DE102009047183A1 - Dye mixture, useful for coloring leather, comprises a first anionic dye, a second anionic dye, and third anionic dye, where the first and third anionic dye are azo dyes, and the second anionic dye is the azo dye or napthalene-azo dye - Google Patents

Abstract

Dye mixture comprises a first anionic dye; a second anionic dye, which exhibits different color from the first anionic dye; and optionally third anionic dye, which exhibits different color from the first and second anionic dye, where: the first anionic dye is an azo dye (I)-(III), the second anionic dye is (I)-(III) or their salt or metal complex or napthalene-azo dye of formula (IV) or its salt or metal complex, and the third anionic dye is (II)-(IV) or their salt or metal complex. Dye mixture comprises a first anionic dye; a second anionic dye, which exhibits different color from the first anionic dye; and optionally third anionic dye, which exhibits different color from the first and second anionic dyes, where: the first anionic dye is an azo dye of formulae (I)-(III), the second anionic dye is (I)-(III) or their salt or metal complex or napthalene-azo dye of formula (IV) or its salt or metal complex, and the third anionic dye is (II)-(IV) or their salt or metal complex. Dk : SO 3H; n : 0 or 1; A : SO 3H or substituted benzene group of formula (A1); X : H or SO 3H; Y 1>H, halo, 1-4C-alkyl, CN or SO 3H; B 1>CH=CH 2or CH 2-CH 2-Q; Q : a group, which is cleavable under alkali conditions; Dk : phenyl or naphthyl (both optionally substituted by 1-3 R1a); R1a : 1-4C-alkylaminosulfonylamino, di-1-4C-alkylaminosulfonylamino, phenylamino, phenylaminocarbonyl, phenoxy, phenylsulfonyl, phenylsulfonylamino, phenylaminosulfonyl, phenylcarbonylamino, phenylaminocarbonyloxy or phenylaminocarbonylamino (all optionally substituted by 1-4C-alkyl, OH, COOH, 1-4C-alkoxy, 1-4C-alkylcarbonyloxy, 1-4C-alkylcarbonylamino, 1-4C-alkoxycarbonyl, NH 2, NO 2, SO 3H or halo at the phenyl ring), SO 3H, COOH, CN, CONH 2, OH, NH 2, NO 2, halo, 1-4C-alkyl, 1-4C-hydroxyalkyl, carboxy-1-4C-alkyl, 1-4C-alkoxy, 1-4C-alkylamino, 1-4C-dialkylamino, 1-4C-alkylaminocarbonyl, 1-4C-dialkylaminocarbonyl, 1-4C-alkylcarbonylamino, N-(1-4C-alkylcarbonyl)-N-(1-4C-alkylcarbonyl)amino, 1-4C-alkylaminocarbonyloxy, 1-4C-dialkylaminocarbonyloxy, 1-4C-alkylaminocarbonylamino, 1-4C-dialkylaminocarbonylamino, 1-4C-alkoxycarbonylamino, 1-4C-hydroxy-1-4C-alkylamino, carboxy-1-4C-alkylamino, 1-4C-alkylsulfonyl, hydroxy-1-4C-alkylsulfonyl, 1-4C-alkylaminosulfonyl, 1-4C-alkylsulfonylamino, aminocarbonyl, SO 2NR 1>1>R 1>2>, or 5- or 6-membered heterocyclyl (optionally substituted by one or two of OH, halo, 1-4C-alkyl or phenyl (optionally substituted by 1-4C-alkyl, OH, COOH, 1-4C-alkoxy, 1-4C-alkylcarbonyloxy, 1-4C-alkylcarbonylamino, 1-4C-alkoxycarbonyl, NH 2, NO 2, SO 3H or halo)); R 1>1>, R 1>2>H, 1-4C-alkyl, formyl, 1-4C-alkylcarbonyl, 1-4C-alkyloxycarbonyl, NH 2-CO or 1-4C-alkylaminocarbonyl; Ar 1>a bivalent residue of benzene or naphthalene (optionally substituted by 1-4 substituents of R1b); R1b : R1a; R 1>NH 2or OH; R 2>OH, NH 2, 1-4C-alkoxy, 1-4C-alkylamino, 1-4C-hydroxyalkylamino, (HO 3S-1-4C-alkyl)amino, 1-4C-dialkylamino, 1-4C-alkylcarbonylamino, N-(1-4C-alkyl)-N-(1-4C-alkylcarbonyl)amino, 1-4C-alkylaminocarbonyloxy, 1-4C-dialkylaminocarbonyloxy, 1-4C-alkylaminocarbonylamino, 1-4C-dialkylaminocarbonylamino, 1-4C-alkoxycarbonylamino, carboxy-1-4C-alkylamino, 1-4C-alkylsulfonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, phenylcarbonylamino or phenylsulfonylamino (where the phenyl ring is optionally substituted by 1-3 OH, NO 2, halo, 1-4C-alkoxy, 1-4C-alkyl or SO 3H); either m-s : 0 or 1; or n+q : 0 or 1; or r+s : 1 or 2; k : 0-2; Ar 2>Ar 1>; R2x : R 2>; T : SO 3H or a bivalent residue of formula (T1); R 3>, R3a : H, halo, COOH, OH or SO 3H; D 1>a chemical bond, 1-4C-alkan-1,1-diyl, ethen-1,2-diyl, O, NH, C(O), S(O) 2, C(O)NH, NHC(O)NH or S(O) 2NH; KK : coupling component; X : R 1>; Y 2>H or R 2>; and T 1>T. Where: at least one of A or Dk contains SO 3H group, and k is not equal to 0. An independent claim is included for a method for coloring leather comprising treating the leather with an aqueous dye bath having a pH of 7.5-11 and containing the dye mixture. [Image] [Image] [Image] [Image].

Description

• a) als Komponente a) einen ersten anionischen Farbstoff,
• b) als Komponente b) einen zweiten anionischen Farbstoff, der eine von dem Farbstoff der Komponente a) verschiedene Farbe aufweist, und gegebenenfalls
• c) als Komponente c) einen dritten anionischen Farbstoff, der eine von den Farbstoffen der Komponenten a) und b) verschiedene Farbe aufweist.

The present invention relates to dye mixtures comprising

• a) as component a) a first anionic dye,
• b) as component b) a second anionic dye which has a different color from the dye of component a), and optionally
• c) as component c) a third anionic dye which has a different color from the dyes of components a) and b).

The Dye mixtures according to the invention are in special way to dye leather. Accordingly The invention also relates to a process for dyeing Leather with an aqueous dyeing liquor, at least contains two anionic dyes, each of which have different colors.

The Coloring of tanned leather is currently predominantly with acid dyes, direct dyes, sulfur dyes or basic dyes. Achieving high color intensities and high color fastnesses, especially high wetness and perspiration fastness is difficult with these dyes and can not be satisfactory for medium to high color depths be solved.

Around The wet and perspiration fastness is going to be improved Leather often treated with cationic complexing agents, to complex the dye on the leather and so its solubility to reduce on contact with water. The achievable wet and However, perspiration and rubbing fastness are for intense color nuances not sufficient. Furthermore, they tend to be made Leather articles when used to discolorations. Achieving high fastness at medium to high color depths also requires a very careful dye selection and the vote the dye used with the leather auxiliaries used, furthermore special fatliquors and a retanning choice. In addition, it is usually to achieve the desired Fastness required, dye and fatliquor and in some Cases to apply the retanning agent in a separate fleet, which, of course, an extension of the Total process time and increased sewerage entails.

In the production of brown leather, there is also the problem that the available dyes, which are suitable for the production of intense colorations, often do not have the desired color shade and therefore must be combined with other dyes. However, this results in the problem that due to the different dyeing behavior of the dyes, but especially because of the strongly differing dye affinity of meat and grain side of the leather a level dyeing with dye mixtures is usually not reached and often stained dyeings are obtained ( see also K. Eitel, in Bayer Color Revue, Special Issue 19, p. 31 (1981) ).

The EP-A 61670 proposes to solve this problem, a dye mixture of various 1: 2 chromium or cobalt complex dyes of azo, azo-azomethine or azo-methine series, which have a defined and comparable penetration depth with respect to standard chrome leather and no or only a slight inclination for aggregation in an electrolyte-containing, aqueous solution. By means of these strict selection criteria, naturally the available dyes and dye combinations and thus also the achievable color shades are severely restricted. In addition, the dyed leather obtained there have only moderate wet and perspiration fastness.

From the EP 2311478 Similar dye mixtures are known for dyeing leather. Again, the achievable color shades are severely limited by the choice of dye. With higher color depth, no good fastness properties, in particular no good wet and perspiration fastness are achieved.

From the EP 558450 discloses a process for dyeing leather with dye mixtures using certain dyes having a comparatively high molecular weight in the range of 790 to 1100 daltons. Also, this method is limited to a few available dyes, so that the possibilities of shading are low. In addition, the achievement of uniform colorations at high color depth is difficult and the wet and perspiration fastness achieved are not satisfactory.

From the EP 577556 Again, a process for dyeing leather with dye mixtures is known, which comprises using a mixture of at least two metal-free dyes selected from azo dyes having a central triazine unit and triphendioxazine dyes. Again, not all desired nuances can be produced due to the highly restricted dye selection. The achieved wet and perspiration fastness are also unsatisfactory.

From the WO 2005/040490 and the WO 2005/121439 For example, processes for dyeing leather are known in which dyes or dye mixtures are used at slightly alkaline pH values, where the dyes have vinylsulfone groups or functional groups which can be converted into vinylsulfone groups. The problems that can occur when using dye mixtures in leather dyeing, are not addressed there. Dye mixtures that result in brown leathers are also not described.

Of the The present invention is therefore based on the object, a method for dyeing leather, which is the manufacture Of leather with a red or brown color of any shade through to olive tones. Especially should the leather even at high color depth a uniform Have coloring. In addition, the leather obtained should be high Have wet and perspiration fastness.

It it was surprisingly found that certain anionic azo dyes of the formulas I defined below, II and III with each other or with dyes of formula IV combine let and manufacture leather red or brown color any Nuance to olive tones with a uniform Allow coloration and high color depth. moreover the resulting leathers have very good wet and perspiration fastnesses on.

• a) als Komponente a) einen ersten anionischen Farbstoff,
• b) als Komponente b) einen zweiten anionischen Farbstoff, der eine von dem Farbstoff der Komponente a) verschiedene Farbe aufweist, und gegebenenfalls
• c) als Komponente c) einen dritten anionischen Farbstoff, der eine von den Farbstoffen der Komponenten a) und b) verschiedene Farbe aufweist, enthalten, wobei der Farbstoff der Komponente a) ausgewählt ist unter;
• i) Farbstoffen der Formel I, deren Salzen und deren Metallkomplexen:
  
  worin wenigstens einer der Reste A oder Dk eine SO₃H-Gruppe aufweist und worin n für 0 oder 1, insbesondere 0 steht, A für einen Rest der Formel:
  
  steht, worin # die Bindung zur Azogruppe bedeutet, X für Wasserstoff oder SO₃H steht, Y für Wasserstoff, Halogen, C₁-C₄-Alkyl, CN oder eine Gruppe SO₃H bedeutet; B für eine Gruppe CH=CH₂ oder eine Gruppe CH₂-CH₂-Q steht, worin Q eine unter alkalischen Bedingungen abspaltbare Gruppe bedeutet; Dk für Phenyl oder Naphthyl steht, das 1, 2 oder 3 Substituenten R^a aufweist, wobei R^a ausgewählt ist unter SO₃H, COOH, CN, CONH₂, OH, NH₂, NO₂, Halogen, C₁-C₄-Alkyl, C₁-C₄-Hydroxyalkyl, Carboxy-C₁-C₄-alkyl, C₁-C₄-Alkoxy, C₁-C₄-Alkylamino, C₁-C₄-Dialkylamino, C₁-C₄-Alkylaminocarbonyl, C₁-C₄-Dialkylaminocarbonyl, C₁-C₄-Alkylcarbonylamino, N-(C₁-C₄-Alkylcarbonyl)-N-(C₁-C₄-alkylcarbonyl)amino, C₁-C₄-Alkylaminocarbonyloxy, C₁-C₄-Dialkylaminocarbonyloxy, C₁-C₄-Alkylaminocarbonylamino, C₁-C₄-Dialkylaminocarbonylamino, C₁-C₄-Alkoxycarbonylamino, C₁-C₄-Hydroxy-C₁-C₄-alkylamino, Carboxy-C₁-C₄-alkylamino, C₁-C₄-Alkylsulfonyl, Hydroxy-C₁-C₄-alkylsulfonyl, C₁-C₄-Alkylaminosulfonyl, C₁-C₄-Alkylsulfonylamino, Aminocarbonyl, ein Rest der Formel SO₂NR¹¹R¹², worin R¹¹ und R¹² unabhängig voneinander für Wasserstoff, C₁-C₄-Alkyl, Formyl, C₁-C₄-Alkylcarbonyl, C₁-C₄-Alkyloxycarbonyl, NH₂-CO oder C₁-C₄-Alkylaminocarbonyl stehen, C₁-C₄-Alkylaminosulfonylamino, Di-C₁-C₄-alkylaminosulfonylamino, Phenylamino, Phenylaminocarbonyl, Phenoxy, Phenylsulfonyl, Phenylsulfonylamino, Phenylaminosulfonyl, Phenylcarbonylamino, Phenylaminocarbonyloxy, Phenylaminocarbonylamino, wobei die 11 letztgenannten Reste am Phenylring unsubstituiert sind oder einen oder zwei Substituenten, ausgewählt unter C₁-C₄-Alkyl, OH, COOH, C₁-C₄-Alkoxy, C₁-C₄-Alkylcarbonyloxy, C₁-C₄-Alkylcarbonylamino, C₁-C₄-Alkoxycarbonyl, NH₂, NO₂, SO₃H oder Halogen aufweisen kann, und 5- oder 6-gliedrigem Heterocyclyl, das unsubstituiert ist oder einen oder zwei Substituenten, ausgewählt unter: OH, Halogen, C₁-C₄-Alkyl oder Phenyl aufweisen kann, wobei Phenyl seinerseits unsubstituiert ist oder einen oder zwei Substituenten, ausgewählt unter C₁-C₄-Alkyl, OH, COOH, C₁-C₄- Alkoxy, C₁-C₄-Alkylcarbonyloxy, C₁-C₄-Alkylcarbonylamino, C₁-C₄-Alkoxycarbonyl, NH₂, NO₂, SO₃H oder Halogen aufweisen kann, oder für einen Rest der Formel A steht; Ar für einen zweiwertigen, von Benzol oder Naphthalin abgeleiteten, aromatischen Rest steht, der gegebenenfalls 1, 2, 3 oder 4 Substituenten R^b trägt, wobei R^b eine der für R^a angegebenen Bedeutungen aufweist; R¹ ausgewählt ist unter NH₂ und OH, und R² ausgewählt ist unter OH, NH₂, C₁-C₄-Alkoxy, C₁-C₄-Alkylamino, C₁-C₄-Hydroxyalkylamino, (HO₃S-C₁-C₄-alkyl)amino, C₁-C₄-Dialkylamino, C₁-C₄-Alkylcarbonylamino, N-(C₁-C₄-Alkyl)-N-(C₁-C₄-alkylcarbonyl)amino, C₁-C₄-Alkylaminocarbonyloxy, C₁-C₄-Dialkylaminocarbonyloxy, C₁-C₄-Alkylaminocarbonylamino, C₁-C₄-Dialkylaminocarbonylamino, C₁-C₄-Alkoxycarbonylamino, Carboxy-C₁-C₄-alkylamino, C₁-C₄-Alkylsulfonylamino Phenylaminocarbonyloxy, Phenylaminocarbonylamino, Phenylcarbonylamino und Phenylsulfonylamino, wobei der Phenylring in den 4 zuletzt genannten Resten unsubstituiert ist oder 1, 2 oder 3 unter OH, NO₂, Halogen, C₁-C₄-Alkoxy, C₁-C₄-Alkyl, und SO₃H ausgewählte Reste aufweisen kann
• ii. Farbstoffen der Formel II, deren Salzen und deren Metallkomplexen,
  
  worin m für 0 oder 1 steht, k 0, 1 oder 2 bedeutet, p und q für 0 oder 1 stehen mit der Maßgabe dass n + q für 0 oder 1 steht, Ar' eine der für Ar in Formel I angegebenen Bedeutungen aufweist, R^2x eine der für R² in Formel I angegebenen Bedeutungen aufweist, und worin Dk, Ar, A und R¹ eine der für Formel I angegebenen Bedeutungen aufweisen und worin wenigstens einer der Reste A oder Dk eine SO₃H-Gruppe aufweist und/oder k ≠ 0 ist;
• iii. Farbstoffen der Formel III, deren Salzen oder deren Metallkomplexen,
  
  worin A, R¹ und R² eine der für Formel 1 angegebenen Bedeutungen aufweisen und worin wenigstens einer der Reste A oder T eine SO₃H-Gruppe aufweist, und T für einen bivalenten Rest der Formel:
  
  steht, worin * die zuvor genannten Bedeutungen hat; R³ und R^3a unabhängig voneinander für Wasserstoff, Halogen, COOH, OH oder SO₃H stehen; D für eine chemische Bindung, C₁-C₄-Alkan-1,1-diyl, Ethen-1,2-diyl, Sauerstoff, NH, C(O), S(O)₂, C(O)NH, NH(C(O)NH oder eine Gruppe S(O)₂NH steht; wobei der Farbstoff der Komponente b) ausgewählt ist unter; i. Farbstoffen der Formel I, deren Salzen und deren Metallkomplexen, ii. Farbstoffen der Formel II, deren Salzen und deren Metallkomplexen, iii. Farbstoffen der Formel III, deren Salzen und deren Metallkomplexen, und
• iv. Farbstoffen der Formel IV, deren Salzen und deren Metallkomplexen,
  
  worin A eine der für Formel 1 angegebenen Bedeutungen aufweist, Kk einen von einer Kupplungskomponente abgeleiteten Rest steht, X eine der für R¹ angegebenen Bedeutungen hat, Y für Wasserstoff steht oder eine der für R² angegebenen Bedeutungen hat, T* eine der für T angegebenen Bedeutungen hat, r und s für 0 oder 1 stehen, wobei r + s 1 oder 2 ist; und wobei der Farbstoff der Komponente c) ausgewählt ist unter; ii. Farbstoffen der Formel II, deren Salzen und deren Metallkomplexen, iii. Farbstoffen der Formel III, deren Salzen und deren Metallkomplexen, und iv. Farbstoffen der Formel IV, deren Salzen und deren Metallkomplexen.

Accordingly, the present invention relates to dye mixtures which

• a) as component a) a first anionic dye,
• b) as component b) a second anionic dye which has a different color from the dye of component a), and optionally
• c) as component c) a third anionic dye which has a different color from the dyes of components a) and b), wherein the dye of component a) is selected from;
• i) dyes of the formula I, their salts and their metal complexes:
  
  wherein at least one of the radicals A or Dk has an SO ₃ H group and in which n is 0 or 1, in particular 0, A is a radical of the formula:
  
  where # is the bond to the azo group, X is hydrogen or SO ₃ H, Y is hydrogen, halogen, C ₁ -C ₄ -alkyl, CN or a group SO ₃ H; B is a group CH = CH ₂ or a group CH ₂ -CH ₂ -Q, where Q is a group cleavable under alkaline conditions; Dk is phenyl or naphthyl having 1, 2 or 3 substituents R ^a , wherein R ^{a is} selected from SO ₃ H, COOH, CN, CONH ₂ , OH, NH ₂ , NO ₂ , halogen, C ₁ -C ₄ Alkyl, C ₁ -C ₄ hydroxyalkyl, carboxy C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, C ₁ -C ₄ -Alkylaminocarbonyl, C ₁ -C ₄ -dialkylaminocarbonyl, C ₁ -C ₄ -alkylcarbonylamino, N- (C ₁ -C ₄ -alkylcarbonyl) -N- (C ₁ -C ₄ -alkylcarbonyl) amino, C ₁ -C ₄ - Alkylaminocarbonyloxy, C ₁ -C ₄ -dialkylaminocarbonyloxy, C ₁ -C ₄ -alkylaminocarbonylamino, C ₁ -C ₄ -dialkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino, C ₁ -C ₄ -hydroxy-C ₁ -C ₄ -alkylamino, Carboxy-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylsulfonyl, hydroxy-C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -alkylaminosulfonyl, C ₁ -C ₄ -alkylsulfonylamino, aminocarbonyl, a radical of the formula SO ₂ NR ¹¹ R ¹² , wherein R ¹¹ and R ^{12 are} independently hydrogen, C ₁ -C ₄ -alkyl, formyl, C ₁ -C ₄ -alkylcarbonyl, C ₁ -C ₄ -alkyloxycarbonyl, NH ₂ -CO or C ₁ -C ₄ -alkylaminocarbonyl, C ₁ -C ₄ -alkylaminosulfonylamino, C ₁ -C ₄ -alkylaminosulfonylamino, phenylamino, phenylaminocarbonyl, phenoxy, phenylsulfonyl, phenylsulfonylamino, phenylaminosulfonyl, phenylcarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, where the last mentioned radicals on the phenyl ring are unsubstituted or one or two substituents selected from C ₁ -C ₄ -alkyl , OH, COOH, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylcarbonyloxy, C ₁ -C ₄ -alkylcarbonylamino, C ₁ -C ₄ -alkoxycarbonyl, NH ₂ , NO ₂ , SO ₃ H or halogen , and 5- or 6-membered heterocyclyl, which is unsubstituted or may have one or two substituents selected from: OH, halogen, C ₁ -C ₄ -alkyl or phenyl, wherein phenyl is in turn unsubstituted or one or two substituents selected under C ₁ -C ₄ -alkyl, OH, COOH, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylcarbonyloxy, C ₁ -C ₄ -alkylcarbonylamino, C ₁ -C ₄ -alkoxycarbonyl, NH ₂ , NO ₂ , SO _{3 may have} H or halogen, or is a radical of formula A; Ar is a bivalent, derived from benzene or naphthalene, aromatic radical which optionally carries 1, 2, 3 or 4 substituents R ^b , wherein R ^{b has} one of the meanings given for R ^a ; R ^{1 is} selected from NH ₂ and OH, and R ^{2 is} selected from OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ C ₄ -C ₄ alkyl) amino, C ₁ -C ₄ dialkylamino, C ₁ -C ₄ alkylcarbonylamino, N- (C ₁ -C ₄ alkyl) -N- (C ₁ -C ₄ alkylcarbonyl) amino, C C ₁ -C ₄ alkylaminocarbonyloxy, C ₁ -C ₄ dialkylaminocarbonyloxy, C ₁ -C ₄ alkylaminocarbonylamino, C ₁ -C ₄ dialkylaminocarbonylamino, C ₁ -C ₄ alkoxycarbonylamino, carboxyC ₁ -C ₄ alkylamino, C C ₁ -C ₄ -alkylsulfonylamino phenylaminocarbonyloxy, phenylaminocarbonylamino, phenylcarbonylamino and phenylsulfonylamino, where the phenyl ring is unsubstituted in the 4 last-mentioned radicals or 1, 2 or 3 under OH, NO ₂ , halogen, C ₁ -C ₄ -alkoxy, C ₁ - C ₄ alkyl, and SO ₃ H may have selected radicals
• ii. Dyes of the formula II, their salts and their metal complexes,
  
  where m is 0 or 1, k is 0, 1 or 2, p and q are 0 or 1, with the proviso that n + q is 0 or 1, Ar 'has one of the meanings given for Ar in formula I, R ^{2x has} one of the meanings given for R ² in formula I, and in which Dk, Ar, A and R ^{1 have} one of the meanings given for formula I and in which at least one of the radicals A or Dk has an SO ₃ H group and / or k ≠ 0;
• iii. Dyes of the formula III, their salts or their metal complexes,
  
  wherein A, R ¹ and R ^{2 have} one of the meanings given for formula 1 and in which at least one of the radicals A or T has an SO ₃ H group, and T is a bivalent radical of the formula:
  
  in which * has the meanings given above; R ³ and R ^{3a are} independently hydrogen, halogen, COOH, OH or SO ₃ H; D for a chemical bond, C ₁ -C ₄ alkane-1,1-diyl, ethene-1,2-diyl, oxygen, NH, C (O), S (O) ₂ , C (O) NH, NH (C (O) NH or a group S (O) ₂ NH; wherein the dye of component b) is selected from; i. Dyes of the formula I, their salts and their metal complexes, ii. Dyes of the formula II, their salts and their metal complexes, iii. Dyes of the formula III, their salts and their metal complexes, and
• iv. Dyes of the formula IV, their salts and their metal complexes,
  
  wherein A has one of the meanings given for formula 1, K k is a radical derived from a coupling component, X has one of the meanings given for R ¹ , Y is hydrogen or one of the meanings given for R ² , T * one of for T r and s are 0 or 1, where r + s is 1 or 2; and wherein the dye of component c) is selected from; ii. Dyes of the formula II, their salts and their metal complexes, iii. Dyes of the formula III, their salts and their metal complexes, and iv. Dyes of the formula IV, their salts and their metal complexes.

