EP1799772A1

EP1799772A1 - Reactive polyazo dyes

Info

Publication number: EP1799772A1
Application number: EP05791995A
Authority: EP
Inventors: Gunter GÖRLITZ; Horst Klingenmeier
Original assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Current assignee: Dystar Textilfarben GmbH and Co Deutschland KG
Priority date: 2004-10-08
Filing date: 2005-10-05
Publication date: 2007-06-27
Also published as: CN101040011A; AR053976A1; AU2005293613A1; ZA200700126B; JP2008516032A; MX2007004154A; WO2006040285A1; DE102004049092A1; BRPI0516480A; US20080047079A1; IN2007KO00103A

Abstract

The invention relates to the polyazo dyes of formula (I), wherein the variables are defined as in claim 1. The invention also relates to methods for producing said dyes and to their use for dyeing or printing on hydroxy and/or carbonamide group-containing materials.

Description

description

Reactive polyazo dyes

The present invention is in the field of reactive dyes.

Reactive dyestuffs are dyestuffs which can be covalently bound via so-called reactive anchors to fibrous materials which have hydroxyl or amino groups. Most of the available reactive dyes are mainly suitable for dyeing cotton, only a few for other substrates such as polyamide, wool or silk. This is especially true for the dyeing of leather, where the commercially available reactive dyes have poor drawability and low Fixierausbeuten.

Most dyes used today to dye leather are anionic dyes which can be assigned to the acid dyes, direct dyes or metal complex dyes (see, for example, K. Eitel in H. Herfeld (ed.): The Leather Library, Vol , Umschau Verlag, Frankfurt 1 987. G. Otto: The Dying of the Leather, Roether Verlag, Darmstadt 1962. Color Index, 3rd ed, Lund and Humphreys, Bradford - London 1 971 - 1 976.). Since these dyes are not covalently bound to the substrate, it can come under extreme conditions for the separation of the dyes from the leather.

Moreover, for example, WO97 / 244O5, EP 0 71 6 130 A1 and EP 1 035 171 A1 disclose polyazo dyes which may also contain or contain reactive agents and which are also suitable for dyeing leather, without, however, solving the mentioned problems ,

There is thus a need for dyes for dyeing leather, which are the do not have mentioned disadvantages and in particular by a good

Distinguishing pull and a good fixation.

Surprisingly, it has now been found that certain polyazo

Reactive dyes have these properties and the described technical

Can solve the problem.

The present invention thus relates to polyazo dyes of the general formula I.

and mixtures thereof with one another, in which Ar ¹ and Ar ² independently of one another are optionally substituted aryl, where at least Ar ¹ or Ar ² bears a fiber-reactive group; T is a radical of the general formula II

wherein B is a bridge member of the formula -NH-, -CO-, -SO ₂ -,

-CH = CH-, -CH ₂ CH ₂ -, -NH-CO-, -NH-SO ₂ -, -SO ₂ -NH-SO ₂ - or a direct bond;

R ⁶ , R ⁷ , R ^s and R ⁹ are each independently hydrogen, -SO ₃ M,

Hydoxy, amino, (C ₁ -C ₁₂ I -AlkVIaITHnO, optionally in the

Aikylgruppe is substituted, di- (C _r C ₁₂ ) alkylamino, which is optionally substituted in the alkyl groups, optionally substituted

(C ₁ -C ₄ J--alkyl, optionally substituted (C _r C _4} -Alkoxγ, halogen or

Mean cyano; and s, t, u and v independently represent the number 0, 1 or 2; or T is a radical of general formula III wherein R ⁸ , R ⁷ , s and t are as defined above; R ¹ and R ^{2 are} hydrogen, amino or hydroxy, where not both radicals

Amino and not both radicals may be hydroxy; M is hydrogen, an alkali metal or the equivalent of an alkaline earth metal; x is the number O, 1 or 2; R ³ and R ⁴ independently of one another have one of the meanings of R ⁵ or

-COOM, -COOR ¹⁰ , -CONR ¹¹ R ¹² , SO ₂ NR ¹³ R ¹⁴ or -CO-R ¹⁵ ; and

R ^{5 is} hydrogen, OR ¹⁶ or -NR ¹⁷ R ¹⁸ , wherein

R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ are each independently

Hydrogen, [C _r C ₄ ) alkyl or by hydroxy, vinyl, phenyl, -CN or

-COO {C _r C ₄ ) -Alkγl substituted {C _r C ₄ ) alkyl; and r is the number 1 or 2, with the exception of polyazo dyes in which r is the number 2, R ⁵ and one of the radicals R ³ and R ^{4 are} amino and the other of the radicals R ³ and R ^{4 is} -COOM, -COOR ¹⁰ , -CONR ¹¹ R ¹² or -CO-R ¹⁶ .

