JPH07166081A - Trisazo compound, method of dyeing fibrous material, paper, or leather with the same, and recording liquid containing the same - Google Patents

Abstract

PURPOSE:To improve performances required for a dye or a recording liquid, in particular storage stability, water resistance, and light resistance, without using benzidine or a derivative thereof by obtaining a specific trisazo compound. CONSTITUTION:This compound is represented by formula VII (wherein one of A and B is -OH and the other is -NH2). It is obtained by diazotizing an amine compound represented by formula I [wherein X and Y each is -OR<1>, -SR<2>, a group represented by formula II (where R<3> and R<4> each is H, an alkyl, phenyl, or naphthyl), or a group represented by formula III (where Z is -CH2-, -O-, -SO2-, or -NR<5>; r is 1 or 2; and R<5> is H or a 1-4C alkyl), and Q1 is phenylene] and coupling the diazo compound with an aminonaphthol compound (a) represented by formula IV (wherein k is 1 or 2). Alternatively, it is obtained by tetrazotizing a diaminodiphenylamine compound represented by formula V (wherein one of m and n is 1 and the other is 0) and coupling the tetrazo compound with the compound (a) and an aromatic compound represented by formula VI (wherein Q2 is phenyl or naphthyl). This compound is used for dyeing fibers, paper, or leathers or as a colorant for a recording liquid for ink-jet recording, etc.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a trisazo compound and its use. More specifically, it relates to a novel trisazo compound, a method for dyeing a fiber material, paper or leather black with the trisazo compound, and a recording liquid containing the trisazo compound.

[0002]

2. Description of the Related Art Conventionally, polyazo direct dyes or acid dyes based on benzidine or its derivatives have been used for dyeing fiber materials having a hydroxy group or an amino group. However, benzidine is a prohibited substance, and benzidine analogues such as orthotolidine and dianisidine are designated as specific chemical substances. Therefore, in producing a benzidine dye, various restrictions are imposed on the handling of these raw materials. Therefore, various compounds have been proposed as non-benzidine dyes. However, no compound has yet been able to satisfy the needs of customers regarding the various performances required as a dye.

CI Direct Bla
ck) 168 was proposed as a non-benzidine dye and is represented by the following formula.

[0004]

Japanese Patent Laid-Open No. 63-105079 describes a recording liquid containing CI Direct Black 168. However, when CI Direct Black 168 is used for dyeing a fiber material or paper, a dark black color cannot be obtained because of poor build-up properties. Further, when this is used as a recording liquid dye, the solubility of the dye and the water resistance of the recorded image are insufficient. In particular, when used as an inkjet recording liquid, there are problems such as nozzle clogging due to dye deposition and insufficient water resistance of the recorded image. in this way,
CI Direct Black 168 wasn't good enough for performance in any application.

[0006]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted extensive studies to solve the above problems, and as a result, can be produced without using benzidine or a derivative thereof as a raw material and are required as dyes and recording liquids. The present invention has been completed by finding a compound that satisfies the performance.

[0007]

That is, the present invention provides a trisazo compound represented by the following formula (I) in the form of a free acid.

[0008]

(In the formula, Q ¹ represents an optionally substituted phenylene group; Q ² represents an optionally substituted phenyl or naphthyl group; one of A and B is hydroxy. , The other represents amino; k represents 1 or 2, one of m and n represents 1 and the other represents 0; X and Y independently of ^one another are -OR ¹ , -SR ² ,

[0010]

Where R ¹ , R ² , R ³ and R ⁴
Each independently represent hydrogen or an optionally substituted alkyl, phenyl or naphthyl group, r represents 1 or 2, Z is —CH ₂ —, —O—, —SO ₂ — or —NR ⁵ —. Where R ⁵ is hydrogen or C ₁ -C ₄
Represents an alkyl group. )

The present invention also provides a method for dyeing a fiber material, paper or leather using the trisazo compound represented by the above formula (I), and further provides a recording liquid containing the trisazo compound.

In the formula (I), Q ¹ is a phenylene group, which may be unsubstituted or substituted.
Preferably Q ¹ is an unsubstituted phenylene group or a phenylene group substituted with an alkyl, alkoxy, sulfo or carboxy, such a preferred Q
¹ is represented by the following formula (II).

[0014]

(In the formula, R ⁶ represents hydrogen, alkyl, alkoxy, sulfo or carboxy, and * means that it is bonded to an azo group.) Here, alkyl and alkoxy are usually lower members, for example, It may have about 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms.

In the formula (I), Q ² is a phenyl group or a naphthyl group, each of which may be unsubstituted or substituted. Examples of the group capable of substituting the phenyl group or the naphthyl group include hydroxy, unsubstituted or substituted amino, sulfo, alkyl, alkoxy, carboxy and the like. Here, when the phenyl group or the naphthyl group has amino, examples of the group capable of substituting for amino include methyl, ethyl, hydroxyethyl, cyanoethyl, acetyl, carbamoyl,
Examples thereof include phenyl, sulfophenyl, disulfophenyl and benzoyl. Alkyl and alkoxy as used herein can also be those usually having a lower member, for example, having about 1 to 4 carbon atoms, preferably 1 or 2 carbon atoms.

When Q ² is a phenyl group, one of the following is particularly preferable.

A phenyl group which is substituted with 1 to 3 hydroxy groups and which may be further substituted with unsubstituted or substituted amino, sulfo, alkyl, alkoxy or carboxy, or

A phenyl group which is substituted with 1 to 2 unsubstituted or substituted amino and which may be further substituted with hydroxy, sulfo, alkyl, alkoxy or carboxy.

The amino substituted on the phenyl group may be unsubstituted or substituted, and examples of the substituted amino include amino substituted with methyl, ethyl, hydroxyethyl, cyanoethyl, acetyl or carbamoyl. To be done. Further, examples of the alkyl substituting the phenyl group include methyl and ethyl, and examples of the alkoxy substituting the phenyl group include methoxy and ethoxy.

Of these, particularly preferable phenyl represented by Q ² is 2-amino-4-hydroxyphenyl and 2-hydroxy-4-aminophenyl.