Here and below, C ₁ -C ₄ -alkyl (as well as the alkyl moieties in C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, di-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino , (HO ₃ SC ₁ -C ₄ -alkyl) amino, C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -alkylaminosulfonyl, C ₁ -C ₄ -alkylaminocarbonyl, di-C ₁ -C ₄ -alkylaminosulfonyl, di- C ₁ -C ₄ alkylaminocarbonyl and C ₁ -C ₄ alkylcarbonylamino) for a linear or branched aliphatic hydrocarbon radical such as methyl, ethyl, n-propyl, isopropyl, n-butyl and the like.

C ₁ -C ₄ -hydroxyalkyl and the C ₁ -C ₄ -hydroxyalkyl moieties in C ₁ -C ₄ -hydroxyalkylamino are C ₁ -C ₄ -alkyl which carries an OH group, such as 2-hydroxyethyl. Accordingly, C ₁ -C ₄ -Hydroxyalkylamino is C ₁ -C ₄ -alkylamino which carries an OH group in the alkyl radical, such as 2-hydroxyethylamino.

C ₁ -C ₄ carboxyalkyl is C ₁ -C ₄ alkyl bearing a carboxyl group (COOH group) such as carboxymethyl (CH ₂ COOH) and 2-carboxyethyl (CH ₂ CH ₂ COOH). Accordingly, C ₁ -C ₄ carboxyalkylamino is C ₁ -C ₄ -alkylamino which carries a carboxyl group (COOH group) in the alkyl moiety, such as carboxymethylamino (NH-CH ₂ COOH) and 2-carboxyethylamino (NH-CH ₂ CH ₂ COOH ).

(HO ₃ SC ₁ -C ₄ -alkyl) amino is C ₁ -C ₄ -alkylamino, in which the alkyl group carries a sulfonyl radical, such as sulfonylmethylamino (NH-CH ₂ SO ₃ H) and 2-carboxyethylamino (NH-CH ₂ CH ₂ SO ₃ H).

5 or 6-membered heterocyclyl usually has 1, 2 or 3 heteroatoms, selected from nitrogen, oxygen and sulfur, in particular 1 or 2 nitrogen atoms and optionally an oxygen or sulfur atom as ring members and can be saturated, unsaturated or be aromatic. Examples of saturated Heterocyclyl are morpholinyl, piperidinyl, piperazinyl and pyrrolidinyl. Examples of aromatic heterocyclyl are pyridinyl, Pyrazolyl, oxazolyl, thiazolyl, etc.

The dyes of formulas I to IV, both in free form, in the form of their salts and, if two by a diazo group -N = N- connected radicals each have an ortho position to the diazo group arranged radical OH, COOH or NH ₂ - as Metal complexes are used.

According to the invention, the dyes of the formulas I, II, III and IV have at least one radical of the formula A. The radical A has a vinyl group bonded via a sulfonyl group or a group of the formula CH ₂ -CH ₂ -Q (group B), where the radical Q in the group CH ₂ -CH ₂ -Q stands for a group cleavable under alkaline conditions so that the vinylsulfone group can be formed under the alkaline dyeing conditions. Correspondingly, a group Q which can be split off under alkaline conditions is taken to mean radicals which are cleaved off under alkaline conditions, ie at pH values of 7.5 or above, with elimination to form a vinylsulfone group. Examples of such groups are halogen, e.g. Chlorine, bromine or iodine, furthermore -O-SO ₃ H, -S-SO ₃ H, dialkylamino, quaternary ammonium radicals such as tri-C ₁ -C ₄ -alkylammonium, benzyldi-C ₁ -C ₄ -alkylammonium or N- bound pyridinium, as well as remainders of Formulas R ^3B S (O) ₂ -, R ^4B S (O) ₂ -O-, R ^5B C (O) -O-. Herein R ^3B , R ^4B and R ^5B independently of one another are C ₁ -C ₄ -alkyl, C ₁ -C ₄ -haloalkyl or optionally substituted phenyl (for example unsubstituted or for 1, 2 or 3 times C ₁ -C ₄ -alkyl, halogen, nitro, CN, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -alkoxy or SO ₃ H-substituted phenyl), where R ^{5B can} also be hydrogen. Preferably Q is a group -O- (CO) CH ₃ and especially -O-SO ₃ H. In particular, B is a group CH ₂ -CH ₂ -O-SO ₃ H or a group CH ₂ -CH ₂ -OC (O) CH _3.

Preferably, the group SO ₂ B in the meta or para position, based on the bond #, bound to the phenyl ring.

Preferably, X in the radical of the formula A is a group SO ₃ H.

Preferably, Y in formula A is hydrogen or a group SO ₃ H, in particular hydrogen.

Particular preference is given to azo dyes of the general formulas I, II, III or IV and their salts, in which the group of the formula A is selected from the radicals of the formulas A1 to A18:

this includes are in particular those dyes of the general formulas I, II, III and IV are preferred, wherein the group A is selected among the residues A1, A8, A13 and A15.

In the dyes of the formulas I and II, the radicals Dk are generally derived from optionally substituted aniline or optionally substituted α- or β-naphthylamine Dk-NH ₂ , which is also referred to below as diazonium components and wherein Dk has the abovementioned meaning and in particular phenyl, which is substituted by 1, 2 or 3 of the aforementioned radicals R ^a .

Preferred radicals R ^a are OH, chlorine, CH ₃ , OCH ₃ , NO ₂ , COOH, SO ₃ H, SO ₂ CH ₃ , SO ₂ NHCH ₃ , NHCH ₃ , N (CH ₃ ) ₂ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ , C (O) CH ₃ , C (O) NH ₂ and phenylsulfonyl, in which the phenyl ring may be unsubstituted or 1 or 2 in OH, chlorine, CH ₃ , OCH ₃ , NO ₂ , COOH, SO ₃ H, SO ₂ CH _3, SO ₂ NHCH _3, NHCH _3, N (CH _{3) 2,} NHC (O) CH _3, NHC (O) CH ₂ CH _3, C (O) CH ₃ and C (O) NH _{2 may have} selected radicals.

Preferably, Dk in formulas I and II is a radical derived from an optionally substituted aniline, an optionally substituted α-naphthylamine, or an optionally substituted β-naphthylamine, or a group A. Particularly preferred is Dk of one through 1 , 2 or 3 radicals R ^a substituted aniline derived, ie Dk is phenyl which is substituted by 1, 2 or 3 radicals R ^a , in particular by 1, 2 or 3 of the radicals R ^a mentioned as preferred, or Dk is a Radical A, in particular one of the radicals A1 to A18 mentioned as being preferred.

Examples of suitable monoamines Dk-NH ₂ are the following compounds DK1 to DK39:

The radicals Q in the formulas DK21 to DK25 are hydrogen C ₁ -C ₄ -alkyl, carboxy-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -hydroxyalkyl, C ₁ -C ₄ -alkoxy or phenylcarbonyl.

Suitable diazo components Dk-NH ₂ are furthermore the following naphthylamines DK 40 to 59: 4-amino-3-hydroxy-s-halphalin-1-sulfonic acid (DK 4 O), 4-amino-3-hydroxy-6-nitronaphthalene-1-sulfonic acid (DK 41) , 6-amino-4-hydroxynaphthalene-2-sulfonic acid (gamma acid, DK42), 4-amino-5-hydroxynaphthalene-1-sulfonic acid (Chicago S acid, DK43), 4-amino-5-hydroxynaphthalene-2,7 disulfonic acid (H-acid DK44), 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid (K-acid, DK45), 8-aminonaphthalene-2-sulfonic acid (Cleves acid 7, DK46), 6-aminonaphthalene-1 sulfonic acid (D-acid, DK47), 4-aminonaphthalene-2,7-sulfonic acid (DK48), 5-aminonaphthalene-2-sulfonic acid (DK49), 7-amino-4,8-dihydroxynaphthalene-2-sulfonic acid (DK50), 2-Amino-5-hydroxynaphthalene-1,7-disulfonic acid (DK51), 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid (DK52), 3-amino-1,5-disulfonic acid (DK53), 7-aminonaphthalene 1-sulfonic acid (DK54), 4-aminonaphthalene-1-sulfonic acid (DK55), 5-aminonaphthalene-1-sulfonic acid (DK56), 7-amino naphthalene-1,3,5-trisulfonic acid (DK57), 4-amino-3-hydroxy-7 - [(4-methylphenyl) sulfonylamino] naphthalene-1-sulfonic acid (DK58) and 7-amino-4-hydroxynaphthalene-2 sulfonic acid (I acid, DK59).

Examples of suitable monoamines Dk-NH ₂ are furthermore the compounds DK60 to DK116 given below:

The radicals Ar in the formulas I and II are divalent radicals derived from benzene or naphthalene and may have 1, 2, 3 or 4 substituents R ^b , where R ^{b may have} the meanings given for R ^a . In particular, R ^{b is} selected from OH, NH ₂ , halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino, C ₁ -C ₄ Dialkylamino, C ₁ -C ₄ alkylcarbonylamino, N- (C ₁ -C ₄ alkyl) -N- (C ₁ -C ₄ alkylcarbonyl) amino, C ₁ -C ₄ alkylaminocarbonyloxy, C ₁ -C ₄ - Dialkylaminocarbonyloxy, C ₁ -C ₄ -alkylaminocarbonylamino, C ₁ -C ₄ -dialkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino, carboxy-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylsulfonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, phenylcarbonylamino and Phenylsulfonylamino, wherein the phenyl ring in the last 4 radicals is unsubstituted or 1, 2 or 3 under OH, NO ₂ , halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, and SO ₃ H have selected radicals can. In particular, R ^{b is} selected from OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -dialkylamino, C ₁ -C ₄ -hydroxyalkylamino and C ₁ -C ₄ -alkylcarbonylamino , in particular OH, NH ₂ , OCH ₃ , NHCH ₃ , N (CH ₃ ) ₂ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ and NH-CH ₂ CH ₂ OH. Ar is preferably a 1,3-phenylene radical which has one or two substituents R ^b , in particular one or two of the radicals R ^b indicated as being preferred.

Preferably n stands for 0 in formula I.

R ¹ in formula I is preferably OH.

R ² in formula I preferably represents OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylcarbonylamino, C ₁ -C ₄ -alkylaminocarbonyloxy, C ₁ -C ₄ Dialkylaminocarbonyloxy, C ₁ -C ₄ -alkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino or hydroxy-C ₁ -C ₄ -alkylamino. In particular, R ^{2 is} selected from OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino and C ₁ -C ₄ -alkylcarbonylamino, in particular OH, NH ₂ , OCH ₃ , NHCH ₃ , N (CH ₃ ) ₂ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ and NH-CH ₂ CH ₂ OH and especially OH and NH ₂ .

Under The dyes of the formula I are especially those of the formula I 'and especially those of formula Ia preferred. equally preferred are their salts and metal complexes.

In formulas I 'and Ia, A, R ¹ and Dk have the abovementioned meanings, in particular the meanings mentioned as being preferred. R ^2a has one of the meanings given for R ² and is preferably OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylcarbonylamino, C ₁ -C ₄ - Alkylaminocarbonyloxy, C ₁ -C ₄ -dialkylaminocarbonyloxy, C ₁ -C ₄ -alkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino or C ₁ -C ₄ -hydroxy-C ₁ -C ₄ -alkylamino. In particular, R ^{2a is} selected from OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino and C ₁ -C ₄ -alkylcarbonylamino, in particular OH, NH ₂ , OCH ₃ , NHCH ₃ , N (CH ₃ ) ₂ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ and NH-CH ₂ CH ₂ OH and especially OH and NH ₂ . R2A is preferably located in the meta-position to R ¹ or to the OH group.

• Dk2: 2-Hydroxy-3-(hydroxysulfonyl)-5-nitrophenyl
• Dk5: 2-Hydroxy-3,5-dinitrophenyl
• Dk8: 2-Hydroxy-5-(hydroxysulfonyl)-3-nitrophenyl
• Dk8: 2-Hydroxy-3,5-bis(hydroxysulfonyl)phenyl

Examples of particularly preferred dyes of the formula I are those of the general formula Ia in which Dk, A and R ^{2a have} the meanings given in the following Table I and the metal complexes. Table I:

• Dk2: 2-hydroxy-3- (hydroxysulfonyl) -5-nitrophenyl
• Dk5: 2-hydroxy-3,5-dinitrophenyl
• Dk8: 2-hydroxy-5- (hydroxysulfonyl) -3-nitrophenyl
• Dk8: 2-hydroxy-3,5-bis (hydroxysulfonyl) phenyl

The radicals Ar 'in the formula II are divalent radicals derived from benzene or naphthalene which may have 1, 2, 3 or 4 substituents R ^b' , where R ^{b 'may have} the meanings given for R ^b , in particular, R ^{b 'is} selected from OH, NH ₂ , halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino, C ₁ -C _4- dialkylamino, C ₁ -C ₄ alkylcarbonylamino, N- (C ₁ -C ₄ alkyl) -N- (C ₁ -C ₄ alkylcarbonyl) amino, C ₁ -C ₄ alkylaminocarbonyloxy, C ₁ -C ₄ Dialkylaminocarbonyloxy, C ₁ -C ₄ alkylaminocarbonylamino, C ₁ -C ₄ dialkylaminocarbonylamino, C ₁ -C ₄ alkoxycarbonylamino, carboxy C ₁ -C ₄ alkylamino, C ₁ -C ₄ alkylsulfonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, phenylcarbonylamino and phenylsulfonylamino, wherein the phenyl ring in the last 4 radicals is unsubstituted or 1, 2 or 3 radicals selected from OH, NO ₂ , halogen, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkyl, and SO ₃ H. can have. In particular, R ^{b is} selected from OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -dialkylamino, C ₁ -C ₄ -hydroxyalkylamino and C ₁ -C ₄ -alkylcarbonylamino , in particular OH, NH ₂ , OCH ₃ , NHCH ₃ , N (CH ₃ ) ₂ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ and NH-CH ₂ CH ₂ OH. Ar is preferably a 1,3-phenylene radical which has one or two substituents R ^{b '} , in particular one or two of the radicals R ^b' indicated as being preferred.

In of formula II is preferably p = 0. Particularly preferred Dyes of the general formula II and their salts and metal complexes, where both p = 0 and q = 0.

worin Dk, A, R^2x, k und m die zuvor genannten Bedeutungen aufweisen, wobei Dk und A vorzugsweise die als bevorzugt angegebenen Bedeutungen aufweisen.Among the dyes of the formula II, those of the formula II 'and especially those of the formula IIa are particularly preferred. Equally preferred are their salts and metal complexes.

wherein Dk, A, R ^2x , k and m have the meanings given above, wherein Dk and A preferably have the meanings given as preferred.

In Formulas II, II 'and IIa, the variable m is preferably for 1.

In Formulas II, II 'and IIa, the variable k is preferably for 1.

R ^2x in the formulas II, II 'and IIa is preferably selected from NH ₂ , C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ -C ₄ -alkyl) amino, C ₁ - C ₄ alkylcarbonylamino, N- (C ₁ -C ₄ alkyl) -N- (C ₁ -C ₄ alkylcarbonyl) amino, C ₁ -C ₄ alkylaminocarbonylamino, C ₁ -C ₄ dialkylaminocarbonylamino, carboxyC ₁ C ₄ -C ₄ alkylamino, C ₁ -C ₄ alkylsulfonylamino, phenylaminocarbonylamino, phenylcarbonylamino and phenylsulfonylamino, wherein the phenyl ring is unsubstituted in the last three mentioned radicals or 1, 2 or 3 under OH, NO ₂ , halogen, C ₁ -C ₄ Alkoxy, C ₁ -C ₄ alkyl, and SO ₃ H may have selected radicals. In particular, R ^{2x is} selected from NH ₂ , NHCH ₃ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ , NH-CH ₂ CH ₂ OH and NH-CH ₂ SO ₃ H.

Examples of particularly preferred dyes of formula II are those of general formula IIa, wherein Dk, A and R ^{2x have} the meanings given in the following Table II, the group SO ₃ H in the 3-position and the group R ^2x in the 6 Position of the naphthalene ring are arranged, as well as the metal complexes. Table II:

Among the dyes of formula III, their salts and their metal complexes are those in which R ^{1 is} an OH group. In formula III, the radicals R ¹ may be the same or different and are in particular the same.

In Formula III, the radicals A preferably one of A as preferred meanings indicated. In particular, stand the A radicals A are radicals of the formulas A1 to A18 and specifically selected from residues A1, A8, A13 and A15. In formula III, the radicals A may be identical or different be and are in particular the same.

R ² in formula III is preferably OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylcarbonylamino, C ₁ -C ₄ -alkylaminocarbonyloxy, C ₁ -C ₄ Dialkylaminocarbonyloxy, C ₁ -C ₄ -alkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino or hydroxy-C ₁ -C ₄ -alkylamino. In particular, R ^{2 is} selected from OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino and C ₁ -C ₄ -alkylcarbonylamino, in particular from OH, NH ₂ , OCH ₃ , NHCH ₃ , N (CH ₃ ) ₂ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ and NH-CH ₂ CH ₂ OH and especially OH and NH ₂ . In formula III, the radicals R ² may be the same or different and are in particular the same.

In the radical T in formula IV, the radicals R ³ and R ^{3a are} independently of one another preferably selected from hydrogen, COOH, SO ₃ H and OH. Preferably, the nodes # are arranged in the para position to the group D. In the radical T in formula III, the bivalent radical D is preferably selected from a bond CH ₂ , NH, SO ₂ , ethene-1,2-diyl, S (O) ₂ NH and C (O) NH. Accordingly, the radicals T in formula III are preferably selected from the following radicals T-1, T-2, T-3, T-4, T-5, T-6 and T-7:

In the radicals T-1, T-2, T-3, T-4, T-5, T-6 and T-7 R ³ and R ^3a preferably have the meanings mentioned above. In particular, in formula T-1, R ³ and R ^{3a are} each hydrogen, OH or COOH. In formula T-2, R ^{3 is} preferably hydrogen and R ^3a is preferably a sulfonyl group. In the formula T-3, R ³ and R ^{3a are} preferably hydrogen. In the formula T-4, R ³ and R ^{3a are} preferably hydrogen. In the formula T-5, R ³ and R ^{3a are} preferably SO ₃ H. In the formula T-6, R ³ and R ^{3a are} preferably hydrogen. Preferably, R ³ and R ^3a in the formula T-7 independently of one another are OH, SO ₃ H or COOH, where one of the radicals R ^3a or R ^{3 may} also be hydrogen. In residues T-1, T-2, T-3, T-4 and T-6, the nodes # are located in the para position to the group D.

Examples of preferred radicals T-1 are the following radicals T-1.1, T-1.2, T-1.3 and TI.4:

Examples of preferred radicals T-2, T-3 and T-4 are the radicals T-2.1, T-2.2, T-3.1 and T-4.1:

Examples of preferred radicals T-5 and T-6 are the radicals T-5.1 and T-6.1:

Examples preferred radicals T-7 are those mentioned below Remains T-7.1, T-7.2, T-7.3, T-7.4 and T-7.5.

Under the dyes of the formula III are especially those of the formula IIIa preferred. Equally preferred are their salts and metal complexes.

In formula IIIa, T and A have the abovementioned meanings, in particular the meanings given as being preferred. In particular, T is one of T-1, T-2, T-3, T-4, T-5 or T-6 wherein the linking points # are preferably located in the para position to the group D and wherein R ^3a and R ³ preferably have one of the meanings given as preferred.

Examples of particularly preferred dyes of the formula III are those of the general formula IIIa, in which A and T have the meanings given in the following Table III, as well as the metal complexes. Table III: dye Rest A Rest T metal complex III.1 A1 T-1.4 III.2 A13 T-1.4 III.3 A4 T-1.4 III.4 A7 T-1.4 III.5 A13 T-1.1 III.6 A13 T-1.1 Cu III.7 A1 T-1.1 III.8 A1 T-1.1 Cu III.9 A1 T-3.1 III.10 A13 T-3.1 III.11 A4 T-3.1 III.12 A7 T-3.1 III.13 A1 T-4.1 III.14 A13 T-4.1 III.15 A4 T-4.1 III.16 A7 T-4.1 III.17 A1 T-5.1 III.18 A13 T-5.1 III.19 A4 T-5.1 III.20 A7 T-5.1 III.21 A1 T-6.1 III.22 A1 T-1.3 III.23 A13 T-1.3 III.24 A4 T-2.2 III.25 A7 T-07.05 III.26 A1 T-1.2 III.27 A1 T-1.2 Cu

In Formula IV, the radical A is preferably one of for A as preferred given meanings. In particular, stands the A is a radical of the formulas A1 to A18 and is special selected from the radicals A1, A8, A13 and A15.

X in formula IV is preferably OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ -C ₄ -alkyl) amino, C C ₁ -C ₄ -dialkylamino, C ₁ -C ₄ -alkylcarbonylamino, N- (C ₁ -C ₄ -alkyl) -N- (C ₁ -C ₄ -alkylcarbonyl) -amino, C ₁ -C ₄ -alkylaminocarbonyloxy, C ₁ -C ₄ -dialkylaminocarbonyloxy, C ₁ -C ₄ -alkylaminocarbonylamino, C ₁ -C ₄ -dialkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino, carboxy-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylsulfonylamino, phenylaminocarbonyloxy, Phenylaminocarbonylamino, phenylcarbonylamino and phenylsulfonylamino, wherein the phenyl ring in the last 4 radicals is unsubstituted or 1, 2 or 3 under OH, NO ₂ , halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, and SO ₃ H may have selected radicals. In particular, X is selected from OH, NH ₂ , C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -dialkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ -C ₄ -alkyl) amino, phenylcarbonylamino and C C ₁ -C ₄ -alkylcarbonylamino, especially OH, NH ₂ , OCH ₃ , NHCH ₃ , N (CH ₃ ) ₂ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ , NHC (O) -phenyl, NH-CH ₂ -SO ₃ H and NH-CH ₂ CH ₂ OH. X is particularly preferably OH or NH ₂ .

Y in formula IV is preferably hydrogen, OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ -C ₄ -alkyl) -amino , C ₁ -C ₄ -dialkylamino, C ₁ -C ₄ -alkylcarbonylamino, N- (C ₁ -C ₄ -alkyl) -N- (C ₁ -C ₄ -alkylcarbonyl) -amino, C ₁ -C ₄ -alkylaminocarbonyloxy, C ₁ -C ₄ dialkylaminocarbonyloxy, C ₁ -C ₄ -alkylaminocarbonylamino, C ₁ -C ₄ -dialkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino, carboxy-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylsulfonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, phenylcarbonylamino and phenylsulfonylamino, wherein the phenyl ring in the last four radicals is unsubstituted or may have 1, 2 or 3 selected from OH, NO ₂ , halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, and SO ₃ H selected radicals. In particular, Y is selected from hydrogen, OH, NH ₂ , C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -dialkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ -C ₄ -alkyl) amino, phenylcarbonylamino and C ₁ -C ₄ -alkylcarbonylamino, in particular hydrogen, OH, NH ₂ , OCHS, NHCH ₃ , N (CH ₃ ) ₂ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ , NHC (O) Phenyl, NH-CH ₂ -SO ₃ H and NH-CH ₂ CH ₂ OH. Y is particularly preferably OH or NH ₂ .

In particular, one of the two radicals X or Y is OH and the remaining radical X or Y is hydrogen or one of the following substituents: NH ₂ , C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ -C ₄ alkyl) amino, C ₁ -C ₄ alkylcarbonylamino, N- (C ₁ -C ₄ alkyl) -N- (C ₁ -C ₄ alkylcarbonyl) amino, C ₁ -C ₄ alkylaminocarbonylamino , C ₁ -C ₄ -dialkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino, carboxy-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylsulfonylamino, phenylaminocarbonylamino, phenylcarbonylamino and phenylsulfonylamino, where the phenyl ring is in the 3 last-named radicals is unsubstituted or may have 1, 2 or 3 selected from OH, NO ₂ , halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, and SO ₃ H selected radicals. In particular, the remaining radical X or Y is selected from hydrogen, NH ₂ , C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -dialkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ -C ₄ -alkyl) amino, phenylcarbonylamino and C ₁ -C ₄ -alkylcarbonylamino, especially under hydrogen, NH ₂ , NHCH ₃ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ , NHC (O) -phenyl, NH-CH ₂ - SO ₃ H and NH-CH ₂ CH ₂ OH. Particularly preferably, the remaining radical X or Y is NH ₂ .

