EP0501197A1 - Process for dyeing leather with water insoluble sulfurdyes - Google Patents

Process for dyeing leather with water insoluble sulfurdyes Download PDF

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Publication number
EP0501197A1
EP0501197A1 EP92102027A EP92102027A EP0501197A1 EP 0501197 A1 EP0501197 A1 EP 0501197A1 EP 92102027 A EP92102027 A EP 92102027A EP 92102027 A EP92102027 A EP 92102027A EP 0501197 A1 EP0501197 A1 EP 0501197A1
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EP
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Prior art keywords
sulfur
water
black
dyes
pigment
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP92102027A
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German (de)
French (fr)
Inventor
Wolfgang Dr. Bauer
Hubert Kruse
Gert Dr. Nagl
Jan-Hilbert Mast
Lothar Dr. Schlösser
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Sanofi Aventis Deutschland GmbH
Cassella Farbwerke Mainkur AG
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Cassella AG
Cassella Farbwerke Mainkur AG
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Publication of EP0501197A1 publication Critical patent/EP0501197A1/en
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
    • D06P1/30—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using sulfur dyes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/02—Material containing basic nitrogen
    • D06P3/04—Material containing basic nitrogen containing amide groups
    • D06P3/32—Material containing basic nitrogen containing amide groups leather skins
    • D06P3/3246—Material containing basic nitrogen containing amide groups leather skins using vat, sulfur or indigo dyes

Definitions

  • the present invention relates to a process for dyeing leather with water-insoluble sulfur dyes in finely divided form, the dyeing being carried out from an aqueous liquor by the exhaust process without the addition of reducing agents and / or oxidizing agents.
  • the water-insoluble sulfur dye with reducing agents is first converted into the water-soluble leuco form, which is drawn onto the cotton fiber and then oxidized on the fiber with oxidizing agents to the water-insoluble form.
  • This well-known dyeing process is described, for example, in the following review articles: Melliand Textilber. 12 , 1314 (1973); Ullmann's Encyclopedia of Technical Chemistry, Volume 21, 65 (1982); Rev. Progress Coloring, Vol. 7, 80 (1976)).
  • reducing agents no dye fixation occurs on the cotton fiber impregnated with finely dispersed sulfur dyes.
  • water-soluble sulfur dyes can also be used for dyeing non-textile fiber materials, for example for dyeing chrome-tanned leather types (Rev. Progress Coloring Vol. 7, 83 (1976)).
  • Colored salts are used as water-soluble sulfur dyes (K.Venkataraman, The Chemistry of Synthetic Dyes, Vol. VII, 36 (1974)) are obtained by the dyeing processes (Leather 178 , 27 (1976)) which are weak in color with good coloration (Leather 177 , 4406 (1975)) by the dyeing processes customary for acid dyes. Due to the low substantivity, these colored salts do not completely absorb leather and cause a high pollution of the dyeing waste water. Deeper dyeings with colored salts can only be obtained if special aids are used at the same time (German patents 3 601 721, 3 617 636), the aids in the dyeing waste water also being environmentally harmful.
  • the present invention accordingly relates to a process for dyeing leather by the exhaust process, characterized in that water-insoluble sulfur dyes are used in dispersed form.
  • pretreat leather prefferably to be dyed in the manner that is customary in the known exhaust process with water-soluble leather dyes (see, for example, K.Eitel "The Dyeing of Leather", Volume 5, pp. 269 ff., Umschau-Verlag, Frankfurt / m. (1987)).
  • the process according to the invention itself is also advantageously carried out under the dyeing conditions which are customary for the known exhaust process with water-soluble leather dyes.
  • the leather is dyed in an aqueous liquor which contains 20 to 400%, preferably 50 to 200% water, based on the fold weight of the leather, at a temperature of 20 to 100 ° C., preferably 30 to 60 ° C., with 0, 5 to 8%, preferably 1.5 to 6% of dispersed sulfur dyes in pigment form.
  • the pH is preferably 3.8 to 5.5.
  • the sulfur dyes can be combined in dispersed form with a dispersion of an inorganic or organic pigment and / or with a water-soluble acid or direct dye.
  • Pigment dispersions are preferred in amounts of 0.1 to 6 % By weight, particularly preferably 0.1 to 3% by weight, based on the shaved weight of the leather.
  • Water-soluble acid or direct dyes are preferably used in amounts of 0.1 to 6% by weight, particularly preferably 0.1 to 4% by weight, based on the shaved weight of the leather.
  • the dispersed sulfur dyes can be combined in any order in the dye liquor with the other colorants mentioned. In addition, it is possible to mix the individual color components used before they are introduced into the dyeing liquor.
  • the total dyeing time is normally 20 to 300, preferably 30 to 120 minutes.
  • additives for example wetting or dispersing agents, leveling aids, color deepening agents and / or degreasing agents, can be added to the dyebath before, during or after the dyeing.
  • salts such as sodium sulfite, sodium hydrogen sulfite or sodium pyrosulfite act as color deepening agents.
  • the entire dyeing process is normally completed by lowering the pH of the dye liquor, to pH 3.8 to 5.5, preferably with formic acid.
  • the added formic acid is allowed to act in the usual way for 10 to 60 minutes.
  • the dyed leather is then prepared and finished in a manner known per se.
  • the water-insoluble sulfur dyes used in the process according to the invention are in dispersed form and preferably have an average particle size of 10 nm to 2000 nm, particularly preferably 50 nm to 1000 nm.
  • the finely divided sulfur dye dispersions are obtained in a manner known per se by grinding the water-insoluble sulfur dyes in suitable grinding units, for example in bead or sand mills, preferably in the presence of dispersants.
  • Anionic surfactants and / or amphoteric surfactants and / or nonionic and / or cationic surfactants are preferred as dispersants.
  • An overview of suitable surfactants can be found e.g. in Ullmann's Encyclopedia of Technical Chemistry, volume 16, 724-742 (1965), volume 22, 455-516 (1982), A 8, 315-350 (1987); E. Daruwalla, in K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. VII, pages 86-92 (1974).
  • sulfur dyestuff dispersions are used in the form of an aqueous dough, they can also contain organic solvents, e.g. from the series of mono- or polyhydric alcohols, polydiols or polyethylene, or polypropylene glycols, and / or contain preservatives known per se.
  • Dispersed sulfur dyestuffs in pigment form are yellow, red, blue, green, brown and black sulfur dyestuffs, which are prepared using known processes, for example by baking or cooking melts of aromatic compounds with sulfur or alkali polysulfides, or by special processes, for example using disulphur dichloride, can be obtained.
  • sulfur dyes based on copper phthalocyanine, perylene tetracarboxylic acid and oxazine dyes can also be used.
  • Preferred sulfur dyes which can be used in finely divided, dispersed form by the dyeing process according to the invention are, for example, the sulfur dyes listed in the Color Index, Vol.5, 3rd Edition (1982) and (1987): Sulfur Black 1, Sulfur Black 2, Sulfur Black 6, Sulfur Black 8, Sulfur Black 9, Sulfur Black 11; Sulfur Brown 1, Sulfur Brown 10, Sulfur Brown 12, Sulfur Brown 15, Sulfor Brown 16, Sulfur Brown 20, Sulfur Brown 21, Sulfur Brown 31, Sulfur Brown 38, Sulfur Brown 46, Sulfur Brown 51, Sulfur Brown 52, Sulfur Brown 60, Sulfur Brown 93, Sulfur Brown 96; Sulfur Blue 2, Sulfur Blue 5, Sulfur Blue 6, Sulfur Blue 7, Sulfur Blue 10, Sulfur Blue 11, Sulfur Blue 12, Sulfur Blue 13; Sulfur Orange 2; Sulfur Green 2, Sulfur Green 3, Sulfur Green 5, Sulfur Green 8, Sulfur Green 9, Sulfur Green 12, Sulfur Green 19,
  • sulfur or sulfur vat dyes are: Sulfur Black 1, Sulfur Black 2, Sulfur Black 6, Sulfur Black 8, Sulfur Black 11; Sulfur Brown 51, Sulfur Brown 96; Sulfur Green 36; Vat Green 14; Sulfur Red 10, Sulfur Red 14.
  • Preferred pigments which can be used in combination with finely dispersed sulfur dyes of the type mentioned by the dyeing process according to the invention are, for example: black pigments based on elemental carbon, e.g. Pigment Black 6, 7, 8, 9, 10, Pigment Yellow 74, Pigment Orange 34, Pigment Orange 36, Pigment Brown 1, Pigment Red 112, Pigment Blue 15: 3. Pigment Black 7 is particularly preferred.
  • Preferred acid and direct dyes which can be used in combination with finely dispersed sulfur dyes of the type mentioned by the dyeing process according to the invention are, for example: Solubilized Sulfur Black 1, Direct Black 168.
  • the method according to the invention is for all types of leather, e.g. mineral or vegetable tanned grain, suede, suede or nubuck leather, suitable for beef, goat, sheep or pork.
  • leather e.g. mineral or vegetable tanned grain, suede, suede or nubuck leather, suitable for beef, goat, sheep or pork.
  • All types of leather have level dyeings of high color strength with good fastness properties, in particular good light fastness, wet fastness, wet and dry rubbing fastness, lick fastness, solvent fastness, sweat fastness and diffusion fastness compared to soft PVC.
  • the good coloration of the leather dyed by the process according to the invention is surprising.
  • percentages mean percentages by weight, based on the shaved weight (Examples 1 and 4) or on the dry weight (Examples 2 and 3) of the leather.
  • the dyed leather is finished by rinsing with water, stretching, drying at 50 to 60 o C and millen.
  • the dyed leather is finished in accordance with Example 1.
  • the dyed leather is finished in accordance with Example 1.
  • the dyed leather is finished in accordance with Example 1.

