JP5126824B2 - Azo compound, ink composition, recording method and colored body - Google Patents

Description

The present invention relates to a novel azo compound or a salt thereof, an ink composition containing these, and a colored product thereby.

A recording method using an inkjet 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. This method has been spreading rapidly in recent years due to the fact that the recording head and the recording material are not in direct contact, so there is little noise and quietness, and it is easy to reduce the size and speed. Expected. Conventionally, as inks for fountain pens, felt pens, and inks for ink jet recording, water-based inks in which water-soluble dyes are dissolved in an aqueous medium have been used. In order to prevent clogging of ink, a water-soluble organic solvent is generally added. With these inks, it is possible to provide a recording image with sufficient density, no clogging of the pen tip and nozzles, good drying on the recording material, less bleeding, and storage stability. It is required to be excellent. The water-soluble dye used is required to have particularly high solubility in water and high solubility in the water-soluble organic solvent added to the ink. Further, the formed image is required to have image fastness such as water resistance, light resistance, gas resistance and moisture resistance.

Among these, the gas resistance is resistance to a phenomenon in which ozone gas having an oxidizing action existing in the air acts on the dye in the recording paper and discolors the printed image. In addition to ozone gas, examples of the oxidizing gas having this kind of action include NOx, SOx, etc. Among these oxidizing gases, ozone gas is a main causative substance that further promotes the discoloration and discoloration phenomenon of inkjet recording images. In particular, it is also called ozone gas resistance. Ink-receiving layers provided on the surface of photographic image-dedicated inkjet paper often use materials such as porous white inorganic materials to accelerate ink drying and reduce bleeding at high image quality. Discoloration due to ozone gas or the like is remarkably observed on a fresh recording paper. Since the discoloration phenomenon due to the oxidizing gas is characteristic of ink jet images, improvement of gas resistance is one of the most important issues in the ink jet recording method.

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 light resistance, gas resistance, moisture resistance and water resistance. There is a strong demand for improvement.

Various hues of ink are prepared from various dyes, of which black ink is an important ink used for both monocolor and full color images. Many dyes for these black inks have been proposed to date, but they have not yet been able to provide products that fully satisfy market demands. Many of the proposed dyes are azo dyes, of which C.I. I. Disazo dyes such as Food Black 2 have problems such as poor water resistance and moisture resistance, insufficient light resistance and gas resistance, and poor metamerism. A polyazo dye having an extended conjugated system generally has problems such as low water solubility and a tendency to cause a bronzing phenomenon in which a recorded image partially has a metallic luster, and insufficient light resistance and gas resistance. Similarly, many proposed azo-containing dyes have good light resistance, but they contain metal ions, which are undesirable for biological safety and environmental problems, and have extremely weak ozone gas resistance. There are problems such as.

Examples of the compounds (pigments) for black ink for ink jet improved with respect to ozone gas resistance, which has become the most important issue in recent years, include compounds described in Patent Documents 1 and 2, for example. These compounds are not sufficient in terms of light resistance because ozone gas resistance does not sufficiently satisfy market requirements. Further, azo compounds having a benzimidazolopyridone skeleton, which is a feature of the coloring compound for black ink of the present invention, are described in Patent Documents 3 to 6 and the like. Patent Documents 4 and 5 disclose trisazo compounds, but do not disclose anything similar to the asymmetric tetrakisazo compound of the present invention. Moreover, there are few water-soluble compounds and there is no usage example as a black compound for inkjet inks.

JP 2003-183545 A JP 2003-201412 A International Patent Publication No. 2004-050768 German published patent No. 2004488 German Published Patent No. 2023295 JP 05-134435 A

The present invention has high solubility in a medium containing water as a main component, is stable even when a high-concentration aqueous solution and ink are stored for a long period of time, has a very high density of the printed image, and is robust to the printed image. It is an object to provide a black ink dye composition and an ink composition thereof which can provide a black recorded image having excellent properties, particularly light resistance and ozone gas resistance, and which is easily synthesized and inexpensive.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific azo compound can solve the above problems, and have reached the present invention. That is, the present invention
(1)
An azo compound represented by the following formula (1) or a salt thereof

(In the formula (1), R ¹ represents a (C1 -C4) alkyl group (which may be substituted by carboxyl group), may be substituted with a phenyl group (sulfo group), or a carboxyl group.
R ² represents a cyano group, a carbamoyl group or a carboxyl group.
R ³ and R ⁴ each independently represents a hydrogen atom, a methyl group, a chlorine atom or a sulfo group.
R ⁵ and R ⁶ are each independently a hydrogen atom, carboxyl group, sulfo group, acetylamino group, (C1-C4) alkyl group, (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group, And may be substituted with a sulfo group and a carboxyl group.
One of R ⁷ and R ⁸ represents a (C1 to C4) alkylthio group (which may be substituted with a hydroxy group, a sulfo group or a carboxyl group), and the other represents a hydrogen atom, a carboxyl group, a sulfo group or an acetyl group. An amino group, a (C1-C4) alkyl group, a (C1-C4) alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group and a carboxyl group).
R ⁹ and R ¹⁰ are each independently a hydrogen atom, carboxyl group, sulfo group, acetylamino group, (C1-C4) alkyl group, (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group, And a (C1-C4) alkylthio group (which may be substituted with a hydroxy group, a sulfo group and a carboxyl group).
R ¹¹ to R ¹³ are each independently a hydrogen atom, carboxyl group, sulfo group, hydroxy group, acetylamino group, chlorine atom, cyano group, nitro group, sulfamoyl group, (C1-C4) alkyl group, (C1-C4) ) Alkoxy group (may be substituted with a hydroxy group, (C1-C4) alkoxy group, sulfo group and carboxyl group), (C1-C4) alkylsulfonyl group (substituted with a hydroxy group, sulfo group and carboxyl group) May be). )
(2)
The azo compound according to the above (1), wherein at least one of R ¹¹ to R ¹³ is a sulfo group or a carboxyl group, and at least one of R ⁵ to R ¹⁰ is a sulfo group, a sulfopropoxy group, or a 4-sulfobutoxy group ( 3)
The azo compound according to the above (1) represented by the following formula (2)