When Q ² is a naphthyl group, one of the following is particularly preferable.

A naphthyl group which is substituted with 1 or 2 hydroxy and which may be further substituted with unsubstituted or substituted amino, carboxy or sulfo, or

A naphthyl group which is substituted with 1 or 2 unsubstituted or substituted amino and which may be further substituted with hydroxy, carboxy or sulfo.

Examples of the substituted amino in the above case include amino substituted with methyl, acetyl, phenyl, sulfophenyl, disulfophenyl or benzoyl. Further, as the substituted amino in the above case, methyl,
Examples are amino substituted with ethyl, hydroxyethyl, cyanoethyl, acetyl or carbamoyl.

X and Y in formula (I) are as defined above, and the alkyl group represented by R ¹ , R ² , R ³ and R ⁴ has, for example, about 1 to 6 carbon atoms. However, those having 1 to 4 carbon atoms are usually preferable. When R ¹ , R ² , R ³ and / or R ⁴ is an alkyl group, examples of the group which may be substituted therefor include lower alkoxy, sulfo, carboxy, hydroxy, halogen, phenyl, substituted phenyl, cyano and substituted amino. , Lower alkanoyl and the like. Specific examples of the substituted phenyl mentioned here are halophenyl, lower alkylphenyl, sulfophenyl and the like. Further, specific examples of the substituted amino are mono- or di-lower alkylamino and the like.

When R ¹ , R ² , R ³ and / or R ⁴ is a phenyl group, the group which can be substituted therefor is, for example, lower alkyl, lower alkoxy, sulfo, carboxy, halogen, sulfo lower alkyl, hydroxy. And so on. When R ¹ , R ² , R ³ and / or R ⁴ are naphthyl groups, examples of the group which can be substituted on the naphthyl group include sulfo and the like.

X and Y are each independently --O.
Preferred is R ¹ or —NR ³ R ⁴ . Among them, X and Y are independently of each other, -OR ¹¹ or -NR ³¹
Represented by R ⁴¹ , R ¹¹ is an unsubstituted alkyl group having 1 to 4 carbon atoms, or alkoxy having 1 to 4 carbon atoms, sulfo, carboxy, hydroxy, chloro, phenyl. And one selected from the group of cyano
Or an alkyl group having 1 to 4 carbon atoms substituted by 2 substituents, an unsubstituted phenyl group, or an alkyl group having 1 to 4 carbon atoms, 1 to 4 An alkoxy having the carbon atom of, sulfo,
1 or 2 selected from the group of carboxy and chloro
A phenyl group substituted with 4 substituents; and R ³¹
And R ⁴¹ is, independently of each other, hydrogen, an unsubstituted alkyl group having 1 to 4 carbon atoms, or 1 to 4
Amino substituted twice with alkyl having 1 carbon atom, alkoxy having 1 to 4 carbon atoms, sulfo,
An alkyl group having 1 to 4 carbon atoms substituted by 1 or 2 substituents selected from the group of carboxy and hydroxy, an unsubstituted phenyl group, or 1 to 4 carbons Alkyl having atoms, 1
Preferred is a phenyl group substituted with 1 or 2 substituents selected from the group of alkoxy, sulfo, carboxy and chloro having 4 carbon atoms.

Further, when the preferable combinations of X and Y are finely classified, the following (1) to (10) are obtained.

(1) X is represented by --NR ³² R ⁴² , wherein R ³² and R ⁴² are independently of each other hydrogen or amino substituted twice with alkyl having 1 to 4 carbon atoms,
1 or 2 selected from the group consisting of alkoxy having 1 to 4 carbon atoms, sulfo, carboxy and hydroxy.
Is an alkyl group having 1 to 4 carbon atoms which may be substituted with 4 substituents, and Y is -NR ³³ R
⁴³ , wherein R ³³ and R ⁴³ are independently of each other hydrogen or alkyl having 1 to 4 carbon atoms, 1 to
A phenyl group which may be substituted with 1 or 2 substituents selected from the group consisting of alkoxy, sulfo, carboxy and chloro having 4 carbon atoms;

(2) X and Y are independently of each other --NR ³²
R ⁴² , wherein R ³² and R ⁴² are independent of each other,
Hydrogen or an alkyl group as defined above;

(3) X and Y are independently of each other --NR ³³
R ⁴³ , wherein R ³³ and R ⁴³ are independent of each other,
Hydrogen or a phenyl group as defined above;

(4) X is represented by -OR ¹² , where R ¹²
Is an alkoxy having 1 to 4 carbon atoms, sulfo,
An alkyl group having 1 to 4 carbon atoms which may be substituted by 1 or 2 substituents selected from the group of carboxy, hydroxy, chloro, phenyl and cyano, and Y is represented by --OR ¹³ . And R here
¹³ is phenyl optionally substituted with 1 or 2 substituents selected from the group consisting of alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy and chloro. If it is a group;

(5) X and Y are independently -OR ¹²
Where R ¹² is an alkyl group as defined above;

(6) X and Y are independently -OR ¹³
Where R ¹³ is a phenyl group as defined above;

(7) X is represented by --NR ³² R ⁴² , wherein R ³² and R ⁴² are independently of each other hydrogen or an alkyl group as defined above, and Y is represented by --OR ¹² . Where R ¹² is an alkyl group as defined above;

(8) X is represented by --NR ³² R ⁴² , wherein R ³² and R ⁴² are independently of each other hydrogen or an alkyl group as defined above, and Y is represented by --OR ¹³ . And R ¹³ is a phenyl group as defined above;

(9) X is represented by --NR ³³ R ⁴³ , wherein R ³³ and R ⁴³ are independently of each other hydrogen or a phenyl group as defined above, and Y is represented by --OR ¹³ . And R ¹³ is a phenyl group as defined above; or

(10) X is represented by --NR ³³ R ⁴³ , wherein R ³³ and R ⁴³ are independently of each other hydrogen or a phenyl group as defined above, and Y is represented by --OR ¹² . Where R ¹² is an alkyl group as defined above.

