EP0528269A2 - Flowable dyestuff preparations containing polyazodyes - Google Patents

Abstract

Flowable dyestuff preparations, containing a) at least 15% by weight, relative to the weight of the dyestuff preparation, of one or more polyazo dyes in salt form, the polyazo dyes containing one or more hydroxysulphonyl and/or carboxyl groups and optionally being present in the form of a 1:1 or 1:2 metal complex, b) 2 to 15% by weight, relative to the weight of the dyestuff preparation, of a surfactant and c) water, and their use for the dyeing of leather or wool.

Description

• a) mindestens 15 Gew.-%, bezogen auf das Gewicht der Farbstoffpräparation, eines oder mehrerer Polyazofarbstoffe in Salzform, wobei die Polyazofarbstoffe eine oder mehrere Hydroxysulfonyl- und/oder Carboxylgruppen aufweisen und gegebenenfalls in Form eines 1:1- oder 1:2-Metallkomplexes vorliegen,
• b) 2 bis 15 Gew.-%, bezogen auf das Gewicht der Farbstoffpräparation, eines Tensids aus der Reihe der anionischen, kationischen oder nichtionischen Tenside und
• c) Wasser,

sowie deren Verwendung zum Färben von Leder oder Wolle.The present invention relates to novel flowable dye preparations containing

• a) at least 15% by weight, based on the weight of the dye preparation, of one or more polyazo dyes in salt form, the polyazo dyes having one or more hydroxysulfonyl and / or carboxyl groups and optionally in the form of a 1: 1 or 1: 2- Metal complex are present,
• b) 2 to 15 wt .-%, based on the weight of the dye preparation, of a surfactant from the range of anionic, cationic or nonionic surfactants and
• c) water,

and their use for dyeing leather or wool.

When dyeing leather or wool with polyazo dyes or their metal complexes, liquid dyes are increasingly being used for reasons of workplace hygiene. These are usually aqueous solutions of the respective dyes. In order to arrive at such solutions, high demands must be placed on the solubility of the respective dyes. Such a dye should normally have a solubility in water which is greater than 100 g / l. This high solubility is usually only achieved by a large number of sulfonic acid groups in the dye molecule, but this is often unfavorable for the application properties of the dye.

The object of the present invention was therefore to provide new flowable dye preparations which have polyazo dyes as chromophore which are not suitable for the production of the classic liquid dyes.

Accordingly, the flowable dye preparations described in more detail at the beginning were found.

Suitable polyazo dyes on which the flowable dye preparations according to the invention are based are, for example, dis-, tris- or tetrakisazo-dyes, dis- or trisazo-dyes being preferred.

Those polyazo dyes which have one or two hydroxysulfonyl and / or carboxyl groups, preferably one hydroxysulfonyl group, in the molecule are particularly suitable.

If the polyazo dyes have suitable substituents, they can also be used in the form of their 1: 1 or 1: 2 metal complexes.

Copper, cobalt, chromium, nickel or iron are particularly suitable as complexing metals, with iron being preferred.

The metallized groups are preferably each ortho to the azo group, e.g. in the form of o, o'-dihydroxy, o-hydroxy-o'-carboxy, o-carboxy-o'-amino or o-hydroxy-o'-amino-azo groups.

In the new flowable dye preparations, the polyazo dyes are generally not in the form of their free acid, but in the form of salt.

Suitable salts are metal or ammonium salts. Metal salts are, in particular, the lithium, sodium or potassium salts. Ammonium salts in the sense of the invention are understood to mean those salts which have either unsubstituted or substituted ammonium cations. Substituted ammonium cations are e.g. Monoalkyl, dialkyl, trialkyl, tetraalkyl or benzyltrialkylammonium cations or those cations which are derived from nitrogen-containing five- or six-membered saturated heterocycles, such as pyrrolidinium, piperidinium, morpholinium, piperazinium or N-alkylpiperazinium cations or their nanoalkyl cations - or N, N-dialkyl substituted products. Alkyl is generally to be understood as straight-chain or branched C₁-C₂₀-alkyl which can be substituted by hydroxyl groups and / or interrupted by ether oxygen atoms.

The lithium salts are particularly noteworthy.

Free or complexed polyazo dyes which are particularly suitable for the flowable dye preparations according to the invention are described, for example, in US Pat. Nos. 4,285,860, 4,479,906, 4,491,543, 4,547,566 or EP -A-355 601.

