JPH07166086A - Bisazo compound and method of dyeing or printing fibrous material with the same - Google Patents

Abstract

PURPOSE:To obtain a reactive dye excellent in dyeing performances including build-up property and in fastness to light, resistance to water and moisture, etc., by obtaining a specific bisazo compound. CONSTITUTION:A mixture of a bisazo intermediate represented by formula I [wherein B in a group represented by formula II or III (where * is the bond linked to the azo group and R<5> is H, methyl, methoxy, or sulfo); D is phenylene or naphthylene R<1> is H or an alkyl; one of X<1> and X<2> is NH2 and the other is OH; and Z<1> is-SO2CH=CH2 or -SO2CH2CH2Q (where Q is a group eliminable with an alkali)], an aromatic amine represented by formula IV (wherein R<2>, A, and Z<2> are the same as R<1>, S, and Z<1>, respectively), and an aliphatic amine represented by formula V [wherein R<3> is the same as R<1> and Y is an alkylene or -(CH2)m-X-(CH2)n-(where X is-O-, -S-, or -NR<4>-; m and n each is 2-4; and R<4> is H, an alkyl, or phenyl)] is condensed with a 2, 4, 6-trihalogeno-s-triazine to obtain either a bisazo compound represented by formula VI (wherein X<1>, X<2>, Y, Z<1>, Z<2>, Z<3>, A, B, D, R<1>, R<2>, and R<3> are as defined above) or a salt thereof.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a hydroxy group and / or
Or a material containing amide groups, especially cellulose fibers,
An improved compound suitable for dyeing and printing natural or synthetic polyamide fibers, polyurethane fibers or leather, and further mixed fibers containing any of them, which enables light-fast and wet-fast navy blue dyeing, and Regarding its application.

[0002]

2. Description of the Related Art Bisazo compounds having a triazinyl group and a plurality of vinyl sulfone-based reactive groups in the same molecule are known in JP-A-63-118376 and JP-A-3-250056, but the dyeing performance is known. In terms of aspects, for example, build-up property and fastness, it is not always sufficient, and further improvement is desired.

Conventionally, various reactive dyes have been widely used in the field of dyeing and printing fiber materials. However, the current state of the art is not yet sufficiently satisfactory in terms of high requirements regarding suitability for a particular dyeing method and higher requirements regarding fastness of dyed products.

[0004]

The above-mentioned known reactive dyes are insufficient in terms of dyeing performance (for example, build-up property) and fastness (for example, light fastness, wet fastness, etc.),
It is highly desirable to provide improved dyes.

The excellent build-up property is an extremely important factor in today's demand level of economical dyeing method. In addition, excellent toughness is also an extremely important factor in today's demand for higher quality clothing and the like is increasing.

The inventors of the present invention have made extensive studies in order to improve the deficiencies of the above-mentioned known dyes and to find new compounds that can widely satisfy the requirements required for dyes. completed.

[0007]

The present invention provides a compound of the following general formula (I) in the form of a free acid.

[0008]

[In the formula, A represents an optionally substituted phenylene group or naphthylene group; Y represents an optionally substituted alkylene or-(CH ₂ ) m-X- (CH ₂ ) n-, wherein X is -O -, - S- or -NR ⁴ - represents, m and n are independently 2, 3 or 4 to each other,
R ⁴ represents hydrogen or an optionally substituted alkyl or phenyl group; B represents the following general formula (II) or (I
II)

[0010]

## STR3 ## wherein * represents a bond connecting to an azo group, R ⁵ represents hydrogen, methyl, methoxy or sulfo; D represents an optionally substituted phenylene or naphthylene group. Representation; R ¹ , R ² and R ³
Each independently represent hydrogen or optionally substituted alkyl; Z ¹ , Z ² and Z ³ independently of each other, —SO ₂ CH═CH ₂ or —SO ₂ CH ₂ CH _2;
Q represents a group capable of leaving by the action of an alkali; ^one of X ¹ and X ² represents NH ₂ and the other represents OH].
The present invention also provides a method for dyeing or printing a fiber material using such a bisazo compound.

In the general formula (I), the phenylene and naphthylene represented by A may each be unsubstituted or substituted. Preferred is phenylene optionally substituted by 1 or 2 substituents selected from the group of methyl, ethyl, methoxy, ethoxy, chloro, bromo, carboxy and sulfo, and substituted by 1 or 2 sulfo. The naphthylene which may be contained is exemplified. Specific examples include the following groups.

[0013]

(In the formula, ** indicates a bond connecting to -N (R ² )-)

Among them, preferable A is phenylene which may be substituted with 1 or 2 groups selected from methyl and methoxy, and naphthylene which may be substituted with 1 or 2 sulfo. Include such things.

[0016]

(In the formula, ** indicates the above meaning). Among these, unsubstituted phenylene and phenylene substituted with 1 or 2 groups selected from methyl and methoxy are more preferable.

The alkylene represented by Y is preferably an alkylene having 2 or 3 or 4 carbon atoms which may have a substituent. The alkylene substituent is C _1-
C ₄ alkyl, halogen, hydroxy, sulfo, carboxy, cyano, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkoxycarbonyl, C ₁ -C ₄ alkylcarbonyloxy, such as carbamoyl and the like. Particularly preferred alkylene among them is unsubstituted ethylene, trimethylene and tetramethylene.