At least one of X and Y is 1
~ Amino substituted twice with alkyl having 4 to 4 carbon atoms, substituted by 1 or 2 substituents selected from the group consisting of alkoxy having 1 to 4 carbon atoms, sulfo, carboxy and hydroxy Good 1-4
1 or 2 selected from the group consisting of alkylamino having 1 to 4 carbon atoms, or alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy and chloro. The case where it is phenylamino which may be substituted with a substituent is also preferable. Among them, at least one of X and Y is -NH
The case of (CH ₂ ) ₃ N (C ₂ H ₅ ) ₂ is exemplified as being preferable in the present invention.

Preferred trisazo compounds represented by the formula (I) are represented by the following formula (III) or (IV) in the form of free acid.

[0042]

(In the formula, Q ¹ , Q ² , X and Y have the above-mentioned meanings.)

The trisazo compound of the present invention exists in the form of a free acid or a salt thereof. Preferably an alkali metal salt,
It is an ammonium salt or an organic amine salt. Examples of the alkali metal forming the salt include lithium, sodium or potassium, and examples of the organic amine forming the salt include monoethanolamine, diethanolamine or triethanolamine.

The compound represented by the formula (I) is, for example, a compound represented by the following formula (V)

[0046]

(Wherein X, Y and Q ¹ have the above-mentioned meanings), an amine compound represented by the following formula (VI) in the form of a free acid.

[0048]

(Wherein, m and n have the above meanings), a diaminodiphenylamine compound represented by the following formula (VII) in the form of a free acid.

[0050]

(Wherein k has the above-mentioned meaning), and an aminonaphthol compound represented by the following formula (VIII)

Q ² —H (VIII)

The aromatic compound represented by the formula (wherein Q ² has the above-mentioned meaning) is used as a starting material, provided that the amine compound of the formula (V) is diazotized, and the diaminodiphenylamine compound of the formula (VI) is Tetrazotized and used in any order so that the diazotized compound of the amine compound of formula (V) will couple with the aminonaphthol compound of formula (VII) and the diaminodiphenylamine compound of formula (VI). It can be produced by reacting the compound thus converted with the aminonaphthol compound of the formula (VII) and the aromatic compound of the formula (VIII), respectively.

The amine compound represented by the above formula (V) is
For example, the following formula (Va)

NH ₂ --Q ¹ --R ⁷ (Va)

(Wherein Q ¹ has the above-mentioned meaning and R ⁷ represents nitro, amino or acetylamino) and the following formulas (Vb) to (Ve)

[0057]

(Wherein R ¹ , R ² , R ³ , R ⁴ , Z and r have the above-mentioned meanings), and one or two selected independently from each other. Two
A compound of formula (Va) in which R ⁷ is acetylamino or nitro is condensed with 4,6-trihalogeno-s-triazine in any order, and then the compound is produced by hydrolysis or reduction. You can

In the formula (I), the trisazo compound in which A is hydroxy and B is amino is specifically produced, for example, as follows.

The diaminodiphenylamine compound represented by the formula (VI) in the form of the free acid is tetrazolated by a conventional method, and the tetrazo compound and the aminonaphthol compound represented by the formula (VII) in the form of the free acid are mixed in an aqueous medium. A monoazodiazo compound is obtained by coupling under medium and acidic conditions. Next, the monoazodiazo compound and the diazo compound obtained by diazotizing the amine compound represented by the formula (V) by a conventional method are coupled in a weakly acidic or weakly alkaline aqueous medium. The compound obtained by this coupling and the aromatic compound represented by the formula (VIII) are coupled in a weakly acidic to weakly alkaline aqueous medium to give a compound of the formula (I The trisazo compound of 1) is obtained.

In addition, a tetrazo compound obtained by tetrazotizing a diaminodiphenylamine compound represented by the formula (VI) in the form of a free acid by a conventional method and an aminonaphthol compound represented by the formula (VII) in the form of a free acid are prepared. , In an aqueous medium, after coupling under acidic conditions to obtain a monoazodiazo compound, the monoazodiazo compound and the aromatic compound represented by the formula (VIII) are coupled in a weakly acidic or weakly alkaline aqueous medium. A disazo compound is obtained, and this disazo compound is then coupled with a diazo compound obtained by diazotizing an amine compound represented by the formula (V) by a conventional method in a weakly acidic or weakly alkaline aqueous medium. , A is hydroxy and B is amino, a trisazo compound of formula (I) is obtained.

In the formula (I), the trisazo compound in which A is amino and B is hydroxy is specifically produced, for example, as follows. That is, the amine compound represented by the formula (V) is diazotized by a conventional method, and the diazo compound and the aminonaphthol compound represented by the formula (VII) in the form of a free acid are coupled in an aqueous medium under acidic conditions. Then, a monoazo compound is obtained. With this monoazo compound,
The diaminodiphenylamine compound represented by the formula (VI) in the form of a free acid is tetrazotized by a conventional method to obtain a tetrazo compound, which is then coupled in a weakly acidic to weakly alkaline aqueous medium. By coupling the compound obtained by this coupling with the aromatic compound represented by the formula (VIII) in a weakly acidic to weakly alkaline aqueous medium, a compound of the formula (I The trisazo compound of 1) is obtained.

Examples of the compound represented by the formula (Va) include 4-nitroaniline, 3-nitroaniline, 1-amino-4-acetylaminobenzene, 1-amino-3-acetylaminobenzene and 1-amino-2. -Methyl-5-
Nitrobenzene, 1-amino-2-methoxy-4-nitrobenzene, 1-amino-2-methoxy-5-nitrobenzene, 1,3-diaminobenzene-4-sulfonic acid,
1-amino-4-nitrobenzene-2-sulfonic acid, 2
-Carboxy-1,4-diaminobenzene, 1-amino-2-carboxy-4-acetylaminobenzene and the like are mentioned as preferable ones.

Examples of the compound represented by the formula (Vb) include the followings.

