JP6924162B2 - Azo compounds, ink compositions, recording methods and colorants - Google Patents

Description

The present invention relates to novel azo compounds or tautomers thereof, or salts thereof, ink compositions containing them, and colored bodies colored by them.

The recording method by an inkjet printer, that is, the inkjet recording method is one of the typical methods among various color recording methods. In the inkjet recording method, small droplets of ink are generated and attached to various recording materials (paper, film, cloth, etc.) for recording. This method is quiet with less noise because the recording head and the material to be recorded do not come into direct contact with each other. In addition, since it has the feature of being easy to miniaturize and speed up, it has been rapidly spreading in recent years, and great growth is expected in the future.
Conventionally, as fountain pens, felt-tip pens and the like, and inks for inkjet recording, water-based inks in which a water-soluble dye is dissolved in an water-based medium have been used. A water-soluble organic solvent is generally added to these water-based inks in order to prevent clogging of the ink at the pen tip or the ink ejection nozzle. In these inks, a recorded image having a sufficient density is given, the pen tip and the nozzle are not clogged, the drying property on the material to be recorded is good, there is little bleeding, and the storage stability. It is required to be excellent. Further, the water-soluble dye used is required to have particularly high solubility in water and high solubility in a 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.

Of these, gas resistance refers to resistance to the phenomenon that ozone gas or the like having an oxidizing action existing in the air acts on the dye on the recording material or in the recording material to discolor or fade the recorded image. Is. In addition to ozone gas, NOx, SOx and the like can be mentioned as an oxidizing gas having this kind of action. However, among these oxidizing gases, ozone gas is considered to be the main causative substance that promotes the discoloration and fading phenomenon of inkjet recorded images, and ozone gas resistance is particularly important. An ink receiving layer is provided on the surface of the inkjet paper, which can obtain photographic image quality, in order to accelerate the drying of the ink and reduce bleeding in the high image quality. As the material of the ink receiving layer, a material such as a porous white inorganic substance is often used. Discoloration and fading due to ozone gas and the like are noticeably observed on such recording paper. Since this discoloration / fading phenomenon due to the oxidizing gas is characteristic of inkjet recorded images, improvement of gas resistance, particularly ozone gas resistance, is one of the most important issues in inkjet recording.

In addition, the bronzing phenomenon may become a problem. The bronzing phenomenon is a phenomenon in which the dye becomes a metal piece on the surface of the non-recording material and glares due to the association of dyes or malabsorption of ink. When this phenomenon occurs, the glossiness, print quality, and print density are all inferior. In particular, when a metallic phthalocyanine dye is used as the dye, it often appears as a "red floating phenomenon" in the part printed at a high density, and the balance of the entire image becomes uneven and the quality is deteriorated. A dye that does not cause a phenomenon is desired. Further, in recent years, glossy paper is often used as a recording medium having a texture close to that of a photograph, but when a bronzing phenomenon occurs, the glossiness on the surface of a recorded object varies, and the texture of an image is significantly impaired. From this point of view, a dye that does not cause a bronzing phenomenon is strongly desired. In addition, in this specification, a dye which does not cause this bronzing phenomenon is described as a dye which is excellent in bronzing property.

In the future, in order to expand the fields of use of inkjet recording, there is a strong demand for further improvement of light resistance, gas resistance, moisture resistance, water resistance, bronzing resistance, etc. of inkjet recorded images. In addition to this, the black image is required to have excellent color rendering properties. The phenomenon in which the hue appears to change depending on the type of light source is called color rendering, and this phenomenon is generally likely to occur in black dyed materials and recorded materials. In the field of dyeing processing, it is common to use a compound having absorption at a long wavelength as a method for improving color rendering properties, and for example, Patent Document 6 discloses these methods.

Inks of different hues are prepared from different 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 sufficiently satisfy the demands of the market. Most of the proposed dyes are azo dyes, of which C.I. I. Disazo dyes such as Food Black2 have problems such as poor water resistance and moisture resistance, insufficient light resistance and gas resistance, and high color rendering properties. The polyazo dye having an extended conjugated system generally has low water solubility, tends to cause a bronzing phenomenon in which the recorded image has a partially metallic luster, and has problems such as insufficient light resistance and gas resistance. Similarly, many proposed azo gold-containing dyes have good light resistance, but because they contain metal ions, they are not preferable for biological safety and environmental problems, and their gas resistance is extremely weak. There are problems such as.

Examples of the black compound (black dye) for inkjet recording, which has been improved in terms of gas resistance, which has become the most important issue in recent years, include the compound described in Patent Document 1. Although the gas resistance of these compounds has improved, they do not fully meet the market demands. Further, an azo compound having a benzimidazolopyridone skeleton, which is one of the features of the black dye of the present invention, is disclosed in Patent Documents 3 to 5 and the like. Patent Documents 3 and 4 disclose that a trisazo compound and a water-soluble black compound are used for inkjet recording. Further, Patent Documents 5 and 8 disclose that a tetrakisazo compound and a water-soluble black compound are used for inkjet recording, but a black dye having a further excellent hue and good ozone gas resistance is strong. It has been demanded.

International Publication No. 2005/05/37474 International Publication No. 2004/050768 International Publication 2007/077931 International Publication No. 2009/069279 Japanese Unexamined Patent Publication No. 2008-169374 Japanese Unexamined Patent Publication No. 01-284562 Japanese Unexamined Patent Publication No. 2004-75719 International Release 2012/081640 International Publication 2014/132926

The present invention is particularly excellent in ozone gas resistance, light resistance and moisture resistance, very high print density, excellent bronzing resistance and color playability, and low saturation when recorded on inkjet paper. An object of the present invention is to provide a dye having a high-quality black hue, and an ink composition containing the dye, particularly a black ink composition for inkjet recording.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific azo compound solves the above-mentioned problems, and have completed the present invention.

That is, the present invention relates to the following 1) to 10).
1)
An azo compound represented by the following formula (1), a tautomer thereof, or a salt thereof.

[In equation (1),
R ₁ represents a (C1-C4) alkyl group or a (C1-C4) alkyl group substituted with a carboxy group.
R ₂ represents a cyano group
R ₃ and R ₄ independently represent a hydrogen atom, an (C1 to C4) alkoxyl group, or a sulfo group, respectively.
R ₅ represents an (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of hydroxy, sulfo and carboxy groups.
R ₆ represents an (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of hydroxy, sulfo and carboxy groups.
R ₇ represents an (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of hydroxy, sulfo and carboxy groups.
R ₈ represents the (C1-C4) alkylcarbonylamino group
R ₉ is a (C1-C4) alkylcarbonylamino group
R ₁₀ represents the (C1-C4) alkylcarbonylamino group
R _{11 to} R ₁₃ are independently hydrogen atoms, sulfo groups, carboxy groups, hydroxy groups or nitro groups, respectively. Further, when the ring represented by the broken line does not exist, it is a benzene ring, when the ring represented by a broken line exists, it is a naphthalene ring, and when it is a naphthalene ring, the substituents R _{11 to} R ₁₃ are naphthalene rings, respectively. Can be replaced with any position of. ]
2)
In the above formula (1)
R ₁ represents a (C1-C4) alkyl group or a (C1-C4) alkyl group substituted with a carboxy group.
R ₂ represents a cyano group
R ₃ and R ₄ independently represent a hydrogen atom, an (C1 to C4) alkoxyl group, or a sulfo group, respectively.
R ₅ represents a sulfo (C1-C4) alkylthio group and represents
R ₆ represents a sulfo (C1-C4) alkylthio group and R ₇ represents a sulfo (C1-C4) alkylthio group.
R ₈ represents the (C1-C4) alkylcarbonylamino group
R ₉ is a (C1-C4) alkylcarbonylamino group
R ₁₀ represents the (C1-C4) alkylcarbonylamino group
The azo compound according to claim 1, or a tautomer thereof, or a salt thereof, wherein R _{11 to} R ₁₃ are each independently a hydrogen atom, a sulfo group, a carboxy group, a hydroxy group or a nitro group.
3)
In the above formula (1)
R ₁ is a methyl group,
R ₂ is a cyano group,
R ₃ is a methoxy group or a hydrogen atom,
R ₄ is a sulfo group,
R ₅ is a sulfo (C1-C4) alkylthio group,
R ₆ is a sulfo (C1-C4) alkylthio group,
R ₇ is a sulfo (C1-C4) alkylthio group,
R ₈ is an acetylamino group,
R ₉ is an acetylamino group,
R ₁₀ is an acetyl amino group,
R _{11 to} R ₁₃ are independently hydrogen atoms, sulfo groups, carboxy groups, hydroxy groups or nitro groups, respectively. The azo compounds according to 1) or 2), tautomers thereof, or salts thereof. ..
4)
An aqueous ink composition containing at least one kind of azo compound according to any one of 1) to 3), a tautomer thereof, or a salt thereof as a dye.
5)
The water-based ink composition according to 4), which further contains a water-soluble organic solvent.
6)
An inkjet recording method in which the water-based ink composition according to 4) or 5) is used as an ink, and ink droplets of the ink are ejected in response to a recording signal to record on a recording material.
7)
The inkjet recording method according to 6), wherein the material to be recorded is an information transmission sheet.
8)
The inkjet recording method according to 7), wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance.
9)
An inkjet printer loaded with a container containing the aqueous ink composition according to 4) or 5).
10)
a) The azo compound according to any one of 1) to 3), a tautomer thereof, or a salt thereof.
b) The water-based ink composition according to 4) or 5), or
c) A colored body colored by any of the three methods of the inkjet recording method according to 6).

