and an improvement to the problem is strongly desired. In addition, unlike pigment ink, dye ink tends to cause a problem that a dye attached to the surface of plain paper by ink jet recording penetrates more quickly toward the back side of the paper, resulting in a decrease in color density.

  One method for obtaining a photographic image-recorded inkjet image is to provide an ink-receiving layer on the surface of a recording material. The ink receiving layer provided for such a purpose often contains a porous white inorganic substance in order to speed up drying of the ink and to reduce bleeding of the pigment with high image quality. However, particularly in such a recording material, the color fading due to the ozone gas is noticeable. With the recent spread of digital cameras and color printers, there are increasing opportunities to print images obtained with digital cameras and the like as photographic image quality at home, so the above-mentioned color change of recorded images due to oxidizing gas is regarded as a problem. . Compared to the other three primary colors, magenta and cyan, yellow dyes have been proposed that have good resistance to oxidizing gas as well as light resistance. However, a yellow pigment and yellow ink for ink-jet recording that sufficiently satisfy the high sharpness and various fastnesses required by the market have not been obtained yet.

  In recent years, in addition to the above-mentioned performance, the characteristics required of pigments include less harm to humans and the environment. The aniline derivatives used in conventional existing pigments are recognized to be highly harmful, are subject to laws and regulations regarding their use and discharge, work under extremely strict protective equipment, and the remaining raw materials contained in pigments. It is a limiting factor for improving safety and health management and production efficiency such as volume restrictions.

  Examples of known yellow pigments for inkjet which are excellent in water solubility and sharpness include C.I. I. (Color index) Direct yellow 132 is exemplified. Patent Documents 1 to 3 include C.I. I. An example in which (color index) direct yellow 132 is used for inkjet is disclosed. Patent Document 4 discloses an example in which a yellow pigment that can be produced by the method disclosed in Example 1 of Patent Document 5 is used for inkjet.

JP-A-11-70729 Japanese Patent No. 3346755 Japanese Patent No. 4100800 International Publication No. 2011/122426 International Publication No. 2009/154142

  The present invention is a water-soluble yellow dye (compound) having high solubility in water, high color development (printing density) of recorded images, excellent chroma and light resistance, and various recordings containing the same, particularly An object is to provide a yellow ink composition for inkjet recording.

  As a result of intensive studies, the present inventors have solved the above-mentioned problems by a water-soluble azo compound represented by a specific formula or a salt thereof and an ink composition containing the same. The present invention was completed.

（式中、Ａ及びＴはそれぞれ独立して水溶性置換基を表し、Ｑ及びＲはそれぞれ独立して水素原子、ハロゲン原子、カルボキシ基、カルバモイル基、スルホ基、スルファモイル基、ヒドロキシ基、アミノ基、シアノ基、ホスホ基、ニトロ基、アシル基、Ｃ１〜Ｃ４アルキル基（ヒドロキシ基、カルボキシ基、カルバモイル基、及びスルホ基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルコキシ基（ヒドロキシ基、カルボキシ基、カルバモイル基、及びスルホ基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルキルスルホ基（ヒドロキシ基、カルボキシ基、カルバモイル基、又及びスルホ基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルキルチオ基（ヒドロキシ基、カルボキシ基、カルバモイル基、及びスルホ基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルキルアミノ基（ヒドロキシ基、カルボキシ基、カルバモイル基、及びスルホ基から選択される１又は２以上の置換基で置換されていても良い）、又はアシルアミノ基を表し、ｘは２から４の整数を表し、ａ及びｂはＡ又はＲの置換位置を表す。）
０−１）
式（１）において、Ａの置換位置がａであり、Ｒの置換位置がｂである上記０）に記載のアゾ化合物又はその塩、
０−２）
式（１）において、Ａがスルホ基である上記０）に記載のアゾ化合物又はその塩、
０−３）
式（１）において、ｘが３であり、Ａの置換位置がａであり、Ｒの置換位置がｂであり、Ａがスルホ基である上記０）に記載のアゾ化合物又はその塩、
０−４）
式（１）において、ｘが３であり、Ａの置換位置がａであり、Ｒの置換位置がｂであり、Ａがスルホ基であり、Ｒが塩素原子又はメトキシ基であり、Ｔがスルホ基又はカルボキシ基であり、Ｑが塩素原子である上記０）に記載のアゾ化合物又はその塩、
１）
下記式（１ａ）で表されるアゾ化合物又はその塩、

（式中、Ａ^１、Ａ^２及びＴはそれぞれ独立して水溶性置換基を表し、Ｑはそれぞれ独立して水素原子、ハロゲン原子、カルボキシ基、カルバモイル基、スルホ基、スルファモイル基、ヒドロキシ基、アミノ基、シアノ基、ホスホ基、ニトロ基、アシル基、Ｃ１〜Ｃ４アルキル基（ヒドロキシ基、カルボキシ基、カルバモイル基、及びスルホ基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルコキシ基（ヒドロキシ基、カルボキシ基、カルバモイル基、及びスルホ基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルキルスルホ基（ヒドロキシ基、カルボキシ基、カルバモイル基、又及びスルホ基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルキルチオ基（ヒドロキシ基、カルボキシ基、カルバモイル基、及びスルホ基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルキルアミノ基（ヒドロキシ基、カルボキシ基、カルバモイル基、及びスルホ基から選択される１又は２以上の置換基で置換されていても良い）、又はアシルアミノ基を表し、Ｒはそれぞれ独立して水素原子、ハロゲン原子、カルバモイル基、スルファモイル基、ヒドロキシ基、アミノ基、シアノ基、ニトロ基、アシル基、Ｃ１〜Ｃ４アルキル基（ヒドロキシ基、及びカルバモイル基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルコキシ基（ヒドロキシ基、及びカルバモイル基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルキルスルホ基（ヒドロキシ基、及びカルバモイル基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルキルチオ基（ヒドロキシ基、及びカルバモイル基から選択される１又は２以上の置換基で置換されていても良い）、Ｃ１〜Ｃ４アルキルアミノ基（ヒドロキシ基、及びカルバモイル基から選択される１又は２以上の置換基で置換されていても良い）、又はアシルアミノ基を表し、ｙは０又は１を表し、ｚは０又は１を表し、但しｙ＋ｚ＝１であり、ｘは２から４の整数を表し、ａ及びｂはＡ^１、Ａ^２又はＲの置換位置を表す。）
２）
式（１）又は式（１ａ）において、ｘが３である上記０）又は１）に記載のアゾ化合物又はその塩、
３）
式（１ａ）において、Ａ^１の置換位置がａであり、Ａ^２又はＲの置換位置がｂである上記１）又は２）に記載のアゾ化合物又はその塩、
４）
式（１ａ）において、Ａ^１及び／又はＡ^２がスルホ基である上記１）乃至３）のいずれか一項に記載のアゾ化合物又はその塩、
５）
式（１）又は式（１ａ）において、Ｔがスルホ基又はカルボキシ基である０）乃至４）のいずれか一項に記載のアゾ化合物又はその塩、
６）
式（１）又は式（１ａ）において、Ｒが塩素原子又はメトキシ基である上記０）乃至５）のいずれか一項に記載のアゾ化合物又はその塩、
７）
式（１）又は式（１ａ）において、Ｑが塩素原子又は臭素原子である上記０）乃至６）のいずれか一項に記載のアゾ化合物又はその塩、
８）
式（１ａ）において、ｘが３であり、Ａ^１の置換位置がａであり、Ａ^２又はＲの置換位置がｂであり、Ａ^１及び／又はＡ^２がスルホ基である上記１）に記載のアゾ化合物又はその塩、
９）
式（１ａ）において、ｘが３であり、Ａ^１の置換位置がａであり、Ａ^２又はＲの置換位置がｂであり、Ａ^１及び／又はＡ^２がスルホ基であり、Ｒが塩素原子又はメトキシ基であり、Ｔがスルホ基又はカルボキシ基であり、Ｑが塩素原子である上記１）に記載のアゾ化合物又はその塩、
１０）
上記０）乃至９）のいずれか一項に記載のアゾ化合物又はその塩を含有するインク組成物、
１１）
水溶性有機溶剤をさらに含有する上記１０）に記載のインク組成物、
１２）
インクジェット記録用である上記１０）又は１１）に記載のインク組成物、
１３）
上記１０）乃至１２）のいずれか一項に記載のインク組成物をインクとして用い、該インクのインク滴を記録信号に応じて吐出させて被記録材に付着させ、記録を行うインクジェット記録方法、
１４）
被記録材が情報伝達用シートである上記１３）に記載のインクジェット記録方法、
１５）
情報伝達用シートが普通紙又は多孔性白色無機物を含むインク受容層を有するシ−トである上記１４）に記載のインクジェット記録方法、
１６）
（ａ）上記０）乃至９）のいずれか一項に記載のアゾ化合物若しくはその塩、
（ｂ）上記０）乃至９）のいずれか一項に記載のアゾ化合物若しくはその塩を含有するインク組成物、又は、
（ｃ）上記０）乃至９）のいずれか一項に記載のアゾ化合物若しくはその塩及び水溶性有機溶剤を含有するインク組成物、のいずれかにより着色された着色体、
１７）
上記１３）乃至１５のいずれか一項に記載のインクジェット記録方法により着色された着色体、
１８）
上記１０）又は１１）に記載のインク組成物を含む容器が装填されたインクジェットプリンタ、
１９）
０）乃至０−４）のいずれか一項に記載のアゾ化合物又はその塩を製造する方法であって、
下記式（５）で表される化合物とハロゲン化ギ酸エステルとを縮合することを含む、方法。