The group represented by Y,-(CH ₂ ) m--X--
Preferred as (CH ₂ ) n- is that X is O and m
And n are 2 or 3 independently of each other. Specific examples include the following groups.

--CH ₂ CH ₂ --O--CH ₂ CH ₂ --CH ₂ CH ₂ --O--CH ₂ CH ₂ CH ₂ --CH ₂ CH ₂ CH ₂ --O--CH ₂ CH ₂ CH _2-

(Each of the free ends in the formula is -N (R ³ )-
May be combined with). Examples of preferable R ⁴ when X is NR ⁴ include hydrogen, methyl and ethyl.

In the general formula (I), the particularly preferred groups represented by Y are unsubstituted ethylene, trimethylene and --CH ₂ CH ₂ OCH ₂ CH _2- .

The general formula (II) or (II
Examples of the group of I) include the following.

[0024]

(In the formula, * indicates the above meaning). Among these, preferred are the first example (2-sulfo-1,5-phenylene) and the second example (2,4-disulfo-).
1,5-phenylene) and the like.

D is preferably selected from lower groups such as methyl and ethyl, particularly lower groups such as C ₁ -C ₄ alkyl, methoxy and ethoxy, especially C ₁ -C ₄ alkoxy, halogen such as chloro and bromo, sulfo and carboxy. And phenylene optionally substituted by 1 or 2 substituents as well as naphthylene optionally substituted by 1 or 2 sulfo. Specific examples of D include the same groups as those exemplified as the specific examples of A above (however, in the above-mentioned examples, they are bonded to the azo group at the portion marked with **).

Among these, unsubstituted phenylene,
Sulfophenylene and sulfonaphthylene are preferred.
Especially, when X ¹ is OH, those having sulfo at the ortho position of the azo group are preferable, and examples thereof include the following.

[0028]

(In the formula, *** indicates a bond connecting to an azo group). When X ¹ is NH ₂ , D is preferably p-phenylene, particularly unsubstituted p-phenylene.

Examples of the group represented by Q which is eliminated by the action of an alkali include sulfuric acid ester, thiosulfuric acid ester,
Phosphoric acid ester, acetic acid ester, halogen, etc. correspond to this, and among them, sulfuric acid ester and halogen are preferable. Therefore, preferred as Z ¹ , Z ² and Z ³ are, independently of each other, —SO ₂ CH ₂ CH ₂ OSO ₃ H, —
Is SO ₂ CH ₂ CH ₂ Cl or -SO ₂ CH = CH _2,

The optionally substituted alkyl represented by R ¹ , R ² and R ³ is preferably a C _{1 to} C ₄ , and the alkyl optionally substituted group is hydroxy, cyano, Alkoxy, halogen, carbamoyl,
Examples thereof include carboxy, alkoxycarbonyl, alkylcarbonyloxy, sulfo, sulfamoyl and the like.
Preferable R ¹ , R ² and R ³ are, for example, hydrogen, methyl, ethyl, n-propyl, isopropyl, n
-Butyl, isobutyl, sec-butyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl, 3-hydroxybutyl,
4-hydroxybutyl, 2,3-dihydroxypropyl, 3,4-dihydroxybutyl, cyanomethyl, 2-
Cyanoethyl, 3-cyanopropyl, methoxymethyl,
Ethoxymethyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl,
2-hydroxy-3-methoxypropyl, chloromethyl, bromomethyl, 2-chloroethyl, 2-bromoethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl, 4-bromobutyl, carboxymethyl, 2
-Carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, 1,2-dicarboxyethyl, carbamoylmethyl, 2-carbamoylethyl, 3-carbamoylpropyl, 4-carbamoylbutyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, 2- Methoxycarbonylethyl, 2-ethoxycarbonylethyl,
3-methoxycarbonylpropyl, 3-ethoxycarbonylpropyl, 4-methoxycarbonylbutyl, 4-ethoxycarbonylbutyl, methylcarbonyloxymethyl, ethylcarbonyloxymethyl, 2-methylcarbonyloxyethyl, 2-ethylcarbonyloxyethyl, 3- Methylcarbonyloxypropyl, 3-ethylcarbonyloxypropyl, 4-methylcarbonyloxybutyl, 4-ethylcarbonyloxybutyl, sulfomethyl, 2-sulfoethyl, 3-sulfopropyl, 4-
Examples thereof include sulfobutyl, sulfamoylmethyl, 2-sulfamoylethyl, 3-sulfamoylpropyl, 4-sulfamoylbutyl and the like. Of these, hydrogen or unsubstituted lower alkyl is preferable. Particularly excellent are hydrogen as R ¹ and R ³ ,
R ² is hydrogen, methyl or ethyl.

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

[0033]

(In the formula, R ² , R ³ , A, Y, Z ¹ , Z ²
And Z ³ have the above meanings, and R ⁶ and R ⁷ independently of each other represent hydrogen or sulfo). Among them, A
Is phenylene optionally substituted with methyl or methoxy, and Y is unsubstituted ethylene, trimethylene or --CH ₂ CH ₂ OCH ₂ CH _2- , that is, the following general formula (IVa) in the form of a free acid.