Aryl groups Ar ¹ and Ar ² are preferably phenyl and naphthyl. If these are substituted, they carry 1, 2 or 3 substituents from the series -SO ₃ M, hydroxy, amino, (C ₁ -C ₄ ) -alkylamino, DHCrCJ-Alkylamiπo, nitro, (C _r C ₄ ) alkyl , (C ₁ -CJ -alkoxy, (C _r C _4> -AlkyI-SO ₂ -., -C00M, -NHCOCH _3, and halogen the listed (C _ϊ can -CJ-alkyl groups may also be substituted, for example by Hydroxy, vinyl, phenyl, -CN or -COO (C ₁ -C ₄ -alkyl).

At least one of Ar ¹ and Ar ^{2 also} carries a fiber-reactive group. As fiber-reactive groups are used in the context of the present invention Understood groups that can form covalent bonds with hydroxyl- and / or carboxamido-containing materials, ie about with the hydroxy groups of cellulose materials or the carbonamide groups of wool, leather or polyamide. Such groups are known to those skilled in the art and described in detail in the literature.

Preferred fiber-reactive groups are, for example, groups of the formulas -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Z, where Z is a grouping which can be eliminated by the action of alkali.

In addition, preferred fiber-reactive groups are heterocyclic groups of the formulas 1, 2 and 3

wherein

* indicates binding to Ar ¹ and Ar ² ;

FT represents hydrogen, phenyl or (C _r C ₄₎ alkyl;

X ¹ to X ³ independently of one another are hydrogen, cyano or halogen, with the proviso that at least one radical X ₂ or X _{3 is} halogen, X ^{4 is} chlorine or fluorine,

X ^{5 is} a group of the general formula -N (R ^b ) -YR ', wherein R ^{b is} hydrogen, phenyl or (C _r C ₄ ) -alkyl; S

Y is (C ₁ -Cg) -alkyl, which may also be interrupted by -O-, or a group of the formula

R ^{c is} hydrogen, {C, -C ₄ ) -alkyl, (C _r C ₄ ) -alkoxy, sulfo or chlorine; and R ^'is -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Z wherein Z is as defined above; or a group of the general formula -N (R ^b ) -R "wherein R ^{b is} as defined above, and R" is phenyl, by one, two or three substituents from the series

Sulfo, (C ₁ -C ₄ J-AIlCyI, (C ₁ -C ₄ -alkoxy J substituted phenyl, naphthyl, by one, two or three substituents from the group sulfo, (C ₁ -C ₄ -alkyl _J-1 (C ₁ -C ₄ J-AIkOXy substituted naphthyl or cyano, wherein R ^b and R "can also together form a heterocyclic ring, such as piperidino, piperazino or morpholino.

For an alkaline eliminable substituent Z are, for example, chlorine, sulfato, thiosulfato, phosphato or (C _z -C ₅ ) alkanoyloxy, such as acetyloxy, and sulfobenzoyloxy. Preferably, Z is sulfato.

Preferred fiber-reactive groups are, for example, the groups -SO ₂ CH = CH ₂ , -SO ₂ CH ₂ CH ₂ OSO ₃ H, and

wherein * indicates binding to Ar ¹ and Ar ² ; X ^{6 is} fluorine or chlorine;

R ^{d is} sulfo, (C ₁ C ₄ J-AIM, <C _r C ₄ ) alkoxy, -SO ₂ CH = CH ₂ or

-SO ₂ CH ₂ CH ₂ OSO ₃ H; and p is a number 0, 1, 2 or 3.

A (C _r C ₄ ) -alkyl group which is a substituent R ⁶ to R ¹⁸ can be straight-chain and branched and is, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec Butyl or tert-butyl. The same applies to (C ₁ -C ₄ ) -alkoxy, (C ₁ -C ₄ ) -alkylamino and DMCrC 1 -alkylamino groups.

Halogen is preferably fluorine, chlorine or bromine.

An alkali metal for M is preferably lithium, sodium or potassium. An equivalent of an alkaline earth metal for M is preferably one equivalent of calcium.

Preferred polyazo dyes according to the invention are those of the general formula I in which T is a group of the general formula II. It is particularly preferred if B is -NH-, -NH-CO- or -NH-SO ₂ - stands.