（式中、Ａ、Ｔ、Ｑ、Ｒ、ｘ、ａ及びｂは、それぞれ上記式（１）における意味と同じ。）
２０）
１）乃至９）のいずれか一項に記載のアゾ化合物又はその塩を製造する方法であって、
下記式（５ａ）で表される化合物とハロゲン化ギ酸エステルとを縮合することを含む、方法。

（式中、Ａ^１、Ａ^２、Ｔ、Ｑ、Ｒ、ｘ、ｙ、ｚ、ａ及びｂは、それぞれ上記式（１ａ）における意味と同じ。）
に関する。In formula (1), A represents a water-soluble substituent. Here, the water-soluble substituent is highly hydrophilic, that is, the present invention
0)
An azo compound represented by the following formula (1) or a salt thereof,

(In the formula, A and T each independently represent a water-soluble substituent, and Q and R each independently represent a hydrogen atom, a halogen atom, a carboxy group, a carbamoyl group, a sulfo group, a sulfamoyl group, a hydroxy group, or an amino group. , A cyano group, a phospho group, a nitro group, an acyl group, a C1-C4 alkyl group (which may be substituted with one or more substituents selected from a hydroxy group, a carboxy group, a carbamoyl group, and a sulfo group) A C1-C4 alkoxy group (which may be substituted with one or more substituents selected from a hydroxy group, a carboxy group, a carbamoyl group, and a sulfo group), a C1-C4 alkylsulfo group (a hydroxy group, a carboxy group). A C1-C4 alkyl group, which may be substituted with one or more substituents selected from a group, a carbamoyl group, and a sulfo group) Thio group (which may be substituted with one or more substituents selected from hydroxy group, carboxy group, carbamoyl group, and sulfo group), C1-C4 alkylamino group (hydroxy group, carboxy group, carbamoyl group) And may be substituted with one or more substituents selected from a sulfo group), or an acylamino group, x represents an integer of 2 to 4, and a and b are substituted positions of A or R Represents.)
0-1)
In formula (1), the azo compound or salt thereof according to 0) above, wherein the substitution position of A is a and the substitution position of R is b,
0-2)
In the formula (1), the azo compound or a salt thereof according to 0) above, wherein A is a sulfo group,
0-3)
In formula (1), x is 3, the substitution position of A is a, the substitution position of R is b, and A is a sulfo group, or the azo compound or salt thereof according to 0) above,
0-4)
In the formula (1), x is 3, the substitution position of A is a, the substitution position of R is b, A is a sulfo group, R is a chlorine atom or a methoxy group, and T is a sulfo group. An azo compound or a salt thereof according to 0) above, wherein Q is a chlorine atom,
1)
An azo compound represented by the following formula (1a) or a salt thereof,

(In the formula, A ¹ , A ² and T each independently represent a water-soluble substituent, and Q each independently represents a hydrogen atom, a halogen atom, a carboxy group, a carbamoyl group, a sulfo group, a sulfamoyl group, a hydroxy group, An amino group, a cyano group, a phospho group, a nitro group, an acyl group, a C1-C4 alkyl group (which may be substituted with one or more substituents selected from a hydroxy group, a carboxy group, a carbamoyl group, and a sulfo group) Good), a C1-C4 alkoxy group (which may be substituted with one or more substituents selected from a hydroxy group, a carboxy group, a carbamoyl group, and a sulfo group), a C1-C4 alkylsulfo group (hydroxy group). , A carboxy group, a carbamoyl group, or a sulfo group, which may be substituted with one or more substituents), C1-C4 a Kirthio group (which may be substituted with one or more substituents selected from hydroxy group, carboxy group, carbamoyl group and sulfo group), C1-C4 alkylamino group (hydroxy group, carboxy group, carbamoyl group) And may be substituted with one or more substituents selected from a sulfo group), or an acylamino group, and each R independently represents a hydrogen atom, a halogen atom, a carbamoyl group, a sulfamoyl group, a hydroxy group , Amino group, cyano group, nitro group, acyl group, C1 to C4 alkyl group (which may be substituted with one or more substituents selected from hydroxy group and carbamoyl group), C1 to C4 alkoxy group (Which may be substituted with one or more substituents selected from a hydroxy group and a carbamoyl group), C1 C4 alkylsulfo group (which may be substituted with one or more substituents selected from a hydroxy group and a carbamoyl group), C1-C4 alkylthio group (1 or 2 selected from a hydroxy group and a carbamoyl group) A C1-C4 alkylamino group (which may be substituted with one or more substituents selected from a hydroxy group and a carbamoyl group), or an acylamino group. Y represents 0 or 1, z represents 0 or 1, provided that y + z = 1, x represents an integer of 2 to 4, a and b represent the substitution positions of A ¹ , A ² or R. To express.)
2)
In the formula (1) or formula (1a), x is 3 and the azo compound or salt thereof according to 0) or 1) above,
3)
In the formula (1a), the azo compound or a salt thereof according to the above 1) or 2), wherein the substitution position of A ¹ is a and the substitution position of A ² or R is b,
4)
In the formula (1a), the azo compound or a salt thereof according to any one of 1) to 3) above, wherein A ¹ and / or A ² is a sulfo group,
5)
In formula (1) or formula (1a), T is a sulfo group or a carboxy group, and the azo compound or salt thereof according to any one of 0) to 4),
6)
In the formula (1) or the formula (1a), R is a chlorine atom or a methoxy group, and the azo compound or the salt thereof according to any one of 0) to 5),
7)
In the formula (1) or the formula (1a), the azo compound or the salt thereof according to any one of 0) to 6), wherein Q is a chlorine atom or a bromine atom,
8)
In the formula (1a), x is 3, the substitution position of A ¹ is a, the substitution position of A ² or R is b, and A ¹ and / or A ² is a sulfo group The azo compound or a salt thereof,
9)
In the formula (1a), x is 3, the substitution position of A ¹ is a, the substitution position of A ² or R is b, A ¹ and / or A ² is a sulfo group, and R is chlorine An azo compound or a salt thereof according to 1) above, which is an atom or a methoxy group, T is a sulfo group or a carboxy group, and Q is a chlorine atom,
10)
An ink composition containing the azo compound or a salt thereof according to any one of 0) to 9) above;
11)
The ink composition as described in 10) above, further comprising a water-soluble organic solvent,
12)
The ink composition as described in 10) or 11) above, which is for inkjet recording,
13)
An ink jet recording method in which the ink composition according to any one of 10) to 12) above is used as an ink, and ink droplets of the ink are ejected in accordance with a recording signal to adhere to a recording material;
14)
The inkjet recording method according to 13) above, wherein the recording material is an information transmission sheet,
15)
14) The ink jet recording method according to the above 14), wherein the information transmission sheet is a sheet having an ink receiving layer containing plain paper or a porous white inorganic substance.
16)
(A) The azo compound or a salt thereof according to any one of 0) to 9) above,
(B) an ink composition containing the azo compound or a salt thereof according to any one of 0) to 9), or
(C) A colored body colored with any of the ink composition containing the azo compound or salt thereof according to any one of 0) to 9) and a water-soluble organic solvent,
17)
A colored body colored by the inkjet recording method according to any one of 13) to 15 above,
18)
An ink jet printer loaded with a container containing the ink composition according to 10) or 11) above;
19)
A method for producing the azo compound or salt thereof according to any one of 0) to 0-4),
A method comprising condensing a compound represented by the following formula (5) and a halogenated formate.