Abstract

The invention relates to a process for dyeing leather by the exhaust process, characterised in that water-insoluble sulphur dyes are employed in dispersed form.

Description

Gegenstand der vorliegenden Erfindung ist ein Verfahren zum Färben von Leder mit wasserunlöslichen Schwefelfarbstoffen in feinteiliger dispergierter Form, wobei die Färbung aus wäßriger Flotte nach dem Ausziehverfahren ohne Zusatz von Reduktions- und/oder Oxidationsmittel durchgeführt wird.The present invention relates to a process for dyeing leather with water-insoluble sulfur dyes in finely divided form, the dyeing being carried out from an aqueous liquor by the exhaust process without the addition of reducing agents and / or oxidizing agents.

Es ist bereits bekannt, wasserunlösliche Schwefelfarbstoffe in feinteiliger dispergierter Form zum Färben von Baumwollfasern einzusetzen (Textile J. Australia 1972, 22; Melliand Textilber.12, 833 (1984)).It is already known to use water-insoluble sulfur dyes in finely divided form for dyeing cotton fibers (Textile J. Australia 1972 , 22; Melliand Textilber. 12 , 833 (1984)).

Bei diesem Färbeprozeß wird der wasserunlösliche Schwefelfarbstoff mit Reduktionsmitteln zunächst in die wasserlösliche Leukoform übergeführt, die auf die Baumwollfaser aufzieht und anschließend auf der Faser mit Oxidationsmitteln zur wasserunlöslichen Form oxidiert wird. Dieser bekannte Färbeprozeß wird beispielsweise in folgenden Übersichtsartikeln beschrieben: Melliand Textilber.12, 1314 (1973); Ullmann's Enzyklopädie der Technischen Chemie, Band 21, 65 (1982); Rev.Progr.Coloration, Vol.7, 80 (1976)). Ohne die Verwendung von Reduktionsmitteln tritt auf der mit feindispergierten Schwefelfarbstoffen imprägnierten Baumwollfaser keine Farbstoffixierung ein.In this dyeing process, the water-insoluble sulfur dye with reducing agents is first converted into the water-soluble leuco form, which is drawn onto the cotton fiber and then oxidized on the fiber with oxidizing agents to the water-insoluble form. This well-known dyeing process is described, for example, in the following review articles: Melliand Textilber. 12 , 1314 (1973); Ullmann's Encyclopedia of Technical Chemistry, Volume 21, 65 (1982); Rev. Progress Coloring, Vol. 7, 80 (1976)). Without the use of reducing agents, no dye fixation occurs on the cotton fiber impregnated with finely dispersed sulfur dyes.