Phenol, 1-hydroxy-2-, -3
-Or-4-methylbenzene, 1-hydroxy-3,
4- or -3,5-dimethylbenzene, 1-hydroxy-2-, -3- or -4-ethylbenzene, 1-hydroxy-2-, -3- or -4-methoxybenzene, 1-hydroxy-2- , -3- or -4-ethoxybenzene, 1-hydroxy-2-, -3- or -4
-Chlorobenzene, 3- or 4-hydroxyphenylmethanesulfonic acid, 3- or 4-hydroxybenzenesulfonic acid, 5-hydroxybenzene-1,3-disulfonic acid, 2-hydroxybenzene-1,4-disulfonic acid, 4 -Hydroxybenzene-1,2-disulfonic acid,
4-hydroxy-5-methylbenzene-1,2-disulfonic acid, 3- or 4-hydroxybenzoic acid, 5-hydroxybenzene-1,3-dicarboxylic acid, 5-hydroxy-2-ethoxybenzenesulfonic acid, 2- , 4-, 5
-, 6-, 7- or 8-hydroxynaphthalene-1-
Sulfonic acid, 1-, 4-, 5-, 6-, 7- or 8
-Hydroxynaphthalene-2-sulfonic acid, 4, -5
-, 6-, 7- or 8-hydroxynaphthalene-1,
3-disulfonic acid, 2-, 3- or 4-hydroxynaphthalene-1,5-disulfonic acid, 4- or 8-hydroxynaphthalene-1,6-disulfonic acid, 4-hydroxynaphthalene-1,7-disulfonic acid, 3- or 4-hydroxynaphthalene-2,6-disulfonic acid, 3
-Or 4-hydroxynaphthalene-2,7-disulfonic acid, 6- or 7-hydroxynaphthalene-1,3,
5-trisulfonic acid, 4-hydroxynaphthalene-1,
Aromatic hydroxy compounds such as 3,6-trisulfonic acid; and

Methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, 2-chloroethanol, 2-methoxyethanol, 2-ethoxyethanol, 3-methoxypropanol, 3-ethoxypropanol, 2 -Hydroxyethanesulfonic acid, 3-hydroxy-1-propanesulfonic acid, 2-cyanoethanol, glycolic acid, 3-hydroxypropionic acid, benzyl alcohol, 2-, 3- or 4-chlorobenzyl alcohol,
4-methylbenzyl alcohol, 2-, 3- or 4-
Sulfobenzyl alcohol, 2-phenylethanol,
Aliphatic hydroxy compounds such as 1-phenyl-2-propanol.

Specific examples of the compound represented by the formula (Vc) include compounds exemplified as the compound of the above formula (Vb) in which hydroxy is replaced with mercapto.

Examples of the compound represented by the formula (Vd) include the followings.

Ammonia;

1-aminobenzene, 1-amino-2
-, -3- or -4-methylbenzene, 1-amino-
3,4- or -3,5-dimethylbenzene, 1-amino-2-, -3- or -4-ethylbenzene, 1-amino-2-, -3- or -4-methoxybenzene,
1-amino-2-, -3- or -4-ethoxybenzene, 1-amino-2-, -3- or -4-chlorobenzene, 3- or 4-aminophenylmethanesulfonic acid, 2-, 3- Or 4-aminobenzenesulfonic acid,
3-methylaminobenzenesulfonic acid, 3-ethylaminobenzenesulfonic acid, 4-methylaminobenzenesulfonic acid, 4-ethylaminobenzenesulfonic acid, 5-aminobenzene-1,3-disulfonic acid, 6-aminobenzene-1 , 3-disulfonic acid, 2-aminobenzene-
1,4-disulfonic acid, 4-aminobenzene-1,2-
Disulfonic acid, 4-amino-5-methylbenzene-1,
2-disulfonic acid, 2-, 3- or 4-aminobenzoic acid, 5-aminobenzene-1,3-dicarboxylic acid, 5-
Amino-2-hydroxybenzenesulfonic acid, 4-amino-2-hydroxybenzenesulfonic acid, 5-amino-
2-Ethoxybenzenesulfonic acid, N-methylaminobenzene, N-ethylaminobenzene, 1-methylamino-3- or 4-methylbenzene, 1-ethylamino-4-chlorobenzene, 1-ethylamino-3- Or -4-methylbenzene, 1- (2-hydroxyethyl)
Amino-3-methylbenzene, 3- or 4-methylaminobenzoic acid, 3- or 4-methylaminobenzenesulfonic acid, 2-, 4-, 5-, 6-, 7- or 8
-Aminonaphthalene-1-sulfonic acid, 1-, 4-, 5
-, 6-, 7- or 8-aminonaphthalene-2-sulfonic acid, 7-methylaminonaphthalene-2-sulfonic acid, 7-ethylaminonaphthalene-2-sulfonic acid, 7
-Butylaminonaphthalene-2-sulfonic acid, 7-isobutylaminonaphthalene-2-sulfonic acid, 4, -5
-, 6-, 7- or 8-aminonaphthalene-1,3-
Disulfonic acid, 2-, 3- or 4-aminonaphthalene-1,5-disulfonic acid, 4- or 8-aminonaphthalene-1,6-disulfonic acid, 4-aminonaphthalene-
1,7-Disulfonic acid, 3- or 4-aminonaphthalene-2,6-disulfonic acid, 3- or 4-aminonaphthalene-2,7-disulfonic acid, 6- or 7-aminonaphthalene-1,3,5 -Trisulfonic acid, 4-, 7-
Or an aromatic amine such as 8-aminonaphthalene-1,3,6-trisulfonic acid, 4-aminonaphthalene-1,3,7-trisulfonic acid; and

Methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, dimethylamine, diethylamine, methylethylamine, 2-chloroethylamine, 2-methoxyethylamine, 2-aminoethanol, 2-methylaminoethanol, bis (2-
Hydroxyethyl) amine, 2-acetylethylamine, 1-amino-2-propanol, 3-methoxypropylamine, 2-aminoethanesulfonic acid, aminomethanesulfonic acid, 2-methylaminoethanesulfonic acid, 3
-Amino-1-propanesulfonic acid, aminoacetic acid, methylaminoacetic acid, β-alanine, ε-aminocaproic acid,
Benzylamine, 2-, 3- or 4-chlorobenzylamine, 4-methylbenzylamine, N-methylbenzylamine, 2-, 3- or 4-sulfobenzylamine, 2-phenylethylamine, 1-phenylethylamine, 1 -Phenyl-2-propylamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N-di-n-butyl-1,3-propanediamine Aliphatic amines like.