(In the formula, A, T, Q, R, x, a and b have the same meanings as in the above formula (1)).
20)
A method for producing the azo compound or salt thereof according to any one of 1) to 9),
A method comprising condensing a compound represented by the following formula (5a) with a halogenated formate.

(In the formula, A ¹ , A ² , T, Q, R, x, y, z, a and b have the same meanings as in the above formula (1a).)
About.

  The azo compound of the present invention represented by the above formula (1) or formula (1a) or a salt thereof is highly soluble in water and may be said to be a water-soluble azo compound or a salt thereof. It has a feature of good filterability in the process of producing the ink composition of the present invention containing a salt, for example, filterability for a membrane filter. In addition, an image recorded by the ink composition of the present invention containing the compound of the present invention is excellent in printing density, saturation and light resistance as compared with those using a conventional compound. As described above, the azo compound of the present invention represented by the formula (1) or the formula (1a) or a salt thereof, and the ink composition containing the same are used for various recording inks, particularly for ink jet recording. Very useful.

The present invention will be described in detail.
The azo compound of the present invention represented by the above formula (1) or a salt thereof is a water-soluble yellow dye. In the present specification, unless otherwise specified, acidic functional groups such as sulfo groups and carboxy groups are represented in the form of free acids. In addition, as described above, the present invention includes both the azo compound represented by the formula (1) or a salt of the compound, but it is complicated to always write both of them together as “a compound or a salt thereof”. . Therefore, unless otherwise specified, for convenience, both the “(azo) compound of the present invention or a salt thereof” and the “azo compound of the present invention”, that is, “the azo compound of the present invention” or “the present invention” are included. The following is simply described as “the compound of the invention”. The same applies to the azo compound represented by the formula (1a) or a salt thereof.

The compound of the present invention is represented by the above formula (1).
In formula (1), x represents an integer of 2 to 4, preferably 3.

  In formula (1), A is substituted at the position of a or b, a is more preferred, R is substituted at the position of a or b, and b is more preferred. When A is substituted at position a, R is substituted at position b, and when A is substituted at position b, R is substituted at position a. The case where R is a hydrogen atom described later is also referred to as “substituted” for the sake of convenience in this specification.

In formula (1), A represents a water-soluble substituent. Here, the water-soluble substituent means a highly hydrophilic substituent, and is a sulfo group, a carboxy group, a phospho group, a C1-C4 alkyl group (substituted with one or more sulfo groups, a carboxy group, or a phospho group. ), C1-C4 alkoxy group (substituted with one or more sulfo group, carboxy group or phospho group), C1-C4 alkyl sulfo group (substituted with one or more sulfo group, carboxy group or phospho group) C1-C4 alkylthio group (substituted with one or more sulfo group, carboxy group or phospho group), C1-C4 alkylamino group (substituted with one or more sulfo group, carboxy group or phospho group), etc. Represents. Of these, a sulfo group or a carboxy group is more preferable, and a sulfo group is more preferable.

In formula (1), T represents a water-soluble substituent. Here, the water-soluble substituent means a highly hydrophilic substituent, and is a sulfo group, a carboxy group, a phospho group, a C1-C4 alkyl group (substituted with one or more sulfo groups, a carboxy group, or a phospho group. ), C1-C4 alkoxy group (substituted with one or more sulfo group, carboxy group or phospho group), C1-C4 alkyl sulfo group (substituted with one or more sulfo group, carboxy group or phospho group) C1-C4 alkylthio group (substituted with one or more sulfo group, carboxy group or phospho group), C1-C4 alkylamino group (substituted with one or more sulfo group, carboxy group or phospho group), etc. Represents. Of these, a sulfo group or a carboxy group is more preferable.
A and T may be the same or different, and more preferably the same.

Q and R are each independently a hydrogen atom, halogen atom, carboxy group, carbamoyl group, sulfo group, sulfamoyl group, hydroxy group, amino group, cyano group, phospho group, nitro group, acyl group, C1-C4 alkyl group ( A C1-C4 alkoxy group (which may be substituted with one or more substituents selected from a hydroxy group, a carboxy group, a carbamoyl group, and a sulfo group), a hydroxy group, a carboxy group, a carbamoyl group, and a sulfo group 1 or 2 or more substituents selected from a C1-C4 alkylsulfo group (hydroxy group, carboxy group, carbamoyl group, and sulfo group). Optionally substituted with a C1-C4 alkylthio group (hydroxy group, carboxy group, carbamoyl group, and 1 or 2 or more substituents selected from a C1-C4 alkylamino group (hydroxy group, carboxy group, carbamoyl group, and sulfo group). Or an acylamino group, Q is preferably a halogen atom, more preferably a chlorine atom. R is a halogen atom, a hydroxy group, an amino group, a C1-C4 alkoxy group (which may be substituted with one or more substituents selected from a hydroxy group, a carboxy group, a carbamoyl group and a sulfo group), C1- A C4 alkylthio group (which may be substituted with one or more substituents selected from a hydroxy group, a carboxy group, a carbamoyl group, and a sulfo group) is preferred, and a halogen atom, a C1-C4 alkoxy group (hydroxy group, More preferably 1 or 2 or more substituents selected from a carboxy group, a carbamoyl group, and a sulfo group), and a C1 to C4 alkoxy group that is not substituted with a halogen atom or a substituent is more preferable. More preferred are a chlorine atom and a methoxy group. The acyl group is preferably a C1-C4 alkanoyl group, and examples thereof include a formyl group, an acetyl group, a propionyl group, and a butanoyl group. The acylamino group is preferably an amino group substituted with one acyl group.

  Among the above substitution positions of x, Q, A, T and R, a compound in which preferable ones are combined is more preferable, and a compound in which more preferable ones are combined is more preferable. The same applies to combinations of preferable and more preferable ones.

The azo compound represented by the above formula (1) or a salt thereof is preferably the azo compound represented by the above formula (1a) or a salt thereof. A in Formula (1) can be represented by A ¹ and (A ² ) _y (y represents 0 or 1) in Formula (1a). R in Formula (1) can be represented by (R) _z (z represents 0 or 1) in Formula (1a). y + z = 1. y is preferably 0 and z is preferably 1.