Suitable radicals Kk are in principle all monovalent aromatic radicals which are derived from an optionally substituted benzene, naphthalene, pyrazole, diphenylamine, diphenylmethane, pyridine, pyrimidine or diphenyl ether, which still have a free position to which a diazonium compound can be coupled. The compounds underlying the radicals Kk are also referred to in the art as coupling components. If appropriate, unsubstituted in this context means that the radicals derived from benzene, naphthalene, pyrazole, diphenylamine, diphenylmethane, pyridine, pyrimidine or diphenyl ether may have 1, 2, 3 or 4 substituents which are chosen from SO ₃ H, COOH, CN, CONH ₂ , OH, NH ₂ , NO ₂ , halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -hydroxyalkyl, carboxy-C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ Alkylamino, C ₁ -C ₄ -dialkylamino, C ₁ -C ₄ -alkylaminocarbonyl, C ₁ -C ₄ -dialkylaminocarbonyl, C ₁ -C ₄ -alkylcarbonylamino, N- (C ₁ -C ₄ -alkylcarbonyl) -N- ( C ₁ -C ₄ -alkylcarbonyl) amino, C ₁ -C ₄ -alkylaminocarbonyloxy, C ₁ -C ₄ -dialkylaminocarbonyloxy, C ₁ -C ₄ -alkylaminocarbonylamino, C ₁ -C ₄ -dialkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino, C ₁ -C ₄ -hydroxy-C ₁ -C ₄ -alkylamino, carboxy-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylsulfonyl, hydroxy-C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ - Alkylaminosulfonyl, C ₁ -C ₄ -alkylsulfonylamino, aminocarbonyl, a radical of the formula SO ₂ NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² independently of one another represent hydrogen, C ₁ -C ₄ -alkyl, formyl, C ₁ -C ₄ -alkylcarbonyl, C ₁ -C ₄ -alkyloxycarbonyl, NH ₂ -CO or C ₁ -C ₄ -alkylaminocarbonyl , C ₁ -C ₄ -alkylaminosulfonylamino, di-C ₁ -C ₄ -alkylaminosulfonylamino, phenyl, phenylamino, phenylaminocarbonyl, phenoxy, phenylsulfonyl, phenylsulfonylamino, phenylaminosulfonyl, phenylcarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, where the 12 latter radicals on the phenyl ring are unsubstituted or 1 , 2 or 3 substituents selected from C ₁ -C ₄ -alkyl, OH, COOH, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylcarbonyloxy, C ₁ -C ₄ -alkylcarbonylamino, C ₁ -C ₄ - Alkoxycarbonyl, NH ₂ , NO ₂ , SO ₃ H and halogen may have, wherein one of the substituents on phenyl may also stand for a group SO ₂ -B, wherein B has the abovementioned meanings and in particular for a group CH = CH ₂ , CH ₂ CH ₂ OSO ₃ H or CH ₂ CH ₂ OSO ₃ H.

Suitable coupling components are radicals which are, for example, benzene-derived compounds of the general formula Kk-A, naphthalene-derived compounds of the formula Kk-B, quinoline-derived compounds of the formula Kk-C, pyrazole-derived compounds of the formula Kk-D, of Diphenylmethane derived compounds of the formula Kk-E, derived from diphenylamine compounds of the formula Kk-F derived pyridine derived compounds of the formula Kk-G and pyridone derived compounds of the formula Kk-H, ie an aromatic hydrogen atom in these compounds Kk-A -Kk-H is replaced by a bond to the diazo group attached to Kk:

In the formula Kk-A, R ^{11 is} NH ₂ , OH, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, di-C ₁ -C ₄ -alkylamino, hydroxy-C ₁ -C ₄ -alkylamino , Carboxy-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylcarbonylamino or phenylamino, R ^{12 is} hydrogen, NH ₂ , OH, C ₁ -C ₄ -alkoxy, hydroxy-C ₁ -C ₄ -alkylamino, carboxy -C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylamino, di-C ₁ -C ₄ -alkylamino and R ^{13 represents} hydrogen, CN, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, CONH ₂ , C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -alkylsulfonyloxy, SO ₂ -phenyl, SO ₃ H, C ₁ -C ₄ -alkylcarbonyl, C ₁ -C ₄ -alkoxycarbonyl, 1-hydroxyethyl, COOH, Cl, Br, F, SO ₂ NR ⁵⁶ R ⁵⁷ , NO ₂ , or NH ₂ , wherein R ⁵⁶ and R ^{57 are} independently hydrogen, C ₁ -C ₄ alkyl, formyl, C ₁ -C ₄ alkylcarbonyl, C C ₁ -C ₄ alkyloxycarbonyl, NH ₂ -CO, C ₁ -C ₄ alkylaminocarbonyl.

In formula Kk-B, R ¹⁴ and R ¹⁵ independently of one another represent hydrogen or have one of the meanings mentioned as R ¹¹ , where R ^{15 may} also be SO ₃ H. R ¹⁶ is hydrogen, OH, SO ₃ H, C ₁ -C ₄ -alkylsulfonylamino, C ₁ -C ₄ -alkylaminosulfonyl, C ₁ -C ₄ -alkylaminosulfonylamino, di-C ₁ -C ₄ -alkylaminosulfonylamino, C ₁ -C _4- alkoxycarbonylamino, phenylsulfonylamino which may have on the phenyl ring one or two substituents selected from C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy or halogen. R ¹⁷ is hydrogen, OH or a group SO ₃ H.

In formula Kk-C, R ¹⁸ to R ²⁰ independently of one another represent hydrogen, OH or C ₁ -C ₄ -alkyl.

In formula Kk-D, R ^{21 is} hydrogen, phenyl or naphthyl, where the 2 last-mentioned groups may have 1, 2 or 3 substituents which are selected from hydrogen, OH, halogen, C ₁ -C ₄ -alkyl, SO ₃ H , NO ₂ and the previously defined group B-SO ₂ -. In one embodiment of the invention, R ^{21 is} one of the previously defined groups A and in particular one of the groups A1 to A18. R ²² is hydrogen, COOH, COO-C ₁ -C ₄ -alkyl or C ₁ -C ₄ -alkyl.

In formula Kk-E, R ²³ and R ²⁵ independently of one another are hydrogen, COOH, hydroxy or C ₁ -C ₄ -alkyl. R ²⁴ and R ²⁶ independently of one another are hydrogen, hydroxyl or C ₁ -C ₄ -alkyl,

In formula Kk-F, R ²⁷ and R ²⁹ independently of one another are hydrogen, SO ₃ H, COOH, hydroxy or C ₁ -C ₄ -alkyl. R ²⁸ and R ³⁰ independently of one another are hydrogen, hydroxyl or C ₁ -C ₄ -alkyl,

In formula Kk-G, R ⁴⁸ , R ⁴⁹ , R ⁵⁰ and R ⁵¹ independently of one another are hydrogen, SO ₃ H, COOH, NH ₂ , CN, hydroxy or C ₁ -C ₄ -alkyl.

In formula Kk-H, R ⁵² , R ⁵³ , R ⁵⁴ and R ⁵⁵ independently of one another are hydrogen, SO ₃ H, COOH, NH ₂ , CN, hydroxy or C ₁ -C ₄ -alkyl.

Examples of coupling components of the formula Kk-A are the abovementioned aniline compounds DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39, DK60 to DK83, also salicylic acid (Kk1), 3-aminophenol (Kk2), resorcinol (Kk3), 3-phenylaminophenol (Kk4), 1,3-diaminobenzene (Kk5), 3-acetylamino-aniline (Kk6), 2-nitroaniline (Kk7 ), 3- (diethylamino) phenol (Kk8), 3- (morpholin-1-yl) phenol (Kk9), 3- (diethylamino) aniline (Kk10), N-acetyl-3- (diethylamino) aniline (Kk11) , N- (3-hydroxyphenyl) glycine (Kk12), 3- (2-hydroxyethyl) aminophenol (Kk13), 2,4-diaminotoluene (Kk14), 2,4-diaminobenzenesulfonic acid (Kk15), 2,4-diamino-1 nitrobenzene (Kk16), N- (3-amino-6-methylphenyl) glycine (Kk17), 2,4-diamino-5-methylbenzenesulfonic acid (Kk18), 2,4-diamino-1-hydroxybenzene (Kk54), 2, 4-diamino-1-methoxybenzene (Kk55), 2,4-diamino-1-chlorobenzene (Kk56), 1,2,4-triaminobenzene (Kk57), 3- (dimethylamino) -aniline (Kk58), 3- (dimethylamino ) -1-nitrobenzene (Kk59), 2- (N, N-diethylamino) 4-acetylamino-1-methoxybenzene (Kk60), 2- (N, N -diethylamino) -4-amino-1-methoxybenzene (Kk61), 2,4-diamino-1-benzenesulfonamide (Kk62), 2-amino-4-acetylamino-1-methoxybenzene (Kk63), 2-amino-4-acetylamino-1-chlorobenzene (Kk64) and 3-methoxyaniline (Kk65).

Examples for coupling components of the formula Kk-B are 2-naphthol (Kk19), 2-phenylaminonaphthalene (Kk20), 4-methyl-1-naphthol (Kk21), 8-methoxycarbonylamino-2-naphthol (Kk22), 8-acetylamino-2-naphthol (Kk23), 8-methylaminosulfonyl-2-naphthol (Kk24), 8-dimethylaminosulfonylamino-2-naphthol (Kk25) 6 - [(4-methylphenyl) sulfonyl] amino-4-hydroxynaphthalene-2-sulfonic acid (Kk26), 8-phenylaminonaphthalene-1-sulfonic acid (Kk27), 6-amino-4-hydroxynaphthalene-2-sulfonic acid (DK42), 4-amino-5-hydroxynaphthalene-1-sulfonic acid (DK43), 4-Amino-5-hydroxynaphthalene-2,7-disulfonic acid (DK44), 4-amino-5-hydroxynaphthalene-1,7-disulfonic acid (DK45), 8-aminonaphthalene-2-sulfonic acid (DK46), 6-aminonaphthalene-1-sulfonic acid (DK47), 4-aminonaphthalene-2,7-disulfonic acid (DK48), 5-aminonaphthalene-2-sulfonic acid (DK49), 7-amino-4,8-dihydroxynaphthalene-2-sulfonic acid (DK50), 2-Amino-5-hydroxynaphthalene-1,7-disulfonic acid (DK51), 3-amino-5-hydroxynaphthalene-2,7-disulfonic acid (DK52), 3-amino-1,5-disulfonic acid (DK53), 7-aminonaphthalene-1-sulfonic acid (DK54), 4-aminonaphthalene-1-sulfonic acid (DK55), 5-aminonaphthalene-1-sulfonic acid (DK56), 7-aminonaphthalene-1,3,5-trisulfonic acid (DK57), 7-amino-4-hydroxynaphthalene-2-sulfonic acid (DK59), 4-hydroxynaphthalene-2,7-disulfonic acid (Kk28), 3-hydroxynaphthalene-2,7-disulfonic acid (Kk29), 4- (phenylcarbonyl) amino-5-hydroxynaphthalene-2,7-disulfonic acid (Kk30), 4,6-dihydroxynaphthalene-2-sulfonic acid (Kk31), 4,5-dihydroxynaphthalene-2,7-disulfonic acid (Kk32), 4- (phenylcarbonyl) amino-5-hydroxynaphthalene-1-sulfonic acid (Kk33), 4-hydroxynaphthalene-1-sulfonic acid (Kk34), 4,5-dihydroxynaphthalene-1-sulfonic acid (Kk35), 7-hydroxynaphthalene-1,3-disulfonic acid (Kk36), 8-hydroxynaphthalene-1-sulfonic acid (Kk37), 4,6-Dihydroxy-7-hydroxycarbonylnaphthalene-2-sulfonic acid (Kk38) and 4-acetylamino-5-hydroxynaphthalene-2,7-disulfonic acid (Kk39).

Examples for coupling components Kk-C are 2,4-dihydroxyquinoline (Kk40) and 8-hydroxyquinoline (Kk41).

Examples for coupling components Kk-D are 3-methyl-5-hydroxypyrazole (Kk42), 1-phenyl-3-methyl-5-hydroxypyrazole (Kk43), 1- [4- (2-hydroxysulfonyloxyethyl) -2-hydroxysulfonylphenyl] -3-methyl-5-hydroxypyrazole (Kk44), 1- [4- (2-hydroxysulfonyloxyethyl) -2-hydroxysulfonylphenyl] -5-hydroxypyrazole-3-carboxylic acid (Kk45), 1- [4-hydroxysulfonylphenyl] -5-hydroxypyrazol-3-carboxylic acid (Kk46) and 1- [6-hydroxysulfonylnaphthalen-2-yl] -5-hydrox-3-methylpyrazole (Kk47), 1- [4-hydroxysulfonylphenyl] -3-methyl-5-hydroxypyrazole (Kk48).

One Example of coupling components Kk-E is 4,4'-dihydroxydiphenylmethane-3,3'-dicarboxylic acid (Kk49).

One Example of a Coupling Component Kk-F is 4,4'-dihydroxydiphenylamine (KK50).

One Example of a Coupling Component Kk-G is 2,6-diamino-pyridine (KK51).

Examples for coupling components Kk-H are 1-methyl-2-pyridone (Kk52) and 3-cyano-4-methyl-6-hydroxy-1-ethylpyridone (Kk53).

suitable Kk radicals are especially monovalent ones of an optionally substituted one Benzene, naphthalene or pyrazole derived radicals, e.g. B. from the coupling components Kk-A, Kk-B and Kk-D derived monovalent Residues such as those of the aniline compounds DK3, DK4, DK6, DK7, DK11, DK13, DK14, DK15, DK18, DK21 to DK27, DK29, DK30, DK33, DK36, DK38, DK39, DK42 to DK83, Kk1 to Kk18 and Kk54 to Kk65 derived Radicals selected from naphthalene compounds Kk27 to Kk39 and DK42 to DK59 derived residues as well as those of the pyrazole compounds Kk42 to Kk48 derived residues.

The radicals T * in formula IV are divalent aromatic radicals of the formula T, as have been defined in connection with the formula III. In the radical T * in formula IV, the radicals R ³ and R ^{3a are} independently of one another preferably selected from hydrogen, COOH, SO ₃ H and OH. Preferably, the nodes # are arranged in the para position to the group D. In the radical T in formula IV, the bivalent radical D is preferably selected from a chemical bond, CH ₂ , NH, SO ₂ , ethene-1,2-diyl, S (O) ₂ NH and C (O) NH. Accordingly, the radicals T * in formula IV are preferably selected from the abovementioned radicals T-1, T-2, T-3, T-4, T-5, T-6 and radical T-7.

In the radicals T-1, T-2, T-3, T-4, T-5, T-6 and T-7 R ³ and R ^3a preferably have the meanings mentioned above. In particular, in formula T-1, R ³ and R ^{3a are} each hydrogen, OH or COOH. In For mel T2, R ³ is preferably hydrogen and R ^3a is preferably a sulfonyl group. In the formula T-3, R ³ and R ^{3a are} preferably hydrogen. In the formula T-4, R ³ and R ^{3a are} preferably hydrogen. In the formula T-5, R ³ and R ^{3a are} preferably SO ₃ H. In the formula T-6, R ³ and R ^{3a are} preferably hydrogen. In the residues T-1, T-2, T-3, T-4, T-5 and T-6, the nodes # are located in the para position to the group D.

Examples preferred radicals T-1 are the abovementioned radicals T-1.1, T-1.2, T-1.3 and T-1.4. Examples of preferred Residues T-2, T-3, T-4, T-5, T-6 and T-7 are the aforementioned radicals T-2.1, T-2.2, T-3.1, T-4.1, T-5.1, T-6.1, T-7.1, T-7.2, T-7.3, T-7.4 and T-7.5.

Under The dyes of formula IV are particularly preferred such wherein r and s are each 1 dyes of the formula IVa). In particular, those of the formula IVa are preferred, wherein the both sulfonyl groups in the 2 and the 7-position of the naphthalene ring are arranged. Equally preferred are their salts and metal complexes.

In formula IVa, A, Kk, X, Y and T * have the abovementioned meanings, in particular the meanings given as being preferred. In particular, T * stands for one of the radicals T-1, T-2, T-3, T-4, T-5, T-6 or T-7 in which the linking points # are preferably arranged in para position to the group D and wherein R ^3a and R ³ preferably have one of the meanings given as preferred. In particular, one of the two radicals X or Y is OH and the remaining radical X or Y is hydrogen or one of the following substituents: NH ₂ , C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ -C ₄ alkyl) amino, C ₁ -C ₄ alkylcarbonylamino, N- (C ₁ -C ₄ alkyl) -N- (C ₁ -C ₄ alkylcarbonyl) amino, C ₁ -C ₄ alkylaminocarbonylamino , C ₁ -C ₄ -dialkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino, carboxy-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylsulfonylamino, phenylaminocarbonylamino, phenylcarbonylamino and phenylsulfonylamino, where the phenyl ring is in the 3 last-named radicals is unsubstituted or may have 1, 2 or 3 radicals selected from OH, NO ₂ , halogen, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkyl, and SO ₃ H; In particular, the remaining radical X or Y is selected from hydrogen, NH ₂ , C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -dialkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ -C ₄ -alkyl) amino, phenylcarbonylamino and C ₁ -C ₄ -alkylcarbonylamino, especially under hydrogen, NH ₂ , NHCH ₃ , NHC (O) CH ₃ , NHC (O) CH ₂ CH ₃ , NHC (O) -phenyl, NH-CH ₂ - SO ₃ H and NH-CH ₂ CH ₂ OH. Particularly preferably, the remaining radical X or Y is NH ₂ .

Examples of particularly preferred dyes of the formula IV are those of the general formula IVa ', in which X, Y, A and T * have the meanings given in the following Table IV, as well as the metal complexes. Table IV:

Included in the invention the dye mixtures at least two mutually different dyes, wherein each of the dyes has a group of formula A and wherein each of the dyes is in the form of the free acid, in Form of a salt, in the form of a metal complex or in the form of a Salt of such a metal complex may be included.

According to the invention, the dyes of the formulas I, II, III or IV and their metal complexes contained in the mixtures are anionic, ie they have at least one, for. B. 1 to 10, in particular 2 to 6 anionic or acidic functional groups per dye molecule. These groups impart water solubility to the dyes under mildly acidic, neutral or alkaline conditions. In particular, they are anionic or acidic functional groups which dissociate in an aqueous medium at pH values above 4, forming anionic groups. Examples of such groups are hydroxysulfonyl (-SO ₃ H), carboxyl (COOH) and hydroxysulfonyloxy (-O-SO ₃ H) and the anions of these groups, preferably at least one and especially at least two of these groups Hydroxysulfonylgruppen. Accordingly, the dyes of formulas I, II, III and IV may be monobasic or polybasic, preferably at least 2 basic, e.g. B. 2 to 10 or 2 to 6 basic acids or salts are present. If the acid groups are present in the dye as anionic groups, ie the dye is a salt, it goes without saying that the dye also comprises the counterions required for neutralization. Suitable counterions are in particular alkali metal ions, especially sodium, potassium and lithium ions and ammonium ions, for. As NH ₄ + and ammonium ions derived from mono- di or trialkylamines or mono-, di- or tri (hydroxyalkyl) amines such as mono-, di- or triethanolamine.

In the mixtures according to the invention can instead of or together with the dyes of the formulas I, II, III or IV, the metal complexes, preferably transition metal complexes the aforementioned dyes, in particular complexes of the transition metals of Groups VI to X of the Periodic Table and hereunder in particular of Cu, Cr, Fe, Ni, Co, Mn, Zn and Cd and their salts and the Salts of these metal complexes can be used. The molar ratio from transition metal to dye molecule in these Metal complexes are usually in the range of 2: 1 to 1: 2. As a rule, the complexation takes place in these dyes the metal ions do not have the aforementioned anionic But via deprotonated hydroxyl groups, via Amino groups, imino groups, nitrogen atoms that are in an aromatic π-electron system or azo groups.

The dyes of the formulas I, II, III and IV contained in the mixtures according to the invention are those cited above WO 2005/040490 and the WO 2005/121439 are known or can analogously to known manufacturing processes for structurally similar dyes, as in the cited prior art and in EP 602,562 . EP-A 597 411 . EP-A 592 105 or DE 43 196 74 , as well as in relevant monographs are described (see, for example: basics of the synthesis of intermediates and dyes. NN Woroshzow, Akademie-Verlag, Berlin, 1966 (493-524) . Chemistry of azo dyes, H. Zollinger, Birkhäuser-Verlag Berlin 1958 , Artificial organic dyes and their intermediates, HR Swiss, Springer-Verlag, Berlin-Göttingen-Heidelberg 1964 (416-495) . H. Baumann, HR Hensel, Advances in Chemical Research Bd. 7, 1967, 643-761 and literature cited therein).

zunächst diazotieren und dann auf ein entsprechendes Farbstoffvorprodukt kuppeln. Das bei der Reaktion der Aminoverbindung A-NH₂ bzw. ihres Diazoniumsalzes mit dem Farbstoff-Vorprodukt erhaltene Reaktionsprodukt kann bereits der Farbstoff sein oder seinerseits ein Vorprodukt für den Farbstoff darstellen, das in Analogie zu bekannten Verfahren zum Farbstoff F weiterverarbeitet wird. Verfahren hierzu sind aus dem hier zitierten Stand der Technik bekannt oder können in analoger Weise zur Herstellung der Farbstoffe der Formeln I, II, III oder IV angewendet werden.For the preparation of the dyes F is usually an amino compound of the formula A-NH ₂

first diazotize and then couple to a corresponding dye precursor. The reaction product obtained in the reaction of the amino compound A-NH ₂ or its diazonium salt with the dye precursor may already be the dye or, in turn, be a precursor for the dye, which is further processed into the dye F in analogy to known processes. Processes for this purpose are known from the prior art cited here or can be used in an analogous manner for the preparation of the dyes of the formulas I, II, III or IV.

The Production of the invention for use coming azo dyes of the general formulas I, II, III or IV and their metal complexes usually includes a multi-level Diazotization / coupling sequence, the respective dyes by successive diazotization / coupling are constructed, d. H. The link the individual building blocks diazo groups takes place successively, or by a convergent synthesis, d. H. Molecular groups of the dye, which already have azo groups are generated and then over a further diazotization / coupling with another part of the molecule the dye, which also already one or more azo groups has linked.

Dyes of the formula 1 can be prepared, for example, by successively coupling a compound A-NH ₂ as defined above and a compound Dk-NH ₂ or Dk-N = N-Ar-NH ₂ onto a benzene compound substituted by R ¹ and R ² ,

Compounds of formula II are z. B. by successively coupling a compound of a compound A-NH ₂ , as defined above, or a compound AN = N-Ar'-NH ₂ , and a compound Dk-NH ₂ or Dk-N = N-Ar-NH ₂ on a naphthalene compound substituted by R ¹ , (SO ₃ H) _k and (R ^2x ) _m .

Dyes of the formula III can be prepared, for example, by tetrazotizing a diamine of the formula T- (NH ₂ ) ₂ , in which T has the abovementioned meanings (ie converted into the tetrazonium salt), the tetrazotised product to a by R ¹ and Coupling R ² substituted benzene compound and coupling the diazonium salt of the compound A-NH ₂ on the coupling product. Alternatively, one can first diazotize the compound A-NH ₂ and once coupled to a benzene compound substituted by R ¹ and R ² , and the reaction product with the tetrazonium salt of the diamine of the formula T- (NH ₂ ) ₂ in a stoichiometry of 2: 1 implements.

Dyes of the formula IV are prepared, for example, by first diazotizing a compound A-NH _2, coupling to a suitable, by X, Y, (SO ₃ H) _p and (SO ₃ H) _p substituted naphthalene compound, and the coupling product with which reacts with the diazonium salt ⁺ N ₂ -T * -N = N-Kk. The latter is generally prepared in situ by reacting the tetrazonium compound of T- (NH ₂ ) ₂ with the coupling component KkH on which the radical Kk is based. Alternatively, the compound T- (NH _{2) 2 are} first converted into the tetrazonium salt, followed by coupling with one equivalent of the coupling component Kkh, the coupling product thus obtained, which still has a diazonium pointed by X, Y, (SO ₃ H) Coupling _p and (SO ₃ H) _p- substituted naphthalene compound and then coupled to the coupling product thus obtained, the diazonium salt of the compound A-NH ₂ . Dyes of the formula IV are in particular also prepared by first preparing the tetrazonium compound of T- (NH ₂ ) ₂ and coupling it to a suitable, by X, Y, (SO ₃ H) _p and (SO ₃ H) _p substituted naphthalene compound , one being one Clutch product K1 receives, wherein still a diazonium group of the tetrazonium compound is present unreacted. The coupling product is then reacted with that with the diazonium salt ⁺ N2-A to give a coupling product K2 in which the one diazonium group of the tetrazonium compound is still present. K2 is then coupled in a final reaction step to the KkH underlying the radical Kk coupling component, to obtain the dye of formula IV.

such Methods are known in the art for anionic Azo dyes are known and can be applied analogously to the preparation the dyes I, II, III and IV are transferred.

The Diazotization and the coupling of the resulting diazonium or The tetrazonium compound is usually carried out in one aqueous reaction medium under pH control in per se known way.

If the reacted molecular components already have a group A carrying a radical B of the formula CH ₂ CH ₂ -Q, then the pH of the reaction mixture will preferably not exceed a value of pH 8, otherwise a cleavage of the group Q under training a vinyl group takes place.

at Couplings of diazonium or tetrazonium salts to a naphthalene compound, which carries both an OH group and an amino group and at least two possible coupling points, is to take into account that at pH levels of at most 3, the first coupling regioselectively in ortho position to the amino group whereas at pH values of pH ≥ 6 a regioselective Coupling takes place in the ortho position of the OH group.