Particularly preferred polyazo dyes according to the invention are represented by the general formula Ia

wherein Ar ¹ , Ar ² , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , M, r, s, t, u and v are as defined above; B is -NH-, -NH-CO- or -NH-SO ₂ -; and one of R ¹ and R ^{2 is} hydroxy and the other is amino, and

R ^{5 is} OR ¹⁶ or -NR ¹⁷ R ¹⁸ , wherein R ¹⁶ , R ¹⁷ and R ^{18 are} as indicated above

are defined.

Very particularly preferred polyazo dyes according to the invention are represented by the general formula Ib

wherein Ar ¹ , Ar ² , R ³ , R ⁴ , M and r are as defined above; and

R ^{5 is} OR ¹⁶ or -NR ¹⁷ R ¹⁸ wherein R ¹⁸ , R ¹⁷ and R ^{18 are} as defined above.

The compounds of the general formula I can be prepared by reacting compounds of the general formulas IV to VIIJ

Ar ¹ -NH ₂ (IV)

Ar ² -NH ₂ (V)

H ₂ NT-NH ₂ (VII)

wherein Ar ¹ , Ar ² , R ¹ to R ⁵ , T, M and x are as defined above, are synthesized in diazotization and coupling reactions in any desired order. The diazotization and

Coupling reactions are known to the person skilled in the art and exhaustively described in the relevant literature.

In one variant, for example, one mole equivalent of a compound of general formula IV in the usual way with nitrites, for example

Sodium nitrite, diazotized in acidic, for example hydrochloric, medium and the diazotized compound with about 1 molar equivalent of a coupling component of the general formula VI in an acidic medium in such a manner that a compound of general formula IX

arises. This can then be reacted with a tetrazonium salt obtained from the compound of general formula VII in acidic, neutral or alkaline medium and the resulting intermediate in turn reacted in acidic, neutral or alkaline medium with the coupling component of the general formula VIII. The result is a compound of general formula X.

which can be implemented without isolation, but also For example, by salting out with, for example, sodium chloride or by precipitation, for example, with ethanol or by evaporation of the reaction solution, optionally after Druckpermeatioπ, can be isolated.

Finally, 1 to 3 molar equivalents of a compound of general formula V in the usual manner with nitrites, such as sodium nitrite, diazotized in acidic, for example hydrochloric, medium and the diazotized compound with about 1 molar equivalent of the compound of general formula X in acidic, neutral or alkaline Medium brought to reaction- The resulting polyazo dye of the general formula I can then either be used without isolation, for example for dyeings or it can be prepared by salting out with eg Sodium chloride or by precipitation with e.g. Ethanol or by evaporation of the reaction solution, optionally after the pressure permeation, are isolated.

In an alternative variant, a compound of general formula VII in a conventional manner, for example as described above, tetrazotized and the tetrazotised compound with 1 molar equivalent of a coupling component of the general formula VI, for example, as described above, implemented. Then, the obtained intermediate compound with a diazotized compound of general formula IV and then with a

Coupling component of the general formula VIII implemented. The result is a compound of general formula X, which can be further reacted as described above to Poiyazofarbstoff the general formula I.

If particularly reactive coupling components of the general formula VIII are used and the compounds of the general formulas IV and V are identical, it is also possible to work according to a further variant. For this purpose, about 1 molar equivalent of a compound of general formula VII tetrazotized and the tetrazotised compound with 1 molar equivalent of a Kupplungskompoπente the general formula VI and then reacted with 1 molar equivalent of a coupling component of the general formula VIII. It results the compound of general formula XI

which is then further reacted with 2 to 4 molar equivalents of a diazotized compound of general formula IV or V to the polyazo dye of general formula I.

In particular, polyazo dyes of the general formula I according to the invention, in which r is 1, can be obtained by the following further variant. For this purpose, 1 to 3 molar equivalents of a diazotized compound of the general formula V with a coupling component of the general formula VIII to the compound of general formula XII

implemented. This compound is then reacted with a diazonium salt obtained by reacting a diazotised compound of the general formula IV with a coupling component of the general formula VI and reacting the resulting intermediate with a tetrazotised compound of the general formula VII.