(In formula (2), R ¹ represents a (C1 -C4) alkyl group (which may be substituted by carboxyl group), may be substituted with a phenyl group (sulfo group), or a carboxyl group.
R ² represents a cyano group, a carbamoyl group or a carboxyl group.
R ³ and R ⁴ each independently represents a hydrogen atom, a methyl group, a chlorine atom or a sulfo group.
R ⁵ is a sulfo group, a sulfoethoxy group, a sulfopropoxy group or a sulfobutoxy group,
One of R ⁷ and R ⁸ represents a (C1 to C4) alkylthio group (which may be substituted with a hydroxy group, a sulfo group or a carboxyl group), and the other represents a hydrogen atom, a carboxyl group, a sulfo group or an acetyl group. An amino group, a (C1-C4) alkyl group, a (C1-C4) alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group and a carboxyl group);
R ⁹ is a sulfoethoxy group, a sulfopropoxy group or a sulfobutoxy group, and R ⁶ and R ¹⁰ are each independently a group selected from a hydrogen atom, an acetylamino group, a methyl group, an ethyl group, a methoxy group or an ethoxy group. Represent. )
(4)
The azo compound (5) according to (1), wherein R ¹ is a methyl group, R ² is a cyano group or a carbamoyl group, R ³ is a hydrogen atom, and R ⁴ is a sulfo group.
R ¹ is methyl group, R ² is cyano group or carbamoyl group, R ³ is hydrogen atom, R ⁴ is sulfo group, R ⁵ is sulfo group or sulfopropoxy group, R ⁷ is sulfopropylthio group, R ⁹ is sulfopropoxy group The groups (R ⁶ , R ⁸ and R ¹⁰ are hydrogen atoms or methyl groups), and R ¹¹ to R ¹³ are hydrogen atoms, sulfo groups, carboxyl groups, sulfopropylsulfonyl groups or acetylamino groups (1) or ( Azo compound according to 3) (6)
R ¹ is methyl group, R ² is cyano group or carbamoyl group, R ³ is hydrogen atom, R ⁴ is sulfo group, R ⁵ is sulfo group or sulfopropoxy group, R ⁷ is sulfopropylthio group, R ⁹ is sulfopropoxy group The groups R ⁶ and R ¹⁰ are a hydrogen atom or a methyl group, R ⁸ is a methoxy group, and R ¹¹ to R ¹³ are a hydrogen atom, a sulfo group, a carboxyl group, a sulfopropylsulfonyl group, or an acetylamino group. The azo compound (7) according to (1) or (3)
R ¹ is a methyl group or an n-propyl group, R ² is a cyano group or a carbamoyl group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group or 3-sulfopropoxy R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a 3-sulfopropylthio group or 2-carboxyethylthio group, R ⁸ and R ¹⁰ are methyl groups, and R ⁹ is 3- A sulfopropoxy group or a 4-sulfobutoxy group, and R ^{11 to} R ¹³ are those in which R ¹¹ is in the 2-position or 3 when the substitution position of the azo group of the benzene ring substituted by R ^{11 to} R ¹³ is 1-position. A sulfo group substituted at the position, a carboxyl group or a hydrogen atom, R ¹² is a sulfo group substituted at the 4-position, an acetylamino group, a sulfopropylsulfonyl group or a hydrogen atom, and R ¹³ is substituted at the 5-position or the 6-position Sulfo group Azo compounds described in the above (3) is a carboxyl group or a hydrogen atom (8)
R ¹ is a methyl group or an n-propyl group, R ² is a cyano group or a carbamoyl group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group or 3-sulfopropoxy R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a 3-sulfopropylthio group or 2-carboxyethylthio group, R ⁸ is a methoxy group, R ¹⁰ is a methyl group, R ⁹ is 3-sulfopropoxy group, or a 4-sulfobutoxy group, R ¹¹ to R ^13, when R ¹¹ to R ¹³ is a 1-position substitution position of the azo group on the benzene ring substituted, R ¹¹ Is a sulfo group, carboxyl group or hydrogen atom substituted at the 2-position or 3-position, R ¹² is a sulfo group, acetylamino group, sulfopropylsulfonyl group or hydrogen atom substituted at the 4-position, and R ¹³ is at the 5-position Or 6th place The sulfo group, an azo compound according to (3) is a carboxyl group or a hydrogen atom (9)
R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group, R ⁶ is a hydrogen atom, R ⁷ is a 3-sulfopropylthio group, R ⁹ Is a 3-sulfopropoxy group, R ⁸ and R ¹⁰ are methyl groups, R ¹² is a sulfo group, the substitution position is para to the azo group, and R ¹¹ and R ¹³ are hydrogen atoms (3) or ( 7) Azo compound (10)
R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group, R ⁶ is a hydrogen atom, R ⁷ is a 3-sulfopropylthio group, R ⁹ Is a 3-sulfopropoxy group, R ⁸ is a methoxy group, R ¹⁰ is a methyl group, R ¹² is a sulfo group, the substitution position is para to the azo group, R ¹¹ is a hydrogen atom, and R ¹³ is a hydrogen atom The azo compound (11) according to any one of (3), (6) or (8) above
R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group, R ⁶ is a hydrogen atom, R ⁷ is a 3-sulfopropylthio group, R ⁹ Is a 3-sulfopropoxy group, R ⁸ and R ¹⁰ are methyl groups, R ¹¹ is a sulfo group, the substitution position is ortho to the azo group, R ¹² is a sulfo group, and the substitution position is para to the azo group. The azo compound (12) according to the above (3) or (7), wherein the position and R ¹³ are hydrogen atoms
An ink composition (13) comprising at least one azo compound according to any one of (1) to (11) above
An ink-jet print recording method (14), characterized by using the ink composition as described in (12) above.
The inkjet print recording method (15) according to (13), wherein the recording material in the inkjet print recording method is an information transmission sheet.
The inkjet print recording method (16) according to (14), wherein the information transmission sheet contains a porous white inorganic substance.
Inkjet printer (17) loaded with a container containing the ink composition according to (15)
A colored body colored with the azo compound according to any one of (1) to (11) above,
About.

Since the azo compound of the present invention and tautomers thereof, or salts thereof (hereinafter collectively referred to simply as azo compounds) are excellent in water solubility, the filterability of the membrane filter during the ink composition production process is good. In addition, the storage stability of the recording liquid and the ejection stability are also excellent. Further, the ink composition of the present invention containing this azo compound has good storage stability without crystal precipitation, physical property change, color change and the like after long-term storage. In addition, the ink composition containing the azo compound of the present invention is suitably used for inkjet recording and writing instruments, and has a very high print density of recorded images when recorded on plain paper and inkjet dedicated paper. Various fastnesses, especially light resistance and ozone gas resistance are excellent. By using it together with an ink composition using magenta, cyan and yellow dyes, full-color ink jet recording with excellent fastness and storage stability 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.
As tautomers of the azo compound represented by the formula (1), the following formulas (3) and (4) are considered in addition to the compound of the formula (1), and these compounds are also included in the present invention.

(In formula (3), R ^{1 to} R ¹³ have the same meaning as in formula (1).)

(In formula (4), R ^{1 to} R ¹³ have the same meaning as in formula (1).)

In R ¹ and R ^{5 to} R ¹³ in the formula (1), examples of the (C1 to C4) alkyl group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl Examples include butyl.

Examples of (C1-C4) alkyl group optionally substituted with a carboxyl group in R ¹ in formula (1) include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl. , T-butyl, carboxymethyl, 2-carboxyethyl and the like.

Examples of R ¹ and R ^{5 to} R ¹³ in the formula (1) include (C1 to C4) alkoxy groups optionally substituted with a hydroxy group, a (C1 to C4) alkoxyl group, a sulfo group, and a carboxyl group. , Methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, t-butoxy, 2-hydroxyethoxy, 2-hydroxypropoxy, 3-hydroxypropoxy, methoxyethoxy, ethoxyethoxy, n-propoxyethoxy, Isopropoxyethoxy, n-butoxyethoxy, methoxypropoxy, ethoxypropoxy, n-propoxypropoxy, isopropoxybutoxy, n-propoxybutoxy, 2-hydroxyethoxyethoxy, carboxymethoxy, 2-carboxyethoxy, 3-carbo Shipuropokishi, 3-sulfopropoxy, 4-sulfobutoxy and the like.

Examples of (C1-C4) alkylsulfonyl group optionally substituted with a hydroxy group, a sulfo group, and a carboxyl group in R ^{11 to} R ¹³ in formula (1) include, for example, methylsulfonyl, ethylsulfonyl, propylsulfonyl, Examples include butylsulfonyl, 2-hydroxyethylsulfonyl, 2-hydroxypropylsulfonyl, 2-sulfoethylsulfonyl, 3-sulfopropylsulfonyl, 2-carboxyethylsulfonyl, 3-carboxypropylsulfonyl, and the like.

Examples of the phenyl group which may be substituted with a sulfo group in R ¹ in the formula (1) include, for example, phenyl, 3-sulfophenyl, 4-sulfophenyl, 2,4-disulfophenyl, 3,5- And disulfophenyl.