Among the compounds represented by the formula (Vd), N, N-diethyl-1,3-propanediamine is particularly preferable.

Examples of the compound represented by the formula (Ve) include morpholine, piperazine, piperidine and pyrrolidine.

The amine compound represented by the formula (V) includes the compound of the above-exemplified formula (Va) and the above-exemplified formula (Vb) to
It is obtained by condensing any one or two compounds selected from (Ve) with 2,4,6-trihalogeno-s-triazine in any order, and optionally hydrolyzing or reducing the compound. .

As the diaminodiphenylamine compound represented by the formula (VI), 4,4'-diaminodiphenylamine-2-sulfonic acid is particularly preferable.

Examples of the aminonaphthol compound represented by the formula (VII) include 1-amino-8-naphthol-4
-Sulfonic acid, 1-amino-8-naphthol-3,6-
Alternatively, -4,6-disulfonic acid and the like can be mentioned.

Examples of the aromatic compound represented by the formula (VIII) include aniline and its derivatives, phenol and its derivatives, aminophenol and its derivatives,
Examples thereof include naphthol and its derivatives, naphthoic acid and its derivatives, naphthylamine sulfonic acid and its derivatives, naphthol sulfonic acid and its derivatives.

Of these, 1-hydroxybenzene, 1-hydroxy-2-, -3- or -4-methylbenzene, 1,3-dihydroxybenzene, 1-hydroxy-3-methoxybenzene and 1-hydroxy- are preferred. 3-
Aminobenzene, 3-di (β-hydroxyethyl) amino-1-hydroxybenzene, 1-di (β-hydroxyethyl) aminobenzene, 1,3-diamino-4-methylbenzene, 1-hydroxy-2-benzoic acid , 1,3-
Diaminobenzene-6-sulfonic acid, 1-acetylamino-4-methoxy-3-di (β-hydroxyethyl) aminobenzene, 3-diethylamino-1-hydroxybenzene, 1-hydroxynaphthalene, 1-hydroxy-
2-naphthoic acid, 1-hydroxynaphthalene-4-,-
5- or -3-sulfonic acid, 1-hydroxynaphthalene-3,8- or -3,6-disulfonic acid, 1-hydroxynaphthalene-3,6,8-trisulfonic acid, 2-
Hydroxynaphthalene, 2-hydroxy-3-naphthoic acid, 2-hydroxynaphthalene-8-, -7- or-
6-sulfonic acid, 2-hydroxynaphthalene-6,8-
Or -3,6-disulfonic acid, 2-amino-, methylamino-, ethylamino-, acetylamino-, propionylamino-, benzoylamino-, carbamoylamino-, sulfamoylamino- or phenylamino-8-hydroxy. Naphthalene-6-sulfonic acid, 3-amino-, methylamino-, ethylamino-, propionylamino-, acetylamino-, benzoylamino-,
Carbamoylamino-, sulfamoylamino- or phenylamino-8-hydroxynaphthalene-6-sulfonic acid, 1-amino- or acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid, 1-amino- or acetylamino -8-hydroxynaphthalene-
4,6-disulfonic acid, 1-amino-8-hydroxynaphthalene-2,4-disulfonic acid, 1,8-dihydroxynaphthalene-3,6-disulfonic acid and the like can be mentioned. Among them, 1-hydroxy-3-aminobenzene is particularly preferable.

The trisazo compound of the present invention, alone or in the form of a mixture, can be used for dyeing or printing fiber materials having hydroxy groups and / or amino groups, paper or leather, and particularly cellulose such as rayon or cotton. It is useful for dyeing and printing fibers, paper, leather, silk, synthetic polyamides, etc. The dyeing is performed by various methods such as exhaust dyeing. The trisazo compound of the present invention has an excellent solubility while exhibiting a high dyeing property, and thus gives a deep black dyed product. In particular, when used for dyeing paper, it gives a dyed product having good build-up properties and excellent fastness.

Further, the trisazo compound of the present invention can be used alone or in the form of a mixture, for example, as a dye for an ink for an ink jet printer using a piezo oscillator or heat energy. If necessary, a compound conventionally used in this field, for example, a known dye such as CI Direct Black 154 can be used in combination.

As the recording liquid, for example, an aqueous recording liquid can be applied. This aqueous recording liquid is a composition containing a water-soluble organic solvent and water. Examples of water-soluble organic solvents include C ₁ -C ₄ alkanols such as methanol,
Ethanol, n-propanol, isopropanol, n
-Butanol, sec-butanol, tert-butanol, isobutanol, benzyl alcohol; amides such as dimethylformamide, diethylformamide; ketones or ketone alcohols such as acetone, diacetone alcohol; ethers such as tetrahydrofuran, dioxane; polyalkylene glycols such as Polyethylene glycol, polypropylene glycol; C
Alkylene glycols and thioglycols having _{2 to} C ₆ alkylenes such as ethylene glycol, propylene glycol, butylene glycol, triethylene glycol, thiodiglycol, hexylene glycol, diethylene glycol; other polyols such as glycerol, 1,2,6 -Hexanetriol; lower alkyl ethers of polyhydric alcohols, such as 2-methoxyethanol, 2- (2-methoxyethoxy) ethanol, 2-ethoxyethanol, 2- (2-ethoxyethoxy) ethanol, 2- [2- (2 -Methoxyethoxy) ethoxy] ethanol, 2- [2- (2-ethoxyethoxy) ethoxy] ethanol; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine Nitrogen-containing heterocyclic ketones,
For example, 2-pyrrolidone, N-methyl-2-pyrrolidone,
N-ethyl-2-pyrrolidone, N-vinylpyrrolidone,
N-octyl-2-pyrrolidone, N- (2-hydroxyethyl) -2-pyrrolidone, N-cyclohexyl-2-
Pyrrolidone, N-dodecyl-2-pyrrolidone, N-isopropyl-2-pyrrolidone, Nn-butyl-2-pyrrolidone, N-tert-butyl-2-pyrrolidone, N-hexyl-2-pyrrolidone, N- (3 -Hydroxypropyl) -2-pyrrolidone, N- (2-methoxyethyl)-
2-pyrrolidone, N- (3-methoxypropyl) -2-
Pyrrolidone, N-benzyl-2-pyrrolidone, polyvinylpyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like can be mentioned. These water-soluble organic solvents may be used alone or as a mixture of two or more as long as they do not adversely affect each other.