The above-mentioned azo compound or a mutant thereof, or a salt thereof, and an ink composition containing the same have high storage stability and are suitably used as an ink for inkjet recording, and when recorded on inkjet paper. The print density is very high, the color playability is excellent, the saturation is low, the hue is high-quality black, and the (ozone) gas resistance is particularly excellent. Therefore, the ink composition containing the azo compound of the present invention, a tautomer thereof, or a salt thereof is extremely useful as a black ink for inkjet recording.

Hereinafter, the present invention will be described in detail.
For convenience, in the present specification, all of "azo compounds or tautomers thereof, or salts thereof" are collectively referred to as "azo compounds" below. Here, examples of the tautomer include structures represented by the following formulas (3) and (4). In the formula (3) and (4), R ₁ to R _13, have the same meaning as in the formula (1).

In the above formula (1), R ₁ represents an (C1 to C4) alkyl group or a (C1 to C4) alkyl group substituted with a carboxy group.

Examples _{of the (C1 to C4) alkyl group in R 1} include a linear or branched alkyl group, and a linear alkyl group is preferable. Specific examples of the (C1 to C4) alkyl groups include linear alkyl groups such as methyl group, ethyl group, n-propyl group and n-butyl group, isopropyl group, isobutyl group, sec-butyl group and tert-butyl. Branched chain alkyl groups such as groups, and the like can be mentioned. Preferred specific examples include a methyl group and an n-propyl group, and a methyl group is more preferable.

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

As the above R ₁ , both the (C1 to C4) alkyl group and the (C1 to C4) alkyl group substituted with the carboxy group are preferable, but the (C1 to C4) alkyl group is more preferable. A methyl group or an n-propyl group is more preferable, and a methyl group is particularly preferable.

In the above formula (1), R ₂ represents a cyano group.

In the above formula (1), R ₃ and R ₄ independently represent a hydrogen atom, (C1 to C4) alkoxyl group, or a sulfo group, respectively.

Examples _{of the (C1 to C4) alkoxyl groups in R 3} and R ₄ include straight-chain or branched-chain alkoxyl groups, and straight-chain alkoxyl groups are preferable. Specific examples include linear alkoxyl groups such as methoxy group, ethoxy group, n-propoxy group and n-butoxy group, branched alkyl alkoxyl groups such as isopropoxy group, isobutoxy group, sec-butoxy group and tert-butoxy group. And so on. Of these, the methoxy group is more preferred.

As R ₃ and R ₄ , one of them is preferably a methoxy group and the other is a combination of sulfo groups, or one of them is a hydrogen atom and the other is a combination of sulfo groups, and more preferably one of them. Is a methoxy group and the other is a combination of sulfo groups.

The _{substitution positions of R 3} and R ₄ are not particularly limited, but when one of them is a hydrogen atom and the other is a sulfo group, the sulfo group is a four carbon atom that does not form an imidazole ring of the benzimidazolopyridone ring. It is preferable to replace with any two of.

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

As a preferable combination _{of R 1 to} R ₄ in the above formula (1) _{, R 1} is a (C1 to C4) alkyl group (preferably a methyl group or an n-propyl group, more preferably a methyl group), and R ₂ is a cyano group. A group, R ₃ is a hydrogen atom, or a methoxy group (preferably a methoxy group), and R ₄ is a combination of a sulfo group.

In the above formula (1), R _{5 to} R ₇ represent (C1 to C4) alkylthio groups independently substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group, respectively.

The (C1 to C4) alkylthio group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group, and a carboxy group as the substituent in _{R 5 to} R _{7 is (C1 to C4).} ) Arbitrary carbon atoms in the alkylthio group include those having these substituents. The number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited, but it is preferable to replace the sulfur atom with a carbon atom other than the carbon atom to which the sulfur atom is bonded in the alkylthio group.
Specific examples thereof include 2-hydroxyethylthio group, 2-hydroxypropylthio group, 3-hydroxypropylthio group, 2-sulfoethylthio group, 3-sulfopropylthio group, 2-carboxyethylthio group, 3 Examples thereof include a −carboxypropylthio group and a 4-carboxybutylthio group.

Among the above, preferred R _{5 to} R ₇ include sulfo (C1 to C4) alkylthio groups or carboxy (C1 to C4) alkylthio groups, with sulfo (C1 to C4) alkylthio groups being more preferred, and 3-sulfopropyl. A thio group is particularly preferred.

In the above formula (1), R _{8 to} R ₁₀ independently represent (C1 to C4) alkylcarbonylamino groups.

Examples of the (C1 to C4) alkylcarbonylamino groups in R _{8 to} R ₁₀ include those in which the alkyl moiety is a straight chain or a branched chain, and those having a straight chain are preferable. Specific examples thereof include linear ones such as acetylamino group (methylcarbonylamino group), propionylamino group (ethylcarbonylamino group), n-propylcarbonylamino group and n-butylcarbonylamino group, and isopropylcarbonylamino. Examples thereof include those having a branched chain such as a group, an isobutylcarbonylamino group, a sec-butylcarbonylamino group and a pivaloylamino group (tert-butylcarbonylamino group), and an acetylamino group is more preferable.

R _{11 to} R ₁₃ are independently hydrogen atom, carboxy group, sulfo group, hydroxy group, acetylamino group, halogen atom, cyano group, nitro group, sulfamoyl group, (C1 to C4) alkyl group and (C1). ~ C4) (C1 to C4) alkoxyl group substituted with at least one group selected from the group consisting of an alkoxyl group, a hydroxy group, (C1 to C4) alkoxyl group, a sulfo group and a carboxy group, (C1 to C4). ) An alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group (C1 to C4), and any of _{R 11 to} R ₁₃ Or at least one is a sulfo group.