Wasserlösliche Schwefelfarbstoffe können außer bei der bekannten Anwendung zum Färben von Cellulosefasern auch zum Färben von nichttextilen Fasermaterialien, beispielsweise zum Färben von chromgegerbten Lederarten, eingesetzt werden (Rev.Progr.Coloration Vol.7, 83 (1976)).In addition to the known application for dyeing cellulose fibers, water-soluble sulfur dyes can also be used for dyeing non-textile fiber materials, for example for dyeing chrome-tanned leather types (Rev. Progress Coloring Vol. 7, 83 (1976)).

Kommen als wasserlösliche Schwefelfarbstoffe Bunte-Salze zum Einsatz (K.Venkataraman, The Chemistry of Synthetic Dyes, Vol. VII, 36 (1974)), werden nach den für Säurefarbstoffe üblichen Färbeverfahren farbschwache Färbungen (Leather 178, 27 (1976)) mit guter Durchfärbung erhalten (Leather 177, 4406 (1975)). Aufgrund der geringen Substantivität ziehen diese Bunte-Salze nicht vollständig auf Leder auf und verursachen eine hohe Belastung der Färbereiabwässer. Tiefere Färbungen mit Bunte-Salzen können nur bei gleichzeitiger Verwendung spezieller Hilfsmittel erhalten werden (deutsche Patentschriften 3 601 721, 3 617 636), wobei die Hilfsmittel in den Färbereiabwässern ebenfalls eine Umweltbelastung darstellen.Colored salts are used as water-soluble sulfur dyes (K.Venkataraman, The Chemistry of Synthetic Dyes, Vol. VII, 36 (1974)) are obtained by the dyeing processes (Leather 178 , 27 (1976)) which are weak in color with good coloration (Leather 177 , 4406 (1975)) by the dyeing processes customary for acid dyes. Due to the low substantivity, these colored salts do not completely absorb leather and cause a high pollution of the dyeing waste water. Deeper dyeings with colored salts can only be obtained if special aids are used at the same time (German patents 3 601 721, 3 617 636), the aids in the dyeing waste water also being environmentally harmful.

Auch der Einsatz von wasserlöslichen Schwefelfarbstoffen in der Leuko-Form ist zum Färben von Leder bereits bekannt (britische Patentschrift 1 502 966; Leather 179, 4421 (1977); Leather 178, 59 (1976); Leather 178, 4407 (1976); Leather 178, 27 (1976)). Aufgrund der hohen pH-Werte, die bei Färbungen mit Leuko-Schwefelfarbstoffen durch die Verwendung von Reduktionsmitteln wie Natriumsulfid oder Glucose und Alkalihydroxid eingestellt werden, kommt es durch Faserschädigung zu einer unerwünschten Verhärtung des Leders (J .Soc.Dyers Color. 100, 262 (1984)).The use of water-soluble sulfur dyes in the leuco form is also already known for dyeing leather (British Patent 1,502,966; Leather 179 , 4421 (1977); Leather 178 , 59 (1976); Leather 178 , 4407 (1976); Leather 178 , 27 (1976)). Due to the high pH values that are set for dyeing with leuco sulfur dyes by using reducing agents such as sodium sulfide or glucose and alkali hydroxide, fiber damage leads to undesired hardening of the leather (J. Soc. Dyers Color. 100 , 262 ( 1984)).

Weiterhin ist bereits bekannt, Oberflächen von Fasermaterialien, wie Baumwolle, Polyester, Polyamid oder Leder mit wäßrigen Dispersionen von in Wasser schwer löslichen Anthrachinon-, Indigo-, Schwefel- und Phthalocyanin-Farbstoffen zu färben, wobei diese Dispersionen vernetzbare Harze enthalten, die auf den Fasern bei Temperaturen von 160oC appliziert und verbacken werden (jap.Patentschrift 7 231 393, Chem.Abstr. 78, 85 829 (1973)).Furthermore, it is already known to dye surfaces of fiber materials, such as cotton, polyester, polyamide or leather, with aqueous dispersions of anthraquinone, indigo, sulfur and phthalocyanine dyes which are poorly soluble in water, these dispersions containing crosslinkable resins which act on the Fibers are applied and baked at temperatures of 160 o C (Japanese Patent 7 231 393, Chem. Abstr. 78 , 85 829 (1973)).

Überraschenderweise wurde nun gefunden, daß man Leder unter den in der Lederfärberei üblichen Färbebedingungen (vgl. beispielsweise K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. VIII, 37 (1978) und dort zitierte Literatur) mit wasserunlöslichen Schwefelfarbstoffen in feinteiliger dispergierter Form aus wäßriger Flotte in effektiver Weise färben kann. Der Zusatz von Reduktions- und/oder Oxidationsmitteln ist dabei nicht notwendig.Surprisingly, it has now been found that leather is used under the dyeing conditions customary in leather dyeing (cf., for example, K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. VIII, 37 (1978) and literature cited therein) can effectively dye with water-insoluble sulfur dyes in finely divided, dispersed form from an aqueous liquor. The addition of reducing and / or oxidizing agents is not necessary.

Die vorliegende Erfindung betrifft demnach ein Verfahren zum Färben von Leder nach dem Ausziehverfahren, dadurch gekennzeichnet, daß man wasserunlösliche Schwefelfarbstoffe in dispergierter Form einsetzt.The present invention accordingly relates to a process for dyeing leather by the exhaust process, characterized in that water-insoluble sulfur dyes are used in dispersed form.

Es ist vorteilhaft, zu färbendes Leder in der Weise vorzubehandeln, wie es beim bekannten Ausziehverfahren mit wasserlöslichen Lederfarbstoffen üblich ist (siehe z.B. K.Eitel "Das Färben von Leder", Band 5, S. 269 ff., Umschau-Verlag, Frankfurt/m. (1987)). Auch das erfindungsgemäße Verfahren selbst wird vorteilhaft unter den Färbebedingungen ausgeführt, die für das bekannte Ausziehverfahren mit wasserlöslichen Lederfarbstoffen üblich sind.It is advantageous to pretreat leather to be dyed in the manner that is customary in the known exhaust process with water-soluble leather dyes (see, for example, K.Eitel "The Dyeing of Leather", Volume 5, pp. 269 ff., Umschau-Verlag, Frankfurt / m. (1987)). The process according to the invention itself is also advantageously carried out under the dyeing conditions which are customary for the known exhaust process with water-soluble leather dyes.