The compounds of general formulas IV and V preferably have the following structures:

The compounds of the general formulas VI preferably have the following structures:

The compounds of the general formulas VII preferably have the following structures:

The general formulas VIII are preferably the following structures:

The polyazo dyes according to the invention have valuable technical properties. They are used for dyeing or printing hydroxyl- and / or carboxamido-containing materials, for example in fiber form, in the form of fabrics, such as paper and leather or films, such as polyamide, or in the mass, such as polyamide and polyurethane. Also, the resulting in the synthesis of solutions of the polyazo dyes according to the invention, optionally after addition of a buffer substance, optionally after concentration or dilution, directly as a liquid preparation of färberischeπ use can be supplied. Hydroxy-containing materials are those natural or synthetic Origin, such as cellulose fiber materials or their regenerated products and polyvinyl alcohols. Cellulose fiber materials are preferably cotton, but also other vegetable fibers such as linen, hemp, jute and ramie fibers; Regenerated cellulose fibers are, for example, rayon and viscose rayon as well as chemically modified cellulose fibers, such as aminated cellulose fibers or fibers, as described, for example, in WO 96/37641 and WO 96/37642 and in EP-A-0 538 785 and EP-A-0 692 559.

Carbonamidgruppenhaltige materials include synthetic and natural polyamides and polyurethanes, especially in the form of fibers, such as wool and other Tϊerhaare, silk, leather, polyamide-6,6, polyamide-6, polyamide-1 1 and polyamide-4.

The present invention thus also relates to the use of the polyazo dyes according to the invention for dyeing or printing these materials or processes for dyeing or printing such materials in per se conventional procedures in which one uses a polyazo dyes erfiπdungsgemäßen as a colorant.

Methods for dyeing fibrous materials from cellulosic materials, such as cotton, are known to those skilled in the art and described in detail in the pertinent literature. The same applies to the dyeing of materials in bulk or in the form of fabrics.

The polyazo dyes according to the invention are preferably used for dyeing wool, polyamides and leather.

The process of dyeing wool is carried out here in the usual and well-known Därbeweise from an acidic environment. For example, acetic acid and / or ammonium sulfate or acetic acid and ammonium acetate or sodium acetate may be added to the dyebath to obtain the desired pH. In order to achieve a useful levelness of the coloring, it is advisable to add conventional leveling agents, such as based on a reaction product of cyanuric chloride with three times the molar amount of an aminobenzenesulfonic acid and / or a Aminonaphthalinsulfonsäure or based on a reaction product of, for example, stearylamine with ethylene oxide. Thus, for example, the polyazo dyes according to the invention are preferably first subjected to the exhaustion process from acid dyebath having a pH of about 3.5 to 5.5 under the control of the pH, and the pH then, towards the end of the dyeing time, into the neutral and optionally weak shifted alkaline range to a pH of 8.5, especially in order to achieve high color depths, the full reactive bond between the dyes of the inventionπ dye mixtures and the fiber bring about. At the same time, the non-reactively bound dye fraction is removed. The procedure described here also applies to the production of dyeings on fiber materials of other natural polyamides or of synthetic polyamides. As a rule, the material to be colored becomes! introduced at a temperature of about 40 ⁰ C in the bath, there for some time moved therein, the dyebath then adjusted to the desired weakly acid, preferably weakly acetic acid, pH and the actual dyeing at a temperature between 60 and 98 ⁰ C. , The dyeings can also be carried out at boiling temperature or in closed dyeing apparatus at temperatures up to 106 ⁰ C. Since the water solubility of the polyazo dyes according to the invention is very good, they can also be used with advantage in conventional continuous dyeing processes. The color intensity of the dye mixtures according to the invention is very high.

The process for dyeing leather is carried out in several steps known to those skilled in the art, which are preparing the leather, such. As retanning, the actual dyeing and post-processing steps such as washing, stretching and cleats included. The coloring of the leather takes place from an acidic environment. Thus, the dyebath z. As formic acid or acetic acid or mixtures thereof and their Sodium salts are added to adjust the desired pH. To achieve levelness and coloration, the usual tools used in leather processing can be used. For example, the polyazo dyes of the invention are dyed from acid dyebath at a pH of about 3.5 to 4.5 at temperatures of 40, 60 or 80 ⁰ C, wherein the fixation of the dye is carried to the substrate. Further details on the dyeing of leather can, for example, K. Eitel in H. Herfeld (ed.), Library of the leather, Vol. 5, Umschau Verlag, Frankfurt 1987, and G. Otto, Dyeing of the leather, Roether Verlag, Darmstadt 1 962, are taken.

In a preferred variant of the process according to the invention for dyeing leather, the solution of the polyazo dye of the general formula I used has a pH of less than 7 and is obtained without the addition of alkali, e.g. Soda or caustic soda, used for coloring the substrates. Particular preference is given to dyeing at pH values of 2 to 5, in particular at pH values of 3 to 5.

The following examples serve to illustrate the invention. The parts are parts by weight and the process data are by weight unless otherwise stated. Parts by weight refer to parts by volume such as kilograms to liters.