The required for the diazotization / coupling reaction temperatures are usually in the range of 0 ° C to 50 ° C and in particular in the range of 0 to 30 ° C. The necessary Reaction times are usually in the range of 5 min to 2 h and especially in the range of 20 min. until 1 h.

The Reactions are usually stoichiometric, d. H. the reactants are in the desired stoichiometry implemented together. The individual reactants can however, both in surplus and in surplus be used to the desired stoichiometry. The deviation from the desired stoichiometry is usually not more than 20 mol% and especially not more than 10 mol%. In other words, in the implementation a diazonium component with a coupling partner becomes the molar ratio of the two components in the range of 1: 1.2 to 1.2: 1 and in particular ranging from 1.1: 1 to 1: 1.1. In the implementation of a tetrazonium compound With 2 molar equivalents of a coupling partner one becomes this accordingly in an amount of 1.6 to 2.4 moles and in particular in an amount of 1.8 to 2.2 moles per mole of tetrazonium compound deploy.

in the Connection to the diazotization / coupling sequence can be used for the preparation the transition metal complexes the desired transition metal salt in the form of a suitable, preferably water-soluble salt in the stoichiometrically desired amount and optionally to the temperature required for complexation, z. B. to temperatures in the range of 40 to 100 ° C warm.

The Recovery of the dye from the aqueous reaction mixture takes place in a conventional manner, for example by Evaporation, in particular by spray-drying the aqueous Reaction mixture, by salting out the dye and drying the Pressguts. For the preparation of a liquid brand or a liquid formulation of the dye, the dye presscake, or the evaporation or spray drying dissolved dye powder become. It is also possible directly from the reaction solution to prepare a liquid formulation of the dye. Possibly it is then for a sufficiently high dye concentration and for the stability of the liquid adjustment required to perform a slide and / or ultrafiltration process, to deplete the inorganic salts produced in the production and to concentrate the solution.

According to a first preferred embodiment of the invention, the dye mixture contains a dye of the general formula I, in particular the general formula Ia, or a salt or metal complex thereof or a salt of a metal complex of I or Ia as component a) and as component b) another Dye of the general formula I, in particular of the general formula Ia, or a salt or metal complex thereof or a salt of a metal complex of I or Ia. In this embodiment, the dye of component a) is different from the dye of component b), and differs in particular in the radical Dk, z. By the aromatic ring which underlies Dk and / or by the nature or arrangement of any substituent on the aromatic ring. In addition, the dye mixture of the first preferred embodiment may contain one or two further dyes as component c), which among the Dyes of the general formulas II, III and IV, in particular among the dyes of the general formulas IIa, IIIa and IVa, their salts and metal complexes and the salts of the metal complexes and mixtures thereof are selected. In addition, the dye mixture of the first embodiment may contain a further dye which is among the dyes of the general formulas II, III and IV, especially among the dyes of the general formulas IIa, IIIa and IVa, their salts and metal complexes and the salts of the metal complexes and mixtures thereof is selected.

Examples of the first embodiment are the following mixtures 1 to 4: No. Component a) Component b) Component c) 1 Dye of the formula I, in particular of the formula Ia Dye of the formula I, in particular of the formula Ia 2 Dye of the formula I, in particular of the formula Ia Dye of the formula I, in particular of the formula Ia Dye of the formula II, in particular of the formula IIa 3 Dye of the formula I, in particular of the formula Ia Dye of the formula I, in particular of the formula Ia Dye of the formula III, in particular of the formula IIIa 4 Dye of the formula I, in particular of the formula Ia Dye of the formula I, in particular of the formula Ia Dye of the formula IV, in particular of the formula IVa wherein in the mixtures 1 to 4, the dyes of the general formulas I, II, III and IV (or Ia, IIa, IIIa and IVa) also in the form of their salts, in the form of their metal complexes and / or in the form of the salts of the metal complexes and wherein the mixtures 2, 3 and 4 may also contain a further dye which comprises among the dyes of the general formulas II, III and IV, in particular among the dyes of the general formulas IIa, IIIa and IVa, their salts and metal complexes and the Salts of metal complexes and mixtures thereof is selected.

According to one second preferred embodiment of the invention contains the dye mixture is a dye of the general formula I, in particular the general formula Ia, or a salt or a metal complex thereof or a salt of a metal complex of I or Ia as a component a) and as component b) another dye which is among the Dyes of the general formulas II, III and IV, in particular among the dyes of the general formulas IIa, IIIa and IVa, salts and metal complexes and salts of metal complexes and mixtures thereof are selected. In addition, the Dye mixture of the second preferred embodiment contain one or two further dyes as component c), which among the dyes of the general formulas II, III and IV, in particular among the dyes of the general formulas IIa, IIIa and IVa, salts and metal complexes and salts of metal complexes and mixtures thereof are selected. Furthermore For example, the dye mixture of the first embodiment may include another dye of the general formula I, or a salt or Metal complex thereof or a salt of a metal complex of I or Ia included.

Examples of the second embodiment are the following mixtures 5 to 11: No. Component a) Component b) Component c) 5 Dye of the formula I, in particular of the formula Ia Dye of the formula II, in particular of the formula IIa 6 Dye of the formula I, in particular of the formula Ia Dye of the formula II, in particular of the formula IIa Dye of the formula III, in particular of the formula IIIa 7 Dye of the formula I, in particular of the formula Ia Dye of the formula II, in particular of the formula IIa Dye of the formula IV, in particular of the formula IVa 8th Dye of the formula I, in particular of the formula Ia Dye of the formula III, in particular of the formula IIIa 9 Dye of the formula I, in particular of the formula Ia Dye of the formula III, in particular of the formula IIIa Dye of the formula IV, in particular of the formula IVa 10 Dye of the formula I, in particular of the formula Ia Dye of the formula IV, in particular of the formula IVa 11 Dye of the formula I, in particular of the formula Ia Dye of the formula IV, in particular of the formula IVa Dye of the formula IV, in particular of the formula IVa wherein in the mixtures 6 to 11, the dyes of the general formulas I, II, III and IV (or Ia, IIa, IIIa and IVa) also in the form of their salts, in the form of their metal complexes and / or in the form of the salts of the metal complexes and wherein the mixtures 6, 7, 9 and 11 may also contain a further dyestuff which is among the dyestuffs of the general formulas I, II, III and IV, in particular among the dyestuffs of the general formulas Ia, IIa, IIIa and IVa, their salts and metal complexes and salts of metal complexes and mixtures thereof are selected.

According to one third preferred embodiment of the invention contains the dye mixture is a dye of the general formula II, in particular the general formula IIa, or a salt or metal complex thereof or a salt of a metal complex of II or IIa as a component a) and as component b) another dye of the general Formula II, in particular the general formula IIa, or a salt or metal complex thereof or a salt of a metal complex of II or IIa. In this embodiment, the dye is component a) is different from the dye of component b), and differs especially in the rest Dk, z. B. by the aromatic Ring, which Dk is based, and / or by the nature or arrangement any substituent on the aromatic ring. In addition, the dye mixture the third preferred embodiment still one or two further dyes as component c), which are among the Dyes of the general formulas II, III and IV, in particular among the dyes of the general formulas IIa, IIIa and IVa, salts and metal complexes and salts of metal complexes and mixtures thereof are selected. Furthermore For example, the dye mixture of the third embodiment contain a further dye which is among the dyes of the general formulas I, II, III and IV, in particular among the dyes of the general formulas Ia, IIa, IIIa and IVa, their salts and Metal complexes and the salts of metal complexes and mixtures thereof is selected.

Examples of the third embodiment are the following mixtures 12 to 14: No. Component a) Component b) Component c) 12 Dye of the formula II, in particular of the formula IIa Dye of the formula II, in particular of the formula IIa 13 Dye of the formula II, in particular of the formula IIa Dye of the formula II, in particular of the formula IIa Dye of the formula III, in particular of the formula IIIa 14 Dye of the formula II, in particular of the formula IIa Dye of the formula II, in particular of the formula IIa Dye of the formula IV, in particular of the formula IVa wherein in the mixtures 12 to 14, the dyes of the general formulas II, III and IV (or IIa, IIIa and IVa) may also be present in the form of their salts, in the form of their metal complexes and / or in the form of the salts of the metal complexes and wherein the mixtures 13 and 14 may also contain a further dye which is among the dyes of the general formulas I, II, III and IV, in particular among the dyes of the general formulas Ia, IIa, IIIa and IVa, their salts and metal complexes and the salts of Metal complexes and mixtures thereof is selected.

According to one fourth preferred embodiment of the invention contains the dye mixture is a dye of the general formula II, in particular the general formula IIa, or a salt or metal complex thereof or a salt of a metal complex of II or IIa as a component a) and as component b) another dye which is among the Dyes of the general formulas III and IV, in particular under the dyes of the general formulas IIIa and IVa, their salts and metal complexes and salts of metal complexes and mixtures thereof is selected. In addition, the dye mixture the fourth preferred embodiment still one or two further dyes as component c), which are among the Dyes of the general formulas II, III and IV, in particular among the dyes of the general formulas IIa, IIa and IVa, salts and metal complexes and salts of metal complexes and mixtures thereof are selected. Furthermore For example, the dye mixture of the fourth embodiment contain a further dye which is among the dyes of the general formulas I, II, III and IV, in particular among the dyes of the general formulas Ia, IIa, IIIa and IVa, their salts and Metal complexes and the salts of metal complexes and mixtures thereof is selected.

Examples of the fourth embodiment are the following mixtures 15 to 18: No. Component a) Component b) Component c) 15 Dye of the formula II, in particular of the formula IIa Dye of the formula III, in particular of the formula IIIa 16 Dye of the formula II, in particular of the formula IIa Dye of the formula III, in particular of the formula IIIa Dye of the formula IV, in particular of the formula IVa 17 Dye of the formula II, in particular of the formula IIa Dye of the formula IV, in particular of the formula IVa Dye of the formula IV, in particular of the formula IVa 18 Dye of the formula II, in particular of the formula IIa Dye of the formula IV, in particular of the formula IVa wherein in the mixtures 15 to 18, the dyes of the general formulas II, III and IV (or IIa, IIIa and IVa) may also be present in the form of their salts, in the form of their metal complexes and / or in the form of the salts of the metal complexes and wherein the mixtures 16 and 17 may also contain a further dye which, among the dyes of the general formulas I, II, III and IV, in particular among the dyes of the general formulas Ia, IIa, IIIa and IVa, their salts and metal complexes and the salts of Metal complexes and mixtures thereof is selected.

According to a fifth preferred embodiment of the invention, the dye mixture comprises a dye of the general formula III, in particular of the general formula IIIa, or a salt or metal complex thereof or a salt of a metal complex of III or IIIa as component a) and as component b) another Dye which is selected from the dyes of the general formulas III and IV, in particular among the dyes of the general formulas IIIa and IVa, their salts and metal complexes and the salts of the metal complexes and mixtures thereof. In this case, the dye of the formula III in component a) is different from the dye of the formula III in component B and may differ, for example, in the radical R ¹ , R ² or in the group T. In addition, the dye mixture of the fifth preferred embodiment may contain one or two further dyes as component c), among the dyes of the general formulas II, III and IV, in particular among the dyes of the general formulas IIa, IIa and IVa, their salts and metal complexes and the salts of the metal complexes, and mixtures thereof. In addition, the dye mixture of the fifth embodiment egg nen contain further dye, which is among the dyes of the general formulas I, II, III and IV, especially among the dyes of the general formulas Ia, IIa, IIIa and IVa, their salts and metal complexes and the salts the metal complexes and mixtures thereof is selected.

Examples of the fifth embodiment are the following mixtures 19 to 22: No. Component a) Component b) Component c) 19 Dye of the formula III, in particular of the formula IIIa Dye of the formula IV, in particular of the formula IIIa 20 Dye of the formula III, in particular of the formula IIIa Dye of the formula III, in particular of the formula IVa 21 Dye of the formula III, in particular of the formula IIIa Dye of the formula III, in particular of the formula IIIa Dye of the formula IV, in particular of the formula IVa 22 Dye of the formula III, in particular of the formula IIIa Dye of the formula IV, in particular of the formula IVa Dye of the formula IV, in particular of the formula IVa wherein in the mixtures 19 to 22, the dyes of the general formulas III and IV (or IIIa and IVa) may also be present in the form of their salts, in the form of their metal complexes and / or in the form of the salts of the metal complexes and wherein the mixtures 21 and 22 may also contain a further dye which comprises among the dyes of the general formulas I, II, III and IV, in particular among the dyes of the general formulas Ia, IIa, IIIa and IVa, their salts and metal complexes and the salts of the metal complexes and mixtures thereof is selected.

In the mixtures according to the invention, the quantitative ratio and the type of the respective dye of the formulas I, II, III and IV in each case depending on the desired hue, the expert can estimate the color to be achieved over the colors of the pure dyes in an easy way. As a rule, the weight ratio of the dye of component a) to the total amount of dyes of component b), calculated in each case as free acid, is in the range from 2:98 to 98: 2, in particular in the range from 5:95 to 95: 5 or in the range of 10:90 to 90:10. If the dye mixture contains a component c), the weight ratio of the dye of component a) to the dye of component b), calculated in each case as the free acid, is usually in the range from 2:98 to 98: 2, in particular in the range from 5:95 to 95: 5 or in the range of 10:90 to 90:10. The weight ratio of the dye of component a) to the dye of component c), calculated in each case as the free acid, is then generally in the range from 2:98 to 98: 2, in particular in the range from 5:95 to 95: 5 or in the range of 10:90 to 90:10. In particular, the dyes of components a), b) and optionally c) comprise at least 90% by weight of all the dye components of the mixture or are the sole dye components of the dye mixtures according to the invention. If the dye mixtures contain further dyes, the further dyes are preferably exclusively those of the general formulas I, II, III or IV, in particular those of the formulas Ia, IIa, IIIa or IVa, or their salts, their metal complexes or to the salts of these metal complexes.

The Dye mixtures according to the invention are in special way to dye leather. Accordingly the present invention also relates to the use of dye mixtures, as described herein or set forth in the claims, for dyeing leather, in particular for dyeing under alkaline conditions, d. H. at pH values of at least 7.5, often at pH's in the range of 7.5 to 12, in particular 8 to 11, and more preferably 8.5 to 10.5.

The The invention therefore also relates to a method of dyeing of leather, comprising the treatment of the leather with an aqueous Dye liquor, which has a pH of at least 7.5, often pH values in the range of 7.5 to 12, in particular 8 to 11 and especially preferably 8.5 to 10.5 and a dye mixture according to the invention, as described here. Due to the alkaline pH becomes a fixation of the dyes contained in the mixture reached the leather, since under these conditions, the group A with the amino groups of the leather to form a covalent bond responding.

Around to obtain the alkaline pH for fixation, can use any alkalis and buffer systems become. Examples include alkali metal carbonates and bicarbonates such as sodium carbonate, potassium carbonate and sodium bicarbonate, furthermore alkali metal hydroxides such as sodium hydroxide solution, sodium metasilicate, Pyrophosphates such as sodium or potassium pyrophosphate, tripotassium phosphate, Trisodium phosphate, borax / caustic soda buffer and phosphate buffer.

The be required for fixing the dyes required temperatures advantageously not more than 60 ° C, especially not more than 50 ° C, and more preferably not more than 40 ° C, so that a gentle coloring of the leather possible is. Usually one gets the coloring at temperatures of at least 10 ° C, preferably at least 20 ° C, in particular at least 30 ° C perform around a to achieve sufficient reaction rate and thus the Accelerate dyeing process. Basically but also lower temperatures possible. For Organic tanned leather is the preferred temperature range 15 up to 50 ° C and especially 30 to 40 ° C. For Leather tanned with metal oxides is a temperature range of 15 to 60 ° C and especially from 30 to 50 ° C is preferred.

For a sufficient fixation are usually dependent from pH and temperature treatment periods from 0.5 h to 4 h required. The required treatment periods can be determined by the person skilled in the art simple routine experiments for each used Determine the colorant. especially at strongly alkaline pH values in the range of 9.5 to 11, especially 9.5 to 10.5 the dyeing time preferably not more than 2 h, z. B. 0.5 until 2 h.

at The coloring may also include salts, for example Glauber's salt can be added.

Usually, the dye mixture is used depending on the desired color depth in an amount of at least 0.05 wt .-%, often at least 0.1 wt .-%, based on the shaved weight of the leather used or semi-finished product, wherein the amount specified here the dyes including synthesis salts and optionally available adjusting agent relate. Based on the colored, chemically-organic constituents, dye mixture will usually be used in an amount of at least 0.01% by weight, frequently at least 0.05% by weight, based on the shaved weight of the leather or semi-finished product used. In general, the dyes, calculated as a mixture of organic chemical constituents + synthesis salts and optionally existing adjusting agent, in an amount up to 20 wt .-%, or in an amount of up to 15 wt .-%, calculated as colored use organic chemical ingredients and based on the shaved weight, with larger amounts of dye can be used. To achieve light tones, the dye mixture is typically added in amounts of from 0.05 to 1.5% by weight, in particular especially 0.1 to 1 wt .-%, based on the shaved weight of the leather or semi-finished product and calculated as a mixture of organic chemical components + synthesis salts use. To achieve medium tones, the dye mixture is typically added in amounts of from 0.8 to 10% by weight, in particular from 1 to 8% by weight, based on the shaved weight of the leather or semi-finished product and calculated as a mixture of organic-chemical constituents + Use synthesis salts. To achieve low (intense) tones, the dye mixture is typically in amounts of 6 to 20 wt .-%, in particular 8 to 16 wt .-%, based on the folding weight of the leather or semi-finished product and calculated as a mixture of organic-chemical Use ingredients + synthesis salts.

The aqueous liquor may contain conventional anionic dyeing auxiliaries, nonionic surfactants and wet-end chemicals commonly used for retanning, for example tanning agents, e.g. As polymeric retanning, synthetic retanning, vegetable tanning (Vegetabilgerbstoffe) and fatliquor (fatliquor) and water repellents. For further details on this is on the WO 2005/040490 and the WO 2005/121439 directed.

As retanning come for the process of the invention, all commercial systems in question, for. Vegetable tanning agents, mineral tanning agents, fillers, synthetic tanning agents (synthans), resin tanning agents, polymeric tanning agents, aldehydes, dispersants as in US 5,186,846 described and the like:
As tanning agents, it is also possible to use all commercial tanning agents, for example chrome tanning agents, mineral tanning agents, syntheses, polymer tanning agents and vegetable tanning agents, as described, for example, in US Pat. In Ullmann's Encyclopedia of Industrial Chemistry, Volume A 15 pages 259 to 282 and in particular page 268 ff, 5th edition, (1990), Verlag Chemie Weinheim to be described. Commercially available tanning agents may also be mixtures of the various classes of tanning agents.

When Fatliquoring agents are all common in leather manufacturing Fatulants are used, in particular all commercially available Fatliquors. Naturally, fatliquoring agents contain at least a hydrophobic substance based on a hydrocarbon, for example, on a natural or synthetic Wax, a virgin or synthetic oil or on one native or synthetic fat. As a hydrocarbon base for Fatliquoring agents are also suitable for polyisobutene-based substances.

In the process according to the invention, all water repellents known for leather production can be used as hydrophobizing agents, in particular commercially available systems, as described in US Pat M. Hollstein: Library of Leather, Volume 4-degreasing, fats, hydrophobing of leather, 1983 to be discribed.

In addition to other fatliquoring ingredients, silicone based water repellents and water repellents based on copolymers of alpha olefins with dicarboxylic acid anhydrides have been extensively described, e.g. In EP-A 213480 . WO 95/22627 . WO 98/04748 . EP-A 1087021 and WO 01/68584 , Further examples of water repellents can be found in WO 93/17130 and EP-A 372746 ,

kind and amount of tanning agents, fatliers and water repellents used depend on the type of leather article to be produced Type of tanning (mineral tanning or metal-free tanning), the desired haptic profile and required physical behavior in in a known manner.

Accordingly, tanning agents are used to produce the leather in the following amounts:
Polymer tanning agent (adjusted as a solution) in amounts up to 20 wt .-%, often 3-8 wt .-% and / or
Syntheses (as powders) in amounts up to 30 wt .-%, often 4-12 wt .-%, and / or
Resin tanning agent (calculated as powder) up to 15% by weight, often 3-6% by weight and / or up to 30% by weight of vegetable tanning agent, frequently 4-12% by weight
wherein the total amount of tanning agent is usually up to 40 wt .-%, z. B. 4 to 40 wt .-% and often 10 to 40 wt .-% is, all information is based on the wet weight of the leather.

Fettungs and water repellents are commonly used in the following Amounts used: up to 20 wt .-% fatliquor, often 6-12 wt .-% and up to 20 wt .-% water repellents, often 4-8 wt .-%, each based on the wet weight of the leather.

The staining can be carried out either in one stage or in two stages. In a two-stage dyeing is first in a first stage, the leather with the dye-containing liquor at pH below 7.5, z. PH 3 to 7.4 and preferably at pH values in the range of 4 to 7.4. This step serves to uniformly distribute the dye in the leather cross section. Afterwards one is in the second stage at pH's of at least 8, e.g. B. 8 to 11, especially 8.5 to 10.5 and especially 8.5 to 10 fix the dye in the manner described above. It is also possible to carry out the staining in a one-step process without preceding a distribution stage of the fixing step.

Possibly you will be following the dyeing a washing process Do not carry chemical-bound dye as well impurities contained in the dye, for example dyes, which do not contain a group A to remove. This washing process However, this is not absolutely necessary, because in many cases already a quantitative or nearly quantitative fixation of the Dye is present. If you follow a washing process, Will you dye the leather 1 or more times after dyeing, z. B. 1 to 6 times and especially 1 to 4 times with water. The amount of water is usually not more than 300 wt .-%, based on the shaved weight of the semi-finished product, e.g. B. 100 to 300 wt .-% amount. The washing time of the individual washing step is usually 5 to 60 min. and especially 10 to 30 minute be.

Nonionic, anionic, cationic or even zwitterionic auxiliaries can also be used in the washing process. Preference is given to commercially available ionic auxiliaries z. B based on polyvinylformamides, polyvinylpyrolidones, vinylpyrolidone / vinylimidazole copolymers or on condensates of dicarboxylic acid or dicarboxylic anhydrides with amines or of naphthalenesulfonic acid with formaldehyde based. Such auxiliaries are for example in EP 0459 168 . EP 0 520 182 . US 5,342,916 and US 5,186,846 described.

Of the Use of auxiliaries is particularly useful when in the dye mixture colored by-products are included or if during the fixation colored by-products have arisen. Set the tools sure, that's not more than three times, maybe only needs to be washed twice, or ideally only once, to all colored secondary components quantitatively or nearly quantitav to remove.

The leather dyeing including retanning, fatliquoring and aftertreatment is otherwise carried out in a manner known per se, for example by dyeing in the jar or in the reel. Such methods are described in detail in the prior art, e.g. In: "Library of the Leather", Volume 3 (tanning, tanning and retanning) [1985], Volume 4 (degreasing, fats and hydrophobing in leather production) [1987] & Volume 5 (Dyeing leather) [1987] Umschau Verlag ; "Leather Technicians Handbook", 1983, by JH Sharphouse, published by Leather Producers Association ; and "Fundamentals of Leather Manufacturing", 1993, by E. Heidenmann, published by Eduard Roether KG ,

The Staining is usually done after pre-tanning, d. H. before, during or after retanning. The coloring can be in the same bath as the retannage as well as in a separate bathroom. Preferably, the Staining before retanning. Preferably takes place after the coloring and before retanning and greasing one or several of the washing steps described above.

the Dyeing and Nachgerbvorgang closes in the Usually a greasing process to the desired haptic Adjust the properties of the leather. Retanning and greasing can However, also be carried out in one process step. The greasing process can be performed at any point in the wet-end process be carried out, preferred is the implementation at the end of the weather process.

In usually one gets both the fatliquoring and the retannage on Fix the end of the process by acidification. D. H. to Coloring and optionally retanning and greasing follows a final acidification. Usually will to acidify the pH of the aqueous treatment bath by adding an acid, in particular formic acid, to a value below 3.7.

With the method of the invention can basically all leather types, d. H. not retanned Semi-finished products such as metal oxide-tanned leather (wet-blue at Chromium oxide tanning and wet white with alumina tanning) and organic, z. B. aldehyde-tanned leather (wet-white) bwz. vegetable tanned leather, and retanned semi-finished products such as bark or crust leather to be colored.

The inventive method allows in particular the production of dyed leathers for any Leather articles, for example in the field of shoes, clothing, Automobile, glove and furniture. The invention Process also allows the manufacture of pocket leather and of Reptile leather for accessories. The setting of for the respective leather article required haptic, mechanical and physical properties in a conventional manner by a selection suitable for the respective article of auxiliaries, fatliquoring agents, water repellents and retanning agents.