Beispielsweise färbt man das Leder in einer wäßrigen Flotte, die auf das Falzgewicht des Leders bezogen 20 bis 400 %, vorzugsweise 50 bis 200 % Wasser enthält, bei einer Temperatur von 20 bis 100oC, vorzugsweise 30 bis 60oC, mit 0,5 bis 8 %, vorzugsweise 1,5 bis 6 % an dispergierten Schwefelfarbstoffen in Pigmentform. Der pH-Wert liegt bevorzugt bei 3,8 bis 5,5.For example, the leather is dyed in an aqueous liquor which contains 20 to 400%, preferably 50 to 200% water, based on the fold weight of the leather, at a temperature of 20 to 100 ° C., preferably 30 to 60 ° C., with 0, 5 to 8%, preferably 1.5 to 6% of dispersed sulfur dyes in pigment form. The pH is preferably 3.8 to 5.5.

Gegebenenfalls können die Schwefelfarbstoffe in dispergierter Form mit einer Dispersion eines anorganischen oder organischen Pigments und/oder mit einem wasserlöslichen Säure-oder Direktfarbstoff kombiniert werden. Pigmentdispersionen werden bevorzugt in Mengen von 0,1 bis 6 Gew.%, besonders bevorzugt 0,1 bis 3 Gew.%, bezogen auf das Falzgewicht des Leders, eingesetzt.If appropriate, the sulfur dyes can be combined in dispersed form with a dispersion of an inorganic or organic pigment and / or with a water-soluble acid or direct dye. Pigment dispersions are preferred in amounts of 0.1 to 6 % By weight, particularly preferably 0.1 to 3% by weight, based on the shaved weight of the leather.

Wasserlösliche Säure- oder Direktfarbstoffe werden bevorzugt in Mengen von 0,1 bis 6 Gew.%, besonders bevorzugt 0,1 bis 4 Gew.%, bezogen auf das Falzgewicht des Leders, eingesetzt.Water-soluble acid or direct dyes are preferably used in amounts of 0.1 to 6% by weight, particularly preferably 0.1 to 4% by weight, based on the shaved weight of the leather.

Die dispergierten Schwefelfarbstoffe können in beliebiger Reihenfolge in der Färbeflotte mit den genannten anderen Farbmitteln kombiniert werden. Darüberhinaus ist es möglich, die einzelnen, zum Einsatz kommenden Farbkomponenten bereits vor dem Einbringen in die Färbeflotte zu mischen.The dispersed sulfur dyes can be combined in any order in the dye liquor with the other colorants mentioned. In addition, it is possible to mix the individual color components used before they are introduced into the dyeing liquor.

Die gesamte Färbedauer beträgt normalerweise 20 bis 300, vorzugsweise 30 bis 120 Minuten.The total dyeing time is normally 20 to 300, preferably 30 to 120 minutes.

Dem Färbebad können gegebenenfalls vor, während oder nach der Färbung weitere Zusätze, beispielsweise Netz- bzw. Dispergiermittel, Egalisierhilfsmittel, Farbvertiefungsmittel und/oder Fettungsmittel zugesetzt werden. Dabei wirken als Farbvertiefungsmittel überraschenderweise Salze, wie Natriumsulfit, Natriumhydrogensulfit oder Natriumpyrosulfit.If necessary, further additives, for example wetting or dispersing agents, leveling aids, color deepening agents and / or degreasing agents, can be added to the dyebath before, during or after the dyeing. Surprisingly, salts such as sodium sulfite, sodium hydrogen sulfite or sodium pyrosulfite act as color deepening agents.

Der gesamte Färbevorgang wird normalerweise durch Absenken des pH-Werts der Färbeflotte, auf pH 3,8 bis 5,5 vorzugsweise mit Ameisensäure, vervollständigt.The entire dyeing process is normally completed by lowering the pH of the dye liquor, to pH 3.8 to 5.5, preferably with formic acid.

Die zugesetzte Ameisensäure läßt man in üblicher Weise 10 bis 60 Minuten einwirken.The added formic acid is allowed to act in the usual way for 10 to 60 minutes.

Die Zurichtung und Fertigstellung des gefärbten Leders erfolgt dann in an sich bekannter Weise.The dyed leather is then prepared and finished in a manner known per se.

Die nach dem erfindungsgemäßen Verfahren eingesetzten wasserunlöslichen Schwefelfarbstoffe liegen in dispergierter Form vor und weisen bevorzugt eine mittlere Teilchengröße von 10 nm bis 2000 nm, besonders bevorzugt 50 nm bis 1000 nm, auf.The water-insoluble sulfur dyes used in the process according to the invention are in dispersed form and preferably have an average particle size of 10 nm to 2000 nm, particularly preferably 50 nm to 1000 nm.

Die feinteiligen Schwefelfarbstoff-Dispersionen werden in an sich bekannter Weise durch Mahlen der wasserunlöslichen Schwefelfarbstoffe in geeigneten Mahlaggregaten, beispielsweise in Perl- oder Sandmühlen, vorzugsweise in Gegenwart von Dispergiermitteln erhalten. Als Dispergiermittel kommen vorzugsweise Aniontenside und/oder Amphotenside und/oder nichtionogene und/oder kationische Tenside in Betracht. Eine Übersicht über geeignete Tenside findet sich z.B. in Ullmann's Enzyklopädie der Technischen Chemie, Band 16, 724-742 (1965), Band 22, 455-516 (1982), A 8, 315-350 (1987); E.H.Daruwalla, in K.Venkataraman, The Chemistry of Synthetic Dyes, Vol. VII, Seiten 86-92 (1974). Werden Schwefelfarbstoff-Dispersionen in wäßriger Teigform eingesetzt, können diese zur Erhöhung der Lagerstabilität noch organische Lösungsmittel, z.B. aus der Reihe der ein- oder mehrwertigen Alkohole, Polydiole oder Polyethylen, bzw. Polypropylenglykole, und/oder an sich bekannte Konservierungsmittel enthalten.The finely divided sulfur dye dispersions are obtained in a manner known per se by grinding the water-insoluble sulfur dyes in suitable grinding units, for example in bead or sand mills, preferably in the presence of dispersants. Anionic surfactants and / or amphoteric surfactants and / or nonionic and / or cationic surfactants are preferred as dispersants. An overview of suitable surfactants can be found e.g. in Ullmann's Encyclopedia of Technical Chemistry, volume 16, 724-742 (1965), volume 22, 455-516 (1982), A 8, 315-350 (1987); E. Daruwalla, in K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. VII, pages 86-92 (1974). If sulfur dyestuff dispersions are used in the form of an aqueous dough, they can also contain organic solvents, e.g. from the series of mono- or polyhydric alcohols, polydiols or polyethylene, or polypropylene glycols, and / or contain preservatives known per se.