When the trisazo compound represented by the formula (I) is used as a dye for a recording liquid, it is usually preferably used in a desalted form by a known method. For example, desalting can be performed by a method of crystallization from a mixed solvent of water and alcohols, a method of using an ultrafiltration membrane or a reverse osmosis membrane, and the like. The amount of the trisazo compound added is usually 0.5 to 20 parts by weight, preferably 1 to 15 parts by weight, based on 100 parts by weight of the recording liquid.

An antiseptic / antifungal agent such as sodium dehydroacetate, an ultraviolet absorber, an infrared absorber, a viscosity adjuster, a surface tension adjuster, a pH adjuster, a specific resistance adjuster, and a permeation agent are added to the aqueous recording liquid. Various additives such as agents may be added.

The aqueous recording liquid can be easily obtained by dissolving the trisazo compound represented by the formula (I), the water-soluble organic solvent and various additives in water or warm water, and as it is, or when cooled, through a filter membrane having a fine pore size.

The trisazo compound of the present invention has excellent solubility. Therefore, the storage stability is good and there is no clogging of the nozzle due to precipitates. Moreover, the recording liquid using the trisazo compound of the present invention gives a deep black image excellent in sharpness, water resistance and light resistance.

[0086]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. In the examples, part means part by weight.

Example 1 18.4 parts of 2,4,6-trichloro-s-triazine
After dissolving in 150 parts of acetone at 0 to 5 ° C. and adding 15.0 parts of 1-amino-3-acetylaminobenzene, 5.3 parts of sodium carbonate was added to cause condensation, and the reaction solution was mixed with water 2 parts.
It is poured into 00 parts and the precipitated crystals are collected by filtration. The obtained crystals were dispersed in 500 parts of water, and N, N-diethyl-1,
39.1 parts of 3-propanediamine are added, and the mixture is reacted at 70 ° C. for 5 hours. Then, hydrochloric acid is added to make the solution strongly acidic and the acetyl group is hydrolyzed to obtain an amine compound.

On the other hand, 27.9 parts of 4,4'-diaminodiphenylamine-2-sulfonic acid was tetrazotized by a conventional method, and this tetrazo compound was converted to 11.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid. And under acidic conditions, 0-5
Allow to couple at ° C. Then 1-hydroxy-3
-Aminobenzene (10.9 parts) was added to terminate the coupling reaction under mildly acidic conditions to obtain a disazo compound.

Next, the amine compound obtained above is diazotized by a conventional method, coupled with the above-mentioned disazo compound under weak alkalinity, salted out by a conventional method, and the precipitated crystal is collected by filtration. The crystals were redissolved in water, desalted and dried to obtain a trisazo compound represented by the following structural formula in the form of a free acid.

[0090]

This trisazo compound had a λmax of 630 nm in an aqueous medium.

Example 2 18.4 parts of 2,4,6-trichloro-s-triazine
After dissolving in 150 parts of acetone at 0 to 5 ° C., adding 13.8 parts of 4-nitroaniline and then adding 5.3 parts of sodium carbonate for condensation, the reaction solution was poured into 200 parts of water to precipitate crystals. Is collected by filtration. To the liquid obtained by dispersing the obtained crystals in 500 parts of water, 39.1 parts of N, N-diethyl-1,3-propanediamine is added and reacted at 95 ° C. for 1 hour. Next, iron powder is added and the nitro group is reduced by a conventional method to obtain an amine compound.

On the other hand, 27.9 parts of 4,4'-diaminodiphenylamine-2-sulfonic acid was tetrazotized by a conventional method, and this tetrazo compound was converted to 11.9-amino-8-naphthol-3,6-disulfonic acid 31.9. Parts and acidic conditions, 0
Coupling at ~ 5 ° C. Then, a diazonium compound obtained by diazotizing the amine compound obtained above by a conventional method is injected, and the mixture is coupled at 0 to 10 ° C. under mildly acidic conditions. Further, 10.9 parts of 1-hydroxy-3-aminobenzene is added to terminate the coupling reaction under a weakly acidic condition. Next, salting out was carried out by a conventional method, and the precipitated crystal was collected by filtration, redissolved in water, desalted and dried to obtain a trisazo compound represented by the following structural formula in the form of a free acid. .

[0094]

This trisazo compound had a λmax of 645 nm in an aqueous medium.

Example 3 18.4 parts of 2,4,6-trichloro-s-triazine
Disperse in 150 parts of water at 0-5 ° C., add 18.8 parts of 1,3-diaminobenzene-4-sulfonic acid and condense under acidic condition, then N, N-diethyl-1,3-propanediamine After adding 39.1 parts and making the mixture alkaline with sodium hydroxide, the mixture is heated to 70 ° C. and reacted for 7 hours to obtain an amine compound.

On the other hand, 27.9 parts of 4,4'-diaminodiphenylamine-2-sulfonic acid was tetrazotized by a conventional method, and the tetrazo compound was converted to 11.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid (31.9 parts). And under acidic conditions, 0-5
Allow to couple at ° C. Then 1-hydroxy-3
-Aminobenzene (10.9 parts) was added to terminate the coupling reaction under mildly acidic conditions to obtain a disazo compound.

Next, the amine compound obtained above is diazotized by a conventional method, coupled with the above-mentioned disazo compound under weak alkalinity, salted out by a conventional method, and the precipitated crystal is collected by filtration. The crystals were redissolved in water, desalted and dried to obtain a trisazo compound represented by the following structural formula in the form of a free acid.

[0099]

This trisazo compound had a λmax of 625 nm in an aqueous medium.