The dyed by the process according to the invention Leather is also characterized by very high color depth or intense Dyes by an excellent fastness level and high Equality. Particularly outstanding are rubbing fastness and in particular washing, perspiration and migration fastnesses, which is not the case with conventionally dyed leathers or only in to a much lesser extent. The after dyed the process of the invention Leather show in migration fastness tests even in high humidity and high temperatures, d. H. above 50 ° C, z. B. 60 to 100 ° C no or almost no soiling of the contact material.

qualitative and quantitative determination via UV / VIS spectroscopy and HPLC show that with the dyes of the invention the formula fixes between 70 and 100% and frequently above 80% or even 90% can be achieved.

The following examples are intended to illustrate the invention without restricting it: Dyeing instructions:
All parts in parts are to be understood as parts by weight. All information regarding tannins, water repellents, grease and auxiliary agents refer to commercial products (merchandise). The information relating to the dye refers to the total amount of colored organic-chemical constituents, if appropriate production-related salts (synthesis salts) and optionally existing adjusting agents.

The Fixierausbeute was qualitatively by HPLC and quantitative means UV-VIS spectroscopic examination of the dyeing liquor determined. Here are 5 ml samples after staining (pH <7), after 60 min, 120 min, 180 min fixation (pH> 7) and taken from each washing water liquor and with 1 ml of formic acid solution adjusted to pH 3-4. The samples were recorded by HPLC Investigated dye and its hydrolysis products out. The investigation carried out on HPLC columns Nucleodur C18 Gravity 3μ, CC70 / 2 and Hypersil 120-5 ODS, CC100 / 2 from Macherey-Nagel. The eluents used were acetonitrile / buffer (1.6 g tetrabutyl ammonium hydrogensulfate, 6 g of dipotassium hydrogen phosphate trihydrate in 1 L of water).

• Schweißechtheit: in Anlehnung an Veslic C4260
• Waschechtheit: in Anlehnung an DIN EN ISO 15703
• Migrationsechtheit: in Anlehnung an DIN EN ISO 15701 , sowie durch 16 h Lagern bei 85°C in einer Feuchte von 95% unter ansonsten analogen Bedingungen zu DIN EN ISO 15701
• Reibechtheit: in Anlehnung an DIN EN ISO 105–X12 (Crockmeter, Reibung mit Baumwollgewebe) sowie in Anlehnung an DIN EN ISO 11640 (Veslic, Reibung mit Filz)
• Maeser: in Anlehnung an ASTM D 2099
• Penetrometer: in Anlehnung an DIN EN ISO 5403
• Wasserdampfdurchlässigkeit: in Anlehnung an DIN EN ISO 14268
• Dauerbiegefestigkeit: in Anlehnung an DIN EN ISO 5402
• Stichausreißversuch: in Anlehnung an DIN 5331
• Weiterreißversuch: in Anlehnung an DIN EN ISO 3377
• Zugfestigkeit: in Anlehnung an DIN EN ISO 3376

The determination of the fastness properties was carried out according to the following internationally recognized standards:

• Perspiration-fastness: in accordance with Veslic C4260
• Wash fastness: in accordance with DIN EN ISO 15703
• Migration fastness: based on DIN EN ISO 15701 , and by 16 h storage at 85 ° C in a humidity of 95% under otherwise analogous conditions too DIN EN ISO 15701
• Rubbing fastness: in accordance with DIN EN ISO 105-X12 (Crockmeter, friction with cotton fabric) and in reference to DIN EN ISO 11640 (Veslic, friction with felt)
• Maeser: in reference to ASTM D 2099
• Penetrometer: based on DIN EN ISO 5403
• Water vapor permeability: in accordance with DIN EN ISO 14268
• Bending fatigue strength: based on DIN EN ISO 5402
• Stichausreißversuch: in reference to DIN 5331
• Tearing test: based on DIN EN ISO 3377
• Tensile strength: in accordance with DIN EN ISO 3376

Main ingredients of commercial Fatliquoring agent (F):

• F1: aqueous emulsion of vegetable oils and sulfited fish oils.
• F2: aqueous preparation based on the sodium salt an anionic vinyl polymer and a nonionic surfactant (ethoxylated oleic acid).
• F3: aqueous preparation based on modified fatty acids.
• F4: aqueous preparation based on synthetic oils and phosphoric esters of ethoxylated fatty alcohols containing Fatty alcohol sulfonates and butyl diglycol.
• F5: aqueous preparation based on bisulfated fish oils (Sodium salts) and the hydrolysates of sulfochlorinated paraffin oils, ethoxylated isotridecanol.
• F6: aqueous preparation based on the sodium salts sulfonated vegetable oils and modified synthetic oils and polymer.
• F7: aqueous preparation based on sulfated fatty acid esters.
• F8: aqueous preparation based on nonionic Surfactants, sulfited oils (sodium salt).
• F9: Mixture of surfactants based on paraffin sulfonate, alkyl phosphate and monoalkyl sulfate in the form of a preparation of the ammonium salts in solvent / water.
• F10: aqueous preparation of a sulfited, oxidized fish oil
• F11: anionic combination of sulfited esters based on renewable raw materials

Main ingredients of commercial Hydrophobizing agent (H):

• H1: aqueous preparation based on paraffins, functionalized polysiloxanes, N-Oleoylsarkosin Na salt.
• H2: aqueous preparation based on paraffins, modified silicones, N-Oleoylsarcosine-Na-salt
• H3: aqueous preparation based on paraffins and anionic surfactants.
• H4: aqueous preparation based on functionalized Polysiloxanes and an emulsifier system
• H5: aqueous preparation based on modified Silicone with a salt of a vinyl polymer.
• H6: aqueous preparation based on functionalized Polysiloxane with anionic surfactants.
• H7: aqueous preparation based on functionalized Polysiloxane.
• H8: Aqueous preparation based on paraffins and the sodium salts of anionic surfactants.

Of the used in the following with the retanning agents and aids Term "mixture" can mean both that the mixture by mixing the compo nents at room temperature and normal pressure as well as by mixing at elevated temperatures and pressing for a short to longer Period is made.

Main ingredients of commercial Retanning agents (G):

• G1: condensation product of phenolsulfonic acid, Formaldehyde and aniline in the form of the sodium salt.
• G2: Aqueous preparation of the sodium salt of a condensation product from phenolsulfonic acid, formaldehyde and aniline.
• G3: Aqueous preparation of a mixture of a sodium / ammonium salt a condensation product of phenolsulfonic acid, formaldehyde, Melamine, urea, and aniline with an amphoteric copolymer Base of acrylic acid and a basic monomer.
• G4: aqueous preparation of the ammonium salt of a condensation product of phenol, phenolsulfonic acid and formaldehyde.
• G5: sodium salt of a condensation product based on dihydroxydiphenylsulfone, Phenolsulfonic acid, urea and formaldehyde.
• G6: aqueous solution of a sodium / ammonium salt a condensation product based on dihydroxydiphenylsulfone, Phenolsulfonic acid, urea and formaldehyde.
• G7: high molecular weight condensation product based on dihydroxydiphenylsulfone, Phenolsulfonic acid, urea and formaldehyde in the form of Sodium salt.
• G8: Aqueous preparation based on a mixture of Sodium / ammonium salt of a low molecular weight condensation product based on dihydroxydiphenylsulfone, urea and formaldehyde with a low molecular weight condensation product of diphenylsulfone with formaldehyde.
• G9: Fat tanning agent based on a modified paraffin (C ₁₆ -C ₃₄ -alkyl sulfochloride).
• G10: Aqueous preparation based on a copolymer of acrylic acid with acrylonitrile and an amine.
• G11: Mixture of a naphthalenesulfonic acid-melamine condensate with hydroxymethanesulfonate and urea.
• G12: 24% strength by weight solution of glutaric dialdehyde in water.
• G13: 50% strength by weight solution of glutaric dialdehyde in water.
• G14: Aqueous, solvent-containing preparation based on an aldehyde-based polymeric tanning agent (condensation product formaldehyde and glutaric dialdehyde).
• G15: Aqueous preparation based on a copolymer of acrylic acid with acrylonitrile.
• G16: Aqueous preparation based on a low molecular weight Polyacrylic acid (Mn <8000, Number average).
• G17: Aqueous preparation based on a high molecular weight Polyacrylic acid (Mn> 40000, Number average).
• G18: Aqueous preparation based on polymethacrylic acid.
• G19: Aqueous preparation of a copolymer of maleic acid and styrene
• G20: Chromsyntan (mixture of a condensation product based on an aromatic oligosulfone and a chromium preparation)
• G21: Tara.
• G22: Mimosa.
• G23: Chestnut.
• G24: weakly masked chrome tanning agent with a Cr ₂ O ₃ content of 24% by weight and a base citation of 40%.
• G25: liquid preparation of tetrakis (hydroxymethyl) phosphonium chloride and sulfate
• G26: 4,4-dimethyl-1,3-oxazolidine.
• G27: 1-aza-3,7-dioxybicyclo-5-ethyl [3.3.0] octane.
• G28: Mixture of a polycondensation product based on Urea and formaldehyde with a polycondensation on Base of phenol and formaldehyde.
• G29; 30% strength by weight aqueous formaldehyde solution.
• G30: mineral tanning mixture based on aluminum hydroxide in an amount of 14% by weight (calculated as Al ₂ O ₃ ) and 3% by weight of chromium salts (calculated as Cr ₂ O ₃ )
• G31: Quebracho
• G32: Mixture of a urea and formaldehyde-based condensation product with sodium salts of organic sulfonic acids
• G33: Basic aluminum complex
• G34: Basic chromium (III) sulfate
• G35: Aqueous emulsion of a polymer-based fatty tanning agent

Main ingredients of commercial Auxiliary agent (HM):

• HM1: Mixture of hydroxymethanesulfonate with the sodium salt a condensation product of naphthalenesulfonic acid, Urea and formaldehyde.
• HM2: mixture of ethoxylated alkylamines (C ₁₆ -C ₁₈ ).
• HM3: aqueous preparation of a partially hydrolyzed Poly-N-vinylformamide, slightly cationic.
• HM4: aqueous preparation of an anionically modified Copolymer.
• HM5: hydroxymethylated urea.
• HM6: Mixture based on aromatic sulfonic acids Sodium salts, phenol, formaldehyde and urea.
• HM7: aqueous preparation of a cationic, amino-containing Polycondensate.
• HM8: EDTA = ethylenediaminetetraacetic acid dianion
• HM9: Alkoxylated alcohol with emulsifying properties
• HM10: complexing decalcifying agent from sueren Salts of polyvalent aromatic acids
• HM11: sodium salt of an alkanesulfonate
• HM12: bacterial protease
• HM13: fungicides

The The following dyeing examples are to be understood as examples and it can be any dye mixture of the invention according to the instructions given here for leather dyeing be used. In the following examples are all quantities in parts by weight unless otherwise stated becomes.

Example 1:

One Leather piece of 100 parts by weight on usual Way of chrome-tanned cowhide of the folding thickness 1,8-2,0 mm was in one with 200 parts of water and 0.2 parts of formic acid filled Wacker keg 10 minutes at 35 ° C and then in one of 100 parts water, 4 parts Chrome Tanning G24 and 4 parts resin tanning G28 for 30 minutes Retested at 35 ° C. To Nachgerbflotte was 1 part of sodium formate Add and after 60 minutes reaches a pH of 3.8. After that was prepared by adding 0.3 part of sodium bicarbonate after a Walk time of 30 minutes reaches a pH of 4.2. After an encore of another 0.3 part of sodium bicarbonate and a Walk time 60 minutes, a liquor pH of 4.3 was achieved. It was after-chromated for another 12 hours, then the liquor was drained off and with 200 parts of water at 35 ° C Washed for 10 minutes.

The so nachchromierten leather were put on Bock, ausgereckt, at 60 ° C for 2-3 minutes vacuum dried, slightly tension-frame dried for 2-3 hours at room temperature, Staked, folded to 1.8 mm and with 220-240 mm sandpaper sanded as nubuck.

The Nubuck crust leather was washed twice with 200 parts of water at 40 ° C washed for 10 minutes and then in a neutralized for 5 minutes from 100 parts of water and 1.5 parts of sodium formate, after addition of 1.5 parts of sodium bicarbonate was added Driven for 10 minutes, after addition of another 1.5 parts of sodium bicarbonate was neutralized for another 15 minutes. To neutralization fleet were At pH 7.5, 4 parts of dye I.38 and 4 parts of dye III.5 were added and stained for 40 minutes at pH 6.8. By portions Addition of a total of 8.5 parts of sodium carbonate, suspended with water in the ratio 1:10, was used to fix the pH adjusted between 9.4 and 9.9 and at 80 minutes 40 ° C. Subsequent was with 10 minutes Water rinsed and 2 times with 300 parts of water at 40 ° C. washed.

In a freshly prepared fleet of 100 parts of water and 0.8 parts Formic acid became a pH within 30 minutes of 5.5, after adding 50 parts of 60 ° C hot Water was added with 6.5 parts of hydrophilizing agent H1, 1.5 parts of the hydrophobicizing agent H4 and 0.3 parts of the polymeric auxiliary HM4 greased at 50 ° C for 60 minutes. To complete the wasting of the greasing became 50 parts 60 ° C hot Water was added and drummed for a further 10 minutes. Subsequently acidified by portionwise addition of 6 parts of formic acid down to 3.5 and walked 55 minutes.

To a liquor of 150 parts of water and 0.4 parts of formic acid After a 5 minute walk, 4 parts of the chrome tanning agent became G24 and drummed for 90 minutes at 30 ° C. At the end was added twice with 200 parts of water at 30 ° C Washed for 15 minutes. The dyed and hydrophobic Nubuck leather was put on a bench, stretched out, at room temperature span frame dried, conditioned, staked, stretched and brushed.

It were color depth hydrophobized nubuck shoe upper leather in the shade reddish Medium brown, which is particularly characterized by their color depths Leather cross section, the high levelness of coloring and the excellent washing, perspiration and migration fastnesses distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 6 parts I.32 2 parts III.17 Yellowish middle brown 8 parts I.13 1.4 parts I.2 0.6 parts III.1 Reddish medium brown 0.9 parts II.6 3.9 parts III.7 1.2 parts IV.6 Reddish medium brown

Example 2:

One Leather piece of 100 parts by weight on usual Way of chrome-tanned cowhide of the folding thickness 1,8-2,0 mm was in one with 200 parts of water and 0.2 parts of formic acid filled Wacker keg 10 minutes at 35 ° C and then in one of 100 parts of water and 2 parts Natriumformiat existing liquor neutralized for 10 minutes at 35 ° C. To Neutralisationsflotte were 0.5 parts of sodium bicarbonate given and drummed for another 30 minutes. After adding 5 parts Polymer tanning agent G18 was retanned for 50 minutes. To Nachgerbflotte 5 parts of retanning agent G1 were added and drummed for 40 minutes. The Nachgerbflotte were 2 parts of water repellent H3 and 0.2 Parts of auxiliary HM4 added and greased for 60 minutes. Then acidified by adding portions from 1 part of formic acid to 3.8 and walked for 40 minutes. After draining the fleet was with 200 parts of water at 45 ° C. Washed for 10 minutes.

The so fed up leather were put on Bock, outstretched, at 60 ° C for 2-3 minutes vacuum dried, slightly tension-frame dried for 2-3 hours at room temperature, Staked, rebinded to 1.8-2.0 mm and with 220-240 sanded sandpaper as nubuck.

The Nubuck crust leather was washed twice with 200 parts of water at 40 ° C washed for 10 minutes and then in a Liquor from 100 parts of water and 1.5 parts of sodium formate for 5 minutes neutralized, after addition of 1.5 parts of sodium bicarbonate was drummed for another 10 minutes, after adding another 2 parts Sodium hydrogen carbonate was neutralized after 15 minutes. to Neutralization liquor at pH 7.5 4 parts of dye I.38 and 4 parts of dye II.6 and 2 parts of dyestuff IV.21 and 40 Stained at pH 6.8 minutes. By adding in portions of a total of 5 parts of sodium carbonate, suspended with water in the ratio 1:10, was used to fix the pH between Set 9.4 and 10.1 and tumbled for 80 minutes at 40 ° C. The following was rinsed with water for 10 minutes and washed twice with 300 parts of water at 40 ° C.

In a freshly prepared fleet of 100 parts of water and 0.8 parts Formic acid became a pH within 30 minutes of 5.5, after adding 50 parts of 60 ° C hot Water was added with 6.5 parts of hydrophilizing agent H1, 1.5 parts of the hydrophobicizing agent H4 and 0.3 parts of the polymeric auxiliary HM4 greased at 50 ° C for 60 minutes. To complete the wasting of the greasing became 50 parts 60 ° C hot Water was added and drummed for a further 10 minutes. Subsequently acidified by portionwise addition of 6 parts of formic acid down to 3.5 and walked 55 minutes.

To a liquor of 150 parts of water and 0.4 parts of formic acid was added after a walk time of 5 4 parts of the chrome tanning material G24 were added and drummed for 90 minutes at 30 ° C. Finally, it was washed twice with 200 parts of water at 30 ° C for 15 minutes. The dyed and hydrophobized nubuck leather was placed on a pad, stretched out, frame-dried at room temperature, conditioned, staked, stretched and brushed.

It were color depth hydrophobic Nubukschuhoberleder in color Bordo especially distinguished by their color-deep leather cross-section, the high levelness of the coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 5 parts II.4 2.5 parts IV.16 2.5 parts IV.11 bordo 6.4 parts II.6 1.6 parts IV.6 bordo

Example 3:

One Leather piece of 100 parts by weight on usual Way chrome-tanned pigskin of the folding thickness 0.6 mm was in a with 300 parts of water Wackerfass 20 minutes at 35 ° C washed and then in one of 150 parts of water, 4 parts of chrome tanning material G24 and 2 parts of tanning material G1 for 20 minutes retanned at 30 ° C and pH 3.2. To Nachgerbflotte was added 2 parts of fatliquor F1 and 40 minutes at 30 ° C greased. By addition of 1 part of sodium formate became after 60 minutes Walk time reaches a pH of 3.7.

to Nachgerbflotte were given 2 parts of polymeric tanning G16 and more Retanned for 60 minutes. After addition of 0.75 parts of sodium bicarbonate and a walk time of 90 minutes became a liquor pH of Reached 4.3. Then the fleet was drained and the leather, which had been so chromed, was put on a pad, wet-tensioned and sanded twice with 400 mm sandpaper as velor.

The Pork velor crust leather was made in one of 350 parts water and 2 parts of sodium formate neutralized for 5 minutes, after addition of 2 parts of sodium bicarbonate was drummed for another 10 minutes, after Addition of another 3 parts of sodium hydrogen carbonate was after Neutralized for 15 minutes. The neutralization liquor was at pH 7.3, 6 parts of dye I.46 and 14 parts of dye II.26 and stained for 40 minutes at pH 7.0. By portions Add a total of 12 parts of sodium carbonate, suspended with water in the ratio 1:10, was used to fix the pH between Set at 9.3 and 10.2 and tumbled at 40 ° C for 80 minutes. Subsequent was 3 times with 300 parts of water at 40 ° C washed.

In a freshly prepared fleet of 150 parts water, 12 parts of fatliquoring agent F1 and 3 parts of fatliquoring agent F2 became 60 Greased for 40 minutes at 40 ° C. To complete the wasting of the greasing became 200 parts 60 ° C hot Water was added and drummed for a further 10 minutes. Subsequently acidified by portionwise addition of 8 parts of formic acid down to 3.6 and walked 70 minutes. To the fleet were 2 parts of the Hydrophobic H4 added and drummed for 60 minutes.

To Drain the fleet was still twice with 200 parts of water washed at 30 ° C for 15 minutes.

The dyed suede leather was put on a goat, outstretched, at room temperature, tension-frame-dried, conditioned, staked, mellow and tense.

It were color-deep suede leather in the color red, characterized by their color-deep leather cross section, the high levelness of coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 11 parts I.48 11.5 parts II.14 2.5 parts IV.18 red-brown 14 parts I.30 3 parts II.9 3 parts IV.12 Reddish dark brown 17.6 parts I.38 2.2 parts II.6 2.2 parts IV.6 Reddish dark brown

Example 4:

One Leather piece of 100 parts by weight on usual Way chrome-tanned cowhide of the creasing strength 2.0-2.2 mm was in one with 200 parts of water and 0.2 parts of formic acid filled Wacker keg 10 minutes at 35 ° C and then in one of 100 parts of water and 2 parts Aldehyde tanning material G13 drummed for 60 minutes at 35 ° C. To the fleet 2 parts of sodium formate were added after a walk time of 20 1.5 minutes of sodium bicarbonate was added after 10 minutes Another 1.5 parts of sodium bicarbonate were added and continued Neutralized for 15 minutes at 35 ° C. After that, the deacidification fleet had one pH of 7.3. The neutralization liquor was 4.2 parts Dye I.43 and 1 part of dye I.5 and 0.8 part of dye IV.1 given. After a 40 minute walk, the mixture was added by portions Addition of a total of 6 parts of sodium carbonate, with suspended Water in the ratio 1:10, became in the fleet a pH between 9.2 and 10.1 and it was 90 minutes at 35 ° C fulled. It was then rinsed for 10 minutes and washed twice with 300 parts of water at 40 ° C. In a freshly prepared fleet of 150 parts water and 1.2 parts Formic acid was adjusted to a pH of 6.3.

The such dyed leather was in a freshly prepared Fleet of 80 parts of water and 3 parts of the hydrophobing agent H3 drummed for 5 minutes at 45 ° C. Then staggered the liquor with 5 parts of the hydrophobicizing fatliquoring agent H5.

To For 15 minutes, 5 parts of the polymer tanning agent were added G18 and 0.5 parts of the complexing agent HM8 added and 40 minutes retanned. The Nachgerbflotte were 5 parts Vegetabilgerbstoff G31 and 1.5 parts of the resin tanning G28 added 20 minutes walkted. After addition of another 5 parts vegetable tanning material G31, 0.5 parts of the complexing agent HM8 and 1.5 parts of the resin tanning agent G28 retanned for another 40 minutes. The Nachgerbflotte were 2 parts Hydrophobic agent H3, 4 parts of Vegetabilgerbstoffs G31, 4 parts of the vegetable tanning material G22 and 2 parts of the resin tanning material G28 and 20 minutes drummed.

to Nachgerbflotte were 3 parts of the hydrophobizing agent H1, 1.5 parts of the hydrophobizing agent H3, 1 part of the fatliquoring agent F8 and 0.3 Parts of the auxiliary HM4 given and greased for 90 minutes. to Completion of fatigue was 70 Add portions of water and tumble for a further 10 minutes. Subsequently acidified by portionwise addition of 3 parts of formic acid to pH 3.8 and walktin 40 minutes. The so dyed, retanned and greased leather was stored overnight on Bock, then set out, vacuumed at 50 ° C. for 2 minutes, hang-dried at room temperature, conditioned, staked and vacuum dried at 50 ° C for 2 minutes.

It color-deep compact shoe upper leather in olive brown color was obtained characterized by their color-deep leather cross section, the high levelness of coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 4.8 parts I.38 0.6 parts III.7 0.6 parts IV.5 olive brown 1.2 parts I.12 4.2 parts III.8 0.6 parts IV.13 Dark olive brown 0.3 parts I.2 0.1 parts III.22 5.6 parts IV.2 Dark olive green

Example 5:

A piece of leather of 100 parts by weight of a conventionally chrome-tanned cattle-leather nip of 1.4-1.6 mm thickness was washed in 300 parts of water for 10 minutes at 35 ° C and then in 100 parts of water, 5 parts of chrome tanning material G24 and 4 parts of resin tanning material G28 retanned for 30 minutes at 30 ° C. To Nachgerbflotte 1.5 parts of sodium formate was added and reached after 30 minutes, a pH of 3.7. To the liquor was added 5 parts of polymer tanning material G16 and tumbled for 60 minutes. After that 100 parts of water were added and drummed for 30 minutes. By adding 0.3 part of sodium bicarbonate, a pH of 4.2 was achieved after a walk time of 30 minutes. After addition of a further 0.3 part of sodium bicarbonate and a walk time of 60 minutes, a liquor pH of 4.3 was obtained. It was nachchromiert for another 12 hours. Subsequently, the liquor was drained and washed with 300 parts of water at 40 ° C for 10 minutes.

The so nachchromierten leather were in one of 100 parts of water and 1.5 parts sodium formate existing liquor neutralized for 5 minutes, after addition of 1.5 parts of sodium bicarbonate was added Driven for 10 minutes, after addition of another 1.5 parts of sodium bicarbonate was neutralized for another 15 minutes. To neutralization fleet At pH 7.5, 9 parts of dye III..7 and 0.4 parts of dye IV.7 and 0.6 parts of Dye IV.3 and 40 minutes at pH 7,0 dyed. By adding in portions of a total of 8 Divide sodium carbonate, suspended with water in the ratio 1:10, was set to fix the pH between 9.3 and 10.0 and drummed for 80 minutes at 40 ° C. subsequent was rinsed with water for 10 minutes and 2 times with 300 parts Washed water at 40 ° C.