Als dispergierte Schwefelfarbstoffe in Pigmentform kommen gelbe, rote, blaue, grüne, braune und schwarze Schwefelfarbstoffe in Frage, die nach bekannten Verfahren, beispielsweise durch Backschmelze oder Kochschmelze aromatischer Verbindungen mit Schwefel oder Alkali-Polysulfiden, oder durch Spezialverfahren, z.B. unter Verwendung von Dischwefeldichlorid, erhalten werden können. Darüberhinaus können auch Schwefelfarbstoffe auf Basis Kupferphthalocyanin, Perylentetracarbonsäure sowie Oxazinfarbstoffe eingesetzt werden.Dispersed sulfur dyestuffs in pigment form are yellow, red, blue, green, brown and black sulfur dyestuffs, which are prepared using known processes, for example by baking or cooking melts of aromatic compounds with sulfur or alkali polysulfides, or by special processes, for example using disulphur dichloride, can be obtained. In addition, sulfur dyes based on copper phthalocyanine, perylene tetracarboxylic acid and oxazine dyes can also be used.

Die Herstellung von Schwefelfarbstoffen ist beispielsweiser beschrieben in Ullmann's Enzyklopädie der Technischen Chemie, Band 21, Seite 65 ff. (1982); K.Venkataraman, The Chemistry of Synthetic Dyes, Vol.II, Seiten 1059-1100 (1952); Vol.VII, Seiten 1-32 (1974); Kirk-Othmer 19, 424-441; 22, 168-189; Melliand Textilber. 60, 254-256 (1979).The production of sulfur dyes is described, for example, in Ullmann's Encyclopedia of Industrial Chemistry, Volume 21, page 65 ff. (1982); K. Venkataraman, The Chemistry of Synthetic Dyes, Vol. II, pages 1059-1100 (1952); Vol.VII, pages 1-32 (1974); Kirk-Othmer 19 , 424-441; 22 , 168-189; Melliand Textilber. 60: 254-256 (1979).

Bevorzugte Schwefelfarbstoffe, die in feinteiliger dispergierter Form nach dem erfindungsgemäßen Färbeverfahren eingesetzt werden können, sind beispielsweise die im Colour Index, Vol.5, 3.Edition (1982) und (1987) aufgeführten Schwefelfarbstoffe:
Sulfur Black 1, Sulfur Black 2, Sulfur Black 6, Sulfur Black 8, Sulfur Black 9, Sulfur Black 11;
Sulfur Brown 1, Sulfur Brown 10, Sulfur Brown 12, Sulfur Brown 15, Sulfor Brown 16, Sulfur Brown 20, Sulfur Brown 21, Sulfur Brown 31, Sulfur Brown 38, Sulfur Brown 46, Sulfur Brown 51, Sulfur Brown 52, Sulfur Brown 60, Sulfur Brown 93, Sulfur Brown 96;
Sulfur Blue 2, Sulfur Blue 5, Sulfur Blue 6, Sulfur Blue 7, Sulfur Blue 10, Sulfur Blue 11, Sulfur Blue 12, Sulfur Blue 13;
Sulfur Orange 2;
Sulfur Green 2, Sulfur Green 3, Sulfur Green 5, Sulfur Green 8, Sulfur Green 9, Sulfur Green 12, Sulfur Green 19, Sulfur Green 25, Sulfur Green 26, Sulfur Green 36, Sulfur Green 37, Sulfur Green 38; Sulfur Red 3, Sulfur Red 4, Sulfur Red 5, Sulfur Red 6, Sulfur Red 10, Sulfur Red 11, Sulfur Red 12, Sulfur Red 14;
Sulfur Violett 3;
Sulfur Yellow 5, Sulfur Yellow 19, Sulfur Yellow 20. Bevorzugte Schwefelküpenfarbstoffe sind beispielsweise:
Vat Blue 42, Vat Blue 43, Vat Blue 47, Vat Green 14.Preferred sulfur dyes which can be used in finely divided, dispersed form by the dyeing process according to the invention are, for example, the sulfur dyes listed in the Color Index, Vol.5, 3rd Edition (1982) and (1987):
Sulfur Black 1, Sulfur Black 2, Sulfur Black 6, Sulfur Black 8, Sulfur Black 9, Sulfur Black 11;
Sulfur Brown 1, Sulfur Brown 10, Sulfur Brown 12, Sulfur Brown 15, Sulfor Brown 16, Sulfur Brown 20, Sulfur Brown 21, Sulfur Brown 31, Sulfur Brown 38, Sulfur Brown 46, Sulfur Brown 51, Sulfur Brown 52, Sulfur Brown 60, Sulfur Brown 93, Sulfur Brown 96;
Sulfur Blue 2, Sulfur Blue 5, Sulfur Blue 6, Sulfur Blue 7, Sulfur Blue 10, Sulfur Blue 11, Sulfur Blue 12, Sulfur Blue 13;
Sulfur Orange 2;
Sulfur Green 2, Sulfur Green 3, Sulfur Green 5, Sulfur Green 8, Sulfur Green 9, Sulfur Green 12, Sulfur Green 19, Sulfur Green 25, Sulfur Green 26, Sulfur Green 36, Sulfur Green 37, Sulfur Green 38; Sulfur Red 3, Sulfur Red 4, Sulfur Red 5, Sulfur Red 6, Sulfur Red 10, Sulfur Red 11, Sulfur Red 12, Sulfur Red 14;
Sulfur Violet 3;
Sulfur Yellow 5, Sulfur Yellow 19, Sulfur Yellow 20. Examples of preferred sulfur vat dyes are:
Vat Blue 42, Vat Blue 43, Vat Blue 47, Vat Green 14.