Example 4 18.4 parts of 2,4,6-trichloro-s-triazine
After dissolving in 150 parts of acetone at 0 to 5 ° C. and adding 15.0 parts of 1-amino-3-acetylaminobenzene, 5.3 parts of sodium carbonate was added to cause condensation, and the reaction solution was mixed with water 2 parts.
It is poured into 00 parts and the precipitated crystals are collected by filtration. To the liquid obtained by dispersing the obtained crystals in 500 parts of water, 26.7 parts of β-alanine was added, and the mixture was made alkaline with sodium hydroxide, then heated to 70 ° C. and reacted for 7 hours. Then, hydrochloric acid is added to make the solution strongly acidic and the acetyl group is hydrolyzed to obtain an amine compound.

On the other hand, 27.9 parts of 4,4'-diaminodiphenylamine-2-sulfonic acid was tetrazotized by a conventional method, and this tetrazo compound was converted to 11.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid (31.9 parts). And under acidic conditions, 0-5
Allow to couple at ° C. Then 1-hydroxy-3
-Aminobenzene (10.9 parts) was added to terminate the coupling reaction under mildly acidic conditions to obtain a disazo compound.

Then, the amine compound obtained above is diazotized by a conventional method, coupled with the above-mentioned disazo compound under weak alkalinity, and acid-deposited by a conventional method. The obtained cake was dispersed in water, ammonia water was added to make it weakly alkaline, desalted, and dried to obtain an ammonium salt type trisazo compound represented by the following structural formula.

[0104]

This trisazo compound had a λmax of 625 nm in an aqueous medium.

Example 5 0.8 part of the trisazo compound obtained in Example 1 was added to 500 parts of a 20 g / L solution of bleached hardwood kraft pulp (LBKP) that had been beaten to a beating degree of CSF of 400 ml.
After stirring for a minute, 0.3 parts of Size Pine E [size agent, manufactured by Arakawa Chemical Industry Co., Ltd.] was added and stirred for 10 minutes, then 0.3 parts of crystalline aluminum sulfate was added, and stirring was continued for 20 minutes. To dye. This is myogami and dried. The resulting paper had a dark black color shade and had excellent fastness.

Example 6 The following composition was heated to about 70 ° C., sodium hydroxide was added thereto to adjust the pH to 10, dissolved by stirring, and then filtered with a Teflon filter having a pore size of 0.45 μm to prepare a recording liquid. did.

Trisazo compound obtained in Example 1 2 parts Glycerin 4 parts 2-Pyrrolidone 10 parts Ethanol 4 parts 4-Chloro-3-methylphenol 0.01 parts Ion-exchanged water 80 parts

Using this recording liquid, ink jet recording was carried out on a commercially available high-quality paper by a recording device having an on-demand type recording head for ejecting the recording liquid by a piezoelectric vibrator. The nozzle was not clogged even after recording for a long time, and the obtained image was good in water resistance, light resistance, density and sharpness.

Example 7 1-amino-8-naphthol-4,6-disulfonic acid was used in place of 1-amino-8-naphthol-3,6-disulfonic acid used in Example 1, and By the same method, a trisazo compound represented by the following structural formula was obtained in the form of a free acid.

[0111]

This trisazo compound had a λmax of 620 nm in an aqueous medium.

Example 8 18.4 parts of 2,4,6-trichloro-s-triazine
Disperse in 150 parts of water at 0-5 ° C., add 18.8 parts of 1,3-diaminobenzene-4-sulfonic acid to condense under acidic conditions, then add 8.9 parts of β-alanine and add sodium carbonate. Add neutral to react at 20 ° C. next,
After adding 13.0 parts of N, N-diethyl-1,3-propanediamine and making the mixture alkaline with sodium hydroxide, the mixture was heated to 70 ° C. and reacted for 5 hours to obtain an amine compound.

On the other hand, 27.9 parts of 4,4'-diaminodiphenylamine-2-sulfonic acid was tetrazated by a conventional method, and the tetrazo compound was converted to 11.9 parts of 1-amino-8-naphthol-3,6-disulfonic acid (31.9 parts). And under acidic conditions, 0-5
Allow to couple at ° C. Then, 11.0 parts of 1,3-dihydroxybenzene is added to terminate the coupling reaction under a weakly acidic condition to obtain a disazo compound.

Next, the amine compound obtained above is diazotized by a conventional method, coupled with the above-mentioned disazo compound under weak alkalinity, salted out by a conventional method, and the precipitated crystal is collected by filtration. The crystals were redissolved in water, desalted and dried to obtain a trisazo compound represented by the following structural formula in the form of a free acid.

[0116]

This trisazo compound had a λmax of 625 nm in an aqueous medium.

Example 9 1,3-diaminobenzene used in Example 8
4-sulfonic acid, β-alanine, N, N-diethyl-
Instead of 1,3-propanediamine and 1,3-dihydroxybenzene, the formula (V
a) compounds, compounds of formulas (Vb) to (Ve) shown in the third column, compounds of formulas (Vb) to (Ve) shown in the fourth column and the fifth
Using the compound of formula (VIII) shown in the column, the corresponding trisazo compound was obtained in the same manner as in Example 1, 2 or 8. Then, the obtained trisazo compound was used to perform sequential dyeing in the same manner as in Example 5 to obtain a dyed product having a color tone shown in the sixth column of the table below.

[0119]

[Table 1]

[0120]

[Table 2]

[0121]

[Table 3]

[0122]

[Table 4]

Example 10 Aqueous ammonia was added to the following composition to adjust the pH to 9, dissolved by stirring, and then filtered through a Teflon filter having a pore size of 0.45 μm to prepare a recording liquid. InkJet recording was carried out in the same manner as in Example 6 using this recording liquid, and similar results were obtained.

Trisazo compound obtained in Example 4 3 parts Ion-exchanged water 84 parts Diethylene glycol 10 parts Glycerin 3 parts Sodium dehydroacetate 0.01 part

Example 11 The following composition was heated to about 50 ° C., dissolved with stirring, and then filtered through a Teflon filter having a pore size of 0.45 μm to prepare a recording liquid.