Geeignete Tenside, die in den erfindungsgemäßen fließfähigen Farbstoffpräparationen zur Anwendung kommen, sind anionische, kationische oder nichtionische Tenside. Solche Tenside sind an sich bekannt und beispielsweise in Ullmanns Encyklopädie der Technischen Chemie, 4. Auflage, Band 22, Seiten 467 bis 500, oder in J. Falbe, U. Hasserodt "Katalysatoren, Tenside und Mineralölhilfsmittel", Seiten 123 bis 151, Georg Thieme Verlag, Stuttgart, 1978, beschrieben.Dyes of the formula are particularly worth mentioning

Suitable surfactants which are used in the flowable dye preparations according to the invention are anionic, cationic or nonionic surfactants. Such surfactants are known per se and, for example, in Ullmanns Encyklopadie der Technischen Chemie, 4th edition, volume 22, pages 467 to 500, or in J. Falbe, U. Hasserodt "Catalysts, surfactants and mineral oil additives", pages 123 to 151, Georg Thieme Verlag, Stuttgart, 1978.

Examples of anionic surfactants are carboxylates, such as carboxymethylated oxethylates or derivatives of amino acids, sulfonates, such as lignosulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, condensation products of naphthalenesulfonic acids with formaldehyde, alkylsulfonates, olefinsulfonates, sulfofatty acid esters, sulfos fattyoxy amine sulfates, sulfofatty acid amide sulfates, sulfofatty acid amine sulfonatesulfonate sulfates, or to name ether sulfates, phosphonates or phosphates.

Quaternary ammonium compounds such as tetraalkylammonium compounds or benzyl-trialkylammonium compounds, imidazoline derivatives or N-alkylpyridinium salts may be mentioned as examples of cationic surfactants.

Examples of nonionic surfactants are oxalkylates, especially oxethylates or oxypropylates of alcohols, amines, fatty acids or fatty acid amides, fatty acid esters of polyhydroxy compounds, e.g. of glycerol, sorbitol or sucrose, polyethylene or polypropylene glycols or block copolymers of ethylene oxide and propylene oxide, such as alkyl-ethylene oxide-propylene oxide adducts, polypropylene oxide-polyethylene oxide adducts, trifunctional ethylene oxide-propylene oxide adducts which are derived, for example, from glycerol, or tetrafunctional ethylene oxide -Propylene oxide adducts derived, for example, from aliphatic diamines, such as ethylenediamine, propylenediamine, butylenediamine, pentamethylenediamine or hexamethylenediamine.

Flowable dye preparations which contain a nonionic surfactant are preferred.

Flowable dye preparations which contain a nonionic surfactant based on polyglycols are particularly preferred.

The nonionic surfactants based on polyglycols are polyethylene glycols which have an average molecular weight of 200 to 9000, polypropylene glycols which are derived from propane-1,2-diol and which have an average molecular weight of 600 to 4000, or block copolymers of ethylene oxide and Propylene oxide, the proportion of ethylene oxide being 10 to 80% by weight, based on the weight of the block copolymer, and the block copolymer having an average molecular weight of 1000 to 8500.

Nonionic surfactants based on polyethylene glycols are of particular importance, with particular mention being made of those polyethylene glycols which have an average molecular weight of 200 to 400.

The flowable dye preparations according to the invention contain at least 15% by weight, based on the weight of the dye preparation, of one or more polyazo dyes. The new flowable dye preparations preferably have 15 to 30% by weight and in particular 18 to 25% by weight, in each case based on the weight of the dye preparation, of one or more polyazo dyes.

The content of surfactant in the new flowable dye preparations is 2 to 15% by weight, preferably 2.5 to 10% by weight and in particular 3.5 to 7% by weight, in each case based on the weight of the dye preparation.

The water content of the flowable dye preparation according to the invention is 55 to 83% by weight, preferably 65 to 79.5% by weight and in particular 68 to 78.5% by weight, in each case based on the weight of the dye preparation.

The flowable dye preparations according to the invention are expediently prepared by introducing water and surfactant, then adding the polyazo dye in the form of the free acid or in salt form and stirring the resulting mixture at a temperature of 20 to 80 ° C. for 1 to 4 hours.