In a freshly prepared fleet of 100 parts of water and 0.8 parts Formic acid became a pH within 15 minutes set by 6.5. The liquors were 10 parts of the hydrophobizing agent H2, 2 parts of the hydrophobizing agent H8 and 1 part of the auxiliary HM4 and greased at 45 ° C for 80 minutes. To complete the wasting of the greasing became 100 parts 60 ° C hot Water added and drummed for 20 minutes. Then acidified by adding portions of 7 parts of formic acid down to 3.7 and walked 45 minutes.

To Draining the liquor was washed for 10 minutes with 300 parts of water.

In a freshly prepared fleet of 100 parts water, 2 parts Chrome tanning G24 and 3 parts of mineral tanning G30 became 90 minutes drummed at 30 ° C.

To Draining the liquor was done twice with 300 parts each of water washed at 30 ° C for 10 minutes. The dyed and hydrophobized split velor leather was put on a bench, stretched out, vacuum dried at 45 ° C for 3 minutes, at room temperature tension frame dried, conditioned, staked, velor ground, Dusted, milled, tense and brushed.

It were color depth hydrophobic split velor upper in color yellowish middle brown, which is particularly distinguished by its deep leather cross section, the high levelness of coloring and the excellent washing, perspiration and migration fastnesses distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 7.5 parts I.38 2.5 parts III.7 Yellowish middle brown 3.6 parts I.16 5.9 parts I.4 2.5 parts III.17 Yellowish middle brown 2 parts I.12 5.6 parts I.4 2.4 parts III.17 Yellowish tan

Example 6:

One Leather piece of 100 parts by weight on usual Way chrome-tanned goat leather of the folding thickness 0.6-0.7 mm was in one with 300 parts of water and 0.3 parts of formic acid filled Wacker keg 10 minutes at 35 ° C and then in one of 150 parts of water and 2 parts Natriumformiat existing liquor neutralized for 10 minutes at 40 ° C. To Neutralisationsflotte were 0.3 parts of sodium bicarbonate given and drummed for another 40 minutes. After adding 5 parts Polymer tanning agent G18 was retanned for 40 minutes. To Nachgerbflotte 10 parts retanning agent G3 and 2 parts fatliquoring agent F1 were added and 60 minutes rolled. The Nachgerbflotte were 100 parts of water added and retanned for another 30 minutes. By adding 0.5 parts of sodium bicarbonate became within 60 minutes reached a pH of 4.8. It was for another 12 hours retanned. Subsequently, the fleet was drained and Washed twice with 300 parts of water at 40 ° C for 15 minutes.

The so fed up leather were put on Bock, outstretched, at 30 ° C tension frame dried, conditioned, staked, at 60 ° C vacuum dried for 2 minutes, ground as a velor, dedusted and weighed.

The The following quantities of the nachgerbprodukte refer to the Dry weight of the goat crust.

The Goat suede crust leather was treated with 1000 parts of water at 40 ° C washed for 10 minutes and then in a from 500 parts of water and 1.5 parts of auxiliary HM 7 5 minutes fulled. Subsequently, 1.5 parts of sodium formate were added and neutralized for 5 minutes, after adding 2 parts of sodium bicarbonate was drummed for 10 minutes, after adding 1 more portion of sodium bicarbonate was neutralized after 10 minutes. To neutralization fleet were at pH 7.7 8 parts of dye II.8 and 8 parts of dye III.6 and 4 parts of dye IV.17 and stained for 40 minutes at pH 7.3. By adding in portions a total of 13 parts of sodium carbonate, suspended with water in the ratio 1:10, became the Fixing the pH adjusted between 9.6 and 10.3 and 80 minutes long at 40 ° C. Subsequent became 10 Rinsed for a few minutes with water and 2 times with 800 parts of water washed at 40 ° C.

In a freshly prepared liquor consisting of 200 parts of water and 1.1 parts Formic acid became pH within 55 minutes set by 5.9.

To Drain the fleet was in 400 parts of water, 15 parts of greasy Gerbstoff G9, 8 parts water repellent H2, 5 parts water repellent H4 and 0.5 parts of auxiliary HM4 greased for 40 minutes. After portionwise Addition of 0.8 part of formic acid was within Set a pH of 4.8 for 20 minutes.

to complete wasting of greasing, 200 parts were 60 ° C added hot water and drummed for another 10 minutes. The liquor was 2 parts fatliquor F8, 2 parts fatliquoring agent F3 and 0.5 parts of auxiliary HM4 added and greased for 60 minutes. By adding portions of 4.5 parts of formic acid set a pH of 3.3 within 45 minutes.

To Drain the fleet was in a freshly scheduled fleet 500 parts of water and 3 parts of chrome tanning material G24 for 90 minutes 30 nachchromiert. At the end was still twice with 800 each Divide water at 30 ° C for 10 minutes. The dyed Goatskin leather was put on a bench, stretched out, at room temperature span frame dried, conditioned, staked, at 70% relative Moist, milled and brushed.

It were color deep washable goat suede in the color reddish brown especially distinguished by their color-deep leather cross-section, the high levelness of the coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 13 parts II.20 3 parts III.16 4 parts IV.17 red-brown 8 parts I.28 8 parts II.6 4 parts IV.4 red-brown

Example 7

One Leather piece of 100 parts by weight on usual Way chrome-tanned cowhide with a thickness of 1.8 mm was washed in 200 parts of water for 10 minutes at 35 ° C and then in one of 100 parts of water and 2 parts Natriumformiat existing fleet drummed 10 minutes. To the fleet 0.5 parts of sodium bicarbonate and 3 parts of HM4 were added and neutralized for 60 minutes. After draining the fleet was in 200 parts of water for 10 minutes at 45 ° C.

In a freshly prepared fleet of 100 parts water and 1 part Polymer tanning agent G19 was retanned for 40 minutes at 45 ° C. To Nachgerbflotte were 3 parts Gerbstoff G7, 4 parts tannin G32 and 3 parts of tannin G11 and drummed for 90 minutes. By was added portionwise 1.5 parts of formic acid set a pH of 3.7 within 70 minutes. Subsequently was washed with 200 parts of water for 10 minutes at 40 ° C.

In a freshly prepared fleet of 100 parts of water and 1.5 parts Sodium formate was drummed for 5 minutes. To neutralization fleet 1.5 parts of sodium bicarbonate were added and after 10 minutes more were added 2 parts of sodium bicarbonate added and another 15 minutes at 40 ° C. neutralized.

to Neutralization liquor was 2.4 parts of dye II.8 and 2.4 parts Dye III.6 and 1.2 parts of dyestuff IV.17 and 40 minutes stained at pH 7.5. By adding portions of 8 parts Sodium carbonate, suspended with water in the ratio 1:10, was set to fix the pH between 9.7 and 10.2 and drummed for 120 minutes at 40 ° C. Subsequently Followed 3 times a 15 minute washing operation in 300 parts Water at 40 ° C. In a freshly scheduled fleet 100 parts of water and 2 parts of polymer tanning agent G19 were added Retanned for 10 minutes at 45 ° C. To the fleet were 3 parts Fatliquor F7 and 3 parts of fatliquor F4 are added and 40 minutes greased. Finally, it was acidified by adding in portions of 4 parts of formic acid within 50 minutes pH 3.5. After draining the fleet, the dyed, rinsed and greased leather rinsed for 10 minutes and then put on a box, stretched out, at 45 ° C Vacuum dried for 3 minutes, dried, conditioned, primed and vacuum dried at 50 ° C for 2 minutes. There were Shoe upper leather in the color reddish brown get that special through their color-deep leather cross-section, the high levelness coloring and the excellent washing, welding and and migration fastnesses.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 0.9 parts I.38 3.9 parts II.6 1.2 parts IV.6 red-brown 3.9 parts II.20 0.9 parts III.16 1.2 parts IV.17 red-brown

Example 8

One Leather piece of 100 parts by weight on usual Way chrome-tanned cowhide the thickness of 1.4 mm was in one of 200 parts of water and 0.2 parts of formic acid existing fleet at 35 ° C for 10 minutes. In a consisting of 100 parts of water and 1.5 parts of sodium formate Fleet was drummed 10 minutes. To the liquor were added 0.3 parts of sodium bicarbonate and neutralized for 50 minutes. After draining the fleet was in 200 parts of water for 10 minutes at 45 ° C.

In a freshly prepared liquor from 100 parts of water, 1 part of water repellents H3 and 3 parts of adjuvant HM4 were at 45 ° C for 20 minutes fulled. To the liquor were added 5 parts of polymeric tanning material G18 and Retanned for 40 minutes. After addition of 1 part of water repellent H3 and 1 part of adjuvant HM4 were drummed for a further 20 minutes. To Nachgerbflotte were 3 parts polymer tanning G18 and 3 parts Polymer tanning G17 added and retanned for 60 minutes. By portions Addition of 2 parts of formic acid became within 50 A pH of 3.5 minutes.

In a freshly prepared fleet of 100 parts of water and 1.5 parts Sodium formate was drummed for 5 minutes. To neutralization fleet 1.5 parts of sodium bicarbonate were added and after 10 minutes more were added 1.5 parts of sodium bicarbonate added and additional 15 minutes at 40 ° C neutralized.

to Neutralization liquor were 1.5 parts dye I.39 and 4.5 parts Dye III.15 and stained for 40 minutes at pH 7.6. By adding portions of 8 parts of sodium carbonate, aufuspendiert with water in the ratio 1:10, was used to fix the pH adjusted between 9.0 and 9.6 and at 80 minutes 40 ° C.

Subsequently Followed 3 times a 15 minute washing operation in 300 parts Water at 40 ° C.

In a freshly prepared fleet of 200 parts water and 2 parts Formic acid became a liquor pH within 55 minutes set by 5.8.

To Draining the fleet was in a new fleet of 100 parts of water, 2.5 parts fatliquoring agent F7 and 3.5 parts fatliquoring agent F4 60 Greased at 50 ° C for a few minutes.

Subsequently acidified by portionwise addition of 2 parts of formic acid within 45 minutes to pH 3.4. After draining the fleet became the dyed, retanned and greased leather 5 Rinsed for a few minutes and then put on a pad, set out, vacuum-dried at 45 ° C. for 3 minutes, hang-dried, conditioned, staked and vacuum dried at 45 ° C for 2 minutes.

Shoe upper leather in the color orange brown was obtained, which is characterized by its color-deep leather cross-section, the high levelness of the dyeing and the excellent washing, perspiration and migration authenticity distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 2.4 parts I.43 5.6 parts III.16 orange Brown 1.2 parts I.7 3.4 parts I.2 1.4 parts III.5 Yellowish tan

Example 9

One Leather piece of 100 parts by weight on usual Way chrome-tanned cowhide of folding thickness 1,1-1,2 mm was washed with 300 parts of water for 10 minutes at 30 ° C. In one consisting of 100 parts of water and 1.5 parts of sodium formate Liquor was tumbled for 5 minutes at 35 ° C. To neutralization fleet 1.5 parts of sodium bicarbonate were added, after 10 minutes became another 1.5 parts of sodium bicarbonate was added and another 15 minutes neutralized at 35 ° C.

to Neutralization liquor were 4.2 parts dye I.43 and 0.8 parts Dye II.7 and stained for 40 minutes at pH 7.9. By adding portions of 6 parts of sodium carbonate, suspended with water in the ratio 1:10, was used to fix the pH adjusted between 9.3 and 9.8 and at 80 minutes 35 ° C.

Subsequently Followed 3 times a 15 minute washing operation in 300 parts Water at 40 ° C. In a freshly scheduled fleet 150 parts of water and 1.9 parts of formic acid were within of 55 minutes a liquor pH of 4.5 is set.

To Drain the fleet was in a freshly scheduled fleet 100 parts of water and 1.5 parts of sodium formate at 45 ° C for 20 minutes fulled. To the liquor was added 5 parts of polymeric tanning material G18 and retanned for 30 minutes. After addition of 5 parts of the fatliquoring agent F1 were drummed another 30 minutes. To the Nachgerbflotte were 15 parts tannin G6 and 5 parts vegetable tanning G22 given and retanned for 60 minutes. The Nachgerbflotte were 5 parts of fatliquor F1, 3 parts of fatliquor F3 and 2 parts of the hydrophobizing agent H4 given and greased for 60 minutes. For complete consumption To the fatliquoring, 100 parts of 50 ° C hot water were added and drummed for 20 minutes. By adding portions of 4 parts Formic acid became pH within 55 minutes set by 3.6.

To Draining the fleet was the dyed, retanned and greased leather washed twice with 200 parts of water at 45 ° C. Then the leather was put on a bench, stretched out, vacuum dried at 45 ° C for 3 minutes, at room temperature hangsried, conditioned, staked, with 70% relative Moist moisture and slightly tensioned.

It furniture leather in the shade dark red brown were obtained characterized by their color-deep leather cross section, the high levelness of coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 3 parts I.17 3 parts II.25 Yellowish red 0.8 parts I.1 2.8 parts II.6 0.4 parts III.7 Yellowish red 1.8 parts I.16 4.2 parts II.1 Brownish red

Example 10

One Leather piece of 100 parts by weight on usual Way organically tanned cowhide of folding thickness 1,1-1,2 mm was washed with 300 parts of water for 10 minutes at 30 ° C. In one consisting of 100 parts of water and 1.5 parts of sodium formate Liquor was tumbled for 5 minutes at 35 ° C. To neutralization fleet 1.5 parts of sodium bicarbonate were added, after 10 minutes became another 1.5 parts of sodium bicarbonate was added and another 15 minutes neutralized at 35 ° C.

to Neutralization liquor was 4.5 parts of dye I.13 and 0.2 parts Dye IV.5 and 0.3 parts of dyestuff IV.6 are added and 40 minutes stained at pH 7.9. By adding portions of 6 parts Sodium carbonate, suspended with water in the ratio 1:10, was set to fix the pH between 9.5 and 10.0 and drummed for 80 minutes at 35 ° C. Subsequently Followed 3 times a 15 minute washing operation in 300 parts Water at 40 ° C. In a freshly scheduled fleet 150 parts of water and 1.8 parts of formic acid were within of 55 minutes, set a liquor pH of 4.2. After draining the fleet was in a freshly prepared fleet of 100 parts Water and 1.5 parts of sodium formate at 45 ° C for 20 minutes fulled. To the liquor was added 5 parts of polymeric tanning material G18 and retanned for 30 minutes. After addition of 5 parts of the fatliquoring agent F1 were drummed another 30 minutes. The Nachgerbflotte were 15 Parts of tanning material G6 and 5 parts vegetable tanning G22 given and Retanned for 60 minutes. The Nachgerbflotte were 5 parts of fatliquor F1, 3 parts of fatliquor F3 and 2 parts of the hydrophobizing agent H4 given and greased for 60 minutes. For complete consumption The fatliquoring was 100 parts of 50 ° C hot water added and drummed for 20 minutes. By adding portions of 4 parts of formic acid came in within 55 minutes pH adjusted to 3.6.

After draining the fleet was the dyed, retanned and greased leather 2 washed with 200 parts of water at 45 ° C. The leather was then placed on a pad, stretched, vacuum-dried at 45 ° C. for 3 minutes, suspension-dried at room temperature, conditioned, staked, milled with 70% relative humidity and slightly tensioned.

It Organic tanned furniture leather in the shade became greenish Dark brown, which is particularly characterized by their color depths Leather cross section, the high levelness of coloring and the excellent washing, perspiration and migration fastnesses distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 4.2 parts I.48 1.2 parts II.2 0.6 parts IV.11 Reddish dark brown 1.6 parts I.33 1.6 parts III.3 0.8 parts IV.19 Greenish dark brown

Example 11

One Leather piece of 100 parts by weight on usual Way chrome-tanned cowhide with a thickness of 1.8 mm was washed with 300 parts of water for 10 minutes at 35 ° C. In one consisting of 150 parts of water and 1.5 parts of sodium formate Liquor was drummed for 5 minutes at 30 ° C. To neutralization fleet were 2.5 parts of sodium bicarbonate added and 55 minutes at 30 ° C neutralized. The neutralization liquor was 4.2 Parts of dye I.5 and 1.3 parts of dye I.14 and 0.5 part of dye IV.25 and stained for 60 minutes at pH 7.2. By in portions, adding 6 parts of sodium carbonate, suspended with water in the ratio 1:10, was used to fix the pH adjusted between 9.4 and 10.1 and at 120 minutes 40 ° C. Then followed by a 20 times 3 times Minute washing in 300 parts of water at 40 ° C. In a fresh prepared fleet of 150 parts water and 1.5 Parts of formic acid came in within 50 minutes Liquor pH adjusted to 4.2.

To Drain the fleet was in a freshly scheduled fleet 100 parts of water and 2 parts of polymer tanning material G15 retanned for 30 minutes. After adding 2 parts of the hydrophobicizing agent H3 were more Walked for 30 minutes. The Nachgerbflotte were 5 parts tannin Add G7 and 4 parts resin gum G11 and retanned for 60 minutes. To Nachgerbflotte were 4.5 parts of fatliquor F5 and 0.5 parts Greasing agent F8 given and greased for 40 minutes. By portions Addition of 4 parts of formic acid became within 40 A pH of 3.5 minutes.

To Draining the fleet was the dyed, retanned and greased leather with 300 parts of water at 20 ° C for 10 minutes washed. Then the leather was put on the goat, set out, vacuum-dried at 45 ° C for 3 minutes, at room temperature hang-dried, conditioned, staked and at 50 ° C 2 minutes. vacuum dried.

It shoe upper leather became greenish tan in color especially distinguished by their color-deep leather cross-section, the high levelness of the coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 5.4 parts I.39 0.6 parts IV.21 0.6 parts IV.3 Greenish medium brown 1.6 parts I.38 1.6 parts III.7 0.8 parts IV.6 Greenish dark brown 4 parts I.6 0.7 parts I.29 0.4 parts IV.20 Greenish tan

Example 12

One Leather piece of 100 parts by weight on usual Way chrome-tanned cowhide of the folding thickness 1,6-1,8 mm was washed with 300 parts of water for 10 minutes at 40 ° C. In one consisting of 80 parts of water and 1.5 parts of sodium formate Liquor was tumbled for 5 minutes at 43 ° C. To neutralization fleet 1.5 parts of sodium bicarbonate were added, after 10 minutes became another 2 parts of sodium bicarbonate added and another 15 minutes neutralized at 35 ° C.

to Neutralization liquor was 1 part dye I.4 and 7 parts dye IV.1 and stained for 30 minutes at pH 7.9. By portions Add 8 parts of sodium carbonate, suspended with water in the ratio 1:15, was set to fix the pH between 9.3 and 9.8 and drummed for 90 minutes at 43 ° C. The fleet was drained and the leather rinsed with water for 20 minutes. This was followed by a 15-minute washing operation 3 times in 300 parts of water at 38 ° C. In a freshly prepared Liquor from 150 parts of water and 4.5 parts of formic acid overnight a liquor pH of 4.0 was set. To Drain the fleet was in a freshly scheduled fleet 80 parts of water and 2 parts of fatliquor F1 for 20 minutes at 45 ° C fulled. To the liquor was added 5 parts of polymeric tanning material G18 and retanned for 30 minutes. After addition of 4 parts of the tanning agent G5, 3 parts of Gerbstoffes G32 and 2 parts of the Harzgerbstoffes G28 were drummed for another 40 minutes. To the Nachgerbflotte were 3 parts fatliquoring agent F1, 0.5 parts fatliquoring agent F8 and 1 part Greasing agent F4 given and greased for 40 minutes. To the complete Exhaustion of the greasing became 70 parts 55 ° C hot Water added and drummed for 10 minutes. By adding in portions 4.5 parts of formic acid became within 65 minutes adjusted to a pH of 3.6.

To Draining the fleet was the dyed, retanned and greased leather washed once with 300 parts of water at 30 ° C. Then the leather was put on a bench, stretched out, vacuum dried at 45 ° C for 3 minutes, at room temperature hang-dried, conditioned, staked and at 50 ° C Vacuum dried for 2 minutes.

It shoe uppers were obtained in the shade olive green, the especially by their color-depth leather cross-section, the high Levelness of coloring and excellent washing, Welding and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 0.6 parts I.1 0.3 parts III.7 9.2 parts IV.5 Dark olive green 4.8 parts III.22 1.2 parts IV.10 Cloudy green 4.8 parts I.38 1.2 parts IV.6 Dark olive green

Example 13:

One Leather piece of 100 parts by weight on usual Way chrome-tanned cowhide of folding thickness 1,1-1,2 mm was in one with 300 parts of water and 0.3 parts of formic acid filled Wacker keg 15 minutes at 35 ° C washed and then in one of 150 parts of water and 2 parts Natriumformiat existing liquor neutralized for 10 minutes at 35 ° C. The neutralization liquor was 1.8 parts of sodium bicarbonate given and drummed for another 80 minutes.

To Draining the liquor was the leather once with 300 parts of water washed at 45 ° C for 15 minutes.

To a freshly used liquor from 100 parts of water, 4 parts of polymer tanning G18 gege and retanned for 40 minutes at 45 ° C. To Nachgerbflotte 8 parts retanning G2, 5 parts of fatliquor F1 and 5 parts of water repellent H3 were added and drummed for 90 minutes. To Nachgerbflotte 100 parts of water were added and rethenolated at 60 ° C for a further 30 minutes. Addition of 2 parts of formic acid gave a pH of 3.5 within 55 minutes.

The so fed up leather were put on Bock, outstretched, at Room temperature span frame, conditioned, staked, as Nubuck honed, dedusted and weighed.

The The following quantities of the nachgerbprodukte refer to the Dry weight of bovine nubuck trust.

The Rindnubukcrusts was supplemented with 1000 parts water and 0.3 parts auxiliary HM9 washed at 40 ° C for 10 minutes. In a freshly used liquor from 300 parts of water and 1.5 parts HM7 aid, the leather was tumbled at 40 ° C for 5 minutes.

It 2 parts of sodium formate were added and neutralized for 10 minutes, after addition of 3 parts of sodium bicarbonate was 15 minutes fulled. To Neutralisationsflotte were at pH 7.8 8 parts of dye I.4 and 3 parts of dye I.37 and 2 parts of dye IV.7 and stained for 30 minutes at pH 7.3. By portions Addition of a total of 12 parts of sodium carbonate, with suspended Water in the ratio 1:10, was used to fix the pH set between 9.6 and 10.3 and at 40 ° C for 90 minutes fulled. The following was rinsed with water for 10 minutes and washed twice with 800 parts of water at 40 ° C.

In a freshly prepared fleet of 200 parts of water and 2.5 parts Formic acid became pH within 55 minutes set by 4.0.

To Draining the liquor was in 400 parts of water, 10 parts of greasy Gerbstoff G9, 7 parts water repellent H2, 3 parts water repellent H4 and 0.5 parts of auxiliary HM4 greased at 40 ° C for 40 minutes. After portionwise addition of 0.8 part of formic acid a pH of 4.7 was set within 20 minutes.

to complete wasting of greasing, 200 parts were 60 ° C added hot water and drummed for another 10 minutes. The liquor was 2 parts fatliquor F8, 0.8 parts fatliquoring agent Add F3 and 0.2 parts of adjuvant HM4 and grease for 60 minutes. By adding portions of 5 parts of formic acid set a pH of 3.3 within 45 minutes.

To Drain the fleet was in a freshly scheduled fleet 500 parts of water and 2 parts of chrome tanning material G24 and 3 parts of mineral mixture G30 postchromed at 30 ° C for 90 minutes. At the end was two more times each with 800 parts of water at 30 ° C 10 Washed for a few minutes.

The dyed cow nubuck leather was put on a goat, stretched, at room temperature, tension-frame-dried, conditioned, staked, milled at 70% relative humidity and tension-frame-dried.

It were color depth washable cow nubuck leather in the shade greenish Light brown, which is particularly characterized by its color-deep leather cross-section, the high levelness of the coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 2.5 parts I.13 8.4 parts I.1 3.6 parts III.7 Yellowish tan 6.5 parts I.43 2.5 parts III.26 1.5 parts IV.20 Greenish medium brown 7 parts I.1 2.2 parts I.13 0.8 parts IV.5 Greenish tan

Example 14:

A piece of leather of 100 parts by weight of a chromium-tanned cowhide having the folding thickness of 1.8 mm was washed with 300 parts of water at 35 ° C for 10 minutes. A liquor consisting of 150 parts of water and 1.5 parts of sodium formate was tumbled at 30 ° C. for 5 minutes. To neutralization fleet were suspended 3 parts of sodium bicarbonate with water in the ratio 1:10, added and neutralized for a further 25 minutes at 30 ° C. 3 parts of dye I.43 and 3 parts of dye II.10 and 2 parts of dye IV.13 were added to the neutralization liquor and dyed at pH 7.6 for 60 minutes. By adding in portions 6 parts of sodium carbonate, suspended with water in a ratio of 1:10, the pH was adjusted to between 9.4 and 10.1 and fixed at 40 ° C. for 120 minutes. This was followed by 3 times a 20-minute washing operation in 300 parts of water at 40 ° C. In a freshly prepared liquor consisting of 200 parts of water and 4 parts of formic acid, a liquor pH of 4.0 was set within 50 minutes.