[0035]

(Wherein R ² , R ³ , R ⁶ , R ⁷ , Z ¹ ,
Z ² and Z ³ have the above-mentioned meanings, G is ethylene,
A compound represented by trimethylene or —CH ₂ CH ₂ OCH ₂ CH ₂ — and R ⁸ represents hydrogen, methyl or methoxy is particularly preferable. Furthermore, R ² is hydrogen,
Particularly preferred is methyl or ethyl and R ³ is hydrogen.

Another preferred compound of the general formula (I) is represented by the following general formula (V) in the form of free acid.

[0038]

(In the formula, R ² , R ³ , A, Y, Z ¹ and Z ²
And Z ³ has the above meaning). Among them, A is phenylene optionally substituted with methyl or methoxy, and Y is unsubstituted ethylene, trimethylene or —CH ₂ CH ₂ OCH ₂ CH ₂ —, that is, in the form of a free acid: General formula (Va)

[0040]

(In the formula, R ² , R ³ , R ⁸ , G, Z ¹ and Z
² and Z ³ have the above-mentioned meanings), and a compound represented by the above is particularly preferable. Furthermore, it is particularly preferred that R ² is hydrogen, methyl or ethyl and R ³ is hydrogen.

The compound of the present invention is present in the form of a free acid or in the form of a salt thereof, particularly preferably an alkali metal salt and an alkaline earth metal salt, more preferably a sodium salt, a potassium salt and a lithium salt.

The compound of the present invention can be produced, for example, as follows. The following general formula (VI)

[0044]

A bisazo intermediate compound represented by the formula: wherein B, D, R ¹ , X ¹ , X ² and Z ¹ have the above-mentioned meanings, and the following general formula (VII)

[0046]

An aromatic amine compound represented by the formula: wherein R ² , A and Z ² have the above-mentioned meanings, and the following general formula (VIII)

[0048]

An aliphatic amine compound represented by the formula [wherein R ³ , Y and Z ³ have the above meanings] is 2, 4, 6
The compounds of general formula (I) can be obtained by condensation with -trihalogeno-s-triazine in any order.

In the condensation reaction with 2,4,6-trihalogeno-s-triazine, it is preferable to subject the aliphatic amine compound represented by the general formula (VIII) to primary or secondary condensation, but the condensation reaction The order of is not particularly limited. Also, the conditions of the condensation reaction are not particularly limited, but for example, primarily, at a temperature of −10 ° C. to + 40 ° C., pH 1
To 10 and secondarily pH 2 at a temperature of 0 ° C to 70 ° C.
To 10 and thirdly, at a temperature of 10 ° C to 100 ° C, p
Condensation while adjusting to H2 to 9 gives the compound of the general formula (I)
A compound represented by or a salt thereof can be obtained.

The compound of the present invention can also be produced, for example, as follows. Instead of the bisazo intermediate compound of the general formula (VI) used in the above-mentioned production method, the following general formula (IX)

[0052]

A diamine compound represented by the formula: wherein B and R ¹ have the above meanings is used as a condensation component.
The following general formula (X) synthesized as described above

[0054]

[In the formula, B, R ¹ , R ² , R ³ , A, Y and Z ²
And Z ³ represents the above meanings] and the following general formula (XI)

Z ¹ -D-NH ₂ (XI)

An amine compound represented by the formula: wherein D and Z ¹ have the above-mentioned meanings, and each compound is diazotized by a conventional method to give a compound of the following general formula (XII)

[0058]

The compound of the general formula (I) can be obtained by coupling with the 1-amino-8-naphthol compound represented by: in any order. The coupling reaction here is primarily performed at a temperature of -10 ° C to + 30 ° C.
It can be carried out while adjusting the pH to 0 to 4, and secondarily to the pH of 2 to 8 at a temperature of 0 to 40 ° C.

Alternatively, the following general formulas (XIII) and (XI
V) or (XV)

[0061]

[Wherein A, Y, B, R ¹ , R ² , R ³ ,
Z ² and Z ³ have the above-mentioned meanings, and T represents halogen.] A diazo compound of any of the amine compounds represented by the general formula (XI) and a diazo compound of the amine compound represented by the general formula (XI) are generally used in any order. By coupling with a 1-amino-8-naphthol compound of formula (XII) followed by a condensation reaction with an aromatic amine compound of general formula (VII) and / or an aliphatic amine compound of general formula (VIII). Also, a compound represented by the general formula (I) can be produced.

Further, in this case, when the diazo compound of the amine compound represented by the general formula (XI) is secondarily coupled, at the stage of the monoazo intermediate, the general formula (VII)
With an aromatic amine compound of formula (VIII) and / or an aliphatic amine compound of formula (VIII), followed by the reaction of formula (X
The compound represented by the general formula (I) can also be produced by coupling the diazo compound of the amine compound represented by I).