Besonders bevorzugte Schwefel- bzw. Schwefelküpenfarbstoffe sind:
Sulfur Black 1, Sulfur Black 2, Sulfur Black 6, Sulfur Black 8, Sulfur Black 11;
Sulfur Brown 51, Sulfur Brown 96;
Sulfur Green 36;
Vat Green 14;
Sulfur Red 10, Sulfur Red 14.Particularly preferred sulfur or sulfur vat dyes are:
Sulfur Black 1, Sulfur Black 2, Sulfur Black 6, Sulfur Black 8, Sulfur Black 11;
Sulfur Brown 51, Sulfur Brown 96;
Sulfur Green 36;
Vat Green 14;
Sulfur Red 10, Sulfur Red 14.

Bevorzugte Pigmente, die in Kombination mit feindispergierten Schwefelfarbstoffen der genannten Art nach dem erfindungsgemäßen Färbeverfahren eingesetzt werden können, sind beispielsweise: Schwarzpigmente auf der Basis elementeren Kohlenstoffs, z.B. Pigment Black 6, 7, 8, 9, 10, Pigment Yellow 74, Pigment Orange 34, Pigment Orange 36, Pigment Brown 1, Pigment Red 112, Pigment Blue 15:3. Besonders bevorzugt ist Pigment Black 7.Preferred pigments which can be used in combination with finely dispersed sulfur dyes of the type mentioned by the dyeing process according to the invention are, for example: black pigments based on elemental carbon, e.g. Pigment Black 6, 7, 8, 9, 10, Pigment Yellow 74, Pigment Orange 34, Pigment Orange 36, Pigment Brown 1, Pigment Red 112, Pigment Blue 15: 3. Pigment Black 7 is particularly preferred.

Bevorzugte Säure- und Direktfarbstoffe, die in Kombination mit feindispergierten Schwefelfarbstoffen der genannten Art nach dem erfindungsgemäßen Färbeverfahren eingesetzt werden können, sind beispielsweise: Solubilised Sulfur Black 1, Direct Black 168.Preferred acid and direct dyes which can be used in combination with finely dispersed sulfur dyes of the type mentioned by the dyeing process according to the invention are, for example: Solubilized Sulfur Black 1, Direct Black 168.

Das erfindungsgemäße Verfahren ist für alle Lederarten, z.B. mineralisch oder vegetabil gegerbte Narben-, Rauh-, Velour- oder Nubukleder, vom Rind, Ziege, Schaf oder Schwein geeignet.The method according to the invention is for all types of leather, e.g. mineral or vegetable tanned grain, suede, suede or nubuck leather, suitable for beef, goat, sheep or pork.

Auf allen Lederarten erhält man egale Färbungen hoher Farbstärke mit guten Echtheitseigenschaften, insbesondere guter Lichtechtheit, Naßechtheit, Naß- und Trockenreibechtheit, Lickerechtheit, Lösungsmittelechtheit, Schweißechtheit und Diffusionsechtheit gegenüber Weich-PVC.All types of leather have level dyeings of high color strength with good fastness properties, in particular good light fastness, wet fastness, wet and dry rubbing fastness, lick fastness, solvent fastness, sweat fastness and diffusion fastness compared to soft PVC.

Überraschend ist insbesondere die gute Durchfärbung der nach dem erfindungsgemäßen Verfahren gefärbten Leder. Dabei treten die Nachteile der bisherigen bekannten Färbeverfahren mit Bunte-Salzen (geringe Substantivität, hohe Abwasserbelastung) bzw. mit Leuko-Schwefelfarbstoffen (Faserschädigung durch hohe pH-Werte) bzw. mit Farbstoff-Dispersionen in Gegenwart von vernetzbaren Harzen (hoher Energiebedarf durch Färbung bei 160oC) nicht auf.In particular, the good coloration of the leather dyed by the process according to the invention is surprising. The disadvantages of the previously known dyeing processes with colored salts (low substantivity, high wastewater pollution) or with leuco sulfur dyes (fiber damage due to high pH values) or with dye dispersions in the presence of crosslinkable resins (high energy requirement due to dyeing) 160 o C) not.

In den folgenden Beispielen bedeuten Prozente Gewichtsprozente, bezogen auf das Falzgewicht (Beispiele 1 und 4) bzw. auf das Trockengewicht (Beispiele 2 und 3) des Leders.In the following examples, percentages mean percentages by weight, based on the shaved weight (Examples 1 and 4) or on the dry weight (Examples 2 and 3) of the leather.

Beispiel 1example 1

Färhung von chromgegerbtem feuchten Leder zur Verwendung als Schuhoberleder. Folgende Arbeitsgänge werden ausgeführt: Arbeitsgang Menge Produkt Temperatur Zeitdauer Neutralisation 150,0 % Wasser 35oC 1,5 % Natriumformiat 30 min 0,5 % Natriumhydrogencarbonat 30 min Spülen Färbung, Nach-gerbung, Fettung 50,0 % Wasser 25oC 4,0 % dispergierter Schwefelfarbstoff (40 %) Colour Index Sulfur Brown 51 1,0 % Ammoniak (25 %) 40 min 4,0 % handelsüblicher Pflanzlicher Gerbstoff, z.B.Mimosa 40 min 8,0 % Sulfochloriertes gesättigtes lineares C₂₄-C₃₀-Fett 40 min 100,0 % Wasser 60oC 3,0 % Ameisensäure (85 %) 40 min Chrome tanned wet leather used for upper shoe leather. The following operations are carried out: Operation amount product temperature Duration Neutralization 150.0% water 35 o C 1.5% Sodium formate 30 min 0.5% Sodium bicarbonate 30 min do the washing up Coloring, retanning, greasing 50.0% water 25 o C 4.0% dispersed sulfur dye (40%) Color Index Sulfur Brown 51 1.0% Ammonia (25%) 40 min 4.0% commercial vegetable tanning agent, e.g. mimosa 40 min 8.0% Sulfochlorinated saturated linear C₂₄-C₃₀ fat 40 min 100.0% water 60 o C 3.0% Formic acid (85%) 40 min

Die Fertigstellung des gefärbten Leders erfolgt durch Spülen mit Wasser, Ausrecken, Trocknen bei 50 bis 60oC und Millen.The dyed leather is finished by rinsing with water, stretching, drying at 50 to 60 o C and millen.