To Drain the fleet was in a freshly scheduled fleet 100 parts of water and 2 parts of fatliquor F1 suspended with water in the ratio 1: 3, 30 minutes at 45 ° C greased. After addition of 2 parts of the Nachgerbstoffes G18 were another 30 minutes. To Nachgerbflotte were 4 parts tannin Add G7 and 4 parts resin gum G11 and retanned for 60 minutes. To the retanning liquor was added 4 parts of fatliquoring agent F1 and 40 Greased for minutes. By adding portions of 2.5 parts of formic acid pH was adjusted to 3.5 within 40 minutes.

To Draining the fleet was the dyed, retanned and greased leather with 300 parts of water at 20 ° C for 10 minutes washed. Then the leather was put on the goat, set out, vacuum-dried at 45 ° C for 3 minutes, at room temperature hang-dried, conditioned, staked and at 50 ° C 2 minutes. vacuum dried.

It shoe uppers were obtained in the color bordo, which are especially through their color-deep leather cross-section, the high levelness coloring and the excellent washing, welding and and migration fastnesses.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 2.5 parts I.38 2.5 parts II.6 1.25 parts IV.6 Bordo 3.1 parts II.14 0.9 parts IV.10 Bordo 2.5 parts II.24 1.5 parts IV.18 Bordo

Example 15

One Leather piece of 100 parts by weight on usual Way of chrome-tanned cowhide of the folding thickness 1,8-2,0 mm was washed with 300 parts of water for 10 minutes at 40 ° C. In one consisting of 80 parts of water and 1.5 parts of sodium formate Liquor was tumbled for 5 minutes at 43 ° C. To neutralization fleet 1.5 parts of sodium bicarbonate were added, after 10 minutes became another 1.5 parts of sodium bicarbonate was added and another 15 minutes neutralized at 43 ° C.

to Neutralization liquor were 1.25 parts of dye I.6 and 3 parts Dye II.24 and 1.25 parts of dye III.17 and 30 minutes stained at pH 7.7. By adding portions of 8 parts Sodium carbonate, suspended with water in the ratio 1:10, was set to fix the pH between 9.3 and 9.8 and drummed for 90 minutes at 43 ° C. The fleet was drained and the leather rinsed with water for 20 minutes. This was followed by a 15-minute washing operation 3 times in 300 parts of water at 38 ° C. In a freshly prepared Liquor from 150 parts of water and 1.5 parts of formic acid a liquor pH of 4.5 was adjusted within 60 minutes. After draining the fleet was in a freshly scheduled fleet from 80 parts of water and 1.5 parts of water repellent H1 15 minutes at 45 ° C. The liquor was 4 parts of polymer tanning agent G18 and retanned for 30 minutes. After adding 3 parts of tanning material G1, 3 parts of tanning material G32 and 2 parts of Resin Tanning G28 was drummed for another 50 minutes. There were 70 parts of hot water are added, leaving 60 ° C Fleet temperature was reached. It was drummed another 10 minutes. To Nachgerbflotte were 3 parts of fatliquor F1, 0.5 parts of fatliquoring agent Add F8 and 1.5 parts of water repellent H3 and grease for 40 minutes. By adding portions of 4 parts of formic acid was added adjusted to a pH of 3.6 within 60 minutes.

To Drain the fleet were in a freshly deployed fleet 100 parts of water and 0.6 part of a cationic auxiliary HM7 0.2 parts of dye I.6 and 0.5 parts of dye II.24 and 0.2 parts Dye III.17 together with 5 parts of sodium carbonate at 40 ° C and drummed for 15 minutes at pH 9.5.

The liquor was drained and the leather was 3 times with 300 parts of water for 15 minutes at 38 ° C washed. In a freshly prepared liquor of 150 parts of water and 1 part of formic acid, the leather was worked for 15 minutes. To the liquor was added 2 parts of fatliquoring agent F1 and 1 part of water repellent H3 and drumming for a further 15 minutes. The final pH of 3.5 of the leather was adjusted by adding 3 parts of formic acid in portions within 60 minutes.

To Draining the fleet was the dyed, retanned and Greased leather laid on a stand, stretched out, at 45 ° C 3 Vacuum dried for 10 minutes, dried at room temperature, conditioned, staked and vacuum dried at 50 ° C for 2 minutes.

It shoe uppers in the color reddish brown were obtained, which are particularly through their color-deep leather cross-section, the high levelness coloring and the excellent washing, welding and and migration fastnesses.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue (4.5 + 0.75) parts II.6 (1.5 + 0.25) parts III.7 russet (2.5 + 0.4) parts I.29 (4 + 0.66) Parts II.10 (0.5 + 0.1) parts III.26 red-brown (2.4 + 0.4) parts I.38 (2.4 + 0.4) parts II.6 red-brown (2 + 0.33) parts I.8 (2 + 0.33) parts II.21 (1 + 0.17) parts IV.13 red-brown

Example 16

One Leather piece of 100 parts by weight on usual Way chrome-tanned cowhide of the folding thickness 1,4-1,6 mm was in a filled with 300 parts of water Wackerfass Washed at 35 ° C for 10 minutes and then in one of 100 parts of water and 2 parts of sodium formate Fleet neutralized for 10 minutes at 35 ° C. To neutralization fleet were added 0.5 parts of sodium bicarbonate and another 40 Minutes rolled. After addition of 4 parts of a polymer-based Grease Fatty G35 was drummed for another 20 minutes. After adding 4 parts of polymer tanning agent G18 was retanned for 40 minutes. to Nachgerbflotte were 4 parts retanning G1 and 4 parts fatliquoring agent F1 and 120 minutes rolled. After draining the fleet was washed with 300 parts of water at 35 ° C for 10 minutes.

The so fed up leather were put on Bock, outstretched, at 450 ° C for 3 minutes vacuum dried, for Slightly tension-frame dried at room temperature for 2-3 hours, conditioned, staked and sanded as velor. Subsequently the leather was dedusted.

Further Weight data refer to the dry weight of the leather.

The Suede crust leather was made with 800 parts of water and 0.3 part auxiliary HM9 washed at 40 ° C for 40 minutes and then in a fleet of 300 parts of water and 1.3 parts of auxiliaries HM7 drummed for 10 minutes. To the liquor was added 2 parts of sodium formate added and neutralized for 10 minutes. After adding 2 parts Sodium bicarbonate was tumbled for a further 10 minutes. To neutralization fleet At pH 7.6, 1.8 parts of dye II.20, 7.8 parts of dye III.3 and 2.4 parts of dye IV.19 and 40 minutes at pH 7,4 dyed. By adding in portions of a total of 15 Divide sodium carbonate, suspended with water in the ratio 1:15, was set to fix the pH between 9.4 and 10.1. After 5 minutes, an additional 1.8 parts of dye II.20, 7.8 parts Dye III.3 and 2.4 parts of colorant IV.19 added and 90 minutes long at 40 ° C. Subsequent became 10 Rinsed with water for 3 minutes and 3 times with 300 parts of water each washed at 40 ° C for 20 minutes.

to pH regulation was the leather in a freshly prepared liquor made up of 150 parts of water for 20 minutes at 40 ° C and then became a pH of 6.0 by portionwise addition of 1 part of formic acid set within 60 minutes. In a freshly used Fleet of 100 parts 60 ° C hot water, 6.5 Dissolve fatliquoring agent F1, 0.5 part fatliquoring agent F8 and 3 parts Water repellent H3 was added within 40 minutes Greased 50 ° C.

to Completion of the fatigue acidification by adding portions of 4 parts of formic acid within 45 minutes down to 3.5.

Finally, it was washed once more with 300 parts of water at 30 ° C for 10 minutes. The dyed and greased fissure suede was put on a bench, stretched out, tension-frame-dried at room temperature, conditioned, staked, stretched and brushed.

It was color deep suede upper leather in the color reddish medium brown especially distinguished by their color-deep leather cross-section, the high levelness of the coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue (6 + 6) Parts I.38 (6 + 6) Parts III.7 Reddish medium brown (8 + 8) Parts I.28 (2 + 2) parts I.2 (2 + 2) parts III.8 Reddish medium brown (5.5 + 5.5) parts I.48 (4 + 4) Parts II.10 (2.5 + 2.5) parts III.26 Reddish light brown

Example 17

One Leather piece of 100 parts by weight on usual Way of chrome-tanned cowhide of the folding thickness 1,8-2,0 mm was washed in 200 parts of water for 10 minutes at 35 ° C and then in one of 80 parts water, 4 parts Chrome Tanning G34 and 1.5 parts of sodium formate for 60 minutes Retested at 35 ° C. To Nachgerbflotte was 0.4 parts of sodium bicarbonate added and reached a pH of 4.0 overnight. to Fleet were given 5 parts of polymer tanning G16 and 60 minutes fulled. Subsequently, the fleet was drained and with 200 parts of water at 35 ° C for 10 minutes.

The So, the leather was made up of 80 parts of water and nachchromierten 1.5 parts of sodium formate existing liquor neutralized for 10 minutes, after addition of 1 part of sodium bicarbonate, another 10 Minutes, after the addition of a further 2 parts of sodium hydrogen carbonate was neutralized for another 10 minutes. To neutralization fleet At pH 7.5, 6.5 parts dye I.43 and 1.5 parts dye II.8 and 2 parts of dye IV.11 and 40 minutes at pH 7.0 colored. By adding in portions of a total of 8 parts Sodium carbonate, suspended with water in the ratio 1:15, was set to fix the pH between 9.3 and 10.0 and drummed for 80 minutes at 40 ° C. subsequent was rinsed with water for 20 minutes and 2 times with 300 parts Washed water at 40 ° C.

In a freshly prepared fleet of 100 parts water and 1.3 parts Formic acid became a pH within 30 minutes set by 4.8. The liquor was 1.5 parts of the hydrophobizing agent Given H3 and drummed for 10 minutes. There were 1.5 parts of a Nachgerbstoffes G15 added and drummed for another 20 minutes. There were 3 parts Nachgerbstoff G5 and 2 parts retarder G32 supplied and drummed for 30 minutes.

to Hydrophobization were 7 parts of water repellent H1, 1 part of water repellents H3 and 0.3 parts of auxiliary HM4 were added and drummed for 60 minutes.

to Completion of the wasting of hydrophobing were Add 100 parts of 60 ° C hot water and 10 Minutes at 50 ° C. Then you acidified by the portionwise addition of 4 parts of formic acid 3,6 and walked 45 minutes.

To Draining the liquor was washed for 10 minutes with 200 parts of water.

In a freshly prepared fleet of 100 parts of water and 0.8 parts Hydrophobizing agent H6, the leather was at 40 ° C for 20 minutes fulled. The liquor was first 0.3 parts of formic acid and then 4 parts chrome tanning G34 supplied and 60 minutes rolled.

To Draining the liquor was done twice with 200 parts each of water washed at 30 ° C for 10 minutes. The dyed and hydrophobized leather was placed on the bench, stretched out, at Vacuum-dried at 45 ° C. for 3 minutes, tension-frame-dried at room temperature, conditioned, staked and tensioned and at 50 ° C for 2 minutes vacuum dried.

It were color depth hydrophobized shoe upper leather in the shade reddish Dark brown, which is particularly characterized by their color depths Leather cross section, the high levelness of coloring and the excellent washing, perspiration and migration fastnesses distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 7 parts I.14 3 parts II.15 Reddish dark brown 7 parts I.13 1.5 parts II.6 1.5 parts IV.6 Reddish dark brown 5.5 parts I.14 4 parts II.10 0.5 parts IV.20 Reddish dark brown 4 parts I.12 2.5 parts I.48 3.5 parts IV.20 Greenish dark brown

Example 18

One Leather piece of 100 parts by weight on usual Way organically tanned cowhide of folding thickness 1,2-1,3 mm was ground to nubuck.

The Leather was first treated with 300 parts of water for 10 minutes at 30 ° C washed. In one of 100 parts of water and 1.5 parts of sodium formate existing liquor was drummed for 5 minutes at 35 ° C. to Neutralization liquor was added 2.5 parts of sodium bicarbonate and neutralized for 10 minutes at 35 ° C.

to Neutralization liquor was 8.5 parts dye I.13 and 1.5 parts Dye II.6 and stained for 30 minutes at pH 7.4. By adding portions of 9 parts of sodium carbonate, suspended with water in the ratio 1:15, was used to fix the pH adjusted between 9.3 and 9.8 and for 90 minutes at 35 ° C.

The Fleet was drained and the leather rinsed with water for 20 minutes. This was followed by a 15-minute washing operation 3 times in 300 parts of water at 38 ° C. In a freshly prepared Liquor from 150 parts of water and 1.5 parts of formic acid a liquor pH of 5.0 was adjusted within 70 minutes. After Ablas sen the fleet was in a freshly prepared fleet from 100 parts of water, 4 parts of fatliquoring agent F1 and 4 parts of fatty tanning agent G35 drummed for 20 minutes at 45 ° C. To the fleet were 8 parts Polymer tanning agent G18 and retanned for 30 minutes.

To Addition of an additional 4 parts of polymer tanning material G18 and 8 parts of Gerbstoffes G8 were drummed for a further 60 minutes. To Nachgerbflotte 4 parts of fatliquoring agent F1, 3 parts of fatty tanning material G35 and 3 added water repellent H3 and greased for 60 minutes. to complete wasting of greasing, 100 parts were 60 ° C Add hot water and overnight at 50 ° C fulled. By adding portions of 4 parts of formic acid a pH of 3.4 was set within 75 minutes.

To Draining the fleet was the dyed, retanned and Greased leather 2 times with 300 parts of water at 30 ° C washed. In a freshly used liquor made up of 150 parts of water and 5 parts aluminum tanning G33, the leather was 120 minutes drummed at 30 ° C.

Subsequently The leather was put on a bench, stretched out, at room temperature hang-dried, conditioned, staked and 70% moisture dry-drummed.

It Organic tanned nubuck shoe upper became darker in the shade Reddish brown, which is particularly characterized by its color-deep leather cross section, the high levelness of the coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 8 parts I.17 1 part II.4 1 part IV.4 dark Brown 1.5 parts I.1 6 parts I.20 2.5 parts II.9 Reddish dark brown 4 parts I.13 4 parts II.4 1 part IV.20 red-brown

Example 19

A piece of leather of 100 parts by weight of a conventionally chrome-tanned cowhide having a thickness of 1.8-2.0 mm was washed with 300 parts of water at 40 ° C for 10 minutes. A liquor consisting of 80 parts of water and 1.5 parts of sodium formate was tumbled at 43 ° C. for 5 minutes. For neutralization 1.5 parts of sodium bicarbonate were added to the liquor, and after 10 minutes, an additional 1.5 parts of sodium bicarbonate were added and the mixture was neutralized at 35 ° C. for a further 15 minutes.

to Neutralization liquor were 4 parts of dye I.3 and 0.5 parts Dye II.14 and 1.5 parts of dye III.14 and 25 minutes stained at pH 7.7. By adding portions of 8 parts Sodium carbonate, suspended with water in the ratio 1:15, was set to fix the pH between 9.3 and 9.8 and drummed for 90 minutes at 43 ° C. The fleet was drained and the leather rinsed with water for 20 minutes. This was followed by a 15-minute washing operation 3 times in 300 parts of water at 38 ° C. In a freshly prepared Liquor from 150 parts of water and 2.5 parts of formic acid a liquor pH of 4.7 was set within 60 minutes. After draining the fleet was in a freshly scheduled fleet from 100 parts of water and 4 parts of polymeric tanning material G18 for 30 minutes at 45 ° C. The liquor was 4 parts retanning G5, 3 parts Gerbstoffes G32 and 2 parts Harzgerbstoff G28 given and retanned for 60 minutes. After portionwise addition of 0.5 parts Formic acid was drummed for another 40 minutes. The fleet was drained.

The Leather was made with 200 parts of 50 ° C hot water washed.

In a liquor of 100 parts hot water 3 parts fatliquor F11, 1 part fatliquoring agent F4 and 2 parts hydrophobicizing agent H3 was drummed at 50 ° C for 40 minutes. By portions Addition of 2 parts of formic acid became within 50 A pH of 3.5 minutes.

The Fleet was drained and the leather once with 300 parts of water washed at 40 ° C for 10 minutes.

To Draining the fleet was the dyed, retanned and Greased leather laid on a stand, stretched out, at 45 ° C 3 Vacuum dried for 10 minutes, dried at room temperature, conditioned, staked and vacuum dried at 50 ° C for 2 minutes.

It Shoe uppers were obtained in the color orange brown, which themselves especially by their color-deep leather cross-section, the high levelness coloring and the excellent washing, welding and and migration fastnesses.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 1.5 parts I.38 4.5 parts III.7 orange Brown 1 parts I.2 2.5 parts II.9 2.5 part III.10 Yellowish reddish brown 1 part I.2 4.5 parts II.10 0.5 parts III.26 Yellowish red 2 parts I.4 0.5 parts II.10 3.5 parts III.26 orange

Example 20:

One Leather piece of 100 parts by weight on usual Way chromium-tanned cowhide the fold strength 1,0-1,1 mm was in one with 300 parts of water and 0.3 parts of formic acid filled Wacker keg 10 minutes at 35 ° C and then in one of 150 parts of water and 2 parts Tanned aldehyde G13 for 10 minutes at 35 ° C. To the fleet was added 3 parts chrome tanning G24 and continued for 30 minutes retanned. To the retanning liquor was added 1 part of sodium formate and reached a pH of 3.8 after 60 minutes. After that was through Add 0.5 part of sodium bicarbonate after a flexing time reached a pH of 4.5 from 10 minutes. After an addition of another 0.5 part of sodium bicarbonate and a walk time of A liquor pH of 4.3 was achieved for 80 minutes. Subsequently was the liquor drained off and with 300 parts of water at 45 ° C Washed for 15 minutes.

The Leather was in one of 150 parts water and 1 part sodium formate existing fleet for 10 minutes at 45 ° C neutralized. to Neutralization liquor was added 0.8 parts of sodium bicarbonate and a further 30 minutes. After addition of 4 parts of polymer tanning agent G18 was retanned for 30 minutes. The Nachgerbflotte were 4 parts Add retanning agent G5 and 2 parts resin gum G28 and tumble for 30 minutes. 10 parts of fatliquoring agent F1 were added to the retanning liquor and greased for 60 minutes. Then acidified by adding portions of 1.5 parts of formic acid down to 3.5 and walked 45 minutes.

The so fed up leather were put on buck, stretched out, conditioned, staked, vacuum dried at 45 ° C for 2 minutes, sanded with nubuck and 220-240 mm sandpaper weighed. Other weights are based on this dry weight.

The Nubuck crust leather was once with 800 parts of water and 0.3 parts Auxiliary HM9 at 40 ° C for 40 minutes and then in one of 300 parts of water and 1.5 Divide sodium formate for 10 minutes, after addition of 3 parts of sodium bicarbonate was drummed for another 20 minutes. to Neutralization liquor at pH 7.5 4.5 parts of dye I.44 and 4.5 parts of dye I.36 and 1 part of dye IV.19 and stained for 30 minutes at pH 7.4. By portions Addition of a total of 10 parts of sodium carbonate, with suspended Water in the ratio 1:15, was used to fix the pH set between 9.4 and 9.9 and 90 minutes at 40 ° C fulled. The following was rinsed with water for 10 minutes and washed twice with 800 parts of water at 40 ° C.

In a freshly prepared fleet of 200 parts of water and 4 parts Formic acid became a pH within 30 minutes set by 3.9. In a freshly used fleet of 500 Parts of water and 2 part auxiliary HM7 became the leather at 40 ° C Walked for 5 minutes. The liquor was 6.75 parts of dye I.36 and 6.75 parts of dye I.44 and 1.5 parts of dye IV.19 and 15 parts Sodium carbonate fed and drummed for 15 minutes.

To Draining the fleet, the leather was 3 times with 800 parts each Washed water at 40 ° C for 10 minutes.

Of the pH was measured in portions in a liquor of 500 parts of water Add 6 parts of formic acid within 60 minutes set to 3.9 at 40 ° C. The fleet was drained. After adding 500 parts of 60 ° C hot water with 12 parts of the fatliquoring agent F1, 3 parts of the fatliquoring agent F3 and 5 parts of the hydrophobizing agent H4 40 minutes at 50 ° C. greased. It was then acidified by portions Addition of 4 parts of formic acid to 3.5 and walkt 40 minutes.

The dyed and hydrophobized nubuck leather was put on a stand, stretched, frame-dried at room temperature, conditioned, staked, at 70% rel. Moist and moisturized moisture.

It were color depth hydrophobic nubuck furniture leather in the shade Greenish medium brown, which is especially through their color-deep leather cross-section, the high levelness coloring and the excellent washing, welding and and migration fastnesses.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue (9 + 13.5) Parts I.38 (0.6 + 0.9) parts IV.6 (0.4 + 0.6) parts IV.5 Greenish medium brown (1.5 + 2.25) parts I.4 (7 + 10.5) Parts III.18 (1.5 + 2.25) parts IV.25 Greenish medium brown (8 + 12) parts I.48 (1 + 1.5) parts IV.5 (1 + 1.5) parts IV.20 Greenish medium brown

Example 21

One Leather piece of 100 parts by weight on usual Way chrome-tanned cowhide of folding thickness 1,1-1,2 mm was mixed with 300 parts of water and 0.1 parts of HM9 10 Washed at 40 ° C for minutes. In one of 60 parts of water and 1.5 parts of sodium formate-existing liquor was 10 minutes at 43 ° C. The neutralization liquor was 1.5 Sodium bicarbonate was added, after 10 minutes more were added 1.5 parts of sodium bicarbonate added and additional 15 minutes at Neutralized at 43 ° C.

To the neutralization liquor 2 parts of dye I.37 and 2 parts of dye I.43 and 2 parts of dye III.14 were suspended with water in the ratio 1: 7, added and dyed for 40 minutes at pH 7.9. By adding in portions 7 parts of sodium carbonate, suspended with water in a ratio of 1:10, the pH was adjusted to between 9.3 and 9.8 for fixing, and the mixture was tumbled at 43 ° C. for 80 minutes. This was followed by 3 times a 20-minute washing operation in 300 parts of water at 40 ° C. In a freshly prepared liquor of 150 parts of water and 1.5 parts of formic acid was within 60 minutes, a liquor pH of 3.9 set. After draining the liquor was greased in a freshly prepared liquor from 100 parts of water, 3 parts of fat G35 and 3 parts of F1 F1 at 45 ° C for 10 minutes. To the liquor was added 4 parts of polymeric tanning material G18 and retanned for 20 minutes. To Nachgerbflotte 4 parts retanning G5 and 2 parts of tanning G32 were added and retanned for 30 minutes. To Nachgerbflotte 7 parts of fatliquor F1, 1 part of fatliquor F3 and 3 parts of the water repellent H4 were added and greased for 60 minutes. By adding 4 parts of formic acid in portions, a pH of 3.6 was set within 60 minutes.

To Draining the fleet was the dyed, retanned and greased leather washed with 300 parts of water at 40 ° C. Then the leather was put on a bench, stretched out, vacuum dried at 45 ° C for 3 minutes, at room temperature hangsried, conditioned, staked, with 70% relative Moist moisture and slightly tensioned.

It Car upholstery leather was obtained in the color yellowish medium brown, characterized by their color-deep leather cross section, the high levelness of coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 3.5 parts I.4 Part I.16 1.5 parts III.5 Yellowish middle brown 1.5 parts I.3 1 part I.48 3.5 parts III.26 orange Brown 2.9 parts I.1 1.9 parts I.13 1.2 parts III.7 Yellowish middle brown 2 parts I.4 1 part I.48 3 parts II.10 Yellowish reddish brown

Example 22

One Leather piece of 100 parts by weight on usual Way chromium-tanned cowhide the fold strength 1,0-1,1 mm was mixed with 300 parts of water and 0.1 parts of HM9 10 Washed at 40 ° C for minutes. In one of 100 parts of water and 1.5 parts of sodium formate-existing liquor was 10 minutes at 43 ° C. The neutralization liquor was 1.5 Sodium bicarbonate was added, after 10 minutes more were added 2 parts sodium bicarbonate added and another 15 minutes at 43 ° C. neutralized.

to Neutralization liquor was 7 parts of dye I.43 and 2 parts Dye II.15 and 1 part of dyestuff IV.20 were added and 30 minutes stained at pH 7.9. By adding portions of 9 parts Sodium carbonate, suspended with water in the ratio 1:15, was set to fix the pH between 9.3 and 9.8 and drummed for 120 minutes at 40 ° C. After draining the Fleet, the leather was rinsed for 20 minutes.