Z ¹ , Z ² and Z in the general formula (I)
^{In the case} where the group capable of leaving by the action of an alkali represented by Q is an ester such as a sulfuric acid ester or a phosphoric acid ester out of ^3, the ester group is formed after the condensation reaction or the coupling reaction. Good. That is, the general formula (VII), (VIII) used in the production of the compound of the present invention described above.
And (XI) instead of the amine compound represented by the following general formulas (VIIa), (VIIIa) and (XIa)

[0065]

Using the amine compound represented by the formula [wherein A, Y, D, R ² and R ³ have the above meanings], synthesis is carried out according to the above method to obtain a precursor of an esterified product. Then, the compound of general formula (I) can also be obtained by performing esterification according to a conventional method.

As the starting 2,4,6-trihalogeno-s-triazine, cyanuric chloride or cyanuric fluoride is particularly preferable.

1-amino-8-represented by the general formula (XII)
As the naphthol compound, H acid or K acid is preferable, and H acid is particularly preferable.

In the present invention, the dye matrix [the above-mentioned general formula (V
Examples of the compound in I) in which Z ¹ is hydrogen include the following.

1-Hydroxy-2- (1'-sulfonaphtho-2'-ylazo) -7- (5 "-amino-2" -sulfophenylazo) -8-aminonaphthalene-3,6-
Disulfonic acid, 1-hydroxy-2- (1'-sulfonaphtho-2'-ylazo) -7- (5 "-amino-2"-
Sulfophenylazo) -8-aminonaphthalene-3,5
-Disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -7- (1 "-sulfonaphtho-2" -ylazo) -8-aminonaphthalene-3,
6-Disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -7- (1 "-sulfonaphtho-2" -ylazo) -8-aminonaphthalene-
3,5-disulfonic acid, 1-hydroxy-2- (1'-
Sulfonaphtho-2'-ylazo) -7- (5 "-amino-2", 4 "-disulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2
-(1'-sulfonaphtho-2'-ylazo) -7-
(5 "-amino-2", 4 "-disulfophenylazo)
-8-Aminonaphthalene-3,5-disulfonic acid, 1-
Hydroxy-2- (5'-amino-2 ', 4'-disulfophenylazo) -7- (1 "-sulfonaphtho-2"-
Ilazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (5′-amino-2 ′,
4'-disulfophenylazo) -7- (1 "-sulfonaphtho-2" -ylazo) -8-aminonaphthalene-3,
5-disulfonic acid,

1-hydroxy-2- (1 ', 7'-disulfonaphtho-2'-ylazo) -7- (5 "-amino-
2 "-sulfophenylazo) -8-aminonaphthalene-
3,6-disulfonic acid, 1-hydroxy-2- (5'-
Amino-2'-sulfophenylazo) -7- (1 ",
7 "-disulfophenylnaphtho-2" -ylazo) -8
-Aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -7- (6 "-sulfonaphtho-2" -ylazo)-
8-Aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfophenylazo) -7- (8 "-sulfonaphtho-2" -ylazo)
-8-Aminonaphthalene-3,6-disulfonic acid, 1-
Hydroxy-2- (5'-amino-2'-sulfophenylazo) -7- (6 "-sulfonaphtho-2" -ylazo) -8-aminonaphthalene-3,5-disulfonic acid,
1-Hydroxy-2- (1'-sulfonaphtho-2'-ylazo) -7- (4 "-amino-2" -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy- 2- (1'-sulfonaphtho-2 '
-Ylazo) -7- (4 "-amino-2", 5 "-disulfophenylazo) -8-aminonaphthalene-3,6-
Disulfonic acid, 1-hydroxy-2- (1'-sulfonaphtho-2'-ylazo) -7- (4 "-amino-2",
5 ″ -disulfophenylazo) -8-aminonaphthalene-3,5-disulfonic acid,

1-hydroxy-2- (1'-sulfo-
5'-aminomethylnaphtho-2'-ylazo) -7-
(2 ″ -Sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (2 ′)
-Sulfophenylazo) -7- (1 "-sulfo-5"-
Aminomethylnaphtho-2 ″ -ylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2
-(1'-sulfo-5'-aminomethylnaphtho-2'-
Ilazo) -7- (1 ″ -sulfonaphtho-2 ″ -ylazo) -8-aminonaphthalene-3,6-disulfonic acid,
1-hydroxy-2- (1'-sulfonaphtho-2'-ylazo) -7- (1 "-sulfo-5" -aminomethylnaphtho-2 "-ylazo) -8-aminonaphthalene-3,
6-disulfonic acid, 1-hydroxy-2- (1 ', 7'
-Disulfo-5'-aminomethylnaphtho-2'-ylazo) -7- (2 "-sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-
2- (2'-sulfophenylazo) -7- (1 ", 7"
-Disulfo-5 "-aminomethylnaphtho-2" -ylazo) -8-aminonaphthalene-3,6-disulfonic acid,
1-Hydroxy-2- (5'-aminomethyl-4'-methyl-2'-sulfophenylazo) -7- (1 "-sulfonaphtho-2" -ylazo) -8-aminonaphthalene-
3,6-disulfonic acid, 1-hydroxy-2- (1'-
Sulfonaphtho-2'-ylazo) -7- (5 "-aminomethyl-4" -methyl-2 "-sulfophenylazo)-
8-Aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (2'-sulfophenylazo) -7-
(5 "-Amino-2" -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfophenylazo)
-7- (2 "-sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid,