Beispiel 2Example 2

Färbung von rein vegetabil gegerbtem trockenem Leder zur Verwendung als Möbelleder. Folgende Arbeitsgänge werden ausgeführt: Arbeitsgang Menge Produkt Temperatur Zeitdauer Broschur 700,0 % Wasser 40oC 4,0 % Oxysulfitiertes Fischöl 120 min Flotte ablassen Waschen 500,0 % Wasser 35oC Vorfärbung und Fettung 300,0 % Wasser 35oC 0,8 % Stearylamin mit 12 Ethylenoxid-Einheiten 10 min 0,5 % Polyglycol des Molekulargewichts von ca.6000 1,0 % Ammoniak (25 %) 25 min 6,0 % Dispergierter Schwefelfarbstoff (40 %) Colour Index Sulfur Brown 51 45 min 6,0 % Oxysulfitiertes Fischöl 30 min 3,0 % Ameisensäure (85 %) 20 min Spülen 500,0 % Wasser 55oC Überfärbung 500,0 % Wasser 55oC 1,0 % Polyacrylsäure des Molekulargewichts von ca. 1000 10 min 0,1 % primäres Talgfettamin 10 min 2,0 % Melamin-Formaldehyd-Harnstoff-Kondensationsprodukt 1,0 % Dispergierter Schwefelfarbstoff (40 %) Colour Index Sulfur Brown 51 0,5 % Pigmentdispersion (30 %) Colour Index P.Br.1 1,0 % Pigmentdispersion (22 %) Colour Index P.0.36 2,0 % Pigmentdispersion (40 %) Colour Index Pigment White 77891 60 min 1,0 % Ameisensäure (85 %) 10 min 1,5 % Ameisensäure (85 %) 10 min Coloring of purely vegetable-tanned dry leather for use as furniture leather. The following operations are carried out: Operation amount product temperature Duration Paperback 700.0% water 40 o C 4.0% Oxysulfited fish oil 120 min Drain the fleet To wash 500.0% water 35 o C Pre-staining and greasing 300.0% water 35 o C 0.8% Stearylamine with 12 ethylene oxide units 10 min 0.5% Polyglycol with a molecular weight of approx. 6000 1.0% Ammonia (25%) 25 min 6.0% Dispersed sulfur dye (40%) Color Index Sulfur Brown 51 45 min 6.0% Oxysulfited fish oil 30 min 3.0% Formic acid (85%) 20 min do the washing up 500.0% water 55 o C Over-staining 500.0% water 55 o C 1.0% Polyacrylic acid with a molecular weight of approx. 1000 10 min 0.1% primary tallow fatty amine 10 min 2.0% Melamine-formaldehyde-urea condensation product 1.0% Dispersed sulfur dye (40%) Color Index Sulfur Brown 51 0.5% Pigment dispersion (30%) Color Index P.Br.1 1.0% Pigment dispersion (22%) Color Index P.0.36 2.0% Pigment dispersion (40%) Color Index Pigment White 77891 60 min 1.0% Formic acid (85%) 10 min 1.5% Formic acid (85%) 10 min

Die Fertigstellung des gefärbten Leders erfolgt entsprechend Beispiel 1.The dyed leather is finished in accordance with Example 1.

Beispiel 3Example 3

Färbung von chromgegerbtem, nachgegerbtem und gefettetem, trockenem Leder zur Verwendung als Möbelleder. Folgende Arbeitsgänge werden ausgeführt: Arbeitsgang Menge Produkt Temperatur Zeitdauer Broschur 1000,0 % Wasser 45oC 2,0 % Ammoniak (25 %) 120 min Spülen Färben 400,0 % Wasser 45oC 1,0 % Ammoniak (25 %) 10 min 3,0 % Dispergierter Schwefelfarbstoff (40 %) C.I. Sulfur Brown 51 1,5 % handelsüblicher wasserlöslicher Azobraun-Farbstoff 60 min C.I. 14615, Acid Brown 102 1,5 % Ameisensaure (85 %) neue Flotte 20 min Überfärbung 400,0 % Wasser 45oC 1,5 % Dispergierter Schwefelfarbstoff (40 %) C.I. Sulfur Brown 51 0,8 % hanelsüblicher wasserlöslicher Azobraun Farbstoff C.I. 14615, Acid Brown 102 30 min 0,5 % Ameisensäure (85 %) 20 min Coloring chrome-tanned, retanned and greased, dry leather for use as furniture leather. The following operations are carried out: Operation amount product temperature Duration Paperback 1000.0% water 45 o C 2.0% Ammonia (25%) 120 min do the washing up To dye 400.0% water 45 o C 1.0% Ammonia (25%) 10 min 3.0% Dispersed sulfur dye (40%) CI Sulfur Brown 51 1.5% commercially available water-soluble azo brown dye 60 min CI 14615, Acid Brown 102 1.5% Formic acid (85%) new fleet 20 min Over-staining 400.0% water 45 o C 1.5% Dispersed sulfur dye (40%) CI Sulfur Brown 51 0.8% commercially available water-soluble azo brown dye CI 14615, Acid Brown 102 30 min 0.5% Formic acid (85%) 20 min

Die Fertigstellung des gefärbten Leders erfolgt entsprechend Beispiel 1.The dyed leather is finished in accordance with Example 1.