Examples of (C1-C4) alkylthio group optionally substituted with a hydroxy group, a sulfo group and a carboxyl group in R ^{7 to} R ¹⁰ in formula (1) include, for example, methylthio, ethylthio, n-propylthio, isopropylthio , N-butylthio, isobutylthio, sec-butylthio, t-butylthio, 2-hydroxyethylthio, 2-hydroxypropylthio, 3-hydroxypropylthio, 2-sulfoethylthio, 3-sulfopropylthio, 2-carboxyethyl Examples include thio, 3-carboxypropylthio, 4-carboxybutylthio and the like.

Preferable R ^{11 to} R ¹³ in formula (1) are each independently a hydrogen atom, cyano, carboxyl, sulfo, sulfamoyl, methylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, acetylamino, nitro, methyl, Methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy and the like, more preferably a hydrogen atom, cyano, carboxyl, sulfo, Sulfamoyl, methylsulfonyl, 2-hydroxyethylsulfonyl, 3-sulfopropylsulfonyl, and nitro are preferable, and a hydrogen atom, carboxyl, and sulfo are more preferable. As a preferable combination of R ^{11 to} R ¹³ , R ¹¹ is a hydrogen atom, sulfo or carboxyl, R ¹² is a hydrogen atom, sulfo, acetylamino or 3-sulfopropylsulfonyl, and R ¹³ is a hydrogen atom, sulfo or carboxyl. There are particularly preferred combinations in which R ¹¹ is a hydrogen atom, sulfo or carboxyl, R ¹² is a hydrogen atom or sulfo, and R ¹³ is a hydrogen atom, sulfo or carboxyl.

Preferable R ^{5 to} R ⁶ in formula (1) are each independently a hydrogen atom, carboxyl, sulfo, acetylamino, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, and the like, more preferably sulfo, methyl, methoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, carboxymethoxy, and more preferably A hydrogen atom, sulfo, methyl, methoxy, 3-sulfopropoxy. As a preferred combination of R ⁵ and R ⁶ , R ⁵ is sulfo and R ⁶ is a hydrogen atom, or R ⁵ is 3-sulfopropoxy or 4-sulfobutoxy and R ⁶ is methyl.

As preferred R ⁷ and R ⁸ in the formula (1), either one is a (C1-C4) alkylthio group (which may be substituted with a hydroxy group, a sulfo group and a carboxyl group), and among them, preferred are n-propylthio, n-butylthio, 2-hydroxyethylthio, 2-hydroxypropylthio, 3-hydroxypropylthio, 2-sulfoethylthio, 3-sulfopropylthio, 2-carboxyethylthio, 3-carboxypropylthio Yes, more preferably 2-hydroxyethylthio, 2-sulfoethylthio, 3-sulfopropylthio, 2-carboxyethylthio, and still more preferably 3-sulfopropylthio.
The other preferred are hydrogen atom, carboxyl, sulfo, acetylamino, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxy Ethoxy and the like, more preferably a hydrogen atom, sulfo, methyl, methoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy and carboxymethoxy, more preferably methyl and 3-sulfopropoxy. . As a preferred combination of R ⁷ and R ⁸ , R ⁷ is 3-sulfopropylthio and R ⁸ is methyl.

Preferable R ⁹ and R ¹⁰ in formula (1) are each independently a hydrogen atom, carboxyl, sulfo, acetylamino, methyl, methoxy, ethyl, ethoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy, 4-sulfobutoxy, carboxymethoxy, 2-carboxyethoxy, 2-hydroxyethylthio, 2-sulfoethylthio, 3-sulfopropylthio, 2-carboxyethylthio, and the like, more preferably a hydrogen atom, sulfo, methyl , Methoxy, 2-hydroxyethoxy, 2-sulfoethoxy, 3-sulfopropoxy and carboxymethoxy, more preferably methyl, methoxy, 3-sulfopropoxy and 4-sulfobutoxy. As a preferable combination of R ⁹ and R ¹⁰ , R ⁹ is 3-sulfopropoxy or 4-sulfobutoxy and R ¹⁰ is methyl.

Preferred R ¹ in the formula (1) is methyl, ethyl, n-propyl, n-butyl, t-butyl, carboxymethyl, phenyl, 4-sulfophenyl, carboxyl, and more preferably methyl, n-propyl, Carboxymethyl and 4-sulfophenyl, and more preferably methyl.

A preferred combination of R ¹ and R ² in formula (1) is R ¹ is methyl and R ² is cyano, or R ¹ is methyl and R ² is carbamoyl.

Preferred R ³ and R ⁴ than in equation (1) is a hydrogen atom, methyl, sulfo, preferably R ³ and the combination of R ⁴ is R ³ is R ⁴ is sulfo a hydrogen atom or R ³ is sulfo, R ⁴ is a hydrogen atom.

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

In the above formula (2), R ¹ to R ¹⁰ have the same meanings as in the above formula (1), combinations of the preferred groups and preferred groups are also the same as in the formula (1), the above R ⁵ ~ R ¹⁰ is more preferably substituted at the position of formula (2).

R ¹¹ to R ¹³ in the formula (2) represents the same meaning as R ¹¹ to R ¹³ in the formula (1), combinations of the preferred groups and preferred groups are also the same as in the formula (1).
In the formula (2), more preferable R ^{11 to} R ¹³ can specify the substitution position thereof.
That is, in the benzene ring substituted by R ^{11 to} R ^13, when the substitution position of the azo group is 1-position, R ¹¹ is 2-position or 3-position, R ¹² is 4-position, and R ¹³ is 5-position Alternatively, those substituted at the 6-position are preferred.
R ¹¹ is a sulfo group, carboxyl group or hydrogen atom substituted at the 2-position or 3-position, R ¹² is a sulfo group, acetylamino group, sulfopropylsulfonyl group or hydrogen atom substituted at the 4-position, R ¹³ A combination in which is a sulfo group, a carboxyl group or a hydrogen atom substituted at the 5- or 6-position is particularly preferred.
Particularly preferred in the formula (2) is one in which the substitution positions of R ^{5 to} R ¹³ are specified as described above, and the type of the substituent may be the same as in the above formula (1).

The salt of the azo compound represented by the formula (1) is an inorganic or organic cation salt. Of these, specific examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and ammonium salts. Preferred inorganic salts are lithium, sodium, potassium, and ammonium salts, and organic cation salts. Examples of the salt include, but are not limited to, salts of compounds represented by the following formula (5). The free acid, its tautomer, and various salts thereof may be a mixture, such as a mixture of sodium salt and ammonium salt, a mixture of free acid and sodium salt, lithium salt, sodium salt and ammonium salt. Any combination such as a mixture may be used. Depending on the type of salt, the physical properties such as solubility may differ, and if necessary, the type of salt is selected as appropriate, or when multiple salts are included, the ratio can be changed to change the ratio to suit the purpose. It is also possible to obtain a mixture having.

In the formula (5), Z ¹ , Z ² , Z ³ and Z ⁴ each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group, a hydroxyalkyl group and a hydroxyalkoxyalkyl group.
Specific examples of the alkyl group of Z ¹ , Z ² , Z ³ and Z ^{4 in} the formula (5) include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl and the like. Specific examples of the hydroxyalkyl group include hydroxy- (C1-C4) such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl and the like. ) Alkyl groups, examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybuty Etc. Hydroxy (C1 -C4) alkoxy - (C1 -C4) alkyl group. Among these hydroxyethoxy - (C1 -C4) alkyl groups are preferred. Particularly preferred is a hydrogen atom; methyl; hydroxy- (C1-C4) such as hydroxymethyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-hydroxypropyl, 4-hydroxybutyl, 3-hydroxybutyl, 2-hydroxybutyl, etc. ) Alkyl group; hydroxyethoxy- (C1) such as hydroxyethoxymethyl, 2-hydroxyethoxyethyl, 3-hydroxyethoxypropyl, 2-hydroxyethoxypropyl, 4-hydroxyethoxybutyl, 3-hydroxyethoxybutyl, 2-hydroxyethoxybutyl -C4) An alkyl group is mentioned.