In formula (1a), A ¹ and A ² each independently represent a water-soluble substituent. The water-soluble substituent has the same meaning as the water-soluble substituent in formula (1).

  In the formula (1a), each R independently represents a hydrogen atom, a halogen atom, a carbamoyl group, a sulfamoyl group, a hydroxy group, an amino group, a cyano group, a nitro group, an acyl group, a C1-C4 alkyl group (hydroxy group, and carbamoyl). Optionally substituted with one or more substituents selected from a group), C1-C4 alkoxy groups (substituted with one or more substituents selected from a hydroxy group and a carbamoyl group) Good), a C1-C4 alkylsulfo group (which may be substituted with one or more substituents selected from a hydroxy group and a carbamoyl group), a C1-C4 alkylthio group (selected from a hydroxy group and a carbamoyl group) Optionally substituted with one or more substituents), a C1-C4 alkylamino group (hydroxy group, and carba In one or more substituents selected from-yl group may be substituted), or an acylamino group. In formula (1a), preferred R, more preferred R, still more preferred R, and even more preferred R are the same as in R of formula (1).

In the formula (1a), a and b represent the substitution positions of A ¹ , A ² or R. When A ¹ is substituted at position a, A ² or R is substituted at position b, and when A ¹ is substituted at position b, A ² or R is substituted at position a is doing. A ¹ is preferably substituted at position a and A ² or R is preferably substituted at position b, more preferably A ¹ is substituted at position a and R is substituted at position b. In the latter case, z is 1 and y is 0.

  In Formula (1a), T, Q, and x are the same as T, Q, and x in Formula (1).

  The compound of the present invention represented by the above formula (1) can be produced, for example, as follows. In addition, x, A, T, R, Q, a, and b used as appropriate in the following formulas (2a), (3a), (4), and (5) have the same meaning as in the above formula (1). To express.

  The compound represented by the following formula (2a) is converted into a methyl-ω-sulfonic acid derivative represented by the following formula (3a) using sodium bisulfite and formalin.

Preferably, the compound represented by the following formula (2) is converted into a methyl-ω-sulfonic acid derivative represented by the following formula (3) using sodium bisulfite and formalin.
Subsequently, the compound represented by the following formula (4) is diazotized by a conventional method to obtain the methyl-ω-sulfonic acid derivative represented by the formula (3a) obtained above, a reaction temperature of 0 to 15 ° C., pH 4 A compound represented by the following formula (5) is obtained by carrying out a coupling reaction at ˜6 and subsequently carrying out a hydrolysis reaction at a reaction temperature of 80 to 95 ° C. and a pH of 10.5 to 11.5. In addition, this synthesis | combination is a method according to the method as described in international publication 2011/122426.

  Subsequently, the compound represented by the above formula (5) (2 mol) and a halogenated formate (1 mol), for example, paranitrophenyl chloroformate (1 mol) are condensed at a reaction temperature of 30 to 60 ° C. and a pH of 4 to 8. Thus, the compound of the present invention represented by the above formula (1) can be obtained.

The compound represented by the above formula (4) and the compound represented by the above formula (5) are preferably compounds represented by the following formulas (4a) and (5a), respectively. The azo compound represented by (1a) can be obtained.

Specific examples of the compound of the present invention represented by the above formula (1) are shown in Tables 1 to 7 below. However, the present invention is not limited to these specific examples. In Tables 1 to 7, the sulfo group or carboxy group is represented in the form of a free acid. Tables 1 to 7 also show specific examples of the compounds of the present invention represented by the formula (1a). In this case, when y in the formula (1a) is 0, A in Tables 1 to 7 represents the formula (1a). corresponding to ^{a 1} in).

The compound of the above formula (1) (including the compound of the formula (1a), the same shall apply hereinafter) also exists as a free acid or a salt thereof. Examples of the salt of the compound represented by the formula (1) include salts with inorganic or organic cations. Specific examples of the inorganic cation salt include alkali metal salts such as lithium salts, sodium salts, potassium salts and the like; and ammonium salts (NH ₄ ⁺ ). Moreover, as an organic cation, although the salt of the quaternary ammonium represented, for example by following formula (6) is mentioned, It is not limited to these.

In the above formula (6), Z ^{1 to} Z ⁴ each independently represent a hydrogen atom, a C1-C4 alkyl group, a hydroxy C1-C4 alkyl group, or a hydroxy C1-C4 alkoxy C1-C4 alkyl group, and Z ^{1 to} Z ^At least one of ⁴ is a group other than a hydrogen atom.

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

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

As will be apparent to those skilled in the art, the salt or free acid of the compound of formula (1) can be easily obtained by the following method or the like.
For example, in the synthesis reaction of the compound of formula (1), a water-soluble organic solvent such as acetone or C1-C4 alcohol is added to the reaction solution after completion of the final step or an aqueous solution containing a salt of the compound of formula (1). The solid salt precipitated by the method of adding; the method of salting out by adding sodium chloride; and the like are filtered and separated to obtain the sodium salt of the compound of the above formula (1) as a wet cake.
Further, after dissolving the obtained sodium salt wet cake in water, an acid such as hydrochloric acid is added to adjust the pH appropriately, and the precipitated solid is separated by filtration, whereby the free acid of the compound of the above formula (1) is obtained. Or a mixture of a free acid and a sodium salt in which a part of the compound of the formula (1) is a sodium salt.
Also, after dissolving the obtained sodium salt wet cake or its dry solid in water, an ammonium salt such as ammonium chloride is added, and an acid such as hydrochloric acid is added to adjust the pH appropriately, for example, to pH 1 to 3, By separating the precipitated solid by filtration, an ammonium salt of the compound of the above formula (1) can be obtained. A mixture of an ammonium salt of the compound of formula (1) and a sodium salt of the compound of formula (1) by appropriately adjusting the amount or / and pH of ammonium chloride to be added; or the free acid of the compound of formula (1) And a mixture of ammonium salts;
Further, as described later, a free acid solid can be directly obtained by adding a mineral acid (for example, hydrochloric acid, sulfuric acid, etc.) to the reaction solution after completion of the above reaction. In this case, the wet cake of the free acid of the compound of formula (1) is added to water and stirred, for example, potassium hydroxide; lithium hydroxide; aqueous ammonia; or water of organic quaternary ammonium of formula (6) By adding an oxide; etc. to form a salt, a potassium salt, a lithium salt, an ammonium salt, or a quaternary ammonium salt according to each added compound can be obtained. By limiting the number of moles of the above-mentioned hydroxide to be added with respect to the number of moles of free acid, for example, a mixed salt of lithium salt and sodium salt, etc .; and a mixture of lithium salt, sodium salt, and ammonium salt Salts and the like can also be prepared. The salt of the compound of the above formula (1) may change the physical properties such as solubility or the ink performance when used as an ink depending on the type of the salt. For this reason, it is also preferable to select the type of salt according to the intended ink performance.

  After completion of the reaction, the compound of the present invention of the above formula (1) can be isolated as a solid free acid by adding a mineral acid such as hydrochloric acid, and the resulting free acid solid is water or, for example, hydrochloric acid water or the like. By washing with acidic water, inorganic salts (inorganic impurities) contained as impurities, such as sodium chloride and sodium sulfate, can be removed. As described above, the free acid of the compound of the present invention obtained as described above is obtained by treating the obtained wet cake or its dried solid with a desired inorganic or organic base in water to give a salt of the corresponding compound. Solution. Examples of the inorganic base include alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; and ammonium hydroxide (ammonia water). And the like. Examples of the organic base include, but are not limited to, organic amines corresponding to the quaternary ammonium represented by the above formula (6), for example, alkanolamines such as diethanolamine and triethanolamine.