The (C1 to C4) alkoxy group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxyl group, a sulfo group, and a carboxy group in _{R 11 to} R ₁₃ described above is The (C1 to C4) alkoxyl group substituted with at least one group selected from the group consisting of a hydroxy group, a (C1 to C4) alkoxyl group, a sulfo group, and a carboxy group in _{R 8 to} R ₁₀ described above. The same ones including preferable ones can be mentioned. Examples of the (C1 to C4) alkylsulfonyl groups in R _{11 to} R ₁₃ include linear or branched alkyl sulfonyl groups, and linear alkyl sulfonyl groups are preferable. Specific examples include linear alkylsulfonyl groups such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl and n-butylsulfonyl, branched alkylsulfonyl groups such as isopropylsulfonyl and isobutylsulfonyl, and the like. Of the above, methylsulfonyl, ethylsulfonyl, and isopropylsulfonyl are preferred, with methylsulfonyl being particularly preferred. In R ₁₁ to R ₁₃ , the (C1 to C4) alkylsulfonyl group substituted with at least one group selected from the group consisting of a hydroxy group, a sulfo group and a carboxy group as the substituent includes the above (C1 to C4). C4) Any carbon atom in the alkylsulfonyl group may be substituted with the above group, and the number of the substituents is usually 1 or 2, preferably 1. The position of the substituent is not particularly limited. Specific examples include hydroxy-substituted alkyl sulfonyl groups such as hydroxyethyl sulfonyl and 2-hydroxypropyl sulfonyl, sulfo-substituted alkyl sulfonyl groups such as 2-sulfoethyl sulfonyl and 3-sulfopropyl sulfonyl, 2-carboxyethyl sulfonyl and 3-carboxy. Examples thereof include carboxy-substituted alkyl sulfonyl groups such as propyl sulfonyl.

Among the above, preferred R ₁₁ includes a hydrogen atom, a carboxy group, a sulfo group, a nitro group, a chlorine atom, a methyl group, a methoxy group, and an alkylsulfonyl group (C1 to C4), and hydrogen atom or electron-withdrawing substitution. The carboxy group, the sulfo group, the nitro group, the chlorine atom, the (C1 to C4) alkylsulfonyl group, or the methyl group and the methoxy group, which are the groups, are more preferable, and the hydrogen atom and the sulfo group are particularly preferable.

Of the above, preferred R _12, a hydrogen atom, a carboxyl group, a sulfo group, a nitro group, a chlorine atom, a methyl group, a methoxy group, a sulfamoyl group, (C1 -C4) alkylsulfonyl group, carboxy (C1 -C4) alkyl Examples thereof include a sulfonyl group and a sulfo (C1 to C4) alkylsulfonyl group, which are hydrogen atom or electron-withdrawing substituents such as a carboxy group, a sulfo group, a nitro group, a chlorine atom, a sulfamoyl group, and a (C1 to C4) alkylsulfonyl group. A carboxy (C1 to C4) alkylsulfonyl group, a sulfo (C1 to C4) alkylsulfonyl group, or a methyl group or a methoxy group is more preferable, and a sulfo group, a nitro group, a methyl group, a methoxy group, a sulfamoyl group, a sulfopropylsulfonyl group, A carboxyethyl sulfonyl group is more preferred, and a sulfo group is particularly preferred.

Among the above, preferred R ₁₃ includes a hydrogen atom, a carboxy group, a sulfo group, a methoxy group, a nitro group, a chlorine atom, and (C1 to C4) alkylsulfonyl groups, which are hydrogen atoms or electron-withdrawing substituents. A carboxy group, a sulfo group, a nitro group, a chlorine atom, a (C1 to C4) alkylsulfonyl group, or a methoxy group is more preferable, and a sulfo group is particularly preferable.

_{Specific examples of preferable combinations of R 1 to} R ₁₃ in the above formula (1) include the following combinations (i) to (v). (Ii) or (iii) is more preferable, and (iv) or (v) is further preferable.

(I)
R ₁ is a methyl group,
R ₂ is a cyano group,
R ₃ is a hydrogen atom or a methoxy group,
R ₄ is a sulfo group,
(C1-C4) alkylthio groups in which R ₅ is substituted with a sulfo group or a carboxy group,
(C1-C4) alkylthio groups in which R ₆ is substituted with a sulfo group or a carboxy group,
(C1-C4) alkylthio groups in which R ₇ is substituted with a sulfo group or a carboxy group,
R ₈ is the (C1-C4) alkylcarbonylamino group,
R ₉ is the (C1-C4) alkylcarbonylamino group,
R ₁₀ is the (C1-C4) alkylcarbonylamino group,
R ₁₁ is a hydrogen atom or a sulfo group or a nitro group,
R ₁₂ is a hydrogen atom or a sulfo group or a nitro group,
R ₁₃ is a hydrogen atom or a sulfo group or a nitro group,
Combination of.

(Ii)
R ₁ is a methyl group,
R ₂ is a cyano group,
R ₃ is a hydrogen atom or a methoxy group,
R ₄ is a sulfo group,
R ₅ is a sulfo (C1-C4) alkylthio group,
R ₆ is a sulfo (C1-C4) alkylthio group,
R ₇ is a sulfo (C1-C4) alkylthio group,
R ₈ is the (C1-C4) alkylcarbonylamino group,
R ₉ is the (C1-C4) alkylcarbonylamino group,
R ₁₀ is the (C1-C4) alkylcarbonylamino group,
R ₁₁ is a sulfo group,
R ₁₂ is a sulfo group,
R ₁₃ is a hydrogen atom or a sulfo group or a nitro group,
Combination of.

(Iii)
R ₁ is a methyl group,
R ₂ is a cyano group,
R ₃ is a hydrogen atom or a methoxy group,
R ₄ is a sulfo group,
R ₅ is a sulfo (C1-C4) alkylthio group,
R ₆ is a sulfo (C1-C4) alkylthio group,
R ₇ is a sulfo (C1-C4) alkylthio group,
R ₈ is the (C1-C3) alkylcarbonylamino group,
R ₉ is the (C1-C3) alkylcarbonylamino group,
R ₁₀ is the (C1-C3) alkylcarbonylamino group,
R ₁₁ is a sulfo group,
R ₁₂ is a sulfo group,
R ₁₃ is a hydrogen atom or a sulfo group,
Combination of.

(Iv)
R ₁ is a methyl group,
R ₂ is a cyano group,
R ₃ is a hydrogen atom or a methoxy group,
R ₄ is a sulfo group,
R ₅ is a sulfo (C1-C4) alkylthio group,
R ₆ is a sulfo (C1-C4) alkylthio group,
R ₇ is a sulfo (C1-C4) alkylthio group,
R ₈ is an acetylamino group,
R ₉ is an acetylamino group,
R ₁₀ is an acetyl amino group,
R ₁₁ is a sulfo group,
R ₁₂ is a sulfo group,
R ₁₃ is a hydrogen atom or a sulfo group,
Combination of.

(V)
R ₁ is a methyl group,
R ₂ is a cyano group,
R ₃ is a hydrogen atom or a methoxy group,
R ₄ is a sulfo group,
R ₅ is a sulfopropylthio group,
R ₆ is a sulfopropylthio group,
R ₇ is a sulfopropylthio group,
R ₈ is an acetylamino group,
R ₉ is an acetylamino group,
R ₁₀ is an acetyl amino group,
R ₁₁ is a sulfo group,
R ₁₂ is a sulfo group,
R ₁₃ is a hydrogen atom,
Combination of.

Compounds in which various substituents in the above formula (1), combinations thereof, and preferable ones described with respect to their substitution positions are combined are more preferable, and those in which more preferable ones are combined are further preferable. The same applies to more preferable ones and combinations of preferable ones and more preferable ones.

The tetrakisazo compound represented by the above formula (1) can be synthesized by, for example, the following method. The structural formula of the compound in each step shall be expressed in the form of free acid. Further, in the following formulas (5) to (12), R _{1 to} R ₁₃ are the same as those in the above formula (1).
The compound represented by the following formula (5) is diazotized by a conventional method, and the obtained diazo compound and the compound represented by the following formula (6) are coupled by a conventional method and represented by the following formula (7). Obtain the compound to be.

The obtained compound represented by the above formula (7) is diazotized by a conventional method, and then the obtained diazo compound and the compound represented by the following formula (8) are coupled and reacted by a conventional method to obtain the following formula. Obtain the compound represented by (9).

The obtained compound represented by the above formula (9) is diazotized by a conventional method, and then the obtained diazo compound and the compound represented by the following formula (10) are coupled and reacted by a conventional method to obtain the following formula. The compound represented by (11) is obtained.