1-hydroxy-2- (2'-sulfophenylazo) -7- (5 "-amino-2", 4 "-disulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-Hydroxy-2- (1'-sulfonaphtho-2'-ylazo) -7- (1 ", 7" -disulfo-
5 "-aminomethylnaphtho-2" -ylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (1'-sulfonaphtho-2'-ylazo) -7
-(5 "-Amino-4" -methyl-2 "-sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (5'-amino-2'-sulfophenylazo) ) -7-Phenylazo-8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2-
(5'-amino-2 ', 4'-disulfophenylazo)
-7-Phenylazo-8-aminonaphthalene-3,6-
Disulfonic acid, 1-hydroxy-2- (1'-sulfonaphtho-2'-ylazo) -7- (4 "-amino-5"-
Methoxy-2 ″ -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2
-(1'-sulfonaphtho-2'-ylazo) -7-
(5 ″ -amino-4 ″ -methoxy-2 ″ -sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-2- (2′-sulfophenylazo) -7- (4 "-Amino-5" -methoxy-2 "-sulfophenylazo) -8-aminonaphthalene-3,6-
Disulfonic acid, 1-hydroxy-2- (4'-amino-
5'-methoxy-2'-sulfophenylazo) -7-
(1 ″ -sulfonaphtho-2 ″ -ylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy-
2- (5'-amino-4'-methoxy-2'-sulfophenylazo) -7- (1 "-sulfonaphtho-2" -ylazo) -8-aminonaphthalene-3,6-disulfonic acid, 1-hydroxy -2- (4'-amino-5'-methoxy-2'-sulfophenylazo) -7- (2 "-sulfophenylazo) -8-aminonaphthalene-3,6-disulfonic acid.

The compound of the present invention has fiber reactivity and can be used for dyeing or printing hydroxy group-containing or carbonamide group-containing material. The material is preferably used in the form of a fibrous material or of a blended material thereof.

The hydroxy group-containing material can be a natural or synthetic hydroxy group-containing material, such as cellulosic fiber material or regenerated products thereof and polyvinyl alcohol. The cellulosic fiber material is preferably cotton or other vegetable fiber such as linen, hemp, jute and ramie fibers. Regenerated cellulosic fibers are, for example, viscose staples and filament viscose.

Carbonamide group-containing materials are, for example, synthetic or natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other animal hair, silk, leather,
Polyamide-6,6, Polyamide-6, Polyamide-1
1 and polyamide-4.

The compound of the present invention is produced on the above-mentioned material, particularly on the above-mentioned fibrous material, by a method depending on physical and chemical properties,
Can be dyed or printed.

For example, in the case of exhaust dyeing on a cellulose fiber, a neutral salt, for example, mirabilite or sodium chloride is optionally added in the presence of an acid binder such as sodium carbonate, sodium phosphate tribasic, and caustic soda, and dissolved if desired. It is carried out at a relatively low temperature by using an auxiliary agent, a penetrating agent or a leveling agent in combination. The neutral salt which accelerates the exhaustion of the dyestuff can be added only after the original dyeing temperature has been reached or before, optionally in divided portions.

When dyeing cellulosic fibers according to the padding method, they can be fixed at room temperature or at elevated temperature by padding and after drying by steaming or dry heat.

When performing printing on cellulose fibers,
Printing in one phase, for example with a printing paste containing baking soda or other acid binder, and then steaming at 95 ° C to 160 ° C, or in two phases, for example with a neutral or weakly acidic printing paste. It can be carried out by passing it through a hot electrolyte-containing alkaline bath or over-padging with an alkaline electrolyte-containing padding solution and steaming or dry heat treatment.

In the printing paste, a paste or emulsifier, such as sodium alginate or starch ether, and, if desired, conventional printing aids such as urea and / or
Alternatively, it is used in combination with a dispersant.

Suitable acid binders for fixing the compounds according to the invention on cellulose fibers are, for example, hydroxides of alkali metals, water-soluble basic salts of alkali metals or alkaline earth metals with inorganic or organic acids, Alternatively, it can be a compound that liberates an alkali when heated. In particular, alkali metal hydroxides and alkali metal salts of weak to moderately strong inorganic or organic acids are mentioned, and among these, sodium or potassium hydroxides, sodium salts and potassium salts are preferable. Specific examples of such an acid binder include caustic soda, caustic potash, sodium bicarbonate, sodium carbonate, sodium formate, potassium carbonate, primary, secondary or tertiary sodium phosphate, sodium silicate, sodium trichloroacetate and the like.

Dyeing of synthetic or natural polyamide and polyurethane fibers is carried out by first exhausting from an acidic or weakly acidic dyeing bath under the control of the pH value, and then by fixing to neutral.
In some cases, it can be carried out by changing to an alkaline pH value. Dyeing is usually 60 ° C to 120 ° C
Can be carried out at temperatures of. In order to achieve level dyeing, a conventional leveling agent, for example, a condensation product of cyanuric chloride and 3 times mol of aminobenzenesulfonic acid or aminonaphthalenesulfonic acid, or an addition product of stearylamine and ethylene oxide, for example. Can also be used.