  The compounds of the present invention are suitable for the dyeing of natural and synthetic fiber materials or blends, and also for the production of writing inks and ink jet recording ink compositions. For example, the reaction liquid after completion of the final step in the synthesis reaction of the compound of the present invention represented by the formula (1) can be directly used for the production of the ink composition of the present invention. However, for example, after the reaction solution or the like is dried by the above-described method or a spray drying method to isolate the compound, the obtained compound can be processed into an ink composition.

  In the ink composition of the present invention, the compound of the above formula (1) is dissolved in water or a mixed solution (also referred to as an aqueous medium) of water and a water-soluble organic solvent (an organic solvent that can be mixed with water). An ink preparation agent is added as necessary. When this ink composition is used as an ink for an ink jet printer, a metal cation chloride contained as an impurity, such as sodium chloride; sulfate, such as sodium sulfate; Is preferred. In this case, for example, the total content of sodium chloride and sodium sulfate is about 1% by mass or less with respect to the total mass of the compound of formula (1), and the lower limit is 0% by mass, that is, below the detection limit of the detection instrument. Good. As a method for producing a compound having a small amount of inorganic impurities, for example, a method using a known reverse osmosis membrane; or a dry product or a wet cake of the compound of the present invention, for example, acetone or C1-C4 alcohol (for example, methanol, ethanol, In addition to a water-soluble organic solvent such as isopropanol or the like, or a water-containing water-soluble organic solvent, suspension purification or crystallization methods, and the like can be mentioned. Desalination treatment or the like may be performed by these methods.

  In the ink composition of the present invention, the compound of the above formula (1) is usually 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass in the total mass of the ink composition. contains.

  The ink composition of the present invention is prepared using water as a medium, and may optionally contain a water-soluble organic solvent and an ink preparation agent as long as the effects of the present invention are not impaired.

  The water-soluble organic solvent dissolves the dye; prevents the composition from drying (maintains a wet state); adjusts the viscosity of the composition; promotes penetration of the dye into the recording material; adjusts the surface tension of the composition; It is used for the purpose of effects such as defoaming of a product, and is preferably contained in the ink composition of the present invention.

  Examples of the ink preparation agent include antiseptic / antifungal agents, pH adjusting agents, chelating reagents, rust preventive agents, ultraviolet absorbers, viscosity adjusting agents, dye dissolving agents, antifading agents, surface tension adjusting agents, antifoaming agents, etc. Known additives may be mentioned.

  The content of the water-soluble organic solvent is 0 to 60% by mass, preferably 10 to 50% by mass, and the ink preparation agent is 0 to 20% by mass, preferably 0, based on the total mass of the ink composition of the present invention. It is good to use ~ 15 mass%. In the ink composition of the present invention, the balance other than the compound of the above formula (1), the water-soluble organic solvent, and the ink preparation agent is water.

  Examples of the water-soluble organic solvent include C1-C4 alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol and tert-butanol; N, N-dimethylformamide, N , N-dimethylacetamide and the like; 2-pyrrolidone, N-methyl-2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one or 1,3-dimethylhexahydropyrimido Heterocyclic ketones such as 2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; cyclic ethers such as tetrahydrofuran, dioxane; ethylene glycol, 1, 2- or 1,3-propylene glycol, 1,2 Or mono having a C2-C6 alkylene unit such as 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, Oligo, or polyalkylene glycol or thioglycol; polyol (preferably triol) such as trimethylolpropane, glycerin, hexane-1,2,6-triol; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol Monoethyl ether, diethylene glycol monobutyl ether (butyl carbitol), triethylene Recall monomethyl ether, C1-C4 monoalkyl ether of polyhydric alcohol such as triethylene glycol monoethyl ether; .gamma.-butyrolactone; dimethyl sulfoxide; and the like.

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

  Preferred as the water-soluble organic solvent is isopropanol, glycerin, mono-, di- or triethylene glycol, dipropylene glycol, 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, 1,3-dimethylimidazolidin-2-one N-methyl-2-pyrrolidone, trimethylolpropane and butyl carbitol, more preferably isopropanol, glycerin, diethylene glycol, 2-pyrrolidone, N-methyl-2-pyrrolidone and butyl carbitol. These water-soluble organic solvents are used alone or in combination.

Examples of the antiseptic / antifungal agent include organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, benzothiazole, nitrile, pyridine, 8-oxyquinoline, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiadiazine, anilide, adamantane, dithiocarbamate, bromo Indanone compound, benzyl bromacetate compound, inorganic salt compound and the like can be mentioned.
An example of the organic halogen compound is sodium pentachlorophenol.
Examples of the pyridine oxide compound include sodium 2-pyridinethiol-1-oxide.
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, 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 acetate, sodium sorbate, sodium benzoate and the like; and trade names Proxel ^RTM GXL (S) and Proxel ^RTM XL-2 (S) manufactured by Arch Chemical Co., Each is listed. In the present specification, the superscript “RTM” means a registered trademark.

  As the pH adjuster, any substance can be used as long as it can control the pH of the ink within the range of 6.0 to 11.0 for the purpose of improving the storage stability of the ink. For example, alkanolamines such as diethanolamine and triethanolamine; hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide; ammonium hydroxides; or alkali metals such as lithium carbonate, sodium carbonate and potassium carbonate And carbonates; aminosulfonic acids such as taurine; and the like.

  Examples of the chelating reagent include disodium 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 ultraviolet absorber include benzophenone compounds, benzotriazole compounds, cinnamic acid compounds, triazine compounds, and stilbene compounds. In addition, a compound that absorbs ultraviolet rays such as a benzoxazole-based compound and emits fluorescence, a so-called fluorescent whitening agent, and the like can also be used.

  Examples of the viscosity modifier include water-soluble polymer compounds in addition to water-soluble organic solvents, such as polyvinyl alcohol, cellulose derivatives, polyamines, and polyimines.

  Examples of the dye solubilizer include urea, ε-caprolactam, ethylene carbonate, and the like. Of these, urea is preferably used.

  The anti-fading agent is used for the purpose of improving image storage stability. As the antifading agent, various organic and metal complex antifading agents can be used. Examples of organic anti-fading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, and heterocycles, and metal complexes Examples thereof include nickel complexes and zinc complexes.

  Examples of the surface tension adjusting agent include a surfactant, and examples thereof include an anionic surfactant, an amphoteric surfactant, a cationic surfactant, and a nonionic surfactant.

  Examples of anionic surfactants include alkyl sulfocarboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and salts thereof, N-acyl methyl taurate, alkyl sulfate polyoxyalkyl ethers Sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkylaryl sulfonate, diethylsulfosuccinate Salts, diethylhexylsulfosuccinate, dioctylsulfosuccinate and the like.

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

  Amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine, and other imidazoline derivatives. Etc.

Nonionic surfactants include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene alkyl ether; Ester systems such as polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate; 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4-octyne-3,6-diol, 3,5-dimethyl -1-hexyne-3-acetylene glycol (alcohol) -based ol; Nissin Chemical Industry Co., Ltd. trade name Surfynol ^RTM 104, 82, 465, Olfine ^RTM STG; SIGMA-ALDRICH Corp. Product Name Tergitol ^RTM 15-S-7;

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

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

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

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

  As a method for recording on a recording material by the ink jet recording method of the present invention, the following method is exemplified. That is, a container filled with the ink composition of the present invention is loaded into a predetermined position of an ink jet printer, the ink composition of the present invention is used as ink, and ink droplets of the ink are ejected according to a recording signal to be recorded. This is a method for recording on a material. Some inkjet printers use, for example, a piezo method using mechanical vibration; a bubble jet (registered trademark) method using bubbles generated by heating; and the like. The ink jet recording method of the present invention can be used by any method.