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

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

Preferable specific examples of the azo compound represented by the above formula (1) include, but are not limited to, compounds represented by the structural formulas listed in Tables 1 to 3 below.
In each table, functional groups such as sulfo group and carboxy group are described in the form of free acid for convenience. In addition, Ac in the following formula represents an acetyl group.

The diazotization of the compound represented by the above formula (5) is carried out by a method known per se, for example, nitrite, for example, in an inorganic acid medium at a temperature of, for example, −5 to 30 ° C., preferably 0 to 15 ° C. It is carried out using an alkali metal nitrite such as sodium nitrite. Coupling of the diazodized compound represented by the above formula (5) with the compound represented by the above formula (6) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium at a temperature of, for example, −5 to 30 ° C., preferably 0 to 25 ° C., and at an acidic to neutral pH value, such as pH 1-6. Since the diazotization reaction solution is acidic and the inside of the reaction system is further acidified as the coupling reaction progresses, the pH value of the reaction solution is adjusted to a preferable pH condition by adding a base. As the base, for example, 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 can be used. .. The compound represented by the above formula (5) and the compound represented by the above formula (6) are used in a stoichiometric amount.

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

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

The diazotization of the compound represented by the above formula (11) is also carried out by a method known per se, for example, in an inorganic acid medium at a temperature of, for example, −5 to 50 ° C., preferably 10 to 40 ° C., a nitrite, for example, nitrite. It is carried out using an alkali metal nitrite such as sodium. Coupling of the diazodized compound represented by the above formula (11) with the compound represented by the above formula (12) is also carried out under conditions known per se. It is advantageous to carry out in water or an aqueous organic medium at a temperature of, for example, −5 to 50 ° C., preferably 10 to 40 ° C., and a weakly acidic to alkaline pH value. Preferably, the pH value is weakly acidic to weakly alkaline, for example, pH 5-10, and the adjustment of the pH value is carried out by adding a base. The same base as above can be used. The compound represented by the above formula (11) and the compound represented by the above formula (12) are used in a stoichiometric amount.

The salt of the azo compound represented by the above formula (1) is a salt with an inorganic or organic cation. Among them, examples of the salt with the inorganic cation include an alkali metal salt, an alkaline earth metal salt, and an ammonium salt, and preferable inorganic salts are lithium, sodium, potassium salts, and ammonium salts. Examples of the salt with an organic cation include, but are not limited to, a salt with a quaternary ammonium ion represented by the following formula (13).
Further, the free acid of the azo compound represented by the above formula (1), its tautomer, and various salts thereof may be mixed. For example, any combination may be used, such as a mixture of a sodium salt and an ammonium salt, a mixture of a free acid and a sodium salt, a mixture of a lithium salt, a sodium salt, and an ammonium salt. Physical property values such as solubility may differ depending on the type of salt, and it is suitable for the purpose by appropriately selecting the type of salt as necessary or changing the ratio when multiple salts are contained. A mixture having physical characteristics can also be obtained.

In the above formula (13), Z ¹ , Z ² , Z ³ , and Z ⁴ are independently selected from the group consisting of a hydrogen atom, an unsubstituted alkyl group, a hydroxyalkyl group, and a hydroxyalkoxyalkyl group, respectively. Represents a group, at least one is a group other than a hydrogen atom. ^{Specific examples of the alkyl groups of Z 1 to} Z ⁴ in the above formula (13) include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-butyl. Specific examples of the hydroxyalkyl group include a group and the like, and examples thereof include a hydroxymethyl group, a hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, a 4-hydroxybutyl group, a 3-hydroxybutyl group, and a 2-hydroxy group. Examples thereof include hydroxy (C1 to C4) alkyl groups such as butyl groups, and specific examples of hydroxyalkoxyalkyl groups include hydroxyethoxymethyl group, 2-hydroxyethoxyethyl group, 3-hydroxyethoxypropyl group, and 2-hydroxyethoxypropyl group. Examples thereof include a group, a 4-hydroxyethoxybutyl group, a 3-hydroxyethoxybutyl group, a 2-hydroxyethoxybutyl group and the like hydroxy (C1 to C4) alkoxy (C1 to C4) alkyl group. Of these, hydroxyethoxy (C1-C4) alkyl groups are preferred. Particularly preferred are hydrogen atom, methyl group, hydroxymethyl group, hydroxyethyl group, 3-hydroxypropyl group, 2-hydroxypropyl group, 4-hydroxybutyl group, 3-hydroxybutyl group, 2-hydroxybutyl group and the like. Hydroxy (C1-C4) alkyl group, hydroxyethoxymethyl group, 2-hydroxyethoxyethyl group, 3-hydroxyethoxypropyl group, 2-hydroxyethoxypropyl group, 4-hydroxyethoxybutyl group, 3-hydroxyethoxybutyl group, Examples thereof include hydroxyethoxy (C1 to C4) alkyl groups such as 2-hydroxyethoxybutyl group.

^{Specific examples of combinations of Z 1} , Z ² , Z ³ , and Z ^{4 in} the preferred compound represented by the above formula (13) are shown in Table 4 below.

As a method for synthesizing a desired salt of the azo compound represented by the above formula (1), a desired inorganic salt or an organic salt can be obtained after the final step in the synthesis reaction of the compound represented by the above formula (1). A method in which a quaternary ammonium salt is added to a reaction solution for salting, a mineral acid such as hydrochloric acid is added to the reaction solution, the azo compound is isolated from the reaction solution in the form of a free acid, and then the obtained free acid is used. If necessary, wash with water, acidic water, an aqueous organic medium or the like to remove impurities such as attached inorganic salts, and again in an aqueous medium (preferably in water) to obtain the desired free acid. Examples thereof include a method of forming a salt by adding an inorganic base or an organic base corresponding to the above-mentioned quaternary ammonium salt. By these methods, the salt of the desired azo compound can be obtained in the form of a solution or a precipitated solid. The 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 to make it acidic. Further, the aqueous organic medium refers to a miscible product of water with an organic substance and / or an organic solvent or the like that is miscible with water. Examples of the organic substance and the organic solvent that are miscible with water include water-soluble organic solvents described later.
Examples of the inorganic salt used when the azo compound represented by the above formula (1) is a desired salt include halogen salts of alkali metals such as lithium chloride, sodium chloride and potassium chloride, lithium carbonate, sodium carbonate and carbonic acid. Alkali metal carbonates such as potassium, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, halogen salts of ammonium ions such as ammonium chloride and ammonium bromide, ammonium hydroxide (water ammonia) Hydroxides of ammonium ions, etc., and the like. Examples of salts of organic cations include halogen salts of quaternary ammonium ions represented by the above formula (13), such as diethanolamine hydrochloride and triethanolamine hydrochloride.

The ink composition will be described. The azo compound represented by the above formula (1) can be used for dyeing a material made of cellulose by preparing an aqueous composition containing the compound. It is also possible to dye materials having a carboxylic amide bond, and it can be widely used for dyeing leather, woven fabrics, paper and the like. On the other hand, a typical usage of the azo compound represented by the above formula (1) includes an ink composition dissolved in a liquid medium, and it is preferable to use it as an ink composition for inkjet recording.

The reaction solution containing the compound represented by the above formula (1), for example, the reaction solution after the final step in the synthesis reaction of the compound represented by the above formula (1) is directly used for producing the ink composition. be able to. However, a method of drying the reaction solution, for example, spray-drying, a method of salting out by adding inorganic salts such as sodium chloride, potassium chloride, calcium chloride, and sodium sulfate to the reaction solution, and a method of salting out the reaction solution with hydrochloric acid and sulfuric acid. The compound is isolated by a method of salting out by adding a mineral acid such as nitrate, or a method of salting out by combining the above-mentioned salting out and acid analysis, and an ink using this compound is used. Compositions can also be prepared. The azo compound of the present invention is preferably used after isolation.