Subsequently followed twice a 20-minute washing operation in 300 parts Water at 40 ° C. In a freshly scheduled fleet 150 parts of water and 1 part of formic acid were within set a liquor pH of 4.6 for 60 minutes. Let go after the fleet was in a freshly prepared fleet of 100 parts Water, 4 parts of water repellent H2 and 1 part of fatliquoring agent F8 greased at 45 ° C for 20 minutes. To the fleet were 14 parts Tannin G6 and 2 parts resin tanning G28 and 60 minutes retanned. To Nachgerbflotte were 2 parts fatliquor F8, 4 parts of the hydrophobizing agent H4, 2 parts of the hydrophobizing agent H2 and 0.5 parts of auxiliary HM 4 given and hydrophobicized for 60 minutes. By adding portions of 4 parts of formic acid was added adjusted to a pH of 3.6 within 60 minutes.

To Draining the fleet was the dyed, retanned and greased and hydrophobized leather with 300 parts of water at 40 ° C washed. In a freshly used liquor made up of 150 parts of water and 0.3 part of formic acid became 10 at 30 ° C Walkted for a few minutes and by adding 5 parts of a chrome tanning agent G24 overnight nachchromiert.

Subsequently the leather was put on a trestle, stretched out, at 45 ° C 3 Vacuum dried for 10 minutes, dried at room temperature, conditioned, staked, milled with 70% relative humidity and light curious; excited.

It were water repellent upholstered leather in the shade reddish Dark brown, which is particularly characterized by their color depths Leather cross section, the high levelness of coloring and the excellent washing, perspiration and migration fastnesses distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 0.6 parts I.1 8 parts I.13 0.6 parts III.7 Reddish medium brown 6.5 parts I.48 1.5 parts II.2 2 parts IV.21 Reddish dark brown 6 parts I.13 3 parts II.6 1 part IV.6 Reddish dark brown

Example 23:

One Leather piece of 100 parts by weight on usual Way of chrome-tanned cowhide of the folding thickness 1,1 mm was washed with 300 parts of water for 10 minutes at 30 ° C. In one consisting of 100 parts of water and 1.5 parts of sodium formate Liquor was drummed for 10 minutes at 40 ° C. To neutralization fleet were 1.5 parts of sodium bicarbonate were added, after 10 minutes more were added 2 parts of sodium bicarbonate added and another 15 minutes at 40 ° C. neutralized.

to Neutralization liquor was 2 parts of dye I.14 and 3 parts Dye II.3 and 1 part of dye II.14 and 40 minutes stained at pH 7.9. By adding portions of 6 parts Sodium carbonate, suspended with water in the ratio 1:10, was set to fix the pH between 9.3 and 9.8 and drummed for 120 minutes at 40 ° C. Subsequently followed 3 times a 10/20 or 30 minute wash operation in 300 parts of water at 40 ° C. In a freshly prepared Liquor from 150 parts of water and 6 parts of formic acid a liquor pH of 3.4 was set within 120 minutes. After draining the fleet was in a freshly scheduled fleet from 100 parts of water and 3 parts of aldehyde tanning agent G13 at 35 ° C Retanned for 10 minutes. The Nachgerbflotte were 4 parts chrome tanning G34 and 3 parts of retanning G1 and 30 minutes retanned. After retanning, the addition of 2 parts of a fatliquor F1 greased for 60 minutes. The fleet became 1 Part sodium formate and for 20 minutes at 35 ° C forged. To the liquor was added 0.4 part of sodium bicarbonate and 30 Minutes rolled. By another 0.4 parts of sodium bicarbonate a liquor pH of 4.0 was set. After draining the Fleet was the leather with 300 parts of water at 45 ° C 10 Washed for minutes.

In a freshly used fleet of 10 parts water and 2 parts Sodium formate was tumbled at 45 ° C for 10 minutes. To the fleet 2 parts of water repellent H3 were added and tumbled for 15 minutes. To the liquor was added 6 parts of polymeric tanning material G18 and allowed to stand for 30 minutes retanned. To Nachgerbflotte were 3 parts Gerbstoff G1 and Add 3 parts vegetable tanning G22 and retanned for 40 minutes. The pH of the liquor was within 40 minutes by addition of 2 parts of sodium bicarbonate adjusted to 5.6.

to Nachgerbflotte were 7.5 parts of fatliquor F1, 1.5 parts of fatliquor F3 and 3 parts of the water repellent H4 and 60 minutes greased. For complete wasting of fatliquoring were Add 100 parts of 60 ° C hot water and 10 Minutes rolled. By adding portions of 4 parts of formic acid a pH of 3.6 was set within 40 minutes.

Subsequently the leather was put on a trestle, stretched out, at 50 ° C 2 Vacuum dried, wet stretched and hang-dried at room temperature, Stolled, milled with 70% relative humidity, again staked and slightly tense.

It furniture leather in the color brownish red, characterized by their color-deep leather cross section, the high levelness of coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 4.2 parts II.6 1.8 parts IV.6 Bordo 2.25 parts II.22 2.25 parts III.15 1.5 parts IV.19 red-brown 5 parts I.40 0.5 parts II.18 0.5 parts IV.16 Reddish dark brown

Example 24

A piece of leather of 100 parts by weight of a conventionally chrome - tanned sheep leather Folding thickness 0.6-0.7 mm was washed in a Wacker keg filled with 300 parts of water for 10 minutes at 35 ° C and then neutralized in a consisting of 150 parts of water and 1.5 parts of sodium formate liquor at 40 ° C for 5 minutes. 1.5 parts of sodium bicarbonate were added to the neutralization liquor and the mixture was tumbled for a further 10 minutes. To the neutralization liquor was added a further 2.3 parts of sodium bicarbonate and neutralized for a further 15 minutes. 10.5 parts of dye I.38 and 2.25 parts of dye III.7 and 2.25 parts of dye IV.6 were added to the neutralization liquor at pH 7.7 and dyed at pH 7.3 for 40 minutes. By adding a total of 10 parts of sodium carbonate in 10 parts, suspended with water in a ratio of 1:10, the pH was adjusted to between 9.6 and 10.3 and fixed at 40 ° C for 80 minutes for fixation. The following was rinsed with water for 10 minutes and washed twice with 300 parts of water at 40 ° C.

In a freshly prepared fleet of 150 parts of water and 0.9 parts Formic acid became within 38 minutes at 38 ° C adjusted to a pH of 5.9.

To Draining the liquor was done in 150 parts water, 8 parts tannin G3 and 2 parts resin gum G28 fed and at 45 ° C Retanned for 40 minutes. To Nachgerbflotte were 8 parts of water repellent H2, 3 parts of water repellent H4, 0.8 parts of auxiliary HM4 and 3 Parts of fatliquor F8 added and greased for 60 minutes. To In portions, addition of 6 parts of formic acid was within set a pH of 3.5 from 55 minutes.

To Draining the fleet was the dyed, retanned, greased and hydrophobized leather with 300 parts of water at 40 ° C Washed for 15 minutes. In a freshly used fleet of 150 Divide water, 5 parts of chrome tanning G24 and 3 parts Gerbstoff G30 was nachchromiert at 30 ° C for 90 minutes.

To Draining the fleet, the leather was twice, each with 300 parts Washed water at 30 ° C for 15 minutes.

The dyed sheepskin was put on buck, outstretched, at room temperature, tension-frame-dried, conditioned, staked, milled at 70% relative humidity, tension frame dried and brushed.

It were obtained color-deep washable sheepskin in the shade olive brown, characterized by their color-deep leather cross section, the high levelness of coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 10 parts I.48 2.5 parts IV.10 2.5 parts IV.11 olive green 11 parts I.4 3 parts I.8 1 Part IV.23 olive brown 9 parts I.48 1.5 parts III.26 4.5 parts IV.20 olive green 12 parts I.14 1.5 parts II.14 1.5 parts IV.23 dark Brown

Example 25

One Leather piece of 100 parts by weight on usual Way chrome-tanned cowhide, the creasing thickness 2.0 mm was washed with 300 parts of water for 10 minutes at 40 ° C. In a fleet consisting of 80 parts of water and auxiliary HM7 was tumbled at 43 ° C for 5 minutes. The fleet was 1.5 Add sodium formate and tumble for 5 minutes. To neutralization fleet 1.5 parts of sodium bicarbonate were added, after 10 minutes became another 2 parts of sodium bicarbonate added and another 15 minutes neutralized at 43 ° C.

5 parts of dye I.28 and 2.5 parts of dye II.18 and 2.5 parts of dye IV.23 were added to the neutralization liquor and dyed for 30 minutes at pH 7.7. By adding 8 parts of sodium carbonate in portions, suspended with water in a ratio of 1:15, the pH was adjusted to between 9.3 and 9.8 and ramped at 43 ° C. for 90 minutes. The liquor was drained and the leather rinsed with water for 20 minutes. This was followed by 3 times a 20 minute wash in 300 parts of water at 38 ° C. In a freshly prepared liquor of 150 parts of water and 1.8 parts of formic acid, a liquor pH of 4.4 was set within 60 minutes. After draining the fleet was in a freshly prepared fleet of 80 parts of water, 1.2 parts of water repellent H3 and fatliquor F8 15 minutes at 45 ° C ge drumming. To the liquor were added 4 parts of polymer tanning material G18, 4 parts of retanning agent G5, 3 parts of tanning material G32 and 2 parts of resin tanning material G28 and retanned for 40 minutes. 3 parts of fatliquoring agent F1, 0.5 part of fatliquoring agent F8 and 1 part of fatliquoring agent F4 were added to the retanning liquor and greased for 40 minutes. 70 parts of hot water was added so that 55 ° C liquor temperature was reached. It was drummed another 10 minutes. By adding 4.5 parts of formic acid in portions, a pH of 3.6 was set within 60 minutes.

To Draining the liquor was the leather with 300 parts of water at 30 ° C Washed for 10 minutes.

To Draining the fleet was the dyed, retanned and Greased leather laid on a stand, stretched out, at 45 ° C 3 Vacuum dried for 10 minutes, dried at room temperature, conditioned, staked and vacuum dried at 50 ° C for 2 minutes.

It saddle leather in the color reddish dark brown was obtained characterized by their color-deep leather cross section, the high levelness of coloring and the excellent Washing, perspiration and migration fastness distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 2.5 parts II.7 7.5 parts III.8 Reddish medium brown 4 parts I.38 4 parts II.6 2 parts IV.6 red-brown 5 parts I.37 2 parts II.10 3 parts IV.20 Reddish dark brown 4 parts I.48 3.5 parts II.10 2.5 parts III.26 red-brown

Example 26:

One Leather piece of 100 parts by weight on usual Vegetable tanned cowhide with a thickness of 2,8-3,0 mm was washed with 300 parts of water for 10 minutes at 35 ° C. In one consisting of 150 parts of water and 1.5 parts of sodium formate Liquor was tumbled for 5 minutes at 35 ° C. To neutralization fleet 1.5 parts of sodium bicarbonate were added and allowed to stand for 15 minutes 35 ° C neutralized.

to Neutralization liquor was 5.5 parts dye I.17 and 1.3 parts Dye II.14 and 1.7 parts of Dye IV.20 are added and Stained for 40 minutes at pH 7.9. By adding in portions of 11 parts of sodium carbonate, suspended with water in the ratio 1:15, was set to fix the pH between 9.5 and 10.0 and drummed for 80 minutes at 35 ° C. The fleet was drained and the leather with water for 40 minutes at 40 ° C rinsed. Then followed by 3 times a 15 minute Wash operation in 300 parts of water at 40 ° C. In a freshly prepared liquor consisting of 80 parts of water and 2.5 parts of fatliquoring agent F10, 0.5 parts F8 fatliquor and 1.5 parts hydrophobing agent H8 was greased for 40 minutes at 45 ° C. Became the fleet 0.8 parts of formic acid and thereby a pH reached from 3.3 in 20 minutes. For complete consumption The greasing was 70 parts of 60 ° C hot water added and drummed for 20 minutes. By adding portions of 1.5 parts of formic acid became within 45 minutes a pH of 3.5 is set.

To Draining the fleet was the dyed and greased leather rinsed with cold water for 5 minutes. Subsequently the leather was put on a bench, stretched out, at 45 ° C 2 Vacuum dried for 10 minutes, dried at room temperature, moistened, staked and again at 45 ° C for 2 minutes vacuum dried.

It were vegetable tanned pockets / belt leather in the color reddish dark brown, which is particularly by her deep leather cross section, the high levelness of coloring and the excellent washing, perspiration and migration fastnesses distinguished.

The following dye mixtures were used in an analogous manner: Dye A Dye B Dye C hue 3.4 parts II.20 3.4 parts III.17 1.7 parts IV.10 red-brown 2.5 parts I.1 6 parts I.13 Yellowish dark brown 3.4 parts I.30 3.4 parts II.2 1.7 parts IV.25 Bordo

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

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• - DIN EN ISO 11640 [0146]
• ASTM D 2099 [0146]
• - DIN EN ISO 5403 [0146]
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• - DIN 5331 [0146]
• - DIN EN ISO 3377 [0146]
• - DIN EN ISO 3376 [0146]

Claims (27)

A dye mixture comprising a) as component a) a first anionic dye, b) as component b) a second anionic dye having a different color from the dye of component a), and optionally c) as component c) a third anionic dye which has one of the dyes of components a) and b) different color, wherein the dye of component a) is selected from below; i) dyes of the formula I, their salts and their metal complexes:

wherein at least one of A or Dk ^{1 has} an SO ₃ H group and wherein n is 0 or 1, A is a radical of the formula:

where # is the bond to the azo group, X is hydrogen or SO ₃ H, Y is hydrogen, halogen, C ₁ -C ₄ -alkyl, CN or a group SO ₃ H; B is a group CH = CH ₂ or a group CH ₂ -CH ₂ -Q, where Q is a group cleavable under alkaline conditions; Dk is phenyl or naphthyl having 1, 2 or 3 substituents R ^a , wherein R ^{a is} selected from SO ₃ H, COOH, CN, CONH ₂ , OH, NH ₂ , NO ₂ , halogen, C ₁ -C ₄ Alkyl, C ₁ -C ₄ hydroxyalkyl, carboxy C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylamino, C ₁ -C ₄ dialkylamino, C ₁ -C ₄ -Alkylaminocarbonyl, C ₁ -C ₄ -dialkylaminocarbonyl, C ₁ -C ₄ -alkylcarbonylamino, N- (C ₁ -C ₄ -alkylcarbonyl) -N- (C ₁ -C ₄ -alkylcarbonyl) amino, C ₁ -C ₄ - Alkylaminocarbonyloxy, C ₁ -C ₄ -dialkylaminocarbonyloxy, C ₁ -C ₄ -alkylaminocarbonylamino, C ₁ -C ₄ -dialkylaminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino, C ₁ -C ₄ -hydroxy-C ₁ -C ₄ -alkylamino, Carboxy-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylsulfonyl, hydroxy-C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -alkylaminosulfonyl, C ₁ -C ₄ -alkylsulfonylamino, aminocarbonyl, a radical of the formula SO ₂ NR ¹¹ R ¹² , wherein R ¹¹ and R ^{12 are} independently hydrogen, C ₁ -C ₄ alkyl, formyl, C ₁ -C ₄ alkylcarbonyl, C ₁ -C ₄ alkyloxycarbonyl , NH ₂ -CO or C ₁ -C ₄ -alkylaminocarbonyl, C ₁ -C ₄ -alkylaminosulfonylamino, di-C ₁ -C ₄ -alkylaminosulfonylamino, phenylamino, phenylaminocarbonyl, phenoxy, phenylsulfonyl, phenylsulfonylamino, phenylaminosulfonyl, phenylcarbonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino in which the 11 last-mentioned radicals on the phenyl ring are unsubstituted or have one or two substituents selected from C ₁ -C ₄ -alkyl, OH, COOH, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylcarbonyloxy, C ₁ -C _4- alkylcarbonylamino, C ₁ -C ₄ -alkoxycarbonyl, NH ₂ , NO ₂ , SO _{3 may have} H or halogen, and 5- or 6-membered heterocyclyl which is unsubstituted or one or two substituents selected from: OH, halogen , C ₁ -C ₄ alkyl or phenyl, where phenyl is in turn unsubstituted or one or two substituents selected from C ₁ -C ₄ alkyl, OH, COOH, C ₁ -C ₄ alkoxy, C ₁ -C _4- alkylcarbonyloxy, C ₁ -C ₄ -alkylcarbonylamino, C ₁ -C ₄ -alkoxycarbonyl, NH ₂ , NO ₂ , SO ₃ H or halogen, or is a radical of the formula A; Ar is a bivalent, derived from benzene or naphthalene, aromatic radical which optionally carries 1, 2, 3 or 4 substituents R ^b , wherein R ^{b has} one of the meanings given for R ^a ; R ^{1 is} selected from NH ₂ and OH, and R ^{2 is} selected from OH, NH ₂ , C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -hydroxyalkylamino, (HO ₃ SC ₁ C ₄ -C ₄ alkyl) amino, C ₁ -C ₄ dialkylamino, C ₁ -C ₄ alkylcarbonylamino, N- (C ₁ -C ₄ alkyl) -N- (C ₁ -C ₄ alkylcarbonyl) amino, C C ₁ -C ₄ -alkylaminocarbonyloxy, C ₁ -C ₄ -dialkylaminocarbonyloxy, C ₁ -C ₄ -alkylaminocarbonylamino, C ₁ -C ₄ -dialky laminocarbonylamino, C ₁ -C ₄ -alkoxycarbonylamino, carboxy-C ₁ -C ₄ -alkylamino, C ₁ -C ₄ -alkylsulfonylamino, phenylaminocarbonyloxy, phenylaminocarbonylamino, phenylcarbonylamino and phenylsulfonylamino, where the phenyl ring is unsubstituted in the 4 last-mentioned radicals or 1, 2 or 3 may have selected from OH, NO ₂ , halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkyl, and SO ₃ H selected radicals; ii. Dyes of the formula II, their salts and their metal complexes,

where m is 0 or 1, k is 0, 1 or 2, p and q are 0 or 1, with the proviso that n + q is 0 or 1, Ar 'has one of the meanings given for Ar in formula I, R ^{2x has} one of the meanings given for R ² in formula I, and in which Dk, Ar, A and R ^{1 have} one of the meanings given for formula I and in which at least one of the radicals A or Dk has an SO ₃ H group and / or k ≠ 0; iii. Dyes of the formula III, their salts or their metal complexes,

wherein A, R ¹ and R ^{2 have} one of the meanings given for formula I and in which at least one of the radicals A or T has an SO ₃ H group, and T is a bivalent radical of the formula:

in which * has the meanings given above; R ³ and R ^{3a are} independently hydrogen, halogen, COOH, OH or SO ₃ H; D for a chemical bond, C ₁ -C ₄ alkane-1,1-diyl, ethene-1,2-diyl, oxygen, NH, C (O), S (O) ₂ , C (O) NH, NH (C (O) NH or a group S (O) ₂ NH; wherein the dye of component b) is selected from; I dyes of the formula I, their salts and their metal complexes, ii. Dyes of the formula II, their salts and their metal complexes, iii. Dyes of the formula III, their salts and their metal complexes, and iv. Dyes of the formula IV, their salts and their metal complexes,

wherein A has one of the meanings given for formula I, Kk is a radical derived from a coupling component; X has one of the meanings given for R ¹ , Y is hydrogen or has one of the meanings given for R ² , T * has one of the meanings given for T, r and s are 0 or 1, where r + s is 1 or 2 is and wherein the dye of component c) is selected from; ii. Dyes of the formula II, their salts and their metal complexes, iii. Dyes of the formula III, their salts and their metal complexes, and iv. Dyes of the formula IV, their salts and their metal complexes. A dye mixture according to claim 1, wherein X in the radicals of the formula A is hydrogen or a group SO ₃ H and Y is hydrogen. A dye mixture according to claim 1 or 2, wherein B in the radicals of formula A is CH = CH ₂ , a group CH ₂ -CH ₂ -O-SO ₃ H or a group CH ₂ -CH ₂ -OC (O) CH ₃ , Dye mixture according to one of the preceding claims, in which the radical A in the dyes of the formulas 1 to IV is selected from the following radicals A1 to A18:

A dye mixture according to claim 4, wherein the remainder A in the dyes of the formulas I, II, III or IV for a radical of the formulas A1, A8, A13 or A15. Dye mixture according to one of the preceding claims, wherein the dye in component a) is a dye of formula I. or a salt or a metal complex thereof. A dye mixture according to claim 6, wherein the component b) a dye of the formula I or a salt or a metal complex thereof, wherein the dye I of component a) of the dye I of component b) in the radical Dk differs. A dye mixture according to claim 6, wherein the component b) a dye of the formulas II, III or IV or a salt or a metal complex thereof. A dye mixture according to any one of the claims 1 to 5, wherein the dye in component a) is a dye of Formula II or a salt or metal complex thereof. A dye mixture according to claim 9, wherein the component b) a dye of the formulas III or IV, or a salt or a Metal complex thereof. A dye mixture according to any one of the claims 1 to 5, wherein the dye in component a) is a dye of Formula III or a salt or metal complex thereof. A dye mixture according to claim 11, wherein the component b) a dye of the formula IV, or a salt or a metal complex including thereof. A dye mixture according to claim 9, wherein the component b) a dye of the formula II or a salt or a metal complex thereof, wherein the dye II of component a) of differs the dye II of component b) in the radical Dk. Dye mixture according to one of the preceding Claims containing in addition to the dyes of the components a) and b) as component c) another dye of the dyes of the formulas II, III and IV, their salts and their metal complexes is selected. Dye mixture according to one of the preceding claims, which is selected from the mixtures 1 to 22 given in the following table: No. Component a) Component b) Component c) 1 Dye of the formula I Dye of the formula 1 2 Dye of the formula I Dye of the formula I Dye of the formula II 3 Dye of the formula I Dye of the formula I Dye of the formula III 4 Dye of the formula I Dye of the formula I Dye of the formula IV 5 Dye of the formula I Dye of the formula II 6 Dye of the formula I Dye of the formula II Dye of the formula III 7 Dye of the formula I Dye of the formula II Dye of the formula IV 8th Dye of the formula I Dye of the formula III 9 Dye of the formula I Dye of the formula III Dye of the formula IV 10 Dye of the formula I Dye of the formula IV 11 Dye of the formula I Dye of the formula IV Dye of the formula IV 12 Dye of the formula II Dye of the formula II 13 Dye of the formula II Dye of the formula II Dye of the formula III 14 Dye of the formula II Dye of the formula II Dye of the formula IV 15 Dye of the formula II Dye of the formula III 16 Dye of the formula II Dye of the formula III Dye of the formula IV 17 Dye of the formula II Dye of the formula IV Dye of the formula IV 18 Dye of the formula II Dye of the formula IV 19 Dye of the formula III Dye of the formula III 20 Dye of the formula III Dye of the formula IV 21 Dye of the formula III Dye of the formula IV Dye of the formula IV 22 Dye of the formula III Dye of the formula III Dye of the formula IV wherein in the mixtures 1 to 22, the dyes of the general formulas I, II, III and IV may also be present in the form of their salts, in the form of their metal complexes and / or in the form of the salts of the metal complexes. A dye mixture according to any one of the preceding claims, wherein the dyes of the formula I, their salts and their metal complexes are selected from dyes of the general formula Ia, their salts and their metal complexes:

wherein Dk and A have the meanings mentioned above, R ^{2a is} OH or NH ₂ , which is bonded in the ortho or para position to the group N = NA. A dye mixture according to any one of the preceding claims, wherein the dyes of the formula II, their salts and their metal complexes are selected from dyes of the general formula IIa, their salts and their metal complexes:

wherein Dk, A, R ^2x , k and m have the meanings given above. Dyestuff mixture according to one of the preceding claims, wherein the dyes of the formula III, their salts and their metal complexes are selected from dyes of the general formula IIIa, their salts and their metal complexes:

wherein A and T have the meanings given above. A dye mixture according to any one of the preceding claims, wherein the dyes of the formula IV, their salts and their metal complexes are selected from dyes of the general formula IVa, their salts and their metal complexes:

wherein A, Kk, X, Y and T * have the meanings given above. Dye mixture according to one of the preceding Claims, wherein the weight ratio of the dye component a) to the total amount of dyes of the component b), calculated in each case as free acid, in the range from 5:95 to 95: 5 lies. Dye mixture according to one of the preceding Claims comprising a dye of component c), wherein the weight ratio of the dye of the component a) to the dye of component b), calculated in each case as free Acid, ranging from 5:95 to 95: 5, and wherein the Weight ratio of the dye of component a) to the dye of component c), calculated in each case as free acid, ranges from 5:95 to 95: 5. A process for dyeing leather, comprising the treatment of the leather with an aqueous dyeing liquor, which has a pH in the range of 7.5 to 11 and a dye mixture according to any one of claims 1 to 20. The method of claim 22, wherein the leather first with the aqueous dye liquor treated at a pH in the range of 3 to 6.5 and then in the fleet adjusts a pH in the range 7.5 to 11. The method of claim 22, wherein the staining is carried out as a one-step process. The method of claim 22, wherein first a Retanning and then the treatment with the dyeing liquor performs. The method of claim 22, wherein the first Treatment with the dyeing liquor and then a Retanning. The method of claim 22, wherein the treatment with the dyeing liquor at temperatures in the range of 10 up to 60 ° C takes place.