  In order to obtain a higher-definition recorded image, there are cases where two types of ink containing the same pigment are loaded into one inkjet printer. The difference between the two types of inks is the pigment content, one of which has a high content and the other of which has a low content, and is used as an ink set. The ink composition of the present invention can also be used as such an ink set. Further, the ink composition of the present invention may be used for one of the ink sets, and a known ink (composition) may be used for the other.

  The ink composition of the present invention may be a yellow ink composition containing the compound of the present invention and a known yellow dye for the purpose of fine-tuning the hue within the range that does not impair the effects obtained by the present invention. In addition, the compound of the present invention can be used in combination with a magenta dye or a cyan dye for the purpose of toning inks of other colors, such as black ink, or for preparing red ink or green ink. Furthermore, for the purpose of obtaining a full-color recorded image, the ink composition of the present invention can be used in combination with inks of various colors such as magenta, cyan, and, if necessary, green, blue (or violet), red, and black. . In this case, each color ink may be filled in each container, and these containers may be loaded into a predetermined position of the ink jet printer and used for ink jet recording.

Examples of the recording material used in the inkjet recording method of the present invention include information transmission sheets such as paper and film, fibers and fabrics (cellulose, nylon, wool, etc.), leather, base materials for color filters, and the like. A transmission sheet is preferred. The information transmission sheet is not particularly limited, and a plain paper as well as a surface-treated sheet, specifically, a paper, synthetic paper, a substrate such as a film provided with an ink receiving layer, or the like is used. The ink receiving layer is a layer having an action such as absorbing ink and accelerating its drying. The ink receiving layer is formed by, for example, a method of impregnating or coating the base material with a cationic polymer; inorganic fine particles capable of absorbing the pigment in the ink, together with a hydrophilic polymer such as polyvinyl alcohol or polyvinylpyrrolidone, on the surface of the base material. It is provided by the method of coating; Examples of the material of the inorganic fine particles that can absorb the coloring matter in the ink include porous silica, alumina sol, and special ceramics.
The information transmission sheet having such an ink receiving layer is usually called an inkjet exclusive paper, an inkjet exclusive film, a glossy paper, a glossy film or the like. Examples of representative commercial products of information transmission sheets having an ink receiving layer include products manufactured by Canon Inc., trade name Professional Photo Paper, Canon Photo Paper / Glossy Pro [Platinum Grade], and Glossy Gold; Seiko Epson ( Co., Ltd., trade name photo paper Crispia (high gloss), photo paper (gloss); Nihon Hewlett-Packard Co., Ltd., trade name Advanced Photo Paper (gloss); Fuji Film Co., Ltd. Pro; manufactured by Brother Industries, Ltd., trade name: photographic glossy paper BP71G;
Also, plain paper means paper that is not particularly provided with an ink receiving layer, and many different types are commercially available depending on the application. Among commercially available plain papers, for ink-jet recording, double-sided fine plain paper (manufactured by Seiko Epson Corporation); PB PAPER GF-500 (manufactured by Canon Inc.); Multipurpose Paper, All-in-one Printing Paper ( Hewlett Packard). In addition, plain paper copy (PPC) paper or the like whose use is not limited to ink jet recording is also plain paper.

  The colored product of the present invention comprises: (a) the water-soluble azo compound of the present invention or a salt thereof; (b) the ink composition of the present invention containing the compound or a salt thereof; The ink composition of the present invention containing an organic solvent means a colored substance. The substance to be colored is not particularly limited, and examples thereof include, but are not limited to, the recording material described above. Preferably, the above-mentioned recording material is colored. The coloring method for the substance is not particularly limited, and examples thereof include a printing method such as a dip dyeing method, a textile printing method, and screen printing, and the ink jet recording method of the present invention. The ink jet recording method of the present invention is preferable. Among the colored bodies, a colored body colored by the ink jet recording method of the present invention is preferable.

The water-soluble azo compound of the present invention represented by the above formula (1) or a salt thereof is excellent in solubility in water or a water-soluble organic solvent. Moreover, it has the characteristic that the filterability with respect to a membrane filter, for example in the process of manufacturing the ink composition of this invention is favorable. The ink composition of the present invention is very clear on a recording material such as plain paper and an information transmission sheet having an ink receiving layer, has a high saturation and printing density, and is capable of producing a yellow recorded image of an ideal hue. give. Therefore, it is also possible to faithfully reproduce a photographic color image on paper. In addition, the ink composition of the present invention has very good storage stability without solid deposition, physical property change, hue change, etc. after long-term storage.
Even when the ink composition of the present invention is used as an inkjet ink, solid precipitation due to drying of the ink composition in the vicinity of the nozzles is very unlikely to occur, and the ejector (recording head) is not blocked. Further, the ink composition of the present invention uses a continuous ink jet printer, and is used physically even when the ink is recirculated at a relatively long time interval or intermittently used by an on-demand ink jet printer. No change in properties.
Further, the image recorded on the information transmission sheet having the ink receiving layer by the ink composition of the present invention has various fastnesses such as water resistance, moisture resistance, ozone gas resistance, abrasion resistance and light resistance, particularly light resistance. For this reason, it has excellent long-term storage stability of photographic images. In addition, compared to conventional inks, it is also excellent in color development properties such as saturation, brightness, and print density on glossy paper, particularly in high saturation.
As described above, the water-soluble azo compound of the present invention represented by the formula (1) or a salt thereof and the ink composition of the present invention containing the same are used for various recording ink applications, particularly for ink jet recording. Very useful.

  EXAMPLES The present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. Unless otherwise specified, “part” and “%” in the text are based on mass, and the reaction temperature is the internal temperature. Among the synthesized compounds, those measured for λmax (maximum absorption wavelength) showed measured values in an aqueous solution having a pH of 7-8. Moreover, in each structural formula of the compound obtained in the Example, acidic functional groups, such as a carboxy group and a sulfo group, were described in the form of a free acid.

[Raw material synthesis]
To 100 parts of N, N-dimethylformamide, 22.5 parts of 2-acetylamino-4-chlorophenol and 16.8 parts of potassium carbonate are added, and the mixture is heated to 80 to 90 ° C. and stirred for 1 hour. , 20.3 parts of ethyl bromobutyrate diluted with 50 parts of N-dimethylformamide was added dropwise over about 30 minutes. After reacting at the same temperature for 1 hour, cooling to room temperature and adding 200 parts of water, stirring for 1 hour, separating the precipitated solid by filtration, dispersing the resulting wet cake in 400 parts of water, After adjusting the pH to 11, the mixture is stirred at 80 to 95 ° C. for 5 hours while maintaining the same pH. Further, 80 parts of sodium chloride is added to the obtained reaction solution and stirred for 1 hour, and the precipitated solid is separated by filtration. To obtain a wet cake containing 5-chloro-2- (3-carbopropoxy) aniline. The obtained wet cake was washed with 200 parts of isopropyl alcohol, and the obtained wet cake was dried with a hot air dryer at 80 ° C. to obtain 27.0 parts of 5-chloro-2- (3-carbopropoxy) aniline. It was.