The compound of the present invention is characterized in that it exhibits excellent performance in dyeing and printing on fiber materials. Particularly suitable for dyeing cellulosic fiber materials, dyeings obtained from this compound have good light resistance and sweat / sunlight resistance, excellent wet resistance such as washing resistance, peroxidation washing resistance and chlorine resistance. , Sweat resistance, acid hydrolysis resistance and alkali resistance, as well as good abrasion resistance and iron resistance.

Further, it has excellent build-up property, level dyeing property and wash-off property, good solubility and exhaustion / fixing property, dyeing temperature, amount of dyeing aid such as salt or alkali agent, and bath. It is characterized in that it is hardly affected by fluctuations in the ratio and a dyed product of stable quality can be obtained.

Further, it is also characterized in that there is little discoloration at the time of fixing treatment or resin processing of the obtained dyed product, and little change due to contact with a basic substance during storage.

The compounds of the present invention are described in, for example, JP-A-61-1554.
69, JP 59-161463, JP 56-15481, JP 57-89679, JP 60-6754, JP 50-178.
JP-A-56-118976, JP-A-63-77974, JP-A-SHO
57-2365, JP-A-59-15451, JP-A-56-9483,
Good results are also obtained by compounding dyeing with the fiber-reactive dye described in JP-A-60-123559 and JP-A-56-128380. Further, the compound of the present invention gives good results even when compounded with a dye which is commercially available under a generic name such as Sumifix Supra, Sumifix, Levafix and Remazol.

[0088]

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. In the examples, parts represent parts by weight.

Example 1 4.67 parts of β- (β-sulfatoethylsulfonyl) ethylamine and 3.69 parts of cyanuric chloride were added at a temperature of -5 to +1.
Condensate at 0 ° C, pH 5-8, then 3.76 parts of 2,4-diaminobenzenesulfonic acid at temperature 0-25 ° C, pH
It was condensed in 2-6. After diazotizing this, it was coupled with 6.39 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid at a temperature of 0 to 15 ° C. and a pH of 1 to 3.5, and further 2-amino. Naphthalene-6-β
-Sulfate ethyl sulfone-1-sulfonic acid 8.23
Part of the diazo compound was coupled at pH 3 to 8 at a temperature of 0 to 30 ° C. Finally, 1-aminobenzene-3
-Β-sulfatoethyl sulfone 5.63 parts and temperature 5
A bisazo compound represented by the following formula in the form of a free acid was obtained by performing a condensation reaction at 0 to 80 ° C. and pH 2 to 5 and salting out with potassium chloride.

[0090]

(Λ max = 618 nm, in aqueous medium)

Example 2 2-Aminonaphthalene-6-used in Example 1
β-sulfatoethyl sulfone-1-sulfonic acid, 1
-Amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, β-
(Β-sulfatoethylsulfonyl) ethylamine,
And 1-aminobenzene-3-β-sulfatoethylsulfone instead of the second column, the third column, and
Synthesis was carried out in the same manner as in Example 1 using the compounds in columns 4, 5, and 6 to obtain the corresponding bisazo compounds,
The dyeing was performed to obtain a dyed product having a color tone shown in the seventh column of the table below.

[0093]

[Table 1]

[0094]

[Table 2]

[0095]

[Table 3]

[0096]

[Table 4]

[0097]

[Table 5]

Example 3 4.67 parts of β- (β-sulfatoethylsulfonyl) ethylamine and 3.69 parts of cyanuric chloride were added at a temperature of -5 to +1.
Condensate at 0 ° C., pH 5-8, then 1-ethylaminobenzene-4-β-sulfatoethyl sulfone 6.1.9
Parts were condensed at a temperature of 0 to 25 ° C and a pH of 2 to 6, and 3.76 parts of 2,4-diaminobenzenesulfonic acid was condensed at a temperature of 50 to 80 ° C and a pH of 2 to 5. This was diazotized by a conventional method and then coupled with 6.39 parts of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid at a temperature of 0 to 15 ° C. and a pH of 1 to 3.5, and further 2 -Aminobenzene-5-β-sulfatoethylsulfone-1-sulfonic acid 7.23 parts of a diazo compound,
Coupling was performed at pH 3 to 8 and temperature 0 to 30 ° C.
By salting out with potassium chloride, a bisazo compound represented by the following formula in the form of a free acid was obtained.