The compounds described formulaically in the examples are given in the form of the free acid. In general, however, they are in the form of their alkali metal salts, such as lithium, sodium or potassium salts, prepared and isolated and used in the form of their salts for dyeing. Likewise, in the following examples, in particular table examples, in the form of the free acid called Ausgangsverbindungeπ and components as such or in the form of their salts, preferably alkali metal salts, can be used in the synthesis. Example 1 a) 14 parts of 4-nitroaniline are added to 25 parts of water and stirred well. Are added to the suspension obtained 60 parts of 20% hydrochloric acid and cooled with 50 parts of ice to 0-5 ⁰ C then added dropwise slowly a solution of 7 parts of sodium nitrite in 20 parts of water until there is a small excess of nitrite. After the reaction of the amine to the corresponding diazo compound is complete, the excess nitrite is destroyed by the addition of sulfamic acid.

b) In the solution obtained in a) is added dropwise within 90 minutes at 25 ° C to 3O ⁰ C, a neutral solution of 32 parts of 1 ~ amino-8-hydroxy-3,6-disulfonic acid in 100 parts of water, wherein the pH Value of the solution by addition of 25% aqueous sodium hydroxide solution at 0.5 - 1, 5 is maintained. After completion of the addition is stirred until complete coupling.

c) 26 parts of 4-amino-N- (4-amino-phenyl) -beπzeπsu! Fonamid be entered in 87 parts of 20% hydrochloric acid and stirred. It is cooled with 80 parts of ice. Then, a solution of 14 parts of sodium nitrite in 20 parts of water is slowly added dropwise until a slight excess of nitrite is present. After the reaction of the diamine to the corresponding Tetrazoverbindυng is complete, the excess nitrite is destroyed by the addition of sulfamic acid.

d) 100 g of ice are added to the solution prepared according to b) and the reaction mixture prepared according to c) is allowed to run in within 60 minutes, the pH of the solution being 0.5 by the addition of 25% by weight aqueous sodium hydroxide solution - 1, 5 is held. When the addition is complete, the pH is adjusted to 6-7 within 60 minutes and stirred for 10 minutes at this pH. Thereafter, solid soda is added to the Reaktionsmischuπg until a pH of 7 - 8 is reached. It is stirred until complete coupling.

e) To the reaction mixture obtained according to d) is added 1 1 parts m- Phenylendiamiπ. The pH of the reaction mixture is kept at 8-8.5 by addition of 25% aqueous sodium hydroxide solution and stirred until complete coupling. After the coupling has ended, the reaction mixture is heated to 50 ^° C. and the pH is adjusted to 5-6. The resulting dye is precipitated in the usual manner by adding sodium chloride. The suspension obtained is suction filtered and the filter cake dried at 50 ⁰ C. This gives a compound which is in the form of the free acid of the formula

equivalent.

f} 28 parts of [2- (4-amino-benzenesulfonyl) -ethyl] sulfuric acid half ester are added to 1 50 parts of water and stirred well. Are added to the suspension obtained 17 parts of 31% hydrochloric acid and cooled with ice to 0-5 ⁰ C. then added dropwise slowly a solution of 7 parts Natriumnϊtrϊt in 20 parts of water until there is a small excess of nitrite. After the reaction of the amine to the corresponding diazo compound is complete, the excess nitrite is destroyed by the addition of sulfamic acid.

g) Half of the product obtained according to e) is stirred in 250 parts of water and the pH of the solution by addition of 10 wt .-% aqueous lithium hydroxide solution at 6-7 maintained. It is heated to 50 ⁰ C, stirred for 1 20 minutes at this temperature and cooled to 3O ⁰ C. Then slowly dripping one prepared according to f) Diazoniumsalzsuspension, wherein the pH - value by adding 10

Wt .-% aqueous lithium hydroxide solution at 6.5 - 7.0 is maintained. After complete addition, stirred for 60 minutes, warmed to 50 ⁰ C and stirred until the end of the coupling reaction. After completion of the coupling, the reaction mixture is cooled to room temperature and adjusted to a pH of 4-5. The resulting dye is precipitated in the usual manner by adding sodium chloride. The suspension obtained is suction filtered and the filter cake dried at 5O ⁰ C. A mixture obtained in the form of the free acid of the formula

corresponds, wherein the dye of the formula

is included as a main component. The product is obtained as a dark powder, which dyes wool and polyamide in olive green and cow leather in black shades with good general authenticity. The dye draws very well on the substrate and has good Ablöseechtheiten eg solvent fastness.