[(A) Synthesis of Dye]
[Example 1]
(Process 1)
24.9 parts of 5-amino-2-chlorobenzenesulfonic acid was dissolved in 200 parts of water while adjusting the pH to 6 with sodium hydroxide, and then 8.7 parts of sodium nitrite was added. This solution was added dropwise to 200 parts of 5% hydrochloric acid at 0 to 10 ° C. over 30 minutes, followed by stirring at 10 ° C. or lower for 1 hour to carry out a diazotization reaction to prepare a diazo reaction liquid.
Meanwhile, 26.2 parts of 5-chloro-2- (3-sulfopropoxy) aniline was dissolved in 130 parts of water while adjusting the pH to 7 with sodium hydroxide to obtain 11.4 parts of sodium bisulfite and 9.4 parts. Was used as a methyl-ω-sulfonic acid derivative by a conventional method.
The obtained methyl-ω-sulfonic acid derivative was added to the previously prepared diazo reaction solution, and the mixture was stirred at 0 to 15 ° C. and pH 4 to 7 for 24 hours. The reaction solution was adjusted to pH 11 with sodium hydroxide and then stirred at 80 to 95 ° C. for 5 hours while maintaining the same pH. Further, 200 parts of sodium chloride was added to the resulting reaction solution and stirred for 1 hour. The precipitated solid was separated by filtration to obtain 80 parts of an azo compound represented by the following formula (7) as a wet cake.

(Process 2)
65 parts of a wet cake of the compound represented by the above formula (7) was dissolved in 200 parts of hot water at 60 ° C., and 5 parts of paranitrophenyl chloroformate was added over 2 hours. During the charging, the solution was adjusted to pH 5.0 to 7.0 and the liquid temperature to 55 to 65 ° C. with sodium carbonate. After completion of the reaction, 40 parts of sodium chloride was added to the solution and stirred for 1 hour, and the precipitated solid was separated by filtration to obtain 35 parts of a wet cake. The wet cake was added to 100 parts of water and dissolved by stirring, and then a 25% aqueous sodium hydroxide solution was added to adjust the pH to 8-9. The wet cake obtained by adding 400 parts of 2-propanol to this aqueous solution and separating the precipitated solid by filtration is dried with a hot air dryer at 80 ° C., whereby the present invention represented by the following formula (8) is obtained. 13.3 parts of a sodium salt of a water-soluble azo compound (λmax: 421.0 nm) was obtained.

[Example 2]
(Process 1)
Example 1 except that 24.4 parts of 3-amino- 6 -methoxybenzenesulfonic acid is used in place of 24.9 parts of 5-amino-2-chlorobenzenesulfonic acid in Example 1 (Step 1) above. In the same manner as in Step 1, 80 parts of an azo compound represented by the following formula (9) was obtained as a wet cake.

(Process 2)
65 parts of a wet cake of the compound represented by the above formula (9) was dissolved in 200 parts of hot water at 60 ° C., and 5 parts of paranitrophenyl chloroformate was added over 2 hours. During the charging, the solution was adjusted to pH 5.0 to 7.0 and the liquid temperature to 55 to 65 ° C. with sodium carbonate. After completion of the reaction, 40 parts of sodium chloride was added to the solution and stirred for 1 hour, and the precipitated solid was separated by filtration to obtain 35 parts of a wet cake. The wet cake was added to 100 parts of water and dissolved by stirring, and then a 25% aqueous sodium hydroxide solution was added to adjust the pH to 8-9. The wet cake obtained by adding 400 parts of 2-propanol to this aqueous solution and separating the precipitated solid by filtration is dried with a hot air dryer at 80 ° C., whereby the present invention represented by the following formula (10) is obtained. 13.3 parts of a sodium salt of a water-soluble azo compound (λmax: 416.0 nm) was obtained.

[Example 3]
(Process 1)
In Example 1 (Step 1) above, instead of using 26.2 parts of 5-chloro-2- (3-sulfopropoxy) aniline, 31.1 parts of 5-bromo-2- (3-sulfopropoxy) aniline were used. Except for using, in the same manner as in Step 1 of Example 1, 80 parts of an azo compound represented by the following formula (12) was obtained as a wet cake.

(Process 2)
70 parts of a wet cake of the compound represented by the above formula (12) was dissolved in 200 parts of hot water at 60 ° C., and 5 parts of paranitrophenyl chloroformate was added over 2 hours. During the charging, the solution was adjusted to pH 5.0 to 7.0 and the liquid temperature to 55 to 65 ° C. with sodium carbonate. After completion of the reaction, 40 parts of sodium chloride was added to the solution and stirred for 1 hour, and the precipitated solid was separated by filtration to obtain 35 parts of a wet cake. The wet cake was added to 100 parts of water and dissolved by stirring, and then a 25% aqueous sodium hydroxide solution was added to adjust the pH to 8-9. 400 parts of 2-propanol was added to this aqueous solution, and the wet cake obtained by separating the precipitated solid by filtration was dried with a hot air dryer at 80 ° C., whereby the present invention represented by the following formula (13) was obtained. 14.4 parts of a water-soluble azo compound sodium salt (λmax: 418.0 nm) were obtained.

[Example 4]
(Process 1)
In the above Example 1 (Step 1), instead of using 26.2 parts of 5-chloro-2- (3-sulfopropoxy) aniline, 23.0 parts of 5-chloro-2- (3-carbopropoxy) aniline were used. Except for using, in the same manner as in Step 1 of Example 1, 80 parts of an azo compound represented by the following formula (14) was obtained as a wet cake.

(Process 2)
61 parts of a wet cake of the compound represented by the above formula (14) was dissolved in 200 parts of hot water at 60 ° C., and 5 parts of paranitrophenyl chloroformate was added over 2 hours. During the charging, the solution was adjusted to pH 5.0 to 7.0 and the liquid temperature to 55 to 65 ° C. with sodium carbonate. After completion of the reaction, 40 parts of sodium chloride was added to the solution and stirred for 1 hour, and the precipitated solid was separated by filtration to obtain 35 parts of a wet cake. The wet cake was added to 100 parts of water and dissolved by stirring, and then a 25% aqueous sodium hydroxide solution was added to adjust the pH to 8-9. The wet cake obtained by adding 400 parts of 2-propanol to this aqueous solution and separating the precipitated solid by filtration is dried with a hot air dryer at 80 ° C., whereby the present invention represented by the following formula (15) is obtained. 12.4 parts of a sodium salt of a water-soluble azo compound (λmax: 417.0 nm) was obtained.

[(B) Preparation of ink]
[Example 5]
Using the azo compound of the present invention obtained in Example 1 above [sodium salt of the compound represented by formula (8)] as a dye, the composition shown in Table 8 below was mixed to give a solution. An ink composition of the invention was obtained. The obtained ink composition was filtered through a 0.45 μm membrane filter to remove impurities, and a test ink was prepared. The pH of this test ink was in the range of 8.0 to 9.5. Further, in Table 8 below, “surfactant” used was the trade name Surfinol ^RTM 104PG50 manufactured by Nissin Chemical Co., Ltd. The ink prepared using the compound obtained in Example 1 is referred to as Example 5. An ink prepared by mixing the compositions shown in Table 8 below and using the compound obtained in Example 2 is referred to as Example 6.
Ink prepared using the compound obtained in Example 4 was prepared by mixing the composition shown in Table 9 below and using the compound obtained in Example 3 as Example 7. Is taken as Example 8. In Table 9, “Surfactant” is trade name Surfinol ^RTM 104PG50 manufactured by Nissin Chemical Co., Ltd.

[Comparative Examples 1 and 2]
A comparison was made in the same manner as in Example 5 except that the compound (5) (compound represented by the following formula (11)) described in Patent Document 4 was used instead of the compound of the present invention obtained in Example 1. An ink was prepared. This ink preparation is referred to as Comparative Example 1.
Moreover, it replaces with the compound of this invention obtained in Example 1, and uses the compound (5) (compound represented by following formula (11)) of the said patent document 4 similarly to Example 7 except using. Comparative inks were prepared. This ink preparation is referred to as Comparative Example 2.