[0099]

(Λ max = 612 nm, in an aqueous medium)

Example 4 2-Aminobenzene-5-β used in Example 3
-Sulfate ethyl sulfone-1-sulfonic acid, 1-
Amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, β- (β
-Sulfatoethylsulfonyl) ethylamine, and 1-ethylaminobenzene-4-β-sulfatoethylsulfone instead of, in the following table, column 2, column 3
Using the compounds in the columns, 4, 5, and 6, the compounds were synthesized in the same manner as in Example 3 to obtain the corresponding bisazo compounds, which were dyed and dyed in the color tone shown in the seventh column in the table below. Got

[0102]

[Table 6]

[0103]

[Table 7]

[0104]

[Table 8]

[0105]

[Table 9]

Example 5 By a conventional method, 4.03 parts of 1-aminobenzene-4-β-hydroxyethyl sulfone and 3.69 parts of cyanuric chloride were condensed, and then β- (β-hydroxyethylsulfonyl).
Ethylamine (3.06 parts) was condensed, and 2,4-diaminobenzenesulfonic acid (3.76 parts) was added at a temperature of 50 to 90.
Condensation was performed at a temperature of 1 to 6 ° C. After diazotizing this by a conventional method, 1-amino-8-hydroxynaphthalene-
6.39 parts of 3,6-disulfonic acid, temperature 0 to 15 ° C, p
Coupling with H1-3.5, and then 2-aminonaphthalene-6-β-sulfatoethylsulfone-1-
Sulfonic acid 8.23 parts diazo compound, temperature 0-30
Coupling was carried out at a temperature of pH 3-8. This was subjected to sulfuric acid esterification by a conventional method and then salted out to obtain a bisazo compound represented by the following formula in the form of a free acid.

[0107]

(Λ max = 619 nm, in aqueous medium)

Example 6 2-Aminonaphthalene-6-used in Example 5
β-sulfatoethyl sulfone-1-sulfonic acid, 1
-Amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, 1-aminobenzene-4-β-hydroxyethyl sulfone, and β- (β-hydroxyethylsulfonyl) ethylamine instead of In the table below, the second column, the third column, and the fourth column
The compounds in the columns, columns 5 and 6 were synthesized in the same manner as in Example 5 to obtain the corresponding bisazo compounds, which were dyed to obtain a dyed product having a color tone shown in column 7 in the table below. It was In addition, in the synthesis, even if the order of the secondary condensation and the tertiary condensation with respect to cyanuric chloride was changed, the same result was obtained.

[0110]

[Table 10]

[0111]

[Table 11]

Example 7 The procedure of Example 1 was repeated, except that the coupling order of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and the two diazo compounds was reversed to obtain the free acid form. To obtain a bisazo compound represented by the following formula.

[0113]

(Λ max = 628 nm, in aqueous medium)

Example 8 Using the compounds in columns 2 to 6 used in Example 2, a corresponding bisazo compound was synthesized in the same manner as in Example 7 and dyed to obtain a navy dyed product. .

Example 9 2-Aminonaphthalene-6-used in Example 7
β-sulfatoethyl sulfone-1-sulfonic acid, 1
-Amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, β-
(Β-sulfatoethylsulfonyl) ethylamine,
And 1-aminobenzene-3-β-sulfatoethylsulfone instead of the second column, the third column, and
Synthesis was carried out in the same manner as in Example 7 using the compounds in columns 4, 5 and 6 to obtain the corresponding bisazo compounds,
The dyeing was performed to obtain a dyed product having a color tone shown in the seventh column of the table below.

[0117]

[Table 12]

[0118]

[Table 13]

[0119]

[Table 14]

Example 10 The procedure of Example 3 was repeated, except that the coupling order of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and the two diazo compounds was reversed to obtain the free acid form. To obtain a bisazo compound represented by the following formula.

[0121]

(Λ max = 624 nm in aqueous medium)

Example 11 Using the compounds in columns 2 to 6 used in Example 4, the corresponding bisazo compound was synthesized in the same manner as in Example 10,
Dyeing gave a navy dyed product.

Example 12 2-Aminobenzene-5 used in Example 10
β-sulfatoethyl sulfone-1-sulfonic acid, 1
-Amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, β-
(Β-sulfatoethylsulfonyl) ethylamine,
And 1-ethylaminobenzene-4-β-sulfatoethylsulfone in place of the compounds in the second, third, fourth, fifth and sixth columns in the following table, in order.
Synthesis was carried out in the same manner as in Example 10 to obtain the corresponding bisazo compound, and dyeing was performed to obtain a dyed product having a color tone shown in the seventh column of the table below.

[0125]

[Table 15]

[0126]

[Table 16]

[0127]

[Table 17]

Example 13 As in Example 5, except that the coupling order of 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid and the two diazo compounds is reversed and the free acid form is used. To obtain a bisazo compound represented by the following formula.

[0129]

(Λ max = 628 nm, in aqueous medium)

Example 14 Using the compounds in columns 2 to 6 used in Example 6, the corresponding bisazo compound was synthesized in the same manner as in Example 13,
Dyeing gave a navy dyed product.

Example 15 2-Aminonaphthalene-6 used in Example 13
-Β-sulfatoethyl sulfone-1-sulfonic acid,
1-amino-8-hydroxynaphthalene-3,6-disulfonic acid, 2,4-diaminobenzenesulfonic acid, 1-
Aminobenzene-4-β-hydroxyethyl sulfone,
And β- (β-hydroxyethylsulfonyl) ethylamine instead of the second, third, and fourth columns in the table below.
Example 13 using the compounds in columns, columns 5 and 6
Synthesis was carried out in the same manner as described above to obtain the corresponding bisazo compound, and dyeing was performed to obtain a dyed product having a color tone shown in the seventh column of the table below. In addition, in the synthesis, even if the order of the secondary condensation and the tertiary condensation with respect to cyanuric chloride was changed, the same result was obtained.