The polyazo dye can e.g. as an aqueous press cake (dye content approx. 20 to 60% by weight, based on the weight of the press cake), as is obtained, for example, in dye synthesis and in which the dye is usually in the form of its free acid. However, since, as already explained above, it is usually in salt form in the finished preparation, it is advisable to add an amount of base equivalent to the number of water-solubilizing groups in the polyazo dye at the beginning of the stirring phase. If the polyazo dye is already used in salt form, it may be expedient in some cases to use a polyazo dye salt prepared by means of ultrafiltration.

The bases are usually those metal hydroxides or amines on which the metal or ammonium salts listed above are based. The bases can be added either in bulk or in the form of an aqueous solution.

After the stirring phase is complete, the flowable dye preparation is ready for use.

When using the 1: 1 or 1: 2 metal complexes of azo dyes, it can be advantageous in some cases to carry out post-complexing at the same time as or after the production of the flowable dye preparations according to the invention. This is usually done by adding dilute aqueous metal salt solution (concentration about 5 to 20 wt .-%, based on the weight of the metal salt solution) and stirring for 1 to 4 hours at a temperature of 20 to 80 ° C. Suitable metal salts are those salts which, as the cation, also contain the metal cation also present in the 1: 1 or 1: 2 complex (in particular copper, cobalt, chromium, nickel or iron) and as the anion, e.g. Halide (especially chloride) or sulfate.

If, in the post-complexation, the water content of the dye preparation exceeds the above-mentioned values by adding aqueous metal salt solution, it is advisable to reset the water content according to the invention by distilling off excess water under reduced pressure.

The new flowable dye preparations are advantageously suitable for dyeing wool or in particular leather. They have good storage stability at a temperature of -15 to + 60 ° C. There is no segregation. Due to their homogeneity and their flowability, they can be dosed simply and precisely. In addition, the dusts that usually occur with solid preparations can be avoided. In addition, practically no waste water is produced. Because of their chemical constitution, it was not to be expected that the polyazo dyes specified above would be suitable for the production of a flowable dye preparation.

The following examples are intended to explain the invention further.

Example 1 (dye described in US-A-4,547,566, Example 3)

in Form der freien Säure enthielt, wurden in eine Mischung aus 510 ml Wasser und 58 g Polyethylenglykol mit einem mittleren Molekulargewicht von 200 eingetragen. Zum resultierenden Gemisch wurden 27,7 g Lithiumhydroxid und anschließend 73 g 10 gew.-%ige Eisen(II)sulfatlösung gegeben. Man erwärmte auf 50 bis 60°C und rührte 2 Stunden bei dieser Temperatur. Danach wurde unter vermindertem Druck soviel Wasser abdestilliert, bis das Volumen ca. 11,5 l (Gewicht: 1,46 kg; Gehalt an Farbstoff: 21 Gew.-%) betrug.1162 g of a moist press cake, the 26.5 wt .-% of the dye of the formula

contained in the form of the free acid were introduced into a mixture of 510 ml of water and 58 g of polyethylene glycol with an average molecular weight of 200. 27.7 g of lithium hydroxide and then 73 g of 10% strength by weight iron (II) sulfate solution were added to the resulting mixture. The mixture was heated to 50 to 60 ° C. and stirred at this temperature for 2 hours. Then enough water was distilled off under reduced pressure until the volume was about 11.5 l (weight: 1.46 kg; content of dye: 21% by weight).

Example 2

378 g of the press cake mentioned in Example 1 were introduced into a mixture of 170 ml of water and 20 g of polyethylene glycol with an average molecular weight of 200. 9 g of lithium hydroxide and then 24 g of 10% strength by weight iron (II) sulfate solution were added to the suspension. The mixture was heated to 50 to 60 ° C. and stirred at this temperature for 2 hours. 145 ml of water were then distilled off under reduced pressure. 455 g of a 22% by weight dye preparation were obtained.

Example 3

378 g of the press cake mentioned in Example 1 were introduced into a mixture of 170 ml of water and 25 g of polyethylene glycol with an average molecular weight of 400. 9 g of lithium hydroxide and then 24 g of 10% strength by weight iron (II) sulfate solution were added to the suspension. The mixture was heated to 70 to 80 ° C. and stirred at this temperature for 1 hour. Thereafter, 130 ml of water were distilled off under reduced pressure. 475 g of a 21% by weight dye preparation were obtained.