EXAMPLE 2 a) 32 parts of 1-amino-8-hydroxy-3,6-disulfonic acid are introduced into the solution obtained according to Example I f, the pH of the solution being 1 to 2 by the addition of 1 5% sodium carbonate solution is held. It is stirred for 360 minutes, during which time slowly heated to 35 ⁰ C. Thereafter, it is stirred until complete coupling, cooled to 25 ⁰ C and the pH of the solution by adding 1 5% sodium carbonate solution to 4.5 - 5.5 placed.

b) 100 parts of ice are added to the solution prepared according to a), the pH is adjusted to 0.5-1.0 by addition of 20% hydrochloric acid, and the reaction mixture prepared according to Example 1c is allowed to run in within 60 minutes , The pH is then raised to 6-7 within 60 minutes by addition of 25% strength by weight aqueous sodium hydroxide solution and stirred for 10 minutes. Then add enough sodium carbonate to reach a pH of 7.5 - 8. The temperature of the reaction mixture should now be 20 - 25 ⁰ C. It is stirred until complete coupling.

c) To a reaction mixture obtained according to b), 1 l parts of m.p.

Phenylenediamine. The pH of the reaction mixture is kept at 8-8.5 by addition of 25% strength by weight aqueous sodium hydroxide solution and stirred until complete coupling. After completion of the coupling, the pH is adjusted by addition of 25 wt .-% tger aqueous sodium hydroxide to 10 - 1 1, stirred at 20 - 25 ° C for 60 minutes and by addition of 20% hydrochloric acid, a pH of 9 - 10 set. The dye obtained is in the usual manner precipitated by adding sodium chloride. The suspension obtained is filtered off with suction. The resulting filter cake is stirred in 450 parts of water and adjusted by the addition of 20% hydrochloric acid pH 6-7. The suspension obtained is suction filtered and the filter cake dried at 50 ⁰ C. A compound is obtained which is in the form of the free acid of the formula

d) One-tenth of the product obtained according to c) is stirred in 150 parts of water and brought to pH 6-7. It is heated to 50 ⁰ C, stirred for 60 minutes at this temperature and cooled to 35 ⁰ C. Then, the tenth part of a diazonium salt suspeπsioπ prepared according to Example 1 f is slowly added dropwise, the pH being kept at 6-7 by addition of 10% aqueous lithium hydroxide solution. After complete addition, stirred for 60 minutes, warmed to 5O ⁰ C and stirred until the end of the coupling reaction. After completion of the coupling, the reaction mixture is cooled to room temperature. The resulting dye is precipitated in the usual manner by adding sodium chloride. The suspension obtained is suction filtered and the filter cake dried at 5O ⁰ C. A mixture obtained in the form of the free acid of the formula

corresponds, as components of the dyes of the formulas

and

are included. The product is a dark powder, which stains cow leather in black tones with good fastness.

Example 3

The product obtained according to Example t e is described in Example 2d

Reacted with a diazonium salt, which consists of the compound of formula

was obtained according to the method described in Example 1 a. The resulting dye is precipitated in the usual manner by adding sodium chloride. The suspension obtained is suction filtered and the filter cake dried at 5O ⁰ C. A mixture obtained in the form of the free acid of the formula

1 - 2

corresponds, as components, the dyes of the Formein

and

are maintained. The product is obtained as a dark powder, which dyes wool and polyamide in olive shades and leather in black shades with good fastness properties. The dye draws very well on the substrate and has good Ablöseechtheiten eg solvent fastness.

Example 4

The product obtained according to Example Ie is described in Example 2d

Reacted with a diazonium salt, which consists of the compound of formula was obtained according to the method described in Example 1 a. The resulting dye is precipitated in the usual manner by adding sodium chloride. The suspension obtained is filtered off with suction and the filter cake is dried at 50.degree. A mixture obtained in the form of the free acid of the formula

2

corresponds, as a dark powder, which dyes wool and polyamide in olive shades and cowhide in black shades with good fastness properties. The mixture contains components which correspond to the components specified in Examples 1 to 3.

Example 5

The product obtained according to Example 1 e is described in Example 2d

Reacted with a diazonium salt, which consists of the compound of formula

was obtained according to the method described in Example 1 a. The dye obtained is in the usual way by adding Sodium chloride like. The suspension obtained is suction filtered and the filter cake dried at 5O ⁰ C. A mixture is obtained which, in the form of the free acids, dyes of the formulas

and

corresponds, as a dark powder, which dyes wool and polyamide in green shades and cowhide in black shades with good general authenticity. The mixture contains components which correspond to the components specified in Examples 1 to 3.

Example 6

The product obtained according to Example 1 e is described in Example 2d

Reacted with a diazonium salt, which consists of the compound of formula

was obtained according to the method described in Example 1 a.