[0133]

[Table 18]

[0134]

[Table 19]

Example 16 0.1 parts, 0.3 parts and 0.6 parts of the respective bisazo compounds obtained in Examples 1 to 15 were dissolved in 200 parts of water,
Add 10 parts of Glauber's salt and 10 parts of cotton, raise the temperature to 60 ° C,
4 parts of sodium carbonate was added and dyeing was carried out for 1 hour. After washing with water, soaping, washing with water, and drying, a navy dyed product having excellent various fastnesses and good build-up properties was obtained.

Example 17 A color paste having the following composition was prepared using each bisazo compound obtained in Examples 1-15.

Bisazo compound 5 parts Urine 5 parts Sodium alginate (5%) Original glue 50 parts Hot water 25 parts Baking soda 2 parts Water 13 parts

This color paste was printed on mercerized cotton broad cloth, and after intermediate drying, steaming was carried out at 100 ° C. for 5 minutes, followed by hot water washing, soaping, hot water washing, and drying. To obtain a print.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Jun Inoue 3-98 Kasugade, Konohana-ku, Osaka City Sumitomo Chemical Co., Ltd. (72) Inventor, Satoshi Araki 3 Kasugade, Konohana-ku, Osaka City No. 1-98 Sumitomo Chemical Co., Ltd.

Claims (15)

[Claims] 1. The following general formula (I) in the form of a free acid. Wherein, A represents a phenylene which may be substituted or a naphthylene group; Y is alkylene which may be substituted or _{- (CH 2) m-X-} (CH 2) n- and represents, wherein X Represents —O—, —S— or —NR ⁴ —, m and n are each independently 2, 3 or 4, and R ⁴ represents hydrogen or an optionally substituted alkyl or phenyl group; B is the following general formula (II) or (III) Represents a group represented in, here mark * represents a bond that connects to the azo group, R ⁵ is hydrogen, methyl, methoxy or represents the sulpho; represents D is optionally substituted phenylene or naphthylene group; R ¹ , R ² and R ³ independently of each other represent hydrogen or optionally substituted alkyl;
Z ¹ , Z ² and Z ^3, independently of each other, are —SO
Represents ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Q, wherein the Q represents a group capable of leaving by the action of an alkali; X ¹ and one is NH ₂ of X ^2, on the other hand represents OH] The bisazo compound shown. 2. The compound according to claim 1, wherein A is phenylene optionally substituted by 1 or 2 groups selected from methyl and methoxy. 3. The compound according to claim 1, wherein Y is ethylene, trimethylene or tetramethylene. 4. The compound according to claim 1 or 2, wherein Y is represented by-(CH ₂ ) m-O- (CH ₂ ) n-, wherein m and n independently of one another are 2 or 3. 5. D is phenylene optionally substituted by 1 or 2 groups selected from sulfo, lower alkyl, lower alkoxy, halogen and carboxy, or optionally substituted once or twice by sulfo. The compound according to claim 1, which is naphthylene. 6. The compound according to claim 5, wherein D is phenylene, sulfophenylene or sulfonaphthylene. 7. The compound according to claim 1, wherein X ¹ is OH, X ² is NH ₂ , and D is a phenylene or naphthylene group having sulfo at the ortho position of the azo group. 8. A method according to claim 1, wherein X ¹ is NH ₂ , X ² is OH, and D is phenylene having Z ¹ at the para position of the azo group.
5. The compound according to any of 5. 9. The compound according to claim ¹ , wherein R ¹ is hydrogen. 10. The compound according to claim 1, wherein R ² is hydrogen, methyl or ethyl. 11. The compound according to claim 1, wherein R ³ is hydrogen. 12. Z ¹ , Z ² and Z ³ independently of each other, —SO ₂ CH ₂ CH ₂ OSO ₃ H, —SO ₂ CH ₂ CH.
₂ Cl claims 1-1 or -SO ₂ CH = CH _2,
1. The compound according to any one of 1. 13. The following general formula (IVa) in the form of a free acid. [Wherein R ² , R ³ , Z ¹ , Z ² and Z ³ are defined as in the formula 1
The meaning described in, G _{is, -CH 2 CH 2 -, -} CH 2
CH ₂ CH ₂ - or _{-CH 2 CH 2 OCH 2 CH 2} - represents, R ⁶ and R ⁷ represent hydrogen or sulfo, independently of one another, according to claim R ⁸ is hydrogen, represented by a methyl or methoxy] The compound according to 1. 14. The following general formula (Va) in the form of a free acid. [Wherein R ² , R ³ , Z ¹ , Z ² and Z ³ are defined as in the formula 1
The meaning described in, G _{is, -CH 2 CH 2 -, -} CH 2
CH ₂ CH ₂ - or _{-CH 2 CH 2 OCH 2 CH 2} - represents, R ⁸ is hydrogen A compound according to claim 1 represented by a methyl or methoxy]. 15. A method for dyeing or printing a fiber material, which comprises using the bisazo compound according to any one of claims 1 to 14.