Specific examples of Z ¹ , Z ² , Z ³ and Z ^{4 in} the formula (5) are shown in Table 1.

The trisazo compound of the present invention represented by the formula (1) can be synthesized, for example, by the following method. Moreover, the structural formula of the compound in each process shall be represented with the form of a free acid.
In the following formulas (6) to (13), R ^{1 to} R ¹³ represent the same meaning as in the above formula (1).
A compound represented by the following formula (6) is diazotized by a conventional method, and the obtained diazo compound and a compound represented by the following formula (7) are subjected to a coupling reaction by a conventional method to obtain a compound represented by the following formula (8). To obtain the compound.

The obtained compound of the above formula (8) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (9) are subjected to a coupling reaction by a conventional method to obtain the following formula (10) To obtain a compound represented by:

The obtained compound of the above formula (10) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (11) are subjected to a coupling reaction by a conventional method to obtain the following formula (12) To obtain a compound represented by:

The obtained compound of the above formula (12) is diazotized by a conventional method, and then the obtained diazo compound and a compound represented by the following formula (13) are subjected to a coupling reaction by a conventional method. The azo compound of the present invention represented by 1) can be obtained. Moreover, the compound represented by Formula (13) is compoundable according to the method of patent document 4.

The diazotization of the compound of the formula (6) is carried out in a manner known per se, for example nitrite, for example sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 30 ° C., preferably 0 to 15 ° C. It is carried out using an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of formula (6) and the compound of formula (7) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 30 ° C, preferably 0 to 25 ° C, and at an acidic to neutral pH value, for example pH 1-6. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. Examples of the base that can be used include alkali metal hydroxides such as lithium hydroxide and sodium hydroxide, alkali metal carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, acetates such as sodium acetate, ammonia and organic amines. . The compound of formula (6) and the compound of formula (7) are used in approximately stoichiometric amounts.

The diazotization of the compound of the formula (8) is carried out in a manner known per se, for example nitrite, such as sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 40 ° C., preferably 5 to 30 ° C. It is carried out using an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of formula (8) with the compound of formula (9) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 40 ° C, preferably 10 to 30 ° C, and at an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. The same base as described above can be used. The compound of formula (8) and the compound of formula (9) are used in approximately stoichiometric amounts.

The diazotization of the compound of the formula (10) is carried out in a manner known per se, for example nitrite, such as sodium nitrite, in an inorganic acid medium, for example at a temperature of -5 to 50 ° C., preferably 5 to 40 ° C. It is carried out using an alkali metal nitrite salt. Coupling of the diazotized compound of the compound of formula (10) and the compound of formula (11) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium, for example at a temperature of -5 to 50 [deg.] C, preferably 10 to 40 [deg.] C and an acidic to neutral pH value, for example pH 2-7. Since the diazotization reaction liquid is acidic and the reaction system is further acidified by the progress of the coupling reaction, the pH value is adjusted to a preferable pH condition of the reaction liquid by adding a base. The same base as described above can be used. The compound of formula (10) and the compound of formula (11) are used in approximately stoichiometric amounts.

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

Although it does not specifically limit as a suitable specific example of the compound of this invention shown in Formula (1), The compound shown by following Table 2, 3, and 6 is mentioned. In each table, acidic functional groups such as sulfo groups and carboxyl groups are expressed in the form of free acids.

In order to make the azo compound represented by the formula (1) of the present invention into a desired salt, salting out is performed by adding a desired inorganic salt or organic cation salt to the reaction solution after the coupling reaction, Alternatively, it is isolated in the form of a free acid by adding a mineral acid, and this is washed with water, acidified water, an aqueous organic medium or the like as necessary to remove the inorganic salt, and then the desired acid is obtained in an aqueous medium. By neutralizing with an inorganic or organic base, a corresponding salt solution can be obtained. Here, acidic water refers to water obtained by dissolving a mineral acid such as sulfuric acid or hydrochloric acid or an organic acid such as acetic acid in water. The aqueous organic medium refers to water-miscible organic substances miscible with water and so-called organic solvents miscible with water, and specific examples include water-soluble organic solvents described later. Organic substances that are not classified can be used as needed as long as they are miscible with water. Examples of inorganic salts include alkali metal salts such as lithium chloride, sodium chloride and potassium chloride; ammonium salts such as ammonium chloride and ammonium bromide. Examples of organic cation salts include the above-described formula (5). The halogen salt of the organic amine represented by these, etc. are mentioned. Examples of inorganic bases include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide, ammonium hydroxide, or alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate. Examples of the organic base include, but are not limited to, organic amines such as amines represented by the above formula (5) such as diethanolamine and triethanolamine.

The ink composition of the present invention will be described. A typical use of the aqueous composition containing the azo compound represented by the formula (1) of the present invention is an ink composition dissolved in a liquid medium.

The reaction liquid containing the azo compound of the present invention represented by the above formula (1), for example, the reaction liquid in Example 1 (6) described later, can be used directly in the production of the ink composition. However, it is first isolated by drying, eg spray drying, or salted out with inorganic salts such as sodium chloride, potassium chloride, calcium chloride, sodium sulfate or acidified with mineral acids such as hydrochloric acid, sulfuric acid, nitric acid. Alternatively, the azo compound of the present invention can be taken out by acid salting out, which is a combination of salting-out and aciding-out described above, and then used to prepare an ink composition.

The ink composition of the present invention usually contains 0.1 to 20% by mass, preferably 1 to 10% by mass, more preferably 2 to 8% by mass of the azo compound represented by the formula (1) of the present invention. It is a composition which uses as a main medium. The ink composition of the present invention has the purpose of adjusting the viscosity of the ink, adjusting the drying property of the ink, adjusting the permeability of the recording medium after printing and the ink receiving layer on the surface of the recording medium, etc. In addition, the water-soluble organic solvent may further contain, for example, 0 to 30% by mass, and the ink preparation agent may contain, for example, 0 to 5% by mass. The pH of the ink composition is preferably 5 to 11 and more preferably 7 to 10 in terms of improving storage stability. Further, the surface tension of the ink composition is preferably 25 to 70 mN / m, and more preferably 25 to 60 mN / m. Furthermore, the viscosity of the ink composition is preferably 30 mPa · s or less, and more preferably 20 mPa · s or less. The pH and surface tension of the ink composition of the present invention can be appropriately adjusted with a pH adjusting agent and a surfactant as described later.

The ink composition of the present invention is obtained by dissolving the azo compound represented by the above formula (1) in water or a water-soluble organic solvent (an organic solvent miscible with water), and adding an ink preparation agent as necessary. is there. When this ink composition is used as an ink for an ink jet printer, the azo compound of the present invention is preferably one having a low content of inorganic substances such as metal cation chlorides and sulfates. Is approximately 1% by mass or less (relative to the chromogen). In order to produce the azo compound of the present invention with a small amount of inorganic substances, for example, a usual method using a reverse osmosis membrane or a dried product or wet cake of the azo compound of the present invention is stirred in a mixed solvent of alcohol such as methanol and water and filtered. What is necessary is just to desalinate by methods, such as fractionation and drying.