The resulting dye is precipitated in the usual manner by adding sodium chloride. The suspension obtained is suction filtered and the filter cake dried at 50 ⁰ C. A mixture obtained in the form of the free acid of the formula

2

Example 7 Substituting the following starting compounds as described in the preceding examples

this gives the product of the formula

the leather colors in bluish black tones.

Example 8

Substituting as described in the preceding examples, the following starting compounds

this gives the product of the formula

the leather colors in green tones. Example 9

Treating the product obtained according to Example 8 in the manner with sodium hydroxide solution that one stirs a solution in water thereof at pH 10 to pH 1 1 two hours at room temperature and then the pH is adjusted to 7 with hydrochloric acid and the reaction mixture is evaporated, then you get a product of

formula

the leather also colors in green tones.

Example 10

Substituting as described in the preceding examples, the following Ausgaπgsverbindungen

so you get a mixture that in the form of the free acid the formulas and

equivalent. The product dyes leather in gray tones.

Example 1 1

Substituting as described in the preceding examples, the following

Output connections around

respectively. so you get a mixture that in the form of the free acid the formulas

and

matches and colors the leather in gray tones.

Further polyazo dyes according to the invention are obtained by reacting the starting compounds mentioned in the table below:

Dyeing example (process for dyeing cow upper leather)

(The parts mentioned are by weight) a) Preparing the leather:

90 parts of a leather tanned in the usual way with a folding thickness of 2.2 mm were added in 250 parts of water at a temperature of 60 ⁰ C with 0.45 parts of calcium formate and 0.225 parts of sodium carbonate, so that a pH of 4 to 5 sets. The leather is whipped for 60 minutes. The leather is then washed in 500 parts of water.

Thereafter, the retanning is carried out in 250 parts of water at a temperature of 40 ⁰ C with 5 parts of a commercially available synthetic tanning agent. The leather is tumbled for 45 minutes in the Nachgerbflüssigkeit, removed and washed with water.

b) Coloring of the leather:

0.045 parts of the dye to be dyed according to one of the preceding examples are dissolved in 300 parts of water, added to 15 parts of leather and adjusted to a pH of 4 with a buffer. While the leather is tumbling in the dyeing liquor, is heated to 8O ⁰ C within 20 minutes, held for 20 minutes at this temperature, heated in another 15 minutes at 100 ° C and held the temperature for 45 minutes. The mixture is then cooled to 4O ⁰ C and removed the leather to the dyebath. Then the leather is rinsed cold, stretched, dried and placed.

Claims

claims

1 . Polyazo dyes of the general formula I.

and mixtures thereof with one another, in which

Ar ¹ and Ar ² independently represent optionally substituted aryl, wherein at least Ar ¹ or Ar ² carries a fiber-reactive group; T is a radical of the general formula II

wherein B is a bridge member of the formula -NH-, -CO-, -SO ₂ -,

-CH = CH-, -CH ₂ -CH ₂ -, -NH-CO-, -NH-SO ₂ -, -SO ₂ -NH-SO ₂ - or a direct bond;

R ⁶ , R ⁷ , R ⁸ and R ⁹ are each independently hydrogen, -SO ₃ M,

Hydoxy, amino, (C _T -C ^ J-alkylamino, optionally in the

Substituted alkyl group, di-fC _T -C ^ J-alkylamino, which is optionally substituted in the alkyl groups, optionally substituted

(C _r C ₄₎ -alkyl optionally substituted (C ₁ -C ₄ I -alkoxy, halogen or

Mean cyano; and s, t, u and v independently represent the number O, 1 or 2; or T is a radical of the general formula III

wherein R ^e , R ⁷ , s and t are as defined above;

R ¹ and R ^{2 are} hydrogen, amino or hydroxy, where not both radicals may be amino and not both radicals may be hydroxy;

M is hydrogen, an alkali metal or the equivalent of an alkaline earth metal; x is the number O, 1 or 2;

R ³ and R ⁴ independently of one another have one of the meanings of R ⁵ or denote -COOM, -COOR ¹⁰ , -CONR ¹¹ R ¹² , -SO ₂ NR ¹³ R ¹⁴ or -CO-R ¹⁵ ; and R ^{5 is} hydrogen, OR ¹⁶ or -NR ¹⁷ R ¹⁸ , wherein

R ^10, R ^{1 1,} R ¹ ', R ^13, R ^14, R ^15, R ¹⁶ _f R ¹⁷ and R ¹⁸ are independently hydrogen, (C ₁ -C ₄ -alkyl or by hydroxy-J, vinyl, Pheπyl, are -CN or -COO (C ₁ -C ₄ -alkyl I-substituted (C _r C _4} alkyl; and r is the number 1 or 2, wherein polyazo dyes are excluded, wherein r stands for the number 2, R ⁵ and one of R ³ and R ^{4 is} amino and the other of R ³ and R ^{4 is} -COOM, -COOR ¹⁰ , -CONR ¹¹ R ¹² or -CO-R ¹⁵ .