The ink composition is an aqueous ink composition containing 0.1 to 20% by mass, preferably 1 to 10% by mass, and more preferably 2 to 8% by mass of the azo compound represented by the above formula (1) as a dye. It is an ink composition. The ink composition is prepared using water as a medium, and if necessary, a water-soluble organic solvent or an ink preparation may be contained within a range that does not impair the effects of the present invention. The water-soluble organic solvent may have a function as a dye dissolving agent, a drying inhibitor (wetting agent), a viscosity adjusting agent, a penetration accelerator, a surface tension adjusting agent, a defoaming agent, etc. Is preferably contained. Known ink preparation agents include, for example, antiseptic and antifungal agents, pH adjusters, chelating reagents, rust preventives, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye solubilizers, antioxidants, surfactants and the like. Additives can be mentioned. In the ink composition, the water-soluble organic solvent is 0 to 30% by mass, preferably 5 to 30% by mass, and the ink preparation is 0 to 15% by mass, preferably 0 to 7% by mass, respectively, with respect to the total mass. It may be contained. The rest other than the above is water. The pH of the ink composition is preferably pH 5 to 11 and more preferably pH 7 to 10 in terms of improving storage stability. The surface tension of the ink composition is preferably 25 to 70 mN / m, more preferably 25 to 60 mN / m. Further, the viscosity of the ink composition is preferably 30 mPa · s or less, more preferably 20 mPa · s or less.

The ink composition may appropriately contain other dyes for toning, etc., in addition to the azo compound represented by the above formula (1), for the purpose of adjusting a delicate shade of black. Even in such a case, the total mass of the dye contained in the ink composition may be in the above range with respect to the total mass of the ink composition.
Examples of the toning dye include yellow (for example, CI Direct Yellow 34, CI Direct Yellow 58, CI Direct Yellow 86, CI Direct Yellow 132, CI Direct Yellow 161 and the like. ), Orange (eg CI Direct Orange 17, CI Direct Orange 26, CI Direct Orange 29, CI Direct Orange 39, CI Direct Orange 49, etc.), Brown, Scarlet (For example, CI Direct Red 89, etc.), Red (for example, CI Direct Red 62, CI Direct Red 75, CI Direct Red 79, CI Direct Red 80, CI Direct Red 84, CI Direct Red 225, CI Direct Red 226, etc.), Magenta (eg CI Direct Red 227, etc.), Violet, Blue, Navy, Cyan (eg CI Direct) Examples thereof include other pigments having various hues such as blue 199, CI acid blue 249, etc.), green (eg, acid green 1), and black (eg, CI acid black 2).
In the ink composition, one or more of these toning dyes can be blended and used as long as the effects obtained by the azo compound represented by the above formula (1) are not impaired. Even in this case, the total amount of the dye contained in the ink composition may be in the above range. The blending ratio of the azo compound represented by the above formula (1) and the above-mentioned toning dye is approximately 20: 1 to 1: 2, preferably 10 although it depends on the hue of the toning dye and the like. It is from: 1 to 1: 1. When the above ink composition is used as an ink for inkjet recording, one having a small content of inorganic impurities such as chlorides and sulfates of metal cations in the azo compound represented by the above formula (1) is used. Is preferable. The guideline for the content of the inorganic impurities is about 1% by mass or less with respect to the total mass of the dye. The lower limit may be below the detection limit of the analytical instrument, that is, 0%. In order to produce the azo compound represented by the above formula (1) having a small amount of inorganic impurities, for example, a method using a back-penetrating film, a dried product of the azo compound represented by the above formula (1), or a wet cake made of methanol or the like is used. It may be desalted by a known method such as a method of suspending and purifying with stirring in a mixed solvent of alcohol, preferably (C1 to C4) alcohol and water, and filtering and separating and drying the precipitate.

Specific examples of the water-soluble organic solvent that can be used for preparing the ink composition include (C1 to C4) alcohols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, second butanol, and third butanol. Caroxyamides such as N, N-dimethylformamide and N, N-dimethylacetamide, lactams such as 2-pyrrolidone, hydroxyethyl-2-pyrrolidone, N-methyl-2-pyrrolidone and N-methylpyrrolidin-2-one, Cyclic ureas such as 1,3-dimethylimidazolidine-2-one and 1,3-dimethylhexahydropyrimido-2-one, acetone, methyl ethyl ketone, 2-methyl-2-hydroxypentane-4-one and the like. Cyclic ethers such as ketone or keto alcohol, tetrahydrofuran, dioxane, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butylene glycol, 1,4-butylene glycol, 1,6-hexylene Mono, oligo, or polyalkylene glycol or thioglycol having C2-C6 alkylene units such as glycols, diethylene glycols, triethylene glycols, tetraethylene glycols, dipropylene glycols, polyethylene glycols, polypropylene glycols, thiodiglycols, dithiodiglycols, etc. Polycols such as trimethylolpropane, glycerin, hexane-1,2,6-triol (preferably triol), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether (butyl carbi). Examples thereof include (C1 to C4) alkyl ethers of polyhydric alcohols such as triethylene glycol monomethyl ether and triethylene glycol monoethyl ether, γ-butyrolactone, and dimethyl sulfoxide. These organic solvents may be used alone or in combination of two or more. The above-mentioned water-soluble organic solvent also contains substances that are solid at room temperature, such as trimethylol propane, but these are water-soluble even if they are solid, and when dissolved in water, they are water-soluble. 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.

Hereinafter, antiseptic and antifungal agents, pH adjusters, chelating reagents, rust preventives, water-soluble ultraviolet absorbers, water-soluble polymer compounds, dye-dissolving agents, antioxidants, and surfactants that can be used as ink preparation agents. Describe.

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 an ink composition in an amount of 0.02 to 1.00% by mass.

Examples of preservatives include organic sulfur-based, organic nitrogen-sulfur-based, organic halogen-based, haloallyl sulfone-based, iodopropagil-based, N-haloalkylthio-based, nitrile-based, pyridine-based, 8-oxyquinolin-based, and benzothiazole. System, isothiazoline system, dithiol system, pyridine oxide system, nitropropane system, organotin system, phenol system, tetraammonium salt system, triazine system, thiazine system, anilide system, adamantan system, dithiocarbamate system, brominated indanone system, Examples thereof include benzyl bromacetate-based compounds and inorganic salt-based compounds.
Specific examples of the organic halogen-based compound include pentachlorophenol sodium, and specific examples of the pyridine oxide-based compound include, for example, 2-pyridinethiol-1-oxide sodium. Specific examples of the isothiazolin-based compound include 2-pyridinethiol-1-oxide sodium. For example, 1,2-benzisothiazolin-3-one, 2-n-octyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazolin-3-one, 5-chloro-2. Examples thereof include −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. Specific examples of other antiseptic and fungicides include acetic anhydride, sodium sorbate, sodium benzoate and the like.

As the pH adjuster, any substance can be used as long as the pH of the ink can be controlled in the range of approximately 5 to 11 without adversely affecting the prepared ink. Specific examples thereof include alkanolamines such as diethanolamine, triethanolamine and N-methyldiethanolamine, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide and potassium hydroxide, and ammonium hydroxide (water ammonia). , Alkali metal carbonates such as lithium carbonate, sodium carbonate, sodium hydrogencarbonate and potassium carbonate, alkali metal salts of organic acids such as potassium acetate, inorganic bases such as sodium silicate and disodium phosphate and the like.

Specific examples of the chelating reagent include sodium ethylenediaminetetraacetate, sodium nitrilotriacetic acid, sodium hydroxyethylethylenediamine triacetate, sodium diethylenetriamine pentaacetate, sodium uracil diacetate and the like.

Examples of the rust preventive include acidic sulfite, sodium thiosulfate, ammonium thioglucolate, diisopropylammonium nitrate, pentaerythritol tetranitrate, dicyclohexylammonium nitrate and the like.

Examples of the water-soluble ultraviolet absorber include sulfonated benzophenone compounds, benzotriazol compounds, salicylic acid compounds, cinnamic acid compounds, and triazine compounds.

Examples of the water-soluble polymer compound include polyvinyl alcohol, cellulose derivatives, polyamines and polyimines.

Examples of the dye-dissolving agent include ε-caprolactam, ethylene carbonate, urea and the like.