Specific examples of water-soluble organic solvents that can be used in the preparation of the ink composition include (C1-C4) alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and tert-butanol; N Carboxylic acid amides such as N, N-dimethylformamide or N, N-dimethylacetamide; lactams such as 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methylpyrrolidin-2-one; 1,3-dimethylimidazolidine-2 -Cyclic ureas such as on- or 1,3-dimethylhexahydropyrimido-2-one; ketones or ketoalcohols such as acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentan-4-one; tetrahydrofuran, dioxane, etc. Cyclic ethers of ethylene Coal, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene Mono-, oligo- or polyalkylene glycols or thioglycols having (C2-C6) alkylene units such as glycol, polyethylene glycol, polypropylene glycol, thiodiglycol, dithiodiglycol, etc .; trimethylolpropane, glycerin, hexane-1,2 Polyols (triols) such as 1,6-triol; ethylene glycol monomethyl ether or ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethyl Polyvalent (C1 -C4) alkyl ethers of alcohols, such as glycol monoethyl ether or triethylene 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.

The water-soluble organic solvent mentioned above contains substances that are solid at room temperature, such as trimethylolpropane, but these are water-soluble even when they are solid, and when dissolved in water Since it can be used for the same purpose as the water-soluble organic solvent, it is described in the category of the water-soluble organic solvent in this specification for convenience.

Examples of the ink preparation used in the preparation of the ink composition include antiseptic / antifungal agents, pH adjusters, chelating reagents, rust inhibitors, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, and antioxidants. And surfactants. These drugs are described below.

Specific examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one, and salts thereof. . These are preferably used in the ink composition in an amount of 0.02 to 1.00% by mass.

Examples of preservatives include, for example, organic sulfur, organic nitrogen sulfur, organic halogen, haloallylsulfone, iodopropargyl, N-haloalkylthio, nitrile, pyridine, 8-oxyquinoline, benzo Thiazole, isothiazoline, dithiol, pyridine oxide, nitropropane, organotin, phenol, quaternary ammonium salt, triazine, thiazine, anilide, adamantane, dithiocarbamate, brominated indanone , Benzyl bromacetate compounds, inorganic salt compounds and the like.
Specific examples of the organic halogen compound include, for example, sodium pentachlorophenol.
Specific examples of the pyridine oxide compound include sodium 2-pyridinethiol-1-oxide.
Examples of isothiazoline compounds 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 and the like It is done.
Specific examples of other antiseptic / antifungal agents include sodium sorbate, sodium benzoate, and anhydrous sodium acetate.

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. Specific examples thereof include alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine, hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide and potassium hydroxide, ammonium hydroxide (ammonia water), Alternatively, alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogen carbonate, and potassium carbonate, inorganic bases such as potassium acetate, sodium silicate, and disodium phosphate can be used.

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

Specific examples of the rust inhibitor include acidic sulfite, sodium thiosulfate, ammonium thioglycolate, diisopropylammonium nitrite, pentaerythritol tetranitrate, and dicyclohexylammonium nitrite.
Examples of water-soluble ultraviolet absorbers include sulfonated benzophenone compounds, benzotriazole compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.
Specific examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.

Specific examples of the dye solubilizer include ε-caprolactam, ethylene carbonate, urea and the like.
As examples of the antioxidant, for example, various organic and metal complex anti-fading 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. It is done.

Examples of the surfactant include known surfactants such as anionic, cationic, and nonionic surfactants.
Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylates, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acyl amino acids and their salts, N-acyl methyl taurates, alkyl sulfates Salt polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, rosin acid soap, castor oil sulfate ester, lauryl alcohol sulfate ester, alkylphenol type phosphate ester, alkyl type phosphate ester, alkyl allyl sulfonate , Diethylsulfosuccinate, diethylhexylsylsulfosuccinate, dioctylsulfosuccinate and the like.
Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly-4-vinylpyridine derivatives.
Specific examples of amphoteric surfactants include lauryldimethylaminoacetic acid betaine, 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, coconut oil fatty acid amidopropyldimethylaminoacetic acid betaine, polyoctylpolyaminoethylglycine and other imidazolines. There are derivatives.
Specific examples of nonionic surfactants include polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene dodecyl phenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether. Ether type, polyoxyethylene oleic acid, polyoxyethylene oleate, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, poly Esters such as oxyethylene stearate, 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 3,6-dimethyl-4 Acetylene glycol (alcohol) series such as octyne-3,6-diol, 3,5-dimethyl-1-hexyne-3ol (for example, trade name Surfinol 104, 105, 82, 465, Olfin manufactured by Nissin Chemical Co., Ltd.) STG, etc.), polyglycol ether type (eg, Tergitol 15-S-7 manufactured by SIGMA-ALDRICH, etc.) and the like. These ink preparation agents are used alone or in combination.

The 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, if desired, in order to remove impurities. Moreover, in order to adjust the black color as an ink composition, in addition to the azo compound represented by the formula (1) of the present invention, other dyes having various hues may be mixed. In that case, black having other hues, yellow, magenta, cyan, and other colors such as red and blue can be mixed and used.

The ink composition of the present invention can be used in various fields, but is suitable for a writing water-based ink, a water-based printing ink, an information recording ink, and the like, and is particularly preferably used as an ink-jet ink. It is suitably used in the ink jet recording method of the invention.

Next, the ink jet recording method of the present invention will be described. The inkjet recording method of the present invention is characterized in that recording is performed using the ink composition of the present invention. In the ink jet recording method of the present invention, recording is performed on an image receiving material using an ink jet ink containing the ink composition, but there are no particular restrictions on the ink nozzles used at that time, depending on the purpose. Known methods, for example, a charge control method that ejects ink using electrostatic attraction, a drop-on-demand method (pressure pulse method) that uses the vibration pressure of a piezo element, and an electrical signal An acoustic ink jet system that converts ink into an acoustic beam and irradiates the ink by using radiation pressure to eject the ink, thermal ink jet that forms bubbles by heating the ink and uses the generated pressure (Bubble Jet (registered trademark)) A method etc. can be adopted. 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 compound of the present invention can dye a material composed of cellulose. In addition, other materials having a carbonamide bond can be dyed, and can be widely used for dyeing leather, woven fabric, paper and the like.

The colored product of the present invention is colored with the compound of the present invention or an ink composition containing the compound, and more preferably is colored with an ink jet printer using the ink composition of the present invention. Examples of materials that can be colored include information transmission sheets such as paper and film, fibers and cloth (cellulose, nylon, wool, etc.), leather, and base materials for color filters. Among them, the information transmission sheet is preferably a surface-treated sheet, specifically, a sheet, a synthetic paper, a film or other base material provided with an ink receiving layer. For the ink-receiving layer, for example, a porous white inorganic substance capable of absorbing the pigment in the ink such as porous silica, alumina sol, and special ceramics by impregnating or coating the above-mentioned base material with a cationic polymer is used. It is provided by coating the surface of the substrate together with a hydrophilic polymer such as polyvinylpyrrolidone. A paper provided with such an ink receiving layer is usually called ink jet exclusive paper (film), glossy paper (film), etc., for example, professional photo paper, super photo paper, matte photo paper (all manufactured by Canon Inc.) , Photo paper (glossy), PM matte paper, Crispier (all manufactured by Seiko Epson Corporation), advanced photo paper, premium plus photo paper, premium gloss film, photo paper (all manufactured by Hewlett-Packard Japan) Etc., commercially available products are available. Of course, plain paper can also be used.

  Among these, it is known that the image recorded on the information transmission sheet coated with a porous white inorganic substance on the surface is greatly discolored by ozone gas, but the ink composition of the present invention is resistant to ozone gas. Since it is excellent, it is particularly effective when recording on such a recording material.

  In order to record on a recording material such as an information transmission sheet by the ink jet recording method of the present invention, for example, a container containing the above ink composition is set at a predetermined position of an ink jet printer, and recording is performed by a normal method. Record it on the material. In the ink jet recording method of the present invention, a black ink composition of the present invention, a known magenta ink composition, a cyan ink composition, a yellow ink composition, and a green ink composition, a blue (or violet) ink as necessary. It can be used in combination with a composition and a red (or orange) ink composition. The ink composition of each color is poured into each container, and the container is used by being loaded into a predetermined position of the ink jet printer in the same manner as the container containing the aqueous black ink composition for ink jet recording of the present invention.