2. polyazo dyes according to claim 1, characterized in that the Ar ¹ and Ar ² fiber-reactive groups groups of the formulas

-SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Z, wherein Z represents a grouping which can be eliminated by the action of alkali; or heterocyclic groups of the formulas 1, 2 and 3

wherein

* indicates binding to Ar ¹ and Ar ² ;

R ^{a is} hydrogen, phenyl or {C _r C ₄ ) alkyl;

X ¹ to X ³ independently of one another are hydrogen, cyano or halogen, with the proviso that at least one radical X ₂ or X _{3 is} halogen, X ^{4 is} chlorine or fluorine, X ^{5 is} a group of the general formula -N (R ^b } -YR 'stands in which

R ^{b is} hydrogen, phenyl or (C _r C ₄ ) alkyl;

Y for {C _r C ₆ ) alkyl, which may also be interrupted by -O-, or for a group of the formula

R ^{c is} hydrogen, (C _r C ₄ ) alkyl, (C _r C ₄ ) alkoxy, sulfo or chloro; and R ^'is -SO ₂ CH = CH ₂ or -SO ₂ CH ₂ CH ₂ Z wherein Z is as defined above; or a group of the general formula -N (R ^b ) -R ", wherein

R is defined as above; and

R "is phenyl, by one, two or three substituents from the series

Sulfo, (C _r _C4) alkyl, (C _r _C4) -alkoxy-substituted phenyl, naphthyl, by one, two or three substituents from the group sulfo, (C ₁ -C ₄ -alkyl-J,

(C _r C ₄₎ alkoxy substituted naphthyl or cyano, wherein R ^b and R may form "also together form a heterocyclic ring such as piperidino, piperazino or morpholino; are.

3. polyazo dyes according to claim 2, characterized in that the fiber-reactive groups for Ar ¹ and Ar ² groups of the formulas -SO ₂ CH = CH _{2 /} -SO ₂ CH ₂ CH ₂ OSO ₃ H, or

wherein

* indicates binding to Ar ¹ and Ar ² ; X ^{6 is} fluorine or chlorine; R ^d sulfo, sulfo, (C ₁ -C ₄ J -alkyl, (C _r C ₄₎ alkoxy, -SO ₂ CH - CH ₂ or -SO ₂ CH ₂ CH ₂ OSO ₃ H; and p is a number 0, 1, 2 or 3 are.

4. polyazo dyes according to one or more of claims 1 to 3, characterized in that T is a group of the general formula II.

5. polyazo dyes according to one or more of claims 1 to 4, characterized in that it corresponds to the general formula Ia

wherein Ar ¹ , Ar ^z , R ³ , R ⁴ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , M, r, s, t, u and v are as defined in claim 1; B is -NH-, -NH-CO- or -NH-SO ₂ -; and one of R ¹ and R ^{2 is} hydroxy and the other is amino, and R ^{5 is} 0R ^1B or -NR ¹⁷ R ¹⁸ wherein R ¹⁶ , R ¹⁷ and R ^{18 are} as defined in claim 1 ,

6. polyazo dyes according to one or more of claims 1 to 5, characterized in that it has the general formula Ib

wherein Ar ¹ , Ar ² , R ³ , R ⁴ , M and r are as defined in claim 1; and

R ^{6 is} OR ¹⁶ or -NR ¹⁷ R ¹⁸ wherein R ¹⁶ , R ¹⁷ and R ^{18 are} as defined in claim 1.

7. A process for the preparation of a polyazo dye according to one or more of claims 1 to 6, characterized in that it consists of compounds of general formulas IV to VIII

Ar ¹ -NH ₂ (IV)

H ₂ NT-NH ₂ (VII)

wherein Ar ¹ , Ar ² , R ¹ to R ⁵ , T, M and x are defined as defined in claim 1, is built up in diazotization and coupling reactions in any desired order.

8. Use of a polyazo dye according to one or more of claims 1 to 6 for dyeing or printing hydroxy- and / or carboxamido-containing materials.

9. Use of a polyazo dye according to claim 8, characterized in that leather is dyed.

10. Use of a polyazo dye according to claim 9, characterized in that the solution of the polyazo dye used has a pH of less than 7.