As the antioxidant, for example, various organic and metal complex-based anti-fading agents can be used. Examples of the organic anti-fading agent include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indans, chromanes, alkoxyanilines, heterocycles and the like. ..

Examples of the surfactant include known surfactants such as anionic, cationic and nonionic surfactants.
Examples of anionic surfactants include alkyl sulfonates, alkyl carboxylic acid salts, α-olefin sulfonates, polyoxyethylene alkyl ether acetates, N-acylamino acids and salts thereof, N-acylmethyl taurine salts, and alkyl sulfates. Polyoxyalkyl ether sulfate, alkyl sulfate polyoxyethylene alkyl ether phosphate, loginate soap, castor oil sulfate, lauryl alcohol sulfate, alkylphenol phosphate, alkyl phosphate, alkylaryl sulfonate, Examples thereof include diethyl sulfo sulphate, diethyl hexyl sul sulfo sulphate, dioctyl sulphon sulphate and the like.

Examples of the cationic surfactant include 2-vinylpyridine derivatives and poly4-vinylpyridine derivatives.

Examples of the amphoteric surfactant include betaine lauryldimethylaminoacetate, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine, betaine palm oil fatty acid amide propyldimethylaminoacetate, polyoctylpolyaminoethylglycine, and imidazoline derivatives. Can be mentioned.

Examples of the nonionic surfactant include ethers such as polyoxyethylene nonylphenyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene dodecylphenyl ether, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, and polyoxyethylene alkyl ether. Esters such as polyoxyethylene oleic acid ester, polyoxyethylene distearate, sorbitan laurate, sorbitan monostearate, sorbitan monooleate, sorbitan sesquioleate, polyoxyethylene monooleate, polyoxyethylene stearate, etc. 2,4,7,9-Tetramethyl-5-decine-4,7-diol, 3,6-dimethyl-4-octin-3,6-diol, 3,5-dimethyl-1-hexin-3-ol Etc., acetylene glycol (alcohol) type, manufactured by Nissin Chemical Co., Ltd., trade names: Surfinol 104, 105, 82, 465, orphine STG, etc. ), Etc. can be mentioned.
The above ink preparations are used alone or in combination with each other.

The ink composition is obtained by mixing and stirring each of the above components in an arbitrary order. If desired, the obtained ink composition may be microfiltered with a membrane filter or the like in order to remove narrow substances, and when used for inkjet recording, the filtration is preferable. The pore size of the filter for microfiltration is usually 1 μm to 0.1 μm, preferably 0.8 μm to 0.1 μm.

Although the ink composition can be used in various fields, it is suitable for writing water-based inks, water-based printing inks, information recording inks, etc., and is particularly preferably used as ink jet recording inks. It is preferably used in the inkjet recording method of.

The inkjet recording method is a method in which the ink composition of the present invention is used as an ink, and ink droplets of the ink are ejected in response to a recording signal and adhered to a recording material to perform recording. The inkjet recording method of the present invention is not particularly limited with respect to the ink head, ink nozzle, etc. used for recording, and can be appropriately selected depending on the intended purpose. This recording method is a known method, for example, a charge control method for ejecting ink by using an electrostatic attraction, a drop-on-demand method (pressure pulse method) for using the vibration pressure of a piezo element, and an acoustic beam for an electric signal. The acoustic inkjet method that irradiates the ink with the ink and ejects the ink using the radiation pressure, the thermal inkjet method that heats the ink to form bubbles and uses the generated pressure, the so-called bubble jet (registered trademark) method. , Etc. can be used.

The material to be recorded used in the inkjet recording method is not particularly limited, and examples thereof include information transmission sheets such as paper and film, fibers and cloths (cellulose, nylon, wool, etc.), leather, and base materials for color filters. Among them, the information transmission sheet is preferable.
As the information transmission sheet, a surface-treated sheet, specifically, a sheet having an ink receiving layer provided on a base material such as paper, synthetic paper, or a film is preferable. The ink receiving layer is made of, for example, impregnated or coated with a cationic polymer on the above-mentioned base material, and a porous white inorganic substance such as porous silica, alumina sol, special ceramics, etc., which can absorb the dye in the ink, such as polyvinyl alcohol and polyvinyl. It is provided by a method such as coating on the surface of the base material together with a hydrophilic polymer such as pyrrolidone. Information transmission sheets provided with such an ink receiving layer are usually called inkjet paper (film), glossy paper (film), or the like. Specific examples include Canon Co., Ltd., product name Professional Photo Paper, Super Photo Paper or Matte Photo Paper, Seiko Epson Co., Ltd., Product Name Photo Paper (Glossy), PM Matte Paper, Crispia, Nippon Hulett PACKARD Co., Ltd. Company-made, trade name Advanced Photo Paper, Premium Plus Photo Paper, Premium Glossy Film or Photo Paper, etc. can be obtained as commercial products. Of course, plain paper can also be used.

Among the above information transmission sheets, it is known that the image recorded on the sheet coated with the porous white inorganic substance on the surface is particularly significantly discolored and faded by ozone gas. However, since the ink composition of the present invention has excellent ozone gas resistance, it exerts a great effect even when inkjet recording is performed on such a recording material.

In order to record on the material to be recorded by the above-mentioned inkjet recording method, for example, a container containing the above-mentioned ink composition may be loaded at a predetermined position of an inkjet printer and recorded on the material to be recorded by the above-mentioned method. The inkjet recording method comprises the black ink composition and inks of, for example, known magenta, cyan, yellow as described above, and optionally green, blue (or violet), red (or orange), and the like. It can also be used in combination with the composition. The ink composition of each color is injected into each container, and each container is loaded in a predetermined position of an inkjet printer and used for inkjet recording in the same manner as the container containing the black ink composition of the present invention.

The colored body of the present invention is
a) The azo compound according to any one of 1) to 6) above, a tautomer thereof, or a salt thereof.
b) The water-based ink composition according to 7) or 8) above, and
c) It means a substance colored by any one of the three [these a) to c) of the inkjet recording method described in 9) above.
The substance to be colored is not particularly limited, but a recording material or the like used in the above-mentioned inkjet recording method is preferably used.

The azo compound of the present invention is a black dye. Since this compound is easy to synthesize, inexpensive, and has low saturation, it exhibits a more preferable hue as black, and the absolute values of * a and * b as evaluation values of hue are less than 12. Therefore, it becomes a good black color. Moreover, since it is excellent in water solubility, it has good filterability by a membrane filter in the process of producing an ink composition. Further, the ink composition of the present invention containing the azo compound is an aqueous black ink composition, and has good storage stability without solid precipitation, physical characteristic change, color change, etc. after long-term storage. The image recorded with the ink composition of the present invention is particularly excellent in ozone gas resistance, high print density, excellent bronzing property, low color rendering property, low saturation, and high-quality black hue. Has. It also has excellent robustness such as light resistance, moisture resistance, and water resistance. Further, when used in combination with an ink composition containing magenta, cyan, and yellow dyes, full-color inkjet recording with excellent fastness and storage stability is possible. As described above, the ink composition containing the azo compound of the present invention can be used as an ink for inkjet recording, writing tools, etc., and is excellent in ejection stability. Therefore, it is particularly suitable as an ink for inkjet recording. Suitable.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to the following Examples. The terms "part" and "%" in the text are based on mass unless otherwise specified. Unless otherwise specified, each synthetic reaction, crystallization and other operations were carried out under stirring. In each of the following formulas, acidic functional groups such as sulfo and carboxy are expressed in the form of free acids. The pH value and the reaction temperature in the synthetic reaction were both measured values in the reaction system. The maximum absorption wavelength (λmax) of the synthesized compound was measured in an aqueous solution having a pH of 7 to 8, and the measured value of the measured compound was described in Examples. The azo compounds of the present invention synthesized in the following examples all showed a solubility of 100 g / liter or more in water.