The azo compound of the present invention is excellent in water solubility, and the ink composition of the present invention containing this azo compound has good storage stability without crystal precipitation, physical property change, color change, etc. after long-term storage. Further, the black ink composition for recording containing the azo compound of the present invention is used for ink jet recording and writing instruments, and when recorded on plain paper and ink jet dedicated paper, the recorded image exhibits a black with high print density. Furthermore, its gas resistance, light resistance and bronzing properties are excellent.

EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited at all by the following examples. In the text, “parts” and “%” are based on mass unless otherwise specified. In the following formulas, the sulfone group is expressed in the form of a free acid.

Example 1
(1) A mixture of 17.1 parts of 4-chloro-3-nitrotoluene, 22.0 parts of sodium 3-mercaptopropanesulfonate and 60 parts of dimethyl sulfoxide was heated to 60 ° C. with stirring. Parts were added. After the addition, the mixture was heated to 120 to 130 ° C. and stirred at the same temperature for 6 hours. After cooling to room temperature, the reaction solution was added to 330 parts of 2-propanol with stirring. The precipitated crystals were separated by filtration and washed with 100 parts of 2-propanol on a funnel. After adding the obtained crystals to 300 parts of water, the pH value is adjusted to 7.0 to 7.5 with 35% hydrochloric acid, salting out is performed by adding sodium chloride, and the precipitate is separated by filtration to obtain a compound of formula (14). A wet cake containing the compound was obtained.

(2) 16.6 parts of iron powder, 120 parts of water and 3.1 parts of 35% hydrochloric acid were heated to 90 ° C. with stirring. After stirring for 40 minutes, a solution obtained by suspending a wet cake containing the compound of the formula (14) in 60 parts of water was added dropwise to the solution over about 15 minutes. After dripping, it stirred at 85-90 degreeC for 2 hours, and cooled to room temperature. Insoluble matter was removed by filtration, 35% hydrochloric acid was added to cause acid precipitation, and the precipitate was separated by filtration and dried to obtain 16.7 parts of the compound of formula (15).

(3) 10.8 parts of the compound of formula (16) (CI Acid Yellow 9) was suspended in 80 parts of water, and dissolved to a pH value of 4.0 to 5.0 by adding sodium hydroxide. After adding 12.0 parts of 35% hydrochloric acid to this solution, 5.8 parts of 40% aqueous sodium nitrite solution was added at 15 to 25 ° C. to diazotize.

This diazo suspension was dissolved in a solution obtained by dissolving 7.8 parts of the compound of the above formula (15) obtained in the above (2) in 60 parts of water and adding sodium hydroxide to pH 4.0 to 5.0. The solution was added dropwise at 15 to 25 ° C. over about 30 minutes. During the dropwise addition, the pH value of the solution was maintained at 3.0 to 4.0 by adding sodium carbonate. The mixture was then stirred for 3 hours, acidified by adding 35% hydrochloric acid and sodium chloride, and the precipitate was separated by filtration to obtain a wet cake containing the disazo compound of the formula (17).

(4) The wet cake containing the disazo compound of the formula (17) obtained in (3) is dissolved in 130 parts of water, and after adding 4.0 parts of 35% hydrochloric acid, 40% sodium nitrite at 20 to 35 ° C. 2.4 parts of an aqueous solution was added and diazotized. This diazo suspension was adjusted to pH 4.5 to 5.5 by adding 2.9 parts of the compound of the following formula (18) obtained by the method described in JP-A-2004-083492 to 25 parts of water and sodium hydroxide. The solution was added dropwise at 15 to 25 ° C. over about 30 minutes. During the dropwise addition, the pH value of the solution was maintained at 4.5 to 5.0 by adding sodium carbonate. Thereafter, the mixture was stirred for 2 hours, salted out by addition of sodium chloride, and the precipitate was separated by filtration to obtain a wet cake containing a trisazo compound of the formula (19).

(5) 8.9 parts of the compound of the formula (20) obtained by heat-reacting 2- (cyanomethyl) benzimidazole and ethyl acetoacetate in ethanol in the presence of sodium methoxide and acidifying by addition of dilute hydrochloric acid. Slowly added to 64 parts of 6% fuming sulfuric acid at 15-25 ° C. After the addition, the mixture was stirred at the same temperature for 2 hours, and then dropped into 190 parts of ice water in about 10 minutes. The precipitated crystals were separated by filtration, and the obtained crystals were washed with a solution of sodium chloride in dilute hydrochloric acid and dried to obtain 10.7 parts of a compound of formula (21).

(6) The wet cake containing the trisazo compound of the formula (19) obtained in (4) was dissolved in 150 parts of water to a pH value of 6.0 to 7.0 by adding sodium hydroxide, and 40% was added thereto. After adding 2.1 parts of an aqueous sodium nitrite solution, this solution was added dropwise into a mixed solution of 4.7 parts of 35% hydrochloric acid and 40 parts of water at 20 to 35 ° C. to diazotize. This diazo suspension was dissolved in a solution obtained by dissolving 3.0 parts of the compound of the formula (21) obtained in (5) in 50 parts of water to a pH value of 8.0 to 9.0 by adding sodium hydroxide. It was dripped at 20-35 degreeC. During the dropwise addition, the pH value was maintained at 7.0 to 8.0 by adding sodium carbonate. After dropping, the mixture was stirred at the same temperature for 4 hours, salted out by adding sodium chloride, and the precipitate was separated by filtration. The obtained wet cake was dissolved in 150 parts of water, crystallized by adding 120 parts of methanol, and the precipitate was separated by filtration. The obtained wet cake was further dissolved in 150 parts of water and crystallized by adding 220 parts of methanol, and the precipitate was separated by filtration, dried and dried with an azo compound of the formula (22) (No. 2 in Table 2). 9.6 parts of 1 compound) as a sodium salt. The maximum absorption wavelength (λmax) of this compound in an aqueous solution having a pH of 7 to 8 was 586 nm, and the solubility was 100 g / L or more.

Example 2
(A) Preparation of ink By mixing the following components, a black ink composition of the present invention was obtained, and impurities were removed by filtering with a 0.45 μm membrane filter.
The water used was ion exchange water. At the time of ink preparation, the pH of the ink was adjusted to pH 7-9 with sodium hydroxide, and then ion exchange water was added to make a total amount of 100 parts.

Table 4
Compound obtained in Example 1 4.0 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 (Brand name Surfinol 104 manufactured by Nissin Chemical)
Water + sodium hydroxide 76.9 parts Total 100.0 parts

In Table 4, the test using the compound (22) obtained in Example 1 is referred to as Example 3. This aqueous ink did not cause precipitation separation during storage, and did not change its physical properties even after long-term storage.

Example 4
In the same manner as in Example 1 except that 17.1 parts of 4-chloro-3-nitrotoluene in Example 1 (1) is changed to 18.7 parts of 4-chloro-3-nitroanisole, the following formula ( 25) of azo compound (No. 12 compound in Table 6 above) 10.0 parts as a sodium salt. The maximum absorption wavelength (λmax) of this compound in an aqueous solution having a pH of 7 to 8 was 605 nm, and the solubility was 100 g / L or more.