Trisazo compound obtained in No. 1 of Example 9 5 parts Ion-exchanged water 90 parts Diethylene glycol 5 parts Sodium dehydroacetate 0.01 parts

The recording liquid was sealed in a glass container and kept at 20 ° C.
Even after being left at 50 ° C. for a long time, the recording liquid after being left had no crystal precipitation and the quality was stable. Further, using this recording liquid, ink jet recording was carried out on a commercially available high-quality paper by a bubble jet type recording device which ejects the recording liquid by the action of thermal energy. The nozzles were not clogged even after recording for a long time, and the obtained images were good in water resistance, light resistance, density and sharpness.

Example 12 A recording liquid was prepared from the following composition by the same method as in Example 11, and ink jet recording was carried out in the same manner as in Example 11 to obtain the same result.

Compound obtained in Example 10 No. 10 3 parts Ion-exchanged water 84 parts Diethylene glycol 10 parts Glycerin 3 parts Sodium dehydroacetate 0.01 parts

[0130]

The trisazo compound of the present invention exhibits excellent solubility and good storage stability. Moreover, when this compound is used for dyeing or printing, it has good water resistance and light resistance and gives a clear deep dyed product and a recorded image.
Exhibits various excellent effects. Therefore, this compound is useful as a dye for dyeing and recording liquid.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Takashi Omura 3-98 Kasugade, Konohana-ku, Osaka City Sumitomo Chemical Co., Ltd. (72) Inventor Masato Fujita 3-chome, Kasugade, Konohana-ku, Osaka No. 1-98 Sumitomo Chemical Co., Ltd. (72) Inventor Hideo Kawashita 4-2-11 Nishimikuni, Yodogawa-ku, Osaka City Taoka Chemical Co., Ltd. (72) Koji Yuta 4-chome Nishimikuni, Yodogawa-ku, Osaka No. 11 within Taoka Chemical Industry Co., Ltd.

Claims (15)

[Claims] 1. The following formula (I) in the form of a free acid. (In the formula, Q ¹ represents an optionally substituted phenylene group; Q ² represents an optionally substituted phenyl or naphthyl group; one of A and B is hydroxy, the other is -OR ^1, -SR ² X and Y are independently from each other; represents amino; 1 one of m and n, the other represents 0; k is 1 or 2 represents Wherein R ¹ , R ² , R ³ and R ⁴ independently of each other represent hydrogen or an optionally substituted alkyl, phenyl or naphthyl group, r represents 1 or 2,
Z is _{-CH 2 -, - O -,} - SO 2 - or -NR ⁵ - represents, here R ⁵ represents hydrogen or C ₁ -C ₄ alkyl group. ) A trisazo compound represented by. 2. The trisazo compound according to claim 1, wherein Q ¹ is an unsubstituted phenylene group or a phenylene group substituted with alkyl, alkoxy, sulfo or carboxy. 3. A phenyl group in which Q ² is substituted with 1 to 3 hydroxy, and is further substituted with unsubstituted or substituted amino, sulfo, alkyl, alkoxy or carboxy. The trisazo compound according to 1 or 2. 4. Q ² is substituted with 1 or 2 unsubstituted or substituted amino, further hydroxy,
The trisazo compound according to claim 1, which is a phenyl group which may be substituted with sulfo, alkyl, alkoxy or carboxy. 5. The trisazo compound according to claim 1, wherein Q ² is 2-amino-4-hydroxyphenyl or 2-hydroxy-4-aminophenyl. 6. A substituted or substituted amino, wherein Q ² is substituted with 1 or 2 hydroxy,
The trisazo compound according to claim 1, which is a naphthyl group optionally substituted with sulfo or carboxy. 7. Q ² is substituted with 1 or 2 unsubstituted or substituted amino, further hydroxy,
The trisazo compound according to claim 1, which is a naphthyl group optionally substituted with sulfo or carboxy. 8. X and Y are each independently represented by -OR ¹¹ or -NR ³¹ R ⁴¹ , wherein R ¹¹ is an unsubstituted alkyl group having 1 to 4 carbon atoms, 1-4
1 substituted with 1 or 2 substituents selected from the group of alkoxy, sulfo, carboxy, hydroxy, chloro, phenyl and cyano having 4 carbon atoms
An alkyl group having 4 to 4 carbon atoms, an unsubstituted phenyl group, or an alkyl having 1 to 4 carbon atoms, an alkoxy having 1 to 4 carbon atoms, sulfo, carboxy and A phenyl group substituted with one or two substituents selected from the group of chloro; R ³¹ and R ⁴¹ independently of one another are hydrogen,
An amino, which is an unsubstituted alkyl group having 1 to 4 carbon atoms or is substituted twice with an alkyl having 1 to 4 carbon atoms, an alkoxy having 1 to 4 carbon atoms,
An alkyl group having 1 to 4 carbon atoms substituted by 1 or 2 substituents selected from the group of sulfo, carboxy and hydroxy, an unsubstituted phenyl group, or 1 to 4 A phenyl group substituted with 1 or 2 substituents selected from the group consisting of alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo, carboxy and chloro. The trisazo compound as described in 1. 9. An amino, wherein at least one of X and Y is twice substituted with an alkyl having 1 to 4 carbon atoms,
1 or 2 selected from the group consisting of alkoxy having 1 to 4 carbon atoms, sulfo, carboxy and hydroxy.
Alkylamino having 1 to 4 carbon atoms optionally substituted by 4 substituents, or alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, sulfo The trisazo compound according to any one of claims 1 to 8, which is phenylamino which may be substituted with one or two substituents selected from the group consisting of carboxy and chloro. 10. At least one of X and Y is --NH.
The trisazo compound according to claim 9, which is represented by (CH ₂ ) ₃ N (C ₂ H ₅ ) ₂ . 11. The following formula (III) in the form of free acid (Wherein Q ¹ , Q ² , X and Y have the meanings defined in any of the preceding claims).
0. The trisazo compound according to any one of 0. 12. The following formula (IV) in the form of free acid: (Wherein Q ¹ , Q ² , X and Y have the meanings defined in any of the preceding claims).
0. The trisazo compound according to any one of 0. 13. A method for dyeing a fiber material, paper or leather, which comprises using the trisazo compound according to any one of claims 1 to 12. 14. A recording liquid containing the trisazo compound according to claim 1. 15. A recording medium for ink jet recording.
Recording liquid according to.