Example 4

378 g of the press cake mentioned in Example 1 were introduced into a mixture of 170 ml of water and 20 g of a naphthalenesulfonic acid-formaldehyde condensation product. 40 g of 50% strength by weight sodium hydroxide solution and then 24 g of 10% strength by weight iron (II) sulfate solution were added to the suspension. The mixture was heated to 60 to 70 ° C. and stirred at this temperature for 2 hours. Thereafter, 77 ml of water were distilled off under reduced pressure. 555 g of an 18% by weight dye preparation were obtained.

Example 5 (dye described in US-A-4,479,906, Example 109)

in Form der freien Säure enthielt, wurden in eine Mischung aus 60 ml Wasser und 5 g eines Naphthalinsulfonsäure-Formaldehyd-Kondensationsproduktes eingetragen. Zur Suspension wurden 18 g 50 gew.%ige Natronlauge gegeben. Danach wurde auf 50 bis 60°C erwärmt und 1 Stunde bei dieser Temperatur gerührt. Man erhielt 383 g einer 26 gew.%igen Farbstoffpräparation.300 g of a moist press cake, the 33.3 wt .-% of the dye of the formula

contained in the form of the free acid, were introduced into a mixture of 60 ml of water and 5 g of a naphthalenesulfonic acid-formaldehyde condensation product. 18 g of 50% strength by weight sodium hydroxide solution were added to the suspension. The mixture was then heated to 50 to 60 ° C and stirred at this temperature for 1 hour. 383 g of a 26% by weight dye preparation were obtained.

Example 6

300 g of the press cake mentioned in Example 5 were introduced into a mixture of 50 ml of water and 10 g of an alkyl polyglycol ether (with about 20 EO units). 24 g of 50% strength by weight potassium hydroxide solution were added to the suspension. The mixture was then heated to 40 to 50 ° C and stirred at this temperature for 2 hours. 384 g of a 26% by weight dye preparation were obtained.

Example 7

300 g of the press cake mentioned in Example 5 were introduced into a mixture of 80 ml of water and 25 g of polyethylene glycol with an average molecular weight of 300. 10 g of lithium hydroxide were added to the suspension. The mixture was then heated to 60 to 70 ° C and stirred at this temperature for 2 hours. 415 g of a 24% by weight dye preparation were obtained.

Example 8 (dye described in US-A-4,479,906, Example 112)

in Form der freien Säure enthielt, wurden in eine Mischung aus 140 ml Wasser und 30 g Polyethylenglykol mit einem mittleren Molekulargewicht von 300 eingetragen. Zur Suspension wurden 32 g 50 gew.%ige Natronlauge gegeben. Danach wurde auf 50 bis 60°C erwärmt und 1 Stunde bei dieser Temperatur gerührt. Man erhielt 378 g einer 26,5 gew.%igen Farbstoffpräparation.176 g of a moist press cake, the 56.8 wt .-% of the dye of the formula

contained in the form of the free acid, were introduced into a mixture of 140 ml of water and 30 g of polyethylene glycol with an average molecular weight of 300. 32 g of 50% strength by weight sodium hydroxide solution were added to the suspension. The mixture was then heated to 50 to 60 ° C and stirred at this temperature for 1 hour. 378 g of a 26.5% by weight dye preparation were obtained.

Example 9

176 g of the press cake mentioned in Example 8 were introduced into a mixture of 100 ml of water and 20 g of an alkyl polyglycol ether (with about 20 EO units). 34 g of 50% strength by weight potassium hydroxide solution were added to the suspension. The mixture was then heated to 60 to 70 ° C and stirred at this temperature for 1 hour. 330 g of a 30.3% by weight dye preparation were obtained.

Preparations with the dyes listed in the following table are obtained in an analogous manner.

The following dyes also give good results.

Example 43

Example 44

Claims (5)

Flowable dye preparations containing a) at least 15% by weight, based on the weight of the dye preparation, of one or more polyazo dyes in salt form, the polyazo dyes having one or more hydroxysulfonyl and / or carboxyl groups and optionally in the form of a 1: 1 or 1: 2- Metal complex are present, b) 2 to 15 wt .-%, based on the weight of the dye preparation, of a surfactant from the series of anionic, cationic or nonionic surfactants and c) water. Flowable dye preparations according to Claim 1, containing 15 to 30% by weight, based on the weight of the dye preparation, of one or more polyazo dyes. Flowable dye preparations according to claim 1, containing a nonionic surfactant. Flowable dye preparations according to claim 1, containing a nonionic surfactant based on polyglycols. Use of the flowable dye preparations according to claim 1 for dyeing leather or wool.