Beispiel 4Example 4

Färbung von chromgegerbtem feuchtem Leder zur Verwendung als Schuhoberleder. Folgende Arbeitsgänge werden ausgeführt: Arbeitsgang Menge Produkt Temperatur Zeitdauer Waschen 300,0 % Wasser 40oC 10 min Neutralisation 150,0 % Wasser 40oC 1,5 % Natriumformiat 30 min 1,0 % Natriumhydrogencarbonat 60 min Färbung und Pigmentierung 50,0 % Wasser 30oC 0,8 % Ammoniak (25 %ig) 10 min 2,0 % m-Benzoldisulfosäure (Dinatriumsalz) 15 min 4,5 % Dispergierter Schwefelfarbstoff (40 %) C.I. Sulfur Black 11 2,0 % Rußschwarz-Dispersion (40 %) C.I. Pigment Black 7 45 min 1,0 % Melamin-Formaldehyd-Harnstoff-Kondensationsprodukt 15 min Nachgerbung 10,0 % Dihydroxydiphenylsulfon-Naphthalinsulfosäure-Formaldehyd-Kondensationsprodukt 100,0 % Wasser 75oC 8,0 % Oxysulfitiertes Fischöl 45 min 3,0 % Ameisensäure (85 %ig) 20 min neue Flotte Topfärbung und Fixierung 150,0 % Wasser 50oC 1,0 % Dispergierter Schwefelfarbstoff(40 %) C.I. Sulfur Black 11 30 min 1,0 % Rußschwarz-Dispersion (40%) Pigment Black 6 1,0 % Ameisensäure (85 %) 20 min 0,5 % Dicyandiamid-Formaldehyd-Kondensationsprodukt 20 min Dyeing chrome-tanned damp leather for use as upper leather. The following operations are carried out: Operation amount product temperature Duration To wash 300.0% water 40 o C 10 min Neutralization 150.0% water 40 o C 1.5% Sodium formate 30 min 1.0% Sodium bicarbonate 60 min Coloring and pigmentation 50.0% water 30 o C 0.8% Ammonia (25%) 10 min 2.0% m-benzene disulfonic acid (disodium salt) 15 minutes 4.5% Dispersed sulfur dye (40%) CI Sulfur Black 11 2.0% Carbon black dispersion (40%) CI Pigment Black 7 45 min 1.0% Melamine-formaldehyde-urea condensation product 15 minutes Retanning 10.0% Dihydroxydiphenylsulfone-naphthalenesulfonic acid-formaldehyde condensation product 100.0% water 75 o C 8.0% Oxysulfited fish oil 45 min 3.0% Formic acid (85%) 20 min new fleet Pot coloring and fixation 150.0% water 50 o C 1.0% Dispersed sulfur dye (40%) CI Sulfur Black 11 30 min 1.0% Carbon black dispersion (40%) Pigment Black 6 1.0% Formic acid (85%) 20 min 0.5% Dicyandiamide-formaldehyde condensation product 20 min

Die Fertigstellung des gefärbten Leders erfolgt entsprechend Beispiel 1.The dyed leather is finished in accordance with Example 1.

Claims (8)

Verfahren zum Färben von Leder nach dem Ausziehverfahren, dadurch gekennzeichnet, daß man wasserunlösliche Schwefelfarbstoffe in dispergierter Form einsetzt.Process for dyeing leather by the exhaust process, characterized in that water-insoluble sulfur dyes are used in dispersed form. Verfahren zum Färben von Leder nach Anspruch 1, dadurch gekennzeichnet, daß die dispergierten wasserunlöslichen Schwefelfarbstoffe eine Teilchengroße von 10 nm bis 2000 nm aufweisen.Process for dyeing leather according to claim 1, characterized in that the dispersed water-insoluble sulfur dyes have a particle size of 10 nm to 2000 nm. Verfahren zum Färben von Leder nach den Ansprüchen 1 und/oder 2, dadurch gekennzeichnet, daß die dispergierten wasserunlöslichen Schwefelfarbstoffe eine Teilchengröße von 50 nm bis 1000 nm aufweisen.Process for dyeing leather according to claims 1 and / or 2, characterized in that the dispersed water-insoluble sulfur dyes have a particle size of 50 nm to 1000 nm. Verfahren zum Färben von Leder nach einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die dispergierten wasserunlöslichen Schwefelfarbstoffe mit Hilfe von Aniontensiden, Amphotensiden, kationischen Tensiden und/oder nichtionischen Tensiden dispergiert sind.Process for dyeing leather according to one or more of claims 1 to 3, characterized in that the dispersed water-insoluble sulfur dyes are dispersed with the aid of anionic surfactants, amphoteric surfactants, cationic surfactants and / or nonionic surfactants. Verfahren zum Färben von Leder nach einem oder mehreren der Ansprüchen 1 bis 4, dadurch gekennzeichnet, daß man als wasserunläsliche Schwefelfarbstoffe Sulfur Black 1, Sulfur Black 2, Sulfur Black 6, Sulfur Black 8, Sulfur Black 11, Sulfur Brown 51, Sulfur Brown 96, Sulfur Green 36, Vat Green 14, Sulfur Red 10, Sulfur Red 14 einsetzt.Process for dyeing leather according to one or more of Claims 1 to 4, characterized in that Sulfur Black 1, Sulfur Black 2, Sulfur Black 6, Sulfur Black 8, Sulfur Black 11, Sulfur Brown 51, Sulfur Brown 96 are used as water-insoluble sulfur dyes , Sulfur Green 36, Vat Green 14, Sulfur Red 10, Sulfur Red 14. Verfahren zum Färben von Leder nach einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß man die dispergierten wasserunlöslichen Schwefelfarbstoffe mit einer Dispersion eines anorganischen oder organischen Pigments und/oder mit einem wasserlöslichen Säure- oder Direktfarbstoff kombiniert.Process for dyeing leather according to one or more of claims 1 to 5, characterized in that the dispersed water-insoluble sulfur dyes are combined with a dispersion of an inorganic or organic pigment and / or with a water-soluble acid or direct dye. Verfahren zum Färben von Leder nach Anspruch 6, dadurch gekennzeichnet, daß als Pigmente Schwarzpigmente auf der Basis elementaren Kohlenstoffs, beispielsweise Pigment Black 6, 7, 8, 9, 10, Pigment Yellow 74, Pigment Orange 34, Pigment Orange 36, Pigment Brown 1, Pigment Red 112 oder Pigment Blue 15:3 eingesetzt werden.Process for dyeing leather according to claim 6, characterized in that the pigments are black pigments based on elemental carbon, for example pigment black 6, 7, 8, 9, 10, pigment yellow 74, pigment orange 34, pigment orange 36, pigment brown 1 , Pigment Red 112 or Pigment Blue 15: 3 can be used. Verfahren zum Färben von Leder nach Anspruch 6, dadurch gekennzeichnet, daß als Säure- bzw. Direktfarbstoffe Solubilised Sulfur Black 1 oder Direkt Black 168 eingesetzt werden.Process for dyeing leather according to claim 6, characterized in that Solubilised Sulfur Black 1 or Direkt Black 168 are used as acid or direct dyes.
EP92102027A 1991-02-23 1992-02-07 Process for dyeing leather with water insoluble sulfurdyes Withdrawn EP0501197A1 (en)

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