Example 5
(1) 11.4 parts of sodium bisulfite was dissolved in 40 parts of water and heated to 60-70 ° C. 9.4 parts of 35% formalin and then 9.3 parts of aniline were added to the aqueous solution and stirred at the same temperature for 1 hour to obtain an aqueous solution containing a methyl-ω-sulfonic acid derivative of aniline. On the other hand, 27.8 parts of aniline-2,4-disulfonic acid was dissolved in 80 parts of water, 22.9 parts of 35% hydrochloric acid, and then 19.8 parts of 40% aqueous sodium nitrite solution at a reaction temperature of 15 to 20 ° C. Diazotization was carried out by adding dropwise over 5 minutes to obtain a diazo liquid. The obtained aqueous solution containing the methyl-ω-sulfonic acid derivative of aniline obtained above was added to the diazo solution and stirred at a reaction temperature of 15 to 30 ° C. for 3 hours. During this time, sodium carbonate was added to the reaction system to maintain the pH value at 6.0 to 7.0. The reaction solution was adjusted to pH 11 with sodium hydroxide and then stirred at 90 to 95 ° C. for 6 hours while maintaining the same pH.
After cooling the reaction solution to 20-30 ° C, 35% hydrochloric acid was added to adjust the pH to 1.0-1.5. The precipitated solid was collected by filtration and dried to obtain 15.1 parts of a monoazo compound of the following formula (26).

(2) 15.1 parts of the monoazo compound of the formula (26) obtained in the above (1) was slowly added to 13.6 parts of 30% fuming sulfuric acid at 0 to 10 ° C. After the addition, the mixture was stirred at 65 to 70 ° C. for 2 hours, then dropped into 40 parts of ice water in about 10 minutes, and the precipitated solid was collected by filtration to obtain a wet cake containing a monoazo compound of the following formula (27). It was.

(3) Example 1 except that 10.8 parts of the compound of formula (16) in Example 1 (3) is changed to a wet cake containing the monoazo compound of formula (27) obtained in Example 5 (2) above. In the same manner as in Example 1, 10.1 parts of an azo compound of the following formula (28) (No. 14 compound in Table 6) of the present invention was obtained as a sodium salt. The maximum absorption wavelength (λmax) of this compound in an aqueous solution having a pH of 7 to 8 was 573 nm, and the solubility was 100 g / L or more.

Inks of Examples 6 and 7 were prepared in the same manner as in Example 2 using the compounds obtained in Examples 4 and 5, respectively. This aqueous ink did not cause precipitation separation during storage, and did not change its physical properties even after long-term storage.

Comparative Example 1
As a comparative object, an ink of Comparative Example 1 was prepared in the same manner as in Example 2 using 1 of the dye of Table 1-1 of Patent Document 1 (the following formula (23)) as a water-soluble inkjet dye.

Comparative Example 2
Similarly, as a comparative object, as a water-soluble ink-jet dye, a dye AN-250 described in Example 1 of Patent Document 3 (the following formula (24)) was used in the same manner as in Example 2, and Comparative Example 2 was used. Ink was prepared.

(B) Inkjet printing Using the ink obtained above, an exclusive glossy paper 1 (Professional Photo Paper PR-101 made by Canon Inc.) and a dedicated glossy paper 2 (EPSON) are produced by an inkjet printer (trade name: PIXUS iP4100 Canon). Inkjet recording was performed on two types of paper (photographic paper <Glossy> KA420PSK).
At the time of printing, an image pattern was prepared so that the reflection density was obtained with several gradations, and a black printed matter was obtained.

  The light resistance test and the ozone gas resistance test were evaluated using a colorimeter (SpectroEye GRETAG-MACBETH) and using the gradation portion where the reflection density D value of the printed material before the test was closest to 1.0.

(C) Evaluation of recorded image
In the recorded image using the aqueous ink of the present invention, the density change after the light resistance test and after the ozone gas resistance test was evaluated. The test was performed on dedicated glossy papers 1 and 2. The results are shown in Tables 5 and 7. The specific test method is shown below.
1) Light resistance test Using a xenon weatherometer (Ci4000 ATLAS), irradiation was carried out for 50 hours under the conditions of 0.36 W / square meter illuminance, humidity 60% RH, and temperature 24 ° C. After the test, the colorimetry was performed using the above-described colorimeter, and the dye residual ratio was determined by (reflected density after test / reflected density before test) × 100 (%) and evaluated according to the following criteria.
○ Residual rate: 90% or more Δ Residual rate: less than 90% and 80% or more × Residual rate: less than 80% Tables 5 and 7 show the results.
2) Ozone gas resistance test Using an ozone weatherometer (manufactured by Suga Test Instruments Co., Ltd.), the print sample was left for 4 hours at an ozone concentration of 12 ppm, a humidity of 60% RH, and a temperature of 24 ° C. After the test, the colorimetry was performed using the above-described colorimeter, and the dye residual ratio was determined by (reflected density after test / reflected density before test) × 100 (%) and evaluated according to the following criteria.
○ Residual rate: 70% or more Δ Residual rate: 60% or more and less than 70% × Residual rate: less than 60% The results are shown in Tables 5 and 7.

Table 5
Light resistance Ozone gas resistance
Example 3 (Formula (22))
Exclusive glossy paper 1 ○ ○
Exclusive glossy paper 2 ○ ○
Comparative Example 1 (Formula (23))
Exclusive glossy paper 1 × ×
Exclusive glossy paper 2 △ ○
Comparative Example 2 (Formula (24))
Exclusive glossy paper 1 × ×
Exclusive glossy paper 2 △ ○

Table 7
Light resistance Ozone gas resistance
Example 6 (Formula (25))
Exclusive glossy paper 1 ○ ○
Exclusive glossy paper 2 ○ ○
Example 7 (Formula (28))
Exclusive glossy paper 1 ○ ○
Exclusive glossy paper 2 ○ ○
Comparative Example 1 (Formula (23))
Exclusive glossy paper 1 × ×
Exclusive glossy paper 2 △ ○
Comparative Example 2 (Formula (24))
Exclusive glossy paper 1 × ×
Exclusive glossy paper 2 △ ○

As is apparent from the results in Table 5, the image recorded with the ink composition containing the azo compound of the present invention is equivalent to or higher in ozone gas resistance than the image of the conventional black dye (comparative example). And good results were obtained with any special glossy paper. That is, in Comparative Examples 1 and 2, when the dedicated glossy paper 1 is used, the dye residual ratio is less than 60%, whereas in Example 3 of the present invention, 70% or more is used when any of the dedicated glossy papers is used. The residual ratio of dye was shown. Further, the difference in light resistance appeared more clearly, and Example 3 which is an ink composition containing the azo compound of the present invention showed a dye residual ratio of 90% or more in any of the dedicated glossy papers. However, in Comparative Examples 1 and 2, when the dedicated glossy paper 2 is used, the dye residual ratio is less than 90% and 80% or more, and when the dedicated glossy paper 1 is used, both are less than 80%. Compared to these results, Example 3 of the present invention obtained extremely good results. This shows that the fastness of the image recorded by the azo compound of the present invention is extremely excellent.
Further, since the azo compound of the present invention has a high solubility and is stable, a high concentration ink can be designed.

In Table 7, the same results as in Table 5 were obtained, confirming the usefulness of the azo compound of the present invention.

The ink composition containing the azo compound of the present invention is suitably used as a black ink liquid for ink jet recording and writing instruments.