[(A) Dye synthesis]
[Example 1]
(Step 1)
After adding 5.1 parts of aniline-2,4-disulfonic acid represented by the following formula (17) to 50 parts of water, an aqueous solution was obtained with a pH of 4.0 to 5.0 by adding a 25% aqueous sodium hydroxide solution. .. After adding 6.3 parts of 35% hydrochloric acid, 4.2 parts of 40% aqueous sodium nitrite solution was added and the reaction was carried out for about 30 minutes. 0.8 part of sulfamic acid was added thereto, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution. On the other hand, after adding 5.7 parts of the compound of the formula (16) obtained by the method described in International Publication No. 2012/081640 to 100 parts of water, the pH is 4.0 to 5.0 by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as. This aqueous solution was added dropwise to the diazo reaction solution obtained above in about 5 minutes. After the dropping, the reaction was carried out for 3 hours while maintaining the pH at 2.0 to 4.0 by adding a 15% aqueous sodium carbonate solution, and then sodium chloride was added and salted out to a pH of 0.8 to 1.0 with 35% hydrochloric acid. bottom. The precipitated solid was collected by filtration to obtain 24.8 parts of a wet cake containing the compound represented by the following formula (18).

(Step 2)
After adding the entire amount of the wet cake of the compound represented by the formula (18) obtained in Example 1 (Step 1) to 80 parts of water, the pH is 6.0 to 7.0 by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as. After adding 5.63 parts of 35% hydrochloric acid, 3.8 parts of a 40% aqueous sodium nitrite solution was added, and the reaction was carried out for about 30 minutes. 0.8 part of sulfamic acid was added thereto, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution. On the other hand, after adding 5.7 parts of the compound of the formula (16) obtained by the method described in International Publication No. 2012/081640 to 100 parts of water, the pH is 4.0 to 5.0 by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as. This aqueous solution was added dropwise to the diazo reaction solution obtained above in about 5 minutes. After the dropping, the reaction was carried out for 3 hours while maintaining the pH at 2.0 to 2.5 by adding a 15% aqueous sodium carbonate solution, then sodium chloride was added, and the pH was adjusted to 0.8 to 1.0 by adding 35% hydrochloric acid. Salted out. The precipitated solid was collected by filtration to obtain 33.2 parts of a wet cake containing the compound represented by the following formula (19).

(Step 3)
To 100 parts of water, 33.2 parts of a wet cake of the compound represented by the formula (19) obtained in Example 1 (Step 2) was added and stirred to dissolve. After adding 4.7 parts of 35% hydrochloric acid, 3.2 parts of a 40% aqueous sodium nitrite solution was added, and the mixture was stirred for about 30 minutes. 0.4 part of sulfamic acid was added thereto, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution. On the other hand, after adding 5.7 parts of the compound of the formula (16) obtained by the method described in International Publication No. 2012/081640 to 100 parts of water, the pH is 4.0 to 5.0 by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as. This aqueous solution was added dropwise to the diazo reaction solution obtained above in about 5 minutes. After the dropping, the reaction was carried out for 3 hours while maintaining the pH at 2.0 to 2.5 by adding a 15% aqueous sodium carbonate solution, then sodium chloride was added, and the pH was adjusted to 0.8 to 1.0 by adding 35% hydrochloric acid. Salted out. The precipitated solid was collected by filtration to obtain 35.2 parts of a wet cake containing the compound represented by the following formula (20).

(Step 4)
To 80 parts of water, 35.2 parts of a wet cake of the compound represented by the formula (20) obtained in Example 1 (Step 3) was added and stirred to dissolve. After adding 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous sodium nitrite solution was added, and the mixture was stirred for about 30 minutes. 0.5 part of sulfamic acid was added thereto, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution. On the other hand, 4.0 parts of the compound of the following formula (21) obtained by the method described in International Publication No. 2012/081640 was added to 80 parts of water, and the pH was 6.0 to 7 by adding a 5% aqueous sodium hydroxide solution. An aqueous solution was obtained as 0.0. The diazo reaction solution obtained above was added dropwise to this aqueous solution at 15 to 30 ° C. over about 30 minutes. At this time, a 15% aqueous sodium carbonate solution was added to maintain the pH of the reaction solution at 6.5 to 7.5, and the reaction was carried out for another 2 hours while maintaining the same temperature and pH adjustment. Sodium chloride was added to the reaction solution for salting out, and the precipitated solid was separated by filtration to obtain 20.3 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, the pH was adjusted to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of methanol was added, and the precipitated solid was collected by filtration. The obtained wet cake was dissolved again in 40 parts of water, and then 300 parts of methanol was added. The precipitated solid was separated by filtration and dried to obtain 10.3 parts of sodium salt as a black powder of the compound represented by the following formula (22) of the present invention.
λmax: 574 nm.

[Example 2]
(Step 1)
After adding 19.5 parts of naphthalene-1,3,7-sulfonic acid represented by the following formula (27) to 50 parts of water, add a 25% sodium hydroxide aqueous solution to adjust the pH to 4.0 to 5.0 to make the aqueous solution. Obtained. After adding 18.3 parts of 35% hydrochloric acid, 10.5 parts of a 40% aqueous sodium nitrite solution was added and reacted for about 30 minutes. To this, 1.5 parts of sulfamic acid was added and stirred for 5 minutes to obtain a diazo reaction solution. On the other hand, 16.7 parts of the compound of the above formula (16) obtained by the method described in International Publication No. 2012/081640 was added to 50 parts of water, and the pH was 4.0 to 5. An aqueous solution was obtained as 0. This aqueous solution was added dropwise to the diazo reaction solution obtained above over about 5 minutes. After the dropping, the reaction was carried out for 3 hours while maintaining the pH at 4.0 to 6.0 by adding a 15% aqueous sodium carbonate solution, and then sodium chloride was added. The precipitated solid was collected by filtration to obtain 163 parts of a wet cake containing the compound represented by the following formula (28).

(Step 2)
After adding the entire amount of the wet cake of the compound represented by the formula (28) obtained in Example 2 (Step 1) to 150 parts of water, the pH is 6.0 to 7.0 by adding a 25% aqueous sodium hydroxide solution. An aqueous solution was obtained as. After adding 16.5 parts of 35% hydrochloric acid, 10.6 parts of a 40% aqueous sodium nitrite solution was added and reacted for about 30 minutes. 7.5 parts of sulfamic acid was added thereto, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution. On the other hand, 16.7 parts of the compound of the above formula (16) obtained by the method described in International Publication No. 2012/081640 was added to 100 parts of water, and the pH was 4.0 to 5. An aqueous solution was obtained as 0. This aqueous solution was added dropwise to the diazo reaction solution obtained above over about 5 minutes. After the dropping, the reaction was carried out for 3 hours while maintaining the pH at 4.0 to 6.0 by adding a 15% aqueous sodium carbonate solution, and then sodium chloride was added. The precipitated solid was collected by filtration to obtain 163 parts of a wet cake containing the compound represented by the following formula (29).

(Step 3)
To 100 parts of water, 76.0 parts of a wet cake of the compound represented by the formula (29) obtained in Example 2 (Step 2) was added, and the mixture was stirred and dissolved. After adding 7.8 parts of 35% hydrochloric acid, 2.8 parts of a 40% aqueous sodium nitrite solution was added, and the mixture was stirred for about 30 minutes. 0.8 part of sulfamic acid was added thereto, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution. On the other hand, 4.9 parts of the compound of the above formula (16) obtained by the method described in International Publication No. 2012/081640 was added to 80 parts of water, and the pH was 4.0 to 5. An aqueous solution was obtained as 0. This aqueous solution was added dropwise to the diazo reaction solution obtained above over about 5 minutes. After the dropping, the reaction was carried out for 3 hours while maintaining the pH at 4.0 to 6.0 by adding a 15% aqueous sodium carbonate solution. After adjusting the pH to 7.0-7.5 by adding a 25% aqueous sodium hydroxide solution, sodium chloride was added. The precipitated solid was collected by filtration to obtain 53 parts of a wet cake containing the compound represented by the following formula (30).