[(C) Inkjet recording]
For each of the inks prepared in Examples 5 to 8 and Comparative Examples 1 and 2, using an inkjet printer (trade name: PIXUS ^RTM ip7230, manufactured by Canon Inc.), for printing density (Dy value) test, saturation (C * value) Inkjet recording was performed on two types of glossy paper (inkjet dedicated paper) for testing. During ink jet recording, an image pattern was prepared so that the reflection density was obtained in several gradations, and a recorded matter having a yellow gradation was obtained. Various tests were performed using the obtained recorded matter as a test piece.

Glossy paper 1: manufactured by Canon Inc., trade name: Canon photo paper, platinum grade (PT-201)
Glossy paper 2: Seiko Epson, product name: Photographic paper Krispia

Saturation (C * value) and reflection density (Dy value) were measured at the highest gradation. A colorimetry system (trade name: SpectroEye ^RTM , manufactured by X-right) was used for measurement of saturation and reflection density. Colorimetry was performed under the conditions of DIN, a viewing angle of 2 degrees, and a light source D50 as a density reference.
Various test methods for recorded images and evaluation methods for test results are described below.
[(D) Print density test]
Of each test piece, the yellow print density (Dy value) was measured for the gradation portion having the highest reflection density by the colorimetry system. The results are shown in Tables 10 and 11.

表１０、１１の結果から、上記イエロー印字濃度試験（Ｄｙ値）において、実施例は比較例より優れる結果を示し、光沢紙２において特に優れた結果を示した。

From the results of Tables 10 and 11, in the above yellow printing density test (Dy value), the example showed a result superior to the comparative example, and the glossy paper 2 showed a particularly excellent result.

[(E) Saturation test]
Among the test pieces, yellow saturation (C * value) was measured for the gradation portion having the highest reflection density by the color measurement system. The results are shown in Tables 12 and 13 below.

  From the results of Tables 12 and 13, the example showed superior results to the comparative example in any glossy paper in saturation (C * value).

  Therefore, the water-soluble azo compound of the present invention or a salt thereof, and the ink composition of the present invention containing the compound have a clear hue compared to conventional dyes, and have a yellow print density. It can be seen that the value is high and the color developability is excellent.

  The water-soluble azo compound of the present invention or a salt thereof, which is a yellow dye, and the yellow ink composition of the present invention containing the same are recorded images having excellent color developability such as saturation, brightness, and print density on glossy paper give. Further, since an alkoxyaniline substituted with a water-soluble substituent such as a sulfo group is used in place of a raw material such as o-anisidine used for an existing dye, few compounds are generated due to decomposition of the pigment. Therefore, the compound and the ink composition containing the compound are very useful for various recording applications, particularly for inkjet recording applications.

Claims (18)

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

(In the formula, A ¹ and A ² are each independently a sulfo group, a carboxy group, a phospho group, a C1-C4 alkyl group (substituted by one or more sulfo groups, a carboxy group, or a phospho group), C1-C4. Alkoxy group (substituted with one or more sulfo group, carboxy group or phospho group), C1-C4 alkyl sulfo group (substituted with one or more sulfo group, carboxy group or phospho group), C1-C4 alkylthio Represents a group (substituted with one or more sulfo group, carboxy group or phospho group), C1-C4 alkylamino group (substituted with one or more sulfo group, carboxy group or phospho group) , and T represents Each independently represents a sulfo group or a carboxy group, and each Q independently represents a hydrogen atom, a halogen atom, a carboxy group, a carbamoyl group, a sulfo group, or a sulfamoyl group. Group, hydroxy group, amino group, cyano group, phospho group, nitro group, acyl group, C1-C4 alkyl group (one or more substituents selected from hydroxy group, carboxy group, carbamoyl group, and sulfo group) C1-C4 alkoxy group (which may be substituted with one or more substituents selected from a hydroxy group, a carboxy group, a carbamoyl group, and a sulfo group), C1-C4 An alkylsulfo group (which may be substituted with one or more substituents selected from a hydroxy group, a carboxy group, a carbamoyl group, and a sulfo group), a C1-C4 alkylthio group (a hydroxy group, a carboxy group, a carbamoyl group) A C1 to C4 alkylamino group (optionally substituted with one or two or more substituents selected from a group and a sulfo group), Roxy group, optionally substituted with one or more substituents selected from a carboxy group, a carbamoyl group, and a sulfo group), or an acylamino group, each R independently represents a hydrogen atom, a halogen atom, A carbamoyl group, a sulfamoyl group, a hydroxy group, an amino group, a cyano group, a nitro group, an acyl group, a C1-C4 alkyl group (which may be substituted with one or more substituents selected from a hydroxy group and a carbamoyl group) Good), a C1-C4 alkoxy group (which may be substituted with one or more substituents selected from a hydroxy group and a carbamoyl group), a C1-C4 alkylsulfo group (selected from a hydroxy group and a carbamoyl group) Optionally substituted with one or more substituents), a C1-C4 alkylthio group (hydroxy group, and Optionally substituted with one or more substituents selected from rubamoyl groups), C1-C4 alkylamino groups (substituted with one or more substituents selected from hydroxy groups and carbamoyl groups). Or an acylamino group, y represents 0 or 1, z represents 0 or 1, provided that y + z = 1, x represents an integer of 2 to 4, and a and b represent A ^1. , A ² or R represents a substitution position. )   The azo compound or a salt thereof according to claim 1, wherein x is 3 in the formula (1a). The azo compound or a salt thereof according to claim 1 or 2, wherein in formula (1a), the substitution position of A ¹ is a and the substitution position of A ² or R is b. The azo compound or a salt thereof according to any one of claims 1 to 3, wherein in formula (1a), A ¹ and / or A ² is a sulfo group. The azo compound or a salt thereof according to any one of claims 1 to 4 , wherein in the formula (1a), R is a chlorine atom or a methoxy group. The azo compound or a salt thereof according to any one of claims 1 to 5 , wherein in the formula (1a), Q is a chlorine atom or a bromine atom. In the formula (1a), x is 3, the substitution position of A ¹ is a, the substitution position of A ² or R is b, and A ¹ and / or A ² is a sulfo group. The azo compound or its salt as described. In the formula (1a), x is 3, the substitution position of A ¹ is a, the substitution position of A ² or R is b, A ¹ and / or A ² is a sulfo group, and R is chlorine The azo compound or a salt thereof according to claim 1, which is an atom or a methoxy group, and Q is a chlorine atom. An ink composition comprising the azo compound or a salt thereof according to any one of claims 1 to 8 . The ink composition according to claim 9 , further comprising a water-soluble organic solvent. The ink composition according to claim 9 or 10 , which is for inkjet recording. An ink jet recording method in which the ink composition according to any one of claims 9 to 11 is used as an ink, and ink droplets of the ink are ejected according to a recording signal to adhere to a recording material to perform recording. The inkjet recording method according to claim 12 , wherein the recording material is an information transmission sheet. 14. The ink jet recording method according to claim 13 , wherein the information transmission sheet is a sheet having an ink receiving layer containing plain paper or a porous white inorganic substance. (A) the azo compound or a salt thereof according to any one of claims 1 to 8 ,
(B) an ink composition containing the azo compound or a salt thereof according to any one of claims 1 to 8 , or
(C) A colored body colored with any one of the ink composition containing the azo compound or a salt thereof according to any one of claims 1 to 8 and a water-soluble organic solvent. Colored product colored by an ink jet recording method according to any one of claims 12 to 14. Inkjet printer is a container containing the ink composition according loaded in claim 9 or 10. A method for producing the azo compound or a salt thereof according to any one of claims 1 to 8 ,
A method comprising condensing a compound represented by the following formula (5a) with a halogenated formate.

(In the formula, A ¹ , A ² , T, Q, R, x, y, z, a and b have the same meanings as in the above formula (1a).)