Claims (17)

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

(In the formula (1), R ¹ represents a (C1 -C4) alkyl group (which may be substituted by carboxyl group), may be substituted with a phenyl group (sulfo group), or a carboxyl group.
R ² represents a cyano group, a carbamoyl group or a carboxyl group.
R ³ and R ⁴ each independently represents a hydrogen atom, a methyl group, a chlorine atom or a sulfo group.
R ⁵ and R ⁶ are each independently a hydrogen atom, carboxyl group, sulfo group, acetylamino group, (C1-C4) alkyl group, (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group, And may be substituted with a sulfo group and a carboxyl group.
One of R ⁷ and R ⁸ represents a (C1 to C4) alkylthio group (which may be substituted with a hydroxy group, a sulfo group or a carboxyl group), and the other represents a hydrogen atom, a carboxyl group, a sulfo group or an acetyl group. An amino group, a (C1-C4) alkyl group, a (C1-C4) alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group and a carboxyl group).
R ⁹ and R ¹⁰ are each independently a hydrogen atom, carboxyl group, sulfo group, acetylamino group, (C1-C4) alkyl group, (C1-C4) alkoxy group (hydroxy group, (C1-C4) alkoxy group, And a (C1-C4) alkylthio group (which may be substituted with a hydroxy group, a sulfo group and a carboxyl group).
R ¹¹ to R ¹³ are each independently a hydrogen atom, carboxyl group, sulfo group, hydroxy group, acetylamino group, chlorine atom, cyano group, nitro group, sulfamoyl group, (C1-C4) alkyl group, (C1-C4) ) Alkoxy group (may be substituted with a hydroxy group, (C1-C4) alkoxy group, sulfo group and carboxyl group), (C1-C4) alkylsulfonyl group (substituted with a hydroxy group, sulfo group and carboxyl group) May be). ) The azo compound according to claim 1, wherein at least one of R ¹¹ to R ¹³ is a sulfo group or a carboxyl group, and at least one of R ⁵ to R ¹⁰ is a sulfo group, a sulfopropoxy group, or a 4-sulfobutoxy group. The azo compound according to claim 1 represented by the following formula (2):

(In formula (2), R ¹ represents a (C1 -C4) alkyl group (which may be substituted by carboxyl group), may be substituted with a phenyl group (sulfo group), or a carboxyl group.
R ² represents a cyano group, a carbamoyl group or a carboxyl group.
R ³ and R ⁴ each independently represents a hydrogen atom, a methyl group, a chlorine atom or a sulfo group.
R ⁵ is a sulfo group, a sulfoethoxy group, a sulfopropoxy group or a sulfobutoxy group,
One of R ⁷ and R ⁸ represents a (C1 to C4) alkylthio group (which may be substituted with a hydroxy group, a sulfo group or a carboxyl group), and the other represents a hydrogen atom, a carboxyl group, a sulfo group or an acetyl group. An amino group, a (C1-C4) alkyl group, a (C1-C4) alkoxy group (which may be substituted with a hydroxy group, a (C1-C4) alkoxy group, a sulfo group and a carboxyl group);
R ⁹ is a sulfoethoxy group, a sulfopropoxy group or a sulfobutoxy group, and R ⁶ and R ¹⁰ are each independently a group selected from a hydrogen atom, an acetylamino group, a methyl group, an ethyl group, a methoxy group or an ethoxy group. Represent. ) The azo compound according to claim 1, wherein R ¹ is a methyl group, R ² is a cyano group or a carbamoyl group, R ³ is a hydrogen atom, and R ⁴ is a sulfo group. R ¹ is methyl group, R ² is cyano group or carbamoyl group, R ³ is hydrogen atom, R ⁴ is sulfo group, R ⁵ is sulfo group or sulfopropoxy group, R ⁷ is sulfopropylthio group, R ⁹ is sulfopropoxy group The groups R ⁶ , R ⁸ and R ¹⁰ are hydrogen atoms or methyl groups, and R ¹¹ to R ¹³ are hydrogen atoms, sulfo groups, carboxyl groups, sulfopropylsulfonyl groups or acetylamino groups. Azo compounds described R ¹ is methyl group, R ² is cyano group or carbamoyl group, R ³ is hydrogen atom, R ⁴ is sulfo group, R ⁵ is sulfo group or sulfopropoxy group, R ⁷ is sulfopropylthio group, R ⁹ is sulfopropoxy group The groups R ⁶ and R ¹⁰ are hydrogen atoms or methyl groups, R ⁸ is a methoxy group, and R ¹¹ to R ¹³ are hydrogen atoms, sulfo groups, carboxyl groups, sulfopropylsulfonyl groups or acetylamino groups. Item 4. The azo compound according to item 1 or 3. R ¹ is a methyl group or an n-propyl group, R ² is a cyano group or a carbamoyl group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group or 3-sulfopropoxy R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a 3-sulfopropylthio group or 2-carboxyethylthio group, R ⁸ and R ¹⁰ are methyl groups, and R ⁹ is 3- A sulfopropoxy group or a 4-sulfobutoxy group, and R ^{11 to} R ¹³ are those in which R ¹¹ is in the 2-position or 3 when the substitution position of the azo group of the benzene ring substituted by R ^{11 to} R ¹³ is 1-position. A sulfo group substituted at the position, a carboxyl group or a hydrogen atom, R ¹² is a sulfo group substituted at the 4-position, an acetylamino group, a sulfopropylsulfonyl group or a hydrogen atom, and R ¹³ is substituted at the 5-position or the 6-position Sulfo group Azo compounds according to claim 3, wherein the carboxyl group or a hydrogen atom R ¹ is a methyl group or an n-propyl group, R ² is a cyano group or a carbamoyl group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group or 3-sulfopropoxy R ⁶ is a hydrogen atom or a methyl group, R ⁷ is a 3-sulfopropylthio group or 2-carboxyethylthio group, R ⁸ is a methoxy group, R ¹⁰ is a methyl group, R ⁹ is 3-sulfopropoxy group, or a 4-sulfobutoxy group, R ¹¹ to R ^13, when R ¹¹ to R ¹³ is a 1-position substitution position of the azo group on the benzene ring substituted, R ¹¹ Is a sulfo group, carboxyl group or hydrogen atom substituted at the 2-position or 3-position, R ¹² is a sulfo group, acetylamino group, sulfopropylsulfonyl group or hydrogen atom substituted at the 4-position, and R ¹³ is at the 5-position Or 6th place The sulfo group, an azo compound according to claim 3 is a carboxyl group or a hydrogen atom R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group, R ⁶ is a hydrogen atom, R ⁷ is a 3-sulfopropylthio group, R ^{9 8} is a 3-sulfopropoxy group, R ⁸ and R ¹⁰ are methyl groups, R ¹² is a sulfo group, the substitution position is para to the azo group, and R ¹¹ and R ¹³ are hydrogen atoms. Azo compounds described R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group, R ⁶ is a hydrogen atom, R ⁷ is a 3-sulfopropylthio group, R ⁹ Is a 3-sulfopropoxy group, R ⁸ is a methoxy group, R ¹⁰ is a methyl group, R ¹² is a sulfo group, the substitution position is para to the azo group, R ¹¹ is a hydrogen atom, and R ¹³ is a hydrogen atom The azo compound according to claim 3, 6 or 8. R ¹ is a methyl group, R ² is a cyano group, R ³ is a hydrogen atom, R ⁴ is a sulfo group, R ⁵ is a sulfo group, R ⁶ is a hydrogen atom, R ⁷ is a 3-sulfopropylthio group, R ⁹ Is a 3-sulfopropoxy group, R ⁸ and R ¹⁰ are methyl groups, R ¹¹ is a sulfo group, the substitution position is ortho to the azo group, R ¹² is a sulfo group, and the substitution position is para to the azo group. The azo compound according to claim 3 or 7, wherein R and R ¹³ are hydrogen atoms. An ink composition comprising at least one azo compound according to any one of claims 1 to 11. An ink-jet print recording method comprising using the ink composition according to claim 12. 14. The inkjet print recording method according to claim 13, wherein the recording material in the inkjet print recording method is an information transmission sheet. The inkjet print recording method according to claim 14, wherein the information transmission sheet contains a porous white inorganic substance. An ink jet printer loaded with a container containing the ink composition according to claim 12. A colored product colored with the azo compound according to any one of claims 1 to 11.