(Step 4)
To 80 parts of water, 53 parts of a wet cake of the compound represented by the formula (30) obtained in Example 2 (Step 3) was added and stirred to dissolve. After adding 6.3 parts of 35% hydrochloric acid, 2.3 parts of a 40% aqueous sodium nitrite solution was added, and the mixture was stirred for about 30 minutes. 0.5 part of sulfamic acid was added thereto, and the mixture was stirred for 5 minutes to obtain a diazo reaction solution. On the other hand, 4.0 parts of the compound represented by the formula (23) obtained in the above Example 1 (step) was added to 80 parts of water, and the pH was 6.0 to 7. An aqueous solution was obtained as 0. The diazo reaction solution obtained above was added dropwise to this aqueous solution at 15 to 30 ° C. over about 30 minutes. At this time, a 15% aqueous sodium carbonate solution was added to maintain the pH of the reaction solution at 6.5 to 7.5, and the reaction was carried out for another 2 hours while maintaining the same temperature and pH adjustment. Sodium chloride was added to the reaction solution for salting out, and the precipitated solid was separated by filtration to obtain 32.4 parts of a wet cake. The obtained wet cake was dissolved in 40 parts of water, the pH was adjusted to 7.0 to 7.5 with 35% hydrochloric acid, 400 parts of isopropanol was added, and the precipitated solid was collected by filtration. The obtained wet cake was dissolved again in 40 parts of water, and then 300 parts of isopropanol was added. The precipitated solid was separated by filtration and dried to obtain 13.5 parts of sodium salt as a black powder of the compound represented by the following formula (31) of the present invention. λmax: 586.5 nm.

[(B) Ink preparation]
The azo compounds of the present invention obtained in Examples 1 and 2 [formulas (22) and (31)] are used as dyes, and the compositions shown in Table 5 below are mixed to prepare a solution of the present invention. An ink composition 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 7 below, the trade name Surfinol ^RTM 104PG50 manufactured by Nissin Chemical Co., Ltd. was used as the "surfactant". The preparation of the ink using the compound obtained in Example 1 is referred to as Example 3. Further, the test inks were adjusted in the same manner as in Example 3 except that the dye obtained in Example 2 was used instead of the dye obtained in Example 1. This ink is referred to as Example 4.

[Comparative Example 1]
A comparative ink was prepared in the same manner as in Example 3 except that the dye described in International Publication No. 2012/081640 (Example 3) was used instead of the compound of the present invention obtained in Example 1. The preparation of this ink is referred to as Comparative Example 1. The structural formula of the compound used in Comparative Example 1 is shown in the following formula (32).

[(C) Inkjet recording]
Each ink prepared in Examples 3 to 4 and Comparative Example 1 was inkjet-recorded on the following glossy paper using an inkjet printer (manufactured by Canon Inc., trade name: PIXUS ^{RTM ip7230).} At the time of recording, an image pattern was created so that six grades of 100%, 85%, 70%, 55%, 40%, and 25% densities could be obtained, and a halftone recorded material was obtained. The following test was carried out using the obtained recorded material as a test piece.

Glossy paper: manufactured by Seiko Epson Corporation, product name: PM photo paper

[(D) Color measurement of recorded image]
Various tests and their evaluations were carried out by measuring the color of the test piece using a colorimeter manufactured by X-rite, trade name SpectroEye. The color measurement was performed under the conditions of DIN NB, a viewing angle of 2 degrees, and a light source D65 based on the density.

[(D) Hue evaluation test]
The hue (a * b *) of the test piece obtained in the above [(C) Inkjet recording] was measured using the color measuring system. The lower the a * b *, the lower the saturation and the better the black dye. The results are shown in Table 6. The evaluation criteria are as follows.
The absolute value of * a and * b is 10 or less at any concentration.
Absolute values of * a and * b exceed 10 and less than 12 at any concentration.
The absolute value of * a and * b is 12 or more at any concentration.

From the above, it can be seen that the water-soluble azo compound of the present invention and the ink composition of the present invention containing the compound have a better hue of the printed matter as compared with the conventional dye. Moreover, the test piece obtained by using the example ink of the present application showed good ozone resistance.

The azo compound of the present invention and an ink composition containing the azo compound are preferably used for various recordings such as writing instruments, particularly black ink for inkjet recording.

Claims (10)

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

[In equation (1),
R ₁ represents a (C1-C4) alkyl group or a (C1-C4) alkyl group substituted with a carboxy group.
R ₂ represents a cyano group
R ₃ and R ₄ independently represent a hydrogen atom, an (C1 to C4) alkoxyl group, or a sulfo group, respectively.
R ₅ represents an (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of hydroxy, sulfo and carboxy groups.
R ₆ represents an (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of hydroxy, sulfo and carboxy groups.
R ₇ represents an (C1-C4) alkylthio group substituted with at least one group selected from the group consisting of hydroxy, sulfo and carboxy groups.
R ₈ represents the (C1-C4) alkylcarbonylamino group
R ₉ is a (C1-C4) alkylcarbonylamino group
R ₁₀ represents the (C1-C4) alkylcarbonylamino group
R _{11 to} R ₁₃ are independently hydrogen atoms, sulfo groups, carboxy groups, hydroxy groups or nitro groups, respectively. Further, when the ring represented by the broken line does not exist, it is a benzene ring, when the ring represented by a broken line exists, it is a naphthalene ring, and when it is a naphthalene ring, the substituents R _{11 to} R ₁₃ are naphthalene rings, respectively. Can be replaced with any position of. ] In the above formula (1)
R ₁ represents a (C1-C4) alkyl group or a (C1-C4) alkyl group substituted with a carboxy group.
R ₂ represents a cyano group
R ₃ and R ₄ independently represent a hydrogen atom, an (C1 to C4) alkoxyl group, or a sulfo group, respectively.
R ₅ represents a sulfo (C1-C4) alkylthio group and represents
R ₆ represents a sulfo (C1-C4) alkylthio group and R ₇ represents a sulfo (C1-C4) alkylthio group.
R ₈ represents the (C1-C4) alkylcarbonylamino group
R ₉ is a (C1-C4) alkylcarbonylamino group
R ₁₀ represents the (C1-C4) alkylcarbonylamino group
The azo compound according to claim 1, or a tautomer thereof, or a salt thereof, wherein R _{11 to} R ₁₃ are each independently a hydrogen atom, a sulfo group, a carboxy group, a hydroxy group or a nitro group. In the above formula (1)
R ₁ is a methyl group,
R ₂ is a cyano group,
R ₃ is a methoxy group or a hydrogen atom,
R ₄ is a sulfo group,
R ₅ is a sulfo (C1-C4) alkylthio group,
R ₆ is a sulfo (C1-C4) alkylthio group,
R ₇ is a sulfo (C1-C4) alkylthio group,
R ₈ is an acetylamino group,
R ₉ is an acetylamino group,
R ₁₀ is an acetyl amino group,
The azo compound according to claim 1 or 2, or a tautomer thereof, or a salt thereof, in which R _{11 to} R _{13 are independently hydrogen atoms, sulfo groups, carboxy groups, hydroxy groups or nitro groups, respectively.} .. An aqueous ink composition containing at least one kind of azo compound according to any one of claims 1 to 3, a tautomer thereof, or a salt thereof as a dye. The water-based ink composition according to claim 4, further containing a water-soluble organic solvent. An inkjet recording method in which the water-based ink composition according to claim 4 or 5 is used as ink, and ink droplets of the ink are ejected in response to a recording signal to record on a recording material. The inkjet recording method according to claim 6, wherein the material to be recorded is an information transmission sheet. The inkjet recording method according to claim 7, wherein the information transmission sheet is a sheet having an ink receiving layer containing a porous white inorganic substance. An inkjet printer loaded with a container containing the aqueous ink composition according to claim 4 or 5. a) The azo compound according to any one of claims 1 to 3, a tautomer thereof, or a salt thereof.
b) The water-based ink composition according to claim 4 or 5, or
c) A colored body colored by any of the three methods of the inkjet recording method according to claim 6.